WO2008001722A1

WO2008001722A1 - Active energy ray-curable composition for optical purposes, and high refractive index resin

Info

Publication number: WO2008001722A1
Application number: PCT/JP2007/062698
Authority: WO
Inventors: Toru Kurihashi; Hideaki Kametani; Kazuyoshi Yamamoto
Original assignee: Nippon Kayaku Kabushiki Kaisha
Priority date: 2006-06-27
Filing date: 2007-06-25
Publication date: 2008-01-03
Also published as: JP5641554B2; JPWO2008001722A1

Abstract

[PROBLEMS] To provide an active energy ray-curable composition for optical purposes which comprises a compound derived from an epoxy resin having a specific structure. [MEANS FOR SOLVING PROBLEMS] Disclosed is an active energy ray-curable composition for optical purposes, which comprises: an epoxy carboxylate 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, or a polycarboxylic acid compound (B) produced by reacting a hydroxyl group in the epoxy carboxylate compound (A) with a polybasic acid anhydride (c); and a reactive compound (C) which shows a curing reactivity upon being irradiated with an active energy ray. The composition can be used for the production of a high refractive index resin. (1) wherein R1's independently represent a halogen atom or an alkyl group having 1 to 4 carbon atoms; m represents an integer of 0 to 4; and n represents a positive integer of 1 to 6 on average.

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 obtained as described above, an optical multilayer material having a layer of the high refractive index resin, and an optical material containing the high refractive index resin.

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] Among them, an epoxy atrelate compound derived from an epoxy resin having a biphenol structure is known to provide a tough cured product having high thermal stability (Patent Document 1 and Patent Document) 2). However, these documents describe optics based on high refractive index.

It ’s not listed.

Patent Document 1: JP-A-9 211860

Patent Document 2: Japanese Patent Laid-Open No. 11-140144

Disclosure of the invention

Problems to be solved by the invention

[0004] In recent years, higher toughness has been demanded as an optical material, and there has been a demand for a cured film that is not simply hard but does not break by impact or the like.

[0005] 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.

That is, the present invention provides an epoxy resin 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 carboxyl group in the molecule. High refractive index comprising a carboxylate compound (A) and a reactive compound (C) that exhibits curing reactivity by active energy rays other than the epoxy carboxylate compound (A) The present invention relates to an active energy ray-curable optical composition that is used in the production of rate oil.

[0008] [Chemical 1]

(Wherein R1 represents a halogen atom or an alkyl group having 1 to 4 carbon atoms, and may be the same or different. M is an integer of 0 to 4, and n is a positive number of 1 to 6 on average. In addition, the present invention provides a polycarboxylic acid compound (B) obtained by reacting a polybasic acid anhydride (c) with a hydroxyl group of the epoxy carboxylate compound (A), and Active energy used for the production of a high refractive index resin characterized by containing a reactive compound (C) that exhibits curing reactivity with an active energy ray other than the polycarboxylic acid compound (B). The present invention relates to a linear curable optical composition.

[0009] Further, the present invention relates to the above active energy ray-curable optical composition having the m force ^ of the general formula (1).

[0010] Furthermore, the reactive energy (C) force radical reaction type (meth) acrylates, cation reaction type epoxy compounds and other Buly compounds force The above active energy ray which is a selected compound The present invention relates to a curable optical composition. [0011] Further, the present invention relates to the above active energy ray-curable optical composition containing the light stabilizer (D).

[0012] 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.

[0013] Further, the present invention relates to an optical multilayer material having at least one layer of the above high refractive index resin.

Furthermore, the present invention relates to an optical material containing the above-described high refractive index resin.

The invention's effect

[0015] The epoxy carboxylate compound (A) obtained by reacting the epoxy resin having a specific skeleton with a compound (b) having both an ethylenically unsaturated group and a force carboxyl group in the molecule of the present invention, or Polycarboxylic acid compound (B) obtained by reacting the hydroxyl group of epoxy carboxylate compound (A) with polybasic acid anhydride (c) and a reaction showing curing reactivity by active energy rays The cured product obtained by irradiating the active energy ray-curable optical composition containing the active compound (C) by irradiating the active energy ray with a high refractive index is not only excellent in the balance of heat resistance and moisture resistance. Have. Furthermore, the cured product is a material excellent in mechanical properties such as toughness, and particularly as a film-forming material excellent in adhesion to a substrate and scratch resistance, and also in a water-soluble alkali solution with a polycarboxylic acid. Therefore, 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

The active energy ray-curable optical composition of the present invention is a composition used for the production of a high refractive index resin, wherein the general formula (1) (wherein R1 is a halogen atom or a carbon number) Represents an alkyl group of 1 to 4, which may be the same or different, m represents an integer of 0 to 4, n represents an average value of 1 to 6 and an epoxy resin (a ) And an epoxy carboxylate compound (A) obtained by reacting a compound (b) having both an ethylenically unsaturated group and a carboxyl group in the molecule, or the epoxy carboxylate compound (A) A polycarboxylic acid compound (B) obtained by reacting a polybasic acid anhydride (c) with a hydroxyl group, and a reactive compound (C) showing curing reactivity by active energy rays including. [0017] In the general formula (1), Rl should be appropriately selected depending on the intended use, and includes, for example, a methyl group, an ethyl group, an n propyl group, an i propyl group, an n butyl group, i linear or branched saturated hydrocarbon group having 1 to 4 carbon atoms such as butyl group and sbutyl group; halogen atom such as chlorine atom, bromine atom and iodine atom.

