WO2008004630A1

WO2008004630A1 - Active energy ray-curable composition for optical uses, and high-refractive index resin

Info

Publication number: WO2008004630A1
Application number: PCT/JP2007/063491
Authority: WO
Inventors: Toru Kurihashi; Kazuyoshi Yamamoto; Ryutaro Tanaka
Original assignee: Nippon Kayaku Kabushiki Kaisha
Priority date: 2006-07-06
Filing date: 2007-07-05
Publication date: 2008-01-10
Also published as: JPWO2008004630A1

Abstract

Disclosed is an active energy ray-curable composition for optical uses, which can be used in a high-refractive index resin. The composition comprises an epoxycarboxylate compound (A) produced by reacting an epoxy resin (a) represented by the general formula (1) with a compound (b) having both an ethylenically unsaturated group and a carboxyl group in the molecule. (1) wherein R1 to R8 independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms.

Description

Specification

Active energy ray-curable optical composition and high refractive index resin

Technical field

[0001] The present invention includes an active energy ray-curable optical composition containing a compound derived from an epoxy resin having a specific structure and exhibiting high refractive index, and the composition is irradiated with active energy rays. The present invention relates to a high refractive index resin which is a cured product obtained in this manner, an optical multilayer material having a layer of the resin, and an optical material containing the composition.

Background art

[0002] Conventionally, for example, an epoxy talile monolith compound obtained by addition reaction of acrylic acid or the like with epoxy resin, and a polybasic acid anhydride obtained by addition reaction of a polybasic acid anhydride with this epoxy acrylate polymer compound. Carboxylic acid compounds have been widely used because the cured product has excellent adhesion to the substrate, high thermal stability, and dimensional stability. In particular, resist materials for use in electrical and electronic parts can be used as compounds imparted with developability with an aqueous alkali solution by acid modification.

[0003] Japanese Patent No. 2676422 and Japanese Patent Application Laid-Open No. 2005-129139 disclose an active energy ray-curable material of an epoxy atalyte toy product of an epoxy compound having a tetraphenylethane skeleton structure having excellent heat resistance and the like. Use as is described. Japanese Patent Application Laid-Open No. 2005-200527 describes a method for producing an epoxy compound having a high-purity tetrafluoroethane skeleton structure.

[0004] However, it has not been known about the use of an epoxy compound having an tetraphenylethane skeleton structure as an optical yarn containing an epoxy acrylate and its use as a high refractive index resin. .

In addition, adhesion and toughness due to carboxylic acid modification and patterning with alkaline developer

Also, there is no mention!

Disclosure of the invention

Problems to be solved by the invention

In recent years, optical materials having higher toughness have been demanded. Also, There is also a need for a hardened film having a certain degree of hardness that is not only hard but not broken by impact or the like.

Accordingly, an object of the present invention is to provide an optical composition that provides a cured product having excellent heat resistance, moisture resistance, and toughness and exhibiting a high refractive index.

Means for solving the problem

[0006] As a result of intensive studies to solve the above-mentioned problems, the present inventors include an epoxy carboxylate compound or a polycarboxylic acid compound derived from an epoxy resin having a specific skeleton. The present inventors have found that the composition gives a cured product having an excellent balance of the above-mentioned properties, and have reached the present invention.

[0007] That is, as one aspect of the present invention, there is provided an active energy ray-curable optical composition used for a high refractive index resin, the epoxy resin (a) represented by the following general formula (1): And a composition containing an epoxy carboxylate compound (A) obtained by reacting a compound (b) having both an ethylenically unsaturated group and a carboxyl group in the molecule.

[0008] [Chemical 1]

(1)

[Wherein, R to R may be the same or different from each other, and may be a hydrogen atom, a halogen atom or a carbon atom.

1 8

A prime number 1 to 4 alkyl group is shown. )

[0010] Another aspect of the present invention has the following configuration.

That is, the present invention relates to the above-mentioned epoxy carboxylate compound (A) without polybasic acid. The present invention relates to an active energy ray-curable optical composition comprising a polycarboxylic acid compound (B) obtained by reacting water (c).

In the present invention, R to R in the general formula (1) are hydrogen atoms, and

1 8

The present invention relates to an active energy ray-curable optical composition in which the compound (b) having both a sum group and a carboxyl group is (meth) acrylic acid or cinnamic acid.

The present invention further relates to an active energy ray-curable optical composition comprising a reactive compound (C) other than the epoxy carboxylate compound (A) and the polycarboxylic oxide compound (B).

The present invention further relates to an active energy ray-curable optical composition containing a light stabilizer (D).

[0011] Further, the present invention relates to a high refractive index resin that is a cured product obtained by irradiating the above optical composition with active energy rays.

The present invention also relates to an optical material having the above resin layer.

The present invention also relates to an optical material comprising the above optical composition.

The invention's effect

[0012] The activity of the present invention comprising an epoxy carboxylate compound (A) obtained by reacting an epoxy resin having a specific skeleton with a compound (b) having both an ethylenically unsaturated group and a carboxyl group in the molecule. An active energy containing a polystrengthen carboxylic acid compound (B) obtained by reacting a polybasic acid anhydride (c) with an energy ray-curable optical composition or an epoxycarboxylate compound (A). A cured product obtained by irradiating a line-curable optical composition with a line of active energy is not only excellent in the balance between heat resistance and moisture resistance but also has a high transparency and a high refractive index. Further, the cured product is a material excellent in mechanical properties such as toughness, and in particular, it is a film forming material excellent in adhesion to a substrate and scratch resistance. In addition, since the resin composition of the present invention can be developed by alkali water solubility with polycarboxylic acid, it is also suitable as a material used for so-called optical resists. That is, for example, it is suitable for optical applications such as hard coats for display devices such as lenses, optical disks, and liquid crystal displays, films, and photoconductive materials such as optical waveguides.

