Curable composition and cured product thereof

Abstract

To provide a curable resin composition having high refractive index characteristics, antistatic characteristics, and high transparency.SOLUTION: An active energy ray-curable resin composition comprises a copolymer (A) having a quaternary ammonium base, a compound (B) having a polar group and a (meth)acryloyl group, and a compound (C) having a (meth)acryloyl group and at least one aromatic ring structure.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a curable composition and a cured product thereof. [Background technology]

[0002] Many displays are used in environments where external light such as sunlight or fluorescent lights enter. Therefore, in order to prevent reflections and backgrounds from appearing on the display surface, It has a prevention function. In addition to contamination of the display surface due to the adhesion of dust, etc., Due to concerns about the effect of static electricity on the inside of the product, antistatic properties are also required. Furthermore, in recent years, with the trend towards larger screens and higher resolution, there has been a growing demand for greater transparency. There are.

[0003] Usually, anti-reflection function is achieved by forming a laminated structure of high refractive index layers and low refractive index layers alternately using a coating material. By doing so, the difference in refractive index is utilized to cause interference of reflected light, thereby providing the effect.

[0004] Examples of coating materials that form high refractive index layers include inorganic films that use metal oxides such as ITO. A coating material using a conductive metal filler has been proposed (Patent Document 1). By using oxides, it is possible to give not only a high refractive index but also an antistatic function. However, this technology has problems such as loss of transparency.

[0005] On the other hand, Patent Document 2 proposes an organic coating material that increases the refractive index without impairing transparency. This coating material contains a quaternary ammonium base for the purpose of providing antistatic properties. It is described that a copolymer having the above structure is used, and that both transparency and antistatic properties can be achieved. However, the inventors' investigations revealed that there was a problem with transparency under certain conditions. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2010-217873 A [Patent Document 2] JP 2019-52267 A Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention has been made in view of the above circumstances, and provides a method for producing a film having a high refractive index, antistatic properties, and high transparency. The present invention aims to provide a curable resin composition having excellent curability. Another object of the present invention is to provide an optical material using this curable resin composition. .

[0008] The present inventors believe that the cause of the decrease in transparency is the quaternary ammonium base described in Patent Document 2. The compatibility of the copolymer having the above structure and the high refractive index component having an unsaturated double bond is not very good. It is estimated that the copolymer having a quaternary ammonium base and the high refractive index compound having an unsaturated double bond are In order to increase the compatibility of the components, we focused on compounds having polar groups and unsaturated double bonds.

[0009] By using the above compound having an unsaturated double bond with a polar group, Compatibility of copolymers containing um bases with compounds having unsaturated double bonds with aromatic ring structures This has made it possible to improve transparency and antistatic properties, which were previously issues. We have developed an antistatic coating material that achieves both of these. [Means for solving the problem]

[0010] The present invention has the following aspects. That is, the above object of the present invention can be achieved by the following means [1] to [8]. [1] A copolymer (A) having a quaternary ammonium salt group and a polar group and a (meth)acryloyl group. Compound (B) having an acryloyl group (excluding compound (C)) and An active energy ray curable type, comprising a compound (C) having at least one aromatic ring structure. Resin composition. [2] The polar group of the compound (B) is a hydroxyl group, a carboxyl group, an amide group, a sulfur group, or the like. The active energy ray-curable resin according to [1], wherein the active energy ray-curable resin is one or more selected from the group consisting of E groups. composition. [3] The polar group of the compound (B) is a hydroxyl group, and the hydroxyl value is 10 mgKOH / g or more of the active energy ray-curable resin composition according to [1] or [2]. [4] The total amount of solid contents of the copolymer (A), the compound (B), and the compound (C). The proportion of the solid content of the compound (A) in 100 mass% is 0.5 mass% or more and 20 mass% or less. The active energy ray-curable resin composition according to any one of [1] to [3], wherein the active energy ray-curable resin composition is less than 100% by mass. [5] The compound (B) has 1 or more and 10 or less (meth)acryloyl groups. The active energy ray-curable resin composition according to any one of [1] to [4]. [6] The compound (B) includes the following (B-1) and / or (B-2): [1] to [ 5] The active energy ray-curable resin composition according to any one of the above items. (B-1): A compound having 3 to 10 (meth)acryloyl groups (B-2): A compound having one or two (meth)acryloyl groups The active energy ray-curable resin composition according to [1], [7] The compound (A) is a compound obtained by subjecting a quaternary ammonium base and an amine-derived ammonium salt to The molar average SP value of all structural units other than structural units having a silyl group is 7.00 or more and less than 11.00. The active energy ray-curable resin composition according to any one of [1] to [6], wherein the active energy ray-curable resin composition satisfies the above requirement. [8] The haze of a cured film obtained by curing the active energy ray-curable resin composition is 4.0. %, and the refractive index of the cured film is within the range of 1.50 or more and less than 1.80, and the surface resistance of the cured film is Resistance is 1.0×10 7 Ω or more 1.0×10 12 Any one of [1] to [7] that is less than Ω Item 2. A cured product obtained by curing the composition described in item 1. Effect of the Invention

[0011] According to the present invention, there is provided a curable resin composition having a high refractive index, antistatic properties and high transparency. Can be provided. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] As used herein, the following terms have the following meanings: "(Meth)acrylic" is a general term for "acrylic" and "methacrylic." "(Meth)acryloyl" is a general term for "acryloyl" and "methacryloyl". be. "(Meth)acrylate" is a general term for "acrylate" and "methacrylate." be. The "number of (meth)acryloyl functional groups" refers to the number of functional groups contained in one molecule of (meth)acrylate. It means the number of (meth)acryloyl groups. The numerical ranges disclosed in this specification can be arbitrarily combined with the lower and upper limits to form new numerical ranges. It can be a range of values.

