Polymers containing silicone chains and coating compositions comprising the same

Abstract

A polymer is provided that functions as a leveling agent that does not cause defects on the coating surface and imparts high smoothness to the coating. Specifically, a polymer containing organosilicon chains, wherein the organosilicon chains have organosilicon chains at a single end, the number average molecular weight of the organosilicon chains being in the range of 2,000 to 20,000, and the polymer containing organosilicon chains does not contain polymerizable unsaturated groups.

Description

Technical Field

[0001] This invention relates to polymers containing organosilicon chains and coating compositions comprising such polymers. Background Technology

[0002] Leveling agents are added to smooth the coating film obtained from coating compositions such as paint compositions and resist compositions. Specifically, by adding a leveling agent to the coating composition, the leveling agent is oriented on the coating surface, reducing the surface tension of the coating film and thus smoothing it. For coating films with smoothed surfaces, shrinkage and unevenness can be reduced.

[0003] Leveling agents have a variety of uses, including in color resist compositions used in the manufacture of color filters for liquid crystal displays. The manufacturing process of color filters includes the following steps: a color resist composition is typically coated onto a glass substrate using methods such as spin coating or slot coating; the dried coating is exposed using a mask; and then, development is performed to form a colored pattern. At this point, there is a concern about uneven pixel color caused by poor coating smoothness, uneven film thickness, or issues such as uneven coating or shrinkage.

[0004] By adding a leveling agent to the colored resist composition, the smoothness of the resulting coating film is improved. The red (R), green (G), and blue (B) pixels, and the surface of the black matrix (BM) formed between these pixels, can exhibit high smoothness, and a color filter with less color unevenness can be formed.

[0005] As a leveling agent that imparts smoothness to such a coating, a polymeric leveling agent has been proposed (Patent Document 1).

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2002-179991 Summary of the Invention

[0009] The problem the invention aims to solve

[0010] The polymeric leveling agent in Patent Document 1 is introduced by copolymerizing or ionically copolymerizing macromonomers with free radicals. In cases where the aforementioned macromonomers have organosilicon chains, the polymeric leveling agent in Patent Document 1 has multiple organosilicon chains in one polymer. However, the presence of multiple organosilicon chains in a leveling agent can lead to defects on the coating surface.

[0011] The problem to be solved by the present invention is to provide a polymer that functions as a leveling agent that does not cause defects on the coating surface and imparts high smoothness to the coating.

[0012] Solution for solving the problem

[0013] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that if the polymer containing the organosilicon chain has a specific organosilicon chain at a single end and the polymer containing the organosilicon chain does not contain polymerizable unsaturated groups, then the coating surface will not produce defects and excellent leveling performance can be obtained, thus completing the present invention.

[0014] That is, the present invention relates to polymers containing organosilicon chains, which are polymers having organosilicon chains at a single end, wherein the number average molecular weight of the aforementioned organosilicon chains is in the range of 2,000 to 20,000, and the polymers containing organosilicon chains do not contain polymerizable unsaturated groups.

[0015] The effects of the invention

[0016] The present invention provides a polymer that functions as a leveling agent that does not cause defects on the coating surface and imparts high smoothness to the coating. Detailed Implementation

[0017] The following description pertains to one embodiment of the present invention. The present invention is not limited to this embodiment, and may be implemented with appropriate modifications without impairing its effects.

[0018] In addition, in this application specification, "(meth)acrylate" refers to one or both of acrylate and methacrylate.

[0019] [polymer]

[0020] The polymer of the present invention has an organosilicon chain with a number average molecular weight in the range of 2,000 to 20,000 at a single end, and does not contain polymerizable unsaturated groups.

[0021] In addition, "single end" refers to any end of the main chain of a polymer (the longest molecular chain that makes up the polymer).

[0022] The polymers of this invention, by having specific organosilicon chains only at a single end and lacking polymerizable unsaturated groups, do not compromise compatibility with the base polymer and solvent of the coating composition when used as additives, thus exhibiting leveling properties. Because compatibility is not compromised, defects on the resulting coating surface can be prevented.

[0023] The aforementioned organosilicon chains have a number average molecular weight in the range of 2,000 to 20,000, preferably in the range of 3,000 to 20,000, more preferably in the range of 3,500 to 15,000, and even more preferably in the range of 4,000 to 12,000.

[0024] The number-average molecular weight of the aforementioned organosilicon chains was determined using the method described in the examples.

[0025] The aforementioned ratio of organosilicon chains is, for example, in the range of 5 to 95% by mass, preferably in the range of 10 to 90% by mass, more preferably in the range of 15 to 80% by mass, and even more preferably in the range of 20 to 70% by mass.

[0026] Here, the ratio of organosilicon chains refers to a value based on the mass of the polymer of the present invention (mass of organosilicon chains / mass of polymer). The ratio of organosilicon chains is a value calculated based on the raw material feed ratio during manufacturing and can be adjusted by the raw material feed ratio of the organosilicon compounds used in the manufacturing of the polymer of the present invention.

[0027] The organosilicon chain of the polymer of the present invention is preferably the organosilicon chain shown in the following formula (1).

[0028]

[0029] (in the aforementioned formula (1),)

[0030] R 11 R 12 R 13 R 14 and R 15 Each is independently an alkyl or phenyl group having 1 to 18 carbon atoms.

[0031] L 11 It is a divalent organic group or a single bond.

[0032] (n is an integer.)

[0033] R 11 R 12 R 13 R 14 and R 15 The alkyl group having 1 to 18 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms.

[0034] R 11 R 12 R 13 and R 14 Preferably methyl, R 15 Preferably, it is an alkyl group having 1 to 6 carbon atoms.

[0035] n is preferably an integer in the range of 5 to 300, more preferably an integer in the range of 10 to 250, even more preferably an integer in the range of 20 to 200, and most preferably an integer in the range of 25 to 200.

[0036] L 11The divalent organic group is preferably an alkylene group with 1 to 50 carbon atoms or an alkylene oxide group with 1 to 50 carbon atoms.

[0037] As L 11 Alkylenes with 1 to 50 carbon atoms include methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, n-decylene, n-dodecylene, isopropylene, 2-methylpropylene, 2-methylhexylene, tetramethylethylene, etc.

[0038] L 11 The alkylene group having 1 to 50 carbon atoms is preferably an alkylene group having 1 to 15 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably methylene, ethylene, n-propylene, or isopropylene.

[0039] L 11 The alkylene oxide with 1 to 50 carbon atoms is, for example, a group in which one or more -CH2- atoms in the aforementioned alkylene oxides are replaced with -O-.

[0040] L 11 The alkylene oxide with 1 to 50 carbon atoms is preferably an alkylene oxide with 1 to 15 carbon atoms, more preferably an alkylene oxide with 1 to 8 carbon atoms, and even more preferably a methylene oxide, ethylene oxide, propylene oxide, oxytrimethylene, butylene oxide, oxytetramethylene, pentylene oxide, heptylene oxide, or octylene oxide.

[0041] In L 11 When the divalent organic group is an alkylene group having 1 to 50 carbon atoms or an alkylene group having 1 to 50 carbon atoms, a portion of the -CH2- group of these divalent organic groups may optionally be replaced by a carbonyl group (-C(=O)-), a phenylene group, an amide bond, or a urethane bond, and optionally further replaced with a hydroxyl group on the carbon atom.

[0042] The polymers of the present invention are polymers having the aforementioned organosilicon chains at their ends. The structure of the polymer portion is not particularly limited as long as it does not contain polymerizable unsaturated groups. The polymers of the present invention are suitable for use as additives in coating compositions; therefore, the structure of the polymer portion preferably includes a structure that exhibits compatibility with the base polymer of the coating composition.

[0043] The polymer of the present invention is preferably a polymer in which a polymerizable monomer (2) is used as a polymerizing component, and the polymer has an organosilicon chain at a single end, wherein the polymerizable monomer (2) has one or more selected from alkyl groups having 1 to 18 carbon atoms, aromatic groups having 6 to 18 carbon atoms, groups containing polyoxyolefin chains, and groups containing polyester chains.

[0044] The polymer of the polymerizable monomer (2) exhibits high compatibility with the base polymer of the coating composition.

[0045] In addition, "polymer components" refers to the components that make up the polymer, excluding solvents, polymerization initiators, etc., which do not constitute the polymer.

[0046] In this invention, "polymerizable monomer" refers to a compound having a polymerizable unsaturated group. Examples of polymerizable unsaturated groups in the polymerizable monomer (2) include (meth)acryloyl, (meth)acryloyloxy, (meth)acryloylamide, vinyl ether, allyl, styryl, (meth)acryloylamino, and maleimide. Among these, (meth)acryloyl and (meth)acryloyloxy are preferred from the perspectives of ease of obtaining raw materials and good polymerization reactivity.

[0047] The alkyl group having 1 to 18 carbon atoms in the polymerizable monomer (2) can be any of the straight-chain alkyl, branched alkyl and cyclic alkyl groups. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, cyclohexyl, n-octyl, hexadecyl, etc.

[0048] The alkyl group having 1 to 18 carbon atoms in the polymerizable monomer (2) is preferably an alkyl group having 1 to 6 carbon atoms.

[0049] The polymerizable monomer (2) may optionally have an alkyl group having 1 to 18 carbon atoms. The alkyl group having an ether bond with 1 to 18 carbon atoms is a group in which -CH2- is replaced by an ether bond (-O-), including alkyleneoxyalkyl groups having 2 to 18 carbon atoms, polyoxyalkylene alkyl groups having 3 to 18 carbon atoms, and oxocyclic alkyl groups having 2 to 18 carbon atoms.

[0050] Examples of aromatic groups with 6 to 18 carbon atoms in polymerizable monomers (2) include phenyl, naphthyl, anthracene-1-yl, phenanthrene-1-yl, etc.

[0051] The groups containing (poly)oxyalkylene chains in the polymerizable monomer (2) refer to: monovalent groups containing repeating oxyalkylene groups or divalent linking groups containing repeating oxyalkylene groups.

[0052] When the polymerizable unsaturated group of the polymerizable monomer (2) is (meth)acryloyl, the polymerizable monomer having a group containing a (poly)oxyalkylene chain is, for example, a compound represented by the following general formula (2-poa1) or (2-poa2).

