Leveling agent, coating composition, hard coat layer-forming composition, resist composition and article

Abstract

To provide a silicone leveling agent that can exhibit sufficient oil repellency and has reduced water repellency. -[OSi(R)2] x A leveling agent having a polysiloxane structure represented by the formula: - (wherein R is independently an alkyl group having 1 to 6 carbon atoms, and x is the number of repetitions), and containing a polymer having, as at least polymerization components, a polymerizable monomer (A) having one or more polymerizable unsaturated groups, and a polymerizable monomer (B) having two or more polymerizable unsaturated groups (with the proviso that the polymerizable monomer (B) does not have the polysiloxane structure).

Description

[Technical Field]

[0001] The present invention relates to a leveling agent, a coating composition, a composition for forming a hard coat layer, a resist composition, and an article. [Background technology]

[0002] A leveling agent is added to smooth the coating film obtained by applying the coating composition. Specifically, by adding a leveling agent to a coating composition, the leveling agent is oriented on the coating film surface, reducing the surface tension of the coating film and achieving the effect of smoothing the resulting coating film. A coating film with a smooth surface can reduce the occurrence of cissing and unevenness.

[0003] For example, the surface layer of a polarizing plate, which forms the top surface of a liquid crystal display screen, is coated with a coating such as AG, AG / LR, or clear / LR that has anti-glare, anti-reflection, and anti-fouling properties, and a protective film is attached to the coated surface before shipping. Since insufficient smoothness of the coated surface will cause defects in the appearance of the liquid crystal display, the polarizing plate surface must have a high level of smoothness, and a leveling agent is used in the coating composition to meet this requirement.

[0004] The outermost surface of the liquid crystal display screen is required to be anti-fouling, and the leveling agent is also required to be oil-repellent. Fluorine-based leveling agents have been used as oil-repellent leveling agents up until now, but because fluorine-based compounds are suspected of accumulating in the environment, there is an urgent need to replace them with non-fluorine-based leveling agents. Silicone-based compounds, for example, have been proposed as such non-fluorine-based leveling agents (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-226834 Summary of the Invention [Problem to be solved by the invention]

[0006] It is difficult to achieve a balance between the oil and water repellency of a silicone leveling agent. Generally, silicone leveling agents with high oil repellency also have high water repellency. When such a silicone leveling agent is applied to the surface of a display, for example, the high water repellency can make it impossible to apply a protective film to the surface.

[0007] The problem to be solved by the present invention is to provide a silicone-based leveling agent that can exhibit sufficient oil repellency while suppressing water repellency. The problem to be solved by the present invention is to provide a coating composition, a resist composition, and a composition for forming a hard coat layer that can form a coating film that exhibits sufficient oil repellency and suppresses water repellency. [Means for solving the problem]

[0008] As a result of intensive research into solving the above-mentioned problems, the present inventors discovered that the problem of excessively high water repellency can be solved by using a polymerizable monomer having two or more polymerizable unsaturated groups as a polymerization component for a silicone-based leveling agent, which is a polymer having a polysiloxane structure, and thus completed the present invention.

[0009] That is, the present invention relates to the following leveling agent, etc. 1.-[OSi(R)2] x A leveling agent having a polysiloxane structure represented by the formula: - (wherein R is independently an alkyl group having 1 to 6 carbon atoms, and x is the number of repetitions), and containing a polymer having, as at least polymerization components, a polymerizable monomer (A) having one or more polymerizable unsaturated groups, and a polymerizable monomer (B) having two or more polymerizable unsaturated groups (with the proviso that the polymerizable monomer (B) does not have the polysiloxane structure). 2. The leveling agent according to 1, wherein the polymerizable monomer (A) is one or more selected from the group consisting of compounds represented by the following general formula (A-1), compounds represented by the following general formula (A-2), compounds represented by the following general formula (A-3), and compounds represented by the following general formula (A-4). [ka] (In the general formulae (A-1) to (A-4), R 11 are each independently an alkyl group having 1 to 6 carbon atoms or -OSi(R 15 )3, a group (R 15 are each independently an alkyl group having 1 to 6 carbon atoms, R 12 are each independently an alkyl group having 1 to 6 carbon atoms, R 13 is an alkyl group having 1 to 12 carbon atoms, R 14 are each independently a hydrogen atom or a methyl group, x indicates the number of repetitions, y is an integer greater than or equal to 1, z1 and z2 each independently represent an integer of 1 or more, z3 is an integer equal to or greater than 1, L 1 is a divalent organic group, L 11 is an organic group with a valence of z1+1, L 12 is an organic group with a valence of z2+1, L 13 is an organic group with a valence of z+y, L 14 is a divalent organic group. 3. The leveling agent according to 1 or 2, wherein the weight average molecular weight of the polymerizable monomer (A) is in the range of 100 to 4,000. 4. The leveling agent according to any one of 1 to 3, wherein the polymerizable monomer (B) is a compound represented by the following general formula (B-1): [ka] (In the general formula (B-1), R 21 is a hydrogen atom or a methyl group. x is an integer equal to or greater than 2, L 21 is an x-valent organic group. 5. The leveling agent according to any one of 1 to 4, wherein the content of the polymerizable monomer (A) in the polymerization components is in the range of 5 to 90 mass %. 6. The leveling agent according to any one of 1 to 5, wherein the content of the polymerizable monomer (B) in the polymerization components is in the range of 1 to 75 mass %. 7. The leveling agent according to any one of 1 to 6, wherein the polymerization component has one or more groups selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an aromatic group having 6 to 18 carbon atoms, a group containing a polyoxyalkylene chain, and a group containing a polyester chain, and further contains a polymerizable monomer (C) having one polymerizable unsaturated group. 8. The leveling agent according to 7, wherein the polymerizable monomer (C) is one or more selected from the group consisting of a compound represented by the following general formula (C-1), a compound represented by the following general formula (C-2), a compound represented by the following general formula (C-3), a compound represented by the following general formula (C-4), and a compound represented by the following general formula (C-5). [ka] (In the general formulae (C-1), (C-2), (C-3), (C-4) and (C-5), R 31 is a hydrogen atom or a methyl group, R 32 is an alkyl group having 1 to 18 carbon atoms, R 33 is a hydrogen atom or a methyl group, R 34 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, R 35 is a hydrogen atom or a methyl group, R 36 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 1 to 18 carbon atoms and an ether bond, R 37 is a hydrogen atom or a methyl group, R 38 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 1 to 18 carbon atoms and an ether bond, L 3 is a divalent organic group, R 39 is a hydrogen atom or a methyl group, R 40 are each independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, n is an integer ranging from 1 to 4, m is the number of repetitions, the number average value of m is in the range of 1 to 200, p is an integer ranging from 1 to 10, q is the number of repetitions, the number average value of q is in the range of 1 to 100, and l is an integer ranging from 0 to 5. 9. The leveling agent according to 8, wherein the polymerizable monomer (C) contains a compound represented by the general formula (C-2). 10. The leveling agent according to any one of 7 to 9, wherein the content of the polymerizable monomer (C) in the polymerization components is in the range of 0 to 75 mass %. 11. The leveling agent according to any one of 1 to 10, wherein the weight average molecular weight of the polymer is in the range of 2,000 to 200,000. 12. A coating composition containing the leveling agent according to any one of 1 to 11. 13. A resist composition containing the leveling agent according to any one of 1 to 11. 14. A composition for forming a hard coat layer, comprising an active energy ray-curable compound and the leveling agent according to any one of 1 to 11. 15. An article containing the leveling agent according to any one of 1 to 11. [Effects of the Invention]

[0010] The present invention can provide a silicone leveling agent that exhibits sufficient oil repellency and reduced water repellency. According to the present invention, it is possible to provide a coating composition, a resist composition, and a composition for forming a hard coat layer, which can form a coating film that exhibits sufficient oil repellency and has reduced water repellency. DETAILED DESCRIPTION OF THE INVENTION

[0011] An embodiment of the present invention will be described below. The present invention is not limited to the following embodiment, and can be implemented by making appropriate modifications within the scope that does not impair the effects of the present invention. In the present specification, the term "(meth)acrylate" refers to either or both of acrylate and methacrylate.

[0012] [Leveling agent] The leveling agent of the present invention is -[OSi(R)2] x The polymer has a polysiloxane structure represented by the formula - (wherein R is independently an alkyl group having 1 to 6 carbon atoms, and x is the number of repetitions), and contains, as at least polymerization components, a polymerizable monomer (A) having one or more polymerizable unsaturated groups and a polymerizable monomer (B) having two or more polymerizable unsaturated groups (however, the polymerizable monomer (B) does not have the polysiloxane structure). Here, the term "polymerization component" refers to a component that constitutes a polymer, and does not include solvents, polymerization initiators, and the like that do not constitute a polymer.

[0013] In the present invention, the term "polymerizable monomer" means a compound having a polymerizable unsaturated group, and examples of the polymerizable unsaturated group contained in the polymerizable monomer (A) and the polymerizable monomer (B) include a (meth)acryloyl group, a (meth)acryloyloxy group, a (meth)acryloylamide group, a vinyl ether group, an allyl group, a styryl group, a (meth)acryloylamino group, and a maleimide group.

[0014] A polymer containing at least the polymerizable monomer (A) and the polymerizable monomer (B) contained in the leveling agent of the present invention as polymerization components may be referred to as the "polymer of the present invention." Each component constituting the polymer of the present invention will be described below.

[0015] Polymerizable monomer (A) has -[OSi(R)2] x The polysiloxane structure represented by - is preferably a polydimethylsiloxane structure.

[0016] The polymerizable monomer (A) is preferably at least one selected from the group consisting of compounds represented by the following general formula (A-1), compounds represented by the following general formula (A-2), compounds represented by the following general formula (A-3), and compounds represented by the following general formula (A-4).

[0017] [ka] (In the general formulae (A-1) to (A-4), R 11 are each independently an alkyl group having 1 to 6 carbon atoms or -OSi(R 15 )3, a group (R 15 are each independently an alkyl group having 1 to 6 carbon atoms, R 12 are each independently an alkyl group having 1 to 6 carbon atoms, R 13 is an alkyl group having 1 to 12 carbon atoms, P is a polymerizable group represented by the following general formula (P-1), a polymerizable group represented by the following general formula (P-2), or a polymerizable group represented by the following general formula (P-3), x indicates the number of repetitions, y is an integer greater than or equal to 1, z1 and z2 each independently represent an integer of 1 or more, z3 is an integer equal to or greater than 1, L 1 is a divalent organic group, L 11 is an organic group with a valence of z1+1, L 12 is an organic group with a valence of z2+1, L 13 is an organic group with a valence of z3+y. L 14 is a divalent organic group,

[0018] [ka] (In the general formulae (P-1) to (P-3), R 14 is a hydrogen atom or a methyl group. R N is a hydrogen atom or an organic group. * is L 1 , L 11 , L 12 or L 13 )

[0019] In addition, R N The organic group may be, for example, an alkyl group having 1 to 18 carbon atoms. R N Specific examples of the alkylene group having 1 to 18 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-dodecyl group, an isopropyl group, a 2-methylpropyl group, a 2-methylhexyl group, and a tetramethylethyl group.

[0020] The polymerizable monomer (A) is more preferably one or more compounds selected from the group consisting of compounds represented by the following general formula (A-1), compounds represented by the following general formula (A-2), compounds represented by the following general formula (A-3), and compounds represented by the following general formula (A-4), in which P is a polymerizable group represented by general formula (P-1).

[0021] [ka] (In the general formulae (A-1) to (A-4), R 11 are each independently an alkyl group having 1 to 6 carbon atoms or -OSi(R 15 )3, a group (R 15 are each independently an alkyl group having 1 to 6 carbon atoms, R 12are each independently an alkyl group having 1 to 6 carbon atoms, R 13 is an alkyl group having 1 to 12 carbon atoms, R 14 are each independently a hydrogen atom or a methyl group, x indicates the number of repetitions, y is an integer greater than or equal to 1, z1 and z2 each independently represent an integer of 1 or more, z3 is an integer equal to or greater than 1, L 1 is a divalent organic group, L 11 is an organic group with a valence of z1+1, L 12 is an organic group with a valence of z2+1, L 13 is an organic group with a valence of z+y, L 14 is a divalent organic group.

[0022] R 11 , R 12 and R 15 The alkyl group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. R 13 The alkyl group having 1 to 12 carbon atoms is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.

[0023] The number of repetitions of x may be an integer of 1 or more, for example. The number average of x is, for example, in the range of 1 to 150, preferably in the range of 3 to 75, more preferably in the range of 5 to 50, and even more preferably in the range of 5 to 20. The number average value of x can be confirmed by measuring the number average molecular weight of the polymerizable monomer (A) by the method described in the Examples.

[0024] L 1 Regarding the divalent organic group, in the present invention, the term "divalent organic group" includes a "single bond", and L 1When is a single bond, O and Si are directly bonded.

