JP2013156333A - Antireflection paint composition and antireflection film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antireflection paint composition whereby a coating film having excellent antifouling properties and scratch resistance properties can be obtained, and an antireflection film using the antireflection paint composition.SOLUTION: An antireflection paint composition contains a low-refractive index agent (I), an active energy ray curable composition (II), and a polymerizable resin (III) having a silicone chain with a molecular weight of 2,000 or more, a fluoroalkyl group and a polymerizable unsaturated group and other than the active energy ray curable composition (II). An antireflection film contains a cured coating film of the composition.

Description

  The present invention relates to an antireflection coating composition capable of obtaining a coating film having excellent antifouling properties and scratch resistance, and an antireflection film using the antireflection coating composition.

  The surface layer of the polarizing plate, which is the outermost surface of the liquid crystal display, has an anti-glare and anti-reflective coating such as AG, AG / LR, and Clear / LR. Antifouling properties such as fingerprint resistance are required. Here, the fingerprint resistance means that the fingerprint is difficult to adhere to the article, or that the fingerprint can be easily wiped off even if the fingerprint is attached to the article. Among the coatings having antiglare properties and antireflection properties, clear / LR is excellent from the viewpoint of transparency of the coating film.

  Currently, many polarizing plates in mass production for liquid crystal display devices, in particular, are made by stretching and adsorbing dichroic materials such as iodine and dichroic dyes onto a base film made of polyvinyl alcohol film. A film in which an optically transparent protective film having mechanical strength is bonded to both surfaces or one surface of an oriented polarizing film is used. And as said protective film, a triacetyl cellulose (TAC) film is normally used. And as for the coating film which has the said anti-glare property and anti-reflective property, for example, a clear / LR layer is dozens to several on the coating-film layer (base layer) about 10 micrometers thick formed on the TAC film. It is formed as a coating film having a thickness of about 100 nm.

In order to adhere TAC to the polarizing film, it is necessary to saponify the surface of the TAC film with caustic alkali or the like and to hydrolyze a part or most of —OCOCH ₃ groups to —OH which is a hydrophilic group. . To form a coating layer having anti-glare and antireflection properties on the TAC film and to saponify it, 1. Saponify the TAC film and then form the two coating layers on one side of the film. There are methods such as saponification after forming the two coating layers on one side of the TAC film, but usually from the viewpoint of production efficiency of the polarizing plate. The way is done.

  2. In this method, in order to protect the coating layer from a saponifying agent such as caustic when the saponification treatment is performed, a method of protecting the coating layer with a protective film is known. However, in recent years, in order to improve production efficiency and reduce costs, there is a need for a coating layer that does not deteriorate the performance of the coating film even if it is exposed to the saponifying agent without protecting the coating layer with a protective film.

  A coating film having antiglare properties and antireflection properties is required to have hard coat performance, that is, scratch resistance on the surface, in addition to antireflection performance. In particular, the LR layer has a film thickness of only about several tens to several hundreds of nanometers, and stronger scratch resistance is required. As a method for improving the scratch resistance of the LR layer, a method using a hard coat material containing a polyfunctional monomer such as a polyfunctional (meth) acrylate is known. However, when this hard coat material is used, an LR layer having a surface hardness of the cured coating film improved to some extent can be obtained, but the scratch resistance is insufficient.

  Therefore, a silicone-based additive is added to the active energy ray-curable composition, or a silicone compound having a radically polymerizable unsaturated group in the molecule is added to impart slipping property to the cured coating film, resulting in resistance to resistance. It has been proposed to improve the scratch resistance (see, for example, Patent Document 1).

  However, the cured coating film obtained using the active energy ray-curable composition disclosed in Patent Document 1 has a significantly reduced slip property on the surface of the cured coating film after saponification treatment, and has sufficient scratch resistance. There was a problem that could not be obtained.

  Therefore, there has been a demand for an antireflection coating composition capable of obtaining a coating film having antireflection properties having antifouling properties and scratch resistance even after saponification treatment (strong alkali treatment).

JP 2004-182765 A

  The problem to be solved by the present invention is an antireflection coating composition capable of obtaining a coating film having excellent antifouling properties and scratch resistance even after saponification treatment, and reflection using the antireflection coating composition It is to provide a prevention film.

  As a result of intensive studies to solve the above problems, the present inventors have found that a low-refractive index agent (I) and an active energy ray-curable compound (II) have a silicone chain having a molecular weight of 2000 or more, a fluorinated alkyl group, By adding the polymerizable resin (III) having a polymerizable unsaturated group, it is possible to impart excellent antifouling property and scratch resistance to the surface of the obtained cured coating film. The present inventors have found that the antifouling property and scratch resistance do not decrease even when treated with chemicals such as the present invention, and have completed the present invention.

  That is, the present invention relates to the active energy ray curing having a low refractive index agent (I), an active energy ray-curable compound (II), and a silicone chain having a molecular weight of 2000 or more, a fluorinated alkyl group and a polymerizable unsaturated group. It is intended to provide an antireflection coating composition containing a polymerizable resin (III) other than the conductive compound (II).

  The present invention also provides an antireflection film having a cured coating film of the antireflection coating composition.

  Since the cured coating film of the antireflection coating composition of the present invention has excellent antifouling properties and scratch resistance even after saponification treatment, an antireflection film having extremely excellent antifouling properties and scratch resistance is obtained. Can be obtained. Further, an antireflection film having very excellent antifouling properties and scratch resistance can be obtained even by a process that does not involve saponification. Accordingly, the antireflection film using the antireflection coating composition of the present invention can be suitably used as the outermost film of an image display device such as a liquid crystal display (LCD), a plasma display (PDP), or an organic EL display. .

  The low refractive index agent (I) used in the present invention preferably has a refractive index of 1.44 or less, more preferably 1.40 or less. The low refractive index agent may be either inorganic or organic.

  Examples of the inorganic low refractive index agent (I) include fine particles having voids and fine metal fluoride particles. Examples of the fine particles having voids include those in which fine particles are filled with gas, and those having a porous structure containing gas inside. Specific examples include hollow silica fine particles and silica fine particles having a nanoporous structure. Examples of the metal fluoride fine particles include magnesium fluoride, aluminum fluoride, calcium fluoride, and lithium fluoride.

  Among these inorganic low refractive index agents (I), hollow silica fine particles are preferable. Further, these inorganic low refractive index agents (I) can be used alone or in combination of two or more. As these inorganic low refractive index agents (I), any of crystalline, sol, and gel can be used.

  The shape of the silica fine particles may be spherical, chain-like, needle-like, plate-like, scale-like, rod-like, fiber-like, or indefinite shape, and among these, spherical or needle-like is preferable. Moreover, when the shape is spherical, the average particle diameter of the silica fine particles is preferably 5 to 100 nm, more preferably 20 to 80 nm, and further preferably 40 to 70 nm. When the average particle diameter of the spherical fine particles is within this range, excellent transparency can be imparted to the low refractive index layer.