[0053]

[0054] (In the aforementioned formulas (2-poa1) and (2-poa2),

[0055] R a21 Each can be a hydrogen atom or a methyl group independently.

[0056] R a22 It is an alkyl group having 1 to 18 hydrogen atoms or carbon atoms.

[0057] p is an integer greater than or equal to 0, q is an integer greater than or equal to 0, r is an integer greater than or equal to 0, and p+q+r is an integer greater than or equal to 1.

[0058] X, Y, and Z are each independently an alkylene group having 1 to 6 carbon atoms.

[0059] In the above equations (2-poa1) and (2-poa2), -(XO) p -(YO) q -(ZO) r -R a22 The shown groups and -(XO) p -(YO) q -(ZO) r - The group shown corresponds to a group containing a (poly)oxyalkylene chain.

[0060] In the above formulas (2-poa1) and (2-poa2), the alkylene groups of X, Y and Z with 1 to 6 carbon atoms are preferably alkylene groups with 2 to 4 carbon atoms.

[0061] Examples of polymerizable monomers (2) that are alkyl groups having 1 to 18 carbon atoms and whose polymerizable unsaturated group is (meth)acryloyl group include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, and 2-ethylhexyl methacrylate. Alkyl esters of (meth)acrylic acid with 1 to 18 carbon atoms, such as decyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate; and bridged cyclic alkyl esters of (meth)acrylic acid with 1 to 18 carbon atoms, such as dicyclopentyloxyethyl (meth)acrylate, isobornyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantane (meth)acrylate, dimethyl adamantane (meth)acrylate, dicyclopentyl (meth)acrylate, and dicyclopentenyl (meth)acrylate.

[0062] Examples of polymerizable monomers (2) that have 1 to 18 carbon atoms in a hydroxyalkyl group and whose polymerizable unsaturated group is (meth)acryloyl group include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxy methacrylate, 1,4-cyclohexanediethanol mono(meth)acrylate, and 2,3-dihydroxypropyl methacrylate.

[0063] Examples of polymerizable monomers (2) that have a phenylalkyl group having 7 to 18 carbon atoms or a phenoxyalkyl group having 7 to 18 carbon atoms and a polymerizable unsaturated group of (meth)acryloyl group include benzyl methacrylate, 2-phenoxymethyl methacrylate, 2-phenoxyethyl methacrylate, and 2-hydroxy-3-phenoxypropyl methacrylate.

[0064] Examples of polymerizable monomers (2) that have alkyl groups having 1 to 18 carbon atoms and whose polymerizable unsaturated group is a vinyl ether group include, for example, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, etc., alkyl vinyl ethers, cycloalkyl vinyl ethers, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 1-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 1-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 3-hydroxy-2-methylpropyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, cyclohexane-1,4-diethanol monovinyl ether, etc.

[0065] Examples of polymerizable monomers (2) that have alkyl groups having 1 to 18 carbon atoms and polymerizable unsaturated groups being allyl groups include, for example, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether.

[0066] Examples of polymerizable monomers (2) having aromatic groups with 6 to 18 carbon atoms include styrene, α-methylstyrene, p-methylstyrene, and p-methoxystyrene.

[0067] Examples of polymerizable monomers (2) that have alkyl groups having 1 to 18 carbon atoms and whose polymerizable unsaturated group is (meth)acryloylamino include, for example, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, diacetoneacrylamide, acryloylmorpholine, etc.

[0068] Examples of polymerizable monomers (2) that are alkyl groups having 1 to 18 carbon atoms and whose polymerizable unsaturated groups are maleimide groups include, for example, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, cyclohexylmaleimide, etc.

[0069] Examples of polymerizable monomers (2) that have a polyoxyethylene chain and a polymerizable unsaturated group of (meth)acryloyl group include polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polytrimethylene glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate, poly(ethylene glycol·propylene glycol) mono(meth)acrylate, polyethylene glycol·polypropylene glycol mono(meth)acrylate, poly(ethylene glycol·tetramethylene glycol) mono(meth)acrylate, and polyethylene glycol mono(meth)acrylate. Poly(tetramethylene glycol) mono(meth)acrylate, poly(propylene glycol) tetramethylene glycol mono(meth)acrylate, poly(propylene glycol) polytetramethylene glycol mono(meth)acrylate, poly(propylene glycol) 1,2-butanediol mono(meth)acrylate, poly(propylene glycol) poly(1,2-butanediol) mono(meth)acrylate, poly(ethylene glycol) 1,2-butanediol mono(meth)acrylate, poly(tetraethylene glycol) 1,2-butanediol mono(meth)acrylate, poly(tetraethylene glycol) 1,2-butanediol mono(meth)acrylate 1,2-Butanediol mono(meth)acrylate, poly(ethylene glycol·poly(1,2-butanediol)meth)acrylate, poly(ethylene glycol·trimethylenediol)mono(meth)acrylate, poly(ethylene glycol·polytrimethylenediol)mono(meth)acrylate, poly(propylene glycol·trimethylenediol)mono(meth)acrylate, poly(propylene glycol·polytrimethylenediol)mono(meth)acrylate, poly(trimethylenediol·tetramethylenediol)mono(meth)acrylate, polytrimethylenediol·poly(trimethylenediol)mono(meth)acrylate Methyl glycol mono(meth)acrylate, poly(1,2-butanediol·trimethylenediol) mono(meth)acrylate, poly(1,2-butanediol·polytrimethylenediol) mono(meth)acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, poly(1,2-butanediol·tetramethylenediol) mono(meth)acrylate, poly(1,2-butanediol·tetramethylenediol) mono(meth)acrylate, etc.

[0070] It should be noted that the above "poly(ethylene glycol·propylene glycol)" refers to a random copolymer of ethylene glycol and propylene glycol, and "polyethylene glycol·polypropylene glycol" refers to a block copolymer of ethylene glycol and propylene glycol.

[0071] The polymerizable monomer (2) is preferably one or more selected from the group consisting of the compound shown in formula (2-1), the compound shown in formula (2-2), the compound shown in formula (2-3), the compound shown in formula (2-4), and the compound shown in formula (2-5), and more preferably one or more selected from the group consisting of the compound shown in formula (2-1), the compound shown in formula (2-2), the compound shown in formula (2-3), and the compound shown in formula (2-4).

[0072] These compounds exhibit high compatibility when the polymers of the present invention are used as leveling agents.

[0073]

[0074] (In the aforementioned equations (2-1), (2-2), (2-3), (2-4), and (2-5),

[0075] R 21 It can be a hydrogen atom or a methyl group.

[0076] R 22 Alkyl groups having 1 to 18 carbon atoms

[0077] R 23 It can be a hydrogen atom or a methyl group.

[0078] R 24 It is an alkyl group having 1 to 18 hydrogen atoms or carbon atoms.

[0079] R 25 It can be a hydrogen atom or a methyl group.

[0080] R 26 It is an alkyl group having 1 to 18 carbon atoms or an alkyl group having 1 to 18 carbon atoms and containing an ether bond.

[0081] R 27 It can be a hydrogen atom or a methyl group.

[0082] R 28 It is an alkyl group having 1 to 18 carbon atoms or an alkyl group having 1 to 18 carbon atoms and containing an ether bond.

[0083] L 2 It is a divalent organic group.

[0084] R 29 It can be a hydrogen atom or a methyl group.

[0085] R 30 Each is independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.

[0086] n is an integer in the range of 1 to 4, m is an integer in the range of 1 to 200, p is an integer in the range of 1 to 10, q is an integer in the range of 1 to 100, and l is an integer in the range of 0 to 5.

[0087] L in the aforementioned equations (2-3) and (2-4) 2 Examples of divalent organic groups that are related to L 11 The same group as the divalent organic group.

[0088] Polymerizable monomers (2) can be manufactured using known methods.

[0089] In addition, commercially available products can be used for polymerizable monomers (2). For example, commercially available polymerizable monomers (2) having a group containing a polyoxyolefin chain and a polymerizable unsaturated group of (meth)acryloyl group include “NK Ester M-20G”, “NK Ester M-40G”, “NK Ester M-90G”, “NK Ester M-230G”, “NK Ester AM-90G”, “NK Ester AMP-10G”, “NK Ester AMP-20G”, and “NK Ester AMP-60G” manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and “BLEMMER PE-90”, “BLEMMER PE-200”, “BLEMMER PE-350”, “BLEMMER PME-100”, “BLEMMER PME-200”, “BLEMMER PME-400”, “BLEMMER PME-4000”, “BLEMMER PP-1000”, “BLEMMER PP-500”, “BLEMMER PP-800”, “BLEMMER PME-200”, “BLEMMER PME-4000”, “BLEMMER PP-800”, “BLEMMER PME-200”, “BLEMMER PME-200”, “BLEMMER PME-4000”, “BLEMMER PP-1000”, “BLEMMER PP-500”, “BLEMMER PP-800”, “BLEMMER PME-200”, “BLEMMER PME-200”, “BLEMMER PME-4000”, “BLEMMER PP-800”, “BLEMMER PME-200”, “BLEMMER PME-2000”, “BLEMMER PME-4000”, “BLEMMER PME-2000”, “BLEMMER PME-4000”, “BLEMMER PME-2000”, “BLEM 70PEP-350B, BLEMMER 55PET-800, BLEMMER 50POEP-800B, BLEMMER 10PPB-500B, BLEMMER NKH-5050, BLEMMER AP-400, BLEMMER AE-350, Ceramic's PLACEL F series, and Osaka Organic Chemical Industry Co., Ltd.'s Viscoat series, etc.

[0090] The polymer of the present invention is a polymer having one or more polymerizable monomers (2) selected from alkyl groups having 1 to 18 carbon atoms, aromatic groups having 6 to 18 carbon atoms, and groups containing polyoxyalkylene chains. When the polymer has an organosilicon chain at a single end, the polymerizable monomer (2) can be used alone or in combination of two or more.

[0091] In addition, when the above polymer is a copolymer of two or more polymerizable monomers (2), the polymerization form of the copolymer is not particularly limited. It can be a random copolymer of two or more polymerizable monomers (2) with different structures, or a block copolymer of two or more polymerizable monomers (2) with different structures.

[0092] The polymer of the present invention is a polymer having one or more polymeric monomers (2) selected from alkyl groups having 1 to 18 carbon atoms, aromatic groups having 6 to 18 carbon atoms, and groups containing polyoxyalkylene chains as polymeric components, and when the polymer has an organosilicon chain at a single end, the polymer of the present invention may contain a polymer portion of polymeric monomers other than polymeric monomers (2).