[0025] L 1 The divalent organic group is preferably an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms.

[0026] L 1 Examples of the alkylene group having 1 to 50 carbon atoms include a methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, n-heptylene group, n-octylene group, n-nonylene group, n-decylene group, n-dodecylene group, isopropylene group, 2-methylpropylene group, 2-methylhexylene group, and tetramethylethylene group.

[0027] L 1 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 a methylene group, an ethylene group, an n-propylene group, or an isopropylene group.

[0028] L 1 The alkyleneoxy group having 1 to 50 carbon atoms is, for example, a group in which one or more -CH2- groups in the alkylene group are substituted with -O-. L 1 The alkyleneoxy group having 1 to 50 carbon atoms is preferably an alkyleneoxy group having 1 to 15 carbon atoms, more preferably an alkyleneoxy group having 1 to 8 carbon atoms, and even more preferably a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, an oxytrimethylene group, a butyleneoxy group, an oxytetramethylene group, a pentyleneoxy group, a heptyleneoxy group, or an octyleneoxy group.

[0029] L 1When the divalent organic group is an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms, some of the -CH2- groups in these divalent organic groups may be replaced by a carbonyl group (-C(=O)-), a phenylene group, an amide bond, a sulfide bond (-S-), a urethane bond (-NHC(=O)-), or the like.

[0030] L 1 When the divalent organic group is an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms, the carbon atoms of these groups may further be substituted with a substituent such as a hydroxyl group.

[0031] L 11 For example, L 11 When z1 is a divalent organic group (z1=1), the divalent organic group is L 1 is the same as the divalent organic group.

[0032] L 11 When the z1+1-valent organic group is a trivalent or higher organic group, the trivalent or higher organic group is, for example, an organic group in which a hydrogen atom bonded to a carbon atom of the divalent organic group described above is replaced with a bond so as to have a corresponding valence.

[0033] L 12 The z2+1 valent organic group is L 11 It is the same as the z1+1 valent organic group.

[0034] z1 is an integer of 1 or more, preferably an integer in the range of 1 to 4, more preferably an integer of 1 or 2, and even more preferably 1.

[0035] z2 is an integer of 1 or more, preferably an integer in the range of 1 to 4, more preferably an integer of 1 or 2, and even more preferably 1.

[0036] y is an integer of 1 or more, preferably an integer in the range of 1 to 4, more preferably an integer in the range of 1 to 3, and further preferably 1 or 2.

[0037] z3 is an integer of 1 or more, preferably an integer in the range of 1 to 6, more preferably an integer of 1, 2 or 3, and even more preferably 2.

[0038] L 13 The organic group with a valence of z3+y is L 11 The z1+1 valent organic group L 13 The valence of the organic group can be the same as that of the organic group corresponding to L. 13 When L is a trivalent organic group, 13 The trivalent organic group is L 11 It is preferable that the trivalent organic group is the same as the above.

[0039] L 14 The divalent organic group is L 11 is the same as the divalent organic group.

[0040] The weight average molecular weight of the polymerizable monomer (A) constituting the polymer of the present invention is, for example, in the range of 100 to 10,000, preferably in the range of 100 to 4,000, and more preferably in the range of 500 to 3,000. Here, the "weight average molecular weight" is a value measured by the method described in the examples.

[0041] The polymerizable monomer (A) contained in the polymerization components may be one type alone or two or more types having mutually different structures.

[0042] The polymerizable monomer (A) can be produced by a known method, and a commercially available product may also be used.

[0043] In the polymer of the present invention, the lower limit of the content of the polymerizable monomer (A) is, for example, 3 mass% or more, 5 mass% or more, 10 mass% or more, 20 mass% or more, 25 mass% or more, or 30 mass% or more, based on the total amount of the polymerizable components of the polymer. The upper limit of the content of the polymerizable monomer (A) is, for example, 90 mass % or less, 80 mass % or less, 75 mass % or less, 70 mass % or less, or 60 mass % or less, based on the total amount of the polymerizable components of the polymer. The combination of the upper and lower limits of the content of the polymerizable monomer (A) is, for example, in the range of 5% by mass to 90% by mass of the total amount of the polymerizable components of the polymer, preferably 10% by mass to 75% by mass, and more preferably 20% by mass to 70% by mass of the total amount of the polymerizable components of the polymer. The content of the polymerizable monomer (A) can be adjusted by the raw material charge ratio of the polymerizable monomer (A) when producing the polymer of the present invention.

[0044] The proportion of silicone chains in the polymer of the present invention (-[OSi(R)2] x The proportion of the polysiloxane structure represented by -) is, for example, in the range of 3 to 70 mass %, preferably in the range of 8 to 60 mass %, more preferably in the range of 10 to 55 mass %, and even more preferably in the range of 20 to 50 mass %. The proportion of the silicone chains can be calculated from the amount of the polymerizable monomer (A) used.

[0045] The polymerizable monomer (B) is a polymerizable monomer having two or more polymerizable unsaturated groups, and may have two or more of one type of polymerizable unsaturated group, or may have two or more of two or more types of polymerizable unsaturated groups. The polymerizable monomer (B) is preferably a polymerizable monomer having two or more (meth)acryloyl groups or a polymerizable monomer having two or more (meth)acryloyloxy groups.

[0046] The polymerizable monomer (B) is preferably a compound represented by the following general formula (B-1).

[0047] [ka] (In the general formula (B-1), R 21 is a hydrogen atom or a methyl group. n2 is an integer equal to or greater than 2, L 21 is an n2-valent organic group.

[0048] n2 may be an integer of 2 or more, for example, an integer in the range of 2 to 12, preferably an integer in the range of 2 to 8, more preferably an integer in the range of 2 to 6, and even more preferably an integer in the range of 2 to 4.

[0049] L 21 The n2-valent organic group is an organic group having a valence corresponding to the value of n2. For example, when n2 is 2, it is a divalent organic group, and when n2 is 6, it is a hexavalent organic group. In addition, L 21 does not contain the polysiloxane structure contained in the polymerizable monomer (A).

[0050] L 21 is preferably an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms, and is an organic group in which a hydrogen atom bonded to a carbon atom of the alkylene group or the alkyleneoxy group is replaced with a bond so as to have a valence corresponding to the numerical value of n2. Therefore, L 21 When L is a divalent organic group, 21 is preferably an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms.

[0051] L 21 Examples of the alkylene group having 1 to 50 carbon atoms include a methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, n-heptylene group, n-octylene group, n-nonylene group, n-decylene group, n-dodecylene group, isopropylene group, 2-methylpropylene group, 2-methylhexylene group, and tetramethylethylene group.

[0052] L 21 The alkylene group having 1 to 50 carbon atoms is preferably an alkylene group having 1 to 25 carbon atoms, more preferably an alkylene group having 1 to 20 carbon atoms, and even more preferably an alkylene group having 1 to 10 carbon atoms.

[0053] L 21The alkyleneoxy group having 1 to 50 carbon atoms is, for example, a group in which one or more -CH2- groups in the alkylene group are substituted with -O-. L 21 The alkyleneoxy group having 1 to 50 carbon atoms is preferably an alkyleneoxy group having 1 to 30 carbon atoms, and more preferably an alkyleneoxy group having 1 to 20 carbon atoms.

[0054] L 21 When the divalent organic group is an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms, some of the -CH2- groups in these divalent organic groups may be replaced by a carbonyl group (-C(=O)-), a phenylene group, a sulfide bond (-S-), an amide bond or a urethane bond.

[0055] L 21 When the divalent organic group is an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms, the carbon atoms of these groups may further be substituted with a substituent such as a hydroxyl group.

[0056] Specific examples of the polymerizable monomer (B) include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-hydroxy-3-methacrylpropyl acrylate, 2-hydroxy-1,3-dimethacryloxypropane, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethoxylated bisphenol A, Examples of the acrylates include Nol A di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, tris-(2-acryloxyethyl)isocyanurate, bis-(2-acryloxyethyl)isocyanurate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and polypentaerythritol poly(meth)acrylate.

[0057] The polymerizable monomer (B) contained as a polymerization component may be one type alone or two or more types having mutually different structures.

[0058] The polymerizable monomer (B) can be produced by a known method, and a commercially available product may also be used.

[0059] In the polymer of the present invention, the content of the polymerizable monomer (B) is, for example, in the range of 0.1 to 900 parts by mass relative to 100 parts by mass of the polymerizable monomer (A), preferably in the range of 1 to 500 parts by mass relative to 100 parts by mass of the polymerizable monomer (A), more preferably in the range of 3 to 300 parts by mass relative to 100 parts by mass of the polymerizable monomer (A), and even more preferably in the range of 5 to 200 parts by mass relative to 100 parts by mass of the polymerizable monomer (A). The content of the polymerizable monomer (B) can be adjusted by the raw material charge ratio of the polymerizable monomer (B) when producing the polymer of the present invention.

[0060] In the polymer of the present invention, the content of the polymerizable monomer (B) is, for example, in the range of 0.1 to 90 mass % relative to the total amount of the polymerizable components of the polymer, preferably in the range of 1 to 75 mass %, more preferably in the range of 3 to 60 mass %, and even more preferably in the range of 5 to 50 mass %.

[0061] In addition to the polymerizable monomer (A) and the polymerizable monomer (B), the polymerization components of the polymer of the present invention may further include a polymerizable monomer (C) having one or more selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an aromatic group having 6 to 18 carbon atoms, a group containing a polyoxyalkylene chain, and a group containing a polyester chain.

[0062] The alkyl group having 1 to 18 carbon atoms contained in the polymerizable monomer (C) may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, and specific examples thereof include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, and a hexadecyl group. The alkyl group having 1 to 18 carbon atoms contained in the polymerizable monomer (C) is preferably an alkyl group having 1 to 6 carbon atoms.

[0063] Examples of the aromatic group having 6 to 18 carbon atoms contained in the polymerizable monomer (C) include a phenyl group, a naphthyl group, an anthracen-1-yl group, and a phenanthrene-1-yl group.

[0064] The group containing a (poly)oxyalkylene chain contained in the polymerizable monomer (C) is a monovalent group containing a repeating oxyalkylene moiety or a divalent linking group containing a repeating oxyalkylene moiety.

[0065] The group containing a polyester chain contained in the polymerizable monomer (C) is a monovalent group containing a repeating ester bond moiety or a divalent linking group containing a repeating ester bond moiety.

[0066] The alkyl group having 1 to 18 carbon atoms contained in the polymerizable monomer (C) may further have a substituent, and examples of the substituent include a hydroxyl group and an aryl group. The aromatic group having 6 to 18 carbon atoms contained in the polymerizable monomer (C) may further have a substituent, and examples of the substituent include a hydroxyl group and an alkyl group.

[0067] Examples of the polymerizable monomer (C) having an alkyl group having 1 to 18 carbon atoms and in which the polymerizable unsaturated group is a (meth)acryloyl group include methyl(meth)acrylate, ethyl(meth)acrylate, n-propyl(meth)acrylate, isopropyl(meth)acrylate, n-butyl(meth)acrylate, s-butyl(meth)acrylate, isobutyl(meth)acrylate, t-butyl(meth)acrylate, n-pentyl(meth)acrylate, n-hexyl(meth)acrylate, n-heptyl(meth)acrylate, n-octyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, decyl(meth)acrylate, and methyl(meth)acrylate.

[0033] Examples of the methyl acrylate include alkyl esters of (meth)acrylic acid having 1 to 18 carbon atoms, such as dicyclopentanyloxylethyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate; and bridged cyclic alkyl esters of (meth)acrylic acid having 1 to 18 carbon atoms, such as dicyclopentanyloxylethyl (meth)acrylate, isobornyloxylethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dimethyl adamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyl (meth)acrylate.

[0068] Examples of the polymerizable monomer (C) having a phenylalkyl group having 7 to 18 carbon atoms or a phenoxyalkyl group having 7 to 18 carbon atoms and in which the polymerizable unsaturated group is a (meth)acryloyl group include benzyl (meth)acrylate, phenoxymethyl (meth)acrylate, and 2-phenoxyethyl (meth)acrylate.

[0069] Examples of the polymerizable monomer (C) having an alkyl group having 1 to 18 carbon atoms and in which the polymerizable unsaturated group is a vinyl ether group include alkyl vinyl ethers such as 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, and cyclohexyl vinyl ether; and cycloalkyl vinyl ethers.

[0070] Examples of the polymerizable monomer (C) having an aromatic group with 6 to 18 carbon atoms include styrene, α-methylstyrene, p-methylstyrene, and p-methoxystyrene.

[0071] Examples of the polymerizable monomer (C) having an alkyl group having 1 to 18 carbon atoms and in which the polymerizable unsaturated group is a (meth)acryloylamino group include N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, diacetoneacrylamide, and acroylmorpholine.

[0072] Examples of the polymerizable monomer (B) having an alkyl group having 1 to 18 carbon atoms and in which the polymerizable unsaturated group is a maleimide group include methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, and cyclohexylmaleimide.