[0018] m is preferably an integer of 0 to 2! /. Of these, m is 0, that is, it has no substituents! /, And the compound is most preferred from the viewpoint of obtaining materials.

[0019] When R1 is a halogen atom such as a chlorine atom, bromine atom or iodine atom, a higher refractive index can be obtained.

[0020] In the epoxy resin (a), which is a phenol biphenyl methyl type epoxy resin represented by the general formula (1), the bonding position of the biphenyl methyl group and the glycidyl ether group is not particularly limited. However, in view of the production method, it is preferred that the biphenylmethyl group is bonded to the ortho or para position with respect to the glycidyl ether group!

[0021] The production method of the epoxy resin (a) represented by the general formula (1) is described in Patent Document 1, for example, and can be produced according to the method. Obtained as a commercial product (brand name: NC-3000, NC-3000P, NC-3000S, NC-3000H, etc.) It is also possible.

[0022] The epoxycarboxylate compound (A) used in the active energy ray-curable optical composition of the present invention is a compound (b) having both an ethylenically unsaturated group and a carboxyl group in the epoxy resin (a). To obtain (epoxycarboxylate step).

[0023] The polycarboxylic oxide compound (B) used in the active energy ray-curable optical composition of the present invention has a polybasic acid anhydride (c) on the hydroxyl group of the epoxy carboxylate compound (A). (Acid addition step).

[0024] The epoxy carboxylation step will be described.

[0025] The epoxy carboxylate solution process is intended to introduce an ethylenically unsaturated group, which is a reactive group of active energy rays, into the skeleton of epoxy resin by reacting an epoxy group with a carboxyl group. It is.

[0026] Examples of the compound (b) having both the ethylenically unsaturated group and the carboxyl group include:

(Meth) acrylic acids, crotonic acid, a-cyan cinnamic acid, cinnamic acid, or ethylenically unsaturated Examples thereof include compounds obtained by reacting a compound having both a sum group and a hydroxyl group with a saturated or unsaturated dibasic acid.

[0027] In the above, the compound obtained by reacting a compound having both an ethylenically unsaturated group and a hydroxyl group with a saturated or unsaturated dibasic acid is, for example, a (meth) atally having one hydroxyl group in one molecule. Examples include half esters obtained by reacting a rate derivative with a saturated or unsaturated dibasic acid anhydride in an equimolar amount. For example, hydroxyethyl (meth) acrylate, alkyl (meth) acrylate and maleic anhydride Succinic anhydride, phthalic anhydride, phthalic anhydride partly or fully hydrogenated compound, trimellitic anhydride, pyromellitic anhydride and the like are reacted with a saturated or unsaturated dibasic acid. .

Of these, considering the stability of the reaction of the epoxy resin (a) and the compound (b) having both an ethylenically unsaturated group and a carboxyl group, the compound (b) is preferably a monocarboxylic acid. Even when monocarboxylic acid and polycarboxylic acid are used in combination, it is preferable that the mole ratio of monocarboxylic acid to molar ratio of polycarboxylic acid is 15 or more.

[0029] More preferred is (meth) acrylic acid or cinnamic acid from the viewpoint of sensitivity to a line of active energy when an active energy ray-curable optical composition is used.

[0030] The charging ratio of the epoxy resin (a) and the compound (b) having both an ethylenically unsaturated group and a carboxyl group in this reaction should be appropriately changed depending on the application. That is, when all the epoxy groups are carboxylated, no unreacted epoxy groups remain, so that the storage stability as the epoxy carboxylate compound (A) is high. In this case, only the reactivity due to the introduced double bond is used for the curing reaction.

[0031] In the epoxy carboxylate solution process, when no epoxy group remains, the charge ratio of the epoxy resin (a) and the compound (b) having both an ethylenically unsaturated group and a carboxyl group is as follows. The compound (b) is preferably 0.9 to 1.2 equivalents per 1 equivalent of the epoxy group of the fat (a). If it falls below this range, epoxy groups remain, causing gelation in the acid addition step, and deterioration of the storage stability of the resin. Conversely, if the amount of compound (b) charged is greater than this range, excess compound (b) remains. It is not preferable.

[0032] On the other hand, by reducing the amount of the compound (b) having both an ethylenically unsaturated group and a carboxyl group to leave an unreacted epoxy group, the reaction with the introduced ethylenically unsaturated bond remains. It is also possible to use a combination of reactions based on epoxy groups (for example, a polymerization reaction or thermal polymerization reaction using a light power thione catalyst).