[0093] The aforementioned polymeric component may be, for example, at least 90% by mass of a polymeric monomer (2), preferably at least 95% by mass of a polymeric monomer (2), and more preferably composed solely of a polymeric monomer (2). That is, the polymer of the present invention is most preferably a polymer having one or more polymeric monomers (2) selected from alkyl groups having 1 to 18 carbon atoms, aromatic groups having 6 to 18 carbon atoms, and groups containing polyoxyalkylene chains, and the polymer has an organosilicon chain at a single end.

[0094] The polymer of this invention does not contain polymerizable unsaturated groups.

[0095] The polymers of the present invention are suitable for use as leveling agents in coating agents, but the desired effect may be compromised if they contain polymeric unsaturated groups that may react with the base polymer or the like contained in the coating composition.

[0096] Examples of polymerizable unsaturated groups include (meth)acryloyl, (meth)acryloyloxy, (meth)acryloylamide, vinyl ether, allyl, styrene, and maleimide groups, which contain carbon-carbon unsaturated double bonds (C=C).

[0097] The polymers of the present invention preferably do not contain reactive functional groups.

[0098] In this invention, "reactive functional group" refers to a functional group that can react with other functional groups to form cross-linked structures, etc. Examples include isocyanate group, epoxy group, carboxyl group, carboxyl halogen group, carboxylic anhydride group, etc.

[0099] The polymers of the present invention are suitable for use as leveling agents in coating agents, but in cases where they contain reactive functional groups that may react with the base polymer or the like contained in the coating composition, the desired effect may be compromised.

[0100] The number-average molecular weight (Mn) of the polymer of the present invention is preferably in the range of 1,000 to 500,000, more preferably in the range of 2,000 to 100,000, and even more preferably in the range of 2,000 to 40,000.

[0101] The weight-average molecular weight (Mw) of the polymer of the present invention is preferably in the range of 1,000 to 500,000, more preferably in the range of 2,000 to 100,000, and even more preferably in the range of 2,000 to 40,000.

[0102] The dispersion (Mw / Mn) of the polymer of the present invention is preferably in the range of 1.0 to 2.0, more preferably in the range of 1.0 to 1.8, and even more preferably in the range of 1.0 to 1.5.

[0103] The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the polymers of the present invention were determined by the methods described in the examples.

[0104] [Polymer Manufacturing Methods]

[0105] The polymer of the present invention can be manufactured by generating free radicals from the aforementioned compound (1) in a reaction system containing compound (1) and polymerizable monomer (2), and by subjecting the aforementioned polymerizable monomer (2) to living free radical polymerization of the aforementioned compound (1), wherein the compound (1) has a functional group capable of generating free radicals at a single end of an organosilicon chain having a number average molecular weight in the range of 2,000 to 20,000.

[0106] As functional groups possessing the ability to generate free radicals in compound (1), examples include organic groups with halogen atoms, organic groups with alkyl telluryl groups, organic groups with dithioester groups, organic groups with peroxide groups, and organic groups with azo groups.

[0107] From the perspective of ease of synthesis, ease of polymerization control, and diversity of applicable polymerizable monomers, the functional group possessed by compound (1) that has the ability to generate free radicals is preferably an organic group with halogen atoms.

[0108] Examples of organic groups containing halogen atoms include, for example, 2-bromo-2-methylpropionyloxy, 2-bromo-propionyloxy, and p-chlorosulfonylbenzoyloxy.

[0109] Compound (1) with an organosilicon chain having a functional group at a single end capable of generating free radicals in the range of number average molecular weight of 2,000 to 20,000 is preferably a compound represented by the following formula (1-1).

[0110]

[0111] (In the aforementioned equation (1-1),

[0112] R 11 R 12 R 13 R 14 and R 15 Each is independently an alkyl or phenyl group having 1 to 18 carbon atoms.

[0113] L 11 It is a divalent organic group or a single bond.

[0114] n is an integer.

[0115] X is a functional group capable of generating free radicals.

[0116] In the aforementioned equation (1-1), R 11 R 12 R 13 R 14 R 15 L 11 The preferred method for n is the same as R in the aforementioned equation (1). 11 R 12 R 13 R 14 R 15 L 11 The optimal method is the same as that for n.

[0117] In the aforementioned formula (1-1), the functional group of X that has the ability to generate free radicals is, for example, a functional group having halogen atoms, preferably the functional group shown in the following formula (X-1).

[0118]

[0119] (In the aforementioned formula (X-1),

[0120] R HAL It is a halogen atom.

[0121] R 16 and R 17 Each is an alkyl group having 1 to 6 carbon atoms.

[0122] Q represents either an oxygen atom or a sulfur atom.

[0123] As a specific example of a compound (1) having a functional group at a single end of an organosilicon chain with a number average molecular weight in the range of 2,000 to 20,000, the compounds shown in the following formulas (A-1) to (A-5) can be cited.

[0124]

[0125] (In the aforementioned formulas (A-1) to (A-5), n is an integer, preferably an integer of 27 to 270.)

[0126] R is a divalent organic group or a single bond.

[0127] Compounds (1) with organosilicon chains having functional groups at a single end capable of generating free radicals in the range of number average molecular weight of 2,000 to 20,000 can be manufactured using known methods (e.g., Japanese Patent No. 6405647).

[0128] The polymeric monomer (2) used in the manufacturing method of the polymer of the present invention is the same as the polymeric monomer (2) described in the polymer of the present invention.

[0129] As for the feed ratio (mass) of compound (1) and polymerizable monomer (2) when manufacturing the polymer of the present invention, for example, it can be set such that the content of compound (1) in the total reactants is in the range of 5 to 95% by mass. For example, the mass ratio is compound (1): polymerizable monomer (2) = 5:95 to 95:5, preferably compound (1): polymerizable monomer (2) = 10:90 to 90:10, more preferably compound (1): polymerizable monomer (2) = 15:85 to 80:20, and even more preferably compound (1): polymerizable monomer (2) = 20:80 to 70:30.

[0130] In the aforementioned living radical polymerization, the dormant species at the active polymerization terminus, protected by atoms or groups of atoms, reversibly generates free radicals that react with monomers to carry out the growth reaction. Even if the first monomer is consumed, the growth terminus does not lose its activity and can react with a second monomer added sequentially to obtain a block polymer. Examples of such living radical polymerization include atom transfer radical polymerization (ATRP), reversible addition-fragmentation radical polymerization (RAFT), radical polymerization via nitroxide radicals (NMP), and radical polymerization using organotelluric acid (TERP). Any of these methods can be used without particular limitations, but ATRP is preferred from the perspective of ease of control. ATRP is carried out as follows: using an organohalide or sulfonyl halide as a polymerization initiator and a metal complex formed by a transition metal compound and a ligand as a catalyst for polymerization.

[0131] In the polymer manufacturing method of the present invention, compound (1) can function as a polymerization initiator, enabling polymerizable monomer (2) to undergo living radical polymerization with compound (1).

[0132] Transition metal compounds such as M that can be used in ATRP n+ X n As shown.

[0133] As M n+ X n The transition metal M of the transition metal compound shown n+ You can choose free Cu+, Cu 2+ Fe 2+ Fe 3+ Ru 2+ Ru 3+ Cr 2+ Cr 3+ Mo 0 Mo + Mo 2+ Mo 3+ W 2+ W 3+ ,Rh 3+ ,Rh 4+ Co + Co 2+ Re 2+ Re 3+ Ni 0 Ni + Mn 3+ Mn 4+ V 2+ V 3+ Zn + Zn 2+ Au + Au 2+ Ag + and Ag 2+ A group that is formed.

[0134] M n+ X n The X in the transition metal compound shown can be selected from halogen atoms, alkoxy groups with 1 to 6 carbon atoms, or (SO4). 1 / 2 (PO4) 1 / 3 (HPO4) 1 / 2 (H2PO4), trifluoromethanesulfonate, hexafluorophosphate, methanesulfonate, arylsulfonate (preferably benzenesulfonate or toluenesulfonate), SeR 11 CN and R 12 A group consisting of COO. Here, R... 11 R represents an aryl, linear, or branched alkyl group with 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms). 12 The alkyl group (preferably methyl) is a straight-chain or branched chain with 1 to 6 carbon atoms, which may be substituted 1 to 5 times with halogens (suitably substituted 1 to 3 times with fluorine or chlorine) to represent hydrogen atoms.

[0135] M n+ X nIn the transition metal compounds shown, n represents the formal charge on the metal, which is an integer from 0 to 7.

[0136] Examples of ligand compounds that can coordinate with the aforementioned transition metal compounds include: compounds having a transition metal and a ligand containing one or more nitrogen, oxygen, phosphorus, or sulfur atoms that can coordinate via a σ bond; compounds having a transition metal and a ligand containing two or more carbon atoms that can coordinate via a π bond; and compounds having a transition metal and a ligand that can coordinate via a μ bond or η bond.

[0137] There are no particular limitations on the transition metal complexes mentioned above. As preferred examples, transition metal complexes from groups 7, 8, 9, 10, and 11 can be cited. As further preferred examples, complexes of copper with a valence of 0, copper with a valence of 1, ruthenium with a valence of 2, iron with a valence of 2, or nickel with a valence of 2 can be cited.

[0138] Specific examples of catalysts that can be used in ATRP, when the central metal is copper, include complexes formed with ligands of polyamines such as 2,2'-bipyridine and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris(2-aminoethyl)amine, tris[2-(dimethylamino)ethyl]amine, and tris(2-pyridylmethyl)amine. Furthermore, examples of divalent ruthenium complexes include dichlorotris(triphenylphosphine)ruthenium, dichlorotris(tributylphosphine)ruthenium, dichloro(cyclooctadiene)ruthenium, dichlorobenzeneruthenium, dichloro-p-methylisopropylbenzeneruthenium, dichloro(norbornene)ruthenium, cis-dichlorobis(2,2'-bipyridine)ruthenium, dichlorotris(1,10-phenanthroline)ruthenium, and carbonylchlorohydrotris(triphenylphosphine)ruthenium. Examples of divalent iron complexes include bis(triphenylphosphine) complexes and triazacyclononane complexes.

