152 lines
101 KiB
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152 lines
101 KiB
JSON
[
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"id": 1,
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"chunk": "# (12) United States Patent Barr et al.",
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"category": " References"
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},
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"id": 2,
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"chunk": "# (54) FUNCTIONAL POLYMER \n\n(75） Inventors: Robert K. Barr, Shrewsbury, MA (US); Edgardo Anzures, Westborough, MA (US); Daniel E. Lundy, Winchendon, MA (US) \n\n(73） Assignee: Rohm and Haas Electronic Materials LLC, Marlborough, MA (US) \n\n(\\*) Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 U.S.C. 154(b) by 263 days. \n\n(21） Appl.No.: 10/391,154 (22) Filed: Mar. 18, 2003 (65) Prior Publication Data \n\nUS 2004/0063027 A1 Apr.1,2004",
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"category": " References"
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},
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{
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"id": 3,
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"chunk": "# Related U.S. Application Data \n\n(60） Provisional application No. 60/432,875, filed on Dec. 12, 2002, provisional application No. 60/414,759, filed on Sep. 30, 2002, provisional application No. 60/414,758, filed on Sep.30, 2002. \n\n(51) Int. Cl. C08F 2/46 (2006.01) C08G 73/06 (2006.01) G03C 1/73 (2006.01) \n(52) U.S. Cl. 522/34; 522/34; 522/35; 522/48; 522/50; 528/423; 430/286.1 \n(58) Field of Classification Search 430/270.1; 526/319 See application file for complete search history.",
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"category": " References"
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},
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{
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"id": 4,
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"chunk": "# References Cited",
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"category": " References"
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},
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"id": 5,
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"chunk": "# U.S. PATENT DOCUMENTS \n\n3,719,638 A 3/1973 Huemmer et al. \n3,928,299 A 12/1975 Rosenkranz et al. \n4,040,925 A 8/1977 McGinniss \n4,186,069 A 1/1980 Muzyczko et al. \n4,224,398 A 9/1980 Muzyczko et al. \n4,273,851 A 6/1981 Muzyczko et al. \n4,308,394A 零 12/1981 Shuster et al. 560/51 \n4,537,855 A 8/1985 Ide \n(10) Patent No.: US 7,148,265 B2 \n(45) Date of Patent: Dec.12, 2006 \n\n4,795,787A 1/1989 Walz 4,910,119 A 3/1990 Schneller et al. 4,912,018 A 3/1990 Osuch et al. 4,992,354A 2/1991 Axon et al. 5,037,913 A 8/1991 Leussler et al. 5,068,262 A 11/1991 Noguchi 5,108,870 A 4/1992 Shalom 5,153,323 A 10/1992 Rossman et al. 5,415,972 A 5/1995 Mayes 5,492,790 A 2/1996 Hishiro 5,583,163A 12/1996 Muller 5,683,856 A 11/1997 Aoai et al. 5,712,078 A 1/1998 Huang et al. 5,719,008 A 2/1998 Hozumi et al. 5,733,714 A 3/1998 McCulloch et al. 5,807,927 A 9/1998 Stockinger et al. 5,869,220 A 2/1999 Hallock et al. 5,910,395 A 6/1999 Li et al. 5,919,599 A \\* 7/1999 Meador et al. 430/271.1 5,945,489 A 8/1999 Moy et al. 6,007,833A 12/1999 Chudzik et al. 6,025,410 A 2/2000 Moy et al. 6,153,349 A 11/2000 Ichikawa et al. 6,156,345 A 12/2000 Chudzik et al. 6,165,677 A 12/2000 Yako 6,207,356 B1 3/2001 Banba et al. 6,242,597 B1 6/2001 Gupta et al. 6,251,569 B1 6/2001 Angelopoulos et al. 6,297,328 B1 10/2001 Collins et al. 6,406,828 B1 6/2002 Szmanda et al. 6,455,479 B1 9/2002 Sahbari 6,458,517 B1 10/2002 Nohara et al. \n04/0063026 A1\\* 4/2004 Barr et al. 430/270.1 \n04/0063030 A1 4/2004 Barr et al. \n04/0224259 A1\\* 11/2004 Anzures et al. 430/281.1",
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"category": " References"
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},
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"id": 6,
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"chunk": "# FOREIGN PATENT DOCUMENTS \n\nEP 0 469584B1 3/1997 \n\n\\* cited by examiner \n\nPrimary Examiner—Rosemary Ashton (74)Attorney, Agent, or Firm—John J. Piskorski",
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"category": " References"
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},
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{
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"id": 7,
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"chunk": "# ABSTRACT \n\nA polymer having $\\mathbf{\\alpha}_{\\alpha,\\beta}$ unsaturated groups and a group that generates a free radical when exposed to actinic radiation. The polymer may be self-cross-linking. \n\n7 Claims, No Drawings",
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"category": " Abstract"
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},
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"id": 8,
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"chunk": "# 1 FUNCTIONALPOLYMER \n\nThis application claims the benefit of U.S. Provisional Application(s) No(s).: 60/414,759,filed Sep. 30, 2002, 60/414,758, filed Sep.30, 2002, 60/432,875, filed Dec.12, 2002.",
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"category": " References"
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},
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"id": 9,
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"chunk": "# BACKGROUND OF THE INVENTION \n\nThe present invention is directed to a functional polymer. 1 More specifically, the present invention is directed to a functional polymer having unsaturated groups and produces a free radical upon exposure to actinic radiation. \n\nPolymers are employed for numerous purposes in a wide variety of industries. Functional polymers that readily form films on a surface are highly desirable for use in the fields of lithography, optical data storage, decorative pigments, adhesives, cosmetics, paints, shellack, security applications or active and passive optical elements such as polarizers, optical retarders or color filters, electrophotographic imaging members, and the like. \n\nIn addition to polymers, acrylates, methacrylates and other unsaturated monomers are employed in coatings, adhesives, sealants, and elastomers, and may be cross-linked by ultraviolet light (UV) radiation or peroxide initiated free radical cure. Such monomers are typically low molecular weight compounds that may be volatile or readily absorbed through skin and may cause adverse health effects. Additionally, many such unsaturated monomers are unstable in compositions, thus they precipitate out of solution during storage reducing the shelf life of the composition. Further, many unsaturated monomers precipitate out of processing solution leaving an undesirable scum or residue, which may contaminate articles or manufacturing apparatus. Reducing the monomer content of compositions may overcome some of the foregoing problems, however, unsaturated monomers are often needed to provide the cross-linking component in a composition. \n\nIn addition to unsaturated monomers, photoinitiators employed in compositions sensitive to actinic radiation also create unwanted problems. Many photoinitiators are insoluble in aqueous or polar diluents because of their aromatic structures. As a result such photoinitiators precipitate out of solution to contribute to the undesirable scum and residue caused by unsaturated monomers. Such a problem is especially found in a number of photoresists. Also, such photoinitiators may be absorbed through the skin creating a hazard to workers. \n\nPhotoresists include at least a resin binder, a cross-linking monomer or oligomer and a photoinitiator. A wide variety of polymeric binders may be used in photoresists. Such polymeric binders may include, as polymerized components, one or more acid functional monomers such as acrylic acid or methacrylic acid. Photoresists may be employed in a number of industries. Such industries include, but are not limited to, the electronics industry such as the manufacture of printed wiring boards, photomasks, planographic printing plates and semiconductors, color filters for use in color liquid crystal display devices, and color image pick-up elements. \n\nA photoresist may be either positive-acting or negative- 6( acting. For negative-acting photoresists, coating layer portions that are exposed to activating radiation polymerize or cross-link in a reaction between a photoactive compound and polymerizable agents of the photoresist composition. Consequently, the exposed coating portions are rendered 6: less soluble in a developer solution than unexposed portions. For positive-acting photoresists, exposed portions are ren \n\ndered more soluble in a developer solution while areas not exposed remain comparatively less developer soluble. \n\nPhotoresists also may be either liquid or dry film. Liquid photoresists are disposed, coated, or applied on a substrate and then cured.Dry film photoresists may be laminated to a substrate. One problem with many photoresists is that they are difficult to strip from electrolytically plated circuit boards using conventional alkaline aqueous stripping solutions, e.g. $3\\%$ sodium hydroxide solutions. If the photoresist is not completely stripped and removed, ragged metal circuit lines may result after etching and may cause short-circuiting of the board. \n\nOrganic-based (amine- or organic solvent-containing) alkaline stripping solutions may be used which produce smaller stripped particles to facilitate stripping. While such organic-based strippers remove photoresist better than inorganic-based strippers, they are expensive relative to inorganic-based strippers (e.g. sodium or potassium hydroxide) and have more waste treatment and environmental concerns associated with them. Solvent-strippable photoresists are much less desirable due to workplace regulations limiting or reducing solvent emissions. \n\nAnother problem associated with many photoresists is the build-up of organic scum and residue from uncured photo \n25 resist, as briefly mentioned above. Such organic scum and residue may deposit on various articles and apparatus during the manufacture of products made using photoresists such as printed wiring boards, developer solutions and developer apparatus. Much of the organic scum and residue is caused \n30 by unsaturated monomers and oligomers such as (meth) acrylate-based compounds and photoactive agents having numerous aromatic groups. Examples of such photoactive agents that may form part of the scum and residue include, but are not limited to, imidazole dimers, benzophenones, \n35 acetophenones, anthraquinones, naphthaquinones, and triazine-based compounds. Such contaminants are not readily water-soluble or water-dispersible after they form residues in solution or deposit on an article or apparatus.As dissolved photoresists build up in solution (developer loading) \n40 insoluble organic materials begin to form in the developing tank eventually forming scum or residue. Presence of antifoam additives (added to developer solutions to minimize foaming) increases the tendency for residue and scum to form. As the level of scum builds chances increase for a \n45 redeposit of the scum and residue onto the developed circuit board. Such redeposited residues cause a retardation of etching solution (etching chemistries have difficulty penetrating organic residues) and cause plating inhibition. Where etch is retarded, circuit shorts form causing a defec \n50 tive circuit board. In addition to increasing potential for defective circuit boards, the residue and scum also make cleaning equipment difficult, thus increasing maintenance time and cost in circuit board manufacturing. U.S.Pat.No.5,945,489 andU.S.Pat.No. 6.025,410 both \n55 to Moy et al. (also see “Novel Resins That Cure Without Added Photoinitiator\" by Sheridan et al. Chemistry II-New Chemistry, RadTech 2002, pages 462-474 (Technical Conference Proceedings)) disclose photosensitive oligomers that may be cross-linked without an added photoinitiator. The \n60 patents disclose that a Michael addition of acetoacetate donors to multifunctional acrylate receptor compounds yields polyesters with reactive pendent acrylate groups, which may be cross-linked in a subsequent curing reaction. The patents state that pendent methyl ketone substituents \n65 serve as an internal photoinitiator. Upon exposure to UV radiation, an acyl radical with the methyl substituent is believed to be formed which acts as a photoinitiator, thus \n\nphotoinitiators are not added to compositions containing the oligomers. Such oligomers are liquid oligomers, which may be employed as decorative coatings on wood and metal substrates. Odor generated from unreacted photoinitiators and skin absorption of unreacted photoinitiators is avoided, thus compositions containing such oligomers may be employed in materials that include medical and food contact applications.However, such oligomers are not believed to be suitable for use in photoresists because they are not alkali developable, and are not photosensitive at wavelengths greater than $320~\\mathrm{{nm}}$ . Accordingly, the oligomers of Moy et al. are limited in their applications. \n\nAccordingly, in view of the foregoing problems there is a need for photosensitive compositions having components that are more water-soluble or water-dispersible and eliminate or reduce contamination of articles.",