[0013] Unless otherwise specified, the refractive index in this specification is that of the uncured material at 25°C. This refers to the refractive index.

[0014] The present invention will be described in detail below. <Compound (A)> The compound (A) used in the present invention is a copolymer having a quaternary ammonium salt group. The compound (A) is, for example, a monomer having a polymerizable group containing a quaternary ammonium salt group. Copolymerization of monomers with other compounds having polymerizable groups (e.g., monomers, oligomers) The copolymer (A) having such a quaternary ammonium salt group can be obtained by the above-mentioned method. Specific examples include the following (i) to (v). (i) A monomer having a polymerizable group containing a quaternary ammonium salt group and a (meth)acrylic Copolymer with acid ester (ii) An oligomer having a polymerizable group containing a quaternary ammonium salt group and a (meth)acrylic acid Copolymers with esters of carboxylic acids (iii) Quaternary ammonium salt group-containing (meth)acrylic acid ester and other (meth)acrylic acid Copolymers with styrene-based monomers and / or esters (iv) Quaternary ammonium salt group-containing (meth)acrylic acid ester and other (meth)acrylic Copolymers with acid esters and / or styrene oligomers (v) Quaternary ammonium salt group-containing (meth)acrylic acid esters and other (meth)acrylic Copolymers with acrylic acid esters and / or other (meth)acrylic acid ester oligomers

[0015] A compound with a quaternary ammonium base is a compound that has an ammonium group in the molecule. Examples of quaternary amines include aliphatic amines, alicyclic amines, and aromatic amines. The compound having an ammonium base is preferably a compound having a polymeric ammonium group. The quaternary ammonium base is not a counter ion but is present in the main chain or side chain of the polymer. It is preferable that the polymer has a structure in which the antistatic agent is effectively incorporated. In order to provide antibacterial properties, it is preferable to increase the concentration of the quaternary ammonium base. For this reason, it is preferable that the polymer is a (meth)acrylic polymer. For example, a quaternary acrylate polymer capable of addition polymerization is used. Monomers containing ammonium groups or precursors of ammonium groups such as amines and other monomers Examples of such copolymers include those obtained by polymerizing a polymer to obtain a copolymer having a quaternary ammonium salt group.

[0016] Examples of the precursor monomer of the quaternary ammonium group or the ammonium group such as an amine include , (meth)acrylic acid esters of amino alcohols, specifically, N,N-dimethylamino N,N-diethylaminoethyl (meth)acrylate, N,N-Dimethylaminopropyl (meth)acrylate, N,N-Diethylaminopropyl N,N-dimethylaminobutyl (meth)acrylate, N,N -Diethylaminobutyl (meth)acrylate, N,N-dihydroxyethylaminoethyl N,N-dimethylaminoethyl (meth)acrylate is particularly preferred. A rate is preferably used. The ammonium group of the N,N-dialkylamino group-containing monomer may be, for example, an amino alcohol. It can also be produced by the quaternization reaction of (meth)acrylic acid ester of N,N- The ammonium group of the dialkylamino group-containing monomer is, for example, N,N-dimethylamino. An example is the quaternized product of aminoethyl methacrylate with methyl chloride.

[0017] In the case of (meth)acrylic polymers, ammonium groups or amines The polymerizable monomer may contain a polymerizable monomer unit other than the precursor monomer of the aryl group. Examples of the acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, and proline. Pyr(meth)acrylate, Butyl(meth)acrylate, 2-Ethylhexyl(meth)acrylate Acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, trimethylolpropane Alkyl (meth)acrylates such as decyl (meth)acrylate; the amino alcohols mentioned above; (Meth)acrylic esters of 2-hydroxyethyl (meth)acrylate; Hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, etc. Benzyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, ethoxyethyl ethyl carbitol (meth)acrylate, ethyl carbitol (meth)acrylate, butoxyethyl (Meth)acrylate, Cyanoethyl (Meth)acrylate, Glycidyl (Meth)acrylate Examples of such acrylates include various (meth)acrylates, styrene, and methylstyrene. One or more of these may be used in combination. When the polymerizable monomer has a long chain alkyl group, it may segregate at the air interface of the cured film. This is a preferred embodiment since it is possible to improve the antistatic properties of the cured film. The polymerizable monomer having a chain alkyl group is preferably an alkyl group having 8 or more and less than 30 carbon atoms. alkyl(meth)acrylate, more preferably alkyl(meth)acrylate having 12 or more and less than 22 carbon atoms. ) acrylate, for example, lauryl (meth) acrylate, tridecyl (meth) acrylate, acrylate, and stearyl (meth)acrylate.