[0139] Atom transfer radical polymerization (ATRP) is not limited to the methods described above and can also be carried out by other ATRP methods. For example, AGET ATRP, ARGET ATRP, ICAR ATRP, etc., described in "Macromol.Rapid.Commun.2018,1800616" can also be used.

[0140] In living radical polymerization, solvents are preferred.

[0141] Examples of solvents used in living radical polymerization include ester solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; ether solvents such as diisopropyl ether, dimethoxyethane, and diethylene glycol dimethyl ether; halogen solvents such as dichloromethane and dichloroethane; aromatic solvents such as toluene, xylene, and anisole; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohol solvents such as methanol, ethanol, and isopropanol; and aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide.

[0142] The solvents mentioned above can be used alone or in combination with two or more.

[0143] The preferred polymerization temperature for the aforementioned living free radical polymerization is in the range of room temperature to 120°C.

[0144] When the polymers of the present invention are manufactured by living radical polymerization, metals caused by transition metal compounds used in the polymerization sometimes remain in the resulting polymer. The metals remaining in the resulting polymer can be removed using activated alumina or the like after polymerization.

[0145] [Coating Composition]

[0146] The polymers of the present invention are suitable for use as leveling agents in coating compositions comprising the polymers of the present invention. The polymers of the present invention can form fluorine-free leveling agents, thus exhibiting low environmental impact and low accretion rate.

[0147] The content of the polymer of the present invention in the coating composition varies depending on the type of base resin, coating method, target film thickness, etc., and is preferably 0.0001 to 10 parts by weight, more preferably 0.001 to 5 parts by weight, and even more preferably 0.01 to 2 parts by weight, relative to 100 parts by weight of the solids in the coating composition. If the content of the polymer of the present invention is within this range, the surface tension can be sufficiently reduced, the target leveling property can be obtained, and the occurrence of defects such as bubbling during coating can be suppressed.

[0148] The application of the coating composition of the present invention is not particularly limited, and it can be used for any application requiring leveling properties. For example, the coating composition of the present invention can be used as various paint compositions and photosensitive resin compositions.

[0149] When the coating composition of the present invention is used to form a coating composition, examples of coating compositions that use natural resins include petroleum resin coatings, shellac coatings, rosin-based coatings, cellulose-based coatings, rubber-based coatings, lacquer coatings, cashew resin coatings, and oil-based excipient coatings; and coating compositions that use synthetic resins include phenolic resin coatings, alkyd resin coatings, unsaturated polyester resin coatings, amino resin coatings, epoxy resin coatings, vinyl resin coatings, acrylic resin coatings, polyurethane resin coatings, silicone resin coatings, and fluoropolymer coatings.

[0150] By adding the polymer of the present invention to the above-described coating composition, a smooth coating film can be obtained.

[0151] In the coating composition, pigments, dyes, carbon and other colorants can be appropriately added as needed; inorganic powders such as silica, titanium dioxide, zinc oxide, aluminum oxide, zirconium oxide, calcium oxide, and calcium carbonate; organic micro powders such as higher fatty acids, polyacrylic resins, and polyethylene; and various additives such as lightfastness improvers, weather resistance improvers, heat resistance improvers, antioxidants, thickeners, and anti-settling agents.

[0152] For the coating method of the coating composition of the present invention, any known and commonly used coating method can be used, such as slot coater, slot & spin coater, spin coater, roller coater, electrostatic coating, bar coater, gravure coater, die coater, doctor blade coater, inkjet, dip coating, spray coating, spray coating, screen printing, gravure printing, offset printing, reverse coating, etc.

[0153] The physical properties of photosensitive resin compositions change when exposed to light such as visible light or ultraviolet light, including solubility, viscosity, transparency, refractive index, conductivity, and ion permeability.

[0154] In photosensitive resin compositions, resist compositions (photoresist compositions, colored resist compositions for color filters, etc.) require high level of leveling. Resist compositions are typically spin-coated onto silicon wafers or glass substrates deposited with various metals to achieve a thickness of approximately 1–2 μm. At this point, fluctuations in film thickness or uneven coating can reduce the linearity and reproducibility of the pattern, resulting in resist patterns that do not achieve the desired precision. In addition to these problems, various leveling-related issues exist, such as droplet marks, overall unevenness, and beading phenomena where the film thickness at the edges is greater than at the center.

[0155] For the coating composition of the present invention, the polymer of the present invention can exhibit high leveling properties to form a uniform coating film (cured product), and therefore, when used as a corrosion-resistant composition, the above-mentioned problems can be solved.

[0156] When the coating composition of the present invention is used to form a photoresist composition, the photoresist composition contains, in addition to the polymer of the present invention, an alkali-soluble resin, a radiation-sensitive substance (photosensitive substance), a solvent, etc.

[0157] The alkali-soluble resin contained in the photoresist composition refers to a resin that is soluble in the developing solution used for patterning the resist, i.e., an alkaline solution.

[0158] Examples of alkali-soluble resins include phenolic varnish resins obtained by condensing aromatic hydroxyl compound derivatives such as phenol, cresol, xylenol, resorcinol, phloroglucinol, and hydroquinone with aldehyde compounds such as formaldehyde, acetaldehyde, and benzaldehyde; polymers or copolymers of vinylphenol compound derivatives such as o-vinylphenol, m-vinylphenol, p-vinylphenol, and α-methylvinylphenol; (meth)acrylic acid polymers or copolymers such as acrylic acid, methacrylic acid, and hydroxyethyl (meth)acrylate; polyvinyl alcohol; modified resins obtained by introducing radiative linearly sensitive groups such as quinone diazido, naphthoquinone azido, aromatic azido, and aromatic cinnamyl groups into part of the hydroxyl groups of these various resins; and polyurethane resins containing acidic groups such as carboxylic acid and sulfonic acid in their molecules.

[0159] These alkali-soluble resins can be used alone or in combination with two or more.

[0160] The radiation-sensitive substances contained in the photoresist composition refer to substances that alter the solubility of alkali-soluble resin in developer by irradiation with energy rays such as ultraviolet light, far ultraviolet light, excimer laser, X-rays, electron beams, ion beams, molecular beams, and gamma rays.

[0161] Examples of radiation-sensitive substances include quinone diazide compounds, diazo compounds, azide compounds, onium salt compounds, halogenated organic compounds, mixtures of halogenated organic compounds and organometallic compounds, organic acid ester compounds, organic acid amide compounds, organic acid imide compounds, and poly(olefin sulfone) compounds.

[0162] Examples of the aforementioned quinone diazide compounds include, for instance, 1,2-benzoquinone azido-4-sulfonate, 1,2-naphthoquinone diazido-4-sulfonate, 1,2-naphthoquinone diazido-5-sulfonate, 2,1-naphthoquinone diazido-4-sulfonate, 2,1-naphthoquinone diazido-5-sulfonate, and sulfonate chlorides of quinone diazide derivatives such as 1,2-benzoquinone azido-4-sulfonate chloride, 1,2-naphthoquinone diazido-4-sulfonate chloride, 1,2-naphthoquinone diazido-5-sulfonate chloride, 2,1-naphthoquinone diazido-4-sulfonate chloride, and 2,1-naphthoquinone diazido-5-sulfonate chloride.

[0163] Examples of the aforementioned diazo compounds include, for instance, salts of condensates of diazidophenylamine with formaldehyde or acetaldehyde, hexafluorophosphate, tetrafluoroborate, perchlorate or periodate reacting with the aforementioned condensates (i.e., diazo resin inorganic salts), and diazo resin organic salts reacting with sulfonic acids as described in USP3,300,309.

[0164] Examples of the aforementioned azide compounds include azidochalcone acids, diazidobenzylmethyl methylcyclohexanones, azidocinimide acetophenones, aromatic azide compounds, and aromatic diazido compounds.

[0165] Examples of the aforementioned halogenated organic compounds include halogenated oxadiazole compounds, halogenated triazine compounds, halogenated acetophenone compounds, halogenated benzophenone compounds, halogenated sulfoxide compounds, halogenated sulfone compounds, halogenated thiazole compounds, halogenated oxadiazole compounds, halogenated triazole compounds, halogenated 2-pyranone compounds, halogenated aliphatic hydrocarbon compounds, halogenated aromatic hydrocarbon compounds, halogenated heterocyclic compounds, and sulfuryl halide compounds.

[0166] In addition to the above, compounds such as tris(2,3-dibromopropyl) phosphate, tris(2,3-dibromo-3-chloropropyl) phosphate, tetrabromochloromethane, hexachlorobenzene, hexabromobenzene, hexabromocyclododecane, hexabromobiphenyl, tribromophenylallyl ether, tetrachlorobisphenol A, tetrabromobisphenol A, bis(bromoethyl ether)tetrabromobisphenol A, bis(chloroethyl ether)tetrachlorobisphenol A, tris(2,3-dibromopropyl)isocyanurate, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, and 2,2-bis(4-hydroxyethoxy-3,5-dibromophenyl)propane, which are used as halogenated flame retardants, and compounds such as dichlorophenyltrichloroethane, which are used as organochlorine pesticides, can also be used as halogenated organic compounds.

[0167] Examples of organic acid esters include carboxylic acid esters and sulfonate esters. Examples of organic acid amides include carboxylic acid amides and sulfonate amides. Furthermore, examples of organic acid imides include carboxylic acid imides and sulfonate imides.

[0168] Radiation-sensitive substances can be used alone or in combination with two or more.

[0169] In the photoresist composition, the content of the radiation-sensitive substance is preferably in the range of 10 to 200 parts by weight, and more preferably in the range of 50 to 150 parts by weight, relative to 100 parts by weight of the alkali-soluble resin.

[0170] Examples of solvents used in photoresist compositions include: ketones such as acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, 2-heptanone, methyl isobutyl ketone, and butyrolactone; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, pentanol, heptanol, octanol, nonanol, and decanol; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and dioxane; and ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monoethyl ether. Glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and other alcohol ethers; ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, propyl butyrate, ethyl lactate, butyl lactate and other esters; methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate. Monocarboxylic acid esters such as butyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, and butyl 2-methoxypropionate; cellosol esters such as methyl cellosol ester, ethyl cellosol ester, propyl cellosol ester, and butyl cellosol ester; and propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether acetate. Propylene glycols; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, etc.; trichloroethylene, Freon solvents, HCFC, HFC and other halogenated hydrocarbons; fully fluorinated solvents such as perfluorooctane, aromatic solvents such as toluene and xylene; polar solvents such as dimethylacetamide, dimethylformamide, N-methylacetamide, N-methylpyrrolidone, etc.