[0033] In the case of leaving an epoxy group in the epoxy carboxylate solution process, the compound (b) having both an ethylenically unsaturated group and a carboxyl group with respect to 1 equivalent of the epoxy group of the epoxy resin (a). It is preferable to charge 0.2 to 0.9 equivalent of a carboxyl group. If it is outside this range, the effect of composite curing will be diminished. When leaving an epoxy group, it is necessary to pay particular attention to the time-dependent stability of the gel or epoxycarboxylate compound (A) during the subsequent reaction.

[0034] Furthermore, when used as a polycarboxylic acid compound (B) through an acid addition step described later, it is particularly preferable that no epoxy group remains. That is, when a large number of epoxy groups remain, it reacts with the introduced carboxyl group, and storage stability and the like are particularly poor.

[0035] The epoxy carboxylate solution process is performed 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.

[0036] Examples of the solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane, and decane, or mixtures thereof. Some petroleum ethers, white gasoline, and solvent naphtha.

[0037] In addition, as ester solvents, alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate, cyclic esters such as γ-butyrolatatone, ethylene glycol monomethylenoate monoacetate, diethyleneglycolonemonomonomethyl Noreeate Monoacetate, Diethylene Glycol Nole Monoetinoreate Nore Monoacetate, Triethylene Glycol Monoethinorete Tenole Monoacetate, Diethylene Glycol Monobutyl Ether Monoacetate, Propylene Glycol Monomethyl Ether Monoacetate, Butylene Glycol Monomethyl Ether Mono or polyalkylene glycol monoa such as monoacetate Examples include alkyl ether esters such as alkyl ether monoacetates, dialkyl glutarate, dialkyl succinate, and dialkyl adipate.

[0038] In addition, as ether solvents, alkyl ethers such as jetyl ether and ethylbutyl ether, ethylene glycol dimethyl ether, ethylene glycol jetyl ether, dipropylene glycol dimethyl ether, dipropylene glycol jet nole ethere, triethylene glycol dimethyl ether , Dalicol ethers such as triethylene glycol ethyl ether, and cyclic ethers such as tetrahydrofuran.

[0039] Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

In addition to this, the reactive compound (C) and the like described later can also be used as a solvent, and these can be used alone or in combination. In this case, the product is preferable because it can be used as it is as the active energy single-line curable optical composition of the present invention.

[0041] It is preferable to use a catalyst in the epoxy carboxylate step 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 reactants. Examples of the catalyst include tertiary amines such as triethylamine, benzyldimethylamine, salt triethylamine, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, and the like. Quaternary ammonium salts, organometallic salts such as chromium octanoate and zirconium octoate, and basic catalysts such as triphenylphosphine and triphenylstibine.

[0042] The reaction temperature is 60 to 150 ° C, and the reaction time is preferably 5 to 60 hours.

[0043] As the thermal polymerization inhibitor, it is preferable to use a polymerization inhibitor such as hydroquinone monomethyl ether, 2-methyl hydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-dibutyl 4-hydroxytoluene, and the like. ,.

[0044] In the epoxy carboxylate soot process, the acid value of the sample (measured according to α IS K5601-2-1: 1999) is appropriately sampled, and is lmg'KOHZg or less, preferably 0.5 mg'KOHZg or less The end point is the point where

[0045] Next, the acidification process will be described. [0046] The purpose of the acid addition step is to introduce a carboxyl group through an ester bond by reacting the polybasic acid anhydride (c) with the hydroxyl group generated by the epoxy carboxylate solution step.

[0047] 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, a polybasic acid anhydride (c) is a raw material excellent in developability in alkali aqueous solution, heat resistance, hydrolysis resistance, and the like. Succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, Trimellitic anhydride or maleic anhydride is preferred.

[0048] 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.

[0049] 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-developing resist, the finally obtained polycrystal is obtained. A large amount of carboxylic acid compound (B) with a solid content acid value (measured according to JIS K5601-2-1: 1999) of 40 to: LOOmg 'KOHZg, more preferably 60 to 90 mg' KOH / g It is preferable to charge the basic 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 in alkaline aqueous solution is remarkably lowered, and in the worst case, development is impossible. If 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 not be able to make notes.

[0050] In 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 about LO weight% with respect to the total amount of the reactants. Examples of the catalyst include tertiary amines such as triethylamine and benzyldimethylamine, quaternary ammonia such as triethylammonium chloride, benzyltrimethylammonium bromide, and benzyltrimethylammonium iodide. -Umum salts, organic metal salts such as chromium octanoate and zirconium octanoate, and basic catalysts such as triphenylphosphine and triphenylstibine. [0051] The reaction temperature is 60 to 150 ° C, and the reaction time is preferably 5 to 60 hours.

[0052] 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, in the case of producing using a solvent in the epoxy carboxylate step, which is the previous step, there is no influence on the acid addition step, and if it is a solvent, it may be used in the acid addition step without removing the solvent. ,.

[0053] Examples of the solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane, and decane, or mixtures thereof. Some petroleum ethers, white gasoline, and solvent naphtha.