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"category": " Introduction"
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},
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"id": 10,
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"chunk": "# SUMMARYOFTHEINVENTION \n\nThe present invention is directed to a polymer having $\\mathbf{\\alpha}_{\\mathbf{{\\alpha}}_{\\mathbf{{\\beta}}}}$ -unsaturation and a group that generates a free radical upon exposure of the compound to actinic radiation, the polymer has an average molecular weight of at least 1000 daltons. \n\nThe polymers may be employed in various photosensitive compositions, such as coatings, adhesives, decorative pigments, and compositions employed in lithography, optical data storage, active and passive optical elements such as polarizers, optical retarders or color filters, and electrophotographic imaging members. The polymers also are suitable for use in photoresists. \n\nThe $\\mathbf{\\alpha}_{\\mathbf{{\\alpha}}}\\mathbf{{\\alpha}}_{\\mathbf{{\\alpha}}}\\mathbf{{\\beta}}_{\\mathbf{{\\alpha}}}$ -unsaturated functional groups of the polymers of the present invention enable the polymers to self-cross-link, thus compositions containing the polymers have no additional unsaturated monomers or have reduced amounts of unsaturated monomers in contrast to many conventional photosensitive compositions. The free radicals generated by the polymers may act as a photoinitiator, thus compositions containing polymers of the present invention also eliminate or reduce the amounts of added photoinitiator to the compositions. Accordingly, compositions containing polymers of the present invention eliminate or at least reduce scum and residue formation caused by unsaturated monomers and many photoinitiators found in conventional photosensitive compositions. \n\nAdditionally, the polymers of the present invention may have hydrophilic components such that the polymers are water-soluble or water-dispersable. When polymers of the present invention are employed in photoresists, such watersolubility or water-dispersability helps eliminate or reduces scum and residue formation caused by uncured photoresists. Further, the hydrophilicity of the polymers of the present invention also improves developability and strippability of photoresists containing the polymers. \n\nElimination or reduction of unsaturated monomers and photoinitiators reduces the solids content of the photoresist, thus enabling an increase of the diluent or liquid portion of the photoresist. Accordingly, the present invention also is directed to a liquid photoresist. Additionally, reduction of the chemical components of the photoresist reduces the cost in manufacturing of the photoresist. \n\nIn addition to $\\mathbf{\\alpha}_{\\mathbf{{\\alpha}}_{\\mathbf{{\\beta}}}}$ -unsaturation and having an integral photoinitiator, polymers of the present invention also may have dyes, stripping agents, plasticizers, surfactants and other components used in photosensitive compositions joined to them. Thus, polymers of the present invention may compose the entire solids fraction of a photosensitive composition.",
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"category": " Results and discussion"
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},
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"id": 11,
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"chunk": "# DETAILED DESCRIPTION OF THE INVENTION \n\nA “moiety” within the scope of the present invention means a distinct structural component of the functional \n10 polymer and is synonymous with the term“group\". The term \"polymer\" means both polymer and copolymer. A“capping group” is a group that is at a terminus of a polymer's backbone. “Pendent\" means a structural component of the functional polymer that is joined to or suspended from the \n15 main chain or backbone of the functional polymer by a chemical bond. “(Meth)acrylate\" means both acrylate and methacrylate and (meth)acrylic means both acrylic and methacrylic.“Monomer” or “oligomer” means any ethylenically or acetylenically unsaturated compound that may be \n20 polymerized.“Functional group” means a component of a functional polymer that adds serviceability or processability to the polymer or permits the polymer to have a function in a composition other than just as a binder component. “Hydrophilic” within the scope of the present invention \n25 means water-soluble or water-dispersable.“Water-soluble” within the scope of the present invention means that a compound or polymer swells or dissolves in water at normal temperatures (from above $0^{\\circ}$ C.to $100^{\\circ}\\mathrm{~C~}$ .at 1 atmosphere pressure). “Water-dispersable” within the scope of the \n30 present invention means that a compound or polymer forms an emulsion, micro-emulsion or suspension in water at normal temperatures.All numerical ranges are inclusive and combinable in any order, except where it is logical that such numerical ranges are constrained to add up to $100\\%$ \n35 Polymers of the present invention have $\\upalpha,\\upbeta$ -unsaturation and a group that generates a free radical upon exposure of the polymers to actinic radiation, the polymers have an average molecular weight of at least 10oo daltons. Polymers having the $\\mathbf{\\alpha}_{\\alpha,\\upbeta}$ -unsaturation and the group that generates a \n40 free radical are film forming functional polymers. The film forming functional polymers have a main chain or backbone that is derived from $\\mathbf{\\alpha}_{\\alpha,\\beta}$ -ethylenically or acetylenically unsaturated polymerizable monomers or oligomers or combinations thereof and terminate with at least one free unsat \n45 urated group at either end of the polymer. In addition to the at least one free unsaturated group at either end of the polymer, at least one monomer or oligomer employed to make the polymer backbone may have one or more groups that are free to react with another compound to \n50 join that other compound to the polymer to form a pendent functional group. Pendent functional groups may terminate in one or more $\\mathbf{\\alpha}_{\\alpha,\\upbeta}$ -ethylenically or acetylenically unsaturated functional group or another type of functional group. Functional groups enable the polymer to self-cross-link, \n55 generate a free radical, make the polymer hydrophilic or add additional functional components to the polymer.Functional groups make the polymer and compositions in which the polymer is used serviceable or processable. Serviceable, for example, means that the polymer and compositions in which \n60 the polymer is used may be coated on a substrate, durable against solutions such as plating solutions, has less postexposure back cross-linking， or is sensitive to light at wavelengths of at least $300\\mathrm{nm}$ . Processability, for example, means that the polymer and compositions in which the \n65 polymer is used may be developed, stripped, or have an affinity for adhesion to metals. Compounds that may be joined to the polymer to form functional groups or moieties",
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"category": " Materials and methods"
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},
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{
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"id": 12,
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"chunk": "# 6 \n\non the polymer include, but are not limited to, photoinitiators, plasticizers, surfactants, dyes, stripping agents or combinations thereof. Any compound or component that may be joined to a polymer to improve the serviceability or processability of the polymer or a composition in which the polymer is used may be employed to practice the present invention. Specific examples of such compounds are disclosed below. \n\nFunctional polymers may be prepared by any suitable method known in the art. One method of preparing func- 10 tional polymers is to first functionalize one or more monomers or oligomers that are employed to compose the polymer backbone followed by free radical polymerization of the monomers or oligomers or combinations thereof, thus forming a polymer with pendent functional groups. For example, 15 monomers or oligomers having free hydroxyl (-OH), carboxyl $(\\mathrm{-\\mathrm{\\COOH})}$ ，or ester （—COO—R,where R is an organic moiety) groups may react with compounds having free hydroxyl groups, carboxyl groups, ester groups, aminyl $(\\mathrm{-NH}_{2}$ or —NHR), or isocyanate (—NCO) groups to form 20 pendent groups. Examples of such reactions include addition reactions or condensation reactions. Examples of such addition reactions include nucleophilic, electrophilic and free radical addition reactions. Other examples of reactions include, but are not limited to, ether formation, transesteri- 25 fication, anhydride formation, amide formation or, urea formation. Such reaction methods and conditions to carry out the reactions are well known in the art. See Morrison and Boyd, “Organic Chemistry\", $3^{r d}$ edition, New York University, 1973, and March,“Advanced Organic Chemistry, Reac- 30 tions, Mechanisms, and Structures” ${\\bar{2}}^{n d}$ edition, McGrawHill Book Company, 1977. Free radical polymerization of the monomers or oligomers or combinations thereof follow to form a functional polymer. Conditions for free radical polymerization of monomers and oligomers are well known 35 in the art. Free radical polymerization of functionalized monomers or oligomers may be performed in suspension solution (from $60^{\\circ}\\mathrm{C}$ .to $80^{\\circ}\\mathrm{C}.$ )or emulsion (from $-20^{\\circ}\\mathrm{~C~}$ to $60^{\\circ}\\mathrm{~C~}.$ ) form. Pressures employed are near or at 1 atmosphere. Peroxide initiators may be employed in the 40 polymerization process such as dibenzoyl peroxide. Azo initiators also may be employed such as 2,2'-azobis(2 methylpropane nitrile) or 2,2'-azobis(2-methylbutane-nitrile). \n\nAlternative processes for preparing a functional polymer are anionic polymerization, condensation polymerization or 4: by post polymerization functionalization. In post polymerization functionalization, the main chain or polymer backbone and the functional pendent components are prepared separately. Monomers or oligomers or combinations thereof, which compose the backbone, may be joined by free radical 5( polymerization. Compounds that compose the functional pendent groups may be prepared by any suitable method known in the art. Such compounds need only have one free reactive group as described above to bond with a free reactive group on the polymer backbone.After the synthesis 5: of the separate components that make up the polymer, they are then joined together in a separate reaction process to form the final functional polymer. Examples of chemical bonds formed between a polymer backbone and a pendent functional group are an ether bond R—O—P, where R is as 6( defined above and $\\mathrm{\\DeltaP}$ is a polymer backbone, an ester bond P—COO—R, or RCOO—P. \n\nAnother example of such a reaction is between an isocyanate compound and a reactive group from a polymer backbone. After the polymer backbone is prepared, the polymer backbone is mixed with an isocyanate compound at reaction temperatures below $80^{\\circ}\\mathrm{C}$ . Mixing and heating are continued until the reaction is complete. Typically, the reaction continues for 1 hour to 8 hours. Reactions that take place occur between a free isocyanate group on the isocyanate compound and a hydroxyl group, carboxyl group,or primary or secondary aminyl functional group attached to the polymer backbone. One mole of free isocyanate reacts with one mole of a hydroxyl, carboxyl, or primary or secondary aminyl on the polymer main chain. The reaction may be self quenching.Water, alcohol, or other chemical species with labile hydrogen, and a suitable catalyst, such as triethylamine, may be added at the end of the reaction to quench any free isocyanate.Also, a suitable polymerization inhibitor may optionally be added to prevent premature cross-linking of terminal ethylenically or acetylenically unsaturated moieties such as a (meth)acrylate moiety. Reaction completion may be determined by using standard analytical instruments well known in the art. \n\nThe synthesis may be carried out in the presence of an inert dry solvent (inert to reaction conditions), for example, an ether, an ester, ketones, nitriles, sulfones or phosphoric acid esters. To accelerate the reactions, any suitable catalyst employed in polymerization reactions may be used. Tin containing catalysts are an example. Stabilizers or polymerization inhibitors may optionally be added to the reaction steps to stabilize free-radical polymerization. \n\nFree isocyanate, i.e. $-\\mathrm{N}{=}\\mathrm{C}{=}\\mathrm{O}$ , reacts with a hydroxyl group from the polymer backbone, or a hydroxyl group from a carboxyl group from the polymer backbone to form a R—NH—C(O)—P