[0171] These solvents can be used alone or in combination of two or more.

[0172] When the coating composition of the present invention is used to form a colored resist composition, the colored resist composition contains, in addition to the polymer of the present invention, an alkali-soluble resin, a polymeric compound, a colorant, etc.

[0173] The alkali-soluble resin included in the color resist can be the same as the alkali-soluble resin included in the above-described photoresist composition.

[0174] The polymerizable compounds contained in the colored anti-corrosion composition refer to, for example, compounds with photopolymerizable functional groups that can undergo polymerization or cross-linking reactions when irradiated by active energy rays such as ultraviolet light.

[0175] Examples of such polymerizable compounds include: esters of unsaturated carboxylic acids such as (meth)acrylic acid, monohydroxy compounds and unsaturated carboxylic acids; esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; esters obtained by esterification reactions of unsaturated carboxylic acids with polycarboxylic acids and polyhydroxy compounds such as the aforementioned aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds; polymerizable compounds having a carbamate skeleton obtained by reacting a polyisocyanate compound with a hydroxy compound containing a (meth)acryloyl group; and polymerizable compounds having acid groups.

[0176] Polymers can be used alone or in combination with two or more compounds.

[0177] Examples of esters of the aforementioned aliphatic polyhydroxy compounds and unsaturated carboxylic acids include: ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerol (meth)acrylate, and other (meth)acrylates.

[0178] Additionally, examples include replacing the (meth)acrylic portion of these acrylates with itaconic acid esters, crotonic acid esters, or maleic acid esters.

[0179] Examples of esters of the aforementioned aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone di(meth)acrylate, resorcinol di(meth)acrylate, and pyrogallol tri(meth)acrylate.

[0180] Esters obtained through the esterification reaction of unsaturated carboxylic acids, polycarboxylic acids, and polyhydroxy compounds can be single substances or mixtures. Examples of such esters include: esters obtained from (meth)acrylic acid, phthalic acid, and ethylene glycol; esters obtained from (meth)acrylic acid, maleic acid, and diethylene glycol; esters obtained from (meth)acrylic acid, terephthalic acid, and pentaerythritol; and esters obtained from (meth)acrylic acid, adipic acid, butanediol, and glycerol.

[0181] Examples of polymeric compounds with a carbamate skeleton obtained by reacting polyisocyanate compounds with hydroxyl compounds containing (meth)acryloyl groups include: aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isoflurone diisocyanate; aromatic diisocyanates such as toluene diisocyanate and diphenylmethane diisocyanate; and reactants with hydroxyl compounds containing (meth)acryloyl groups such as 2-hydroxyethyl methacrylate and 3-hydroxy[1,1,1-tris(meth)acryloyloxymethyl]propane.

[0182] As for the aforementioned polymerizable compound having an acid group, such as an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, a polyfunctional polymerizable compound having an acid group by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl group of the aliphatic polyhydroxy compound is preferred. Pentaerythritol or dipentaerythritol is preferably the aliphatic polyhydroxy compound used in the preparation of this polyfunctional polymerizable compound.

[0183] From the perspective of improving developability and curability, the acid value of the aforementioned polyfunctional polymeric compound is preferably in the range of 0.1 to 40, more preferably in the range of 5 to 30. When using two or more polyfunctional polymeric compounds with acid groups, or when using a mixture of polyfunctional polymeric compounds with acid groups and polyfunctional polymeric compounds without acid groups, it is preferable to make the acid value of the mixture of polymeric compounds within the above-mentioned range.

[0184] As a specific example of the aforementioned polymeric compounds with acid groups, a mixture mainly composed of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinate of dipentaerythritol pentaacrylate can be cited. This mixture is commercially available as Aronix TO-1382 (manufactured by Toa Synthetic Co., Ltd.).

[0185] Examples of polymerizable compounds other than those mentioned above include methyl acrylamides such as ethylene bis(meth)acrylamide; allyl esters such as diallyl phthalate; and compounds containing vinyl groups such as divinyl phthalate.

[0186] In the colored anti-corrosion composition, the content of the polymeric compound is preferably in the range of 5 to 80% by mass of the total solid components of the colored anti-corrosion composition, more preferably in the range of 10 to 70% by mass, and even more preferably in the range of 20 to 50% by mass.

[0187] As a colorant for colored resist compositions, there are no particular limitations as long as it can color; for example, it can be a pigment or a dye.

[0188] Pigments can be either organic or inorganic. As organic pigments, various shades such as red, green, blue, yellow, purple, orange, and brown can be used. Examples of organic pigment chemical structures include azo, phthalocyanine, quinacridone, benzimidazolone, isoindolone, dioxazine, indanone, and perylene compounds. Examples of inorganic pigments include barium sulfate, lead sulfate, titanium dioxide, yellow lead, ferric oxide, and chromium oxide.

[0189] It should be noted that "CI" in the following text refers to the Color Index.

[0190] Examples of red pigments mentioned above include CI pigments 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, and 53. :3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147,1 49, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232 The following pigments are preferred: 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, etc. Among these, CI Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, or 254 are preferred, and CI Pigment Red 177, 209, 224, or 254 are more preferred.

[0191] Examples of the aforementioned green pigments include CI pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, and 58. Among these, CI pigment green 7, 36, or 58 are preferred.

[0192] Examples of the aforementioned blue pigments include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79. Among these, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6 are preferred, and CI Pigment Blue 15:6 is more preferred.

[0193] Examples of yellow pigments mentioned above include CI pigment yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133. 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, etc. Among these, CI pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 or 185 are preferred, and CI pigment yellow 83, 138, 139, 150 or 180 are more preferred.

[0194] Examples of the aforementioned purple pigments include CI pigment violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among these, CI pigment violet 19 or 23 is preferred, and CI pigment violet 23 is more preferred.

[0195] Examples of the aforementioned orange pigments include CI Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, and 79. Among these, CI Pigment Orange 38 or 71 is preferred.

[0196] The pixels of the color filters used in liquid crystal display devices and organic EL display devices are red (R), green (G), and blue (B). Therefore, with the aforementioned red, green, and blue pigments as the main components, organic pigments of colors such as yellow, purple, and orange can also be used for hue adjustment in order to improve color reproduction.

[0197] To improve the brightness of color liquid crystal display devices and organic EL display devices, the average particle size of the aforementioned organic pigments is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.3 μm or less. It is preferable to use the organic pigments by dispersing them in a manner that achieves these average particle sizes.

[0198] The average primary particle size of the aforementioned organic pigment is preferably less than 100 nm, more preferably less than 50 nm, even more preferably less than 40 nm, and particularly preferably in the range of 10 to 30 nm.

[0199] It should be noted that the average particle size of organic pigments is measured using a dynamic light scattering particle size analyzer, such as the Nanotrac particle size analyzer "UPA-EX150" or "UPA-EX250" manufactured by Nikkiso Corporation.

[0200] As a colorant used in the formation of a black matrix (BM) when a colored resist composition is used, there are no particular limitations as long as it is black, and examples include carbon black, lamp black, acetylene black, bone black, thermal cracking carbon black, channel black, furnace black, lead black, iron black, titanium black, etc. Among these, carbon black and titanium black are preferred from the viewpoint of light blocking rate and image characteristics.

[0201] Alternatively, two or more organic pigments can be mixed to form a black color combination.

[0202] Commercially available carbon black products, such as those manufactured by Mitsubishi Chemical Corporation, include MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #950, and # 960, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600, #3050, #3150, #3250, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B, etc., Evonik can be cited as an example. Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex made by Degussa Japan Co., Ltd. V, PrintexG, SpecialBlack550, SpecialBlack 350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, ColoRBlack FW18, ColoRBlackFW18, ColoRBlack FW200, Color Black S160, ColoRBlack Examples of S170 include Cabot Japan Co., Ltd.Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch14 00, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN XC72R, ELFTEX-8, etc., Colombian Carbon can be cited Company-made RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVE N1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000, etc. .

[0203] Among the aforementioned carbon blacks, those with high optical concentration and high surface resistivity, which are required for the black matrix of color filters, are preferably carbon blacks coated with resin.

[0204] Commercially available titanium black products, such as those manufactured by Mitsubishi Materials Corporation, include titanium black 10S, 12S, 13R, 13M, and 13M-C.

[0205] As a colorant used in the formation of black matrix (BM), it is possible to mix two or more organic pigments to form black through color mixing. Examples of black pigments include those that are a mixture of red, green and blue pigments.

[0206] Examples of pigments that can be mixed for the preparation of black pigments include Victoria Brilliant Blue (CI42595), Auramine O (CI41000), Cachiron Brilliant Flavin (BASIC 13), Rhodamine 6GCP (CI45160), Rhodamine B (CI45170), Safflower OK70:100 (CI50240), Erio Grausin X (CI42080), No.120 / Lionol Yellow (CI21090), Lionol Yellow GRO (CI21090), Shimla First Yellow 8GF (CI21105), Benzidine Yellow 4T-564D (CI21095), Shimla First Red 4015 (CI12355), Lionor Red 7B4401 (CI15850), First Gen Blue TGR-L (CI74160), and Lionol Blue. SM (CI26150), Lionol Blue ES (CI Pigment Blue 15:6), Rio Nogen Red GD (CI Pigment Red 168), Lionol Green 2YS (CI Pigment Green 36), etc.

[0207] Other pigments that can be mixed for the preparation of black pigments include, for example, CI yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166; CI orange pigments 36, 43, 51, 55, 59, 61; CI red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240; CI purple pigments 19, 23, 29, 30, 37, 40, 50; CI blue pigments 15, 15:1, 15:4, 22, 60, 64; CI green pigment 7; and CI brown pigments 23, 25, 26.

[0208] When carbon black is used as a black pigment, the average primary particle size of the carbon black is preferably in the range of 0.01 to 0.08 μm, and more preferably in the range of 0.02 to 0.05 μm from the perspective of improving developability.

[0209] The particle shape of carbon black differs from that of organic pigments. Primary particles exist in a state known as a structure, formed by the fusion of particles with each other, and micropores are sometimes formed on the particle surface through post-processing. Therefore, in order to represent the particle shape of carbon black, in addition to the average particle size of the primary particles determined by the same method as for organic pigments, it is preferable to measure the DBP absorbance (JIS K6221) and the specific surface area based on the BET method (JIS K6217) as indicators of structure and porosity.