  On the other hand, examples of the organic low refractive index agent (I) include fine particles having voids and fluorine-containing copolymers. The fine particles having voids are preferably hollow polymer fine particles. The hollow polymer fine particles are prepared by, in an aqueous dispersion stabilizer solution, (1) at least one crosslinkable monomer, (2) a polymerization initiator, (3) a polymer obtained from at least one crosslinkable monomer, or at least one. A mixture of a copolymer of a kind of crosslinkable monomer and at least one kind of monofunctional monomer, and a poorly water-soluble solvent having low compatibility with the above (1) to (3) is dispersed and suspended. It can manufacture by performing superposition | polymerization. Here, the crosslinkable monomer is one having two or more polymerizable groups, and the monofunctional monomer is one having one polymerizable group.

  The fluorine-containing copolymer used as the organic low refractive index agent (I) is a resin having a low refractive index because the resin contains many fluorine atoms. Examples of the fluorine-containing copolymer include a copolymer using vinylidene fluoride and hexafluoropropylene as monomer raw materials.

  The ratio of each monomer that is a raw material of the fluorinated copolymer is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, further preferably 40 to 70% by mass, and hexafluorofluorovinylidene fluoride. The proportion of propylene is preferably 5 to 50% by mass, more preferably 10 to 50% by mass, and still more preferably 15 to 45%. As this other monomer, tetrafluoroethylene may be used in the range of 0 to 40% by mass.

  The fluorine-containing copolymer includes, as monomer components of other raw materials, fluoroethylene, trifluoroethylene, chlorotrifluoroethylene, 1,2-dichloro-1,2-difluoroethylene, 2-bromo-3,3, 3-trifluoroethylene, 3-bromo-3,3-difluoropropylene, 3,3,3-trifluoropropylene, 1,1,2-trichloro-3,3,3-trifluoropropylene, α-trifluoromethacrylic A polymerizable monomer having a fluorine atom such as an acid can be used. These other raw material monomer components are preferably used in the raw material monomer of the fluorine-containing copolymer in an amount of 20% by mass or less.

  The fluorine content in the fluorine-containing copolymer is preferably 60 to 70% by mass, more preferably 62 to 70% by mass, and further preferably 64 to 68% by mass. When the fluorine content of the fluorine-containing copolymer is within this range, the solubility in a solvent is good, and excellent adhesion to various substrates is exhibited. High transparency, low refractive index, excellent machine A thin film having sufficient strength can be formed.

  The molecular weight of the fluorine-containing copolymer is preferably 5,000 to 200,000, more preferably 10,000 to 100,000, in terms of polystyrene-equivalent number average molecular weight. When the molecular weight of the fluorinated copolymer is within this range, the viscosity of the resulting resin is in a range having excellent coating properties. The refractive index of the fluorinated copolymer itself is preferably 1.45 or less, more preferably 1.42 or less, and even more preferably 1.40 or less.

  The active energy ray-curable compound (II) used in the present invention is not particularly limited as long as it is a compound having a photopolymerizable functional group that can be polymerized or crosslinked by irradiation with active energy rays such as ultraviolet rays. it can.

  Examples of the active energy ray-curable compound (II) include an active energy ray-curable monomer (II-1). Examples of the monomer (II-1) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and polyethylene having a number average molecular weight in the range of 150 to 1,000. Glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) having a number average molecular weight in the range of 150 to 1000 Acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate Hydroxypivalate ester neopentyl glycol di (meth) acrylate, bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dicyclopentenyl (meth) acrylate, methyl (meth) acrylate, propyl ( (Meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, Aliphatic alkyl (meth) acrylates such as sodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, glycerol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3 -Chloro-2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, allyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2- (diethylamino) ethyl (meth) acrylate, 2- (dimethylamino) Ethyl (meth) acrylate, γ- (meth) acryloxypropyltrimethoxysilane, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxydipropylene glyco (Meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydipropylene glycol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, polybutadiene ( (Meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polystyrylethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl ( (Meth) acrylate, dicyclopentenyl (meth) acrylate, isoborni (Meth) acrylate, methoxylated tricyclodecanyloxy triene (meth) acrylate, phenyl (meth) acrylate.

  Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra ( A trifunctional or higher polyfunctional (meth) acrylate such as (meth) acrylate is preferred. These active energy ray-curable monomers (II-1) can be used alone or in combination of two or more.

  In the present invention, “(meth) acrylate” refers to one or both of methacrylate and acrylate, and “(meth) acryloyl group” refers to one or both of methacryloyl group and acryloyl group. “Acrylic acid” refers to one or both of methacrylic acid and acrylic acid.

  Moreover, active energy ray-curable resin (II-2) can also be used as the active energy ray-curable compound (II). Examples of the active energy ray-curable resin (II-2) include urethane (meth) acrylate resins, unsaturated polyester resins, epoxy (meth) acrylate resins, polyester (meth) acrylate resins, and acrylic (meth) acrylate resins. However, in the present invention, a urethane (meth) acrylate resin is particularly preferable from the viewpoint of transparency and low shrinkage.

  The urethane (meth) acrylate resin used here is a resin having a urethane bond and a (meth) acryloyl group obtained by reacting an aliphatic polyisocyanate compound or an aromatic polyisocyanate compound with a (meth) acrylate compound having a hydroxyl group. Is mentioned.

  Examples of the aliphatic polyisocyanate compound include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl- 1,5-pentane diisocyanate, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate , Hydrogenated tolylene diisocyanate, hydrogenated xylile Examples include diisocyanate, hydrogenated tetramethylxylylene diisocyanate, cyclohexyl diisocyanate, and the aromatic polyisocyanate compound includes tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, Examples include toridine diisocyanate and p-phenylene diisocyanate.

  On the other hand, examples of the acrylate compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1, Monovalent dihydric alcohols such as 5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, and hydroxypivalate neopentyl glycol mono (meth) acrylate ( Meth) acrylate; trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane (meth) acrylate, propoxylated trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate Mono- or di (meth) acrylates of trivalent alcohols such as relate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, or hydroxyl groups obtained by modifying some of these alcoholic hydroxyl groups with ε-caprolactone Mono- and di (meth) acrylates having a monofunctional hydroxyl group and tri- or more functional (meth) acryloyl such as pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. A compound having a group, or a polyfunctional (meth) acrylate having a hydroxyl group obtained by modifying the compound with ε-caprolactone; dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, poly (Meth) acrylate compounds having an oxyalkylene chain such as propylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate; polyethylene glycol-polypropylene glycol mono (meth) acrylate, polyoxybutylene-polyoxypropylene mono (meth) (Meth) acrylate compounds having a block structure oxyalkylene chain such as acrylate; random structures such as poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate and poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate And (meth) acrylate compounds having an oxyalkylene chain.