[0018] Polymerizable monomers other than ammonium groups or precursor monomers of ammonium groups such as amines are The molar average SP value of the structural units contained in the molecule is 7.00 or more and less than 11.00. That is, polymerizable monomers other than ammonium groups or precursor monomers of ammonium groups such as amines The molar average SP value of the structural units contained in the molecule is 7.00 or more and less than 11.00. The content is adjusted so as to The molar average SP value is 7.00 or more and less than 11.00, so that the quaternary ammonia The copolymer having an um base is promoted to segregate at the air interface of the cured film, resulting in a low surface resistance. From the viewpoint of surface resistance, the curable composition has excellent antistatic properties. The molar average SP value is preferably 7.00 or more and less than 11.00, and more preferably 8.00 or more and less than 1 It is more preferable that the ratio is less than 0.00, and even more preferable that the ratio is 8.50 or more and less than 9.30. It is preferable that the ratio is not less than 8.60 and not more than 9.28.

[0019] Here, the SP value of each structural unit is calculated according to the Fedors formula (Ref: RFFedors Based on Polym. Eng. Sci., 14[2], 147-154(1974) The molecular formula of each structural unit is calculated from the molecular formula of each structural unit. Unsaturated diamines of polymerizable monomers other than precursor monomers of ammonium groups such as ammonium groups or amines It means a structural unit after polymerization of double bonds. For example, polymerizable monomers other than ammonium groups or precursor monomers of ammonium groups such as amines. If there are five monomers, the SP value of the structural unit of each polymerizable monomer is SP1 to SP5. If the molar content ratios (%) are M1 to M5, the molar average of the SP value is calculated by the following formula: do. (Molar average of SP values) = (SP1 × M1) / 100 + (SP2 × M2) / 100 + (SP 3×M3) / 100+(SP4×M4) / 100+(SP5×M5) / 100

[0020] The distribution of monomer units containing quaternary ammonium bases in copolymers containing quaternary ammonium bases. In this case, the content is preferably 5% by mass or more and less than 95% by mass, more preferably 10% by mass or more and less than 90% by mass, and further Preferably, the range is 20 to less than 80% by mass, and more preferably, the range is 30 to less than 70% by mass. The higher the ratio, the higher the antistatic property, and the lower the ratio, the better the appearance of the cured layer after application. The polymer tends to be improved, and a well-balanced result can be achieved by using the polymer in the above range. The proportion of the long-chain alkyl group-containing monomer unit is preferably 80% by mass or less, more preferably The range is preferably 50% by mass or less, and more preferably 40% by mass or less. This makes it easier for the antistatic property to be exhibited.

[0021] The weight average molecular weight of the copolymer having a quaternary ammonium base is 800 to 120,000. It is preferably less than 0, and more preferably between 2,000 and 60,000.

[0022] The copolymer having a quaternary ammonium salt group is prepared by radical polymerization reaction using the above raw material monomers. The radical polymerization reaction can be carried out by reacting a radical polymerization initiator in an organic solvent. It is preferred to carry out the reaction in the presence of

[0023] Examples of organic solvents used in radical polymerization reactions include acetone and methyl ethyl ketone. Ketone solvents such as (MEK); ethanol, methanol, isopropyl alcohol (IP A) Alcohol solvents such as isobutanol; ethylene glycol dimethyl ether, Ether solvents such as propylene glycol monomethyl ether; ethyl acetate, propylene glycol Esters such as ricin monomethyl ether acetate and 2-ethoxyethyl acetate Solvent: Aromatic hydrocarbon solvents such as toluene. Only one of these organic solvents is used. Alternatively, two or more of them may be used in combination.

[0024] The radical polymerization initiator used in the radical polymerization reaction is, for example, benzoylperoxycarbonyl. peroxides such as di-t-butyl peroxide; 2,2'-azobisbutyronite aryl, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis( 4-Methoxy-2,4-dimethylvaleronitrile and other azo compounds. The radical polymerization initiators may be used alone or in combination of two or more. The radical polymerization initiator is 0.01 to 5 parts by mass per 100 parts by mass of the total raw material monomers. It is preferable to use it in the following range.

[0025] In addition, during radical polymerization reactions, chain transfer is performed to control the weight average molecular weight of the polymer. Examples of the chain transfer agent include butanethiol and octanethiol. thiol, decanethiol, dodecanethiol, hexadecanethiol, octadecanethiol Cyclohexyl mercaptan, thiophenol, octyl thioglycolate, 2-methyl Octyl mercaptopropionate, Octyl 3-mercaptopropionate, Mercaptopropionate Pionic acid 2-ethylhexyl ester, thioglycolic acid 2-ethylhexyl, butyl- 3-Mercaptopropionate, Mercaptopropyltrimethoxysilane, Methyl-3- Mercaptopropionate, 2,2-(ethylenedioxy)diethanethiol, ethanethiol ol, 4-methylbenzenethiol, octanoic acid 2-mercaptoethyl ester, 1, 8-Dimercapto-3,6-dioxaoctane, Decanetrithiol, Dodecylmercapto Tan, diphenyl sulfoxide, dibenzyl sulfide, 2,3-dimethylcapto-1- Propanol, mercaptoethanol, thiosalicylic acid, thioglycerol, thioglycol mercaptopropionic acid, thiomalic acid, mercaptoacetic acid, mercaptoamic acid Examples of such compounds include thiol compounds such as mercaptoethanesulfonic acid and 2-mercaptoethanesulfonic acid. Only one type may be used, or two or more types may be used in combination.