[0210] The preferred absorbance of carbon black for dibutyl phthalate (hereinafter referred to as "DBP") is 40–100 cm⁻¹. 3 Within the range of / 100g, from the perspective of good dispersibility / developability, 50-80cm is more preferable. 3 The specific surface area of ​​carbon black based on the BET method is preferably 50–120 m² / 100g. 2 From the perspective of good dispersion stability, a range of 60–95 mg / g is preferred. 2 The range of / g.

[0211] Examples of dyes used as colorants in colored resist compositions include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methyst dyes.

[0212] Examples of the aforementioned azo dyes include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI BASIC Blue 41, CI BASIC Red 18, CI Mordant Red 7, CI Mordant Yellow 5, and CI Mordant Black 7.

[0213] Examples of the aforementioned anthraquinone dyes include CI Variant Blue 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue 56, and CI Disperse Blue 60.

[0214] Examples of phthalocyanine dyes include CI Vat Blue 5; examples of quinone imine dyes include CI BASIC Blue 3 and CI BASIC Blue 9; examples of quinoline dyes include CI Solvent Yellow 33, CI Acid Yellow 3, and CI Disperse Yellow 64; and examples of nitro dyes include CI Acid Yellow 1, CI Acid Orange 3, and CI Disperse Yellow 42.

[0215] In terms of the excellent lightfastness, weather resistance and fastness of the obtained coating, the colorant of the colored resist composition is preferably a pigment. In order to adjust the hue, the pigment may also be used in combination with a dye as needed.

[0216] In the colored resist composition, the content of the colorant is preferably more than 1% by mass of all solid components of the colored resist composition, more preferably in the range of 5% to 80% by mass, and even more preferably in the range of 5% to 70% by mass.

[0217] When the color resist composition is used to form each pixel of the red (R), green (G), and blue (B) of a color filter, the content of the colorant in the color resist composition is preferably in the range of 5 to 60% by mass of the total solid components of the color resist composition, and more preferably in the range of 10 to 50% by mass.

[0218] When the colored resist composition is used to form the black matrix of a color filter, the content of the colorant in the colored resist composition is preferably in the range of 20 to 80% by mass of the total solid components of the colored resist composition, more preferably in the range of 30 to 70% by mass.

[0219] In colored resist compositions, when the colorant is a pigment, it is preferable to use it in the form of a pigment dispersion prepared by dispersing the pigment in an organic solvent using a dispersant.

[0220] Examples of dispersants include surfactants; pigment intermediates or derivatives; dye intermediates or derivatives; and resin-type dispersants such as polyamide resins, polyurethane resins, polyester resins, and acrylic resins. Among these, graft copolymers containing nitrogen atoms, acrylic block copolymers containing nitrogen atoms, and polyurethane resin dispersants are preferred. These dispersants contain nitrogen atoms, which have an affinity for the pigment surface. By increasing the affinity of the portion other than the nitrogen atom for the medium, the dispersion stability is improved.

[0221] These dispersants can be used alone or in combination of two or more.

[0222] Commercially available dispersants as mentioned above include BASF's "Efka" series ("Efka 46", etc.); BYK Japan's "Disperbyk" series and "BYK" series ("BYK-160", "BYK-161", "BYK-2001", etc.); Japan Lubrizol Co., Ltd.'s "Solsperse" series; Shin-Etsu Chemical Industry Co., Ltd.'s "KP" series; Kyoeisha Chemical Co., Ltd.'s "Polyflow" series; Kusunoki Chemical Co., Ltd.'s "DISPARLON" series; and Ajinomoto Fine Techno Co., Ltd.'s "Ajisper" series ("Ajisper PB-814", etc.).

[0223] Organic solvents used in the preparation of the aforementioned pigment dispersions include, for example, acetate solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; propionate solvents such as ethoxypropionate; aromatic solvents such as toluene, xylene, and methoxybenzene; ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, and diethylene glycol dimethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aliphatic hydrocarbon solvents such as hexane; nitrogen compound solvents such as N,N-dimethylformamide, γ-butyrolactam, and N-methyl-2-pyrrolidone; lactone solvents such as γ-butyrolactone; and carbamates.

[0224] These solvents can be used alone or in combination of two or more.

[0225] Examples of methods for preparing the aforementioned pigment dispersion include: methods involving a mixing and dispersion step and a micro-dispersion step, and methods involving only a micro-dispersion step. In the aforementioned mixing and dispersion step, the colorant, a portion of the alkali-soluble resin, and the aforementioned dispersant as needed are mixed and kneaded. Dispersion is performed using a mixer while applying strong shear force, thereby dispersing the colorant.

[0226] Examples of machinery used in mixing include two-roll mills, three-roll mills, ball mills, dispersers, kneaders, co-kneaders, homogenizers, mixers, single-screw or twin-screw extruders, etc.

[0227] The colorant is preferably finely ground in advance by means of salt milling or other methods before the above-mentioned mixing.

[0228] In the aforementioned micro-dispersion process, a solvent is added to the composition containing the colorant obtained in the aforementioned mixing and dispersing process, or a mixture of colorant, alkali-soluble resin, solvent and the aforementioned dispersant as needed, and a dispersion medium for dispersing glass, zirconium oxide, or ceramic particles is mixed and dispersed together using a disperser, thereby dispersing the colorant particles until they are close to the size of primary particles.

[0229] From the viewpoint of improving the transmittance and contrast of the color filter, the average particle size of the primary particles of the colorant is preferably 10-100 nm, more preferably 10-60 nm. It should be noted that the average particle size of the colorant is measured using a dynamic light scattering particle size analyzer, such as the Nanotrac particle size analyzer "UPA-EX150" or "UPA-EX250" manufactured by Nikkiso Corporation.

[0230] The above examples illustrate coating compositions, photoresist compositions, and colored resist compositions as coating compositions, but are not limited to these.

[0231] Specific examples of applications of the coating composition of the present invention include: coating materials for various display screens such as liquid crystal displays (hereinafter referred to as "LCD"), plasma displays (hereinafter referred to as "PDP"), organic EL displays (hereinafter referred to as "OLED"), and quantum dot displays (hereinafter referred to as "QDD"), namely anti-glare (AG) hard coating materials, anti-reflective (LR) coating materials, low refractive index layer coating materials, high refractive index layer coating materials, transparent hard coating materials, and polymeric liquid crystal coating materials; color resists, inkjet inks, printing inks, or coatings used to form each pixel of color filters (hereinafter referred to as "CF") such as LCDs; and black matrices used to form CFs such as LCDs. Black photoresist, inkjet ink, printing ink, or coating for black column spacers and black optical spacers; coatings for transparent protective films used in the CF (cell) of LCDs, etc., to protect the surface of the CF; resin compositions for liquid crystal materials, column spacers, and optical spacers in LCDs; resin compositions for pixel separators in LCDs, PDPs, OLEDs, QDDs, etc.; positive photoresist for electrode formation; protective films; insulating films; plastic housings; coatings for plastic housings; baffle (frame) inks; backlight components of LCDs, i.e., prism sheets; light diffusion films; coatings for organic insulating films of liquid crystal TFT arrays in LCDs; protective coating materials for the surface of internal polarizers in LCDs; phosphors for PDPs; organic EL materials and sealing materials (protective films, gas barrier materials) for OLEDs; QDDs Quantum dot inks, sealing materials, and protective films; high-refractive-index prisms, low-refractive-index seals, and LED pixels for mini LED displays; positive photoresists, chemically amplified photoresists, anti-reflective films, multilayer materials (SOC, SOG), lower films, buffer coatings, developers, rinsing solutions, anti-pattern tilting agents, polymer residue removal solutions, cleaning agents, and other chemical solutions used in semiconductor manufacturing; nanoimprint release agents; resin compositions (epoxy resins, phenolic resins, polyphenylene ether resins, liquid crystal polymers, polyimide resins, bismaleimide resins, dielyl nadicimide resins, benzoxazine resins, etc.) used in semiconductor back-end processes or printed circuit boards, copper-clad laminates, resin-coated copper foils, and laminates. Thin films, passivation films, interlayer insulating films, flexible copper-clad laminates, dry film resists; color resists for image sensors; liquid repellents for solder fluxes; dispersants, coatings, and green films for multilayer ceramic capacitors; positive electrode materials, negative electrode materials, separators, and electrolytes for lithium-ion batteries; exterior coatings, rubber, elastomers, glass, vapor-deposited anchor coatings, headlight prisms, solid lubricant coatings, heat-dissipating substrates, interior coatings, and repair coatings for automobiles; wallpaper, flooring materials, kitchen components, and bathroom / toilet components for residential equipment; inkjet inks, offset printing inks, gravure printing inks, screen printing inks, photoresists for printing plate manufacturing processes, photosensitive materials for offset printing plates (PS plates), encapsulation adhesives, and ballpoint pen inks;Primers for easy adhesion of plastic films, etc.; water-repellent agents for fibers; non-diffusing agents for lubricating greases; cleaning fluids for cleaning the surfaces of various products or parts; hard coating materials for optical storage media such as CDs, DVDs, and Blu-ray discs; coatings or hard coating materials for the casings or screens of smartphones or mobile phones; hard coating materials for transfer films used in embedded molding (IMD, IMF); release films; coatings or coating materials for various plastic molded products such as the casings of household appliances; printing inks or coatings for various building materials such as decorative panels; coating materials for window glass in residences; woodworking coatings for furniture, etc.; artificial / synthetic coatings. Coating materials for leather; coating materials for rubber rollers in OA equipment such as copiers and printers; coating materials for glass in the reading parts of OA equipment such as copiers and scanners; coating materials for optical prisms or other optical components such as cameras, video cameras, eyeglasses, and contact lenses; coating materials for windshields and other glass components of watches and other clocks; coating materials for windows of various vehicles such as automobiles and railway vehicles; anti-reflective coatings for protective glass or films used in solar cells; coatings or coating materials for FRP baths; PCM for metal building materials or household appliances; single-layer or multi-layer coating compositions for photolithography processes, etc.