linkage where $\\mathrm{~\\bf~P~}$ is the polymer backbone, and R is an organic moiety. Examples of R include, but are not limited to substituted and unsubstituted alkyl, aryl, alkylaryl, or cycloaliphatic. Specific examples include a urethane group containing compound such as a biuret group. \n5 A free isocyanate that reacts with a primary or secondary amine moiety joined to the polymer backbone forms a R—NH—C(O)—NR'-G-P urea (carbamide) linkage where $\\mathbb{R}^{1}$ includes, but is not limited to, hydrogen, a linear, branched or unsubstituted or substituted alkyl, or an unsubstituted or substituted aryl. Substituent groups include, but are not limited to, halogen, such as fluorine, bromine, chloride or iodine, hydroxyl, carboxyl, or primary or secondary amine.A substituent group replaces a hydrogen on a carbon atom. G is an organic moiety that joins the nitrogen \n5 to the polymer chain. G includes, but is not limited to, an alkyl, or a substituted aryl where the nitrogen is joined to the aryl by an alkyl chain. The alkyl of G may be linear or branched $\\displaystyle(\\mathrm{C}_{1}\\mathrm{-}\\mathrm{C}_{24})$ alkyl. A free isocyanate that reacts with a polyalkoxylated moiety from the polymer backbone forms $\\mathrm{a}\\mathrm{R{\\longrightarrow}N H{\\longrightarrow}C(O){\\longrightarrow}O(A O)_{x}{\\longrightarrow}C(O){\\longrightarrow}P}$ linkage where A is a linear or branched $(\\mathbf{C_{1}}\\mathrm{-C_{24})a l k y l}$ and $\\mathbf{x}$ is an integer from 0 to 1,000, preferably from 1 to 200. R, as defined above, may terminate in one or more functional groups such as ethylenically or acetylenically unsaturated moieties that permit functionalized polymers of the present invention to self cross-link as in photoresist compositions described below. \n\nThe main chain or backbone of functional polymers of the present invention may be derived from monomers or oligomers which include, but are not limited to, acid functional monomers, base functional monomers,water-soluble functional monomers, urethane oligomers or mixtures thereof. \n\nExamples of suitable ethylenically or acetylenically unsaturated monomers include, but are not limited to: (meth) acrylic acid, (meth)acrylamides, alkyl (meth)acrylates, alkenyl (meth)acrylates, aromatic (meth)acrylates, vinyl aromatic monomers, nitrogen-containing compounds and their thio-analogs, substituted ethylene monomers, cyclic olefins, ubstituted cyclic olefins, and the like. Preferred monomer nclude (meth)acrylic acid, alkyl (meth)acrylates and viny iromatic monomers. \n\nTypically, the alkyl (meth)acrylates useful in the present invention are $\\mathrm{(C_{1}-C_{24})}$ Dalkyl (meth)acrylates. Suitable alkyl (meth)acrylates include, but are not limited to, “low cut\" alkyl (meth)acrylates, “mid cut\" alkyl (meth)acrylates and \"high cut\" alkyl (meth)acrylates. \n\n“Low cut\" alkyl (meth)acrylates are typically those where the alkyl group contains from 1 to 6 carbon atoms. Suitable low cut alkyl (meth)acrylates include, but are not limited to: methyl methacrylate, methyl acrylate, ethyl acrylate, propyl methacrylate, butyl methacrylate, butyl acrylate, isobutyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, cyclohexyl acrylate and mixtures thereof. \n\n\"Mid cut\" alkyl (meth)acrylates are typically those where the alkyl group contains from 7 to 15 carbon atoms. Suitable mid cut alkyl (meth)acrylates include, but are not limited to: 2-ethylhexyl acrylate (\"EHA\"), 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, isodecyl methacrylate (based on branched $\\mathrm{(C_{10})a l k y l}$ isomer mixture), undecyl methacrylate, dodecyl methacrylate (also known as lauryl methacrylate), tridecyl methacrylate, tetradecyl methacrylate (also known as myristyl methacrylate), pentadecyl methacrylate and mixtures thereof. Particularly useful mixtures include dodecyl-pentadecyl methacrylate, a mixture of linear and branched isomers of dodecyl, tridecyl, tetradecyl and pentadecyl methacrylates; and lauryl-myristyl methacrylate. \n\n“High cut\" alkyl (meth)acrylates are typically those where 3 the alkyl group contains from 16 to 24 carbon atoms. Suitable high cut alkyl (meth)acrylates include, but are not limited to: hexadecyl methacrylate, heptadecyl methacrylate, octadecyl methacrylate, nonadecyl methacrylate, cosyl methacrylate, eicosyl methacrylate and mixtures thereof. 3: 35 Particularly useful mixtures of high cut alkyl (meth)acrylates include, but are not limited to: cetyl-eicosyl methacrylate, which is a mixture of hexadecyl, octadecyl, cosyl and eicosyl methacryl ate; and cetyl-stearyl methacrylate, which is a mixture of hexadecyl and octadecyl methacrylate. \n\nThe mid-cut and high-cut alkyl (meth)acrylate monomers described above are generally prepared by standard esterification procedures using technical grades of long chain aliphatic alcohols, and these commercially available alcohols are mixtures of alcohols of varying chain lengths 4 containing between 10 and 15 or 16 and 20 carbon atoms in the alkyl group.Examples of these alcohols are the various Ziegler catalyzed ALFoL alcohols from Vista Chemical company, i.e.,ALFOL 1618 and ALFOL 1620, Ziegler catalyzed various NEoDoL alcohols from Shell Chemical Company, i.e. 5 NEODoL 25L, and naturally derived alcohols such as Proctor & Gamble's TA-1618 and CO-1270. Consequently, for the purposes of this invention, alkyl (meth)acrylate is intended to include not only the individual alkyl (meth)acrylate product named, but also to include mixtures of the alkyl 5 (meth)acrylates with a predominant amount of the particular alkyl (meth)acrylate named. \n\nThe alkyl (meth)acrylate monomers useful in the present invention may be a single monomer or a mixture having different numbers of carbon atoms in the alkyl portion. Also, the (meth)acrylamide and alkyl (meth)acrylate monomers useful in the present invention may optionally be substituted. Suitable optionally substituted (meth)acrylamide and alkyl (meth)acrylate monomers include, but are not limited to: hydroxy $(\\mathrm{C}_{2}\\mathrm{-}\\mathrm{C}_{20}){\\mathrm{alkyl}}$ (meth)acrylates, dialkylamino $(\\mathrm{C}_{2}\\mathrm{-}\\mathrm{C}_{20})$ alkyl (meth)arylates, dialkaylamino $\\displaystyle(\\mathrm{C}_{2}\\mathrm{-}\\mathrm{C}_{20,})$ alkyl (meth)acrylamides, preferably, hydroxy( $\\mathrm{\\DeltaC}_{2}\\mathrm{-}C_{6}$ )alkyl (meth) \n\nacrylates, dialkylamino $(\\mathrm{C}_{2}\\mathrm{-}\\mathrm{C}_{6})$ alky1 (meth)acrylates, dialkylamino $\\displaystyle{(C_{2}-C_{6})}$ alkyl (meth)acrylamides. \n\nParticularly useful substituted alkyl (meth)acrylate monomers are those with one or more hydroxyl groups in the alkyl radical, especially those where the hydroxyl group is found at the $\\upbeta$ -position (2-position) in the alkyl radical. Hydroxyalkyl (meth)acrylate monomers in which the substituted alkyl group is a $(\\mathrm{C}_{2}\\mathrm{-}\\mathrm{C}_{6})\\mathrm{alkyl}$ ， branched or unbranched, are preferred. Suitable hydroxyalkyl (meth)acrylate monomers ）include, but are not limited to: 2-hydroxyethyl methacrylate (\"HEMA\"), 2-hydroxyethyl acrylate (\"HEA\"), 2-hydroxypropyl methacrylate, 1-methyl-2-hydroxyethyl methacrylate, 2-hydroxy-propyl acrylate, 1-methyl-2-hydroxyethyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxybutyl ） acrylate and mixtures thereof. \n\nHydroxy poly opened-ring lactone polyalkylene oxide (meth)acrylates as described in U.S. Pat. No. 6,045,973 may be employed. Suitable hydroxy polyalkylene oxide (meth) acrylates prepared from poly(propylene glycol) (meth)acry \n20 lates, poly(propylene glycol) alkyl ether (meth)acrylates, poly (propylene glycol) phenyl ether (meth)acrylates, poly (propylene glycol) 4-nonylphenol ether (meth)acrylates, poy (ethylene glycol) (meth)acrylates, poly(propylene/ethylene glycol) (meth)acrylates, poly(ethylene glycol)alkyl ether \n25 (meth)acrylates, poly(ethylene glycol) phenyl ether (meth) acrylates, poly(propylene/ethylene glycol) alkylether (meth) acrylates and mixtures thereof may be employed. The poly (alkylene oxide) may have from 1 to 50 degrees of polymerization. Such compounds may also be joined to the \n30 polymer backbone as a pendent functional group via an isocyanate group by reacting the hydroxyl of the poly (alkylene oxide) with an isocyanate of a polyisocyanate. A free isocyanate may then be reacted with a reactive group on the polymer backbone to join it to the polymer. Other substituted monomers useful in the present invention are those with a tertiary amino group or alkylamino group. Examples include, but are not limited to: dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, N-methylaminoethyl methacrylamide, N-methyl-aminopro \n40 pyl methacrylamide, N-methylaminobutyl methacrylamide, N-ethylaminoethyl methacrylamide, N-ethylaminopropyl methacrylamide, N-ethylaminobutyl methacrylamide, N-(1, 1-dimethyl-3-oxobutyl) acrylamide, N-(1,3-diphenyl-1- ethyl-3-oxobutyl) acrylamide, N-(l-methyl-1-phenyl-3-ox \n45 obutyl) methacrylamide, and 2-hydroxyethyl acrylamide, N-methacrylamide of aminoethyl ethylene urea, N-maleimide of dimethylaminopropylamine and mixtures thereof. \n\nOther substituted (meth)acrylate monomers useful in the present invention are silicon-containing monomers such as $\\upgamma$ -propyl $\\mathrm{tri}({\\mathrm C}_{1}{-}{\\mathrm C}_{6})$ alkoxysilyl (meth)acrylate, $\\upgamma$ -propyl tri $(\\mathrm{C}_{1}\\mathrm{-}\\mathrm{C}_{6}$ Dalkylsilyl (meth)acrylate, -propyl di $\\mathrm{(C_{1}-C_{6}}$ Dalkoxy $(\\mathrm{C_{1}}\\mathrm{-C_{6}}$ Dalkylsilyl (meth)acrylate, $\\upgamma$ -propyl $\\mathrm{{di}(C_{1}-C_{6})a l k y l}$ $\\mathrm{(C_{1}-C_{6,})}$ alkoxysilyl(meth)acrylate,vinyl $\\mathrm{tri}({\\mathrm C}_{1}{-}{\\mathrm C}_{6})$ alkoxysilyl (meth)acrylate, vinyl $\\mathrm{di}(\\mathrm{C_{1}{-}C_{6})a l k o x y(\\mathrm{C_{1}{-}C_{6})}}$ alkylsilyl (meth)acrylate, vinyl $(\\mathrm{C_{1}-C_{6}})\\mathrm{alkoxydi}(\\mathrm{C_{1}-C_{6}})$ alkylsilyl (meth)acrylate, vinyl $\\mathrm{tri}({\\mathrm C}_{1}{-}{\\mathrm C}_{6})$ alkylsilyl (meth) acrylate,2-propylsilsesquioxane (meth)acrylate and mixtures thereof. \n\nThe vinyl aromatic monomers useful as unsaturated \n60 monomers in the present invention include, but are not limited to: styrene, hydroxystyrene, $\\mathbf{\\alpha}_{\\mathrm{~d~}}$ -methylstyrene, vinyltoluene, p-methylstyrene, ethylvinylbenzene, vinylnaphthalene, vinylxylenes, and mixtures thereof. The vinylaromatic monomers also include their corresponding substituted \n65 counterparts, such as halogenated derivatives, i.e., containing one or more halogen groups, such as fluorine, chlorine or bromine; and nitro, cyano, $\\displaystyle{(\\mathrm{C_{1}}\\mathrm{-}\\mathrm{C_{10}})}$ alkoxy, halo $\\mathrm{(C_{1}-C_{10})}$ \n\nalkyl, carb $\\displaystyle{(\\mathrm{C}_{1}\\mathrm{-}\\mathrm{C}_{10})}$ alkoxy, carboxy, amino, $\\mathrm{(C_{1}-C_{10})}$ alkylamino derivatives and the like. \n\nThe nitrogen-containing compounds and their thio-analogs useful as unsaturated monomers in the present invention include, but are not limited to: vinylpyridines such as 2-vinylpyridine or 4-vinylpyridine; $\\mathrm{(C_{1}-C_{8})}$ alkyl substituted N-vinyl pyridines such as 2-methyl-5-vinyl-pyridine, 2-ethyl-5-vinylpyridine, 3-methyl-5-vinylpyridine, 2,3-dimethyl-5-vinyl-pyridine, and 2-methyl-3-ethyl-5-vinylpyridine; methyl-substituted quinolines and isoquinolines; N-vinylcaprolactam; N-vinylbutyrolactam; N-vinylpyrrolidone; vinyl imidazole; N-vinyl carbazole; N-vinyl-succinimide; (meth)acrylonitrile; o-, m-, or p-aminostyrene; hydroxystylene; maleimide; N-vinyl-oxazolidone; N,N-dimethyl aminoethyl-vinyl-ether; ethyl-2-cyano acrylate; vinyl acetonitrile; N-vinylphthalimide; N-vinyl-pyrrolidones such as N-vinyl-thio-pyrrolidone, 3 methyl-1-vinyl-pyrrolidone, 4-methyl-1-vinyl-pyrrolidone, 5-methyl-1-vinyl-pyrrolidone, 3-ethyl-1-vinyl-pyrrolidone, 3-butyl-1-vinyl-pyrrolidone, 3,3-dimethyl-1-vinyl-pyrrolidone, 4,5-dimethyl-1-vinyl-pyrrolidone, 5,5-dimethyl-1-vinyl-pyrrolidone, 3,3,5- trimethyl-1-vinyl-pyrrolidone, 4-ethyl-1-vinyl-pyrrolidone, 5-methyl-5-ethyl-1-vinyl-pyrrolidone and 3,4,5-trimethyl-1- vinyl-pyrrolidone; vinyl pyrroles; vinyl anilines; and vinyl piperidines. \n\nThe substituted ethylene monomers useful as unsaturated monomers in the present invention include, but are not limited to: vinyl acetate, vinyl formamide, vinyl chloride, vinyl fluoride, vinyl bromide, vinylidene chloride, vinylidene fluoride, vinylidene bromide, tetrafluoroethylene, trifluoroethylene, trifluoromethyl vinyl acetate, vinyl ethers and itaconic anhydride. \n\nSuitable cyclic olefin monomers useful in the present invention are $(\\mathrm{C}_{5}\\mathrm{-}\\mathrm{C}_{10})$ cyclic olefins, such as cyclopentene, cyclopentadiene, dicylopentene, cyclohexene, cyclohexadi- 3: ene, cycloheptene, cycloheptadiene, cyclooctene, cyclooctadiene, norbornene, maleic anhydride and the like. Such cyclic olefins also include spirocyclic olefin monomers such as spirocyclic norbornenyl monomers, spirocyclic cyclohexene monomers, spirocyclic cyclopentene monomers and 4( mixtures thereof. Suitable substituted cyclic olefin monomers include, but are not limited to, cyclic olefins having one or more substituent groups selected from hydroxy, aryloxy, halo, $({\\bf C}_{1}{-}{\\bf C}_{12})\\mathrm{alkyl}$ ， $\\displaystyle{(C_{1}-C_{12})}$ haloalkyl, $\\displaystyle{(C_{1}-C_{12})}$ hydroxyalkyl, $\\mathrm{(C_{1}-C_{12})}$ halohydroxyalkyl such as $(\\mathrm{CH}_{2})_{n}\\mathrm{C}(\\mathrm{CF}_{3})_{2}$ 4 OH where $\\mathrm{n}^{\\prime}{=}0$ to 4, $(\\mathrm{C}_{1}\\mathrm{-}\\mathrm{C}_{12})$ alkoxy, thio, amino, $\\mathrm{(C_{1}-C_{6})}$ alkylamino, $\\mathrm{(C_{1}-C_{6})}$ dialkylamino, $\\mathrm{(C_{1}-C_{12})}$ alkylthio, carbo $\\mathrm{(C_{1}-C_{20})}$ Dalkoxy，carboo $\\mathrm{(C_{1}-C_{20})}$ haloalkoxy, $(\\mathbf{C}_{1}\\mathbf{-}\\mathbf{C}_{12})\\mathbf{acyl}$ $\\mathrm{(C_{1}-C_{6,}}$ alkylcarbonyl $(\\mathbf{C_{\\mathrm{1}}}\\mathrm{-}\\mathbf{C_{\\mathrm{6}}})\\mathbf{a}\\mathbf{l}\\mathbf{k}\\mathbf{y}\\mathbf{l}$ ，and the like. Particularly suitable substituted cyclic olefins include maleic anhy- 5( dride and cyclic olefins containing one or more of hydroxy, aryloxy, $(\\mathbf{C}_{1}{-}\\mathbf{C}_{12})\\mathrm{alkyl}$ ， $\\displaystyle{(C_{1}-C_{12})}$ haloalkyl， $\\displaystyle{(C_{1}-C_{12})}$ hydroxyalkyl, $\\mathrm{(C_{1}-C_{12})}$ halohydroxyalkyl, carbo $\\left(\\mathrm{C}_{1}\\mathrm{-}\\mathrm{C}_{20}\\right)$ alkoxy, and carbo $\\mathrm{(C_{1}-C_{20})}$ haloalkoxy. It will be appreciated by those skilled in the art that the alkyl and alkoxy substitu- 5: ents may be optionally substituted, such as with halogen, hydroxyl, cyano, $\\displaystyle{(C_{1}-C_{6,}^{\\mathrm{~~}}}$ alkoxyl, mercapto, $\\displaystyle{(C_{1}-C_{6,})}$ Dalkylthio, amino, or acid labile leaving group. Suitable carbo $\\displaystyle{\\bigl(}\\mathrm{C}_{1}{-}\\mathrm{C}_{20}{\\bigr)}$ alkoxy substituents include, but are not limited to, those of the formula C(O)O-LG, wherein LG is a leaving 60 group including, but are not limited to, alkyl groups having 4 or more carbon atoms with at least one quaternary carbon atom bonded directly to a carboxylate oxygen such as tert-butyl esters, 2,3-dimethylbutyl esters, 2-methylpentyl esters, 2,3,4-trimethylpentyl esters, alicyclic esters, acetals 6: or ketals from vinyl ethers or enols such as —O— $\\mathrm{(CH(CH}_{3})$ $\\mathrm{OC}_{2}\\mathrm{H}_{5},$ )or—o— $\\mathrm{(CH}_{2}\\mathrm{OC}_{2}\\mathrm{H}_{5}\\mathrm{)}$ , tetrahydropyran. Suitable alicyclic esters as leaving groups include adamantyl, methyladamantyl, ethyladamantyl, methylnorbornyl, ethylnorbornyl, ethyltrimethylnorbornyl, ethyl fenchol and the like. \n\nAny of a wide variety of difunctional branch-point mono \n5 mers are suitable for use in preparing the functional polymers of the present invention provided that such branchpoint monomers contain a backbone comprising one or more base cleavable functionalities or moieties, where such functionalities are disposed between the polymerizable groups of \nl0 the branch-point monomer. By “base cleavable functionality\" is meant any functionality or group that can be cleaved by a base such as hydroxide ion, alkoxide ion, ammonia or amines. \n\nA wide variety of difunctional branch-point monomers ； containing base cleavable moieties may be used. Such branch-point monomers have the structure",
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"category": " Materials and methods"
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},
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{
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"id": 13,
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"chunk": "# A'-Z-B \n\n20 where $\\mathbf{A^{\\prime}}$ and B each include one or more polymerizable groups, and Z includes one or more base cleavable groups. Suitable polymerizable groups for $\\mathbf{A^{\\prime}}$ and B include, but are not limited to, isocyanate $(^{64}-\\mathrm{{NCO}^{3})}$ ， $\\mathrm{R}_{1}\\mathrm{R}_{2}\\mathrm{C}=\\mathrm{CR}_{3}-$ $\\mathrm{R_{1}{\\mathrm{-}}C{\\mathrm{=}}C{\\mathrm{-}}}$ ， $\\mathrm{R_{1}R_{2}C=C R_{4}C(O)=O}$ 一， $\\mathrm{R}_{1}\\mathrm{R}_{2}\\mathrm{C}{=}\\mathrm{CR}_{4}-$ \n25 O—，and $\\mathrm{\\longrightarrow}\\mathrm{C(O)}\\mathrm{\\longrightarrow}\\mathrm{O}\\mathrm{\\longrightarrow}\\mathrm{R}_{5}$ ；wherein $\\mathrm{R}_{1}$ ， ${\\mathrm{R}_{2}}$ and $\\mathrm{R}_{4}$ are independently selected from H, $\\mathrm{(C_{1}-C_{4})}$ Dalkyl and halo; $\\mathrm{R}_{5}$ is selected from H, $(\\mathrm{C_{1}-C_{4}})\\mathrm{alkyl}$ ， and $\\mathrm{NR}_{6}\\mathrm{R}_{7}$ ； and $\\mathrm{R}_{6}$ and $\\mathrm{R}_{7}$ are independently selected from H and $\\mathrm{(C_{1}-C_{4}}$ Dalkyl.In addition to one or more base cleavable groups, the group Z \n30 may optionally include one or more spacer groups. Z may suitably have the general formula $\\mathrm{S}_{x4}(\\mathrm{BCG})_{y4}$ whereinS is a spacer group; (BCG) is a base cleavable group; $\\mathbf{\\Deltax}_{4}{=}0{-}20$ and $\\mathrm{y}_{4}{=}1{-}30$ . It is preferred that $y_{4}{=}2–20$ . Suitable spacer groups include, but are not limited to, alkyleneoxy, aryle \n351 neoxy， $\\displaystyle(\\mathrm{C}_{1}\\mathrm{-}\\mathrm{C}_{20})$ alkylene,substituted $(\\mathrm{C}_{1}\\mathrm{-}\\mathrm{C}_{20})$ Dalkylene, $\\displaystyle(\\mathrm{C}_{6}{-}\\mathrm{C}_{20})$ aralkylene, substituted $(\\mathrm{C}_{6}{-}\\mathrm{C}_{20})$ aralkylene, and the like. Suitable alkyleneoxy groups have the general formula $(\\mathrm{~\\longrightarrowCHR_{8}\\mathrm{\\longrightarrowCH}_{2}O\\mathrm{\\longrightarrow}})_{n3}$ $(\\mathrm{~\\longrightarrow~}\\mathrm{OCHR}_{8}\\mathrm{\\ensuremath~{\\longrightarrow~}}\\mathrm{CH}_{2}\\mathrm{\\ensuremath~{\\longrightarrow~}})_{m3}$ or $(-\\mathrm{O-}$ $\\mathrm{CH}_{2}{\\longrightarrow}\\mathrm{CH}_{2}{\\longrightarrow}\\mathrm{CH}_{2}{\\longrightarrow})_{p3}$ ,where $\\mathrm{R}_{8}$ .s1 $\\mathrm{H}$ of $\\mathrm{CH}_{3}$ and ${\\bf n}_{3}$ ${\\mathfrak{m}}_{3}$ \n40 and ${\\mathfrak{p}}_{3}$ are each 1-1000. Exemplary alkylenoxy groups include ethyleneoxy, propyleneoxy and ethyleneoxy/propyleneoxy mixtures. Aryleneoxy or arylene ether spacers include phenyleneoxy (phenylene ether) spacers having the general formula $(\\mathrm{~-~}\\mathrm{C}_{6}\\mathrm{H}_{4}\\mathrm{-~}\\mathrm{O}\\mathrm{-})_{z3}$ where $\\mathbf{z}_{3}{=}1{-}1000$ , biphe \n451 nylene ethers, phenanthryl ethers, naphthyl ethers, and mixtures thereof. When two or more spacer groups are used, they may be the same or different. \n\nSuch spacer groups may be selected to provide additional properties. For example, alkyleneoxy spacers, such as ethyleneoxy and/or propyleneoxy moieties, may help to emulsify the polymeric binders for use in water borne photoresists. Spacers having extended chain length may also provide improved flexibility and be particularly useful in conformal photoresist formulations. The choice of such spacer groups depend upon the particular use of the polymer and the other components in the formulation, and is within the ability of one skilled in the art. \n\nAny base cleavable group is suitable for use in Z, but is preferably selected from anhydrides (—C(O)-O—(O) \n0 $\\mathrm{C-})$ ，esters $(\\longrightarrow\\mathrm{C(O){\\longrightarrow}O\\longrightarrow})$ ，carbonates, sulfonyl esters $(-\\mathrm{SO}_{2}\\mathrm{-}\\mathrm{O}_{-})$ and the like, and more preferably esters. It is more preferred that the difunctional branch-point monomers contain 2 or more base cleavable groups and still more preferably 3 or more base cleavable groups. Particularly \ni5 suitable difunctional branch-point monomers contain 4 base cleavable groups, and more particularly 4 or more ester linkages. It is further preferred that the difunctional branch",
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"category": " Materials and methods"
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},
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{
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"id": 14,
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"chunk": "# 11 \n\npoint monomer contain as polymerizable end groups moieties that also contain one or more base cleavable functionalities, such as (meth)acrylate esters. When the difunctional branch-point monomers contain 2 or more base cleavable groups, such groups may be directly bonded to each other or may be separated by one or more spacer groups. An exemplary structure for such branch-point monomers having multiple base cleavable groups is A' $(\\mathrm{S}1)_{x1}$ (BCG)1- $(\\mathrm{S}2)_{x2}$ 1 $(\\mathrm{BCG})2\\ –(\\mathrm{S}3)_{x3}-$ B,wherein S1, S2 and S3 refer to spacer groups 1-3, respectively, (BCG)1 and (BCG)2 refer to base cleavable groups 1 and 2, respectively, $\\mathbf{x}1+\\mathbf{x}2+\\mathbf{x}3=0-20$ ,and A', B, S, (BCG) and B are as defined above. Other suitable structures having more or fewer spacers and/or base cleavable groups or different configurations of such groups are well within the ability of those skilled in the art. \n\nSuitable difunctional branch-point monomers useful in preparing the polymers of the present invention include, but are not limited to, acrylic anhydride, methacrylic anhydride, and ester linkage containing monomers having (meth)acrylate end groups. Exemplary difunctional branch-point monomers including one or more urethane linkages and having (meth)acrylate end groups are: pdmbi-pcp0200-pdmbi, pdmbi-pcp0201-pdmbi, pdmbi-pcp0230-pdmbi, eh6cl4-hdippg1000-hdi-eh6cl4, eh6cl4-hdi-pcp0230-hdi-eh6cl4, eh6cl4-hdi-ppg425-hdi-dmpa-hdi-ppg425-hdi-eh6cl4, 2hema-hdi-pcp0230-hdi-ppg425-hdi-pcp0230-hdi-2hema, 2hema-hdi-pcp0230-hdi-peg400-hdi-pcp0230-hdi-2hema, 2hema-hdi-pcp0200-hdi-pcp0230-hdi-pcp0200-hdi-2hema, e6hem-hdi-pcp0200-hdi-pcp0230-hdi-pcp0200-hdi-e6hem, e6hem-hdi-pcp0200-hdi-ppg1000-hdi-pcp0200-hdi-e6hem, e6hem-hdi-ppg425-hdi-pcp0230-hdi-ppg425-hdi-e6hem, e6hem-hdi-ppg1000-hdi-pcp0230-hdi-ppg1000-hdi-e6hem, e6hem-hdi-pcp0230-hdi-ppg425-hdi-pcp0230-hdi-e6hem, ande6hem-hdi-ppg1000-hdi-pcp0201-hdi-ppg1000-hdie6hem. In the above described difunctional branch-point monomers, each “dash\" represents a urethane group (formed when an isocyanate group reacts with a hydroxyl group) between the adjacent moieties. Such urethane linkages are not required in the present branch-point monomers. The abbreviations for the moieties are: hd $_{=1}$ ,6-hexamethylene diisocyanate; $\\mathtt{p c p0200=T o N E^{T M}}$ Polyol 0200 Diol (containing carboxylic ester groups); $\\mathrm{pcp}0201{=}\\mathrm{ToNE}^{\\mathbf{TM}}$ Polyol 0201 Diol (contains carboxylic ester groups); $\\mathtt{p c p0230=T o N E^{T M}}$ Polyol_ O230 Diol (contains carboxylic ester groups); $\\mathsf{p p g425}\\mathrm{=}$ polypropylene glycol having a molecular weight of approximately 425; ppg1000=polypropylene glycol having a molecular weight ofapproximately1000; dmpa=dimethylolpropionic acid; pdmbi $^{=3}$ -isopropenyl-alpha,alpha-dimethylbenzyl isocyanate; 2hema $_{1=2}$ -hydroxyethyl methacrylate (contains ester group and a polymerizable end group)； e6hem=ethoxylated hydroxyethyl methacrylate (contains ester group and a polymerizable end group); and eh6cl4=ethoxylated caprolactone-derived methacrylate (contains ester groups and a polymerizable end group). Such branch-point monomers are generally commercially available or may be readily prepared by known methods. ToNETM is a trademark for polycaprolactone diols, available from the Dow Chemical Company (Midland, Mich.). Other suitable polycaprolactone diols are available from Solvay under the CAPA brand name. Typically, the molecular weight of the branch-point monomers is $\\geq450$ and preferably from 450 to 6000. \n\nMore than one difunctional branch-point monomer may be used to prepare the functional polymers. Thus, mixtures of difunctional branch-point monomers may advantageously be used in the present invention. The total amount of such difunctional branch-point monomers in the functional polymers may be from 0.1 to 100 wt $\\%$ based upon the total veight of the monomers used to prepare the polymei ypically from 0.1 to $25\\mathrm{\\wt\\\\%}$ ， and more typically from 0. 