[0054] Further, as ester solvents, alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate, cyclic esters such as γ-butyrolatatone, ethylene glycol monomethylenothenomonoacetate, diethyleneglycolonemonomonomethyl Noreeate Monoacetate, Diethylene Glycol Nole Monoetinoreate Nore Monoacetate, Triethylene Glycol Monoethinorete Tenole Monoacetate, Diethylene Glycol Monobutyl Ether Monoacetate, Propylene Glycol Monomethyl Ether Monoacetate, Butylene Glycol Monomethyl Ether Mono- or polyalkylene glycol monoalkyl ether monoacetates such as monoacetate, dialkyl glutarate, dialkyl succinate, diadipate Examples thereof include polycarboxylic acid alkyl esters such as rualkyl.

[0055] In addition, as ether solvents, alkyl ethers such as jetyl ether and ethylbutyl ether, ethylene glycol dimethyl ether, ethylene glycol jetyl ether, dipropylene glycol dimethyl ether, dipropylene glycol jet alcohol, triethylene glycol dimethyl ether , Dalicol ethers such as triethylene glycol ethyl ether, and cyclic ethers such as tetrahydrofuran.

[0056] Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

In addition to this, the reactive compound (C) and the like described later can also be used as a solvent, and these can be used alone or in combination. In this case, the product is the active energy of the present invention. It is preferable because it can be used as it is as a gear curable optical composition.

[0058] Further, as the thermal polymerization inhibitor, the same one as in the epoxy carboxylate soot process can be used.

[0059] In the acid addition step, the end point is determined when the acid value of the reaction product is within a range of ± 10% of the acid value set according to the intended use while appropriately sampling.

[0060] The reactive compound (C) used in the active energy ray-curable optical composition of the present invention is an active energy ray-curable optical composition containing an epoxy carboxylate compound (A). In the case of the compound other than the epoxycarboxylate compound (A), and in the case of the active energy ray-curable optical composition containing the polystrengthenic acid compound (B), other than the polycarboxylic acid compound (B). This compound is a compound that exhibits curing reactivity with an active energy ray, and can impart physical properties before or after curing according to the purpose of use.

[0061] As the reactive compound (C), a radical reaction type, that is, a (meth) atalylate, a cation reaction type, which generates an active radical upon irradiation with active energy rays and causes a curing reaction by the radical, Examples include so-called reactive oligomers such as epoxy compounds and other vinyl compounds which generate cations (acids) upon irradiation with active energy rays and cause a curing reaction by the cations.

[0062] Examples of the radical reaction type (meth) acrylates include monofunctional (meth) acrylates, polyfunctional (meth) acrylates, epoxy (meth) acrylates, polyester (meth) acrylates. And urethane (meth) acrylates and the like.

[0063] 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.

[0064] Examples of the polyfunctional (meth) acrylates include butanediol di (meth) acrylate, hexane diol di (meth) acrylate, neopentyl glycol di (meth) acrylate, nonane All di (meth) acrylate, glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (meth) ateroyloxychetyl isocyanurate, polypropylene glycol di (meta) ) Atalylate, adipic acid epoxy di (meth) acrylate, bisphenol ethylene oxide di (meth) acrylate, hydrogenated bisphenol ethylene oxide (meth) acrylate, bisphenol di (meth) acrylate, hydroxybiba Di (meth) atalylate of dipentaerythritol and dipentaerythritol and ε-force prolatatone reaction product of neopentyl glycol phosphate , Trimethylol propane pantri (meth) acrylate, triethylol propane tri (meth) acrylate or its ethylene oxide adduct, pentaerythritol tri (meth) acrylate or its ethylene oxide adduct, pentaerythritol tetra Examples include (meth) acrylate, dipentaerythritol hexa (meth) acrylate, or ethylene oxide adducts thereof.

[0065] The cation-reactive epoxy compounds 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 nole レ diglycidino reetenole, 3, 4 epoxycyclohexino retinoyl 3,4-epoxy cyclohex Xancarboxylate (Union Carbide “Syracure UVR-6110”, etc.), 3, 4 Epoxycyclohexenoreethinole 3, 4-Epoxycyclohexanecanoloxylate, Burcyclohexenedioxide (Union Carbide “ELR— 4206” ), Limonene dioxide (such as “Celoxide 3000” manufactured by Daicel Chemical Industries), allylcyclohexene dioxide, 3, 4 epoxy 4-methylcyclohexylene, 2 propylene oxide, 2- (3,4 epoxycyclohexane, 5, 5 —Spiro 3, 4 Epoxy ) Cyclohexane m Dioxane, bis (3,4-epoxycyclohexylene) adipate (eg “Syracure UVR-6128” manufactured by Union® Carbide), bis (3,4 Epoxycyclohexylmethyl) adipate, bis (3 , 4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, bis (3,4-epoxycyclohexyl) ethylsiloxane, and the like.

[0066] Further, examples of the above bull compounds include bull ethers, styrenes, and other bees. Compounds. Examples of the bull ethers include ethyl vinyl ether, propyl vinylenoatenole, hydroxyethylenolevininoatenole, and ethylene glyconoresininoate ether. Examples of styrenes include styrene, methyl styrene, and ethyl styrene. Examples of other vinyl compounds include triallyl isocyanurate.