[0232] The polymer of the present invention possesses excellent surface tension reduction capabilities; therefore, it can be expected to provide not only leveling properties, but also various functions such as wetting, penetration, washability, water repellency, oil repellency, stain resistance, lubrication, anti-blocking, and mold release. Furthermore, when the polymer of the present invention is formulated into coatings or coating agents containing microparticles, it improves the dispersibility of the microparticles, thus providing not only leveling properties but also the function of acting as a dispersant for the microparticles. In addition, the polymer of the present invention can be added to adhesive compositions used in adhesive tapes and the like, in addition to the coating compositions described above, thereby providing not only leveling properties but also functions such as reduced peel force, suppression of peel force variation, and suppression of peel charge.

[0233] Example

[0234] The present invention will now be described in detail with reference to embodiments and comparative examples.

[0235] It should be noted that the present invention is not limited to the following embodiments.

[0236] In the examples and comparative examples, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) were values ​​obtained by gel permeation chromatography (GPC) and conversion to polystyrene.

[0237] The determination conditions for GPC are shown below.

[0238] [GPC Measurement Conditions]

[0239] Measurement apparatus: Tosoh Corporation's high-speed GPC device "HLC-8420GPC"

[0240] Pillars: "TSK GUARDCOLUMN SuperHZ-L" manufactured by Tosoh Corporation + "TSK gelSuperHZM-N" manufactured by Tosoh Corporation + "TSK gel SuperHZM-N" manufactured by Tosoh Corporation + "TSK gel SuperHZM-N" manufactured by Tosoh Corporation + "TSK gel SuperHZM-N" manufactured by Tosoh Corporation

[0241] Detector: RI (Differential Refractometer)

[0242] Data processing: Tosoh Corporation's "EcoSEC Data Analysis version 1.07"

[0243] Column temperature: 40℃

[0244] Developing solvent: Tetrahydrofuran

[0245] Flow rate: 0.35 mL / min

[0246] Test sample: Dissolve 7.5 mg of the sample in 10 ml of tetrahydrofuran, filter the resulting solution through a microfilter, and use the resulting substance as the test sample.

[0247] Sample injection volume: 20 μl

[0248] Standard sample: According to the aforementioned "HLC-8420GPC" test manual, use the following monodisperse polystyrene with a known molecular weight.

[0249] (Monodisperse polystyrene)

[0250] The "A-300" manufactured by Tosoh Corporation

[0251] The "A-500" manufactured by Tosoh Corporation

[0252] The "A-1000" manufactured by Tosoh Corporation

[0253] The "A-2500" manufactured by Tosoh Corporation

[0254] The "A-5000" manufactured by Tosoh Corporation

[0255] The F-1 fighter jet manufactured by Tosoh Corporation.

[0256] The F-2 fighter jet manufactured by Tosoh Corporation.

[0257] The F-4 manufactured by Tosoh Corporation

[0258] The F-10 manufactured by Tosoh Corporation

[0259] The F-20 manufactured by Tosoh Corporation

[0260] The F-40 manufactured by Tosoh Corporation

[0261] The F-80 manufactured by Tosoh Corporation

[0262] The F-128 manufactured by Tosoh Corporation

[0263] The F-288 manufactured by Tosoh Corporation

[0264] (Example 1: Synthesis of a polymer (1) having organosilicon chains at a single end of the polymer backbone)

[0265] In a glass flask equipped with a stirrer, thermometer, condenser, and dropper, 136.76 g of n-heptane as a solvent, 300.00 g of an organosilicon compound with a single terminal hydroxyl group as shown in formula (a-1) below, and 10.48 g of triethylamine as a catalyst are added. The mixture is stirred for 30 minutes while maintaining the temperature inside the flask at 5°C.

[0266]

[0267] (In the formula, n1 has an average value of 65.)

[0268] The molecular weight (Mn) of the organosilicon chain is 5,000.

[0269] Add 19.10 g of 2-bromoisobutyric acid bromide to the above mixture and stir for 3 hours at room temperature. Then, mix 341.89 g of n-heptane and 600 g of 0.36% hydrochloric acid, stir, and allow to stand to separate and remove the hydrochloric acid layer. Next, mix 600 g of saturated sodium bicarbonate aqueous solution, stir, and allow to stand to separate and remove the saturated sodium bicarbonate aqueous solution layer. Further mix 600 g of ion-exchanged water, stir, and allow to stand to separate and remove the ion-exchanged water layer.

[0270] Next, 8 g of magnesium sulfate as a dehydrating agent was added, and the mixture was shaken and dehydrated, then the dehydrating agent was filtered off. Subsequently, the solvent was distilled off under reduced pressure, and the resulting residue was dissolved in 313.31 g of isopropyl ether. 300 g of 0.36% hydrochloric acid was mixed and stirred, then allowed to stand to separate and remove the hydrochloric acid layer. Next, 300 g of 1% sodium hydroxide aqueous solution was mixed and stirred, then allowed to stand to separate and remove the 1% sodium hydroxide aqueous solution layer. Further, 300 g of ion-exchanged water was mixed and stirred, then allowed to stand to separate and remove the ion-exchanged water layer. Next, 8 g of magnesium sulfate as a dehydrating agent was added, and the mixture was shaken and dehydrated, then the dehydrating agent was filtered off. Subsequently, the solvent was distilled off under reduced pressure, thereby obtaining the compound shown in formula (A-4).

[0271]

[0272] 37.8 g of poly(1,2-butanediol) mono(meth)acrylate (1,2-butanediol has an average repeatability of 6) and 79.0 g of methyl ethyl ketone (MEK) as a solvent were added to a nitrogen-purged flask, and the mixture was heated to 50°C while stirring under a nitrogen stream. Next, 4.2 g of 2,2'-bipyridine and 1.5 g of cuprous chloride were added as catalysts, and the mixture was stirred for 30 minutes while maintaining the temperature at 50°C. Subsequently, 12.3 g of the compound shown in formula (A-4) was added as a polymerization initiator, and the mixture was subjected to living polymerization at 50°C for 8 hours under a nitrogen stream.

[0273] 30 g of activated alumina was added to the resulting reactants and stirred. After filtering the activated alumina, the solvent was removed by vacuum distillation to obtain a polymer (1) with organosilicon chains at a single end of the polymer backbone.

[0274] The molecular weight of the obtained polymer (1) was determined by GPC, and the weight-average molecular weight (Mw) was 25,000, the number-average molecular weight (Mn) was 23,000, and the (Mw / Mn) ratio was 1.1.

[0275] In addition, the ratio of organosilicon chains in polymer (1) is 24% by mass.

[0276] (Example 2: Synthesis of a polymer (2) having organosilicon chains at a single end of the polymer backbone)

[0277] 32.8 g of polypropylene glycol monomethacrylate (propylene glycol has an average repetition count of 4–6) and 79.0 g of methyl ethyl ketone (MEK) as a solvent were added to a nitrogen-purged flask, and the mixture was heated to 50 °C while stirring under a nitrogen stream. Next, 4.2 g of 2,2'-bipyridine and 1.5 g of cuprous chloride were added as catalysts, and the mixture was stirred for 30 minutes while maintaining the temperature at 50 °C. Subsequently, 17.2 g of the compound shown in formula (A-4) was added as a polymerization initiator, and the mixture was subjected to living polymerization at 50 °C for 8 hours under a nitrogen stream.

[0278] 30 g of activated alumina was added to the resulting reactants and stirred. After filtering the activated alumina, the solvent was removed by vacuum distillation to obtain a polymer (2) with organosilicon chains at a single end of the polymer backbone.

[0279] The molecular weight of the obtained polymer (2) was determined by GPC. The weight-average molecular weight (Mw) was 16,000, the number-average molecular weight (Mn) was 14,000, and the (Mw / Mn) ratio was 1.1.

[0280] In addition, the ratio of organosilicon chains in polymer (2) is 32% by mass.

[0281] (Example 3: Synthesis of a polymer (3) with an organosilicon chain at a single end)

[0282] 32.8 g of poly(1,2-butanediol) mono(meth)acrylate (1,2-butanediol has an average repeatability of 6) and 79.0 g of methyl ethyl ketone (MEK) as a solvent were added to a nitrogen-purged flask, and the mixture was heated to 50°C while stirring under a nitrogen atmosphere. Next, 4.2 g of 2,2'-bipyridine and 1.5 g of cuprous chloride were added as catalysts, and the mixture was stirred for 30 minutes while maintaining the temperature at 50°C. Subsequently, 17.2 g of the compound shown in formula (A-4) was added as a polymerization initiator, and the mixture was subjected to living polymerization at 50°C for 8 hours under a nitrogen atmosphere.

[0283] Add 30g of activated alumina to the resulting reactants and stir. After filtering the activated alumina, remove the solvent by vacuum distillation to obtain a polymer (3) with organosilicon chains at a single end of the polymer backbone.

[0284] The molecular weight of the obtained polymer (3) was determined by GPC. The weight-average molecular weight (Mw) was 16,000, the number-average molecular weight (Mn) was 13,000, and the (Mw / Mn) ratio was 1.2.

[0285] In addition, the ratio of organosilicon chains in polymer (3) is 32% by mass.

[0286] (Example 4: Synthesis of a polymer (4) with an organosilicon chain at a single end)

[0287] 19.1 g of poly(1,2-butanediol) mono(meth)acrylate (1,2-butanediol has an average repeatability of 6) and 79.0 g of methyl ethyl ketone (MEK) as a solvent were added to a nitrogen-purged flask, and the mixture was heated to 50°C while stirring under a nitrogen atmosphere. Next, 4.2 g of 2,2'-bipyridine and 1.5 g of cuprous chloride were added as catalysts, and the mixture was stirred for 30 minutes while maintaining the temperature at 50°C. Subsequently, 31.0 g of the compound shown in formula (A-4) above was added as a polymerization initiator, and the mixture was subjected to living polymerization at 50°C for 8 hours under a nitrogen atmosphere.

[0288] Add 30g of activated alumina to the resulting reactants and stir. After filtering the activated alumina, remove the solvent by vacuum distillation to obtain a polymer (4) with organosilicon chains at a single end of the polymer backbone.

[0289] The molecular weight of the obtained polymer (4) was determined by GPC. The weight-average molecular weight (Mw) was 11,000, the number-average molecular weight (Mn) was 10,000, and the (Mw / Mn) ratio was 1.1.

[0290] In addition, the ratio of organosilicon chains in polymer (4) is 58% by mass.