BEST MODE FOR CARRYING OUT THE INVENTION [0013] The active energy ray-curable optical composition of the present invention is a composition used for a high refractive index resin, wherein the general formula (1) (wherein R to R are the same or different from each other). Mogugu water

1 8

A compound (b) having both an ethylenically unsaturated group and a carboxy group in the molecule is reacted with an epoxy resin (a) represented by an elementary atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms). The resulting epoxy carboxylate compound (A) or the polycarboxylate compound (B) obtained by reacting the epoxycarboxylate compound (A) with a polybasic acid anhydride (c) is included.

[0014] In the general formula (1), R to R should be appropriately selected according to the intended use

1 8

For example, a straight or branched saturated carbonization having 1 to 4 carbon atoms such as a hydrogen atom, a methyl group, an ethyl group, an n propyl group, an i propyl group, an n butyl group, an i butyl group, and an s butyl group. A hydrogen atom; a halogen atom such as a chlorine atom, a bromine atom or an iodine atom;

Of these, compounds in which R to R are all hydrogen atoms are the most powerful in terms of obtaining materials.

1 8

Is also preferable.

In addition, when R to R are halogen atoms such as chlorine atom, bromine atom and iodine atom,

1 8

Higher refractive index.

[0015] The epoxy resin (a) represented by the general formula (1) has a production method described in, for example, Japanese Patent Application Laid-Open No. 2005-200527, and can be produced according to the method. . In addition, a commercial product (Nippon Kayaku product name: GTR-1800:-R to R in general formula (1) are all hydrogen sources.

1 8

Copolymer with epoxy value of 170 g / eq, manufactured by Japan Epoxy Resin Product name: j ER1031S: —R to R in general formula (1) are all hydrogen atoms, epoxy value is 200 gZeq

1 8

It is also possible to obtain it as a certain fat.

[0016] Of the epoxy resins (a), those having an epoxy equivalent of less than 180 gZ equivalent are particularly preferred. The reason for this is that more ethylenically unsaturated bonds can be introduced, and mechanical strength is imparted to the resulting cured product, resulting in a tougher grease. Further, the high purity epoxy resin (a) represented by the general formula (1) produced by the method described in JP-A-2005-200527 is an epoxy resin having a small epoxy equivalent. The epoxy resin ( _a ) is an optical composition of the present invention, and the composition is irradiated with active energy rays. It is suitable for a high refractive index resin which is a cured product obtained by irradiation, an optical multilayer material having the resin layer, and an optical material containing the composition.

[0017] The epoxycarboxylate compound (A) used in the active energy ray-curable optical composition of the present invention comprises a compound (b) having both an ethylenically unsaturated group and a carboxy group in the epoxy resin (a). It can be obtained by reaction (epoxycarboxylate step). The polycarboxylic oxide compound (B) used in the active energy ray-curable optical composition of the present invention is obtained by further reacting an epoxy carboxylate compound (A) with a polybasic acid anhydride (c) (acid addition). Step).

[0018] The purpose of the epoxy carboxylate solution process is to introduce an ethylenically unsaturated group, which is a reactive group of active energy rays, into the skeleton of the epoxy resin. Specifically, it is a reaction between an epoxy group and a carboxy group.

Examples of the compound (b) having both an ethylenically unsaturated group and a carboxy group include (meth) acrylic acid, crotonic acid, a cyanocinnamic acid, cinnamic acid, or a compound having both an unsaturated group and a hydroxyl group. Or the compound etc. which reacted the unsaturated dibasic acid are mentioned.

[0019] In the above, a compound obtained by reacting a compound having both an unsaturated group and a hydroxyl group with a saturated or unsaturated dibasic acid is, for example, a (meth) acrylate derivative having one hydroxyl group in one molecule. Examples thereof include semiesters obtained by reacting saturated or unsaturated dibasic acid anhydrides in an equimolar amount. For example, hydroxyalkyl (meth) acrylate, such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, maleic anhydride, succinic anhydride, phthalic anhydride, Examples thereof include compounds obtained by reacting a saturated or unsaturated dibasic acid such as partial or total hydrogenated phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like.

[0020] Of these, considering the stability of the reaction between the epoxy resin (a) and the compound (b), the compound (b) is preferably a monocarboxylic acid. When the monocarboxylic acid and the polycarboxylic acid are used in combination, the ratio of the molar amount of the monocarboxylic acid to the molar amount of the polycarboxylic acid is preferably 15 or more.

Compound (b) includes active energy when the active energy ray-curable optical composition is used. (Meth) acrylic acid or cinnamic acid is most preferred from the standpoint of sensitivity to a line of lugi.

[0021] The proportion of the epoxy resin (a) and the compound (b) used in this reaction should be appropriately changed depending on the application. That is, when all of the epoxy groups are carboxylated, unreacted epoxy groups do not remain, so that the storage stability as the epoxy strength noroxylate compound (A) is high. In this case, only the reactivity due to the introduced double bond is used for the curing reaction.

[0022] In the epoxy carboxylate refining process in which no epoxy group remains, the charge ratio of epoxy resin (a) and compound (b) is 1 equivalent of epoxy group of epoxy resin (a). Preferably, the carboxyl group of the compound (b) is 0.990-1.20 equivalent. If it is this range, it will not gelatinize in the acid addition process without an epoxy group remaining, and the storage stability of rosin is good. When the charged amount of the compound (b) is within this range, the stability of the resin with less epoxy groups in which the compound (a) remains is improved.