[0067] Among the above, the reactive compound (C) is preferably a radical reaction type (meth) acrylate. In the case of cation-reactive epoxy compounds, if a carboxyl group remains in the system, it reacts with the epoxy group, so it is necessary to use a two-component mixed type that is mixed at the time of use.

[0068] The above-mentioned epoxy carboxylate compound (A) or polycarboxylic acid compound (B) and the reactive compound (C) are mixed to produce the active energy ray-curable optical composition of the present invention. Obtainable.

[0069] In the active energy ray-curable optical composition of the present invention, the epoxycarboxylate compound (A) and Z or the polycarboxylic acid compound (B) are contained in the composition in an amount of 90 to 5% by weight, Preferably 80 to: LO wt%, preferably 3 to 90 wt%, preferably 13 to 80 wt% of reactive compound (C). You may include other ingredients as needed!

[0070] 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 rays. These can be appropriately selected depending on the use of the active energy ray-curable optical composition of the present invention, and among these, ultraviolet rays, laser beams, visible rays or electron beams are preferred.

[0071] The active energy ray-curable optical composition of the present invention is cured by active energy rays. Examples of the light source used at that time include xenon lamps, carbon arc lamps, germicidal lamps, ultraviolet fluorescent lamps, A pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, an electrodeless lamp, a metal halide lamp, or an electron beam by a scanning type or curtain type electron beam accelerator can be used. 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 is 300 to It's about 3000miZcm ² !

[0072] The present invention also includes a high refractive index resin which is a cured product obtained by the irradiation.

[0073] Furthermore, it is also 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. The light stabilizer is a general term for compounds added to prevent discoloration and brittleness when exposed to light for a long period of time. 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.

[0074] The light stabilizer (D) includes compounds used as ultraviolet absorbers, antioxidants and the like.

[0075] Examples of the light stabilizer (D) include bis (1, 2, 2, 6, 6 pentamethyl-4-piperidyl) [[3,5 bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate. Examples thereof include hindered amine light stabilizers such as “Tinuvin 144” manufactured by Ciba Specialty Chemicals.

[0076] Further, as the light stabilizer (D), for example, 2- (2 hydroxy-5-t-butylphenol) -2H-benzotriazole (for example, “Tinuvin PS” manufactured by Ciba Specialty Chemicals, etc.) , 3— (2H Benzotriazolenol-2-ynole) —5— (1, 1-Dimethylenoethinole) —4 Hydroxybenzenepropanoic acid Branched and straight chain (C7—C9) alkyl esters (eg Cibas Specialty Chemicals “Tinuvin 99-2”, “Tinuvin 384-2”, etc.), 2— (2H benzotriazole-2-yl) —4,6 bis (1-methyl-1-phenylethyl) Benzotriazole-based UV absorbers such as phenol (for example, “Tinuvin 900” manufactured by Ciba Specialty Chemicals); 2— (4, 6 bis (2, 4 dimethylphenol) — 1, 3, 5 Triazine 2—yl) 5 phenol and oxysilane ([(C10— C16 (mainly C12—C13) alkyloxy) methyl] oxysilane) (for example, “Tinuvin 400” manufactured by Ciba Specialty Chemicals, etc.), 2— (2, 4 dihydroxyphenol) 1, 4, 6 bis (2, 4 Dimethylphenol) 1, 3, 5 Triazine and (2 ethylhexyl) -glycidic acid ester reaction products (eg “Tinuv in 405” manufactured by Tino Specialty Chemicals), 2, 4 Bis [2 Hydroxy 1 4-Butoxyphenyl] — 6— (2, 4 Jib Toxylphenol) -1, 3, 5 Triazine (for example, “Tin uvin 460” manufactured by Ciba Specialty Chemicals, etc.) and the like, and hydroxyphenyl triazine (HPT) ultraviolet absorbers.

[0077] In the case where the active energy ray used for the curing reaction is ultraviolet rays, hydroxyphenol triazine (HPT) ultraviolet absorbers are effective.

[0078] Examples of the light stabilizer (D) include tetrakis (2,4di-t-butylphenyl) [1,1-biphenyl] -4,4,1 diylbisphosphonite (for example, Ciba Specialty) Phosphite acids such as “IRGAFOS XP40” manufactured by Chemicals) and bis (2,4di-t-butylphenol) pentaerythritol diphosphite (eg “IRGAFOS XP60” manufactured by Ciba Specialty Chemicals) Anti-wrinkle agent, or pentaerythritol tetrakis [3— (3,5-di-t-butyl-4-hydroxyphenol) propionate (eg “IRGANOX 1010” manufactured by Ciba Specialty Chemicals), thiojetylene Bis [3— (3,5 di-tert-butyl-4-hydroxyphenol) propionate] (for example, riRGANOX 1035 manufactured by Ciba Specialty Chemicals), 4, 6 Bis (octylthiomethyl) o-talezo (For example, “IRGANOX 1520LJ” manufactured by Ciba Specialty Chemicals, etc.)

