JP6441024B2 - Epoxy resin containing silicone-modified epoxy resin and polyvalent carboxylic acid compound and cured product thereof - Google Patents

Description

  Examples of the resin composition for sealing an optical semiconductor element include a bisphenol A type epoxy resin excellent in adhesiveness and mechanical strength, and an epoxy resin having no UV absorption, such as a hydrogenated bisphenol A type epoxy resin or an alicyclic epoxy resin. A composition containing a curing agent and a curing catalyst is frequently used. However, as the luminance and output of the LED element increase, there are problems of discoloration and cracking due to light, heat, etc. from the LED element.

  As a solution to these problems, a resin in which an epoxy group is introduced into a silicone resin that does not absorb UV and gives a flexible cured product is known. For example, a cyclic ether such as a glycidyl group or an epoxycyclohexyl group. Silicone resin having at least one containing group (Patent Document 1), reaction product of epoxyalkoxysilane and silanol (Patent Document 2), and a combination of alicyclic epoxy-modified silicone resin and alicyclic epoxy resin (Patent Document 3) is known. However, since the silicone resin has a very high gas permeability as compared with the epoxy resin, it becomes difficult to use the silicone resin for an application requiring low gas permeability as the silicone content increases. Thus, an addition reaction type phenyl silicone resin composition has been disclosed as a resin composition having low gas permeability (Patent Document 4), but it is still not satisfactory in terms of low gas permeability and adhesiveness. Absent. Furthermore, an epoxy resin composition using an epoxy group-containing polysiloxane and an acid anhydride compound as its curing agent is disclosed (Patent Document 5), but it is not satisfactory from the viewpoint of heat discoloration of the cured product. There wasn't.

JP 2008-45088 A Japanese Patent Laid-Open No. 7-97433 JP 2006-282898 A JP 2002-265787 A JP 2012-092172 A

  The present invention has been made in view of the above circumstances, and a silicone-modified epoxy resin composition that provides a cured product excellent in low gas permeability, mechanical strength, and heat-resistant transparency, and an epoxy obtained by curing the composition. An object is to provide a cured resin.

  As a result of intensive studies in view of the actual situation as described above, the present inventors have completed the present invention.

That is, the present invention relates to the following (1) to (6).
(1) Contains one or more selected from silicone-modified epoxy resins (A) represented by the following formulas (1) to (3) and a polyvalent carboxylic acid compound (B) represented by the following formula (4) An epoxy resin composition.

（式（１）中、Ｒ^１は炭素数１〜６の一価脂肪族炭化水素基又は炭素数６〜１２の一価芳香族炭化水素基を、Ｒ^２は酸素原子もしくはフェニレン基を、Ｘはエポキシ基を有する有機基を、ｍは平均値で１〜１０を、式中、複数存在するＲ^１、Ｒ^２はそれぞれ同一であっても異なっても構わない。）

(In the formula (1), R ¹ represents a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, R ² represents an oxygen atom or a phenylene group, X Represents an organic group having an epoxy group, m represents an average value of 1 to 10, and a plurality of R ¹ and R ² may be the same or different.

（式（２）中、Ｒ^１、Ｘは前記と同じ意味を、ｎは１〜３の整数をそれぞれ表す。式中、複数存在するＲ^１、Ｘはそれぞれ同一であっても異なっても構わない。）

(In the formula (2), R ¹ and X have the same meaning as described above, and n represents an integer of 1 to 3. In the formula, a plurality of R ¹ and X may be the same or different. Absent.)

（式（３）中、Ｒ^１、Ｘは前記と同じ意味をそれぞれ表す。式中、複数存在するＲ^１、Ｘはそれぞれ同一であっても異なっても構わない。）

(In the formula (3), R ¹ and X each have the same meaning as described above. In the formula, a plurality of R ¹ and X may be the same or different.)

（式（４）中、Ｒ^３は炭素数１〜６のアルキレン基を、Ｒ^４は水素原子又は炭素数１〜６のアルキル基又はカルボキシル基をそれぞれ表す。式（４）中、複数存在するＲ^３、Ｒ^４は同一であっても異なっていても構わない。）

(In Formula (4), R ³ represents an alkylene group having 1 to 6 carbon atoms, and R ⁴ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group. R ³ and R ⁴ may be the same or different.)

(2) The epoxy resin composition according to (1), further containing a carboxylic acid anhydride compound (C).

(3) The epoxy resin composition according to any one of claims 1 to 2, wherein one or more carboxylic acid anhydride compounds (C) are selected from the following formulas (5) to (7).

(4) The epoxy resin composition according to any one of claims 1 to 3, further comprising an epoxy resin curing accelerator (D).

(5) The epoxy resin composition according to any one of claims 1 to 4, further comprising a phosphorus-based antioxidant (E) and / or a phenol-based antioxidant (F).