[0023] On the other hand, by reducing the amount of compound (b) charged and leaving unreacted epoxy groups, the reaction by the introduced unsaturated bond and the reaction by the remaining epoxy group (for example, the polymerization reaction by the photopower thione catalyst). And thermal polymerization reaction) can be used in combination for curing. In this case, improvement in adhesion to a metal material or the like and reduction in curing shrinkage can be achieved. However, it is necessary to pay attention to the storage and production conditions of the epoxycarboxylate compound.

[0024] When leaving an epoxy group, the compound is equivalent to 1 equivalent of epoxy group of epoxy resin (a).

It is preferable to charge 0.20 to 0.90 equivalent of the carboxy group of (b). If it is within this range, the effect of composite curing is exhibited. Further, when leaving an epoxy group, it is necessary to pay attention to the aging stability of the gel or epoxycarboxylate compound (A) during the subsequent reaction.

Furthermore, when used as a polycarboxylic acid compound (B) through an acid addition step described later, it is preferable not to leave an epoxy group. That is, when a large number of epoxy groups remain, it reacts with the introduced carboxy group, and the storage stability is particularly deteriorated.

[0025] The epoxy carboxylate solution process may be used without using a solvent. Use solvent When used, the solvent is not particularly limited as long as the reaction is not affected. Examples of the solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzen, aliphatic hydrocarbon solvents such as hexane, octane and decane, petroleum ether which is a mixture thereof, white Examples include gasoline, solvent naphtha, ester solvents, ether solvents, and ketone solvents.

[0026] Examples of ester solvents include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate, cyclic esters such as 0-butyrolatatane, ethylene glycol monomethyl etherate acetate, diethylene glycol nolemonomethineate nole monoacetate. , Diethylene glycol monoethylenoatenore monoacetate, triethyleneglycol monorenoethylenoleate nore monoacetate, diethyleneglycolenobutinorenoatenore monoacetate, propylene glycol monomethyl ether monoacetate, butylene glycol monoremonomethyl Mono- or polyalkylene glycol monoalkyl ether monoacetates such as monoethyl acetate, dialkyl glutarate, dialkyl succinate, dialkyl adipate Polycarboxylic acid alkyl esters, etc. and the like.

[0027] Examples of the ether solvent include alkyl ethers such as jetyl ether and ethylbutyl ether, ethylene glycol-no-resin methinore etherol, ethylene glycol jetyl ether, dipropylene glycol dimethyl ether, dipropylene glycol jetyl ether, Examples thereof include Daricol ethers such as triethylene glycol dimethyl ether and triethylene glycol jetyl ether, and cyclic ethers such as tetrahydrofuran.

Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

In addition to this, as the solvent for the epoxy carboxylate solution step, the reactive compound (C 2) described later can be used, and these can be used alone or in combination. This is preferable because it can be used as it is as the active energy ray-curable optical composition of the present invention.

[0029] A catalyst may be used during the epoxy carboxylate step to promote the reaction. The catalyst is used in an amount of about 0.1 to 10% by weight based on the total amount of the reactants. Is preferred. Examples of the catalyst include triethylamine, benzyldimethylamine, chloride triethylamine, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, and triphenylstibine. And basic catalysts such as methyltristibine, chromium octoate, and zirconium octoate.

[0030] The reaction temperature of the epoxy carboxylate soot process is 60 to 150 ° C. The reaction time is preferably 5 to 60 hours.

Examples of thermal polymerization inhibitors in the epoxy carboxylate tank process include: Hydone quinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-ditert-butyl-4-hydroxytoluene, etc. Is preferred.

In the epoxy carboxylate soot process, the time when the acid value of the sample (according to J IS K5601-2-1: 1999) becomes 3 mg'KOH / g or less, preferably 2 mg'KOH Zg or less, is sampled appropriately. The end point.

[0031] The structure of the epoxycarboxylate compound (A) is represented as follows.

[0032] [Chemical 2]

(A)

In the formula of (A), X is represented by the following structure X ¹ or X ² (R is a residue of compound (b)).

[0034] [Chemical 3]

[0035] Next, the acidification process will be described. In the acid addition step, a polybasic acid anhydride (c) is reacted with the hydroxyl group produced by the epoxy carboxylate oxidation step, and a polycarboxylic acid compound (B) in which a carboxyl group is introduced via an ester bond. ).

[0036] The polybasic acid anhydride (c) is not particularly limited as long as it is a compound having an acid anhydride structure in the molecule. For example, water-free succinic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, water-free itaconic acid, 3-methyl-tetrahydrophthalic anhydride, which are excellent in alkaline aqueous solution developability, heat resistance, hydrolysis resistance, etc. 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride or maleic anhydride are preferred.

[0037] In the acid addition step, a polybasic acid anhydride is added to the reaction solution of the epoxy carboxylate solution step.

It can also be done by adding (c). The addition amount of the polybasic acid anhydride (c) should be appropriately changed according to the use.

[0038] However, when the polyrubonic acid compound (B) used in the active energy ray-curable optical composition of the present invention is used as an alkali development resist, the finally obtained polycrystal is used. The calculated amount of the solid acid value of the carboxylic acid compound (B) (JIS K5601-2-1: 1999) is 40 to: LOOmg'KOHZg, more preferably 60 to 90 mg'KOH / g It is preferable to charge polybasic acid anhydride (c). When the solid content acid value is smaller than this range! /, The developability of the aqueous solution of the active energy ray-curable optical composition is remarkably lowered, and in the worst case, development is impossible. When the solid content acid value exceeds this, the polybasic acid anhydride (c) becomes excessive with respect to the reaction point, and the unreacted polybasic acid anhydride (c) remains in the composition. , Developability may become too high and patterning may not be possible.

[0039] During the acid addition step, it is preferable to use a catalyst to accelerate the reaction. The amount of the catalyst used is preferably about 0.1 to 10% by weight based on the total amount of the reaction product.