[0026] The amount of the chain transfer agent used is preferably 0.1 to less than 25% by mass based on the total amount of the raw material monomers. It is preferably 0.5 to less than 20% by mass, more preferably 1.0 to less than 15% by mass. It is nice.

[0027] The reaction time of the radical polymerization reaction is preferably 1 to less than 20 hours, more preferably 3 to less than 12 hours. More preferred. The reaction temperature is preferably 40 to less than 120° C., more preferably 50 to less than 100° C. It is nice.

[0028] The copolymer (A) having a quaternary ammonium salt group may be used in combination of two or more kinds. good.

[0029] In the curable composition of the present invention, by using the above-mentioned compound (A), As shown in the examples, a cured product having excellent antistatic properties can be obtained.

[0030] <Compound (B)> The compound (B) used in the present invention is a compound having a polar group and a (meth)acryloyl group. Examples of the polar group include a hydroxyl group, a carboxyl group, an amide group, and a sulfo group. Among these, the polar group is preferably a hydroxyl group. is preferably 10 or more and less than 300 mgKOH / g, and more preferably 40 or more and 280 mgKOH / g More preferably, it is 50 to 260 mgKOH / g, and even more preferably, it is 55 to 2 Less than 50 mg KOH / g is most preferred.

[0031] The number of (meth)acryloyl groups in one molecule of the compound (B) is preferably 1 to 10. The more (meth)acryloyl groups there are, the higher the hardness of the coating film becomes. The viscosity of the composition tends to decrease and the appearance of the coating film tends to improve. The lance is removed.

[0032] The compound (B) may include the following compound (B-1) and / or compound (B-2): It is a compound.

[0033] The compound (B-1) is a compound having 3 to 10 (meth)acryloyl groups. . A polyfunctional (meth)acrylate having 3 to 10 polar groups and (meth)acryloyl groups. Examples of the acrylate include dipentaerythritol penta(meth)acrylate, pentaacrylate, Lithritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate acrylate, trimethylolpropane di(meth)acrylate, ethylene oxide modified dipeptide Pentaerythritol penta(meth)acrylate, ethylene oxide modified pentaerythritol Ethylene oxide modified (meth)acrylates such as ethylene oxide tri(meth)acrylate, Polycaprolactone modified dipentaerythritol penta(meth)acrylate, poly ... Polycaprolactone such as lactone-modified pentaerythritol tri(meth)acrylate Modified (meth)acrylates, polyfunctional (meth)acrylates with acids such as succinic acid and phthalic acid Among these, there are also other basic acid-modified (meth)acrylates obtained by reacting with From the viewpoint of hardness of the coating film, dipentaerythritol pentaacrylate, pentaerythritol Triacrylate is preferred.

[0034] The compound (B-2) is a compound having one or two (meth)acryloyl groups. Examples of monofunctional (meth)acrylates having a polar group and one (meth)acryloyl group include: For example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate acrylate, hydroxybutyl (meth)acrylate, and other hydroxyalkyl (meth)acrylates G, diaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate (Meth)acrylates containing amino groups, succinic acid, phthalic acid, and other acids Examples include acid-modified (meth)acrylates obtained by adding an acid.

[0035] Examples of bifunctional (meth)acrylates having a polar group and two (meth)acryloyl groups include: For example, glycerin di(meth)acrylate, ethylene oxide modified glycerin di(meth)acrylate acrylate, propylene oxide modified glycerin di(meth)acrylate, 1, 6-Hexanediol glycidyl ether di(meth)acrylate, etc. Among these, 1,6-hexanediol glycidyl ether diacyl ester is preferred from the viewpoint of hardness of the coating film. Related is preferred.

[0036] The ratio of the compound (B-1) is from 0% by mass to 100% by mass based on the total amount of the component (B). The content is preferably 20% by mass or more and less than 80% by mass, more preferably 40% by mass or more and 60% by mass or less. The higher the ratio, the higher the hardness of the coating film becomes, and the lower the ratio, the lower the composition becomes. The viscosity of the material decreases and the appearance of the coating film tends to improve. By using it in the above range, the balance This means that the material has been removed. The ratio of the compound (B-2) is 0% by mass or more and 100% by mass or less based on the total amount of the component (B). The content is preferably 5% by mass or less and less than 30% by mass, more preferably 10% by mass or more and 20% by mass or less. The higher this ratio, the higher the compatibility with other components will be. When used within the above range, the (meth)acryloyl group concentration increases and the hardness of the coating film tends to improve. Use of it will achieve balance.

[0037] <Compound (C)> The compound (C) used in the present invention has a (meth)acryloyl group and at least one aromatic Compound (C) is a compound having an aromatic ring structure. Compound (C) has an aromatic ring structure and a (meth)acryloyl group. The compound may be either a monomer or a polymer. The compound may have one or more aromatic ring structures, and in that case, The aromatic ring structures of the (meth)acryloyl group may be the same or different. Regarding the above, the number of the first to fourth elements may be only one, or two or more. Among them, the compound (C) is preferably one having a high refractive index. The preferred refractive index is 1.50 or less. The ratio is preferably 1.53 or more and less than 1.80, more preferably 1.53 or more and less than 1.70, and even more preferably 1. It is greater than or equal to .55 and less than 1.68, and more preferably greater than or equal to 1.58 and less than 1.65.