[0073] Examples of the polymerizable monomer (C) having a group containing a polyoxyalkylene chain and in which the polymerizable unsaturated group is a (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, polyethylene glycol·polytetramethylene glycol mono(meth)acrylate, poly(propylene glycol·tetramethylene glycol) mono(meth)acrylate, polypropylene glycol·polytetramethylene glycol mono(meth)acrylate, poly(propylene glycol·1,2-butylene glycol) mono(meth)acrylate, polypropylene glycol·poly1,2-butylene glycol mono(meth)acrylate, Poly(ethylene glycol·1,2-butylene glycol) mono(meth)acrylate, Polyethylene glycol·poly1,2-butylene glycol mono(meth)acrylate, Poly(tetraethylene glycol·1,2-butylene glycol) mono(meth)acrylate, Polytetraethylene glycol·poly1,2-butylene glycol mono(meth)acrylate, Poly1,2-butylene glycol mono(meth)acrylate, Poly(ethylene glycol·trimethylene glycol) mono(meth)acrylate, Polyethylene Glycol·Polytrimethylene glycol mono(meth)acrylate, Poly(propylene glycol·trimethylene glycol) mono(meth)acrylate, Polypropylene glycol·Polytrimethylene glycol mono(meth)acrylate, Poly(trimethylene glycol·tetramethylene glycol) mono(meth)acrylate, Polytrimethylene glycol·Polytetramethylene glycol mono(meth)acrylate, Poly(1,2-butylene glycol·trimethylene glycol) mono(meth)acrylate, Poly 1,Examples include 2-butylene glycol polytrimethylene glycol mono(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, poly(1,2-butylene glycol tetramethylene glycol) mono(meth)acrylate, and poly(1,2-butylene glycol polytetramethylene glycol mono(meth)acrylate). In addition, the above "poly(ethylene glycol-propylene glycol)" means a random copolymer of ethylene glycol and propylene glycol, and "polyethylene glycol-polypropylene glycol" means a block copolymer of ethylene glycol and propylene glycol.

[0074] The polymerizable monomer (C) is preferably one or more selected from the group consisting of compounds represented by the following general formula (C-1), compounds represented by the following general formula (C-2), compounds represented by the following general formula (C-3), and compounds represented by the following general formula (C-4).

[0075] [ka] (In the general formulae (C-1), (C-2), (C-3), (C-4) and (C-5), R 31 is a hydrogen atom or a methyl group, R 32 is an alkyl group having 1 to 18 carbon atoms, R 33 is a hydrogen atom or a methyl group, R 34 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, R 35 is a hydrogen atom or a methyl group, R 36 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 1 to 18 carbon atoms and an ether bond, R 37 is a hydrogen atom or a methyl group, R 38 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 1 to 18 carbon atoms and an ether bond, L 3 is a divalent organic group, R 39 is a hydrogen atom or a methyl group, R 40 are each independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, n is an integer ranging from 1 to 4, m is the number of repetitions, the number average value of m is in the range of 1 to 200, p is an integer ranging from 1 to 10, q is the number of repetitions, the number average value of q is in the range of 1 to 100, and l is an integer ranging from 0 to 5.

[0076] In the formula (C-2), the m n's in the parentheses may be the same or different. In the formula (C-3), the q p's in the parentheses may be the same or different. In the formula (C-4), the q p's in the parentheses may be the same or different.

[0077] R 32 , R 34 , R 36 and R 38 The alkyl group having 1 to 18 carbon atoms may further have a substituent, and examples of the substituent include a hydroxyl group and an aryl group. R 36 and R 38 The alkyl group having 1 to 18 carbon atoms and an ether bond may further have a substituent, and examples of the substituent include a hydroxyl group and an aryl group. R 40 The alkyl group having 1 to 6 carbon atoms may further have a substituent, and examples of the substituent include a hydroxyl group and an aryl group. R 40 The alkoxy group having 1 to 6 carbon atoms may further have a substituent, and examples of the substituent include a hydroxyl group and an aryl group.

[0078] L in the formulas (C-3) and (C-4) 3 The divalent organic group is L 11 The divalent organic groups are the same as those mentioned above.

[0079] In the general formula (C-2), m represents the number of repetitions, and may be, for example, an integer of 1 or greater. The number average of m is, for example, in the range of 1 to 200, preferably in the range of 1 to 100, and more preferably in the range of 1 to 50. The number average value of m can be confirmed by measuring the number average molecular weight of the polymerizable monomer (C) by the method described in the examples.

[0080] In the general formulae (C-3) and (C-4), q represents the number of repetitions, and may be, for example, an integer of 1 or greater. The number average of q is, for example, in the range of 1 to 100, preferably in the range of 1 to 80, and more preferably in the range of 1 to 50.

[0081] The polymerizable monomer (C) preferably contains a compound represented by the formula (C-2). When the polymerizable monomer (C) contains a compound represented by the formula (C-2), the content of the compound represented by the formula (C-2) is preferably 50 mass% or more relative to the total amount of the polymerizable monomer (C).

[0082] The polymerizable monomer (C) that is a polymerization component may be one type alone, or may be two or more types of polymerizable monomers (C) that are different in structure from each other.

[0083] The polymerizable monomer (C) can be produced by a known method. Commercially available polymerizable monomers (C) may be used. For example, commercially available polymerizable monomers (C) having a group containing a polyoxyalkylene chain and in which the polymerizable unsaturated group is a (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 Co., Ltd., and "Blemmer PE-90," "Blemmer PE-200," "Blemmer PE-350," and "Blemmer PME-100" manufactured by NOF Corporation. Examples include "Blenmer PME-200", "Blenmer PME-400", "Blenmer PME-4000", "Blenmer PP-1000", "Blenmer PP-500", "Blenmer PP-800", "Blenmer 70PEP-350B", "Blenmer 55PET-800", "Blenmer 50POEP-800B", "Blenmer 10PPB-500B", "Blenmer NKH-5050", "Blenmer AP-400", "Blenmer AE-350", the Plaxel F series manufactured by Daicel Corporation, and the Viscoat series manufactured by Osaka Organic Chemical Industry Ltd.

[0084] When the polymerizable monomer (C) is contained as a polymerization component, the content of the polymerizable monomer (C) is, for example, in the range of 0 to 500 parts by mass per 100 parts by mass of the polymerizable monomer (A), preferably in the range of 10 to 400 parts by mass per 100 parts by mass of the polymerizable monomer (A), more preferably in the range of 20 to 300 parts by mass per 100 parts by mass of the polymerizable monomer (A), and even more preferably in the range of 30 to 200 parts by mass per 100 parts by mass of the polymerizable monomer (A). The content of the polymerizable monomer (C) can be adjusted by the raw material charge ratio of the polymerizable monomer (C) when producing the polymer of the present invention.

[0085] In the polymer of the present invention, the content of the polymerizable monomer (C) is, for example, in the range of 0 to 90 mass % relative to the total amount of polymerization components of the polymer, preferably in the range of 1 to 80 mass %, more preferably in the range of 5 to 70 mass %, and even more preferably in the range of 10 to 60 mass %.

[0086] The polymer of the present invention may be any polymer containing the polymerizable monomer (A), the polymerizable monomer (B), and the optional polymerizable monomer (C) as polymerization components, and may contain other polymerizable monomers as polymerization components other than the polymerizable monomer (A), the polymerizable monomer (B), and the optional polymerizable monomer (C) as long as the effects of the present invention are not impaired. The polymer of the present invention is preferably a polymer whose polymerization components are essentially composed of polymerizable monomer (A), polymerizable monomer (B) and optional polymerizable monomer (C), and more preferably a copolymer whose polymerization components are solely composed of polymerizable monomer (A), polymerizable monomer (B) and optional polymerizable monomer (C). Here, "substantially consisting of" means that the total content of the polymerizable monomer (A), the polymerizable monomer (B) and the optional polymerizable monomer (C) in the polymerization components of the polymer of the present invention is 85% by mass or more, 90% by mass or more, 95% by mass or more, or 99% by mass or more.

[0087] The polymerization method for the polymer of the present invention is not particularly limited. The polymer of the present invention may be a random polymer of the polymerizable monomer (A), the polymerizable monomer (B), and an optional polymerizable monomer (C). Also, the polymer of the present invention may be a block polymer having one or more polymer blocks of the polymerizable monomer (A), the polymerizable monomer (B), and the optional polymerizable monomer (C).

[0088] The polymer of the present invention is preferably a random copolymer having polymerizable monomer (A), polymerizable monomer (B) and optional polymerizable monomer (C) as polymerization components. The method for producing the polymer of the present invention will be described later. From the viewpoint that the polymer can be produced without using a metal catalyst in the polymerization, the polymer of the present invention is more preferably a free radical random copolymer produced by free radical polymerization.

[0089] The polymer of the present invention preferably does not contain fluorine atoms.

[0090] The number average molecular weight (Mn) of the polymer of the present invention is preferably in the range of 1,000 to 50,000, more preferably in the range of 2,000 to 30,000, and even more preferably in the range of 2,000 to 20,000. The weight average molecular weight (Mw) of the polymer of the present invention is preferably in the range of 2,000 to 300,000, more preferably in the range of 3,000 to 100,000, and even more preferably in the range of 4,000 to 50,000.

[0091] In the present invention, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​calculated in terms of polystyrene based on gel permeation chromatography (GPC) measurements. The number average molecular weight (Mn) and weight average molecular weight (Mw) of the polymer of the present invention are measured by the method described in the examples.

[0092] The leveling agent of the present invention may contain a component other than the polymer of the present invention, as long as it contains the polymer of the present invention.

[0093] [Polymer manufacturing method] The method for producing the polymer of the present invention is not particularly limited, and the polymer can be produced by a known method. The polymer of the present invention can be produced by solution polymerization, bulk polymerization, emulsion polymerization, etc., based on a polymerization mechanism such as radical polymerization, cationic polymerization, anionic polymerization, etc. For example, in the case of radical polymerization, the polymer of the present invention can be produced by charging a polymerizable monomer mixture into an organic solvent and adding a general-purpose radical polymerization initiator.

[0094] Various polymerization initiators can be used, and examples thereof include peroxides such as t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, and diacyl peroxide; azo compounds such as azobisisobutyronitrile, dimethyl azobisisobutyrate, and phenylazotriphenylmethane; and metal chelate compounds such as Mn(acac)3. If necessary, a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, ethyl thioglycolic acid, or octyl thioglycolic acid, or a thiol compound having a coupling group such as γ-mercaptopropyltrimethoxysilane may be used as an additive such as a chain transfer agent.

[0095] Examples of the organic solvent include alcohols such as ethanol, isopropyl alcohol, n-butanol, isobutanol, and tert-butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and butyl lactate; monocarboxylic acid esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, and butyl 2-methoxypropionate; dimethylformamide, dimethyl sulfoxide, N-methyl Examples of the solvent include polar solvents such as pyrrolidone, ethers such as methyl cellosolve, cellosolve, butyl cellosolve, butyl carbitol, and ethyl cellosolve acetate, propylene glycols and esters thereof such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether acetate, halogenated solvents such as 1,1,1-trichloroethane and chloroform, ethers such as tetrahydrofuran and dioxane, aromatics such as benzene, toluene, and xylene, and fluorinated inert liquids such as perfluorooctane and perfluorotri-n-butylamine. These solvents can be used alone or in combination of two or more.

[0096] The polymer of the present invention can also be produced by living polymerization such as living radical polymerization or living anionic polymerization.

[0097] In living radical polymerization, a dormant species, whose active polymerization terminals are protected by atoms or atomic groups, reversibly generates radicals and reacts with a monomer to form a propagation reaction. Even after the first monomer is consumed, the propagating terminals retain their activity and react with the successively added second monomer to produce a block polymer. Examples of such living radical polymerization include atom transfer radical polymerization (ATRP), reversible addition-fragmentation radical polymerization (RAFT), nitroxide-mediated radical polymerization (NMP), and organotellurium radical polymerization (TERP). While there are no particular restrictions on which of these methods is used, ATRP is preferred due to its ease of control. ATRP uses an organic halide or sulfonyl halide compound as a polymerization initiator and a metal complex consisting of a transition metal compound and a ligand as a catalyst.

[0098] Specific examples of polymerization initiators that can be used in ATRP include 1-phenylethyl chloride, 1-phenylethyl bromide, chloroform, carbon tetrachloride, 2-chloropropionitrile, α,α'-dichloroxylene, α,α'-dibromoxylene, hexakis(α-bromomethyl)benzene, and alkyl esters of 2-halogenated carboxylic acids having 1 to 6 carbon atoms (e.g., 2-chloropropionic acid, 2-bromopropionic acid, 2-chloroisobutyric acid, 2-bromoisobutyric acid, etc.) having 1 to 6 carbon atoms. More specific examples of C1-C6 alkyl esters of C1-C6 2-halogenated carboxylic acids include methyl 2-chloropropionate, ethyl 2-chloropropionate, methyl 2-bromopropionate, and ethyl 2-bromoisobutyrate.