0 $10\\mathrm{\\mi\\%}$ \n\nPolymers of the present invention contain sufficient acid ； functionality to render the polymers soluble and removable upon development. The term “acid functionality” refers to any functionality capable of forming a salt upon contact with alkaline developer, such as dilute alkaline aqueous sodium or potassium hydroxide, e.g.1 to $3\\mathrm{wt\\%}$ solutions. Suitable acid functionality includes, but is not limited to, carboxylic acids, sulfonic acids, phosphonic acids and phenols. The polymers have an acid number of up to 250, preferably up to 200. Typical ranges of acid numbers are from 15 to 250 and preferably from 50 to 250. Such acid numbers are based on the amount of KOH (potassium hydroxide) in mg to D neutralize $\\mathrm{~1~g~}$ (dry weight) of polymer. \n\nPreferably, functional polymers of the present invention have multiple ester links in the backbone or in pendent side chains, or in the backbone and in the pendent chains. Such ester links permit quick and clean removal of the functional polymers from a substrate using a stripping agent. Quick and clean removal is highly desirable in a photoresist. Preferably, functional polymers have from 2 or more ester links in the backbone or in the pendent side chains or in both the backbone and chains. Preferably the functional polymers have from 5 or more ester links, more preferably from 10 to 50 ester links, most preferably from 20 to 40 ester links in the backbone and/or pendent side chains. Such polyester links may be derived from the hydroxy poly opened-ring lactone or hydroxy polyalkylene oxide (meth)acrylates described above. \n\nIn one embodiment of the present invention, isocyanate compounds used to prepare the functional polymers of the present invention include urethane/ethylenically or acetylenically unsaturated isocyanates. Such compounds have a —NHC(O)— moiety, at least one free isocyanate group \n35 $(-\\mathrm{N}{=}\\mathrm{C}{=}\\mathrm{O})$ , and an ethylenically or acetylenically unsaturated moiety such as a (meth) acrylate that is at a terminus of the isocyanate compound. Biuret ethylenically or acetylenically unsaturated isocyanates have a —NH—C(O)- N—C(O)—NH—moiety, at least one free isocyanate group \n40andanethylenicallyor acetylenically unsaturated moiety at a terminus of the compound. Examples of such compounds include, but are not limited to, the following general formulas: \n\nIII; or \n\nIV \n\n \n\nwhere $Z^{\\prime}$ includes, but is not limited to, alkyl, alkylene, cycloalkyl, aryl, heterocyclic alkyl, heteroaryl, a polymer such as a copolymer including a branched polymer or branched copolymer; Y includes, but is not limited to, alky, alkylene, cycloalkyl, aryl, heterocyclic alkyl, heteroaryl, $-(\\mathrm{(CH_{2})_{\\it u}\\mathrm{\\bar{\\longrightarrow}0\\mathrm{-\\bar{\\jmath}_{\\nu}\\mathrm{\\bar{\\longrightarrow}(C H_{2})_{\\it w}\\mathrm{\\bar{\\longrightarrow}\\mathrm{\\Lambda}_{\\mathrm{B}}}}}}}}$ or— $-(\\mathrm{(C\\dot{H}_{2})_{\\boldsymbol{u}}\\mathrm{-\\nablaC(O)\\dot{-}\\quad}}$ $\\mathrm{O-}\\mathrm{)}_{\\nu}\\mathrm{\\longrightarrow(CH}_{2}\\mathrm{)}_{w}\\mathrm{\\longrightarrow}$ where u, and w are integers of from 1 to 10, and $\\mathbf{v}$ is an integer of from O to greater than 1,000, preferably from 1 to 200, most preferably from 5 to $1\\dot{0}.\\mathrm{R}^{\\dot{2}}$ is hydrogen or $\\mathrm{(C_{1}-C_{4})}$ alkyl. Preferably $\\mathrm{R}^{2}$ is hydrogen or methyl. Hetero-atoms include, but are not limited to, oxygen, sulfur, and nitrogen. The alkyl, alkylene, cycloalkyl, aryl,heterocyclic alkyl, heteroaryl and polymers may be unsubstituted or substituted.Examples of suitable substituent groups include, but are not limited to, carboxyl, hydroxyl, $\\mathrm{(C_{1}-C_{4})}$ alkyl), aminyl such as a_ primary or secondary aminyl, or hydroxyaminyl, or —CN. \n\nExamples of suitable alkyl groups include, but are not limited to, linear or branched $\\mathrm{(C_{1}-C_{20})}$ alkyl. Examples of alkenyl, cycloakyl or aryl groups include, but are not limited to, linear or branched $\\displaystyle(\\mathrm{C}_{2}\\mathrm{-}\\mathrm{C}_{20})$ alkenyl, $\\displaystyle(C_{5}{-}C_{6})$ cycloalky such as an isophorone, and $(\\mathrm{C}_{5}\\mathrm{-}\\mathrm{C}_{6})$ aryl such as phenyl. \n\nThe isocyanate compounds with at least one free isocyanate group may be prepared by any suitable method known in the art. Monoisocyanates with functional groups such as (meth)acrylate groups, diisocyanates or triisocyanates that may be employed are either known or may be prepared by analogy to known compounds. Examples of suitable diisocyanates and triisocyanates include, but are not limited to, ethylene diisocyanate, propylene diisocyanate, butylene-1, 3-diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, 2,4-dimethyl-6-ethyloctamethylene diisocyanate, cyclohexylene diisocyanate, cyclopentylene diisocyanate, 1,4-diisocyanatomethyl-cyclohexane, 1,3-diisocyanatoethyl-cyclohexane, toluylene diisocyanate, 3,3,5-trimethyl-1-isocyanato-5-isocyanatomethylcyclohexane,2-butene-1,4-diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate biuret, 1,6- hexamethylene diisocyanate trimer, or isophorone diisocyanate trimer. Many of the foregoing listed diisocyantes and triisocyantes as well as the biurets and trimers may be purchased from Lyondell (located at 122 Melanney St., Houston, Tex.) or Bayer (located at 100 Bayer Rd., Pittsburg, Pa. 15025). \n\nIsocyanates such as the diisocyanates and triisocyanates described above may then be reacted with a suficient amount of one or more hydroxyl containing compounds such that one free isocyanate group is left to react with the polymer backbone prepared as described above. As men- ：4 tioned above, the reaction mole ratio of hydroxyl group to isocyanate group is about 1:1.Any suitable compound with at least one free hydroxyl group to react with an isocyanate group may be employed. An isocyanate compound of the present invention also may be reacted with another isocy- 5 anate compound having at least one free hydroxyl group. Hydroxyalkyl, hydroxyalkenyl, hydroxyaryl compounds and the like are examples of such compounds that may be employed. Hydroxyalkyl (meth)acrylates are one example of \\*suitable compounds. Hydroxyethyl (meth)acrylate or $55$ hydroxypropyl (meth)acrylate (n or iso compounds） are examples of hydroxyl group-containing esters that are suitable. Other suitable hydroxyalkyl (meth)acrylates include, but are not limited to, 2-hydroxy-butyl (meth)acrylate, 4-hydroxy-butyl (meth)acrylate, 2-hydroxy-cyclohexyl (meth) acrylate, 2-hydroxyethylmethacrylate, and the like. Suitable polyethylene glycol mono (meth)acrylates also may be employed such as, but not limited to, diethylene glycol mono (meth)acrylate, triethylene glycol mono (meth)acrylate and the like. Hydroxyalicyclic (meth)acrylates, and hydroxyaromatic (meth)acrylates such as bis phenol A 6 dimethacrylate also may be employed.U.S. Pat.No. 4,019, 972 discloses a method of preparing urethanes. \n\nFunctional groups that are to be joined to the polymer backbone and have free reactive groups, such as isocyanate groups, may be reacted with compounds having $\\mathbf{\\alpha}_{\\alpha,\\upbeta}$ -ethylenically or acetylenically unsaturated groups to extend the functional pendent groups. Such compounds with unsaturated groups include, but are not limited to, a compound having a formula: \n\n$$\n\\mathrm{CH}_{2}\\mathrm{=CHR^{3}-C(O)-O-(A_{1})\\mathrm{-(B_{1})-(C_{1})-H}}\n$$ \n\n10 where $\\mathrm{R}^{3}$ is hydrogen or methyl, $(\\mathrm{A}_{1})$ ， $\\left(\\operatorname{B}_{1}\\right)$ and $\\mathrm{(C_{1})}$ are in any order, $(\\mathbf{A}_{1})$ is a chain formed of from 1 to 40 alkoxylate monomers, aromatic-substituted alkoxylate monomers having from 1 to 20 carbon atoms, or mixtures thereof, $\\mathrm{(B_{1})}$ is either absent or is a chain formed of from 1 to 40 alkoxylate \n15 monomers, or aromatic-substituted alkoxylate monomers having from 1 to 20 carbon atoms, or mixtures thereof, and the monomer composition of $\\left(\\mathrm{B}_{1}\\right)$ being different than the monomer composition of $(\\mathbf{A}_{1})$ ,and $\\mathrm{(C_{1})}$ is a chain formed of from 1 to 40 open-ring lactone monomers having from 2 to \n20 21 carbon atoms. In addition to unsaturated groups, functional polymers generate a free-radical upon exposure to actinic radiation. Free-radical generating monomers or oligomers may be derived from Michael addition reactions of at least one \n25 diketone or at least one acetoacetate derivative functional donor compound and at least two multifunctional acrylate receptor compounds. The resulting free-radical generating oligomer may contain both capping and pendent acrylate groups which are capable of cross-linking upon exposure to actinic radiation. Michael addition reactions are catalyzed \n30 by a strong base such as diazabicyclo-undecene (DBU). Other cyclic amidines, for example diazabicyclo-nonene (DBN) and guanidines, also are suitable for catalyzing Michael addition reactions. U.S.Pat. No. 5,945,489 and U.S.Pat. No. 6,025,410 disclose Michael addition reactions. \n35Preferablytheoligomerswhichgenerateafredcal absorb light at $300~\\mathrm{nm}$ or greater. Such oligomers may be part of the polymer backbone or joined to a pendent group. \n\nA hydrophilic compound which generates a free-radical polymerization initiator of the present invention may have a general formula: \n\n \n\nwhere m is an integer of from at least 1, generally from 1 to 100, preferably from 5 to 50, R\" and R\"\" may be the same or different and may be groups that provide the oligomer with water-solubility or water-dispersable, R\" and $\\mathrm{R}^{\\dag\\dag}$ may include, but are not limited to unsubstituted or substituted $(\\mathbf{C_{6}}\\mathbf{-}\\mathbf{C_{14}})\\mathbf{aryl}$ such as unsubstituted or substituted phenyl, unsubstituted or substituted naphthyl, unsubstituted or substituted anthracenyl,unsubstituted or substituted phenanthryl, linear or branched $(\\mathbf{C_{1}}\\mathbf{-}\\mathbf{C_{15}})\\mathbf{a}1\\mathbf{ky}1$ ， linear or branched \n50 $(\\dot{C_{2}}\\dot{C_{15}})$ hydroxyalky, substituted or unsubstituted $(\\mathrm{C}_{5}{-}\\mathrm{C}_{14})$ heterocyclic aryl where the heteroatom is S, N, or O, or linear or branched $(\\mathrm{C}_{1}\\mathrm{-}\\mathrm{C}_{5})$ aminylalkyl,- $\\mathrm{-NR_{\\mathrm{9}}R_{\\mathrm{10}}}$ where $\\mathrm{R}_{9}$ and $\\mathrm{R}_{10}$ are the same or different and may be hydrogen, $\\displaystyle{(\\mathrm{C}_{1}-\\mathrm{C}_{3})}$ alkyl or $\\mathrm{(C_{1}-C_{4})}$ hydroxyalkyl. Substituents include, \n55 but are not limited to, $(\\mathbf{C_{1}}\\mathbf{-}\\mathbf{C_{5}})\\mathbf{alkoxy}$ ，hydroxyl, $\\displaystyle(\\mathrm{C}_{1}\\mathrm{-}\\mathrm{C}_{5})$ hydroxyalkyl, $(\\mathbf{C}_{1}\\mathbf{-}\\mathbf{C}_{5})\\mathbf{a}\\mathbf{l}\\mathbf{k}\\mathbf{y}1$ $\\displaystyle{(C_{1}-C_{5})}$ carboxyalkyl, $(\\mathrm{C}_{2}\\mathrm{-}\\mathrm{C}_{5})$ ester, $({\\dot{\\mathrm{C}}}_{1}{-}{\\dot{\\mathrm{C}}}_{5})$ aminylalkyl, phenyl, hydroxyphenyl, $\\mathrm{-NO}_{2}$ D \n\nsulfonate, phosphate, $-\\mathrm{\\mathrm{SH}}$ D $\\displaystyle{(C_{1}-C_{5})}$ thioalkyl, acetyl, benzoyl, aldehyde, $\\displaystyle{(C_{1}-C_{5})}$ ketyl, and the like.Preferably, R\" or $\\mathbb{R}^{\\dag\\dag}$ is unsubstituted or substituted phenyl, unsubstituted or substituted naphthyl, unsubstituted or substituted anthracenyl, $(\\mathbf{C}_{1}\\mathrm{-}\\mathbf{C}_{8})\\mathbf{a}\\mathbf{l}\\mathbf{k}\\mathbf{y}\\mathbf{l}$ ， $(\\mathrm{C}_{2}\\mathrm{-}\\mathrm{C}_{10})$ hydroxyalkyl, unsubstituted or substituted $(\\mathrm{C}_{5}\\mathrm{-}\\mathrm{C}_{10})$ heterocyclic aryl, or $\\displaystyle{(C_{1}-C_{5})}$ aminyla1kyl. $\\mathrm{R}\"$ and $\\mathrm{R}^{\\dag\\dag}$ also may be $\\mathrm{-O-R_{11}}$ ，where $\\mathrm{R}_{11}$ is the same as $\\mathrm{R}\"$ and R\" described above. \n\nR\", R\" and $\\mathrm{R}_{11}$ groups also may absorb light at $300\\mathrm{nm}$ to $365\\mathrm{nm}$ or greater. The most preferred R\", R\" and $\\mathrm{R}_{11}$ are water-soluble or water-dispersable and absorb light at 300 nm to $365~\\mathrm{nm}$ or greater. \n\n$\\mathbf{R^{\\prime}}$ also may be a water-soluble or a water-dispersable group. R' may be a group which provides sufficient acid groups such that the polymer may be developed with an aqueous or aqueous base solution. R' may have an acid number of at least 50. Preferably,R' is water-soluble or water-dispersable and absorb light at $300~\\mathrm{{nm}}$ or greater. R' may be derived from acid functional monomers, non-acid functional monomers, alkylene oxides, polyesters, urethanes, or mixtures thereof. Urethanes are compounds that have at least one —CO(NH)— moiety, and biurets are urethanes that have at least one —NH—CONH—CONHmoiety in the structure. Examples of suitable oligomers are disclosed in U.S.Pat.No. 6,045,973, U.S.Pat.No. 6,166, 245,U.S. Pat.No.6,207,347 B1, U.S.Pat. No. 6,268,111 B1,U.S.Pat.No. 6,319,653,U.S.Pat.No. 6,322,951 B1, and U.S. Pat.No. 6.329,123 B1. \n\nWhile not being bound by theory, it is believed that the pendent ketone substituents, as shown in formula VI, are the source of the free-radical polymerization initiator. Such pendent ketone substituents are integral to the compound and are internal or “built-in\" photoinitiators. Integral means that the ketone substitutent is a basic structural component of the polymer. \n\nIn another embodiment of the invention a source of the free-radical may be a photoinitiator compound.Examples of such photoinitiators include, but are not limited to, imidazole dimers, benzophenones, thioxanthones, ketals, benzoin ethers, acetophenones, anthraquinones, naphthaquinones, or triazine-based compounds. Imidazole dimers such as heaxaarylbiimidazoles (HABl) are very useful in photosensitive formulations, such as in photoresists. \n\nA hexaarylbiimidazole with a reactive group which may undergo an addition or condensation reaction with a reactive group of a carrier component as described above has a general formula: \n\nalkyloxy or alkylthio. At least one of $\\mathrm{R}_{13}$ D $\\mathrm{R}_{14}$ and $\\mathrm{R}_{15}$ is a reactive group which may react with a reactive group of the carrier compound. Such reactive groups may have a labile hydrogen, such as in hydroxyl or aminyl groups. Examples \n5 of reactive groups include, but are not limited to, $\\mathrm{-N}(\\mathrm{CH}_{2}\\mathrm{-OCH}_{3})_{2}$ ， carboxyl, ester, thio or isocyanate. Examples of spacer groups with reactive groups include, but are not limited to, $(\\mathrm{C}_{1}$ to $\\mathrm{C}_{12}\\mathrm{\\cdot}$ hydroxyalkyl, $(\\mathrm{C}_{1}$ to $\\mathbf{C}_{12}\\mathbf{\\Psi},$ carboxyalkyl, $\\mathrm{\\langleC_{1}}$ to $\\mathrm{C}_{12}$ Daminylalkyl, $\\displaystyle(\\mathrm{C}_{1}\\mathrm{-}\\mathrm{C}_{12})$ alkylester, or \n10 hydroxyalkyloxy such as —(O $\\mathrm{\\longrightarrowCH_{2}\\mathrm{\\longrightarrowCH_{2})O H}}$ ，-(0- $\\mathrm{CH}_{2}{\\mathrm{-}}\\mathrm{CH}_{2}{\\mathrm{-}}\\mathrm{CH}_{2})\\mathrm{OH}$ and— $\\mathrm{(O{\\_}C H_{2}{\\_}C H_{2}{\\_}C H_{2}}$ $\\mathrm{CH}_{2}\\mathrm{OH}$ $\\mathrm{(C_{1}}$ to $\\mathrm{C}_{12}\\mathrm{,}$ aliphaticisocyanate， $(\\mathrm{C}_{5}-\\mathrm{C}_{8})\\mathrm{cy-}$ cloaliphatic isocyanate or ( $\\mathrm{\\Delta}\\mathrm{C}_{5}$ to $\\mathrm{C}_{6}$ Daromatic isocyanate. Any aliphatic, aromatic or cycloaliphatic group with a \n15 reactive group attached to it may perform as a spacer group. Preferably, the reactive group is joined to the photoinitiator by a spacer group.A spacer is preferred because bonding the photoinitiator to the carrier component is easier and less disruptive of the photoinitiator capability to form a poly \n20 merization initiator. Preferred reactive groups are $\\mathrm{\\langleC_{1}}$ to $C_{6}$ hydroxy alkyl or $\\mathrm{\\langleC_{1}}$ to $C_{6})$ aminyl alkyl. In addition to $\\mathrm{R}_{15}$ equaling $\\mathrm{R}_{13}$ and $\\mathrm{R}_{14}$ $\\mathrm{R}_{15}$ also may be a halogen group such as chloro, bromo, or fluoro. \n\nExamples of alkyl groups having 1 to 4 carbon atoms are 25 methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl and test-butyl. Examples of suitable aryl groups having from 6 to 10 carbon atoms are phenyl, naphthyl, ortho-tolyl, metatolyl and para-tolyl. Both the alkyl and the aryl groups may be functionalized with a reactive group such as hydroxyl, 30 aminyl or other reactive groups discussed above. \n\nHydrophobic photoactive compounds may be prepared by any suitable method known in the art. For example, hexaarylbiimidazole compounds may be prepared by oxidative coupling of triphenylimidazoles. Preparation of substituted triphenylimidazoles is described in U.S. Pat. No. 3,748,557,U.S.Pat.No.4,311,783,and U.S.Pat.No. 4,622,286. In some cases, reaction mixtures in which more than one hexaarylbiimidazole is produced can be used without complete separation and purification as described in U.S. Pat.No. 4,622,286. \n\nAn example of forming substituted triphenylimidazoles used in the oxidation procedures to prepare the hexaarylbiimidazoles can be prepared by refluxing, in glacial acetic acid containing ammonium acetate, benzil with an appro45 priately substituted benzaldehyde or a benzil and benzaldehyde which are both suitably substituted, then drowning the reaction mass in water or in an ammoniun hydroxide solution, filtering and purifying the product by recrystalization; or by refluxing a benzoin and a benzaldehyde in methanol in 50 the presence of copper acetate and ammonia; or by heating a benzil and a benzaldehyde at $180^{\\circ}\\mathrm{~C~}$ .to $190^{\\circ}\\mathrm{~C~}$ in formamide as described in U.S.Pat.No.3,784,557.Benzils and substituted benzils may be prepared by any suitable method in the literature such as by oxidizing corresponding 55 benzoins as disclosed in U.S. Pat. No. 4,144,156. \n\n \n\nAnother method for forming a photoinitiator component with a reactive group is to react the photoinitiator, such as hexarrylbiimidazole, with an alkyl ether or ester in a Friedal Crafts reaction. The ether or ester group on the alkyl chain \n60 or spacer group attached to the photoinitiator is cleaved to get a hydroxyl group on the spacer group. The photoinitiator may then be reacted with a reactive group on a carrier component by an addition or condensation reaction to form a photoinitiator of the present invention. Such addition and \n65 condensation reactions, as well as the conditions under which they proceed, are well known in the art. Other photoinitiators such as thioxanthones, ketals, benzoin ethers, \n\n$\\mathrm{R}_{13}$ ， $\\mathrm{R}_{14}$ and $\\mathrm{R}_{15}$ are the same or different and may be a hydrogen, unsubstituted or substituted alkyl, alkoxy, unsubstituted or substituted aryl, aryloxy, hydroxyl, aminyl, carboxyl, ester, thio, isocyanate,- $\\mathrm{-N}(\\mathrm{CH}_{2}\\mathrm{-OCH}_{3})_{2}$ ,hydroxy",
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"category": " Materials and methods"
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},
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{
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"id": 15,
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"chunk": "# 17 \n\nbenzophenones, acetophenones, anthraquinones, napthaquinones and triazine-based compounds may be functionalized with reactive groups by analogy using similar procedures. \n\nExamples of such addition reactions that may occur 5 include the reaction of a hydroxyl, carboxyl or aminyl reactive group on the photoinitiator or joined to the photoinitiator by a spacer group with an isocyanate pendent group on the carrier component to obtain a urethane (-NHCOO—)，amide（—NHCO—）or urea bond （—NH- 10 CONH—) between the carrier component and the photoinitiator. Alternatively, an isocyanate group attached to the photoinitiator, or an isocyanate group joined to the photoinitiator by a spacer may react with a hydroxyl, carboxyl or aminyl functional group on the carrier component to form 15 the same types of urethane, amide and urea bonds.Examples of suitable isocyanates which may be employed are described above. Ester bonds $({\\mathrm{-}}\\mathrm{COOR})$ also may form to join a photoinitiator to a carrier such as a reaction between an acid group and an alcohol group. R represents an organic 20 moiety described above. \n\nIn addition to the photoinitiators described above, aromatic chromophores may be employed in the present invention. Aromatic chromophores have groups such as phenyl and naphthyl, which are sensitive to light at wavelengths of : from $320\\ \\mathrm{nm}$ to $450\\ \\mathrm{nm}$ . Typically, such aromatic chromophores are light sensitive from $340~\\mathrm{nm}$ to $400\\mathrm{nm}$ ,more typically from $350\\mathrm{nm}$ to $365\\mathrm{nm}$ . While not being bound by any theory, it is believed that the aromatic groups of the chromophore provide the light sensitivity in the range of 320 nm to $450\\ \\mathrm{nm}$ . Examples of such aromatic chromophores include, but are not limited to, phenylacridine, or substituted phenylacridines. Such aromatic chromophores may be joined to a polymer by the same methods that the photoinitiators described above may be joined to a polymer. \n\nExamples of other suitable compounds include, but are not limited to, plasticizers, surfactants, and complex surfactants. One example of a suitable plasticizer which may be bonded to a chain or backbone of a functional polymer is a urethane plasticizer having formula VIII. \n\nVIII \n\n$Z_{1}$ is the group $\\mathrm{R}_{16}$ is $\\mathrm{R}_{19}$ or $\\mathrm{CONH{\\mathrm{-}}\\mathrm{R}_{19}},$ $\\mathrm{R}_{17}$ and $\\mathrm{R}_{18}$ are hydrogen atoms or methyl groups, \n\n \n\n$\\mathrm{R}_{19}$ is a saturated aliphatic group with 1 to 20 carbon atoms, \n\nn is zero or a whole number from 1 to 15, $\\mathbf{m}^{\\prime}$ is whole number from 2 to 4, $\\boldsymbol{\\mathrm{\\tt~p^{\\prime}~}}$ is zero or a whole number from 1 to 4, $\\mathbf{k}^{\\prime}$ is a whole number from 2 to 12, ${\\bf r}^{\\prime}$ is a whole number from 4 to 12, and $\\boldsymbol{\\mathrm{n^{\\prime}{+}}}\\boldsymbol{\\mathrm{p^{\\prime}}}$ is a whole number from 1 to 10, and wherein _ $\\mathrm{R}_{16}{=}\\mathrm{R}_{19}$ if $\\ensuremath{\\mathbf{p}}^{\\prime}{=}0$ D $\\mathrm{R_{16}{=}C O N H{\\mathrm{{-}}}\\mathrm{R_{10}}}$ if $\\mathrm{\\Delta}\\mathrm{n}{'}{=}0$ \n\nBecause the urethane of formula VIlI terminates in aliphatic or cycloaliphatic groups, a functional group such as a halogen may be added to at least one of the terminal groups in order for the urethane to react with a polymer backbone or pendent group. \n\nExamples of water-soluble or water-emulsifiable surfactants that may be joined to a polymer include alkoxylated emulsifiers. A suitable alkoxylated emulsifier is one having the general formula: \n\nwherein 一 $X_{1}$ is one of the following groups: \n\n$$\n\\mathrm{R}_{20}{\\longrightarrow}\\mathrm{O}{\\cdot}(\\mathrm{A}^{\\prime\\prime}\\mathrm{O})_{n^{\\prime\\prime}}\\mathrm{~-}\\mathrm{H}\n$$ \n\nwhere A\"O are alkylene oxide units selected from ethylene oxide units $\\left(\\mathrm{CH}_{2}{\\longrightarrow}\\mathrm{CH}_{2}{\\longrightarrow}\\mathrm{O}\\right)$ and propylene oxide units $\\mathrm{(CH(CH_{3}){\\_}C H_{2}{\\_}O)}$ or $\\mathrm{(CH_{2}{\\mathrm{-}}C H(C H_{3}){\\mathrm{-}}O)}$ and mixtures of ethylene and propylene oxide units, either in the mixture of molecules, where $\\mathrm{R}_{20}$ is a hydrophobic group, typically a hydrocarbon group, $\\boldsymbol{\\mathrm{n}}\"$ is between 8 and 200, preferably between 15 and 40. Preferably, $\\mathrm{R}_{20}$ is a tristyrylphenol. \n\nDyes may also be joined to functional compounds of the present invention. Suitable dyes include, but are not limited to, triphenylmethane dyes, azo dyes, polyazo dyes, anthraguinones, eosin, eosinate, thazine, fluorocein, phthalein, \n45 xanthene, oxazine, aniline based, anionic and cationic dyes. Such dyes may be joined to the functional polymer by any suitable method in the art. Such dyes have one or more free reactive groups such as, for example, sulfinate, amino,or hydroxyl groups that may react with a group on the polymer. \n50 An exemplary method of joining a dye to a polymer is to place a spacer group on one of the ring structures of the dye molecule employing a Friedal Crafts reaction as described above for the photoinitiators. Once the dye molecule has a spacer group, the reactive group on the spacer is then reacted \n55 with a reactive group of a functional polymer as described above. The functional polymers have an average molecular weight range of at least 10oo daltons. More typically, the average molecular weight range of the functional polymers \n50 is from 10,o0o daltons to 500,o0o daltons. Molecular weights may be measured by such methods as GPC (gel permeation chromatography) or SEC (size exclusion chromatography). The functionalized polymers of the present invention may be functionalized with one or more pendent \n55 functional moieties in ranges of from 1.O to as high as 100 mole percent of reactive sites on the polymer backbone, typically from about 2.0 to about 20 mole percent, more \n\n$\\mathrm{Y}_{1}$ is a saturated apliphatic or cycloaliphatic group with 2 to 12 carbon atoms, \n\ntypically from about 5.0 to about 15 mole percent. Complete functionalization of the polymer backbone with pendent groups is not always desirable because such groups as hydroxyl and carboxyl groups on the backbone provide for solubility in alkaline solutions. Such solubility is highly desirable when the functionalized polymer is employed in photoresist. Acid functionality of the main chain may be a carboxylic acid functionality or may include, for example, a sulfonic acid or phosphoric acid functionality. \n\nThe functionalized polymers of the present invention are film forming polymers that may be employed in any industry where polymer film coatings are desired. Such industries include, but are not limited to lithography, electrophotographic imaging members, optical data storage, decorative pigments, adhesives, cosmetics, security applications or active and passive optical elements such as polarizers, optical retarders or color filters, paints and other surface coating compositions. The functionalized polymers also have good flexibility, and are readily soluble in aqueous alkaline solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, and the like. Because the functionalized polymers have good flexibility and solubility, the functionalized polymers are especially useful in photoresist compositions, particularly in liquid imaging photoresists. The high solubility of the functionalized polymers in aqueous alkaline solutions enables photoresists made with the functionalized polymers to be easily stripped, thus preventing short circuiting on a circuit board. Additionally, undesirable and costly strippers such as organic-based, amine or organic solvent-containing strippers may be avoided. Thus, excessive waste treatment procedures may be eliminated from the printed wiring board procedures as well as environmental and worker safety concerns associated with such organic-based strippers. Good flexibility also provides for a photoresist that is not brittle and does not readily chip. Chipping, due to brittleness, can lead to circuit defects in printed wiring boards. \n\nThe functionalized polymers also have good adhesion to metal surfaces due to their pendent functional groups. The functionalized polymers are also self cross-linking, thus the functionalized polymers may be employed as the sole crosslinking agent in a photoresist composition. Advantageously, cross-linking monomers or oligomers employed in conventional photoresists may be eliminated. Thus, premature polymeriztion between the various components of a photoresist composition are avoided. Accordingly, both the stability and the shelf life of such photoresists are improved. \n\nBecause the functional polymers are hydrophilic, they are suitable for use in liquid