KR102261966B1 - The optical epoxy resin composition and cured product thereof - Google Patents

Abstract

(Project) To provide an excellent epoxy resin composition for optical materials such as LED sealing materials by providing a cured product having high transparency and high heat resistance reliability.
(Solution) In the optical epoxy resin composition containing an epoxy resin (a) and a curing agent (b), the epoxy resin (a) has an epoxy equivalent of 500 to 2000 g/eq, and a softening point of 80 to 150° C., The refractive index (n _D ²⁰ ) is 1.55 to 1.63, has an aromatic ring and an aliphatic ring simultaneously in the molecular structure, and the intensity ratio (B/A) of the aliphatic proton (A) to the aromatic proton (B) in the 1H-NMR spectrum (B/A) ) is 0.3 to 0.7 of the optical epoxy resin composition.

Description

Epoxy resin composition for optics and cured product thereof {THE OPTICAL EPOXY RESIN COMPOSITION AND CURED PRODUCT THEREOF}

[0001] The present invention relates to a cured epoxy resin for optics, which is preferably used for areas exposed to high temperatures in optical materials and electronic materials applications.

Patent Document 1 discloses a method of adding a colorant to the resin itself to make printing clear by heat generated during laser printing, but since there was a problem that the epoxy resin is discolored by heat generated during laser printing, the epoxy resin Fundamental discoloration prevention by improvement of

In addition, Patent Documents 2 and 3 disclose that heat resistance, adhesion, heat yellowing properties, etc. can be improved by using a curing agent incorporating a specific epoxy resin and a terpene skeleton, but both the curing agent and the epoxy resin require a specific skeleton It was a thing and was limited also about a hardening accelerator.

Further, Patent Document 4 discloses an epoxy resin composition for optical components having good adhesion to glass, high transparency and heat resistance reliability (thermal discoloration resistance, heat shrinkage resistance), but this is achieved by using a specific photoacid generator. There is a description that when an epoxy resin having a fluorene skeleton is contained as a suppression of coloring, a high refractive index (1.58 or more) can be achieved due to the effect of the fluorene skeleton, and a sufficient glass transition temperature is obtained. The fluorene skeleton is introduced by curing by cationic polymerization after blending an epoxy resin having a fluorene skeleton to achieve a high refractive index, and is not suitable for thermal polymerization when a known epoxy resin curing agent such as an acid anhydride is used. was of a non-composition.

In addition, Patent Document 5 discloses an epoxy resin composition that is a cured product of an epoxy resin and an acid anhydride reacted with a bifunctional epoxy resin, a fluorene ring-containing phenol, and an acid anhydride, and has high transparency and good heat resistance reliability. This was insufficient.

Japanese Patent Laid-Open No. 6-025513 Japanese Laid-Open Patent Publication No. 2002-12819 Japanese Patent Publication No. 3948980 Japanese Laid-Open Patent Publication No. 2010-265360 Japanese Patent Laid-Open No. 2012-177038

An object of the present invention is to provide a cured epoxy resin for optics that can provide a composition for forming a sealing material and a protective film having low yellow discoloration during heat while satisfying visible light transmittance, which is the conventionally required performance. In addition, in the case where it is important to control the refractive index, such as an optical waveguide, the refractive index can be adjusted by changing the composition of the epoxy resin in the core and the clad, and furthermore, the optical epoxy resin that can maintain the adhesive force during heat between the core and the clad to provide a composition.

As a result of repeated intensive research to solve the above problems, the present inventors use an epoxy resin containing an aromatic ring and an aliphatic ring in the backbone of the epoxy resin to satisfy the visible light transmittance and low yellowing property when heated. Having found out what it has, the present invention was completed.

That is, this invention is an epoxy resin composition for optics containing an epoxy resin (a) and a hardening|curing agent (b) WHEREIN: The epoxy resin (a) has an epoxy equivalent of 500-2000 g/eq, and a softening point is 80-150 _{℃, the refractive index (n D} ²⁰ ) at 20°C and a wavelength of 589.3 nm is 1.55 to 1.63, has an aromatic ring and an aliphatic ring in the molecular structure at the same time, and the aliphatic proton (A) and the aromatic in the 1H-NMR spectrum The strength ratio (B/A) of proton (B) is 0.3-0.7, It is an epoxy resin composition for optics characterized by the above-mentioned.

As an epoxy resin (a), the ester compound (c) containing an aliphatic ring of the terminal carboxyl group obtained by reaction of a dihydric alcohol and an acid anhydride, a dihydric phenol compound (d), or both, and a bifunctional aromatic epoxy resin (e1) , a bifunctional aliphatic ring-containing epoxy resin (e2), or an epoxy resin obtained by reaction with both. More preferably, an epoxy resin obtained by reacting a terminal carboxyl group-containing ester compound (c) with a bifunctional aromatic epoxy resin (e1), or a dihydric phenol compound (d) and a bifunctional aliphatic ring-containing epoxy resin ( It is an epoxy resin obtained by the reaction of e2).

As the terminal carboxyl group-containing aliphatic ring-containing ester compound (c), an aliphatic ring-containing dihydric alcohol and an acid anhydride, a dihydric alcohol and an aliphatic ring-containing acid anhydride, or an aliphatic ring-containing dihydric alcohol and an aliphatic ring-containing acid anhydride obtained by reaction There are ester compounds containing an aliphatic ring of a terminal carboxyl group.

As a dihydric phenol compound (d), it is a fluorene ring containing phenol compound. As a bifunctional aromatic epoxy resin (e1), there exists a fluorene ring containing bifunctional aromatic epoxy resin. As a bifunctional aliphatic ring containing epoxy resin (e2), there exists a bifunctional alicyclic epoxy resin.

It is preferable that the used ratio of an epoxy resin (a) and a hardening|curing agent (b) is the range of 0.4-1.2 mol of active hydrogen groups of a hardening|curing agent (b) with respect to 1 mol of epoxy groups.

The optical epoxy resin composition is excellent as an epoxy resin composition for a film adhesive, an epoxy resin composition for a color filter protective film, or an epoxy resin composition for a surface protective film for an optical semiconductor substrate.

Moreover, this invention is the epoxy resin hardened|cured material obtained by hardening the said epoxy resin composition for optics. Moreover, it is a film adhesive obtained using the said epoxy resin composition for film adhesives, the epoxy resin composition for color filter protective films, or the epoxy resin composition for surface protective films for optical semiconductor substrates, a protective film for color filters, or a surface protective film for optical semiconductor substrates. Moreover, this invention is the sealing material for optical semiconductors or the board|substrate for optical semiconductors obtained using the said epoxy resin composition for optics.

The epoxy resin composition of the present invention can provide a cured product having high transparency and high heat-resistance reliability (high heat-resistant yellowing resistance). In particular, it is suitable for applications requiring heat resistance, light resistance, transparency, and long-term stability, such as LED sealing materials.