[0099] The transition metal compounds that can be used in ATRP are Mn+ X n It is expressed as: M n+ X n The transition metal M of the transition metal compound represented by n+ As for 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+ It can be selected from the group consisting of: M n+ X n X in the transition metal compound represented by the formula (I) is a halogen atom, an alkoxyl group having 1 to 6 carbon atoms, (SO4) 1 / 2 , (PO4) 1 / 3 , (HPO4) 1 / 2 , (H2PO4), triflate, hexafluorophosphate, methanesulfonate, arylsulfonate (preferably benzenesulfonate or toluenesulfonate), SeR 11 , CN and R 12 COO, where R 11 represents an aryl group or a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), R 12represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms (preferably a methyl group) which may be substituted 1 to 5 times with halogen (preferably 1 to 3 times with fluorine or chlorine). M n+ X n In the transition metal compound represented by the formula (I), n represents the formal charge on the metal and is an integer of 0 to 7.

[0100] Examples of the ligand compound capable of forming a coordinate bond to the transition metal of the transition metal compound include a compound having a ligand containing one or more nitrogen atoms, oxygen atoms, phosphorus atoms, or sulfur atoms that can be coordinated to the transition metal via a σ bond, a compound having a ligand containing two or more carbon atoms that can be coordinated to the transition metal via a π bond, and a compound having a ligand that can be coordinated to the transition metal via a μ bond or an η bond.

[0101] The transition metal complex is not particularly limited, but preferred examples include complexes of transition metals of Groups 7, 8, 9, 10, and 11, and more preferred examples include complexes of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel.

[0102] Specific examples of catalysts that can be used in ATRP include complexes with ligands such as 2,2'-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, and polyamines such as tetramethylethylenediamine, pentamethyldiethylenetriamine, and hexamethyltris(2-aminoethyl)amine when the central metal is copper. Divalent ruthenium complexes include dichlorotris(triphenylphosphine)ruthenium, dichlorotris(tributylphosphine)ruthenium, dichloro(cyclooctadiene)ruthenium, dichlorobenzeneruthenium, dichloro-p-cymeneruthenium, dichloro(norbornadiene)ruthenium, cis-dichlorobis(2,2'-bipyridine)ruthenium, dichlorotris(1,10-phenanthroline)ruthenium, and carbonylchlorohydridotris(triphenylphosphine)ruthenium. Divalent iron complexes include bistriphenylphosphine complexes and triazacyclononane complexes.

[0103] In the living radical polymerization, it is preferable to use a solvent. Examples of solvents used in living radical polymerization include ester-based solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; ether-based solvents such as diisopropyl ether, dimethoxyethane, and diethylene glycol dimethyl ether; halogen-based solvents such as dichloromethane and dichloroethane; aromatic solvents such as toluene and xylene; ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohol-based solvents such as methanol, ethanol, and isopropanol; and aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide. The above solvents may be used alone or in combination of two or more.

[0104] The polymerization temperature during the living radical polymerization is preferably in the range of room temperature to 120°C.

[0105] When the polymer of the present invention is produced by living radical polymerization, metals resulting from the transition metal compound used in the polymerization may remain in the resulting polymer. The metals remaining in the resulting polymer may be removed using activated alumina or the like after the polymerization is completed.

[0106] [Coating composition] The polymer of the present invention can be suitably used as a leveling agent for a coating composition, and the coating composition of the present invention contains the polymer of the present invention. The polymer of the present invention can be used as a fluorine-atom-free leveling agent, which does not contain fluorine atoms, and therefore is a leveling agent with low environmental accumulation and low environmental load.

[0107] The content of the polymer of the present invention contained in the coating composition of the present invention varies depending on the type of base resin, the coating method, the desired film thickness, etc., but is, for example, in the range of 0.001 to 10 parts by mass, preferably 0.01 to 5 parts by mass, more preferably 0.02 to 2 parts by mass, and even more preferably 0.02 to 1 part by mass, relative to 100 parts by mass of the solid content of the coating composition. The polymer of the present invention can exert a leveling effect even in a small amount. The "solid content of the coating composition" refers to the components other than water and the solvent contained in the coating composition.

[0108] The application of the coating composition of the present invention is not particularly limited, and it can be used for any application that requires leveling property. For example, the coating composition of the present invention can be used as a paint composition, a photosensitive resin composition, a hard coat layer-forming composition, etc.

[0109] [Paint composition] When the coating composition of the present invention is used as a paint composition, examples of the paint composition include paints using natural resins such as petroleum resin paints, shellac paints, rosin-based paints, cellulose-based paints, rubber-based paints, lacquer paints, cashew resin paints, and oil-based vehicle paints; and paints using synthetic resins such as phenolic resin paints, alkyd resin paints, unsaturated polyester resin paints, amino resin paints, epoxy resin paints, vinyl resin paints, acrylic resin paints, polyurethane resin paints, silicone resin paints, and fluororesin paints. By adding the polymer of the present invention to the above coating composition, smoothness can be imparted to the resulting coating film.

[0110] Various additives may be added to the coating composition as needed, such as colorants such as pigments, dyes, and carbon; inorganic powders such as silica, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, calcium oxide, and calcium carbonate; organic fine powders such as higher fatty acids, polyacrylic resins, and polyethylene; and light resistance improvers, weather resistance improvers, heat resistance improvers, antioxidants, thickeners, and anti-settling agents.

[0111] [Photosensitive composition] The photosensitive resin composition changes its physical properties such as solubility, viscosity, transparency, refractive index, conductivity, and ion permeability when irradiated with light such as visible light or ultraviolet light. Among photosensitive resin compositions, resist compositions (such as photoresist compositions and color resist compositions for color filters) require high leveling properties. Resist compositions are typically applied by spin coating to a thickness of approximately 1 to 2 μm on a silicon wafer or a glass substrate on which various metals have been vapor-deposited. If the applied film thickness fluctuates or unevenness occurs during this process, the linearity and reproducibility of the pattern deteriorate, resulting in the failure to obtain a resist pattern with the desired precision. In addition to these problems, various leveling-related issues also exist, such as drip marks, overall unevenness, and a beading phenomenon in which the film thickness is thicker at the edges than at the center. The coating composition of the present invention can solve the above-mentioned problems when used as a resist composition because the polymer of the present invention exhibits high leveling properties and can form a uniform coating film (cured product).

[0112] When the coating composition of the present invention is used as a photoresist composition, the photoresist composition contains an alkali-soluble resin, a radiation-sensitive substance (photosensitive substance), a solvent, and the like in addition to the polymer of the present invention.

[0113] The alkali-soluble resin contained in the photoresist composition is a resin that is soluble in an alkaline solution, which is the developer used when patterning the resist. Examples of alkali-soluble resins include novolak resins obtained by condensing an aromatic hydroxy compound derivative such as phenol, cresol, xylenol, resorcinol, phloroglucinol, or hydroquinone with an aldehyde compound such as formaldehyde, acetaldehyde, or benzaldehyde; polymers or copolymers of vinylphenol compound derivatives such as o-vinylphenol, m-vinylphenol, p-vinylphenol, or α-methylvinylphenol; (meth)acrylic acid polymers or copolymers such as acrylic acid, methacrylic acid, or hydroxyethyl (meth)acrylate; polyvinyl alcohol; modified resins in which radioactive ray-sensitive groups such as quinone diazide groups, naphthoquinone azide groups, aromatic azide groups, or aromatic cinnamoyl groups have been introduced via some of the hydroxyl groups of these various resins; and urethane resins containing acidic groups such as carboxylic acid and sulfonic acid in the molecule. These alkali-soluble resins may be used alone or in combination of two or more.

[0114] When the coating composition of the present invention is used as a photoresist composition, the content of the polymer of the present invention is, for example, 0.05 parts by mass or less, and preferably in the range of 0.0001 to 0.05 parts by mass, per 100 parts by mass of the alkali-soluble resin.

[0115] The radiation-sensitive substance contained in the photoresist composition is a substance that changes the solubility of the alkali-soluble resin in a developer when irradiated with energy rays such as ultraviolet rays, far ultraviolet rays, excimer laser light, X-rays, electron beams, ion beams, molecular beams, and gamma rays. 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.

[0116] Examples of the quinone diazide compounds include 1,2-benzoquinone azide-4-sulfonic acid ester, 1,2-naphthoquinone diazide-4-sulfonic acid ester, 1,2-naphthoquinone diazide-5-sulfonic acid ester, 2,1-naphthoquinone diazide-4-sulfonic acid ester, 2,1-naphthoquinone diazide-5-sulfonic acid ester, and sulfonic acid chlorides of quinone diazide derivatives such as 1,2-benzoquinone azide-4-sulfonic acid chloride, 1,2-naphthoquinone diazide-4-sulfonic acid chloride, 1,2-naphthoquinone diazide-5-sulfonic acid chloride, 2,1-naphthoquinone diazide-4-sulfonic acid chloride, and 2,1-naphthoquinone diazide-5-sulfonic acid chloride.

[0117] Examples of the diazo compounds include salts of condensates of p-diazodiphenylamine with formaldehyde or acetaldehyde, inorganic diazo resin salts which are reaction products of the above condensates with hexafluorophosphates, tetrafluoroborates, perchlorates or periodates, and organic diazo resin salts which are reaction products of the above condensates with sulfonic acids, as described in U.S. Pat. No. 3,300,309.

[0118] Examples of the azide compounds include azidochalconic acid, diazidobenzalmethylcyclohexanones, azidocinnamylideneacetophenones, aromatic azide compounds, and aromatic diazide compounds.

[0119] Examples of the halogenated organic compound include halogen-containing oxadiazole compounds, halogen-containing triazine compounds, halogen-containing acetophenone compounds, halogen-containing benzophenone compounds, halogen-containing sulfoxide compounds, halogen-containing sulfone compounds, halogen-containing thiazole compounds, halogen-containing oxazole compounds, halogen-containing trizole compounds, halogen-containing 2-pyrone compounds, halogen-containing aliphatic hydrocarbon compounds, halogen-containing aromatic hydrocarbon compounds, halogen-containing heterocyclic compounds, and sulfenyl halide compounds. In addition to the above, examples of halogenated organic compounds include compounds used as halogen-based flame retardants such as tris(2,3-dibromopropyl)phosphate, tris(2,3-dibromo-3-chloropropyl)phosphate, chlorotetrabromomethane, hexachlorobenzene, hexabromobenzene, hexabromocyclododecane, hexabromobiphenyl, tribromophenyl allyl 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, and compounds used as organic chloro-based pesticides such as dichlorophenyltrichloroethane.

[0120] Examples of the organic acid ester include carboxylic acid ester and sulfonic acid ester. Examples of the organic acid amide include carboxylic acid amide and sulfonic acid amide. Examples of the organic acid imide include carboxylic acid imide and sulfonic acid imide. The radiation sensitive substance may be used alone or in combination of two or more kinds.

[0121] In the photoresist composition, the content of the radiation-sensitive substance is preferably in the range of 10 to 200 parts by mass, and more preferably in the range of 50 to 150 parts by mass, per 100 parts by mass of the alkali-soluble resin.

[0122] Examples of solvents for 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-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, pentanol, heptanol, octanol, nonanol, and decanol; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and dioxane; alcohol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monopropyl ether; ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, and butyl methyl butylate. esters such as ethyl butyrate, butyl butyrate, propyl butyrate, ethyl lactate, butyl lactate, etc.; monocarboxylic acid esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, etc.; cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate. Cellosolve esters such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether acetate; diethylene glycols such as diethyl glycol monomethyl ether, diethyl glycol monoethyl ether, diethyl glycol dimethyl ether, diethyl glycol diethyl ether, and diethyl glycol methyl ethyl ether;Examples of suitable solvents include halogenated hydrocarbons such as trichloroethylene, chlorofluorocarbon solvents, HCFCs, and HFCs; fully fluorinated solvents such as perfluorooctane, aromatic solvents such as toluene and xylene; and polar solvents such as dimethylacetamide, dimethylformamide, N-methylacetamide, and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more.

[0123] When the coating composition of the present invention is used as a color resist composition, the color resist composition contains an alkali-soluble resin, a polymerizable compound, a colorant, and the like in addition to the polymer of the present invention.

[0124] The alkali-soluble resin contained in the color resist can be the same as the alkali-soluble resin contained in the photoresist composition described above.

[0125] The polymerizable compound contained in the color resist composition is a compound having a photopolymerizable functional group that can undergo a polymerization or crosslinking reaction when irradiated with active energy rays such as ultraviolet rays. Examples of the polymerizable compound include unsaturated carboxylic acids such as (meth)acrylic acid, esters of 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 polyvalent carboxylic acids and polyvalent hydroxy compounds such as the above-mentioned aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds, polymerizable compounds having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth)acryloyl group-containing hydroxy compound, and polymerizable compounds having an acid group. The polymerizable compounds may be used alone or in combination of two or more.