[0079] When a light stabilizer is used, one or more of the above may be used.

[0080] 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 in the composition, and more preferably. 0.5 to 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 much, the curing reaction by active energy rays may be inhibited.

[0081] 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.

[0082] Examples of the photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenyl. Ruacetophenone, 2, 2-diethoxy-1, 2-phen-acetophenone, 1, 1-dichloroacetophenone, 2-hydro Acetofenones such as xyl-2-methyl-phenylpropane 1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenol ketone, 2-methyl-1- [4 (methylthio) phenol] 2 -morpholinopropan 1-one; Anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone, and the like; 2,4 thixanthones such as jetylthioxanthone, 2-isopropylthixanthone, and 2-chlorothiaxanthone Ketals such as acetophenone dimethyl ketal and benzil dimethyl ketal; benzophenones such as benzophenone, 4-benzoyl, 4-methyldiphenylsulfide, 4, 4, monobismethylaminobenzophenone; 2, 4, 6 Rudiphenol-phosphine Kishido, bis (2, 4, 6-trimethyl Benzoiru) Hue - Le phosphine O sulfoxide such phosphine O dimethylsulfoxide radical type opening initiator, such compounds can be mentioned.

[0083] Other photopolymerization initiators include “NK” manufactured by Nippon Photosensitizer, which is a baud rate initiator.

3876 "," NK-3881 ", etc .; photoacid generators, for example, 9 phenolacridine, 2, 2, 1bis (o black mouth) 1, 4, 4, 5, 5, 1 tetraphenol -Lu 1, 2 Biimidazole (such as “Biimidazole” manufactured by Kurokin Kasei), 2, 2-azobis (2-aminopropane) dihydric chloride (such as “V50” manufactured by Wako Pure Chemical Industries), 2, 2 Azobis [2- (Imidazoline-1 2-yl) propan] dihydrochloride (such as “VA044” manufactured by Wako Pure Chemical Industries), [Eter 5—2-4 (cyclopentadecyl) (1, 2, 3, 4, 5, 6, And cation initiators such as “Irgacure 261” manufactured by Ciba Geigy).

[0084] In addition, radical type and cationic groups may be used in combination with azo type initiators such as azobisisobutyoritol-tolyl and peroxide sensitive radical type initiators such as benzoyl peroxide which are sensitive to heat. Both initiators of the mold may be used together.

[0085] When these initiators are included in the active energy ray-curable optical composition of the present invention, the content of the initiator is about 0.1 to 10% by weight.

[0086] Examples of the coloring material include organic pigments such as phthalocyanine, azo, and quinacridone, inorganic pigments such as titanium oxide, carbon black, bengara, zinc oxide, barium sulfate, and talc, and known general coloring. And extender pigments can be used. [0087] Other additives include, for example, thermosetting catalysts such as melamine, talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, hydroxyaluminum hydroxide, acidic aluminum, silica Polymerization prohibition of fillers such as clay, thixotropic agents such as “Aerosil”, phthalocyanine blue, phthalocyanine green, titanium oxide, silicone, fluorine leveling agents and antifoaming agents, hydroquinone, hydroquinone monomethyl ether, etc. An agent or the like can be used.

[0088] Further, the active energy ray-curable optical composition of the present invention includes other non-reactive resins (so-called inert polymers), such as epoxy resin other than those described above. , Phenolic resin, urethane resin, polyester resin, ketone phenolic resin resin, cresol resin, xylene resin, diallyl phthalate resin, styrene resin, guanamine resin, natural Alternatively, synthetic rubber, acrylic resin, polyolefin resin, or modified products thereof can also be used. These are preferably used in the composition up to 40% by weight! /.

[0089] For the purpose of adjusting the viscosity according to the purpose of use, a solvent such as an epoxycarboxylate salting step and an acid addition step are used in the composition up to 40% by weight, preferably 20% by weight. Solvents exemplified as being usable can also be added.

[0090] The present invention also includes an optical material containing a high refractive index resin obtained by irradiating the above-mentioned optical composition with active energy rays and used for the purpose of optically refracting light. It is.

[0091] Optical materials include, for example, lens materials such as convex lenses, concave lenses, microlenses, Fresnel lenses, and lenticular lenses; light guide materials used in liquid crystal display devices; sheets and films processed into plates, Discs, etc .; so-called nanoimprint materials that perform micro-molding by pressing a micro-molded “mold” into an uncured composition; furthermore, sealing materials for protecting elements, especially light-emitting diodes, photoelectric conversion Examples thereof include sealing materials such as elements.

[0092] Coating materials such as hard coats, top coats, overprint varnishes, clear coats; adhesive materials for laminating, optical discs and other various adhesives, adhesives; solder resists, etching resists, resists for micromachines, etc. It is also suitably used for film formation that requires a high refractive index such as a resist material. [0093] Furthermore, after the film-forming material is temporarily applied to a peelable substrate to form a film, it can be used as a so-called dry film in which a film is formed by being bonded to the originally intended substrate. .