  The reaction between the aliphatic polyisocyanate compound or the aromatic polyisocyanate compound and the acrylate compound having a hydroxyl group can be performed by a conventional method in the presence of a urethanization catalyst. Specific examples of urethanization catalysts that can be used here include amines such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine, phosphines such as triphenylphosphine and triethylphosphine, dibutyltin dilaurate, octyltin trilaurate, and octyl. Examples thereof include organotin compounds such as tin diacetate, dibutyltin diacetate, and tin octylate, and organometallic compounds such as zinc octylate.

  Among these urethane acrylate resins, those obtained by reacting an aliphatic polyisocyanate compound with a (meth) acrylate compound having a hydroxyl group are excellent in transparency of the cured coating film and have good sensitivity to active energy rays. It is preferable from the viewpoint of excellent curability.

  Next, the unsaturated polyester resin is a curable resin obtained by polycondensation of α, β-unsaturated dibasic acid or acid anhydride thereof, aromatic saturated dibasic acid or acid anhydride thereof, and glycols. The α, β-unsaturated dibasic acid or its acid anhydride includes maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, and esters thereof. As aromatic saturated dibasic acid or acid anhydride thereof, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, halogenated phthalic anhydride and these Examples include esters. Examples of the aliphatic or alicyclic saturated dibasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, and esters thereof. As glycols, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, triethylene glycol, Examples include tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2-di- (4-hydroxypropoxydiphenyl) propane, and others. In addition, oxides such as ethylene oxide and propylene oxide can be used in the same manner.

  Next, as an epoxy vinyl ester resin, (meth) acrylic acid is reacted with an epoxy group of an epoxy resin such as a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, or a cresol novolak type epoxy resin. What is obtained is mentioned. These active energy ray-curable resins (B-2) can be used alone or in combination of two or more.

  The mass ratio between the low refractive index agent (I) and the active energy ray-curable compound (II) is preferably in the range of (I) :( II) = 30: 70 to 90:10, 40:60 to 80: The range of 20 is more preferable, and the range of 50:50 to 70:30 is more preferable.

  The polymerizable resin (III) used in the present invention has a silicone chain having a molecular weight of 2000 or more, a fluorinated alkyl group, and a polymerizable unsaturated group. And other than the said active energy ray hardening compound (II).

  The molecular weight of the silicone chain needs to be 2000 or more. By having a silicone chain having such a molecular weight, the sliding property of the silicone chain can be suitably expressed, and as a result, the surface friction of the coating film can be reduced. By reducing it, excellent friction resistance can be imparted. The molecular weight of the silicone chain is preferably from 2,000 to 20,000, more preferably from 5,000 to 10,000.

  The fluorinated alkyl group preferably has 4 to 6 carbon atoms because of a good balance of surface segregation, water / oil repellency and reduction of environmental load, and more preferably has 6 carbon atoms. .

  The polymerizable resin (III) used in the present invention is not limited to the production method. For example, the polymerizable unsaturated monomer (A) having a silicone chain having a molecular weight of 2000 or more and a polymerization having a fluorinated alkyl group. Polymer (P) obtained by copolymerizing polymerizable unsaturated monomer (B) and polymerizable unsaturated monomer (C) having reactive functional group (c) as essential monomer components And at least one functional group (d) having reactivity with respect to the functional group (c) and a compound (D) having a polymerizable unsaturated group can be easily produced.

  Below, each raw material used for the said method is demonstrated.

  The monomer (A) will be described. As a silicone group which the said monomer (A) has, what is represented by the following general formula (1) or (2) is mentioned, for example.

(In the formula, n is the number of repeating units and represents an integer of 25 to 300.)

  Moreover, as a polymerizable unsaturated group which the said monomer (A) has, the carbon-carbon unsaturated double bond which has radical polymerizability is preferable, and a (meth) acryloyl group, a vinyl group, a maleimide group, etc. are mentioned. . Among these, (meth) acryloyl is easy because of the availability of raw materials, the ease of controlling the compatibility with each compounding component in the active energy ray-curable composition described later, or the good polymerization reactivity. Groups are preferred.

  Specific examples of the monomer (A) include monomers represented by the following general formulas (A1) to (A2). Moreover, these monomers (A) can be used alone or in combination of two or more.

(In the formula, ^{R 1} represents a hydrogen atom or a methyl ^{group, R 3,} R 10 ^{~R 17} each independently represent an alkyl group or a phenyl group having 1 to 18 carbon ^atoms, R ^2, R 7 ^{~R 9} And R ^{18 to} R ²⁰ each independently represents an alkyl group having 1 to 8 carbon atoms or a phenyl group, and m and l each independently represents an integer of 1 to 6, and n, r, s, t, v, w, x, y, and z each independently represents an integer of 25 to 250.)

  The polymerizable unsaturated monomer (B) having the fluorinated alkyl group will be described. This monomer (B) is a monomer having a fluorinated alkyl group. Moreover, as a polymerizable unsaturated group which the said monomer (B) has, the carbon-carbon unsaturated double bond which has radical polymerizability is preferable, and a (meth) acryloyl group, a vinyl group, a maleimide group, etc. are mentioned. . Among these, (meth) acryloyl is easy because of the availability of raw materials, the ease of controlling the compatibility with each compounding component in the active energy ray-curable composition described later, or the good polymerization reactivity. Groups are preferred. As this monomer (A), what is represented by following General formula (1) is mentioned, for example.

（上記一般式（１）中、Ｒは水素原子又はメチル基を表し、Ｌは、下記式（Ｌ−１）〜（Ｌ−１０）のいずれか１つの基を表し、Ｒｆは下記式（Ｒｆ−１）〜（Ｒｆ−７）のいずれか１つの基を表す。）

(In the general formula (1), R represents a hydrogen atom or a methyl group, L represents any one of the following formulas (L-1) to (L-10), and Rf represents the following formula (Rf -1) to any one of (Rf-7).

  N in the above formulas (L-1), (L-3), (L-5), (L-6) and (L-7) represents an integer of 1 to 8. M in the above formulas (L-8), (L-9) and (L-10) represents an integer of 1 to 8, and n represents an integer of 0 to 8. Rf ″ in the above formulas (L-6) and (L-7) represents any one of the following formulas (Rf-1) to (Rf-7).

  N in the above formulas (Rf-1) to (Rf-4) represents an integer of 4 to 6. M in the said formula (Rf-5) is an integer of 1-5, n is an integer of 0-4, and the sum total of m and n is 4-5. M in the above formula (Rf-6) is an integer of 0 to 4, n is an integer of 1 to 4, p is an integer of 0 to 4, and the total of m, n, and p is 4 to 4 5.