. Examples of the catalyst include triethylamine, benzyldimethylamine, sodium salt triethylamine, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide. Examples include yuum, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium oxalate, and zirconium octoate.

[0040] The reaction temperature in the acidification step is 60 to 150 ° C. The reaction time is preferably 5 to 60 hours.

In the acid addition step, the reaction is carried out without solvent or diluted with a solvent. When a solvent is used, the solvent is not particularly limited as long as the reaction is not affected. In addition, when a solvent is used in the preceding carboxylation step, a solvent that does not affect the acid addition step may be used in the acid addition step without removing the solvent.

Examples of the solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetramethylbenzen, aliphatic hydrocarbon solvents such as hexane, octane, and decane, petroleum ether that is a mixture thereof, white Examples include gasoline and solvent naphtha.

[0041] Further, as ester solvents, alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate, y cyclic esters such as butyrolatatane, ethylene glycol monomethyl etherate acetate, diethyleneglycolone monomethineate nole monoacetate , Diethylene glyconomonoethylenoatenole monoacetate, triethyleneglycolenomonoethylenoleate termonoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate, butylene glycol monorenomethylenoleate termonoacetate Such as mono- or polyalkylene glycol monoalkyl ether monoacetates, dialkyl glutarate, dialkyl succinate, dialkyl adipate, etc. Carboxylic acid alkyl esters.

[0042] In addition, as ether solvents, alkyl ethers such as jetyl ether and butylbutyl ether, ethylene glyconoresin methinore etherol, ethylene glycol jetyl ether, dipropylene glycol dimethyl ether, dipropylene glycol jetyl ether , Dalicol ethers such as triethylene glycol dimethyl ether and triethylene glycol jetyl ether, and cyclic ethers such as tetrahydrofuran.

Also, as ketone solvents, acetone, methyl ethyl ketone, cyclohexanone, isophorone Etc.

[0043] In addition, as the solvent in the acid addition step, the reactive compound (C) described later can be used, and these can be used alone or in combination. In this case, since it can be used as it is as the active energy ray-curable optical composition of the present invention, a preferable heat polymerization inhibitor in the acidification step is the same as that in the epoxy carboxylate step. Can be used.

The acid addition step is terminated when the acid value of the reaction product is in the range of plus or minus 10% of the acid value set according to the intended application while sampling appropriately.

[0044] The structure of the polycarboxylic acid compound (B) is represented as follows.

[0045] [Chemical 4]

[0046] In the formula (B), Y is the following structure Y ¹ or Y ² (R is the residue of the compound (b), R ¹ is the compound

It is a residue of (c). ).

[0047] [Chemical 5]

[0048] The reactive compound (C) other than the epoxycarboxylate compound (A) and the polycarboxylic acid compound (B) used in the active energy ray-curable optical composition of the present invention is an activity. It is a compound that shows reactivity by energy rays. The reactive compound (C) is useful for imparting physical properties before and after curing according to the purpose of use, depending on its properties. Examples of the reactive compound (C) include so-called reactive oligomers such as radical-reactive (meth) acrylates, cation-reactive epoxy compounds, and other Bury compounds. .

[0049] The (meth) acrylates include monofunctional (meth) acrylates, polyfunctional (meth) acrylates, epoxy carboxylate compounds (A), and polycarboxylic acid compounds (B). Epoxy (meth) acrylates, polyester (meth) acrylates, urethane (meth) acrylates and the like.

[0050] Monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate. , Polyethylene glycol (meth) acrylate monomethyl ether, phenyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl ( (Meta) Atarirate.

[0051] Polyfunctional (meth) acrylates include butanediol di (meth) acrylate, hexane diol di (meth) acrylate, neopentyl glycol di (meth) acrylate, nonanediol all (meth) acrylate, Glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (meth) ateroyloxyschetil isocyanurate, polypropylene glycol di (meth) acrylate, adipic acid Epoxy di (meth) acrylate, bisphenol ethylene oxide di (meth) ate relay , Hydrogenated bisphenol ethylene oxide (meth) acrylate, bisphenol di (meth) acrylate, di- (meth) acrylate, dipentaerythritol with ε-strength prolatatone of hydroxypentavalylate neopentyl glycol And ε-force prolatatatone reaction product poly (meth) acrylate, dipentaerythritol poly (meth) acrylate, trimethylol propane tri (meth) acrylate, triethylol propane tri (meth) acrylate or addition of ethylene oxide , Pentaerythritol tri (meth) atalylate or its ethylene oxide adduct, pentaerythritol tetra (meth) atarylate, dipentaerythritol hexa (meth) atarylate or its ethylene oxide adduct It is.

[0052] The cation-reactive epoxy compounds that are the reactive compound (C) are not particularly limited as long as they are generally compounds having an epoxy group. For example, glycidyl (meth) acrylate, methyl glycidyl ether, ethyl daricidyl ether, butyl daricidyl ether, bisphenol Α diglycidyl ether, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane Hexanecarboxylate ("Syracure UVR-6110" manufactured by Union Carbide, etc.), 3, 4 Epoxycyclohexenoreethinore 3, 4 Epoxy cyclohexanecarboxylate, Burcyclohexenediodide ("Union 'Carbide" ELR " — 4206 ”), limonene dioxide (such as“ Celoxide 300 00 ”manufactured by Daicel Chemical Industries), allylcyclohexenedioxide, 3, 4 epoxy-4-methylcyclohexyl 2 propylene oxide, 2- (3, 4 epoxycyclo Hexyl 5,5-spiro 3, 4 epoxy) cyclo Xan m dioxane, bis (3,4-epoxycyclohexyl) adipate (such as “Syracure UVR-6128” manufactured by Union Carbide), bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy) (Cyclohexenole) ether, bis (3,4-epoxycyclohexylmethyl) ether, bis (3,4-epoxycyclohexyl) jetylsiloxane and the like.