1 is a 1H-NMR spectrum of an epoxy resin 1 obtained in Synthesis Example 1. FIG.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

The optical epoxy resin composition of the present invention, in addition to a general optical disk, lens, light guide plate, or optical fiber, is a glass substrate replacement resin substrate, LED (Light Emitting Diode) sealing material, film adhesive, color filter, which is strongly required to have transparency. It is suitable for a protective film for Optical use is meant to include these uses. The epoxy resin composition for optics of the present invention is particularly suitable as a film adhesive, or a color filter or a protective film on the surface of an optical semiconductor substrate.

The epoxy resin composition for optics of the present invention contains an epoxy resin (a) and a curing agent (b). The epoxy resin (a) has an epoxy equivalent of 500 to 2000 g/eq, a softening point of 60 to 130° C., a refractive index (n _D ²⁰ ) at 20° C. and a wavelength of 589.3 nm of 1.55 to 1.63, and an aromatic ring and an aliphatic ring. It is essential that it has in the molecular structure simultaneously, and that the intensity ratio (B/A) of the aliphatic proton (A) to the aromatic proton (B) in the proton NMR spectrum (B/A) is 0.3 to 0.7.

The range of the epoxy equivalent of an epoxy resin (a) is 500-2000 g/eq, 700-1500 g/eq is more preferable, 850-1200 g/eq is still more preferable. If the epoxy equivalent is small, there is a fear that the effect of high refractive index and good heat resistance to yellowing cannot be expected. Conversely, if the epoxy equivalent is large, the softening point of the obtained epoxy resin increases, and molding or coating may become difficult. Here, the epoxy equivalent is the number of grams (g/eq) of a resin containing 1 gram equivalent of an epoxy group, and is measured according to the method prescribed in JIS K 7236.

The range of the softening point of an epoxy resin (a) is 80-150 degreeC, 100-145 degreeC is more preferable, 110-140 degreeC is still more preferable. If the softening point is low, blocking properties may increase and workability may deteriorate. Conversely, if the softening point is high, molding or application may become difficult, and processing must be performed at a high temperature, which causes coloration.

20 ℃ of the epoxy resin (a), the range of the refractive index (n _D ²⁰⁾ at a wavelength of 589.3 ㎚ is 1.55 ~ 1.63. Since this range is a range frequently used by an optical use, it is preferable, and can be set as this range by adjusting frame|skeleton of an epoxy resin (a), and content of an aromatic.

The epoxy resin (a) has both an aromatic ring and an aliphatic ring in the molecular structure. When an aliphatic ring is not contained, even if an aromatic ring exists, there exists a possibility that heat resistance may deteriorate. Moreover, when an aromatic ring is not contained, transparency and light resistance will become fully satisfactory, but heat-resistant yellowing-discoloration resistance (heat resistance) deteriorates remarkably, and it is difficult to use in optical applications with large heat generation. The ratio of the aromatic ring to the aliphatic ring also relates to the intensity ratio (B/A) of the aliphatic proton (A) to the aromatic proton (B) in the 1H-NMR spectrum described later.

The epoxy resin (a) which has an aromatic ring and an aliphatic ring simultaneously in a molecular structure can be obtained by the following method, for example.

1) Condensation polymerization of a phenol compound having both an aromatic ring and an aliphatic ring and epihalohydrin, 2) an epoxy resin having an aromatic ring, an aliphatic ring, or both, and an aromatic ring, an aliphatic ring, or both addition polymerization of a phenol compound having an acid anhydride having an aromatic ring, an aliphatic ring, or both, and an aromatic ring, an aliphatic Addition polymerization of an epoxy resin having a ring or both (provided that the epoxy resin and the acid anhydride simultaneously have only an aromatic ring or an aliphatic ring), 4) A terminal carboxyl group having an aromatic ring, an aliphatic ring, or both Addition polymerization of an ester compound of and an epoxy resin having an aromatic ring, an aliphatic ring, or both (except when the epoxy resin and the ester compound have only an aromatic ring or an aliphatic ring at the same time).

However, it is not limited to these methods. Further, the epoxy resin (a) may be obtained by combining these methods. And in any case, it is necessary to always use the raw material which has an aliphatic ring and an aromatic ring. One of the raw materials may have an aliphatic ring and an aromatic ring, one of the raw materials may have an aliphatic ring, and one of the other raw materials may have an aromatic ring.

Among the above manufacturing methods, a preferred manufacturing method for obtaining the epoxy resin (a) is an addition polymerization reaction of (1) a bifunctional epoxy resin, a dihydric phenol compound having a fluorene skeleton, and an ester compound containing an aliphatic ring having a terminal carboxyl group, (2) flu It is an addition polymerization reaction of a bifunctional epoxy resin having an orene skeleton and an ester compound containing an aliphatic ring having a terminal carboxyl group, (3) an addition reaction of a bifunctional alicyclic epoxy resin, an ester compound having a terminal carboxyl group, and a phenol compound, (4) It is addition polymerization reaction of a bifunctional alicyclic epoxy resin and a phenol compound. A more preferable production method is (1) addition polymerization reaction of a bifunctional epoxy resin, a dihydric phenol compound having a fluorene skeleton, and an ester compound containing an aliphatic ring having a terminal carboxyl group. Moreover, since adjustment of the introduction amount of an aromatic ring is difficult when using a bifunctional alicyclic epoxy resin independently, it is preferable to use a general bifunctional epoxy resin together.

In addition, in the present invention, the aliphatic ring refers to a cyclic part of an aliphatic hydrocarbon, and may contain a hetero atom such as oxygen. Those that do not represent a form are not included in the aliphatic ring. Preferred aliphatic rings are rings containing 3 or more carbons in ring constituent atoms and having no unsaturated bonds, and C4-C8 monocyclic cycloalkyl, C8-C16 bicycloalkyl, C7-C16 condensed or spiro-type cycloalkyl is more preferably. Specifically, a monocyclic structure such as a cyclobutane ring, a cyclopentane ring, or a cyclohexane ring, a bridged ring such as bicyclopentane, bicyclooctane, or bicycloundecane, and a spiro ring such as spirooctane or spirobicyclopentane Although polycyclic structures, such as these, and heterocyclic rings, such as an oxane ring, an oxepane ring, and a thiane ring, are mentioned, It is not limited to these.

The range of the intensity ratio (B/A) of the aliphatic proton (A) to the aromatic proton (B) in the 1H-NMR (proton NMR) spectrum of the epoxy resin (a) is 0.3 to 0.7, and 0.35 to 0.65 is More preferably, 0.4-0.6 are still more preferable. When there are many aromatic protons, heat resistance is improved and there is an effect of raising the refractive index, but transparency and light resistance deteriorate and there is a possibility that it cannot be used for optical applications. Conversely, if there are few aromatic protons, heat yellowing resistance (heat resistance) is poor There is a risk of worsening.