[0038] Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorine ring. In the present invention, examples of the aromatic ring structure include a fluorene ring, a 1-fluorene ring, and the like. It is preferable that the aromatic ring structure has a phenoxybenzyl group or a biphenyl group. It is preferable to use a (meth)acrylate compound having the following structure. Specifically, acrylic acid ( CH2=CH-COOH) or methacrylic acid (CH2=C(CH3)-COOH) and bis(methacrylic acid) Phenoxyethanol fluorene, bis(4-glycidyloxyphenyl)fluorene, Obtained by esterification with phenoxybenzyl alcohol or biphenyl alcohol (Meth)acrylate compounds are included.

[0039] The compound (C) used in the present invention is, for example, a fluorene-based (meth)acrylate. , 2-phenylphenoxyethyl (meth)acrylate, fluorene-based epoxy (meth) Acrylate, 3-phenoxybenzyl (meth)acrylate, biphenyl (meth)acrylate Relate, EO modified orthophenylphenol (meth)acrylate, bisphenol A (meth)acrylate, Bisphenol A epoxy (meth)acrylate, Benzyl (Meth)acrylate, Phenoxyethyl (meth)acrylate, Phenoxydiethylene Glycol (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate 2-Acryloyloxyethyl-2-hydroxyethyl-phthalate, 2-Hydroxyethyl -3-phenoxypropyl (meth)acrylate, 1-naphthylmethyl (meth)acrylate 4,4'-bisacryloxymethylbiphenyl, 4-methacryloyloxybenzene Examples include zofenone and 4-hydroxyphenyl methacrylate.

[0040] The curable composition of the present invention generally contains an organic solvent. Examples of the organic solvent include n-Hexane, n-Heptane, n-Octane, n-Decane, n-Dodecane, 2,3-Dimethyl 2-methylhexane, 2-methylheptane, 2-methylhexane, 3-methylhexane, cyclohexane Saturated hydrocarbon solvents such as hexane; aromatic solvents such as toluene and xylene; methyl ethyl Ketones, acetone, methyl isobutyl ketone, cyclohexanone, and other ketone solvents; dienes Diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol Coal dimethyl ether, ethylene glycol diethyl ether, diethylene glycol Dimethyl ether, diethylene glycol diethyl ether, propylene glycol mono Ether solvents such as methyl ether, anisole, and phenetole; ethyl acetate, butyric acid ester solvents such as ethyl acetate, isopropyl acetate, and ethylene glycol diacetate; Amide solvents such as formamide, diethylformamide, and N-methylpyrrolidone; Cellosolve solvents such as cellosolve, ethyl cellosolve, and butyl cellosolve; methanol, Alcoholic solvents such as ethanol, propanol, isopropanol, butanol, etc.; Examples of the solvent include halogen-based solvents such as chloromethane and chloroform.

[0041] The proportions of the above-mentioned components in the curable composition of the present invention are as follows: The proportion of compound (A) relative to the total amount of compound (A), compound (B) and compound (C) is: Usually, 0.5 to less than 20% by mass, preferably 1 to less than 10% by mass, and more preferably 2 The compound (B) is usually 10 to less than 89% by mass, preferably 2 0% or more and less than 80% by mass, more preferably 30% or more and less than 70% by mass, and is usually 10 to less than 89% by mass, preferably 20 to less than 80% by mass, and more preferably The proportion of the polymerization initiator used is 30% by mass or more and less than 70% by mass. The organic solvent is usually 0.01 to less than 5% by mass based on the solid content of the solvent. It is used in an amount of about less than 95% by mass.

[0042] <Photopolymerization initiator> A photopolymerization initiator may be added to promote the curing of the curable composition. The molecular weight is preferably 1000 or less. Specific examples include benzoin, benzoin methyl ether, Benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-bromo Benzoin phenyl ether, benzyl diphenyl disulfide, diphenyl Diacetyl, anthraquinone, naphthoquinone, 3,3'-dimethyl-4-methoxy Benzophenone, Benzophenone, p,p'-bis(dimethylamino)benzophenone, 4,4'-Bis(diethylamino)benzophenone, pivaloin ethyl ether, benzyl dimethyl ketal, 1,1-dichloroacetophenone, pt-butyl dichloroacetophenone Phenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthio Oxanthon, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl Acetophenone, 2,2-dichloro-4-phenoxyacetophenone, phenylglyoxal Silane, α-hydroxyisobutylphenone, dibenzosparone, 1-(4-isopropyl pylphenyl)-2-hydroxy-2-methyl-1-propanone, 2-methyl-[4-( Methylthio)phenyl]-2-morpholino-1-propanone, Tribromophenylsulfonate These photopolymerization initiators include phenyl, tribromomethylphenyl sulfone, and tribromomethylphenyl sulfone. They may be used alone or in combination of two or more. When a photopolymerization initiator is used, its content should be determined from the viewpoints of curing promotion and hardness of the cured film. Preferably, the content is 20% by mass or less, more preferably 10% by mass or less, based on the non-volatile content. The range is preferably 8% by mass or less, and particularly preferably 5% by mass or less.