  Moreover, the following monomers (B-1)-(B-11) etc. are mentioned as a specific example of the said monomer (B). These monomers (B) can be used alone or in combination of two or more.

（式中のｎは３〜５の整数を表す。）

(In the formula, n represents an integer of 3 to 5.)

  The polymerizable unsaturated monomer (C) will be described. Examples of the functional group (c) of the compound (C) include a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, and an acid anhydride group. The polymerizable unsaturated group of the monomer (C) is preferably a carbon-carbon unsaturated double bond having radical polymerizability, and more specifically, a vinyl group, a (meth) acryloyl group, a maleimide. A (meth) acryloyl group is more preferable from the viewpoint of easy polymerization.

  Specific examples of the monomer (C) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, N- (2-hydroxyethyl) (meth) acrylamide, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene Glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, lactone-modified (meth) acrylate having a hydroxyl group at the terminal Unsaturated monomer having a hydroxyl group such as relate; 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate, 1,1-bis ((meth) acryloyloxymethyl) Isocyanate group-containing unsaturated monomers such as ethyl isocyanate; Epoxy group-containing unsaturated monomers such as glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether; (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid Carboxyl group-containing unsaturated monomers such as 2- (meth) acryloyloxyethylphthalic acid, maleic acid and itaconic acid; acid anhydrides having an unsaturated double bond such as maleic anhydride and itaconic anhydride It is done. These monomers (C) can be used alone or in combination of two or more.

  Further, when producing the polymer (P) which is an intermediate of the polymerizable resin of the present invention, in addition to the compound (A), the monomer (B) and the monomer (C), Other polymerizable unsaturated monomers that can be copolymerized may be used. Examples of such other polymerizable unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n -Pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate , Dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylates such as (meth) acrylate having a polyoxyalkylene chain; styrene, α-methylstyrene, p-methylstyrene , - aromatic vinyl such as methoxystyrene; maleimide, methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, maleimide such as cyclohexyl maleimide.

  Next, the compound (D) will be described. Examples of the functional group (d) possessed by the compound (D) include a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, and an acid anhydride group. When the reactive functional group (c) of the monomer (C) is a hydroxyl group, examples of the functional group (d) include an isocyanate group, a carboxyl group, a carboxylic acid halide group, and an epoxy group. When the group (c) is an isocyanate group, examples of the functional group (d) include a hydroxyl group. When the reactive functional group (c) is an epoxy group, the functional group (d) includes a carboxyl group and a hydroxyl group. In the case where the reactive functional group (c) is a carboxyl group, examples of the functional group (d) include an epoxy group and a hydroxyl group. These may be a combination of a plurality of functional groups. Among these combinations, the reactive functional group (c) is a hydroxyl group and the functional group (d) is an isocyanate group, the reactive functional group (c) is an epoxy group, and the functional group (d) is A combination of carboxyl groups is preferred.

  The polymerizable unsaturated group possessed by the compound (D) is preferably a carbon-carbon unsaturated double bond having radical polymerizability, more specifically, a vinyl group, a (meth) acryloyl group, a maleimide group, and the like. (Meth) acryloyl group is more preferable from the viewpoint of good curability in the active energy ray-curable composition described below.

  Specific examples of the compound (D) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, N- (2-hydroxyethyl) (meth) acrylamide, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (Meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, lactone-modified (meth) acrylate having a hydroxyl group at the terminal Unsaturated monomer having a hydroxyl group such as relate; 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate, 1,1-bis ((meth) acryloyloxymethyl) Unsaturated monomers having an isocyanate group such as ethyl isocyanate; unsaturated monomers having an epoxy group such as glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether; (meth) acrylic acid, 2- (meth) acryloyloxyethyl Carboxyl group-containing unsaturated monomers such as succinic acid, 2- (meth) acryloyloxyethylphthalic acid, maleic acid and itaconic acid; acid anhydrides having unsaturated double bonds such as maleic anhydride and itaconic anhydride Is mentioned. Moreover, 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate etc. can also be used as what has a several polymerizable unsaturated group. These compounds (D) can be used alone or in combination of two or more.

  Among the specific examples of the compound (D), 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate are preferable. Hydroxybutyl acrylate, 1,4-cyclohexanedimethanol monoacrylate, N- (2-hydroxyethyl) acrylamide, 2-acryloyloxyethyl isocyanate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate 4-hydroxybutyl acrylate glycidyl ether Acrylic acid is preferred.

  Next, a more specific method for producing the polymerizable resin (III) used in the present invention using the above-mentioned raw materials will be described.

  The method for producing the polymer (P), which is an intermediate of the polymerizable resin (III), includes the compound (A), the monomer (B) and the monomer (C), and further if necessary. A method of polymerizing other polymerizable unsaturated monomers in an organic solvent using a polymerization initiator can be mentioned. As the organic solvent used here, ketones, esters, amides, sulfoxides, ethers, hydrocarbons are preferable. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, Examples include propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These are appropriately selected in consideration of boiling point, compatibility, and polymerizability. Examples of the polymerization initiator include peroxides such as benzoyl peroxide and azo compounds such as azobisisobutyronitrile. Furthermore, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethylthioglycolic acid, octylthioglycolic acid and the like can be used as necessary.

  The polymer (P) obtained as described above is reacted with a functional group (d) having reactivity with the reactive functional group (c) and a compound (D) having a polymerizable unsaturated group. Thus, the polymerizable resin (III) used in the present invention is obtained.

  The method of reacting the compound (D) with the polymer (P) may be performed under the condition that the polymerizable unsaturated group of the compound (D) or the like does not polymerize. For example, the temperature condition is 30 to 120 ° C. It is preferable to adjust the reaction to the range. This reaction is preferably carried out in the presence of a catalyst or a polymerization inhibitor, and if necessary in the presence of an organic solvent.

  For example, when the reactive functional group (c) is a hydroxyl group and the functional group (d) is an isocyanate group, p-methoxyphenol, hydroquinone, 2,6-di-t-butyl is used as a polymerization inhibitor. Using 4-methylphenol or the like, and using dibutyltin dilaurate, dibutyltin diacetate, tin octylate, zinc octylate, etc. as the urethanization reaction catalyst, the reaction temperature is 40 to 120 ° C., particularly 60 to 90 ° C. The method of making it preferable is. When the reactive functional group (c) is an epoxy group and the functional group (d) is a carboxyl group, or the reactive functional group (c) is a carboxyl group, the functional group When (d) is an epoxy group, p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol or the like is used as a polymerization inhibitor, and triethylamine or the like is used as an esterification reaction catalyst. Using tertiary amines, quaternary ammoniums such as tetramethylammonium chloride, tertiary phosphines such as triphenylphosphine, quaternary phosphoniums such as tetrabutylphosphonium chloride, etc., reaction temperature 80 to 130 ° C. In particular, the reaction is preferably performed at 100 to 120 ° C.