When the intensity ratio (B/A) is explained using FIG. 1 showing 1H-NMR of the epoxy resin (a) obtained in the synthesis example, the peak based on the aromatic proton (B) is a, and the aliphatic proton (A) is The base peak is all of the proton b of the alcohol, ether, or epoxide and the proton c of the ester and the proton d of methylene, and the intensity ratio (B/A) of the aliphatic proton (A) and the aromatic proton (B) is [a/ (b+c+d)].

Here, the aromatic proton (B) means H bonded to the aromatic ring constituent carbon, and the aliphatic proton (A) means H other than the aromatic proton (B).

Specifically, as a phenol compound having an aliphatic ring used in the method for introducing an aliphatic ring, 4,4'-cyclohexylidenebisphenol, 4,4'-cyclohexylidenebis(2-methylphenol), 4 ,4'-isopropylidenebis(2-cyclohexylphenol), 4,4'-(3,3,5-trimethylcyclohexylidene)bisphenol, etc. are mentioned, and can be used individually or as a mixture of 2 or more types. However, it is not limited to these.

Specifically as the bifunctional aliphatic ring-containing epoxy resin (e2), 3-oxiranyl-7-oxabicyclo[4.1.0]heptane, 3',4'-epoxycyclohexenylmethyl-3,4-epoxy Bifunctional alicyclic epoxy resins such as cyclohexenecarboxylate and limonene dioxide, 1,4-cyclohexanedimethanol, 4,4'-bis(hydroxymethyl)bicyclohexyl, 2,2-bis(4 -Hydroxycyclohexyl)propane (hydrogenated bisphenol A), bis(4-hydroxycyclohexyl)methane, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8, 10-tetraoxaspiro[5.5]undecane (spiroglycol), 5-ethyl-2-(2-hydroxy-1,1-dimethylethyl)-5-hydroxymethyl-1,3-dioxane, isosorbate Diglycidyl ether resin of dihydric alcohol having an aliphatic ring such as beads, 1,2-cyclohexanedicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, bi diglycidyl ester resin of dicarboxylic acid having an aliphatic ring, such as cyclo[2.2.1]heptane-2,3-dicarboxylic acid, etc., which can be used alone or as a mixture of two or more, It is not limited to these. In addition, diglycidyl ether resin of dihydric alcohol or diglycidyl ester resin of dicarboxylic acid has a high total chlorine content and there is a possibility that it cannot be used for electronic material applications, so the total chlorine content is reduced. It is preferred to use distilled products. Moreover, a bifunctional alicyclic epoxy resin is more preferable from a heat resistant point.

Specifically, as the acid anhydride having an aliphatic ring, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid anhydride, bicyclo[2.2.1 ]Heptane-2,3-dicarboxylic anhydride etc. are mentioned, Although it can use individually or as a mixture of 2 or more types, it is not limited to these.

The ester compound (c) having an aliphatic ring of a terminal carboxyl group used in the method for introducing an aliphatic ring can be obtained by the following method, but is not limited thereto.

addition reaction of a dihydric alcohol having an aliphatic ring with an acid anhydride,

addition reaction of a dihydric alcohol with an acid anhydride having an aliphatic ring,

addition reaction of a dihydric alcohol having an aliphatic ring and an acid anhydride having an aliphatic ring,

a dehydration condensation reaction of a dihydric alcohol having an aliphatic ring and a dicarboxylic acid;

a dehydration condensation reaction of a dihydric alcohol and a dicarboxylic acid having an aliphatic ring;

Dehydration condensation reaction of a dihydric alcohol having an aliphatic ring and a dicarboxylic acid having an aliphatic ring, etc.

In these reactions, more than equimolar acid anhydride and/or dicarboxylic acid are used with respect to the dihydric alcohol. In these reactions, it is necessary to completely ring-open the acid anhydride and not to remain as an unreacted acid anhydride, and it is also necessary that the compound whose both terminals are hydroxyl groups does not remain alone. Further, specific examples of the dihydric alcohol include, in addition to the dihydric alcohol having an aliphatic ring, aliphatic glycols such as ethylene glycol, propylene glycol, neopentyl glycol, and 1,6-hexanediol. no. Further, the acid anhydride and dicarboxylic acid include, but are not limited to, the acid anhydride and dicarboxylic acid described above. From the simplicity of the reaction, addition reaction of a dihydric alcohol having an aliphatic ring and an acid anhydride, an addition reaction of a dihydric alcohol and an acid anhydride having an aliphatic ring, or addition of a dihydric alcohol having an aliphatic ring and an acid anhydride having an aliphatic ring The reaction is preferred.

Moreover, even if it is the ester compound obtained by the other reaction mechanism, if it is an ester compound which has an aliphatic ring of a terminal carboxyl group, it does not matter. These ester compounds can be used individually or as a mixture of 2 or more types.

As a method of introducing an aromatic ring into the skeleton of the epoxy resin (a), condensation polymerization of a bifunctional phenol compound and epihalohydrin, addition polymerization of a bifunctional phenol compound and an epoxy resin, an epoxy resin having an aromatic ring, Various methods such as addition polymerization of a phenol compound, addition polymerization of an acid anhydride having an aromatic ring and an epoxy resin, and addition polymerization of an ester compound having an aromatic ring at a terminal carboxyl group and an epoxy resin, etc. are mentioned, but are limited to these methods no. Moreover, you may obtain an epoxy resin (a) combining these methods.

As an epoxy resin having an aromatic ring, it is a bifunctional aromatic epoxy resin which is a glycidyl ether product of a bifunctional phenol compound, and as the bifunctional phenol compound, bisphenol A (BPA), bisphenol F, bisphenol S, 4,4'-bi Phenol, tetramethylbisphenol A, dimethylbisphenol A, tetramethylbisphenol F, dimethylbisphenol F, tetramethylbisphenol S, dimethylbisphenol S, tetramethyl-4,4'-biphenol, dimethyl-4,4'-biphenol, 1-(4-hydroxyphenyl)-2-[4-(1,1-bis-(4-hydroxyphenyl)ethyl)phenyl]propane, 2,2'-methylene-bis(4-methyl-6- tert-butylphenol), 4,4'-butylidene-bis(3-methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, 9,9-bis(4- and bifunctional aromatic phenols such as hydroxyphenyl)-9H-fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)-9H-fluorene, and may be used alone or as a mixture of two or more types. However, it is not limited to these. 9,9-bis(4-hydroxyphenyl)-9H-fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)-9H-fluorene are preferable from a heat resistant point.

Examples of the acid anhydride having an aromatic ring include phthalic anhydride, 1,2-naphthalenedicarboxylic anhydride, 2,3-naphthalenedicarboxylic anhydride, 1,2,3,4-tetrahydro-1,2-naphthalene. Dicarboxylic acid anhydride etc. are mentioned, Although it can use individually or as a mixture of 2 or more types, it is not limited to these.