[0053] Examples of the beryl compound as the reactive compound (C) include butyl ethers, styrenes, and other bur compounds. Examples of bur ethers include ethyl bilene ethere, propino levino eno ethenore, hydroxy ethino levino eno ethenore, and ethylene glycol dibule ether. Examples of styrenes include styrene, methyl styrene, ethyl styrene and the like. Other Birui compound is triallyl isocyanu Rate and the like.

[0054] Of these, as the reactive compound (C), radical-curable (meth) acrylates are preferred. In the case of cation-reactive epoxy compounds, carboxylic acid and epoxy group react, so it is necessary to use a two-component mixed type that is mixed at the time of use.

[0055] The above-described epoxy carboxylate compound (A) or polycarboxylic acid compound (B) and a reactive compound other than the epoxycarboxylate compound (A) and the polycarboxylic acid compound (B). By mixing with compound (C), the active energy ray-curable optical composition of the present invention can be obtained.

[0056] When the active energy ray-curable optical composition of the present invention contains the reactive compound (C), the epoxy carboxylate compound (A) or the polycarboxylic acid compound ( B) is 90 to 5% by weight, preferably 80 to 10% by weight, and the reactive compound (C) is 3 to 90% by weight, preferably 13 to 80% by weight. Other components may be included as necessary.

[0057] The active energy ray-curable optical composition of the present invention is cured by irradiation with active energy rays. Examples of the active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays, and laser rays, and particle rays such as alpha rays, beta rays, and electron beams. The active energy ray-curable optical composition of the present invention can be appropriately selected depending on the use, but among these, ultraviolet rays, laser beams, visible rays, or electron beams are preferable. For curing with active energy rays, for example, a xenon lamp, a carbon arc, etc. Use light sources such as germicidal lamps, fluorescent lamps for ultraviolet rays, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, electrodeless lamps, metal halide lamps, or electron beams from scanning or curtain-type electron beam accelerators. Can do. In addition, when the active energy ray-curable optical composition of the present invention is cured by ultraviolet irradiation, the amount of ultraviolet irradiation necessary for curing may be about 300 to 3000 mjZcm ² .

The present invention also includes a high refractive index resin which is a cured product.

[0058] Furthermore, it is preferable to add a light stabilizer (D) for the purpose of imparting light resistance to the active energy ray-curable optical composition of the present invention. A light stabilizer means that light is applied for a long time. A generic term for compounds added to prevent discoloration and brittleness when dripping. Since the active energy ray-curable optical composition of the present invention has an aromatic ring in its skeleton, the light resistance as an optical material can be further improved by adding a light stabilizer.

[0059] The light stabilizer (D) includes compounds used as ultraviolet absorbers, antioxidants, and the like.

As the light stabilizer (D), bis (1, 2, 2, 6, 6 pentamethyl-4-piperidyl) [[3,5 bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate (for example, Hindered amine light stabilizers such as Tinuvin 144 manufactured by Ciba Specialty Chemicals).

[0060] Examples of the light stabilizer (D) include 2- (2 hydroxy-5 t-butylphenol) -2H benzotriazole (for example, Tinuvin PS manufactured by Ciba Specialty Chemicals), 3-(2H benzo Triazole-2-yl) -5- (1,1-dimethylethyl) -4 hydroxybenzenepropanoic acid branched and straight chain (C7-C9) alkyl esters (for example, Tinuvin 99-2 from Ciba Specialty Chemicals) ), 3- (2H benzotriazole 2-yl) -5- (1,1-dimethylethyl) -4-hydroxybenzenepropanoic acid branched and straight chain (C7-C9) alkyl esters (eg, Tinuv from Ciba Specialty Chemicals) in 384-2 etc.), 2- (2H benzotriazole 2-yl) 4, 6 Bis (1-methyl-1-fe-ruethyl) phenol (eg, Tinuvin from Ciba Specialty Chemicals)

Benzotriazole-based UV absorbers such as 2)-(4,6 bis (2,4 dimethylphenol) -1,1,3,5 triazine-2-yl) 5 hydroxyphenol and oxysilane ( Products of reaction with [(C10-C 16 mainly C 12—C 13 alkyloxy) methyl] oxysilane) (for example, Tinuvin 400 manufactured by Ciba Specialty Chemicals), 2— (2,4-dihydroxyphenyl) , 6 bis (2,4 dimethylphenol) 1, 3, 5 product of reaction of triazine with (2-ethylhexyl) -glycidic acid ester (eg Tinuvin 405 from Ciba Specialty Chemicals), 2, 4 bis [2 Hydroxy 4-butoxyphenyl] —6— (2, 4 Dibutoxyphenyl) — 1, 3, 5 Triazine (eg Tinuvin 460 from Ciba Specialty Chemicals) etc. Hydroxytritriazine (HPT) Ultraviolet rays An absorbent is mentioned.

In the case where the active energy ray used for the curing reaction is ultraviolet rays, hydroxyphenyl triazine (HPT) ultraviolet absorbers are effective.

[0061] As the light stabilizer (D), for example, tetrakis (2,4 tert-butylphenol) [1,1,2-biphenyl] -4,4,1 dilbisphosphonite (eg Cibas) Phosphite-based anti-oxidants such as IRGAFOS XP40 manufactured by Chemicals Chemicals, Inc.), bis (2,4 di-t-butylphenol) pentaerythritol diphosphite (eg IRGAFOS XP60 manufactured by Ciba Specialty Chemicals Co., Ltd.) Or pentaerythritol tetrakis [3— (3,5 tert-butyl 4-hydroxyphenol) propionate (eg, IRGANOX 1010 manufactured by Ciba Specialty Chemicals), thiojetylene bis [3— (3,5 di- t-butyl 4-hydroxyphenyl) propionate] (for example, IRGANOX 1035 manufactured by Ciba Specialty Chemicals), 4, 6 bis (octylthiomethyl) o-taresol (for example, And hindered phenolic acid inhibitors such as IRGANOX 1520L manufactured by Ciba Specialty Chemicals.