[0043] <Leveling agent> To improve the appearance of the cured film, a leveling agent can be added to the curable composition. Examples of the leveling agent include an acrylic leveling agent and a silicone leveling agent. and fluorine-based leveling agents. These leveling agents can be used alone or in combination. More than one species may be used in combination. When a leveling agent is added, its content is adjusted to the non-volatile content from the viewpoint of improving the appearance of the cured film. Preferably, it is 10% by mass or less, more preferably, it is 8% by mass or less, and further preferably The range is 5% by mass or less.

[0044] <Various additives> The curable composition may contain an antifouling agent, a plasticizer, a surfactant, or the like, as long as the effect of the present invention is not impaired. Antioxidants, UV absorbers, light stabilizers, polymerization accelerators such as compounds containing thiol groups, etc. Various additives such as those listed above may also be added.

[0045] The curable composition of the present invention can be cured by applying it to a substrate and then irradiating it with active energy rays. The coating method includes, for example, a reverse coating method and a gravure coating method. , rod coating method, bar coating method, Mayer bar coating method, die coating method, spray coating method Examples of active energy rays include ultraviolet rays, electron beams, X-rays, infrared rays, and visible rays. Examples of the radiation-generating agent include light rays, but ultraviolet rays and electron beams are preferably used.

[0046] For example, when using ultraviolet light, the cumulative light intensity is 20 to 5000 mJ / cm 2 Less than Preferably, 100 to 3000 mJ / cm 2 Less than 200m is preferable, and 200 to 2000m is preferable. J / cm 2 More preferably, the illuminance is 50 to 600 mW / cm. 2 Not yet Less than 75 is preferable, and more than 450 mW / cm 2 Less than 100 is preferable, and 300 mW is preferable. / cm 2 The light source may be a medium pressure mercury lamp, a high pressure mercury lamp, or an ultra-high pressure mercury lamp. , electrodeless lamp, metal halide lamp, or scanning or curtain type electron beam acceleration path. A high-pressure mercury lamp such as a stator wire, an ultra-high-pressure mercury lamp, a low-pressure mercury lamp, etc. can be used.

[0047] In addition, when curing is performed by electron beam irradiation, various electron beam irradiation devices can be used. The dose (Mrad) of the electron beam is preferably 0.5 or more and less than 20 Mrad. From the viewpoints of the curability of the active energy ray-curable composition, the flexibility of the cured product, and prevention of damage to the substrate, etc. More preferably, it is 1 or more and less than 15 Mrad.

[0048] <Cured product> The cured product obtained from the curable composition of the present invention has a high refractive index, antistatic properties and excellent transparency. Therefore, it is useful as a hard coat layer (high refractive index layer) for optical films such as anti-reflection films. In addition, in the application as a high refractive index layer, a cured film made of the curable composition of the present invention is There is no particular restriction on the thickness of the film, but it is usually 0.1 to less than 20 μm, preferably 1 to 10 μm. is less than.

[0049] <Base material> The substrate may be a known one, for example, a resin substrate, a metal substrate, or a paper substrate. Among these, the resin substrate is preferable from the viewpoint of processability. The resin substrate is a single-layer structure. It may be a single-layer structure or a multi-layer structure of two or more layers, and is not particularly limited. The resin substrate is preferably one that is transparent, smooth, heat resistant, and has excellent mechanical strength. Specific examples of materials for forming the transparent substrate include polyester and cellulose triacetate. , Cellulose diacetate, Cellulose acetate butyrate, Polyamide, Polyimide , polyethersulfone, polysulfone, polypropylene, cycloolefin, poly Methylpentene, polyvinyl chloride, polyvinyl acetal, polyether ketone, Examples of the thermoplastic resin include methyl methacrylate, polycarbonate, and polyurethane. Of these, polyester and cellulose triacetate are preferred, and cellulose triacetate is more preferred. Examples include roasted triacetate. The thickness of the substrate is 10 μm or more and 300 μm or less, preferably 20 μm or more and 200 μm or less. In the case where the substrate is a plate-like body, the substrate may have a thickness exceeding these values. When forming a hardened layer on the surface, corona discharge treatment and oxidation treatment are used to improve adhesion. In addition to physical treatments such as those mentioned above, coating with an anchor agent or a paint called a primer is also performed in advance. It's okay to be.

[0050] Haze The coating film haze of the cured product obtained from the curable composition of the present invention is preferably less than 4.0, more preferably The haze is preferably less than 1.5, and more preferably less than 0.5. tends to be better.

[0051] <Surface resistance value> The antistatic properties of the cured product obtained from the curable composition of the present invention were evaluated by the surface resistance value. The surface resistance is 1.0 x 10 7 Ω or more 1.0×10 12 Less than 1.0×10 Ω is preferable. 8 Ω or more 1.0×10 10 Less than 5.0×10 Ω is preferable. 8 Ω or more 2.0×10 9 Ω Within the above range, the generation of static electricity on the coating film surface can be suppressed, This can prevent dust from adhering during the process.

[0052] <Refractive index of cured film> The refractive index of the cured product obtained from the curable composition of the present invention is preferably 1.50 or more and 1.8 or less. Less than 0, more preferably 1.55 or more and less than 1.70, and even more preferably 1.56 or more and 1. It is preferably less than 65, and most preferably between 1.57 and 1.60. , the occurrence of interference fringes can be prevented.