Examples of the dicarboxylic acid having an aromatic ring include phthalic acid, 1,2-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and 1,2,3,4-tetrahydronaphthalene-2,3-dicarboxylic acid. carboxylic acid, 1-phenyl-2,6-naphthalenedicarboxylic acid, etc. are mentioned, Although it can use individually or as a mixture of 2 or more types, it is not limited to these.

It is comparatively more difficult to introduce|transduce an aliphatic ring into an epoxy resin to make an epoxy resin (a) than introduce|transduce an aromatic ring. Although it is important that the epoxy resin is a high-purity product in the use of electric materials or optical material applications, most of the epoxy resins having an aliphatic ring other than the alicyclic epoxy resin have low purity and require high purity. For this reason, there are methods such as high-purity by repeating distillation separation and re-refining reaction of the epoxy resin, or methods by aliphatic cyclization of aromatic rings due to hydrogenation of the epoxy resin, but either method increases the number of steps, becomes complicated, and costly. It is also disadvantageous, so it is not a commercially desirable method. Therefore, as a raw material other than the epoxy resin, it is preferable to introduce it from a raw material having a functional group capable of reacting with an epoxy group, specifically, an acid anhydride having an aliphatic ring, dicarboxylic acid, or an ester compound of a terminal carboxyl group with an epoxy resin. It is preferable to introduce by reaction.

When the epoxy resin is a diglycidyl ether product of a phenol compound, a so-called aromatic epoxy resin, it is preferable to obtain an epoxy resin (a) by reaction with an ester compound containing an aliphatic ring of a terminal carboxyl group described above. In this case, it is preferable to use the carboxyl group of the ester compound of the terminal carboxyl group in the range of 0.2-0.7 mol with respect to 1 mol of the epoxy groups of an epoxy resin, Refractive index and heat-resistant yellowing property become high by increasing content of a carboxyl group within this range. When there are too few ester compounds of a terminal carboxyl group, the heat resistance of an epoxy resin (a) will fall, and when too large, the softening point of the epoxy resin (a) obtained will become high, and practicality will fall.

Moreover, you may use together a dihydric phenol compound. In this case, it is preferable to use the sum total of the carboxyl group of the ester compound of a terminal carboxyl group and the hydroxyl group of a dihydric phenol compound in 0.2-0.7 mol with respect to 1 mol of the epoxy groups of an epoxy resin. When the strength ratio (B/A) of the aliphatic proton (A) to the aromatic proton (B) is in the range of 0.3 to 0.7, the heat resistance is improved by increasing the content of the dihydric phenol compound. In the case of a dihydric phenol compound containing a fluorene skeleton, the effect is remarkable and it is more preferable.

The curing agent (b) is not particularly limited as long as it has a function of curing the epoxy resin, and a known curing agent such as a phenol-based curing agent, an amine-based curing agent, an acid anhydride curing agent, or a cationic polymerization initiator can be preferably used, but an alcoholic hydroxyl group A curing agent that also reacts with heat resistance is more preferable from the viewpoint of yellowing resistance. As a more preferable hardening|curing agent, specifically, cationic polymerization initiators, such as a photocationic polymerization initiator and a thermal cationic polymerization initiator, the said acid anhydride, 3,3',4,4'- diphenylsulfone tetracarboxylic dianhydride, Carboxylic acid dianhydrides, such as 1,2,3,4- butanetetracarboxylic dianhydride, etc. are mentioned. Although these hardening|curing agents can be used individually or as a mixture of 2 or more types, it is not limited to these.

In the epoxy resin composition of the present invention, the compounding amount of the epoxy resin (a) and the curing agent (b) is preferably in the range of 0.4 to 1.2 moles of active hydrogen groups of the curing agent (b) with respect to 1 mole of the epoxy groups of the epoxy resin (a), , 0.5-1.1 mol is more preferable, and 0.7-1.0 mol is still more preferable. For example, when a phenol-based or amine-based curing agent is used, an active hydrogen group is blended in substantially sugar moles with respect to the epoxy group, and when an acid anhydride-based curing agent is used, 0.5 to 1.2 moles of an acid anhydride group per mole of the epoxy group, preferably is blended by 0.6 to 1.0 mol. When the reaction proceeds by contact with imidazole compounds or a cationic polymerization initiator, it may be blended in a predetermined mass ratio with respect to the epoxy resin. The active hydrogen group as used in the present invention refers to a functional group having reactive active hydrogen with an epoxy group, and specific examples thereof include an acid anhydride group, a carboxyl group, an amino group, a phenolic hydroxyl group, and the like. In addition, about the active hydrogen groups, a carboxyl group or a phenolic hydroxyl group of 1 mole is calculated 1 mol, an amino group (NH ₂₎ 2 mol.

In the epoxy resin composition for optics of the present invention, if necessary, various epoxy resins other than the epoxy resin (a) may be used in combination so as not to impair the properties of the present invention. Specific examples of the epoxy resin that can be used in combination include Epottoto YDC-1312, ZX-1027 (manufactured by Nippon Tetsu Sumikin Chemical Co., Ltd., hydroquinone type epoxy resin), YX-4000 (manufactured by Mitsubishi Chemical Co., Ltd.), ZX- 1251 (manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd., non-phenolic epoxy resin), EPOTOT YD-127, EPOTTO YD-128, EPOTTO YD-128, EPOTTO YD-825GS, EPOTTO YD- 011, EPOTTO YD-900, EPTOTO YD-901 (manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd., BPA-type epoxy resin), EPOTTO YDF-170, EPOTTO YDF-8170, EPOTTOTO YDF-870GS , EPOTTO YDF-2001 (manufactured by Nittetsu Sumikin Chemical Co., Ltd., BPF-type epoxy resin), EPOTTO YDPN-638 (manufactured by Nippon Tetsu Sumikin Chemical Co., Ltd., phenol novolac type epoxy resin), EPOTTOTO YDCN- 701 (Shin-Nippon Sumikin Chemical Co., Ltd., cresol novolak-type epoxy resin), ZX-1201 (Shin-Nippon Sumikin Chemical Co., Ltd., bisphenol fluorene-type epoxy resin), NC-3000 (Nippon Kayaku Co., Ltd., biphenylar) Alkylphenol type epoxy resin), EPPN-501H, EPPN-502H (Nippon Kayaku Co., Ltd., polyfunctional epoxy resin), ZX-1355 (Nippon Kayaku Co., Ltd., Naphthalenediol type epoxy resin), ESN-155, ESN -185V, ESN-175 (manufactured by Nittetsu Sumikin Chemical Co., Ltd., β-naphthol aralkyl-type epoxy resin), ESN-355, ESN-375 (manufactured by Shin-Nippon Sumikin Chemical Co., Ltd., dinaphthol aralkyl-type epoxy resin), ESN -475V, ESN-485 (manufactured by Nippon-Sumikin Chemical Co., Ltd., α naphthol aralkyl type epoxy resin) Epototo YH-434, an epoxy resin produced from a phenol compound such as a polyhydric phenol resin and epihalohydrin , Epottoto YH-434GS (manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd., diaminodiphenylmethane tetraglycidyl ether), etc., and Epi an epoxy resin produced from halohydrin, an epoxy resin produced from epihalohydrin and a carboxylic acid such as YD-171 (manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd., dimer acid-type epoxy resin); It is not possible, and two or more types may be used in combination. When used in combination, a physical property values as a mixture of each of the epoxy resin, and an epoxy equivalent of 500 ~ 2000 g / eq, a softening point is 80 ~ 150 ℃, refractive index at 20 ℃, wavelength 589.3 ㎚ (n _D ²⁰⁾ is 1.55 ~ It is 1.63, and the intensity ratio (B/A) of the aliphatic proton (A) to the aromatic proton (B) in the 1H-NMR spectrum needs to be 0.3 to 0.7. Therefore, 20 mass parts or less are preferable with respect to 100 mass parts of epoxy resins (a), and, as for the other epoxy resin which can be used together, 10 mass parts or less are more preferable.