[0126] Examples of the esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include (meth)acrylic acid esters such as 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, and glycerol (meth)acrylate. Further, examples of the (meth)acrylic acid portion of these acrylates include itaconic acid esters in which itaconic acid is substituted, crotonic acid esters in which crotonic acid is substituted, and maleic acid esters in which maleic acid is substituted.

[0127] Examples of the esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone di(meth)acrylate, resorcinol di(meth)acrylate, and pyrogallol tri(meth)acrylate. The ester obtained by the esterification reaction of an unsaturated carboxylic acid, a polycarboxylic acid, and a polyhydroxy compound may be a single substance or a mixture. Examples of such esters include an ester obtained from (meth)acrylic acid, phthalic acid, and ethylene glycol, an ester obtained from (meth)acrylic acid, maleic acid, and diethylene glycol, an ester obtained from (meth)acrylic acid, terephthalic acid, and pentaerythritol, and an ester obtained from (meth)acrylic acid, adipic acid, butanediol, and glycerin.

[0128] Examples of the polymerizable compound having a urethane skeleton obtained by reacting the polyisocyanate compound with a (meth)acryloyl group-containing hydroxy compound include reaction products of aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; and aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate with a hydroxy compound having a (meth)acryloyl group, such as 2-hydroxyethyl (meth)acrylate and 3-hydroxy[1,1,1-tri(meth)acryloyloxymethyl]propane.

[0129] The polymerizable compound having an acid group is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and is preferably a polyfunctional polymerizable compound in which an acid group is provided by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. The aliphatic polyhydroxy compound used to prepare the polyfunctional polymerizable compound is preferably pentaerythritol or dipentaerythritol. The acid value of the polyfunctional polymerizable compound is preferably in the range of 0.1 to 40, more preferably in the range of 5 to 30, in order to improve developability, curability, etc. When two or more polyfunctional polymerizable compounds having an acid group are used in combination, or when a polyfunctional polymerizable compound having an acid group and a polyfunctional polymerizable compound not having an acid group are used in combination, it is preferable that the acid value of the mixture of polymerizable compounds be within the above range.

[0130] Specific examples of the polymerizable compound having an acid group include a mixture containing dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and a succinate ester of dipentaerythritol pentaacrylate as the main components, and this mixture is commercially available as Aronix TO-1382 (manufactured by Toagosei Co., Ltd.).

[0131] Examples of polymerizable compounds other than those mentioned above include (meth)acrylamides such as ethylene bis(meth)acrylamide; allyl esters such as diallyl phthalate; and compounds having a vinyl group such as divinyl phthalate.

[0132] In the color resist composition, the content of the polymerizable compound is preferably in the range of 5 to 80 mass % of the total solid content of the color resist composition, more preferably in the range of 10 to 70 mass %, and even more preferably in the range of 20 to 50 mass %.

[0133] The colorant for the color resist composition is not particularly limited as long as it is capable of imparting color, and may be, for example, a pigment or a dye. The pigment may be either an organic pigment or an inorganic pigment. Examples of the organic pigment include red, green, blue, yellow, purple, orange, and brown pigments. Examples of the chemical structure of the organic pigment include azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. Examples of the inorganic pigment include barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, and chromium oxide. In addition, "CI" below stands for color index.

[0134] Examples of the red pigment include CI Pigment Red 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, and 53:2. , 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, 233 3, 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 is preferred, and CI Pigment Red 177, 209, 224, or 254 is more preferred.

[0135] Examples of the green pigment 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, and 58 are preferred.

[0136] Examples of the blue pigment 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 is preferred, and CI Pigment Blue 15:6 is more preferred.

[0137] Examples of the yellow pigment 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, 191:1, 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 is preferred, and CI Pigment Yellow 83, 138, 139, 150, or 180 is more preferred.

[0138] Examples of the purple pigment 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.

[0139] Examples of the orange pigment 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.

[0140] The three primary color pixels of color filters used in liquid crystal display devices and organic EL display devices are red (R), green (G), and blue (B). Therefore, the red, green, and blue pigments are used as the main components, and organic pigments of colors such as yellow, purple, and orange may be used to adjust the hue in order to improve color reproducibility.

[0141] The average particle size of the organic pigment is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.3 μm or less, in order to enhance the brightness of color liquid crystal displays and organic EL display devices. The organic pigment is preferably used after being subjected to a dispersion treatment so as to have such an average particle size. The average primary particle size of the organic pigment is preferably 100 nm or less, more preferably 50 nm or less, even more preferably 40 nm or less, and particularly preferably in the range of 10 to 30 nm. The average particle size of the organic pigment is measured using a dynamic light scattering particle size distribution analyzer, and can be measured using, for example, Nanotrac particle size distribution analyzers "UPA-EX150" and "UPA-EX250" manufactured by Nikkiso Co., Ltd.

[0142] When the color resist composition is used to form a black matrix (BM), the colorant is not particularly limited as long as it is black, and examples thereof include carbon black, lamp black, acetylene black, bone black, thermal black, channel black, furnace black, graphite, iron black, titanium black, etc. Among these, carbon black and titanium black are preferred from the viewpoint of light-shielding rate and image characteristics. In addition, two or more organic pigments may be mixed to produce a black color.

[0143] Commercially available carbon black products include, for example, 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, #960, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600, #3050, #3150, and # 3250, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, and OIL31B manufactured by Evonik Degussa Japan Co., Ltd., and Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, and Printex A, Print ex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack 350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170, and examples thereof include Monarch 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 250, REGAL 250R, REGAL 330, REGAL 400R, REGAL 55R0, REGAL 660R, and BLACK manufactured by Cabot Japan Co., Ltd.Examples include PEARLS480, PEARLS130, VULCAN XC72R, and ELFTEX-8, and examples thereof include RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, and RAVEN 1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000, and the like.

[0144] Among the above carbon blacks, resin-coated carbon black is preferred as it has the high optical density and high surface resistivity required for the black matrix of a color filter.

[0145] Examples of commercially available titanium black include titanium black 10S, 12S, 13R, 13M, and 13M-C manufactured by Mitsubishi Materials Corporation.

[0146] As a colorant used to form a black matrix (BM), two or more organic pigments may be mixed to produce a black color, and examples thereof include a black pigment made by mixing three color pigments: red, green, and blue. Colorants that can be mixed to prepare black pigments include Victoria Pure Blue (CI 42595), Auramine O (CI 41000), Catilon Brilliant Flavin (Basic 13), Rhodamine 6GCP (CI 45160), Rhodamine B (CI 45170), Safranin OK70:100 (CI 50240), Erioglaucine X (CI 42080), No. 120 / Lionol Yellow (CI 21090), Lionol Yellow GRO (CI 21090), and Shimla First Yellow. -8GF (CI 21105), Benzidine Yellow 4T-564D (CI 21095), Shimla First Red 4015 (CI 12355), Lionor Red 7B4401 (CI 15850), Firstgen Blue TGR-L (CI 74160), Lionor Blue SM (CI 26150), Lionor Blue ES (CI Pigment Blue 15:6), Lionor Red GD (CI Pigment Red 168), Lionor Green 2YS (CI Pigment Green 36), etc.

[0147] Other colorants that can be mixed and used to prepare a black pigment include, for example, CI Yellow Pigment 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, CI Orange Pigment 36, 43, 51, 55, 59, 61, CI Red Pigment 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, CI Violet Pigment 19, 23, 29, 30, 37, 40, 50, CI Blue Pigment 15, 15:1, 15:4, 22, 60, 64, CI Green Pigment 7, and CI Brown Pigment 23, 25, 26.

[0148] When carbon black is used as the 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 in view of good developability.

[0149] Carbon black has a particle shape that differs from that of organic pigments, etc., in that the primary particles are fused together to form what is called a structure, and fine pores may be formed on the particle surface through post-treatment. Therefore, to express the particle shape of carbon black, it is generally preferable to measure the DBP absorption (JIS K6221) and the specific surface area (JIS K6217) measured by the BET method in addition to the average particle size of the primary particles, which is determined in the same way as for the organic pigments, and use these as indicators of the structure and pore volume. The dibutyl phthalate (DBP) absorption of carbon black is preferably in the range of 40 to 100 cm3 / 100 g, more preferably in the range of 50 to 80 cm3 / 100 g, due to good dispersibility and developability. The specific surface area of ​​carbon black measured by the BET method is preferably in the range of 50 to 120 m2 / g, more preferably in the range of 60 to 95 m2 / g, due to good dispersion stability.

[0150] Examples of dyes that can be used as colorants in the color resist composition include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

[0151] Examples of the 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.

[0152] Examples of the anthraquinone dyes include CI Vat 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.

[0153] Examples of the phthalocyanine dyes include CI Pad Blue 5, examples of the quinoneimine dyes include CI Basic Blue 3 and CI Basic Blue 9, examples of the quinoline dyes include CI Solvent Yellow 33, CI Acid Yellow 3 and CI Disperse Yellow 64, and examples of the nitro dyes include CI Acid Yellow 1, CI Acid Orange 3 and CI Disperse Yellow 42.

[0154] It is preferable to use a pigment as the colorant for the color resist composition, since the resulting coating film will have excellent light resistance, weather resistance, and fastness. However, in order to adjust the hue, a dye may be used in combination with the pigment, if necessary.

[0155] In the color resist composition, the content of the colorant is preferably 1% by mass or more, more preferably in the range of 5 to 80% by mass, and even more preferably in the range of 5 to 70% by mass, based on the total solid content of the color resist composition.

[0156] When the color resist composition is used to form red (R), green (G), and blue (B) pixels of a color filter, the content of the colorant in the color resist composition is preferably in the range of 5 to 60 mass % of the total solid content of the color resist composition, and more preferably in the range of 10 to 50 mass %.

[0157] When the color resist composition is used to form a black matrix of a color filter, the content of the colorant in the color resist composition is preferably in the range of 20 to 80 mass % of the total solid content of the color resist composition, and more preferably in the range of 30 to 70 mass %.

[0158] In the color resist composition, when the colorant is a pigment, it is preferable to use the pigment as a pigment dispersion liquid prepared by dispersing the pigment in an organic solvent using a dispersant. Examples of the dispersant 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 having nitrogen atoms, acrylic block copolymers having nitrogen atoms, and urethane resin dispersants are preferred. Since these dispersants contain nitrogen atoms, the nitrogen atoms have affinity for the pigment surface, and the portions other than the nitrogen atoms increase affinity for the medium, thereby improving dispersion stability. These dispersants may be used alone or in combination of two or more.

[0159] Commercially available dispersants include the "EFKA" series (such as "EFKA 46") manufactured by BASF; the "Disperbyk" series and "BYK" series (such as "BYK-160", "BYK-161", and "BYK-2001") manufactured by BYK Japan Co., Ltd.; the "Solsperse" series manufactured by Lubrizol Japan Co., Ltd.; the "KP" series manufactured by Shin-Etsu Chemical Co., Ltd.; the "Polyflow" series manufactured by Kyoeisha Chemical Co., Ltd.; the "Disparon" series manufactured by Kusumoto Chemical Co., Ltd.; and the "Ajisper" series (such as "Ajisper PB-814") manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0160] Examples of organic solvents used in preparing the pigment dispersion include acetate-based solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; propionate-based solvents such as ethoxypropionate; aromatic solvents such as toluene, xylene, and methoxybenzene; ether-based solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, and diethylene glycol dimethyl ether; ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aliphatic hydrocarbon-based solvents such as hexane; nitrogen compound-based solvents such as N,N-dimethylformamide, γ-butyrolactam, and N-methyl-2-pyrrolidone; lactone-based solvents such as γ-butyrolactone; and carbamic acid esters. These solvents may be used alone or in combination of two or more.

[0161] The pigment dispersion liquid can be prepared by a method including a colorant kneading / dispersing step and a fine-dispersing step, or by a method including only the fine-dispersing step. In the kneading / dispersing step, the colorant, a portion of the alkali-soluble resin, and, if necessary, the dispersant are mixed and kneaded. The colorant can be dispersed by dispersing the mixture while applying a strong shear force using a kneader. Examples of machines used for kneading include two-roll mills, three-roll mills, ball mills, tron ​​mills, dispersers, kneaders, co-kneaders, homogenizers, blenders, and single- or twin-screw extruders. It is preferable that the particle size of the colorant be reduced by salt milling or the like before the above kneading.

[0162] In the fine dispersion step, a solvent is added to the composition containing the colorant obtained in the kneading and dispersion step, or a mixture of a colorant, an alkali-soluble resin, a solvent, and, if necessary, the dispersant is mixed and dispersed together with a dispersion medium such as fine particles of glass, zirconia, or ceramic using a disperser, thereby dispersing the colorant particles to a fine state close to primary particles.