[0094] Among them, use as a lens material such as a convex lens, a concave lens, a micro lens, a Fresnel lens, and a lenticular lens, and a coating material such as a hard coat, top coat, overprint varnish, and clear coat is particularly preferable.

[0095] In addition, in the case of an active energy ray-curable optical composition containing the polycarboxylic acid compound (B), the adhesion to the base material is enhanced by the carboxyl group in view of the above use. It can also be used as an application for coating a plastic substrate or a metal substrate. The composition can also be used as an alkali-developable optical resist material composition that requires a high refractive index by taking advantage of its solubility in an alkali solution. That is, an active energy ray-sensitive type in which a film layer of the composition is formed on a substrate, irradiated with active energy rays such as ultraviolet rays, and unirradiated portions are dissolved and removed with an alkaline solution or the like to draw. It is used as an optical composition.

[0096] 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.

[0097] In the present invention, a high refractive index resin means a value of 1.55 or more when the refractive index of a cured product obtained by irradiating active energy rays is measured according to JIS K7142: 1996. It is greaves.

The present invention also includes an optical multilayer material having a high refractive index resin layer obtained by forming a film on the substrate and curing the above active energy ray-curable optical composition.

Example

[0099] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Moreover, unless otherwise indicated in an Example, a part shows a weight part. In addition, each physical property value in an Example was measured with the following method.

(1) Epoxy equivalent: Measured by the method described in JIS—K7236: 2001. (2) Hardness: Measured by the method described in JIS K5600-5-4: 1999.

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

[0100] Synthesis Example 1 1, Synthesis Example 1 2: Synthesis of epoxy carboxylate compound (A)

Epoxy resin (a) is phenol bimethyl methyl type epoxy resin, Nippon Kayaku NC-3000H (epoxy value 288gZeq, n = 2.1) 144g, compound having both ethylenically unsaturated group and carboxyl group in the molecule As (b), add acrylic acid (abbreviation AA, molecular weight = 72) in Table 1, 1.5 g of triphenylphosphine as a catalyst, and lOOg of propylene glycol monomethyl ether monoacetate as a solvent. Reacted for hours.

[0101] Comparative Synthesis Example 1 1: Synthesis of epoxy carboxylate compound

As the epoxy resin (a), add NER-1202 (epoxy value 292g / eq) 146g mucoacrylic acid (AA), which is a polyfunctional bisphenol A type epoxy resin, in Table 1. Reacted. Reaction conditions and the like were the same as those in Synthesis Example 11 and Synthesis Example 12.

[0102] [Table 1] Synthesis example AA. Weight (molar ratio)

Synthesis Example 1-1 36 g (1.0)

Synthesis Example 1-2 18g (0.5)

Specific example 1-1 36g (1.0)

[0103] Synthesis Example 2-1 and Synthesis Example 2-2: Synthesis of polycarboxylic acid compound (B)

[0104] In Synthesis Example 1-1, tetrahydrophthalic anhydride as polybasic acid anhydride (c) was added to the epoxy carboxylate compound (A) obtained in the above manner. for example, the addition of propylene glycol monomethyl ether monoacetate as a solvent so that the solid content would be 70 by weight ^_0/0, by addition reaction by heating for 10 hours at 100 ° C, polycarboxylic acid compound (B) soluble A liquid was obtained.

[0105] [Table 2] Synthesis example AA amount (molar ratio) Water (setting 薩) Solid 5 fffi (MM) Synthesis example 2-1 36 g (1.0) 67 g (100) 101 Synthesis example 2-2 36 g (1. 0) 10 g (20) 21

Example 1 1, Example 1 2, Example 1 3: Active energy ray-curable optical composition Preparation and evaluation

20 g of the epoxycarboxylate compound (A) or polycarboxylic acid compound (B) synthesized in Synthesis Example 1-1, Synthesis Example 1-2, and Synthesis Example 2-2, a radical reaction type monomer Thus, 4 g of dipentaerythritol hexatalylate as the reactive compound (C) and 1.5 g of “Irgacure 184” as an ultraviolet reactive photopolymerization initiator were added and dissolved by heating.

[0107] This was coated on a polycarbonate plate with a hand applicator so that the film thickness upon drying was 20 µm, and the solvent was dried in an electric oven at 80 ° C for 30 minutes. After drying, it was cured by irradiating with an ultraviolet ray having an irradiation dose of lOOOmiZcm ² by an ultraviolet vertical exposure apparatus (manufactured by Oak Seisakusho) equipped with a high-pressure mercury lamp to obtain a multilayer material.

[0108] The hardness of the coating film of this multilayer material was measured according to JIS K5600-5: 4: 1999, shown in Table 3 as pencil hardness, and an impact test was conducted according to IS06272-1: 2002. It was shown in 3.

[0109] Further, as a sample for refractive index measurement, the above composition was applied to a polypropylene plate by the same method, dried, cured, and the cured coating film was peeled off. According to JIS K7142: 1996 The refractive index was measured and shown in Table 3.