Moreover, 50 mass % or more of the sum total of an epoxy resin and a hardening|curing agent is preferable with respect to 100 mass % of non-volatile matter in the epoxy resin composition for optics of this invention. When there is too little, the effect of this invention will not be expressed.

A hardening accelerator can be used for the epoxy resin composition for optics of this invention as needed. Specific examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole, 2-(dimethylaminomethyl)phenol; Tertiary amines such as 1,8-diazabicyclo(5,4,0)undecene-7, phosphines such as triphenylphosphine, tricyclohexylphosphine, and triphenylphosphine triphenylborane, octylic acid and metal compounds such as tin. A hardening accelerator may be used independently and may use 2 or more types together. 0.01-5.0 mass parts of hardening accelerators are used as needed with respect to 100 mass parts of epoxy resins (a) in the epoxy resin composition for optics of this invention. By selectively using these curing accelerators, the curing temperature can be lowered or the curing time can be shortened.

An organic solvent can also be used for the epoxy resin composition for optics of this invention for viscosity adjustment. The organic solvent that can be used is not specifically defined, but specifically exemplified, amides such as N,N-dimethylformamide, ethers such as ethylene glycol monomethyl ether, acetone, methyl ethyl ketone, and methyl isobutyl ketone ketones such as ketones, alcohols such as methanol and ethanol, aromatic hydrocarbons such as benzene, toluene and xylene, esters such as methyl acetate and ethyl acetate, and aprotic polar solvents such as N-methylpyrrolidone. have. These solvents may be used independently and may be used in mixture of 2 or more types.

The epoxy resin composition for optics of this invention may mix|blend curable resin and thermoplastic resin other than an epoxy resin in the range which does not impair a characteristic. Specifically, phenol resins, acrylic resins, petroleum resins, indene resins, indencumarone resins, phenoxy resins, cyanate resins, epoxy acrylate resins, vinyl compounds, polyurethanes, polyesters, polyamides, polyimides, Polyamideimide, polyetherimide, bismaleimide triazine resin, polyethersulfone, polysulfone, polyetheretherketone, polyphenylenesulfide, polyvinylformal, etc. are mentioned, but are not limited to these. In the optical epoxy resin composition of the present invention, the content in the case of using these resins is preferably 5 to 30 parts by mass, when the total amount of the epoxy resin (a) and the curing agent (b) used is 100 parts by mass, 15-20 mass parts is more preferable. When there is too little content, the effect of mix|blending these resins will not fully be acquired, but when there is too much content, there exists a tendency for the moisture resistance of hardened|cured material, etc. to fall.

A filler can be used for the epoxy resin composition for optics of this invention as needed. Specific examples include inorganic fillers such as aluminum hydroxide, magnesium hydroxide, talc, calcined talc, clay, kaolin, titanium hydroxide, glass powder, and silica balloon, and organic or inorganic moisture-resistant pigments, flaky pigments, etc. may be blended. . As a reason for using a general inorganic filler, the improvement of impact resistance is mentioned. Moreover, fibrous fillers, such as glass fiber, pulp fiber, synthetic fiber, and ceramic fiber, organic fillers, such as particulate rubber and a thermoplastic elastomer, etc. can be mix|blended. Content in the case of using a filler in the epoxy resin composition for optics of this invention makes the sum total of the usage-amount of an epoxy resin (a) and a hardening|curing agent (b) 100 mass parts, 5-80 mass parts is preferable, and 15- 60 mass parts is more preferable, and 30-50 mass parts is still more preferable. When the content is too small, the effect of blending cannot be sufficiently obtained. When the content is too large, the viscosity of the composition tends to increase, or the strength of the cured product tends to decrease and become brittle.

Moreover, you may mix|blend additives, such as a flame retardant, a thixotropy imparting material, and a fluidity|liquidity improving agent, in the epoxy resin composition for optics of this invention as needed. Examples of the thixotropic material include silicone-based, castor oil-based, aliphatic amide wax, polyethylene oxide wax, and organic bentonite-based material. In addition, if necessary, in the resin composition of the present invention, a release agent such as carnauba wax and OP wax, a colorant such as carbon black, a flame retardant such as antimony trioxide, a stress reducing agent such as silicone oil, and a lubricant such as calcium stearate. can

In addition, in the epoxy resin composition for optics of this invention, you may mix|blend antioxidant and an optical stabilizer as needed. The addition of an antioxidant and a light stabilizer is preferable for improving the storage stability of the optical epoxy resin composition and improving the weather resistance of the cured composition. As antioxidant and light stabilizer, a commercial item can be used. For example, Smirrizer BHT, Smirrizer S, Smirrizer BP-76, Smirrizer MDP-S, Smirrizer GM, Smirrizer BBM-S, Smirrizer WX-R, Smirizer NW, Smirrizer BP-179, Sumilizer BP-101, Sumilizer GA-80, Sumilizer TNP, Sumilizer TPP-R, Sumilizer P-16 (manufactured by Sumitomo Chemical Co., Ltd.), ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50, ADEKA STAB AO-60, ADEKA STAB AO-70, ADEKA STAB AO-80, ADEKA STAB AO-330, ADEKA STAB Stave PEP-4C, Adeka Stab PEP-8, Adeka Stave PEP-24G, Adeka Stab PEP-36, Adeka Stab HP-10, Adeka Stave 2112, Adeka Stave 260, ADEKA STAB 522A, ADEKA STAB 329K, ADEKA STAB 1500, ADEKA STAB C, ADEKA STAB 135A, ADEKA STAB 3010 (manufactured by Asahi Denka Industrial Co., Ltd.), Tinubin 770, Tinubin 765 , Tinuvin 144, Tinuvin 622, Tinuvin 111, Tinuvin 123, Tinuvin 292 (manufactured by Chiba Specialty Chemicals), Pancryl FA-711M, FA-712HM (manufactured by Hitachi Kasei Industrial Co., Ltd.), Double Chisorb292 (Bond) Chemical company make) etc. are mentioned. Although the compounding quantity of these antioxidant and light stabilizer is not specifically limited, When the sum total of the usage-amount of an epoxy resin (a) and a hardening|curing agent (b) is 100 mass parts, 0.001-5 mass parts is preferable, and 0.01-3 mass parts is more preferable. Do.