[0163] From the viewpoint of improving the transmittance, contrast, etc. of the color filter, the average particle size of the primary particles of the colorant is preferably 10 to 100 nm, more preferably 10 to 60 nm. The average particle size of the colorant is measured with a dynamic light scattering particle size distribution analyzer, and can be measured with, for example, Nanotrac particle size distribution analyzers "UPA-EX150" and "UPA-EX250" manufactured by Nikkiso Co., Ltd.

[0164] [Hard Coat Layer Forming Composition] The coating composition of the present invention can be suitably used as a composition for forming a hard coat layer. The hard coat layer is a layer provided on the outermost surface of an optical control film such as a polarizing plate for the purpose of imparting scratch resistance.

[0165] When the coating composition of the present invention is used as a composition for forming a hard coat layer, the composition for forming a hard coat layer contains an active energy ray-curable compound in addition to the polymer of the present invention.

[0166] In the present invention, the "active energy ray-curable compound" refers to a compound that has the property of being cured by exposure to active energy rays such as electron beams, ultraviolet rays, visible light, etc. The active energy ray-curable compound may be in the form of a monomer, oligomer, or polymer. The ultraviolet rays mentioned above refer to active energy rays with a wavelength in the range of 10 nm or more and less than 380 nm, and the visible rays mentioned above refer to active energy rays with a wavelength of 380 nm or more and 800 nm or less.

[0167] When the active energy ray-curable compound is a resin (polymer), examples of the active energy ray-curable resin include polyester resins, (meth)acrylic resins, urethane resins, (meth)acrylic urethane resins, amide resins, silicone resins, silicate resins, epoxy resins, melamine resins, and oxetane resins. Among the above, (meth)acrylic resins, (meth)acrylic urethane resins, and epoxy resins are preferred because they have high hardness, can be cured with ultraviolet light, and are excellent in productivity, and (meth)acrylic resins and (meth)acrylic urethane resins are more preferred.

[0168] When the active energy ray-curable compound is a monomer, the active energy ray-curable monomer may be an acrylic monomer having two or more acryloyl groups, which are ultraviolet-polymerizable functional groups, and preferably an acrylic monomer having 3 to 6 acryloyl groups.

[0169] Examples of the active energy ray-curable acrylic monomer include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, EO-modified pentaerythritol tetra(meth)acrylate, PO-modified pentaerythritol tetra(meth)acrylate, and pentaerythritol tri(meth)acrylate. acrylate, trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, and the like.

[0170] The active energy ray-curable acrylic monomer is preferably pentaerythritol tetra(meth)acrylate, EO-modified pentaerythritol tetra(meth)acrylate, PO-modified pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, or tricyclodecane dimethanol di(meth)acrylate.

[0171] The active energy ray-curable compounds used may be used alone or in combination of two or more.

[0172] The content of the active energy ray-curable compound is, for example, in the range of 10 to 99 mass % of the solid content of the composition for forming a hard coat layer, and preferably in the range of 50 to 99 mass %. The term "solid content of the composition for forming a hard coat layer" means the total amount of components excluding the solvent from the composition for forming a hard coat layer when the composition for forming a hard coat layer contains a solvent.

[0173] (fine particles) When antiglare properties are also imparted to the hard coat layer, the composition for forming the hard coat layer preferably further contains fine particles, and the fine particles are dispersed in the hard coat layer. Examples of the fine particles include metal oxide fine particles such as silica, alumina, titania, zirconia, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide; organic fine particles made of transparent polymers such as polymethyl methacrylate, polystyrene, polyurethane, acrylic-styrene copolymer, benzoguanamine, melamine, and polycarbonate; glass fine particles, and silicone fine particles.

[0174] The lower limit of the average particle size of the microparticles is, for example, 0.001 μm or more. The upper limit of the average particle size of the microparticles is, for example, 10 μm or less, preferably 1 μm or less, and more preferably 0.5 μm or less. The average particle size of the microparticles can be measured using a coulometer.

[0175] The fine particles used may be of one type alone or in combination of two or more types.

[0176] The content of the fine particles is, for example, in the range of 6 to 20 parts by mass with respect to 100 parts by mass of the active energy ray-curable compound.

[0177] (Photopolymerization initiator) When the composition for forming a hard coat layer is radically curable, the composition for forming a hard coat layer preferably further contains a photopolymerization initiator. Examples of the photopolymerization initiator include an α-hydroxyacetophenone-based photopolymerization initiator, an α-aminoacetophenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, and an intramolecular hydrogen abstraction photopolymerization initiator, and preferably an α-hydroxyacetophenone-based photopolymerization initiator or an α-aminoacetophenone-based photopolymerization initiator.

[0178] Examples of commercially available photopolymerization initiators include Omnirad2959, Omnirad184, Omnirad127D, and Omnirad1173 (IGMResins), as examples of commercially available α-hydroxyacetophenone-based photopolymerization initiators, and Omnirad907 and Omnirad369E (IGMResins), as examples of commercially available α-aminoacetophenone-based photopolymerization initiators.

[0179] The content of the photopolymerization initiator is, for example, in the range of 0.1 to 15 parts by mass, preferably in the range of 1 to 10 parts by mass, more preferably in the range of 2 to 8 parts by mass, and even more preferably in the range of 3 to 6 parts by mass, relative to 100 parts by mass of the active energy ray-curable compound.

[0180] (ultraviolet absorber) The composition for forming a hard coat layer preferably further contains an ultraviolet absorber. By containing an ultraviolet absorber in the composition for forming a hard coat layer, ultraviolet absorption properties can be imparted to the resulting hard coat layer. The ultraviolet absorber may be any compound that absorbs ultraviolet light (e.g., at a wavelength of 355 nm), and examples thereof include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers, with triazine-based ultraviolet absorbers and benzotriazole-based ultraviolet absorbers being preferred. When a triazine-based ultraviolet absorber is used as the ultraviolet absorber, the triazine-based ultraviolet absorber is preferably a hydroxyphenyltriazine-based ultraviolet absorber.

[0181] The content of the ultraviolet absorber is, for example, in the range of 0.1 to 3 parts by mass, and preferably in the range of 0.5 to 2.5 parts by mass, relative to 100 parts by mass of the active energy ray-curable compound.

[0182] (solvent) The hard coat layer-forming composition may contain a solvent for the purpose of adjusting the viscosity and the like to provide coating suitability. Examples of the solvent include dibutyl ether, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3-dioxolane, 1,3,5-trioxane, tetrahydrofuran, anisole, phenetole, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, acetone, methyl ethyl ketone (MEK), diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, 2-methoxymethyl acetate, 2-ethoxymethyl acetate, 2-ethoxyethyl acetate, 2-ethoxymethyl ... Examples of suitable alcohols include methyl alcohols such as ethyl propionate, 2-methoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 1,2-diacetoxyacetone, acetylacetone, diacetone alcohol, methyl acetoacetate, and ethyl acetoacetate, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, cyclohexyl alcohol, isobutyl acetate, methyl isobutyl ketone (MiBK), 2-octanone, 2-pentanone, 2-hexanone, ethylene glycol ethyl ether, ethylene glycol isopropyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, ethyl carbitol, butyl carbitol, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, benzene, toluene, and xylene.

[0183] The solvents used may be one type alone or two or more types in combination.

[0184] The content of the solvent may be appropriately determined so as to obtain a desired viscosity, and may be set, for example, so that the solid content of the composition for forming a hard coat layer falls within the range of 5 to 90% by mass.

[0185] (Other additives) In addition to the above-mentioned components, the composition for forming a hard coat layer may optionally contain other additives such as a plasticizer, an infrared absorber, a colorant (pigment, dye, etc.), a fluorescent brightener, a dispersant, a heat stabilizer, a light stabilizer, an antistatic agent, an antioxidant, etc. The content of these other additives may be appropriately determined depending on the purpose and application.

[0186] The method for producing the composition for forming a hard coat layer is not particularly limited, and the composition can be produced by a known method. For example, the above-mentioned components may be mixed all at once, or may be mixed in portions and in stages.

[0187] (Hard coat layer) The hard coat layer can be formed by applying the composition for forming a hard coat layer onto a substrate and curing the resulting coating by irradiating it with active energy rays such as electron beams, ultraviolet rays, or visible light. When the active energy rays are ultraviolet rays, the irradiation intensity of the ultraviolet rays is, for example, 10 to 5,000 mW / cm 2 The irradiation dose is preferably in the range of 10 to 10,000 mJ / cm 2 It is recommended to set the range as follows.

[0188] The thickness of the hard coat layer is, for example, in the range of 1 μm to 30 μm, preferably in the range of 3 μm to 15 μm, and more preferably in the range of 5 μm to 12 μm.

[0189] The substrate is not particularly limited, but examples thereof include cellulose ester films, polycarbonate films, polyester films such as polyethylene terephthalate and polyethylene naphthalate, (meth)acrylic films such as polymethyl methacrylate, styrene copolymer films such as polystyrene and acrylonitrile-styrene copolymer, and cyclic polyolefin films.

[0190] The thickness of the substrate may be, for example, in the range of 20 μm to 1000 μm. When the substrate is a cellulose ester film, the thickness of the cellulose ester film is preferably in the range of 20 μm to 70 μm.

[0191] (polarizing plate) The polarizing plate has a polarizer and a hard coat layer.

[0192] (polarizer) The polarizer may be one in which a dichroic dye is adsorbed and aligned in a layer containing a polyvinyl alcohol (hereinafter sometimes referred to as "PVA")-based resin.

[0193] Known polarizers can be used, and examples thereof include a film formed by dyeing a PVA-based resin film with a dichroic dye and uniaxially stretching the dye; and a film formed by applying a coating liquid containing a PVA-based resin to a substrate, dyeing the PVA-based resin layer of the laminate with a dichroic dye, and uniaxially stretching the laminate.

[0194] The polarizer is formed from, for example, a PVA resin obtained by saponifying a polyvinyl acetate resin. Examples of the polyvinyl acetate resin include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate with other copolymerizable monomers, such as unsaturated carboxylic acids, olefins such as ethylene, vinyl ethers, and unsaturated sulfonic acids.

[0195] The PVA resin may be modified, for example, polyvinyl formal, polyvinyl acetal, polyvinyl butyral, etc., modified with aldehydes.

[0196] The saponification degree of the PVA resin is preferably 85 mol % or more, more preferably 90 mol % or more, and even more preferably 99 mol % to 100 mol %. The degree of polymerization of the PVA-based resin is, for example, in the range of 1,000 to 10,000, and preferably in the range of 1,500 to 5,000.

[0197] The polarizer preferably exhibits absorption dichroism at any wavelength between 380 nm and 780 nm. The single transmittance of the polarizer is, for example, 41.0% or more, preferably in the range of 43.0% to 46.0%, and more preferably in the range of 44.5% to 46.0%. The degree of polarization of the polarizer is preferably 97.0% or more, more preferably 99.0% or more, and even more preferably 99.9% or more.

[0198] The thickness of the polarizer is, for example, in the range of 5 μm to 50 μm, preferably in the range of 5 μm to 40 μm, and more preferably in the range of 8 μm to 30 μm.

[0199] The polarizing plate may be a laminate having a polarizer and a hard coat layer, and may have other layers. The layer structure of the polarizing plate may be, for example, a polarizer / adhesive layer / protective layer / hard coat layer, and a layer having an optical function, such as a retardation layer, may be further laminated on the hard coat layer.

[0200] (protective layer) The protective layer may be a known one, and examples thereof include transparent resin films such as cellulose-based resins such as triacetyl cellulose (TAC), polyester-based resins, polyvinyl alcohol-based resins, polycarbonate-based resins, polyamide-based resins, polyimide-based resins, polyethersulfone-based resins, polysulfone-based resins, polystyrene-based resins, polynorbornene-based resins, polyolefin-based resins, (meth)acrylic resins, and acetate-based resins.

[0201] The thickness of the protective layer is, for example, in the range of 1 to 300 μm, preferably in the range of 5 μm to 200 μm, more preferably in the range of 10 μm to 100 μm, and even more preferably in the range of 10 μm to 60 μm.

[0202] (adhesive layer) The adhesive constituting the adhesive layer may be an adhesive that is applicable to optical applications, and examples of such adhesives include water-based adhesives and photo-curable adhesives.

[0203] As the water-based adhesive, a water-based adhesive containing a PVA-based resin (PVA-based adhesive) is preferably used. The average degree of polymerization of the PVA resin contained in the aqueous adhesive is, for example, in the range of 100 to 5,500, and preferably in the range of 1,000 to 4,500, from the viewpoint of adhesiveness. The average degree of saponification of the PVA resin contained in the aqueous adhesive is, from the viewpoint of adhesiveness, for example, in the range of 85 mol % to 100 mol %, and preferably in the range of 90 mol % to 100 mol %.