photoresists, such as waterborne photoresists. Such photoresists may be positive-working or negative-working. Functionalized polymers of the present invention compose from $5\\%$ by weight to $90\\%$ by weight of the photoresist composition. Preferably the functionalized polymers comprise from $25\\%$ by weight to $70\\%$ by weight, most preferably from $30\\%$ by weight to $50\\%$ by weight of the liquid photoresist composition. In addition to a diluent, the balance of the photoresist composition may optionally include additional binder polymers, cross-linking monomers or oligomers, and conventional additives as described below. Diluents employed include water an organic solvent or mixtures thereof. A mono-alcohol or a polyol is a preferred organic diluent. Water is the most preferred diluent. \n\nOptional cross-linking agents may be employed, but are preferably excluded. Such cross-linking agents include a monomer, or a short chain oligomer having ethylenic unsaturation, particularly, $\\mathbf{\\alpha}_{\\mathrm{{\\alpha}}}\\mathbf{\\mathrm{{\\alpha}}}_{\\mathrm{{\\alpha}}}\\mathbf{\\mathrm{{\\beta}}}$ -ethylenic unsaturation functionality of 2 or greater. A mixture of conventional monofunctional and multi-functional monomers may be used. Such optional cross-linking agents are included in amounts of from $5\\%$ to $15\\%$ by weight of the photoresist. \n\nOptionally the functionalized polymers of the present 10 invention may contain an additional photoinitiator chemical system. Preferably such photoinitiators are excluded. The photoinitiator chemical system may compose from $0.1\\%$ to $5\\%$ by weight of the photoresist composition. Conventional photoinitiators or photoinitiator systems may be employed. \n\nPhotoresist compositions of the present invention may also include an optional color former. Color formers are employed in amounts of from $0.1\\%$ to $1.0\\%$ by weight of the composition. Examples of suitable color formers include, but are not limited to, diphenylamine, dibenzylaniline, triphenylamine, diethylaniline, diphenyl-p-phenylenediamine, p-toluidine, $^{4,4^{\\prime}}$ -biphenyldiamine, o-chloroaniline， leuco crystal violet, leuco malachite green, and the like. \n\nAdditionally, the photoimageable compositions may contain a wide variety of additional adjuvants including stabilizers, flexibilizing agents, adhesion promoters, plasticizers, fillers or mixtures thereof. Such adjuvants are additives that contribute to the effectiveness of the primary ingredients. Optionally, additional polymeric or resin binders may be added to the liquid photoresists. Such additional polymeric binders may include, as polymerized components, one or more acid functional monomers such as (meth)acrylic acid. For example, U.S. Pat. No. 5,952,153, discloses polymeric binders that have suficient acid functionality to be employed in the photoresists of the present invention. When employed, such polymers may be used in amounts of from $5\\%$ to $20\\%$ by weight of the photoresist composition. \n\nProcessing of the liquid photoresist compositions is by any suitable means employed in the art. For example,a \n40 photoimageable composition layer formed from a liquid composition is applied to a substrate, such as a surface, of a metal-clad board. An example of a suitable metal is copper. Any substrate on which a liquid photoresist may be applied may be employed. The liquid photoresist composition may \n45 be applied to a substrate by any known means, such as spinning, dipping or roller coating. Once applied, most of the diluent is removed and the photoresist is then exposed to actinic radiation through appropriate artwork. Exposure to actinic radiation polymerizes the cross-linking components \n50 in the light-exposed areas, if the photoresist is negativeworking, resulting in a cross-linked structure that is resistant to developer. Next, the unexposed portion of the photoresist is developed in dilute alkaline aqueous solution, such as a $1\\%$ sodium carbonate solution. The alkali solution causes \n55 salt formation with carboxylic acid groups of the functionalized polymer rendering the unexposed portions of the photoresist soluble and removable. After development, an etchant may be used to remove metal from areas where the photoresist was removed thereby forming a printed circuit \n$_{60}$ pattern. The remaining photoresist may be removed using an appropriate stripper, such as $1\\%$ to $3\\%$ sodium or potassium hydroxide aqueous solution.Organic based developers, such as tetraalkylammonium hydroxide based developers, may be used but are less preferred. \n\n55The following examples are intended to further illustrate the present invention but are not intended to limit the scope of the invention.",
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"category": " Materials and methods"
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},
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{
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"id": 16,
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"chunk": "# 21 EXAMPLE1 \n\nPolymer of Methacrylic Acid and Methyl Methacrylate functionalized with: 1,6-Hexamethylene Diisocyanate Biuret—Polypropoxylated Hydroxypropylmethacrylate Moieties \n\nA homogeneous solution containing 62.0 grams of methacrylic acid and 265.0 grams of methyl methacrylate was prepared. $75\\%$ by weight of the homogeneous solution were transferred into a second flask. The homogeneous solution of the first flask was diluted to $26.0\\%$ by weight solids and the homogeneous solution of the second flask was diluted to $86.50\\%$ by weight solids by adding sufficient methyl ethyl ketone. \n\nThe first flask was mixed and heated to reflux under atmospheric conditions. 2.0 grams of $^{2,2^{\\dag}}$ -azobis (2-methylbutyronitrile) was added to the reaction mixture, mixed and held at reflux for about 3O minutes. \n\n6.25 grams of 2,2'-azobis (2-methylbutyronitrile) was mixed with 38.0 grams of methyl ethyl ketone and fed into the first flask along with the contents of the second flask over 4 hours while maintaining reflux. An additional amount of 9.0 grams of methyl ethyl ketone was then added to the first flask and the mixture was refluxed for an additional hour.",
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"category": " Materials and methods"
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},
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{
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"id": 17,
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"chunk": "# 22 \n\nIn a separate clean dry air sparged addition funnel, 193.0 grams of polypropoxylated hydroxypropylmethacrylate (hydroxyl number $^{-158}$ ）was weighed out. The polypropoxylated hydroxypropylmethacrylate was added to the flask \n5 containing the 1,6-hexamethylene diisocyanate biuret over about 1 hour with mixing and maintaining a temperature of $35^{\\circ}\\mathrm{C}$ The addition funnel was then rinsed with 118.0 grams of methyl ethyl ketone to remove any remaining polypropoxylated hydroxypropylmethacrylate. The rinse was added \n.0 to the flask containing the biuret with a temperature increased to $60^{\\circ}\\mathrm{C}$ . The reaction was maintained for 3 hours at $60^{\\circ}\\mathrm{C}$ The reaction was monitored to determine completion of the synthesis of a urethane acrylate moiety by known analytical methods in the art. \n\n5 The functionalized polymer was prepared by weighing out 763.0 grams of the acrylic polymer ( $47\\%$ solids）and 55.0 grams of methyl ethyl ketone to a clean, dry air sparged flask. The combination was mixed and heated to $45^{\\circ}\\mathrm{C}$ .The urethane/acrylate moiety was then added to the acrylic :0 polymer over about 1 hour. 0.50 grams of Irganox $\\textsuperscript{\\textregistered}$ 1076 and 28.0 grams of methyl ethyl ketone was added to the reaction mixture. The reaction contents were held at $45^{\\circ}\\mathrm{C}$ for 3 hours with constant mixing. The polymer main chain was 6 mole percent functionalized with the moiety. P rep!5 resents the polymer backbone with one functional moiety attached. \n\n \n\n4.55 grams of 2,2'-azobis (2-methylbutyronitrile) were dissolved in 48.0 grams of methyl ethyl ketone and mixed. The mixture was then added to the first flask over a period of 90 minutes while maintaining reflux. \n\n55 \n\n8.5 grams of 2,2'-azobis (2-methylbutyronitrile) were mixed with 48.0 grams of methyl ethyl ketone and then fed into the reaction mixture over about 150 minutes while maintaining reflux. An additional amount of 23.0 grams of methyl ethyl ketone were added to the reaction mixture. At the end of the reaction, 2,2'-azobis (2-methylbutyronitrile) was thermally killed off to below parts per million concentrations. The acrylic polymer main chain or back bone product was set aside. \n\n150.0 grams of 1,6-hexamethylene diisocyante biuret $(23.0\\%$ NCO) were added to a clean dry, nitrogen sparged flask. 0.06 grams of dibutylin dilaurate, 0.05 grams of Irganox $\\textsuperscript{\\textregistered}$ 1076 (antioxidant) and 160.0 grams of methyl ethyl ketone were also added to the flask. The flask was sparged with dry air and stoppered. The components were mixed and heated at about $35^{\\circ}\\mathrm{~C~}$",
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"category": " Materials and methods"
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},
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{
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"id": 18,
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"chunk": "# EXAMPLE2 \n\nPolymer of 2-Hydroxyethyl Methacrylate, \nMethacrylic Acid and Methyl Methacrylate Functionalized with: Isophorone Diisocyanate—Polypropoxylated Hydroxypropylmethacrylate Moieties \n\nThe step of preparing the acrylic polymer backbone was the same as in the method described in Example 1 above except that 70.0 grams of 2-hydroxyethyl methacrylate was added to the mixture of methacrylic acid and methyl methacrylate. \n\nThe reaction conditions for preparing the functionalized pendent groups were the same as described in Example 1 above except that 1 mole of isophorone diisocyanate was reacted with about one mole of hydroxy methacrylate to form a isophorone diisocyante hydroxy methacrylate moiety.",
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"category": " Materials and methods"
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},
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{
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"id": 19,
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"chunk": "# 23 \n\nThe isocyanate groups of the isophorone diisocyanate hydroxy methacrylate moiety were reacted with the hydroxyl groups of the 2-hydroxyethyl methacrylate moiety under the conditions described in Example 1 to form a functionalized polymer with functionalized pendent groups as shown below. The polymer was 6 mole percent functionalized. P represents the polymer backbone.",
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"category": " Materials and methods"
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},
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{
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"id": 20,
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"chunk": "# 24 EXAMPLE 3 \n\n \n\nSynthesis of 1,6-Hexamethylene Diisocyanate Trimer-Polyalkoxylated Hydroxyalkyl (meth)acrylate, or a 1,6-Hexamethylene \nDiisocyanate Trimer-Hydroxyalkyl (meth)acrylate \n(urethane/acrylate with at least one free isocyanate) \n\n10 \n\nOne mole of 1,6-hexamethylene diisocyanate trimer is added to a clean dry, nitrogen sparged flask. 0.06 grams of dibutylin dilaurate, 0.05 grams of Irganox $\\mathbb{R}$ (antioxidant) 15 and 160.0 grams of methyl ethyl ketone are also added to the flask. The flask is sparged with dry air and stoppered. The components are mixed and heated at $35^{\\circ}\\mathrm{C}$ Two moles of a polyalkoxylated hydroxyalkyl (meth)acrylate, or two moles 20 of hydroxyalkyl (meth)acrylate are added to the flask, mixed with the trimer, and heated at $35^{\\circ}\\mathrm{~C~}$ .for one hour. The reaction temperature is increased to $60^{\\circ}\\mathrm{C}$ and the reaction 25 is maintained for 3 hours. The resulting compound has the following general structure where n is an integer of from 0 to 1000, preferably from 1 to 200, 1 is an integer of from 1 to $10,\\mathrm{~m~}$ is an integer of from 1 to 10 and $\\mathrm{R}^{3}$ is (meth) 30 acrylate. \n\n \n\nThe foregoing urethane/acrylate with one free isocyanate 65 group may be reacted with a polymer main chain containing free carboxyl, hydroxyl, or aminyl groups to form a functionalized polymer of the present invention.",
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"category": " Materials and methods"
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},
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{
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"id": 21,
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"chunk": "# 25 EXAMPLE 4",
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"category": " Materials and methods"
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},
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{