In order to manufacture the film adhesive which concerns on this invention or the protective film for color filters, the method of processing the epoxy resin composition for optics into a sheet form or a film form is not specifically limited, A well-known technique can be used. For example, (A) extrusion molding method in which the optical epoxy resin composition of the present invention is kneaded with an extruder and then extruded and molded into a sheet using a T-die or a circular die, (B) the optical epoxy resin of the present invention and a casting molding method in which the composition is dissolved or dispersed in a solvent such as an organic solvent and then cast to form a sheet, (C) other conventionally known sheet molding methods, and the like.

Among these molding methods, the casting molding method of (b) is preferable. The optical epoxy resin composition of the present invention is diluted with an organic solvent to prepare a liquid varnish, and the varnish is applied on a support by a flow coating method, a roll coating method, a gravure roll method, a wire bar method, a lip die coating method, etc. Then, by drying the solvent, a sheet-like or film-like composition having an arbitrary film thickness can be obtained. The support for applying the varnish is not particularly limited, but a generally known material such as a polyester-based, polyolefin-based, polyimide-based, or fluorine-based plastic film, metal foil, or metal plate can be used, and these supports are pre-released or electrostatically treated. It is preferable that etc. are performed. In preparation of a varnish, it is also possible to dilute with a solvent after mixing|blending each component, or it is also possible to dilute with a solvent beforehand before mixing|blending each component. Moreover, although there is no restriction|limiting in particular in drying conditions, 3 to 15 minutes are preferable at 50-100 degreeC.

Although limitation in particular is not carried out as for the film thickness of the film or sheet|seat formed after drying, 3-300 micrometers is preferable, 5-200 micrometers is more preferable, 10-180 micrometers is a further more preferable range. In the case of a color filter or a protective film of an optical semiconductor substrate, 10-50 micrometers is the most preferable. If the film thickness is 3 µm or more, insulation can be obtained, and when it is 300 µm or less, transparency can be ensured. Moreover, content of the solvent in a film or a sheet|seat is although it does not specifically limit, It is preferable that it is 0.01-5 mass % with respect to the whole resin composition. When content of the solvent in a film is 0.01 mass % or more with respect to the whole resin composition, when laminating|stacking on a board|substrate etc., adhesiveness and adhesiveness will be acquired, and if it is 5 mass % or less, flatness after heat curing will be obtained.

The epoxy resin composition for optics of the present invention can be molded and cured by the same method as a known epoxy resin composition to obtain a cured product. The molding method and the curing method can adopt the same method as that of a known epoxy resin composition, and a method unique to the resin composition of the present invention is unnecessary. The optical epoxy resin cured product of the present invention can take the form of a laminate, a molded product, an adhesive, a coating film, a film, etc., and has good transparency and heat-resistance reliability (high heat-resistance yellowing resistance) used in areas exposed to high temperatures. It is useful as a material for sealing materials, laminates, insulating materials, composites, insulating adhesives, etc. used in electrical and electronic components for optical applications.

Example

The present invention will be specifically described based on Examples and Comparative Examples, but the scope of the present invention is not limited to these Examples. In the following synthesis examples, examples, and comparative examples, "part" represents a mass part, and "%" represents a mass %, respectively. And in the present invention, the following test method was used.

(1) Epoxy equivalent: Measured according to JIS K-7236.

(2) Softening point: Measured according to JISK-7234.

(3) Refractive index: Using an Abbe refractometer (manufactured by ERMA, ER-7MW), it is dissolved in cyclohexanone so as to have a solid content of 30%, measured at 20°C and a wavelength of 589.3 nm, and calculated as 100% of a solid content The refractive index of was obtained.

(4) Glass transition temperature (Tg): Using a differential scanning calorimetry apparatus (manufactured by SII, EXTER DSC6200), it was measured at a temperature increase rate of 10°C/min from 20°C.

(5) Heat yellowing resistance: Measurement is performed using a colorimetric colorimeter (manufactured by Tokyo Denshoku Co., Ltd., TC-1500MC-88), and YI value before application of heat history is used as a blank, and a constant temperature is maintained at 250°C. The difference with the YI value after storage in an oven for a predetermined time is shown. It shows that heat-resistant yellowing property is so favorable that a numerical value is small.

(6) UV discoloration resistance: Measurement is performed using a colorimetric colorimeter, and YI value before light irradiation is used as a blank, and YI after irradiation for 24 hours at an irradiation intensity of 400 W/m 2 (using the ATLS line test XLS) The difference with the value is shown. It shows that ultraviolet-ray discoloration resistance is so favorable that a numerical value is small.

(7) Transmittance: The transmittance|permeability (%) in wavelength 450nm was measured using the spectrophotometer (The Nippon Spectroscopy Co., Ltd. make, V-650). The measured value of the test piece before heat history or light irradiation is taken as the initial value, and the test piece after holding for 30 minutes in an oven maintained at a constant temperature at 250 ° C. and the test piece after 24 hours irradiation at an irradiation intensity of 400 W/m 2 are also respectively. measured.

Explanation of the abbreviation used by the synthesis example, an Example, and a comparative example.

(epoxy resin)

Epottoto YD-128 ; Diglycidyl ether of 2,2-bis(4-hydroxyphenyl)propane, epoxy equivalent 187 g/eq, viscosity 13000 mPs s/25° C., manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd.

ESF-300 ; Diglycidyl ether of 9,9-bis(4-hydroxyphenyl)-9H-fluorene, epoxy equivalent 250 g/eq, softening point 87° C., manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd.

Celoxide 2021P; 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, epoxy equivalent 133 g/eq, viscosity 240 mPa·s/25°C, manufactured by Daicel Chemical Industry Co., Ltd.

Epottoto ZX-1658GS ; Diglycidyl ether of 1,4-cyclohexanedimethanol, epoxy equivalent 134 g/eq, viscosity 37 mPs s/25° C., manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd.

(acid anhydride)

ricassid HH; Hexahydrophthalic anhydride, manufactured by New Nippon Rica Co., Ltd.

licacid MH ; 4-Methylhexahydrophthalic anhydride, manufactured by Nippon Rika Co., Ltd.

(dihydric alcohol)

ricabinol HB; Hydrogenated bisphenol A, manufactured by New Nippon Rica Co., Ltd.

SPG ; Spiroglycol, manufactured by Mitsubishi Gas Chemical Co., Ltd.

HDL ; 1,6-hexanediol, manufactured by Ubekosan Co., Ltd.

(bifunctional phenolic compound)

BPF; 9,9-bis(4-hydroxyphenyl)-9H-fluorene, hydroxyl equivalent = 175 g/eq, manufactured by Osaka Gas Chemical Co., Ltd.