[0204] The PVA resin contained in the aqueous adhesive is preferably a PVA resin containing an acetoacetyl group, and the degree of acetoacetyl group modification of the acetoacetyl group-containing PVA resin is, for example, 0.1 mol% or more, and preferably in the range of 0.1 mol% to 20 mol%. The concentration of the PVA resin contained in the water-based adhesive is, for example, in the range of 0.1% by mass to 15% by mass, and preferably in the range of 0.5% by mass to 10% by mass.

[0205] The aqueous adhesive containing the PVA resin may further contain a crosslinking agent, such as a water-soluble epoxy compound, a dialdehyde, or an isocyanate. When the PVA resin is an acetoacetyl group-containing PVA resin, the crosslinking agent is preferably one or more selected from glyoxal, glyoxylates, and methylolmelamine.

[0206] The water-based adhesive may contain an organic solvent, which is preferably an alcohol because it is miscible with water, and among alcohols, methanol and / or ethanol are preferred. When the aqueous adhesive contains alcohol, the concentration of the alcohol is, for example, in the range of 10% to 70% by mass, preferably in the range of 15% to 60% by mass, and more preferably in the range of 20% to 60% by mass.

[0207] Photocurable adhesives are adhesives that harden when irradiated with active energy rays including ultraviolet rays, and examples thereof include compositions containing photopolymerizable monomers such as photocurable epoxy monomers, photocurable acrylic monomers, and photocurable urethane monomers, and oligomers derived from these monomers, as well as substances that generate active species such as neutral radicals, anion radicals, and cation radicals when irradiated with active energy rays.

[0208] The thickness of the adhesive layer is, for example, in the range of 0.01 to 10 μm, preferably in the range of 0.01 to 5 μm, more preferably in the range of 0.01 to 2 μm, and even more preferably in the range of 0.01 to 1 μm.

[0209] (optical functional layer) The optical function layer is a layer that adds an optical function to the polarizing plate, and an example of such a layer is a retardation layer. Examples of the retardation layer include a layer that imparts a λ / 2 retardation, a layer that imparts a λ / 4 retardation (positive A plate), and a positive C plate. When the polarizing plate has a layer that imparts a λ / 4 retardation as an optically functional layer, the polarizing plate can be a circular polarizing plate.

[0210] The optically functional layer may include an alignment layer and a substrate, or may have two or more liquid crystal layers, two or more alignment layers, and two or more substrates. The protective layer may also serve as a retardation layer, or a retardation layer may be laminated separately from the protective layer. The retardation layer may be laminated on the polarizing plate via a pressure-sensitive adhesive layer, which will be described later.

[0211] Examples of the retardation layer include a birefringent film made of a stretched film of a light-transmitting thermoplastic resin, and a liquid crystal layer formed on a substrate film of a cellulose ester resin such as triacetyl cellulose.

[0212] Examples of the thermoplastic resin constituting the retardation layer include polycarbonate-based resins, polyester carbonate-based resins, polyester-based resins, polyvinyl acetal-based resins, polyarylate-based resins, cyclic olefin-based resins, cellulose-based resins, polyvinyl alcohol-based resins, polyamide-based resins, polyimide-based resins, polyether-based resins, polystyrene-based resins, and acrylic-based resins.

[0213] When the optical functional layer is a retardation layer, the thickness of the retardation layer may be appropriately determined depending on the required optical properties, and is, for example, in the range of 50 to 300 μm.

[0214] Examples of other optical functional layers include a light collecting plate, a brightness enhancing film, a reflective layer (reflective film), a semi-transmissive reflective layer (semi-transmissive reflective film), a light diffusing layer (light diffusing film), and an anti-reflection film.

[0215] (Adhesive layer) A pressure-sensitive adhesive layer may be used for laminating the optical functional layer. The pressure-sensitive adhesive layer is a layer used for bonding the optical functional layer, and is made of a pressure-sensitive adhesive composition containing, as a base polymer, a pressure-sensitive adhesive resin such as a (meth)acrylic resin, a rubber resin, a urethane resin, an ester resin, a silicone resin, or a polyvinyl ether resin. The pressure-sensitive adhesive composition may be either a photocurable or a thermosetting type.

[0216] Examples of the (meth)acrylic resin used in the pressure-sensitive adhesive layer include polymers or copolymers having (meth)acrylic acid esters as monomers, such as butyl (meth)acrylate, ethyl (meth)acrylate, isooctyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. The (meth)acrylic resin may further be copolymerized with a polar monomer. Examples of the polar monomer include monomers having a carboxyl group, a hydroxyl group, an amide group, an amino group, an epoxy group, or the like, such as (meth)acrylic acid, 2-hydroxypropyl (meth)acrylate, hydroxyethyl (meth)acrylate, (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylate, and glycidyl (meth)acrylate.

[0217] The adhesive composition forming the adhesive layer preferably contains a crosslinking agent in addition to the adhesive resin. Examples of the crosslinking agent include metal compounds, polyamine compounds, polyepoxy compounds, polyols, and polyisocyanate compounds.

[0218] The thickness of the pressure-sensitive adhesive layer is, for example, in the range of 1 μm to 200 μm, preferably in the range of 2 μm to 100 μm, more preferably in the range of 2 μm to 80 μm, and even more preferably in the range of 3 μm to 50 μm.

[0219] The polarizing plate can be produced by a known method, for example, by forming a hard coat layer on a protective layer and bonding the protective layer having the hard coat layer to a polarizer via an adhesive layer.

[0220] Polarizing plates are suitably used in image display devices, and examples of such image display devices include liquid crystal displays, electroluminescence (EL) displays, plasma displays (PDs), and field emission displays (FEDs).

[0221] The coating method for the coating composition of the present invention can be any known and commonly used coating method, and examples thereof include methods such as a slit coater, a slit and spin coater, a spin coater, a roll coater, electrostatic coating, a bar coater, a gravure coater, a die coater, a knife coater, inkjet coating, dipping coating, spray coating, shower coating, screen printing, gravure printing, offset printing, and reverse coating.

[0222] As the coating composition, a paint composition, a photoresist composition, a color resist composition, and a hard coat layer-forming composition have been exemplified above, but the coating composition is not limited to these.

[0223] Specific examples of uses of the coating composition of the present invention include anti-glare (AG) hard coating materials, anti-reflection (LR) coating materials, low refractive index layer coating materials, high refractive index layer coating materials, clear hard coating materials, and polymerizable liquid crystal coating materials, which are coating materials for various display screens such as liquid crystal displays (hereinafter abbreviated as "LCD"), plasma displays (hereinafter abbreviated as "PDP"), organic light-emitting diode displays (hereinafter abbreviated as "OLED"), and quantum dot displays (hereinafter abbreviated as "QDD"); color resists, inkjet inks, printing inks, or paints for forming each pixel such as RGB in color filters (hereinafter abbreviated as "CF") of LCDs, etc.; black resists, inkjet inks, printing inks, or paints for forming black matrices, black column spacers, and black photospacers in CFs of LCDs, etc.; transparent protective film paints for protecting the CF surfaces used in CFs of LCDs, etc.; resin compositions for liquid crystal materials, column spacers, and photospacers in LCDs; resin compositions for pixel partition walls of LCDs, PDPs, OLEDs, QDDs, etc., positive photoresists for forming electrodes, protective Films, insulating films, plastic housings, paints for plastic housings, bezel (frame) inks; prism sheets and light diffusion films used as backlight components for LCDs; paints for organic insulating films in LCD liquid crystal TFT arrays; protective coating materials for the internal polarizer surface of LCDs; phosphors for PDPs; organic EL materials and encapsulants (protective films, gas barriers) for OLEDs; quantum dot inks, encapsulants, and protective films for QDDs; high-refractive index lenses, low-refractive index encapsulants, and LED pixels for micro (mini) LED displays; positive photoresists, chemically amplified photoresists, anti-reflective films, and other materials used in semiconductor manufacturing. Layer materials (SOC, SOG), underlayer films, buffer coats, developers, rinse solutions, pattern collapse prevention agents, polymer residue removers, cleaning agents and other chemicals, nanoimprint release agents; resin compositions for semiconductor post-processing or printed wiring boards (epoxy resins, phenolic resins, polyphenylene ether resins, liquid crystal polymers, polyimide resins, bismaleimide resins, bisallylnadiimide resins, benzoxazine resins and other resin compositions), copper-clad laminates, resin-coated copper foils, build-up films, passivation films, interlayer insulating films, flexible copper-clad laminates, dry film resists;Color resists for image sensors; liquid repellents for solder flux; dispersants, paints, and green sheets for multilayer ceramic capacitors; cathode materials, anode materials, separators, and electrolytes for lithium-ion batteries; automotive exterior paints, rubber, elastomers, glass, vapor deposition anchor coats, headlamp lenses, solid lubricant paints, heat dissipation substrates, interior paints, and repair paints; wallpaper, flooring, kitchen components, bathroom and toilet components for residential facilities; inkjet inks for printed materials, offset printing inks, gravure printing inks, screen printing inks, photoresists for the printing plate manufacturing process, photosensitive materials for lithographic printing plates (PS plates), packaging adhesives, and ballpoint pen inks; primers for easily adhering plastic films; water repellents for textiles; anti-diffusion agents for grease; cleaning solutions for cleaning the surfaces of various products or parts; hard coating materials for optical recording media such as CDs, DVDs, and Blu-ray discs; smartphones or Examples of suitable applications include paints or hard coatings for mobile phone housings or screens; hard coatings for transfer films for insert molds (IMD, IMF); release films; paints or coatings for various plastic molded products such as home appliance housings; printing inks or paints for various building materials such as decorative panels; coatings for residential window glass; woodworking paints for furniture; coatings for artificial and synthetic leather; coatings for rubber rollers in office equipment such as copy machines and printers; coatings for the glass of reading parts in office equipment such as copy machines and scanners; optical lenses or coatings for cameras, video cameras, glasses, contact lenses, etc.; coatings for watch crystals and glass such as wristwatches; coatings for windows of various vehicles such as automobiles and railway cars; anti-reflective coatings for solar cell cover glass or films; paints or coatings for FRP bathtubs; PCMs for metal building materials or home appliances; and single-layer or multi-layer coating compositions for photofabrication processes. [Example]

[0224] The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to the following examples.

[0225] In the examples and comparative examples, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​calculated in terms of polystyrene based on gel permeation chromatography (GPC) measurements. The GPC measurement conditions are as follows:

[0226] [GPC measurement conditions] Measurement equipment: Tosoh Corporation's high-speed GPC equipment "HLC-8320GPC" Column: Tosoh Corporation "TSKGUARD COLUMN Super HZ-L" + Tosoh Corporation "TSKgel Super HZM-N" + Tosoh Corporation "TSKgel Super HZM-N" + Tosoh Corporation "TSKgel Super HZM-N" + Tosoh Corporation "TSKgel Super HZM-N" Detector: RI (differential refractometer) Data processing: Tosoh Corporation's "EcoSECDataAnalysis version 1.07" Column temperature: 40℃ Developing solvent: tetrahydrofuran Flow rate: 0.35mL / min Measurement sample: 7.5 mg of the sample was dissolved in 10 mL of tetrahydrofuran, and the resulting solution was filtered through a microfilter to prepare a measurement sample. Sample injection volume: 20 μL Standard sample: In accordance with the measurement manual for the above-mentioned "HLC-8320GPC," the following monodisperse polystyrene with known molecular weight was used.

[0227] (monodisperse polystyrene) Tosoh Corporation "A-300" Tosoh Corporation "A-500" Tosoh Corporation "A-1000" Tosoh Corporation "A-2500" Tosoh Corporation "A-5000" "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation "F-10" manufactured by Tosoh Corporation "F-20" manufactured by Tosoh Corporation "F-40" manufactured by Tosoh Corporation "F-80" manufactured by Tosoh Corporation Tosoh Corporation "F-128" Tosoh Corporation "F-288"

[0228] (Synthesis Example 1: Synthesis of Silicone-Containing Copolymer (1)) A glass flask equipped with a stirrer, thermometer, condenser, and dropping device was charged with 200.0 g of propylene glycol monomethyl ether as a solvent and heated to 105°C while stirring under a nitrogen stream. Next, a monomer polymerization initiator solution containing 40.0 g of a silicone-containing polymerizable monomer (weight average molecular weight 1,000) represented by the following formula, 60.0 g of polyethylene glycol dimethacrylate (with approximately 4 repeating ethylene oxide chains), and 15.0 g of the polymerization initiator t-butylperoxy-2-ethylhexanoate dissolved in 150.0 g of propylene glycol monomethyl ether was placed in the dropping device, and added dropwise over 2 hours while maintaining the temperature inside the flask at 105°C. After the addition was complete, the mixture was allowed to react for 5 hours at 105°C under a nitrogen stream. After the reaction was completed, the solvent was removed under reduced pressure to obtain a silicone-containing copolymer (1).

[0229] [ka] (In the general formula (a1-1-1), the number average of x1 is 10.)