  The organic solvent used in the above reaction is preferably ketones, esters, amides, sulfoxides, ethers, hydrocarbons, specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, Examples include propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These may be appropriately selected in consideration of the boiling point and compatibility.

  The polymerizable resin (III) used in the present invention obtained as described above can prevent gelation during production and has excellent antifouling properties, so that its number average molecular weight (Mn) is 1,000 to 10,000. Is preferably in the range of 000, and more preferably in the range of 1,500 to 8,000. The weight average molecular weight (Mw) is preferably in the range of 2,000 to 50,000, more preferably in the range of 3,000 to 20,000.

  Here, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values converted to polystyrene based on gel permeation chromatography (hereinafter abbreviated as “GPC”) measurement. The measurement conditions for GPC are as follows.

[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HHR-H” manufactured by Tosoh Corporation (6.0 mm ID × 4 cm)
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
Detector: ELSD ("ELSD2000" manufactured by Oltech Japan Co., Ltd.)
Data processing: “GPC-8020 Model II data analysis version 4.30” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min Sample: A 1.0% by mass tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (5 μl).
Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II Data Analysis Version 4.30”.

(Monodispersed polystyrene)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“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
“F-128” manufactured by Tosoh Corporation
“F-288” manufactured by Tosoh Corporation
“F-550” manufactured by Tosoh Corporation

  Furthermore, since the polymerizable unsaturated group equivalent in the polymerizable resin (III) used in the present invention is excellent in scratch resistance of the cured coating film, it is 200 to 3,500 g / eq. The range of 250 to 2,000 g / eq. The range of 300-1500 g / eq. Is more preferable, 400-1,000 g / eq. The range of is particularly preferable.

  The blending amount of the polymerizable resin (III) is preferably in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass in total of the low refractive index agent (I) and the active energy ray-curable compound (II). The range of 0.5-15 mass parts is more preferable, and the range of 1-12 mass parts is further more preferable. When the blending amount of the polymerizable resin (III) is within this range, the antifouling property and scratch resistance are also good.

  When the antireflection coating composition of the present invention is cured by irradiating active energy rays such as ultraviolet rays, a polymerization initiator (IV) is blended in the antireflection coating composition of the present invention. Examples of the polymerization initiator (IV) include benzophenone, acetophenone, benzoin, benzoin ethyl ether, benzoin isobutyl ether, benzyl methyl ketal, azobisisobutyronitrile, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2- Methyl-1-phenyl-1-one, 1- (4′-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4′-dodecylphenyl) -2-hydroxy-2-methyl Propan-1-one, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4 ″ -diethylisophthalophene, 2,2-dimethoxy-1,2-diphenylethane -1-one, benzoin isopropyl ether, thioxanthone, -Chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethyl Amino-1- (4-morpholinophenyl) -butanone-1, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6, -trimethylbenzoyl) -Phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. may be mentioned, or two or more of them may be used in combination.

  Moreover, if necessary, a photosensitizer such as an amine compound or a phosphorus compound can be added to promote photopolymerization.

  The blending amount of the polymerization initiator (IV) is 0.01 to 15 with respect to a total of 100 parts by mass of the low refractive index agent (I), the active energy ray-curable compound (II) and the polymerizable resin (III). It is preferable that it is the range of a mass part, and it is more preferable that it is the range of 0.3-7 mass parts.

  Furthermore, the antireflective coating composition of the present invention is an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity modifier, within the range not impairing the effects of the present invention, depending on the purpose of use, characteristics, etc. Additives such as a light-resistant stabilizer stabilizer, a heat-resistant stabilizer, and an antioxidant can be blended.

  In addition, in order to impart coating suitability to the antireflection coating composition of the present invention, an organic solvent may be added to adjust the viscosity. Examples of the organic solvent that can be used here include acetate solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; propionate solvents such as ethoxypropionate; aromatics such as toluene, xylene, and methoxybenzene. Group solvents; ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aliphatic hydrocarbon solvents such as hexane; N, N- Nitrogen compound solvents such as dimethylformamide, γ-butyrolactam, N-methyl-2-pyrrolidone; Lactone solvents such as γ-butyrolactone; Examples thereof include bamic acid esters. These solvents can be used alone or in combination of two or more.

  Here, the amount of the organic solvent used varies depending on the application and the target film thickness and viscosity, but the total amount of the low refractive index agent (I), the active energy ray curable compound (II) and the polymerizable resin (III). On the other hand, the amount is preferably in the range of 4 to 200 times the mass.

  Examples of active energy rays for curing the antireflection coating composition of the present invention include active energy rays such as light, electron beam, and radiation. Specific energy sources or curing devices include, for example, germicidal lamps, ultraviolet fluorescent lamps, carbon arcs, xenon lamps, high pressure mercury lamps for copying, medium or high pressure mercury lamps, ultrahigh pressure mercury lamps, electrodeless lamps, metal halide lamps, natural light, etc. Or an electron beam using a scanning type or curtain type electron beam accelerator. In addition, when making it harden | cure with an electron beam, the mixing | blending of the said polymerization initiator (D) to the antireflection coating composition of this invention is unnecessary.

  Among these active energy rays, ultraviolet rays are particularly preferable. Further, it is preferable to irradiate in an inert gas atmosphere such as nitrogen gas since the surface curability of the coating film is improved. Further, if necessary, heat may be used as an energy source and heat treatment may be performed after curing with active energy rays.

  Examples of the application method of the antireflection coating composition of the present invention include a gravure coater, a roll coater, a comma coater, a knife coater, a curtain coater, a shower coater, a spin coater, a slit coater, dipping, screen printing, spraying, an applicator, and a bar. The coating method using a coater etc. is mentioned.

Although the antireflection film of the present invention has a cured coating film of the antireflection coating composition of the present invention, specifically, it can be produced by the following method.
(1) First, a hard coat material is applied to a substrate and cured to form a hard coat layer coating.
(2) The antireflective coating composition of the present invention is applied to the hard coat layer and cured to form a coating film having a low refractive index layer. This low refractive index layer becomes the outermost surface of the antireflection film.
A medium refractive index layer and / or a high refractive index layer may be provided between the hard coat layer and the low refractive index layer.

  The hard coat material can be used without particular limitation as long as a cured coating film having a relatively high surface hardness can be obtained, but the active energy ray curable exemplified as the active energy ray curable compound (II). A combination of the monomer (II-1) and the active energy ray-curable resin (II-2) is preferable.