[0062] When the light stabilizer (D) is used, one or more of the above may be used.

When the light stabilizer (D) is used, the use ratio in the active energy ray-curable optical composition of the present invention is preferably 0.1 to 5% by weight, more preferably 0.5. ~ 3% by weight. When the amount is less than this, the effect as a sufficient stabilizer is not exhibited, and when the amount is too large, the curing reaction by active energy rays may be inhibited.

[0063] In addition, for the purpose of adapting the active energy ray-curable optical composition of the present invention to various applications, other components may be added up to 70% by weight of the composition. Other components include photopolymerization initiators, coloring materials, other additives, and the like.

[0064] Examples of the photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutinoreethenole; acetophenone, 2,2-diethoxy-1- Phenolacetophenone, 2, 2-diethoxy-1, 2-phenacetophenone, 1,1-dichloroacetophenone, 2-hydroxy 2-methyl-phenylpropane 1-one, diethoxyacetophenone, 1-hydroxyxin cyclohexylphene Luketone, 2-methyl-1 [4 (methylthio) phenol] 2 Acetophenones such as 2-morpholinopropane 1-one; 2-anthylanthraquinone, 2-tert-butylanthraquinone, 2-chloro anthraquinone, anthraquinones such as 2-amylanthraquinone; 2, 4 jetylthioxanthone Thioxanthones such as thixanthone and 2-chlorothixanthone; ketals such as acetophenone dimethyl ketal and benzil dimethyl ketal; 2, 4, 6 Trimethylbenzoyl diphosphine phosphine oxide, radical type initiators such as bis (2, 4, 6 trimethyl benzoyl) phosphine phosphoxide, etc. Can be mentioned.

[0065] As other photopolymerization initiators, Nippon Senshoku Dye NK, a borate initiator, is used.

3876, NK-3881, etc .; photoacid generators, for example, 9-phenolacridine, 2, 2, —bis (o-cross-hole), 4, 4 ,, 5, 5, one tetraphenol 1, 2 Biimidazole (Kurokin Kasei Biimidazole, etc.), 2, 2-azobis (2-aminopropane) dihydrochloride (Wako Pure Chemicals V50, etc.), 2, 2 Azobis [2— (Imidazoline 1 2 yl ) Propane] dihydrotalolide (VA044, etc., manufactured by Wako Pure Chemical Industries, Ltd.), [eater 5-2-4- (cyclopentadecyl) (1, 2, 3, 4, 5, 6, ita) (methylethyl) benzene] iron ) Cationic initiators such as hexafluorophosphonate (Irgacure 261, etc., manufactured by Ciba Geigy).

[0066] Further, an azo-based initiator such as azobisisobutyryl-tolyl, or a peroxide-based radical-type initiator sensitive to heat such as benzoyl peroxide may be used in combination with the photopolymerization initiator. Also, use both radical and cationic initiators together.

When the active energy ray-curable optical composition of the present invention contains these initiators, the content of the initiator is about 0.1 to 10%.

[0067] Examples of coloring materials include organic pigments such as phthalocyanine, azo, and quinacridone, organic pigments such as titanium oxide, carbon black, bengara, zinc oxide, barium sulfate, and talc, and publicly known general coloring. And extender pigments can be used.

[0068] Examples of other additives include thermosetting catalysts such as melamine, talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, hydroxyaluminum hydroxide, acidic aluminum, silica. , Fillers such as clay, thixotropy imparting agents such as Aerosil, lid opening It is possible to use cyanine blue, phthalocyanine green, titanium oxide, silicone, fluorine-based repellents and antifoaming agents, polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether, and the like.

[0069] Further, in the active energy ray-curable optical composition of the present invention, rosins (so-called inert polymers) that are not reactive with the active energy ray can also be used. Examples of such resins include epoxy resins other than the above, phenol resins, urethane resins, polyester resins, ketone formaldehyde resins, cresol resins, xylene resins, diallyl phthalate resins, styrene resins. , Guanamine resin, natural or synthetic rubber, acrylic resin, polyolefin resin, or modified products thereof. These are preferably used in the range of up to 40% by weight in the composition!

[0070] For the purpose of adjusting the viscosity according to the purpose of use, a solvent may be added in the composition in the range of about 60% by weight, preferably about 50% by weight. For example, a solvent in the above-mentioned carboxylate reaction and acid addition step may be used.

[0071] The present invention also includes an optical material containing the above active energy ray-curable optical composition and used for the purpose of optically refracting light.

Optical applications include, for example, lens materials such as convex lenses, concave lenses, micro lenses, Fresnel lenses, and lenticular lenses; light guide materials used in liquid crystal display devices; sheets and films processed into plates, disks, etc .; uncured A so-called nanoimprint material, which is formed by pressing a finely processed “mold” into the composition; a sealing material for protecting the element, particularly a sealing material for a light emitting diode, a photoelectric conversion element, etc. Etc.

[0072] The optical composition of the present invention comprises a coating material such as a hard coat, a top coat, an overprint varnish, and a clear coat; an adhesive material such as a laminate, an optical disc, and various other adhesives; an adhesive; It is also suitably used for film formation that requires a high refractive index, such as a resist material such as a ladder resist, etching resist, or micromachine resist. Furthermore, it can be used as a so-called dry film in which a film-forming material is temporarily applied to a peelable substrate to form a film and then bonded to the originally intended substrate to form a film.