[0053] <Application> The composition of the present invention provides a film having extremely high hardness, antistatic properties and transparency. Therefore, it is suitable for use as an antistatic coating agent in flat panel displays, touch panels, etc. Optical products such as panel displays, DVDs and next-generation optical information media, automotive lamps, It has excellent antistatic properties for the surfaces of various items such as (semi)transparent items such as windows and the housings of electrical equipment. It can provide anti-static properties, surface protection properties, and transparency. EXAMPLES

[0054] The present invention will be described in more detail below with reference to examples. The following examples are not intended to be limiting. The measurement and evaluation methods used in the present invention are as follows.

[0055] (1) Liquid appearance: The liquid appearance of the prepared curable composition was visually confirmed. When the liquid was uniform and transparent, it was rated as "transparent"; When the liquid is homogeneous but cloudy, it is considered "turbid," and when undissolved matter is found in the liquid, it is considered "insoluble." When using it as a coating material, it is better to avoid the level of "insoluble." .

[0056] (2) Transparency (haze): The cured film for measuring transparency (haze) was prepared according to the examples. Based on the above, the haze meter ("NDH7000" manufactured by Nippon Denshoku Industries Co., Ltd.) was used to measure the haze of the substrate alone. (The present invention does not include a cured film layer formed by curing the active energy ray-curable resin composition. After performing standard calibration using the substrate, the substrate having the cured film obtained according to the example was measured to determine the coating film. The haze was measured.

[0057] (3) Measurement of surface resistance: The cured film for measuring the surface resistance was prepared according to the example. The substrate having the cured film obtained according to the example was conditioned for 30 minutes and then analyzed by Mitsubishi Chemical Analytical Co., Ltd. A high resistivity meter Hi-Resta UP MCP-HP450 / URS probe manufactured by TECHNOLOGY CO., LTD. was used. The cured film side was measured with an applied voltage of 500 V, and the value 10 seconds after the start of the measurement was recorded as the surface resistance value.

[0058] (4) Pencil hardness: The cured film for pencil hardness measurement was prepared according to the example. JIS K5600-5-4:1 999 General Test Methods for Paints - Part 5: Mechanical Properties of Coatings - Section 4: Scratch Hardness (Pencil Method) Therefore, the pencil hardness of the cured film was measured.

[0059] (5) Refractive index measurement: The cured film for refractive index measurement was prepared according to the example. R-M2, wavelength: 589 nm) was used, and 1-bromonaphthalene was used as an intermediate liquid on the prism surface. After placing a drop of ethanol on the film, place the cured film side of the film on which the cured film has been formed on the film and measure at a temperature of 25°C. The measurements were performed in the following cases. The refractive index of the liquid before curing was measured using a multi-wavelength Abbe refractometer (DR-M2, wavelength: 589 nm) manufactured by Atago Co., Ltd. The compound before curing was dropped onto the prism surface of m) and the measurement was performed at 25°C.

[0060] (7) Measurement of weight average molecular weight (Mw) and number average molecular weight Equipment: Tosoh Corporation "HLC-8120GPC" Column: TSKgel SuperHZM-M*HZM-M*HZ manufactured by Tosoh Corporation 2000", Detector: Differential refractive index detector (RI detector / built-in), Solvent: tetrahydrofuran, Temperature: 40℃, Flow rate: 0.5mL / min, Injection volume: 10μL, Concentration: 0.2% by mass, Calibration sample: monodisperse polystyrene, Calibration method: polystyrene equivalent.

[0061] (Antistatic agent A1 synthesis example) The antistatic agent (A1), which is a copolymer having a quaternary ammonium salt group, was prepared by the following method. Ta. A reactor equipped with a stirrer, reflux condenser, and thermometer was charged with methacryloyloxyethyl Trimethylammonium chloride 180g, lauryl methacrylate and tridecyl methacrylate 75 g of a 45:55 (mass %) mixture of acrylates, N,N-dimethylaminoethyl methacrylate, 45g acrylate, 200g methyl ethyl ketone (MEK), isopropyl alcohol 500 g of IPA was charged, and after stirring was started, the system was replaced with nitrogen and the temperature was raised to 55°C. After adding 6 g of 2,2'-azobis(2,4-dimethylvaleronitrile) to the system, The temperature was raised to 65°C and the mixture was stirred for 3 hours, after which 2,2'-azobis(2,4-dimethylbutanediol) was added. 6 g of ethyl nitrile was added and stirred at 65°C for 3 hours. The temperature in the system was raised to 80°C and stirred for 2 hours. After stirring for 1 hour, the mixture was cooled to room temperature to obtain a polymer solution. The composition of this solution was polymer / MEK The weight average molecular weight (Mw) of the polymer was The value was 45,200. Ammonium groups or precursors of ammonium groups such as amines were also The molar average SP value of the structural units of the polymerizable monomers other than the monomer was 9.26.