  The thickness of the hard coat layer is preferably in the range of 0.1 to 100 μm, more preferably in the range of 1 to 30 μm, and still more preferably in the range of 3 to 15 μm. When the thickness of the hard coat layer is within this range, the adhesion to the substrate and the surface hardness of the antireflection film are increased. Further, the refractive index of the hard coat layer is not particularly limited. However, when the refractive index is high, good antireflection can be achieved without providing the medium refractive index layer and the high refractive index layer.

  The thickness of the low refractive index layer formed by applying and curing the antireflection coating composition of the present invention is preferably in the range of 50 to 300 nm, more preferably in the range of 50 to 150 nm, and 80 to More preferably, it is in the range of 120 nm. When the thickness of the low refractive index layer is within this range, the antireflection effect can be improved. In addition, the refractive index of the low refractive index layer is preferably in the range of 1.20 to 1.45, and more preferably in the range of 1.23 to 1.42. When the refractive index of the low refractive index layer is within this range, the antireflection effect can be improved.

  The thickness of the medium refractive index layer or the high refractive index layer is preferably in the range of 10 to 300 nm, and more preferably in the range of 30 to 200 nm. Further, the refractive index of the medium refractive index layer or the high refractive index layer is selected depending on the refractive indexes of the low refractive index layer and the hard coat layer existing above and below, but is arbitrarily selected within the range of 1.40 to 2.00. Can be set.

  Examples of the material for forming the medium refractive index layer or the high refractive index layer include epoxy resins, phenol resins, melamine resins, alkyd resins, cyanate resins, acrylic resins, polyester resins, Resins that can be cured by heat, ultraviolet curing, and electron beam, such as urethane resins and siloxane resins. These resins can be used alone or in combination of two or more. Moreover, it is more preferable to mix inorganic fine particles having a high refractive index with these resins.

  As the high refractive index inorganic fine particles, those having a refractive index of 1.65 to 2.00 are preferable. For example, zinc oxide having a refractive index of 1.90, titania having a refractive index of 2.3 to 2.7, Ceria having a refractive index of 1.95, tin-doped indium oxide having a refractive index of 1.95 to 2.00, antimony-doped tin oxide having a refractive index of 1.75 to 1.85, a refractive index of 1.87 And yttria, and zirconia having a refractive index of 2.10. These high refractive index inorganic fine particles can be used alone or in combination of two or more.

  In addition, since the productivity can be improved by making the medium refractive index layer or the high refractive index layer the same as the antireflective coating composition of the present invention, the antireflective coating composition of the present invention can be improved. When the product is cured with ultraviolet rays, it is preferable that the ultraviolet curable composition is used to form a medium refractive index layer or a high refractive index layer.

  Examples of the substrate used for the antireflection film of the present invention include, for example, polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefin films such as polypropylene, polyethylene, and polymethylpentene-1; triacetyl cellulose (TAC) Cellulose film such as polystyrene film, polyamide film, polycarbonate film, norbornene resin film (for example, “ZEONOR” manufactured by ZEON CORPORATION), modified norbornene resin film (for example, “ARTON” manufactured by JSR Corporation), Cyclic olefin copolymer films (for example, “Apel” manufactured by Mitsui Chemicals, Inc.), etc. Two or more of these films may be used together. Lum may be a sheet. The thickness of the film substrate, 20 to 500 [mu] m is preferred.

  The reflectance of the antireflection film of the present invention is preferably 2.0% or less, more preferably 1.5% or less, and further preferably 1.0% or less.

  Hereinafter, the present invention will be described in more detail with reference to specific examples.

[IR spectrum measurement conditions]
Apparatus: “IR Prestige-21” manufactured by Shimadzu Corporation
The resins obtained in the examples were measured by the KBr method.

[ ^13C -NMR spectrum measurement conditions]
Apparatus: “AL-400” manufactured by JEOL Ltd.
Solvent: acetone-d ₆

[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HHR-H” manufactured by Tosoh Corporation (6.0 mm ID × 4 cm)
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
Detector: ELSD ("ELSD2000" manufactured by Oltec)
Data processing: “GPC-8020 Model II data analysis version 4.30” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min Sample: A 1.0% by mass tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (5 μl).
Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II Data Analysis Version 4.30”.

(Monodispersed polystyrene)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“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
“F-128” manufactured by Tosoh Corporation
“F-288” manufactured by Tosoh Corporation
“F-550” manufactured by Tosoh Corporation

Synthesis Example 1 [Preparation of polymerizable resin (III)]
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 72.8 parts by mass of methyl isobutyl ketone as a solvent, and the temperature was raised to 90 ° C. while stirring in a nitrogen stream. Subsequently, 35 parts by mass of tridecafluorohexylethyl methacrylate and a polymerizable unsaturated monomer having a silicone group represented by the following formula (B1-1) (hereinafter abbreviated as “monomer (B1-1)”) 10 parts by weight and 3-hydroxypropyl methacrylate (hereinafter abbreviated as “HPMA”) 27.8 parts by weight of a monomer solution dissolved in 131.9 parts by weight of methyl isobutyl ketone, and t as a radical polymerization initiator -Two types of dripping liquid with a polymerization initiator solution in which 4.4 parts by mass of butylperoxy-2-ethylhexanoate was dissolved in 12.3 parts by mass of methyl isobutyl ketone were set in separate dropping devices, Was simultaneously added dropwise over 2 hours while maintaining at 90 ° C. After completion of dropping, the mixture was stirred at 90 ° C. for 13 hours to obtain a polymer (P1) solution.

（式中、ｎは平均６５である。）

(Where n is an average of 65)

  The polymer (P1) solution was charged with 0.1 parts by mass of p-methoxyphenol as a polymerization inhibitor and 0.03 parts by mass of tin octylate as a urethanization catalyst, and stirring was started under an air stream. While maintaining the temperature, 27.2 parts by mass of 2-acryloyloxyethyl isocyanate (hereinafter abbreviated as “AOI”) was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 2 hours, then heated to 80 ° C. and stirred for 10 hours, whereby disappearance of the isocyanate group was confirmed by IR spectrum measurement. Subsequently, methyl isobutyl ketone was added to obtain a methyl isobutyl ketone solution containing 30% by mass of the fluorine-containing polymerizable resin (III-1). As a result of measuring the molecular weight of the obtained fluorine-containing polymerizable resin (III-1) by GPC (polystyrene equivalent molecular weight), it has a number average molecular weight of 5,000 and a weight average molecular weight of 12,000, and the polymerizable unsaturated group equivalent is 710 g / eq. Met.