Above all, based on high refractive index, lens materials such as convex lens, concave lens, micro lens, Fresnel lens, lenticular lens, hard coat, top coat, overprint Use as a coating material such as tonis and clear coat is particularly preferred.

[0073] Further, in the case of the active energy ray-curable optical composition containing the polycarboxylic acid compound (B), the adhesion to the base material was enhanced by the carboxyl group in view of the above-mentioned use. Therefore, it can be used as an application for coating a plastic substrate or a metal substrate. The composition can also be used as a resist material composition for alkali developable optics that requires a high refractive index by taking advantage of its solubility in an alkaline solution. That is, it is used for forming a film layer of the composition on a substrate, partially irradiating active energy rays such as ultraviolet rays, and dissolving and removing unirradiated portions with an alkaline solution or the like to draw. .

[0074] The method of forming the film is not particularly limited, and intaglio printing method such as gravure, relief printing method such as flexo, stencil printing method such as silk screen, lithographic printing method such as offset, etc. Various coating methods such as "Ta '~", Knife co ^ ~ "'~", Daiko ¹ ~~ Ta '~ "Power" ~ "Tenko. ~"Ta' ~ ", Spinco ¹ ~~ Ta '~", etc. Can be arbitrarily adopted.

[0075] In the present invention, a high refractive index resin is a value obtained by measuring the refractive index of a cured product obtained by irradiating active energy rays in accordance with J IS K7142: 1996, which is approximately 1.55 or more. Is greaves

[0076] In the present invention, the active energy ray-curable optical composition is formed into a film on a substrate.

-An optical multilayer material comprising at least two layers of a high refractive index resin obtained by curing is also included.

Example

[0077] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. Moreover, unless otherwise indicated in an Example, a part shows a weight part. The physical property values in the examples were measured by the following methods.

(1) Epoxy equivalent: Measured by the method described in JIS—Κ7236: 2001.

(2) Hardness: Measured by the method described in JIS Κ5600-5-4-4: 1999.

(3) Refractive index: Measured by the method described in JIS K7142: 1996.

[0078] Synthesis Example 1 1, Synthesis Example 1 2 Synthesis of Epoxy Carboxylate Compound (I)

85g of Nippon Kayaku GTR-1800 (epoxy value 170g / eq), which is an epoxy resin having a tetrafluoroethane structure as epoxy resin (a), is ethylenically unsaturated in the molecule. The amount of acrylic acid (abbreviation AA, molecular weight = 72) listed in Table 1 as the compound (b) having both a sum group and a carboxy group, 1.5 g of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether monoacetate as a solvent Were mixed and reacted at 100 ° C for 24 hours.

Synthesis Example 1 3 Synthesis of epoxycarboxylate compound (A)

Epoxy resin (a) as epoxy resin having tetraphenol structure made of Japan Epoxy Resin jER1031S (epoxy value 200g / eq) 100g, acrylic acid (abbreviation AA, molecular weight = 72) are listed in Table 1. The amounts were mixed and reacted. Reaction conditions and the like are the same as those in Synthesis Example 1-1 and Synthesis Example 12.

[0080] Comparative Synthesis Example 1 1 Synthesis of Epoxy Carboxylate Compound

As an alternative to epoxy resin (a), NERg 1202 (epoxy value 292gZeq), a multifunctional bisphenol A type resin, 146g and acrylic acid (abbreviation AA, molecular weight = 72) are listed in Table 1. The amounts were mixed and reacted. Table 1 also shows the finished acid value of the sample. The reaction conditions and the like are the same as those in Synthesis Example 1-1 and Synthesis Example 1-2.

[0081] [Table 1]

Synthesis Example 2-1 and Synthesis Example 2-2 Synthesis of polycarboxylic acid compound (B)

In Synthesis Example 1-1, the amount of tetrahydrophthalic anhydride shown in Table 2 was added as the polybasic acid anhydride (c) to the epoxy carboxylate compound (A) obtained above, resulting There was added pressure of propylene glycol monomethyl ether monoacetate as a solvent so as to be 65 by weight ^_0/0, by addition reaction by heating for 10 hours at 100 ° C polycarboxylic Sani匕合was (B) solution It was. The set acid value in Table 2 means the desired solid acid value for the finally obtained polycarboxylic acid compound. The polybasic acid anhydride (c), which is a calculated amount for achieving the set acid value, was used.

[0083] [Table 2]

[0084] Example 1-1, Example 1-2, Example 1-3, Example 1-4: Preparation and evaluation of active energy ray-curable optical composition

Synthesis Example 1-1, Synthesis Example 1-2, Synthesis Example 1-3, Synthesis Example 2-2 Epoxy carboxylate compound (A) or polycarboxylic acid compound (B) 20g, radical curable type 4g of dipentaerythritol hexaatalylate as a reactive compound (C) and 1.5g of Irgacure 184 as an ultraviolet-reactive photopolymerization initiator are mixed and dissolved by heating. A composition was obtained.

[0085] This was coated on a polycarbonate plate with a hand applicator so as to have a film thickness of 20 microns when dried, and solvent-dried in an electric oven at 80 ° C for 30 minutes. After drying, the irradiation dose is 10% using a UV vertical exposure device (Oak Seisakusho) equipped with a high-pressure mercury lamp.

The ultraviolet OOmiZcm ² was obtained by irradiating the optical material is cured.

[0086] The film hardness (pencil hardness) of this optical material was measured according to JIS 1¾600-5-4: 1999, and an impact resistance test (weight drop test) was conducted according to IS06272-1: 2002. The results are shown in Table 3. In the weight drop test, “no scratches visually” was evaluated as “no scratches”, and “scratches that can be visually confirmed on the coating surface” were evaluated as “scratches”.