BPA; 2,2-bis(4-hydroxyphenyl)propane, hydroxyl equivalent = 114 g/eq, manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd.

(catalyst)

hycicholine BTPPBr; n-Butyltriphenylphosphonium bromide, manufactured by Nippon Chemical Industry Co., Ltd.

TPP; Triphenylphosphine, manufactured by Hokko Chemical Co., Ltd.

Curesol 2E4MZ ; 2-ethyl-4-methylimidazole, manufactured by Shikoku Chemical Co., Ltd.

Synthesis Example 1

In a reaction apparatus equipped with a stirrer, a thermometer, a nitrogen blowing tube, and a cooling tube, 121.5 parts of ricaside HH as an acid anhydride and 113.6 parts of ricabinol HB as a dihydric alcohol were added, and the mixture was stirred in a nitrogen gas atmosphere. While reacting at 130 ° C. for 2 hours to obtain a terminal carboxyl group-containing ester compound, then 567.5 parts of Epottoto YD-128 as an epoxy resin, 197.4 parts of BPF as a bifunctional phenol compound, and hysicoline BTPPBr as a catalyst 0.43 parts were injected|thrown-in, it stirred and mixed at 150 degreeC for 4 hours, and the epoxy resin 1 was obtained.

Synthesis Example 2

112.9 parts of ricaside HH as an acid anhydride, 105.6 parts of ricabinol HB as a dihydric alcohol, 527.5 parts of Epottoto YD-128 as an epoxy resin, 254.0 parts of BPF as a bifunctional phenol compound, and hycicholine BTPPBr as a catalyst Except having used 0.47 parts, it carried out similarly to the synthesis example 1, and obtained the epoxy resin 2.

Synthesis Example 3

In a reactor equipped with a stirrer, a thermometer, a nitrogen blowing tube, and a cooling tube, 621.8 parts of Celoxide 2021P as an epoxy resin, 131.2 parts of BPF and 247.0 parts of BPA as a difunctional phenol compound, and 0.38 parts of TPP as a catalyst It was added and stirred and mixed at 150 degreeC for 4 hours, and the epoxy resin 3 was obtained.

Synthesis Example 4

229.9 parts of ricaside MH as an acid anhydride, 195.4 parts of ricabinol HB as a dihydric alcohol, 574.7 parts of ESF-300 as an epoxy resin, without using a bifunctional phenol compound, 0.42 parts of hycicholine BTPPBr as a catalyst Except having used, it carried out similarly to the synthesis example 1, and obtained the epoxy resin 4.

Synthesis Example 5

97.6 parts of ricaside HH as an acid anhydride, 79.5 parts of ricabinol HB as a dihydric alcohol, 502.9 parts of Epottoto ZX-1658GS as an epoxy resin, 320.0 parts of BPF as a bifunctional phenol compound, and hycicholine BTPPBr as a catalyst Except having used 0.50 part, it carried out similarly to the synthesis example 1, and obtained the epoxy resin 5.

Synthesis Example 6

149.2 parts of phthalic anhydride as an acid anhydride, 125.8 parts of ricabinol HB as a dihydric alcohol, 493.2 parts of Epottoto ZX-1658GS as an epoxy resin, 230.4 parts of BPF as a difunctional phenol compound, and 0.51 parts of hycicholine BTPPBr as a catalyst Epoxy resin 6 was obtained in the same manner as in Synthesis Example 1 except that it was partially used.

Synthesis Example 7

131.8 parts of phthalic anhydride as an acid anhydride, 113.4 parts of ricabinol HB as a dihydric alcohol, 493.0 parts of Epottoto YD-128 as an epoxy resin, 103.7 parts of Celoxide 2021P, and 158.1 parts of BPA as a difunctional phenol compound , Epoxy resin 7 was obtained in the same manner as in Synthesis Example 1 except that 0.40 parts of hycicholine BTPPBr was used as a catalyst.

Synthesis Example 8

ESF-300 was used in the same manner as in Synthesis Example 3 except that 334.5 parts of ESF-300 and 353.3 parts of Celoxide 2021P were used, 312.2 parts of BPA was used as a difunctional phenol compound, and 0.31 parts of hycicholine BTPPBr was used as a catalyst. got it

Synthesis Example 9

95.9 parts of lycaside HH as an acid anhydride, 106.5 parts of SPG as a dihydric alcohol, 569.3 parts of Epottoto YD-128 as an epoxy resin, 228.3 parts of BPF as a difunctional phenol compound, and 0.43 parts of hycicholine BTPPBr as a catalyst Except having used, it carried out similarly to the synthesis example 1, and obtained the epoxy resin 9.

Synthesis Example 10

An epoxy resin 10 was obtained in the same manner as in Synthesis Example 3 except that 698.0 parts of Epottoto YD-128 as an epoxy resin, 302.0 parts of BPA as a bifunctional phenol compound, and 0.03 parts of Curesol 2E4MZ as a catalyst were used.

Synthesis Example 11

An epoxy resin 11 was obtained in the same manner as in Synthesis Example 3 except that 641.0 parts of Epottoto YD-128 as an epoxy resin, 386.0 parts of BPF as a bifunctional phenol compound, and 0.39 parts of TPP as a catalyst were used.

Synthesis Example 12

189.6 parts of phthalic anhydride as an acid anhydride, 369.6 parts of HDL as a dihydric alcohol, 440.8 parts of Epottoto YD-128 as an epoxy resin, without using a bifunctional phenol compound, 0.56 parts of hycicholine BTPPBr as a catalyst Except having used, it carried out similarly to the synthesis example 1, and obtained the epoxy resin 12.

Synthesis Example 13

64.0 parts of ricaside HH as an acid anhydride, 59.7 parts of ricabinol HB as a dihydric alcohol, 594.8 parts of epottoto YD-128 as an epoxy resin, 281.5 parts of BPF as a bifunctional phenol compound, and hycicholine BTPPBr as a catalyst Except having used 0.41 part, it carried out similarly to the synthesis example 1, and obtained the epoxy resin 13.

Synthesis Example 14

An epoxy resin 14 was obtained in the same manner as in Synthesis Example 3 except that 508.9 parts of Celoxide 2021P as an epoxy resin, 491.1 parts of BPF as a bifunctional phenol compound, and 0.49 parts of TPP as a catalyst were used.

Synthesis Example 15

220.2 parts of ricaside HH as an acid anhydride, 205.4 parts of ricabinol HB as a dihydric alcohol, 464.4 parts of Celoxide 2021P as an epoxy resin, 110.0 parts of BPA as a difunctional phenol compound, and 0.54 parts of hycicholine BTPPBr as a catalyst. Except for that, it carried out similarly to the synthesis example 1, and obtained the epoxy resin 15.

Synthesis Example 16

302.7 parts of ricaside HH as an acid anhydride, 282.4 parts of ricabinol HB as a dihydric alcohol, 414.9 parts of Celoxide 2021P as an epoxy resin, 0.59 parts of hycicholine BTPPBr as a catalyst without using a bifunctional phenol compound Except having used, it carried out similarly to the synthesis example 1, and obtained the epoxy resin 16.