Synthesis example 2 (same as above)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 66.7 parts by mass of methyl isobutyl ketone as a solvent, and the temperature was raised to 90 ° C. while stirring in a nitrogen stream. Next, 18 parts by mass of tridecafluorohexylethyl methacrylate, 18 parts by mass of monomer (B1-1) and 30.7 parts by mass of 2-hydroxyethyl methacrylate (hereinafter abbreviated as “HEMA”) were added to methyl isobutyl ketone. 2 of a monomer solution dissolved in 120.1 parts by mass and a polymerization initiator solution in which 6 parts by mass of t-butylperoxy-2-ethylhexanoate was dissolved in 13.3 parts by mass of methyl isobutyl ketone as a radical polymerization initiator. Each type of dropping solution was set in a separate dropping device, and dropped simultaneously over 2 hours while maintaining the inside of the flask at 90 ° C. After completion of the dropping, the mixture was stirred at 90 ° C. for 13 hours to obtain a polymer (P2) solution.

  The polymer (P2) solution was charged with 0.1 parts by mass of p-methoxyphenol as a polymerization inhibitor and 0.03 parts by mass of tin octylate as a urethanization catalyst, and stirred under an air stream. While maintaining the temperature, 33.3 parts by mass of AOI was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 2 hours, then heated to 80 ° C. and stirred for 10 hours, whereby disappearance of the isocyanate group was confirmed by IR spectrum measurement. Subsequently, methyl isobutyl ketone was added to obtain a methyl isobutyl ketone solution containing 20% by mass of the fluorine-containing polymerizable resin (III-2). As a result of measuring the molecular weight of the obtained fluorine-containing polymerizable resin (2) by GPC (polystyrene equivalent molecular weight), it had a number average molecular weight of 2,900 and a weight average molecular weight of 7,500, and the polymerizable unsaturated group equivalent was 423 g / eq. Met.

Synthesis example 3 (same as above)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 78.7 parts by mass of methyl isobutyl ketone as a solvent, and the temperature was raised to 90 ° C. while stirring in a nitrogen stream. Next, 18 parts by mass of tridecafluorohexylethyl methacrylate, a monomer solution in which 18 parts by mass of monomer (B1-1) and 42.7 parts by mass of glycidyl methacrylate were dissolved in 140.2 parts by mass of methyl isobutyl ketone, and radical polymerization Two kinds of dripping solutions with a polymerization initiator solution prepared by dissolving 9 parts by mass of t-butylperoxy-2-ethylhexanoate in 17.2 parts by mass of methyl isobutyl ketone as initiators were set in separate dripping devices, respectively. While keeping the inside of the flask at 90 ° C., it was dropped simultaneously over 2 hours. After completion of the dropwise addition, the mixture was stirred at 90 ° C. for 13 hours, and then 202.4 parts by mass of methyl isobutyl ketone was distilled off to obtain a polymer (P3) solution.

  The polymer (P3) solution was charged with 0.1 parts by mass of p-methoxyphenol as a polymerization inhibitor, stirred under an air stream, and maintained at 80 ° C. while maintaining 21.3 parts by mass of acrylic acid. First, 0.5 part by mass of triphenylphosphine was charged as a catalyst. After the preparation, the temperature was raised from 80 ° C. to 120 ° C. over 1 hour, and the mixture was stirred for 10 hours while maintaining 120 ° C., whereby the disappearance of the carboxylic acid group was confirmed by acid value measurement. Subsequently, methyl isobutyl ketone was added to obtain a methyl isobutyl ketone solution containing 40% by mass of the fluorine-containing polymerizable resin (III-3). The molecular weight of the obtained fluorine-containing polymerizable resin (III-3) was measured by GPC (polystyrene equivalent molecular weight). As a result, the number average molecular weight was 4,700, the weight average molecular weight was 15,000, and the polymerizable unsaturated group equivalent was 345 g / eq. Met.

Synthesis example 4 (same as above)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 72.8 parts by mass of methyl isobutyl ketone as a solvent, and the temperature was raised to 90 ° C. while stirring in a nitrogen stream. Next, 35 parts by mass of tridecafluorohexylethyl methacrylate, a monomer solution in which 35 parts by mass of monomer (B1-1) and 27.8 parts by mass of HPMA are dissolved in 131.9 parts by mass of methyl isobutyl ketone, and a radical polymerization initiator Set two kinds of dropping solutions as a polymerization initiator solution in which 4.4 parts by mass of t-butylperoxy-2-ethylhexanoate is dissolved in 12.3 parts by mass of methyl isobutyl ketone, respectively, in separate dropping devices, While keeping the inside of the flask at 90 ° C., it was dropped simultaneously over 2 hours. After completion of dropping, the mixture was stirred at 90 ° C. for 13 hours to obtain a solution of fluororesin (III-4). Methyl isobutyl ketone was added to this solution to obtain a methyl isobutyl ketone solution containing 20% by mass of the fluororesin (III-4). As a result of measuring the molecular weight of the obtained fluororesin (III-4) by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight 5,300 and a weight average molecular weight 11,000.

Example 1
<Preparation of antireflection coating composition>
15 parts by mass of methyl isobutyl ketone dispersion containing 20% by mass of hollow silica fine particles (average particle size 50 nm), 1.6 parts by mass of pentaerythritol triacrylate, 2-hydroxy-1- {4- [4 as a photopolymerization initiator 0.1 part by mass of-(2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one ("Irgacure 127" manufactured by Ciba Japan Co., Ltd.), methyl isobutyl as a solvent 81.8 parts by mass of ketone was mixed and dissolved to obtain a base composition of an antireflection coating composition.

  0.4% by mass of a resin containing 20% by mass of the polymerizable resin (III-1) obtained in Synthesis Example 1 with respect to 98.5 parts by mass of the base composition of the antireflection coating composition obtained above. The antireflective coating composition (1) of the present invention was prepared by adding the components so as to form parts and mixing them uniformly.

<Preparation of antireflection film>
50 parts by mass of pentafunctional non-yellowing urethane acrylate, 50 parts by mass of dipentaerythritol hexaacrylate, 25 parts by mass of butyl acetate, 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator 5 54 parts by mass of toluene, 28 parts by mass of 2-propanol, 28 parts by mass of ethyl acetate, and 28 parts by mass of propylene glycol monomethyl ether as a solvent were mixed and dissolved to obtain a coating composition for a hard coat layer.

The obtained coating composition for a hard coat layer was applied to a bar coater no. 13 is applied to a TAC film having a thickness of 80 μm, and then put into a dryer at 60 ° C. for 5 minutes to evaporate the solvent. ² ), a hard coat film having a 10 μm thick hard coat layer on one side was prepared.

The bar coater No. 1 was applied on the hard coat layer of the hard coat film obtained above so that the coating amount of the antireflection coating composition (1) was 2 g / m ² . Then, the solvent is volatilized in a dryer at 60 ° C. for 5 minutes and cured with an ultraviolet curing device (in a nitrogen atmosphere, using a high pressure mercury lamp, an ultraviolet irradiation amount of ² kJ / m ² ). An antireflection film (1) having an antireflection layer having a thickness of 0.1 μm on the hard coat layer was produced.