[0291] (Example 5: Synthesis of a polymer (5) with an organosilicon chain at a single end)

[0292] In a glass flask equipped with a stirrer, thermometer, condenser, and dropper, 136.76 g of n-heptane as a solvent, 300.00 g of an organosilicon compound with a single hydroxyl group at a single end as shown in formula (a-2) below, and 10.48 g of triethylamine as a catalyst are added. The mixture is stirred for 30 minutes while maintaining the temperature inside the flask at 5°C.

[0293]

[0294] (In the formula, n2 averages 132.)

[0295] The molecular weight (Mn) of the organosilicon chain is 10,000.

[0296] Add 19.10 g of 2-bromoisobutyric acid bromide to the above mixture and stir for 3 hours at room temperature. Then, mix 341.89 g of n-heptane and 600 g of 0.36% hydrochloric acid, stir, and allow to stand to separate and remove the hydrochloric acid layer. Next, mix 600 g of saturated sodium bicarbonate aqueous solution, stir, and allow to stand to separate and remove the saturated sodium bicarbonate aqueous solution layer. Further mix 600 g of ion-exchanged water, stir, and allow to stand to separate and remove the ion-exchanged water layer.

[0297] Next, 8 g of magnesium sulfate as a dehydrating agent was added, and the mixture was shaken and dehydrated, then the dehydrating agent was filtered off. Subsequently, the solvent was distilled off under reduced pressure, and the resulting residue was dissolved in 313.31 g of isopropyl ether. 300 g of 0.36% hydrochloric acid was mixed and stirred, then allowed to stand to separate and remove the hydrochloric acid layer. Next, 300 g of 1% sodium hydroxide aqueous solution was mixed and stirred, then allowed to stand to separate and remove the 1% sodium hydroxide aqueous solution layer. Further, 300 g of ion-exchanged water was mixed and stirred, then allowed to stand to separate and remove the ion-exchanged water layer. Next, 8 g of magnesium sulfate as a dehydrating agent was added, and the mixture was shaken and dehydrated, then the dehydrating agent was filtered off. Subsequently, the solvent was distilled off under reduced pressure, thereby obtaining the compound shown in formula (A-5).

[0298]

[0299] 21.7 g of poly(1,2-butanediol) mono(meth)acrylate (1,2-butanediol has an average repeatability of 6) and 61.5 g of methyl ethyl ketone (MEK) as a solvent were added to a nitrogen-purged flask. The mixture was stirred under a nitrogen atmosphere while the temperature was raised to 60°C. Next, 0.62 g of 2,2'-bipyridine and 0.2 g of cuprous chloride were added as catalysts, and the mixture was stirred for 30 minutes while maintaining the temperature at 60°C. Subsequently, 20.0 g of the compound shown in formula (A-5) was added as a polymerization initiator, and the mixture was subjected to living polymerization at 60°C under a nitrogen atmosphere for 18 hours.

[0300] Add 30 g of activated alumina to the resulting reactants and stir. After filtering the activated alumina, remove the solvent by vacuum distillation to obtain a polymer (5) with organosilicon chains at a single end of the polymer backbone.

[0301] The molecular weight of the obtained polymer (5) was determined by GPC. The weight-average molecular weight (Mw) was 22,000, the number-average molecular weight (Mn) was 20,000, and the (Mw / Mn) ratio was 1.1.

[0302] In addition, the ratio of organosilicon chains in polymer (5) is 47% by mass.

[0303] (Comparative Example 1: Synthesis of free radical copolymer (1') using organosilicon monomers)

[0304] 200.0 g of butyl acetate as a solvent was added to a nitrogen-purged flask, and the mixture was heated to 90 °C while stirring under a nitrogen stream. Next, a monomer polymerization initiator solution, prepared by dissolving 63.2 g of a polymerizable unsaturated monomer with organosilicon chains (as shown in formula (A'), 136.8 g of poly(1,2-butanediol) mono(meth)acrylate (1,2-butanediol has an average repeat number of 6), and 3.0 g of tert-butyl peroxide-2-ethylhexanoate as a polymerization initiator in 266.0 g of butyl acetate, was placed in a dropping apparatus. The mixture was added dropwise over 2 hours while maintaining the flask at 90 °C. After the addition was complete, the mixture was reacted at 90 °C for 6 hours under a nitrogen stream to obtain a random copolymer (1').

[0305] Random copolymers (1') are polymers having multiple organosilicon chains in their polymer chains.

[0306]

[0307] (In the formula, the number of n3 is 65.)

[0308] The molecular weight (Mn) of the organosilicon chain is 5,000.

[0309] The molecular weight of the obtained random copolymer (1') was determined by GPC, and the weight-average molecular weight (Mw) was 14,000, the number-average molecular weight (Mn) was 1,700, and the (Mw / Mn) ratio was 7.8.

[0310] In addition, the ratio of organosilicon chains in the random copolymer (1') is 31% by mass.

[0311] (Comparative Example 2: Synthesis of free radical copolymer (2') using organosilicon monomers)

[0312] 200.0 g of butyl acetate as a solvent was added to a nitrogen-purged flask, and the mixture was heated to 90°C while stirring under a nitrogen stream. Next, a monomer polymerization initiator solution obtained by dissolving 63.2 g of the polymerizable unsaturated monomer with organosilicon chains shown in formula (A'), 136.8 g of poly(1,2-butanediol) mono(meth)acrylate (1,2-butanediol has an average repeat number of 6), and 3.0 g of tert-butyl peroxide-2-ethylhexanoate as a polymerization initiator in 100.0 g of butyl acetate was placed in a dropping apparatus, and the mixture was added dropwise over 2 hours while maintaining the flask at 90°C. After the addition was complete, the mixture was reacted at 90°C for 6 hours under a nitrogen stream to obtain a random copolymer (2').

[0313] The molecular weight of the obtained random copolymer (2') was determined by GPC. The weight-average molecular weight (Mw) was 34,000, the number-average molecular weight (Mn) was 3,400, and the (Mw / Mn) ratio was 9.9.

[0314] In addition, the ratio of organosilicon chains in the random copolymer (2') is 31% by mass.

[0315] The following evaluation was performed using the polymer (1) manufactured in Example 1. The results are shown in Table 1.

[0316] In Table 1, "Si chain" refers to "organosilicon chain".

[0317] (Film formation and evaluation of coatings)

[0318] An anti-corrosion composition was prepared by mixing 3.0 g of alkali-soluble resin solution (ACRYDIC ZL-295, manufactured by DIC Corporation) of 40% by mass, 1.2 g of ARONIXM-402 (manufactured by Dong-A Synthetic Chemical Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), 0.001 g of polymer (1) on a solids basis, and 3.8 g of propylene glycol monomethyl ether acetate (PGMEA).

[0319] 3 ml of the obtained anti-corrosion composition was dropped onto the central part of a 10 cm × 10 cm chrome-plated glass substrate. After spin coating at a speed of 1,000 rpm for 10 seconds, the substrate was heated and dried at 100 °C for 100 seconds to produce a laminate with a coating layer.

[0320] The smoothness and coating defects of the fabricated laminate were evaluated using the following methods. The results are shown in Table 1.

[0321] (Smoothness)

[0322] The coating layer of the resulting laminate is visually inspected, and the smoothness of the coating layer is evaluated according to the following criteria.

[0323] AA: No uneven coating was observed.

[0324] A: Almost no coating unevenness was observed.

[0325] C: Overall, uneven coating was observed.

[0326] (Coating defects)

[0327] The coating layers of the resulting laminate are visually inspected, and coating defects are evaluated according to the following criteria.

[0328] A: Almost no coating defects were observed.

[0329] B: Several coating defects were observed.

[0330] C: Multiple coating defects were observed.

[0331] Polymers prepared in Examples 2-5 and Comparative Examples 1-2 were used instead of polymer (1), and the same evaluation as in Example 1 was performed. The results are shown in Table 1.

[0332] [Table 1]

[0333]

[0334] As shown in Table 1, when polymers (polymers (1) to (5)) having only silicone chains at the ends are used as leveling agents, excellent smoothness is achieved while almost no coating defects are generated. On the other hand, it can be seen that the polymers (random copolymers (1') and (2')) of Comparative Examples 1 and 2, which have multiple silicone chains, still generate multiple coating defects, even though the content of silicone chains is almost the same as that of polymer (1) in Example 1.

Claims

1. A coating composition comprising a polymer containing organosilicon chains, The polymer containing organosilicon chains is a polymer that has organosilicon chains only at a single end and does not contain polymerizable unsaturated groups. The polymer containing organosilicon chains uses the polymerizable monomer (2) of the compound shown in formula (2-2) as the polymerization component. The number-average molecular weight of the organosilicon chain is in the range of 2,000 to 20,000. The content of the polymer containing organosilicon chains is 0.0001 to 10 parts by weight relative to 100 parts by weight of the solid components of the coating composition. In the above formula (2-2), R 23 It can be a hydrogen atom or a methyl group. R 24 It is an alkyl group having 1 to 18 hydrogen atoms or carbon atoms. n is an integer in the range of 3 to 4, and m is an integer in the range of 1 to 200.

2. The coating composition according to claim 1, wherein, The polymer containing organosilicon chains does not contain any of the following groups: isocyanate group, epoxy group, carboxyl group, carboxyl halide group, and carboxylic anhydride group.

3. A corrosion-resistant composition comprising a polymer containing organosilicon chains, The polymer containing organosilicon chains is a polymer that has organosilicon chains only at a single end and does not contain polymerizable unsaturated groups. The polymer containing organosilicon chains uses the polymerizable monomer (2) of the compound shown in formula (2-2) as the polymerization component. The number-average molecular weight of the organosilicon chain is in the range of 2,000 to 20,000. The content of the polymer containing organosilicon chains is 0.0001 to 10 parts by weight relative to 100 parts by weight of the solid components of the coating composition. In the above formula (2-2), R 23 It can be a hydrogen atom or a methyl group. R 24 It is an alkyl group having 1 to 18 hydrogen atoms or carbon atoms. n is an integer in the range of 3 to 4, and m is an integer in the range of 1 to 200.

4. The corrosion-resistant composition according to claim 3, wherein, The polymer containing organosilicon chains does not contain any of the following groups: isocyanate group, epoxy group, carboxyl group, carboxyl halide group, and carboxylic anhydride group.

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