[0230] The molecular weight of the obtained copolymer (1) was measured by GPC and found to be a weight average molecular weight (Mw) of 7000. Based on the raw material charging ratio, the content of the silicone-containing polymerizable monomer in the copolymer (1) was 40% by mass.

[0231] (Synthesis Example 2: Synthesis of Silicone-Containing Copolymer (2)) A glass flask equipped with a stirrer, thermometer, condenser, and dropping device was charged with 30.0 g of dipropylene glycol methyl ether acetate as a solvent and heated to 110°C while stirring under a nitrogen stream. Next, a monomer polymerization initiator solution prepared by dissolving 12.5 g of silicone dimethacrylate monomer (number average molecular weight: 1,000) represented by the following general formula (A1), 12.5 g of polyethylene glycol dimethacrylate (repeating number of ethylene oxide chains: approximately 9), and 7.5 g of polymerization initiator t-butylperoxy-2-ethylhexanoate in 195.0 g of dipropylene glycol methyl ether acetate was placed in the dropping device, and added dropwise over 2 hours while maintaining the flask at 110°C. After the addition was complete, the mixture was allowed to react for 5 hours at 110°C under a nitrogen stream. After the reaction was completed, the solvent was removed by distillation under reduced pressure to obtain a silicone-containing copolymer (2).

[0232] [ka]

[0233] The molecular weight of the obtained copolymer (2) was measured by GPC and found to be a weight average molecular weight (Mw) of 37,000. Based on the raw material charging ratio, the content of the silicone-containing polymerizable monomer in copolymer (2) was 50% by mass.

[0234] (Synthesis Example 3: Synthesis of Silicone-Containing Copolymer (3)) A glass flask equipped with a stirrer, thermometer, condenser, and dropping device was charged with 30.0 g of dipropylene glycol methyl ether acetate as a solvent and heated to 100°C while stirring under a nitrogen stream. Next, a monomer polymerization initiator solution containing 15.0 g of 3-methacryloyloxypropyltris(trimethylsiloxy)silane (molecular weight 423), 13.8 g of methoxypolyethylene glycol acrylate (approximately 9 repeating ethylene oxide chains), 4.5 g of trimethylolpropane triacrylate, and 1.7 g of the polymerization initiator t-butylperoxy-2-ethylhexanoate dissolved in 103.2 g of dipropylene glycol methyl ether acetate was placed in the dropping device and added dropwise over 2 hours while maintaining the flask at 100°C. After the addition was complete, the mixture was allowed to react for 5 hours at 100°C under a nitrogen stream. After the reaction was complete, the solvent was removed under reduced pressure to obtain a silicone-containing copolymer (3).

[0235] The molecular weight of the obtained copolymer (3) was measured by GPC and found to be a weight average molecular weight (Mw) of 20,000. Based on the raw material charging ratio, the content of the silicone-containing polymerizable monomer in the copolymer (3) was 45% by mass.

[0236] (Comparative Synthesis Example 1: Synthesis of Silicone-Containing Copolymer (1')) A glass flask equipped with a stirrer, thermometer, condenser, and dropping device was charged with 100.0 g of butyl acetate as a solvent and heated to 95°C while stirring under a nitrogen stream. Next, a monomer polymerization initiator solution containing 67.0 g of 3-methacryloyloxypropyltris(trimethylsiloxy)silane (molecular weight 423), 33.0 g of polypropylene glycol monomethacrylate (with approximately 4-6 repeating propylene oxide chains), and 3.0 g of the polymerization initiator t-butylperoxy-2-ethylhexanoate dissolved in 112.5 g of butyl acetate was placed in the dropping device and added dropwise over 2 hours while maintaining the flask at 95°C. After the addition, the mixture was allowed to react for 5 hours at 95°C under a nitrogen stream. After the reaction was completed, the solvent was removed by distillation under reduced pressure to obtain silicone-containing copolymer (1').

[0237] The molecular weight of the obtained copolymer (1') was measured by GPC and found to have a weight average molecular weight (Mw) of 14,000. Based on the raw material charging ratio, the content of the silicone-containing polymerizable monomer in the copolymer (1') was 67 mass%.

[0238] Comparative Synthesis Example 2: Synthesis of Silicone-Containing Copolymer (2') A glass flask equipped with a stirrer, thermometer, condenser, and dropping device was charged with 100.0 g of propylene glycol monomethyl ether acetate as a solvent and heated to 95°C while stirring under a nitrogen stream. Next, a monomer polymerization initiator solution consisting of 33.0 g of 3-methacryloyloxypropyltris(trimethylsiloxy)silane (molecular weight 423), 67.0 g of polypropylene glycol monomethacrylate (with approximately 4-6 repeating propylene oxide chains), and 7.5 g of the polymerization initiator t-butylperoxy-2-ethylhexanoate dissolved in 112.5 g of propylene glycol monomethyl ether acetate was placed in the dropping device and added dropwise over 2 hours while maintaining the flask at 95°C. After the addition, the mixture was allowed to react for 5 hours at 95°C under a nitrogen stream. After the reaction was completed, the solvent was removed under reduced pressure to obtain a silicone-containing copolymer (2').

[0239] The molecular weight of the resulting copolymer (2') was measured by GPC and found to have a weight average molecular weight (Mw) of 10,000. Based on the raw material charging ratio, the content of the silicone-containing polymerizable monomer in the copolymer (2') was 33% by mass.

[0240] (Examples 1-3 and Comparative Examples 1-3: Formation and Evaluation of Coating Films) A coating composition for the hard coat layer was prepared by mixing and dissolving 5 parts by mass of ultraviolet-curable urethane acrylate resin ("Luxidia 17-806" manufactured by DIC Corporation, a butyl acetate solution containing 80% by mass of ultraviolet-curable urethane acrylate resin), 0.2 parts by mass of Irgacure 184 (manufactured by Ciba Specialty Chemicals), 0.02 parts by mass of the copolymer shown in Table 1 as a leveling agent, 2 parts by mass of toluene, 1 part by mass of 2-propanol, 1 part by mass of ethyl acetate, and 1 part by mass of propylene glycol monomethyl ether. The obtained coating composition for the hard coat layer was applied onto a 188 μm thick PET film using a bar coater No. 13, and then placed in a dryer set at 60° C. for 5 minutes to volatilize the solvent. The coating film on the PET film was cured with an ultraviolet curing device (under a nitrogen atmosphere, using a high-pressure mercury lamp, ultraviolet irradiation dose 200 mJ / cm). 2 The coating was cured by irradiating it with ultraviolet light using a UV lamp to prepare a hard coat film having a hard coat layer with a thickness of 8 μm on one side.

[0241] The hard coat layer of the prepared hard coat film was evaluated as follows, and the results are shown in Table 1.

[0242] (smoothness) The hard coat layer of the obtained hard coat film was visually observed, and the smoothness of the hard coat layer was evaluated according to the following criteria. ◯: Virtually no unevenness is observed on the surface of the hard coat layer. Δ: Unevenness is observed in some parts of the hard coat layer surface. ×: Unevenness is observed on the entire surface of the hard coat layer.

[0243] (water contact angle) The contact angle of the hard coat layer of the obtained hard coat film was measured 1 second after dropping 3 μL of ion-exchanged water using a contact angle measuring device (Model CA-W701, manufactured by Kyowa Interface Science Co., Ltd.) and evaluated according to the following criteria. If the water contact angle is less than 100 degrees, there will be no problem even if a protective film is attached to the hard coat layer. ○: Water contact angle is less than 100 degrees ×: Water contact angle is 100 degrees or more

[0244] (Hexadecane contact angle) The contact angle of the hard coat layer of the obtained hard coat film was measured 1 second after dropping 3 μL of hexanedecane using a contact angle measuring device (Model CA-W701, manufactured by Kyowa Interface Science Co., Ltd.) and evaluated according to the following criteria. A hexadecane contact angle of 35 degrees or more can be evaluated as having sufficient oil repellency. ◎: Hexadecane contact angle is 40 degrees or more 〇: Hexadecane contact angle is 35 degrees or more and less than 40 degrees ×: Hexadecane contact angle is less than 35 degrees

[0245] [Table 1]

[0246] The results in Table 1 confirm that the hard coat layers using the silicone-containing copolymers (1) to (3), which are the leveling agents of the present invention, exhibit sufficient oil repellency while suppressing water repellency, whereas the comparative examples do not achieve both sufficient oil repellency and suppressed water repellency.

Claims

1. - [OSi(R)] ２ ] ｘ A leveling agent containing a polymer that does not contain fluorine atoms, comprising at least a polymerizable monomer (A) having a polysiloxane structure represented by - (where R is an alkyl group having 1 to 6 carbon atoms independently, and x is the number of repetitions), and having one or more polymerizable unsaturated groups, and a polymerizable monomer (B) having two or more polymerizable unsaturated groups (wherein the polymerizable monomer (B) does not have the polysiloxane structure).

2. The leveling agent according to claim 1, wherein the polymerizable monomer (A) is one or more selected from the group consisting of a compound represented by the following general formula (A-1), a compound represented by the following general formula (A-2), a compound represented by the following general formula (A-3), and a compound represented by the following general formula (A-4). 【Chemistry 1】 (In the above general formulas (A-1) to (A-4) R １１ Each is independently an alkyl group having 1 to 6 carbon atoms or -OSi(R １５ ) ３ The group represented by (R １５ Each of these is an alkyl group having 1 to 6 carbon atoms. R １２ Each of these is an alkyl group having 1 to 6 carbon atoms, R １３ These are alkyl groups having 1 to 12 carbon atoms. R １４ is, independently of one another, a hydrogen atom or a methyl group, x represents the number of repetitions. y is an integer greater than or equal to 1, z1 and z2 are each independent integers greater than or equal to 1. z3 is an integer greater than or equal to 1, L １ It is a divalent organic group, L １１ is a z1+1 valent organic group, L １２ is a z2+1 valent organic group, L １３ is an organic group with z3+y valence, L １４ (It is a divalent organic group.)

3. The leveling agent according to claim 1, wherein the weight-average molecular weight of the polymerizable monomer (A) is in the range of 100 to 4,000.

4. The leveling agent according to claim 1, wherein the polymerizable monomer (B) is a compound represented by the following general formula (B-1). 【Chemistry 2】 (In the general formula (B-1), R ２１ This is either a hydrogen atom or a methyl group. x is an integer greater than or equal to 2, L ２１ (This is an x-valent organic group.)

5. The leveling agent according to claim 1, wherein the content of the polymerizable monomer (A) in the polymerization component is in the range of 5 to 90% by mass.

6. The leveling agent according to claim 1, wherein the content of the polymerizable monomer (B) in the polymerization component is in the range of 1 to 75% by mass.

7. The leveling agent according to claim 1, further comprising a polymerizable monomer (C) having one or more polymerizable unsaturated groups, selected from the group consisting of alkyl groups having 1 to 18 carbon atoms, aromatic groups having 6 to 18 carbon atoms, groups containing polyoxyalkylene chains, and groups containing polyester chains.

8. The leveling agent according to claim 7, wherein the polymerizable monomer (C) is one or more selected from the group consisting of a compound represented by the following general formula (C-1), a compound represented by the following general formula (C-2), a compound represented by the following general formula (C-3), a compound represented by the following general formula (C-4), and a compound represented by the following general formula (C-5). 【Transformation 3】 (In the above general formulas (C-1), (C-2), (C-3), (C-4), and (C-5), R ３１ is a hydrogen atom or a methyl group, R ３２ These are alkyl groups having 1 to 18 carbon atoms. R ３３ is a hydrogen atom or a methyl group, R ３４ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. R ３５ is a hydrogen atom or a methyl group, R ３６ This is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having an ether bond with 1 to 18 carbon atoms. R ３７ is a hydrogen atom or a methyl group, R ３８ This is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having an ether bond with 1 to 18 carbon atoms. L ３ It is a divalent organic group, R ３９ is a hydrogen atom or a methyl group, R ４０ Each of these is independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. n is an integer in the range of 1 to 4, m represents the number of repetitions, with the average value of m being in the range of 1 to 200, p is an integer in the range of 1 to 10, q represents the number of repetitions, with the average value of q being in the range of 1 to 100, and l is an integer in the range of 0 to 5.

9. The leveling agent according to claim 8, wherein the polymerizable monomer (C) comprises a compound represented by the general formula (C-2).

10. The leveling agent according to claim 7, wherein the content of the polymerizable monomer (C) in the polymerizing component is in the range of 0 to 75% by mass.

11. The leveling agent according to claim 1, wherein the weight-average molecular weight of the polymer is in the range of 2,000 to 200,000.

12. A coating composition containing the leveling agent according to any one of claims 1 to 11.

13. A resist composition containing the leveling agent according to any one of claims 1 to 11.

14. A composition for forming a hard coat layer, comprising an active energy ray curable compound and a leveling agent according to any one of claims 1 to 11.

15. An article containing the leveling agent according to any one of claims 1 to 11.

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