[0062] (Curable composition) The following materials were mixed in the amounts (parts by mass, calculated as non-volatile content) shown in Table 1. Pyrene glycol monomethyl ether (hereinafter referred to as PGM) and methyl isobutyl ketone (hereinafter referred to as A mixed solvent of PGM and MIBK (PGM:MIBK (mass ratio) 5:5) with a solid content of 50% was used. The mixture was added to obtain a final volume of 100% by weight, and the mixture was stirred until uniform. A composition was obtained. Antistatic agent (A1): Antistatic agent A1 produced by the above method (Meth)acrylate (B1): Main component is pentaerythritol triacrylate A hydroxyl group-containing polyfunctional acrylate compound (hydroxyl value: 131 mgKOH / g, refractive index: 1. 46) (Meth)acrylate (B2): Dipentaerythritol pentaacrylate is the main component A hydroxyl group-containing polyfunctional acrylate compound (hydroxyl value: 59 mgKOH / g, refractive index: 1.49) (Meth)acrylate (B3): Dipentaerythritol pentaacrylate is the main component A hydroxyl group-containing polyfunctional acrylate compound (hydroxyl value: 37 mgKOH / g, refractive index: 1.49) (Meth)acrylate (B4): 1,6-Hexanediol glycidyl ether acrylate Rate (hydroxyl value: 216 mg KOH / g, refractive index: 1.48) (Meth)acrylate (b1): Pentaerythritol tetraacrylate (hydroxyl value : 0 mgKOH / g, refractive index: 1.48) (Meth)acrylate (C1): Bisphenoxyethanol fluorene diacrylate (Refractive index: 1.62) (Meth)acrylate (C2): Ethoxylated o-phenylphenol acrylate ( Refractive index: 1.58) Photopolymerization initiator (D): 1-hydroxycyclohexyl phenyl ketone · Urethane (meth)acrylate (other components): Isophorone diisocyanate and diphenyl A 10-functional urethane acrylate (refractive index) without polar groups that was reacted with taerythritol Rate:1.49)

[0063] [Example 1] Component (A) is 4 parts by mass of the above-mentioned antistatic agent (A1), and component (B) is the above-mentioned (meth) 46 parts by mass of acrylate (B1), and the above-mentioned (meth)acrylate (C1) as component (C). 50 parts by mass of the photopolymerization initiator (D) as component (D) was mixed, and the mixture was then mixed as described above. The composition was adjusted to a solid content of 50% by mass with a solvent and then applied to a triacetyl cellulose film (40 The coating was applied to a surface of 100 μm with a bar coater, and the surface was left to stand in a dryer at about 80°C for 1 minute. A high-pressure mercury lamp with a cumulative light output of 400 mJ / cm2 is used. 2 , peak strength 200m W / cm 2 The triacetylene having a 5 μm layer of cured film was obtained by irradiating it with ultraviolet light under the conditions of A polycellulose film was obtained.

[0064] [Examples 2 to 11 and Comparative Example 1] The same procedure as in Example 1 was repeated except that the blending and composition were as shown in the composition column of Table 1. A radiation-curable resin composition was prepared and evaluated. The results are shown in Table 1.

[0065] [Table 1]

[0066] As can be seen from Table 1, Examples 1 to 11 are acrylic monomers having a hydroxyl group as a polar group. By using this material, it is possible to obtain a coating film with excellent surface resistance and transparency. was created. On the other hand, Comparative Example 1, which does not have a polar group, could not be evaluated due to its poor compatibility with other components. From the above results, it is apparent that the use of the curable composition of the present invention provides high transparency and antistatic properties. It is possible to provide a high refractive index curable resin composition that satisfies the requirements for optical films while achieving both excellent optical properties and excellent refractive index. It became.

Claims

1. A copolymer (A) having a quaternary ammonium base, a copolymer (B) having a polar group and a (meth)acryloyl group and a compound (B) (excluding compound (C)) having a (meth)acryloyl group and at least An active energy ray curable resin composition comprising a compound (C) having at least one aromatic ring structure. thing.

2. The polar group of the compound (B) is a hydroxyl group, a carboxyl group, an amide group, or a sulfo group.

2. The active energy ray-curable resin according to claim 1, which is one or more selected from the group consisting of the following groups: composition.

3. The polar group of the compound (B) is a hydroxyl group, and the hydroxyl value is 10 mgKOH / g or more. The active energy ray-curable resin composition according to claim 1, wherein

4. The total amount of the solid contents of the copolymer (A), the compound (B), and the compound (C) is 100 The proportion of the solid content of the compound (A) in terms of mass% is 0.5 mass% or more and less than 20 mass%. The active energy ray-curable resin composition according to claim 1 .

5. The compound (B) has 1 or more and 10 or less (meth)acryloyl groups.

2. The active energy ray-curable resin composition according to claim 1.

6. The compound (B) according to claim 1, comprising the following (B-1) and / or (B-2): An active energy ray-curable resin composition. (B-1): Compound having 3 to 10 (meth)acryloyl groups (B-2): Compound having one or two (meth)acryloyl groups

7. The compound (A) is composed of a quaternary ammonium base and an ammonium group derived from an amine. The molar average SP value of all structural units other than the structural units having the formula (I) is 7.00 or more and less than 11.

00. The active energy ray-curable resin composition according to claim 1 .

8. The haze of the cured film obtained by curing the active energy ray-curable resin composition is less than 4.0%. The refractive index of the cured film is in the range of 1.50 or more and less than 1.80, and the surface resistance of the cured film is 1.0 x 10 ７ Ω or more 1.0×10 １２ 8. The method according to claim 1 , wherein the resistance is less than Ω. A cured product obtained by curing the composition described above.

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