[0110] Comparative Example 1 1

Comparative Synthesis Example 11 Using the epoxy carboxylate compound synthesized in 1, a composition was prepared, cured, and evaluated in the same manner as in Example 1-1. The results are shown in Table 3.

[0111] [Table 3]

[Table 3] Keisei Tsuji

Example Synthesis Example Refractive Index Hardness

Example 1-1 Synthesis example 1-1 1. 6 0 2 H Slight scratch Example 1-2 Synthesis example 1-2 1.6 1 H 1 Scratch slightly Example 1-3 Synthesis example 2-2 1.5 9 H No scratch Ratio shelf 1-1 Specific age example 1 1 1 1 3 5 3 F No scratch From the above results, the present invention compared to the composition / cured product prepared from the epoxy resin of the comparative example A composition derived from a specific epoxy resin. * The cured product is tough, high in hardness and also has a high refractive index. [0112] Example 2: 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 added and dissolved by heating.

[0113] This was coated on a quartz plate with a hand applicator so that the film thickness at the time of drying was 20 m, and the solvent was dried in an electric oven at 80 ° C for 30 minutes. After drying, the mask pattern is covered on top of the coating, and cured by irradiating with UV radiation of lOOOmiZcm ² using an UV vertical exposure device (manufactured by Oak Seisakusho) equipped with a high-pressure mercury lamp. The material was obtained. Then, a 1% by weight aqueous sodium carbonate solution was sprayed to dissolve the unexposed area and develop.

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

[0115] Example 3: Effect of 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-butoxy file] — 6- (2, 4 dibutoxy file). ) 1, 3, 5 Triazine (Ciba Specialty Chemicals, trade name: Tinuvin 460) 40 mg, bis (1, 2, 2, 6, 6 pentamethyl-4 piperidyl) [[3,5 bis (1, 1 —Dimethylruetyl) -4-hydroxyphenol] methyl] butylmalonate (product name: Tinuvin 144; hindered amine light stabilizer), 40 mg and bis (2,4-diethylbutylbutyl) pentaerythritoldi Add 20 mg of phosphite (Ciba Special Chemicals, trade name: IRGAFOS XP60; acid-fouling inhibitor), and apply onto a quartz glass plate with a hand applicator so that the film thickness when dried is 20 μm. At 30 ° C for 30 minutes. Was solvent drying in an oven. After that, a multilayer material was obtained by irradiating with an ultraviolet ray with an irradiation dose of lOOOmiZcm ² by an ultraviolet vertical exposure apparatus (manufactured by Oak Manufacturing) equipped with a high-pressure mercury lamp.

[0116] A light resistance test was performed by irradiating light for 1000 hours with a Fedometer. Measurement of light transmission at 45 Onm, and transmission after light resistance test as an indicator of light resistance The ratio of transmittance before implementation of rate Z was determined and shown in Table 4.

[0117] [Table 4]

[Table 4] Qualitative

Examples Mitsuyasu (D) Male resistance

Example 3-1 Yes 0.80 Example 3-2 No 0.5 5 From the above results, it was shown that the light stability can be improved by adding the light stabilizer (D).

Industrial applicability

[0118] The active energy ray-curable optical composition derived from the epoxy resin having the specific structure of the present invention provides a cured product having a relatively strong and high refractive index. In addition, it can 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

The scope of the claims

[1] An epoxy carboxylate compound obtained by reacting an epoxy resin represented by the following general formula (1) (a) with a compound (b) having both an ethylenically unsaturated group and a carboxyl group in the molecule For the production of a high refractive index resin characterized by comprising a reactive compound (C) that exhibits curing reactivity by active energy rays other than the product (A) and the epoxy carboxylate compound (A). An active energy ray-curable optical composition used.

[Chemical 2]

(In the formula, R1 represents a halogen atom or an alkyl group having 1 to 4 carbon atoms, and may be the same or different. M is an integer of 0 to 4, and n is a positive number of 1 to 6 on average. [2] A polybasic acid anhydride at the hydroxyl group of the epoxy carboxylate compound (A) according to claim 1.

The polycarboxylic acid compound (B) obtained by reacting (c), and a reactive compound (C) that exhibits curing reactivity with active energy rays other than the polycarboxylic acid compound (B). An active energy ray-curable optical composition used for the production of a high refractive index resin.

[3] The active energy ray-curable optical composition according to claim 1 or 2, wherein the composition is m force ^ of the general formula (1).

[4] The reactive compound (C) is a compound in which radical reaction type (meth) acrylates, cationic reaction type epoxy compounds and other vinyl compounds are also selected. The active energy ray-curable optical composition according to any one of?

[5] The method according to claims 1 to 4, further comprising a light stabilizer (D)! The active energy ray-curable optical composition according to claim 1.

[6] The optical composition according to any one of claims 1 to 5 is irradiated with active energy rays. High refractive index resin that is a cured product obtained by

7. An optical multilayer material comprising at least one high refractive index resin layer according to claim 6. An optical material comprising the high refractive index resin of claim 6.