[0087] The above composition was applied onto a polypropylene plate by the same method, dried and cured to obtain a coating film, and the cured coating film was peeled off. The refractive index of the coating film peeled according to JIS K7142: 1996 was measured and shown in Table 3.

[0088] Comparative Example 1 1: Comparative Synthetic Example 1-1 A reactive epoxycarboxylate compound synthesized in Example 1 was prepared in the same manner as in Example 1-11, and the hardness, impact resistance and refractive index of the coating film were evaluated. . The results are shown in Table 3.

[Table 3] Physical properties of coating film

[0090] From the above results, the cured product of the composition prepared from the specific epoxy resin of the present invention is tougher and harder than the cured product of the composition prepared from the epoxy resin of the comparative example. However, it has a high refractive index and is suitable for optical applications.

Further, by comparing Example 1-1 and Example 1-3, the cured product of the composition prepared from epoxy resin ( _a ) having an epoxy equivalent of less than 180 g / equivalent is a tougher cured product. Was shown to give.

[0091] Example 2: Preparation and evaluation of active energy ray-curable optical resist

20 g of the polycarboxylic acid compound (B) obtained in Synthesis Example 2-1, 4 g of dipentaerythritol hexaatalylate, a radical-reactive monomer as the reactive compound (C), purple 1.5 g of Irgacure 184 as an external-reactive photopolymerization initiator was mixed and dissolved by heating to obtain an optical composition.

[0092] This was coated on a quartz plate with a hand applicator so as to have a film thickness of 20 microns when dried, and solvent-dried in an electric oven at 80 ° C for 30 minutes. After drying, cover the mask pattern from the top of the coated material and cure it by irradiating with UV radiation of lOOOmjZcm ² with UV vertical exposure equipment (Oak Seisakusho) equipped with a high-pressure mercury lamp. Got. Subsequently, a 1% by weight aqueous sodium carbonate solution was sprayed to dissolve the unexposed area and imaged.

As a result, a pattern could be formed, indicating that the polycarboxylic acid compound (B) of the present invention has resist suitability.

[0093] Example 3-1 and Example 3-2: Light stabilizer

To the composition obtained in Example 1-1, 5 g of the same composition as a light stabilizer (D) was added 2, 4-bis [2 hydroxy-4-butoxyphenol] -6- (2, 4 dibutoxyphenol. -1) 1, 3, 5 Triazine (trade name: Tinuvin 460 manufactured by Ciba Specialty Chemicals), 40 mg bis (1, 2, 2, 6, 6 pentamethyl-4 piperidyl) [[3,5 Bis (1 , 1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate (trade name: Tinuvin 144 manufactured by Ciba Specialty Chemicals; hindered amine light stabilizer) and bis (2,4-di-tert-butylphenol) E) Add 20 mg of pentaerythritol diphosphite (trade name: IRGAFOS XP60 manufactured by Ciba Specialty Chemicals; antioxidant), and use a quartz glass plate with a hand applicator so that the film thickness when dried is 20 microns. Coated on top. Next, the solvent is dried in an electric oven at 80 ° C for 30 minutes. After that, the optical material is cured by irradiating with an ultraviolet ray with an irradiation dose of lOOOmiZcm 2 using an ultraviolet vertical exposure device (Oak Manufacturing) equipped with a high-pressure mercury lamp. Obtained (Example 3-1).

An optical material was obtained in the same manner as above except that the light stabilizer (D) was not used! / (Example 32).

[0094] These optical materials were irradiated with light for 1000 hours by a Fedometer, and a light resistance test was conducted. The transmittance of light at 450 nm was measured, and the transmittance after the light resistance test was conducted.

[0095] [Table 4] Light stability

[0096] From the above results, it was shown that the addition of the light stabilizer (D) improves the light stability and is useful as an optical material.

Industrial applicability

The active energy ray-curable optical composition derived from an epoxy resin having a specific structure according to the present invention provides a cured product that is relatively tough and has a refractive index and excellent transparency. It can also be used as an optical resist that can be alkali-developed by acid modification. Further, it can be used as a molding material or a film forming material, and can be suitably used for optical parts such as lenses, paints, films, and the like.

Claims

Claims An active energy ray-curable optical composition used for a high refractive index resin, wherein the epoxy resin (a) represented by the following general formula (1) has an ethylenically unsaturated group in the molecule. And the epoxy carboxylate compound (A) obtained by reacting the compound (b) having both a carboxyl group and a carboxyl group.

[Chemical 1]

(Wherein R to R may be the same or different from each other, hydrogen atom, halogen atom or carbon

1 8

A prime number 1 to 4 alkyl group is shown. )

An epoxy carboxylate compound (A) obtained by reacting an epoxy resin (a) represented by the following general formula (1) with a compound (b) having both an ethylenically unsaturated group and a force carboxyl group in the molecule (A) And a polycarboxylic acid compound (B) obtained by further reacting the polybasic acid anhydride (c) with an active energy ray-curable optical composition.

[Chemical 2]

[3] R to R in the general formula (1) are hydrogen atoms, and ethylenically unsaturated groups and

1 8

The composition according to claim 1 or 2, wherein the compound (b) having a sil group is (meth) acrylic acid or cinnamic acid.

[4] Furthermore, the epoxycarboxylate compound (A) and the epoxycarboxylate compound (

The reactive compound (C) other than the polycarboxylic acid compound (B) obtained by reacting the polybasic acid anhydride (c) with A) is described in any one of claims 1 to 3. Composition.

[5] The composition according to claim 1, further comprising a light stabilizer (D).

[6] A high refractive index resin that is a cured product obtained by irradiating the composition according to claim 1 with active energy rays.

7. An optical material having the resin layer according to claim 6.

[8] An optical material comprising the composition according to claim 1.