Synthesis Example 17

275.0 parts of licaside HH as an acid anhydride, 256.2 parts of ricabinol HB as a dihydric alcohol, 468.8 parts of Epottoto ZX-1658GS as an epoxy resin, without using a bifunctional phenol compound, hycicholine BTPPBr as a catalyst An epoxy resin 17 was obtained in the same manner as in Synthesis Example 1 except that 0.53 parts of was used.

Synthesis Example 18

248.0 parts of licaside HH as an acid anhydride, 229.0 parts of ricabinol HB as a dihydric alcohol, 523.0 parts of Epottoto YD-128 as an epoxy resin, and 0.48 parts of hycicholine BTPPBr as a catalyst without using a bifunctional phenol compound Epoxy resin 18 was obtained in the same manner as in Synthesis Example 1 except that it was partially used.

Synthesis Example 19

140.0 parts of ricaside HH as an acid anhydride, 120.0 parts of ricabinol HB as a dihydric alcohol, 195.0 parts of Epottoto YD-128 and 545.0 parts of ESF-300 as an epoxy resin, without using a difunctional phenol compound, Epoxy resin 19 was obtained in the same manner as in Synthesis Example 1 except that 0.30 parts of hycicholine BTPPBr was used as a catalyst.

Synthesis Example 20

127.9 parts of ricaside HH as an acid anhydride, 100.6 parts of ricabinol HB as a dihydric alcohol, 527.5 parts of Epottoto YD-128 as an epoxy resin, 254.0 parts of BPF as a difunctional phenol compound, and hycicholine BTPPBr as a catalyst Except having used 0.47 parts, it carried out similarly to the synthesis example 1, and obtained the epoxy resin 20.

The properties of the obtained epoxy resins 1 to 20 are shown in Tables 1-2.

Example 1

After dissolving 100 parts of the epoxy resin 1 obtained in Synthesis Example 1 as an epoxy resin and 15 parts of licaside HH as a curing agent in 75 parts of tetrahydrofuran as a solvent, hysicolin PX-4ET (organophosphonium salt compound, Nippon Chemicals) as a curing accelerator (manufactured by Kogyo Co., Ltd.) 0.25 parts was mixed to obtain a liquid composition.

After drying, the liquid composition was coated on a 0.2 mm thick glass plate to a thickness of 100 μm as a film, dried in a hot air circulation oven at 100 ° C. for 2 hours, and cured in a hot air circulation oven at 140 ° C. for 10 hours, and the glass plate was attached A test piece was obtained. Heat yellowing resistance, ultraviolet ray discoloration resistance, and transmittance were measured using the obtained test piece with a glass plate as it is.

Examples 2 to 10

Using 100 parts of epoxy resins 2-9 obtained by Synthesis Examples 2-9 as an epoxy resin, and the hardening|curing agent shown in Table 3, it carried out similarly to Example 1, the test piece was produced, and it evaluated.

Table 3 shows the epoxy resin, the type of curing agent, and the amount of the curing agent used. Table 5 shows the evaluation results. In Table 3, HH is licacid HH, and PA is phthalic anhydride.

Comparative Examples 1 to 12

Using 100 parts of resins 10-20 obtained in Synthesis Examples 10-20 as an epoxy resin, and the hardening|curing agent shown in Table 4, it carried out similarly to Example 1, the test piece was produced, and it evaluated.

Table 4 shows the epoxy resin, the type of curing agent, and the amount of the curing agent used. Table 6 shows the evaluation results.

Claims (16)

The epoxy resin composition for optics containing an epoxy resin (a) and a hardening|curing agent (b) WHEREIN: The epoxy resin (a) has a softening point of 80-150 degreeC, and the refractive index in 20 degreeC and wavelength 589.3nm (n _D ²⁰⁾ ) is 1.55 to 1.63, has an aromatic ring and an aliphatic ring in the molecular structure at the same time, and the intensity ratio (B/A) of the aliphatic proton (A) to the aromatic proton (B) in the 1H-NMR spectrum is 0.3 to 0.7 In addition, the epoxy resin (a) is an epoxy resin having an epoxy equivalent of 1030 to 2000 g/eq obtained by the reaction of the ester compound (c) containing an aliphatic ring having a terminal carboxyl group and the bifunctional aromatic epoxy resin (e1), or an epoxy resin having an epoxy equivalent obtained by reaction of a dihydric phenol compound (d) and a bifunctional aliphatic ring-containing epoxy resin (e2) of 500 to 2000 g/eq. The method of claim 1,
The epoxy resin composition for optics in which an epoxy resin (a) is an epoxy resin obtained by reaction of the ester compound (c) containing an aliphatic ring of a terminal carboxyl group, and a bifunctional aromatic epoxy resin (e1). 3. The method of claim 2,
A terminal obtained by reacting an aliphatic ring-containing ester compound (c) with an aliphatic ring-containing dihydric alcohol and an acid anhydride, a dihydric alcohol and an aliphatic ring-containing acid anhydride, or an aliphatic ring-containing dihydric alcohol with an aliphatic ring-containing acid anhydride An optical epoxy resin composition which is an ester compound containing an aliphatic ring of a carboxyl group. The method of claim 1,
The epoxy resin composition for optics in which the dihydric phenol compound (d) is a fluorene ring containing phenol compound. 3. The method of claim 2,
The epoxy resin composition for optics whose bifunctional aromatic epoxy resin (e1) is a fluorene ring containing bifunctional aromatic epoxy resin. The method of claim 1,
The epoxy resin composition for optics whose bifunctional aliphatic ring containing epoxy resin (e2) is a bifunctional alicyclic epoxy resin. The method of claim 1,
The epoxy resin composition for optics in which the active hydrogen group of the hardening|curing agent (b) is the range of 0.4-1.2 mol with respect to 1 mol of the epoxy groups of the epoxy resin (a). 8. The method according to any one of claims 1 to 7,
An epoxy resin composition for optics which is an epoxy resin composition for film adhesives. 8. The method according to any one of claims 1 to 7,
An epoxy resin composition for optics, which is an epoxy resin composition for a color filter protective film. 8. The method according to any one of claims 1 to 7,
An epoxy resin composition for optics which is an epoxy resin composition for surface protective films for optical semiconductor substrates. An epoxy resin cured product obtained by curing the optical epoxy resin composition according to any one of claims 1 to 7. The film adhesive obtained using the epoxy resin composition of Claim 8. The protective film for color filters obtained using the epoxy resin composition of Claim 9. The sealing material for optical semiconductors obtained using the epoxy resin composition for optics in any one of Claims 1-7. The board|substrate for optical semiconductors obtained using the epoxy resin composition for optics in any one of Claims 1-7. The surface protective film for optical semiconductor substrates obtained using the epoxy resin composition of Claim 10.

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