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"id": 22,
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"chunk": "# Synthetic Procedure \n\n$60\\textrm{g}$ of a diacrylate acceptor compound (formula IX 5 below）and $0.5\\mathrm{~g~}$ of diazabicyclo-undecene (DBU） are weighed into a $500~\\mathrm{ml}~3$ -neck round bottom flask equipped with a mechanical stirrer and addition funnel. $15.0~\\mathrm{g}$ of an acetoacetate derived donor compound (formula X below) is weighed into the addition funnel. The acceptor compound 10 and DBU are mixed for 5 minutes prior to addition of the donor compound. The donor compound is then added dropwise to the stirred acceptor/DBU mixture over a 15 minute period. The solution is warmed to 54 degrees Celsius after addition of the donor compound is complete. After the 1s exotherm subsided in 100 minutes, a viscous yellow liquid is obtained which does not gel upon standing. \n\n \n\nwhere $\\mathbf{R^{\\prime}}$ is a radical derived from a urethane oligomer having a formula:",
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"category": " Materials and methods"
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},
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{
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"id": 23,
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"chunk": "# 26 \n\nparts of cold water whereupon 3.1 parts of reaction product precipitate. The product is isolated by filtration and purified by recrystalling twice from ethanol. The product, a chlorinated hydroxybutyl imidazole, is a white crystalline solid. \n\nTo 1.1 parts of the above prepared imidazole dissolved in 100 parts of ethanol containing 12 parts of potassium hydroxide is added 450 parts of a $1\\%$ by weight water solution of potassium ferricyanide at a rate of 5 parts per minute for 1.5 hours with continuous stirring. The oxidation reaction product in an amount of 1.0 parts precipitates from the reaction mixture, is isolated by filtration, and is washed with water until free from ferricyanide. The product is dried at $56^{\\circ}\\mathrm{C}$ for eight hours at $0.1~\\mathrm{mm}$ . mercury pressure after predrying overnight in a vacuum oven at $50^{\\circ}\\mathrm{C}$ It is solvated with two moles of enthanol for every three moles of biimidazole. The product is a biimidazole having the general formula shown below. \n\nA portion of the ethanol-solvated product was dried azeotropically with cyclohexane to produce non-solvated ’ material. Recrystallization from ether also yields the nonsolvated product. \n\n30 \n\n \n\nThe oligomer of the above reaction between donor compound XI and acceptor compound $\\mathrm{\\DeltaX}$ has the following general formula: \n\n \nEXAMPLE5 \n\n40 The above photoactive component is then reacted with the pendent carboxyl groups of an oligomer composed of methylmethacrylate and acrylic acid to bind the photoactive component with the oligomer by an ester linkage. The oligomer is prepared by free radical polymerization of the \n45 methylmethacrylate and acrylic acid monomers. The methylmethacrylate and acrylic acid monomers are obtainable from Rohm and Haas Company. The reaction takes place in an aqueous acidic environment. The reactants are refluxed in the acidic environment from $90^{\\circ}\\mathrm{~C~}$ .to $100^{\\circ}\\mathrm{~C~}$ .to obtain a \n50 water-soluble photoinitiator yield of from $85\\%$ to $90\\%$ by weight. \n\n \nTo 2.1 parts of hydroxybutyl substituted benzil (0.01 mole) dissolved in 50 parts of glacial acetic acid containing 6 parts of ammonium acetate (0.078 mole) is added 1.4 parts of o-chlorobenzaldehyde (O.o1 mole), and the solution is refluxed for 2 hours. The solution is then drowned in 200 \n\nThe hydrophilic photoinitiator containing compound may be employed as a cross-linking agent or further polymerized and employed as a polymer binder in a photoresist formu；lation. Upon exposure to light, a radical from the photoactive component is generated to polymerize the cross-linking agents of the formulation.",
|
||
"category": " Materials and methods"
|
||
},
|
||
{
|
||
"id": 24,
|
||
"chunk": "# EXAMPLE6",
|
||
"category": " Introduction"
|
||
},
|
||
{
|
||
"id": 25,
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||
"chunk": "# Synthesis of Functionalized Copolymer \n\nA homogeneous solution containing 197 grams of methacrylic acid, 512 grams of methyl methacrylate and 79 grams of poly(ethoxylated) monomethacrylate was prepared. $75\\%$ by weight of the homogeneous solution were prepared into a second flask. The homogeneous solution of",
|
||
"category": " Materials and methods"
|
||
},
|
||
{
|
||
"id": 26,
|
||
"chunk": "# 27 \n\nthe first flask was diluted to $25\\%$ by weight solids and the homogeneous solution of the second flask was diluted to $60\\%$ be weight solids by adding sufficient methyl ethyl ketone. \n\nThe first flask was mixed and heated to reflux under atmospheric conditions. 2.0 grams of 2,2'-azobis (2-methylbutyronitirle) was added to the reaction mixture, mixed and held at reflux for 30 minutes. \n\n6.0 grams of 2,2'-azobis (2-methylbutyronitirle) was mixed with about 40 grams of methyl ethyl ketone and fed into the first flask along with the contents of the second flask over 4 hours while maintaining reflux.An additional amount of 9.0 grams of methyl ethyl ketone was then added to the first flask and the mixture was refluxed for an additional hour. \n\n5.0 grams of 2,2'-azobis (2-methylbutyronitrile) were dissolved in 50.0 grams of methyl ethyl ketone and mixed. The mixture was then added to the first flask over a period of 90 minutes while maintaining reflux. \n\n9.0 grams of 2,2'-azobis (2-methylbutyronitrile) were mixed with 50.0 grams of methyl ethyl ketone and then fed into the reaction mixture over 150 minutes while maintaining reflux. An additional amount of 25.0 grams of methyl ethyl ketone were added to the reaction mixture. At the end of the reaction, 2,2'-azobis (2-methylbutyronitirle) was thermally killed off to below parts per million concentrations. The acrylic copolymer main chain or backbone was set aside.",
|
||
"category": " Materials and methods"
|
||
},
|
||
{
|
||
"id": 27,
|
||
"chunk": "# 28 EXAMPLE7 \n\n5.31 grams of 1,6-hexamethylene diisocyanate biuret $(23.\\%$ free-NCO) were added to a clean dry, nitrogen sparged flask. 0.06 grams of dibutylin dilaurate, 0.05 grams of Irganox $\\textsuperscript{\\textregistered}$ 1076 (antioxidant) and 160.0 grams of methyl ethyl ketone were also added to the flask. The flask was sparged with dry air and stoppered. The components were mixed and heated at $35^{\\circ}\\mathrm{~C~}$ \n\nIn a separate clean dry air sparged addition funnel, 15.97 grams of poly(ethoxylate-b-caprolactone) monomethacrylate oligomer was weighed out. The oligomer was added to the flask containing the 1,6-hexamethylene diisocyanate biuret over 1 hour with mixing and maintaining a temperatureof $35^{\\circ}\\mathrm{C}$ The addition funnel was then rinsed with 118.0 grams of methyl ethyl ketone to remove any remaining oligomer. The rinse was added to the flask containing the biuret with a temperature increased to $60^{\\circ}\\mathrm{~C~}$ The reaction was maintained for 3 hours at $60^{\\circ}\\mathrm{~C~}$ . the reaction was monitored to determine completion of the synthesis of a urethane acrylate moiety by high pressure liquid chromatography (HPLC). \n\nThe functionalized polymer was prepared by weighing out 763.0 grams of the acrylic copolymer ( $47\\%$ solids) and 50.0 grams of methyl ethyl ketone to a clean, dry air sparged flask. The combination was mixed and heated to $45^{\\circ}\\mathrm{C}$ .The urethane/acrylate moiety was then added to the acrylic polymer over 1 hour 0.50 grams of Irganox $\\textsuperscript{\\textregistered}$ 1076 and 30.0 grams of methyl ethyl ketone was added to the reaction mixture. The reaction contents were held at $45^{\\circ}\\mathrm{~C~}$ .for 3 hours with constant mixing. The resulting copolymer was composed of 25 mole $\\%$ of methyacrylic acid, 65 mole $\\%$ of methyl methacrylate and 10 mole $\\%$ of poly(ethoxylated) monomethacrylate residues. The copolymer main chain was 6 mole $\\%$ functionalized with the moiety.",
|
||
"category": " Materials and methods"
|
||
},
|
||
{
|
||
"id": 28,
|
||
"chunk": "# Synthesis of a Functionalized Copolymer \n\n5 A homogeneous solution containing 77.5 grams of 2-hydroxyethyl methacrylate, 194 grams of methacrylic acid, and 504 grams of methyl methacrylate was prepared. $75\\%$ by weight of the homogeneous solution was transferred to a second flask. The homogeneous solution of the first flask \n10 was diluted to $25\\%$ by weight solids and the homogeneous solution of the second flask was diluted to $60\\%$ by weight solids by adding sufficient methyl ethyl ketone. \n\nThe first flask was mixed and heated to reflux under atmospheric conditions. 2.0 grams of 2,2'-azobis (2-meth5 ylbutyronitirle) was added to the reaction mixture, mixed and held at reflux for 30 minutes. \n\n6.25 grams of 2,2'-azobis (2-methylbutyronitirle) was mixed with 40.0 grams of methyl ethyl ketone and fed into the first flask along with the contents of the second flask over 4 hours while maintaining reflux. An additional amount of 9.0 grams of methyl ethyl ketone was then added to the first flask and the mixture was refluxed for an additional hour. \n\n5.0 grams of 2,2'-azobis (2-methylbutyronitrile) were dissolved in 50.0 grams of methyl ethyl ketone and mixed. The mixture was then added to the first flask over a period of 90 minutes while maintaining reflux. \n\n9.0 grams of 2,2'-azobis (2-methylbutyronitirle) were mixed with 50.0 grams of methyl ethyl ketone and then fed into the reaction mixture over 150 minutes while maintain30 ing reflux. An additional amount of 23.0 grams of methyl ethyl ketone were added to the reaction mixture.At the end of the reaction, $^{2,2^{\\dag}}$ -azobis (2-methylbutyronitirle) was thermally killed off to below parts per million concentrations. The acrylic polymer main chain or backbone product was set 35 aside. \n\n150.0 grams of 1,6-hexamethylene diisocyanate biuret $23.0\\%$ -NCO) were added to a clean dry, nitrogen sparged flask. 0.06 grams of dibutylin dilaurate, 0.05 grams of Irganox $\\textsuperscript{\\textregistered}$ 1076 (antioxidant) and 160.0 grams of methyl ethyl ketone were also added to the flask. The flask was sparged with dry air and stoppered. The components were mixed and heated at $35^{\\circ}\\mathrm{~C~}$ \n\nIn a separate clean dry air sparged addition funnel, 190.0 grams of poly(ethoxylate- $\\cdot\\mathbf{b}$ -caprolactone)monomethacrylate oligomer was weighed out. The oligomer was added to the flask containing the 1,6-hexamethylene diisocyanate biuret over 1 hour with mixing and maintaining a temperature of $35^{\\circ}\\mathrm{C}$ . The addition funnel was then rinsed with 120.0 grams of methyl ethyl ketone to remove any remaining oligomer The rinse was added to the flask containing the biuret with a temperature increased to $60^{\\circ}\\mathrm{~C~}$ The reaction was maintained for 3 hours at $60^{\\circ}\\mathrm{C}$ . The reaction was monitored to determine completion of the synthesis of the urethane acrylate moiety. \n\n55 The functionalized polymer was prepared by weighing out 750.0 grams of the acrylic copolymer and 55.0 grams of methyl ethyl ketone to a clean, dry air sparged flask. The combination was mixed and heated to $45^{\\circ}\\mathrm{C}$ The urethane/ arcrylate moiety was then added to the acrylic copolymer \n60 over 1 hour. 0.50 grams of Irganox $\\textsuperscript{\\textregistered}$ 1076 and 30.0 grams of methyl ethyl ketone was added to the reaction mixture. The reaction contents were held at $45^{\\circ}\\mathrm{C}$ . for 3 hours with constant mixing. The polymer main chain was 6 mole percent functionalized with the moiety. \n\n55 What is claimed is: \n\n1. A polymer comprising $\\mathbf{\\alpha}_{\\mathrm{{\\alpha}}}\\mathbf{\\mathrm{{\\alpha}}}_{\\mathrm{{\\alpha}}}\\mathbf{\\mathrm{{\\alpha}}}_{\\mathrm{{\\alpha}}}$ -unsaturation and a photoinitiator joined to the polymer, the photoinitiator generates a",
|
||
"category": " Materials and methods"
|
||
},
|
||
{
|
||
"id": 29,
|
||
"chunk": "# 29",
|
||
"category": " Introduction"
|
||
},
|
||
{
|
||
"id": 30,
|
||
"chunk": "# 30 \n\nfree radical when exposed to actinic radiation, the photoinitiator is chosen from an imidazole dimer, an anthraquinone, a naphthaquinone, a ketal, a triazine compound, or combinations thereof, the polymer has an average molecular weight of at least 1000 daltons. \n\n2. The polymer of claim 1, further comprising multiple ester links. 3. The polymer of claim 2, wherein the ester links in the polymer are greater than 2. 4. The polymer of claim 1, wherein the polymer has one 10 or more side chains comprising greater than 2 ester links. \n\n5. The polymer of claim 1, wherein the imidazole dimer is a hexaarylbiimidazole. 6. The polymer of claim 1, further comprising a stripping agent, a plasticizer, surfactant, aromatic chromophore, dye, or combinations thereof joined to the polymer. 7. The polymer of claim 1, wherein the polymer has an average molecular weight of from 10,00o daltons to 500,000 daltons.",
|
||
"category": " Materials and methods"
|
||
}
|
||
] |