  About the cured coating film surface of the anti-reflective coating composition of the anti-reflective film obtained above, the following external appearance, abrasion resistance, and dirt wiping property were evaluated. Moreover, the reflectance of the antireflection film was measured. These evaluations were performed before and after the alkali treatment shown below.

[Evaluation of appearance]
The antireflection film obtained above was placed on a black plate, the presence or absence of whitening of the cured coating film of the antireflection coating composition was visually observed, and the appearance was evaluated according to the following criteria. The evaluation results are shown in Table 1.
○: No whitening occurs.
X: Whitening occurs.

[Evaluation of scratch resistance]
Tribogear HEIDON reciprocating wear tester TYPE: 30S (manufactured by Shinto Kagaku Co., Ltd.), wear tester (500g /) with Bonstar No. 0000 (manufactured by Nippon Steel Wool Co., Ltd.) attached to a circular jig with a diameter of 27mm The test was performed with 30 reciprocating wear at a load of cm ² . The number of scratches on the coating surface after the test was counted, and the scratch resistance was evaluated according to the following criteria.
A: The number of scratches is less than 5.
○: The number of scratches is less than 10.
Δ: The number of scratches is 10 or more and less than 50.
X: The number of scratches is 50 or more.

[Evaluation of fingerprint dirt wiping property]
Fingerprints are attached to the surface of the cured coating film of the antireflective coating composition of the antireflective film obtained above, and the wiping condition when wiped 10 times with tissue paper is visually observed. The wiping property was evaluated.
A: Fingerprints can be completely wiped off.
○: A fingerprint mark or a linear trace along the wiping direction remained slightly compared to the time of adhesion.
X: A fingerprint mark or a linear mark along the wiping direction remains with a density of more than half that at the time of adhesion.

[Measurement of reflectance]
The reflectance was measured using a spectrophotometer (“UV-3100PC” manufactured by Shimadzu Corporation) equipped with a 5 ° C. regular reflection measuring apparatus. The reflectivity was a value when the local minimum value (minimum reflectivity) was reached near the wavelength of 550 nm.

<Strong alkali (saponification) treatment method for cured coating film>
The antireflection film obtained above was immersed in a 2.0 mol / L potassium hydroxide aqueous solution heated to 70 ° C. for 1 minute, washed with water, dried at 100 ° C. for 3 minutes, and then subjected to a strong alkali treatment. .

Example 2
Instead of the solution containing 20% by mass of the fluororesin (III-1) used in Example 1, a solution containing 20% by mass of the fluororesin (III-2) was added to 0.4 parts by mass as a resin component. Except for the above, the same operation as in Example 1 was performed for evaluation. The evaluation results are shown in Table 1.

Example 3
Instead of the 20% by mass fluorine-containing resin (III-1) containing solution used in Example 1, a 40% by mass fluorine-containing resin (III-3) -containing solution was added so as to be 0.4 parts by mass. The evaluation was performed by operating in the same manner as in Example 1 except that. The evaluation results are shown in Table 1.

Comparative Example 1
Instead of the solution containing 20% by mass of the fluororesin (III-1) used in Example 1, a solution containing 20% by mass of the fluororesin (III-4) was added to a resin content of 0.4 parts by mass. The evaluation was performed by operating in the same manner as in Example 1 except that. The evaluation results are shown in Table 1.

Comparative Example 2
Instead of the solution containing 20% by mass of the fluorine-containing resin (III-1) used in Example 1, silicone oil ("Silane Plain FM-4421" manufactured by Chisso Corporation), -C ₃ at both ends of the polydimethylsiloxane chain The same operation as in Example 1 was performed except that 0.8 parts by mass (0.4 parts by mass as a resin component) of a methyl isobutyl ketone solution containing 50% by mass of H ₆ OC ₂ H ₄ OH) was added. And evaluated. The evaluation results are shown in Table 1.

Comparative Example 3
Instead of the 20% by mass fluorine-containing resin (III-1) containing solution used in Example 1, 0.8 parts by mass (resin content) of methyl isobutyl ketone solution containing 50% by mass monomer (B1-1) As an example, evaluation was performed in the same manner as in Example 1 except that 0.4 parts by mass) was added. The evaluation results are shown in Table 1.

Comparative Example 4
Instead of the solution containing 20% by mass of the fluororesin (III-1) used in Example 1, it contains 50% by mass of a tetrafunctional acrylate having a dimethylsiloxane chain (“BYK-UV3570” manufactured by Big Chemie Japan Co., Ltd.). Evaluation was carried out in the same manner as in Example 1 except that 0.8 parts by mass of methyl isobutyl ketone solution (0.4 parts by mass as the resin content) was added. The evaluation results are shown in Table 1.

Comparative Example 5
The same operation as in Example 1 was carried out except that 0.4 parts by mass of tridecafluorohexylethyl methacrylate was used as the resin content instead of the 20% by mass containing fluororesin (III-1) used in Example 1. And evaluated.

Comparative Example 6
Evaluation was performed in the same manner as in Example 1 without adding anything to the base resin composition of the active energy ray-curable composition prepared in Example 1. The evaluation results are shown in Table 1.

Claims (8)

  Other than the low refractive index agent (I), the active energy ray-curable compound (II), and the active energy ray-curable compound (II) having a silicone chain having a molecular weight of 2000 or more, a fluorinated alkyl group, and a polymerizable unsaturated group An antireflective coating composition comprising the polymerizable resin (III).   The antireflection coating composition according to claim 1, wherein the silicone chain is a silicone chain having a molecular weight of 2000 to 20,000, and the fluorinated alkyl group is a fluorinated alkyl group having 4 to 6 carbon atoms.   The polymerizable resin (III) includes a polymerizable unsaturated monomer (A) having a silicone chain, a polymerizable unsaturated monomer (B) having a fluorinated alkyl group, and a reactive functional group (c). And a polymer (P) obtained by copolymerizing a polymerizable unsaturated monomer (C) having an essential monomer component with at least one having reactivity with the functional group (c). The antireflective coating composition of Claim 1 obtained by making the compound (D) which has a functional group (d) and a polymerizable unsaturated group react.   The antireflection paint according to claim 3, wherein the reactive functional group (c) is at least one functional group selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, and an acid anhydride group. Composition.   The antireflective coating composition according to claim 1, wherein the low refractive index agent (I) is hollow silica fine particles.   5. The polymerizable resin (III) is contained in an amount of 0.1 to 20 parts by mass with respect to a total of 100 parts by mass of the low refractive index agent (I) and the active energy ray-curable compound (II). The antireflection coating composition according to any one of the above.   An antireflection film comprising a cured coating film of the antireflection coating composition according to any one of claims 1 to 6.   The antireflection film according to claim 6, wherein the cured coating film has a thickness of 50 to 300 μm.