(6) Hardened | cured material formed by hardening | curing the epoxy resin composition as described in any one of Claims 1-5.

  The epoxy resin composition of the present invention comprises at least one selected from silicone-modified epoxy resins (A) represented by formulas (1) to (3) and a polyvalent carboxylic acid represented by formula (4) described below. It contains the compound (B).

First, the silicone-modified epoxy resin (A) of the present invention will be described.
The silicone-modified epoxy resin (A) of the present invention is a silicone-modified epoxy resin represented by the following formulas (1) to (3).

In formula (1), R ¹ represents a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, R ² represents an oxygen atom or a phenylene group, and X represents In the organic group having an epoxy group, m is an average value of 1 to 10, and a plurality of R ¹ and R ² may be the same or different.

R ¹ is a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and as a specific example of a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, Is a saturated monovalent aliphatic such as alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, heptyl group, 2-ethylhexyl group, heptyl group, octyl group, etc. Examples thereof include unsaturated monovalent aliphatic hydrocarbon groups such as hydrocarbon groups, vinyl groups, allyl groups, isopropenyl groups, butenyl groups and the like, preferably methyl groups, ethyl groups, n-propyl groups, isopropyl groups. Group, n-butyl group, t-butyl group and heptyl group, more preferably methyl group. Specific examples of the monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms include aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, benzyl group, 2-phenylethyl group, 2-phenylpropylene. An aralkyl group such as an alkyl group, preferably a phenyl group, a benzyl group, a 2-phenylethyl group, or a 2-phenylpropyl group, and more preferably a phenyl group.

R ² is an oxygen atom or a phenylene group. Among these, a phenylene group is preferable from the viewpoint of low gas permeability.

  m is an average value of 0 to 10, preferably 0 to 5, and more preferably 0 to 2.

The organic group in X represents a compound composed of C, H, N, and O atoms, and specific examples of the epoxy group-containing organic group include 3,4 -epoxycyclohexylethyl group and 3-glycidoxypropyl group. From the viewpoint of heat-resistant transparency of the cured product, 3,4 -epoxycyclohexylethyl group is preferable. Here, the number of carbon atoms in the organic group is preferably 1-20, and more preferably 3-15. In addition, a group to which a 3,4 -epoxycyclohexylethyl group or 3-glycidoxypropyl group is added via an alkylene group having 1 to 5 carbon atoms is preferable.

In formula (2), R ¹ and X have the same meaning as described above, and n represents an integer of 1 to 3, respectively. In the formula, a plurality of R ¹ and X may be the same or different.

  n is an integer of 1 to 3, and 2 is particularly preferable.

In formula (3), R ¹ and X each represent the same meaning as described above. In the formula, a plurality of R ¹ and X may be the same or different.

  The silicone-modified epoxy resin (A) represented by the formulas (1) to (3) is an addition of a hydrogen siloxane compound represented by the following formulas (8) to (110) and a compound having an alkenyl group and an epoxy group. It can be obtained by reaction.

In formulas (8) to (10), R ¹ , R ² , m, and n each represent the same meaning as described above. In the formula, a plurality of R ¹ and R ² may be the same or different.

  Although the compound which has an alkenyl group and an epoxy group will not be specifically limited if it is a compound which has an epoxy group and an alkenyl group in the same molecule, the compound represented by following formula (11), (12) is a silicone modified epoxy resin. It is preferable from the viewpoints of reactivity when prepared, transparency of the cured product, and heat resistance.

In the formulas (11) and (12), R ⁵ represents an alkylene group having 0 to 4 carbon atoms which may contain an ester or ether bond, specifically, a methylene group, an ethylene group, a propylene group, or a butylene group. Isopropylene group, methyl ester group, methyl ether group, methyleneoxymethylene group, methyleneoxyethylene group, ethyleneoxyethylene group, and the like.

  The reaction ratio of the hydrogen siloxane compound represented by the formulas (8) to (10) and the compound having an epoxy group and an alkenyl group in the same molecule is the alkenyl of the compound having an epoxy group and an alkenyl group in the same molecule. It is preferable to react with one group at a ratio of 0.25 to 1.0, particularly 0.5 to 0.8 SiH groups in the hydrogen siloxane compound. The hydrosilylation reaction may be performed according to a conventionally known method.

  The compounds represented by the formulas (1) to (3) can be obtained by, for example, the following formula (13) in addition to the method obtained by the hydrosilylation reaction between the above-described hydrogen siloxane and a compound having an epoxy group and an alkenyl group in the same molecule. ) To (15) can also be obtained by oxidative epoxidation of the polyolefin compound represented by (15).

In formulas (13) to (15), R ¹ , R ² , R ⁵ , m, and n each represent the same meaning as described above. In the formula, a plurality of R ¹ , R ² and R ⁵ may be the same or different.

  Examples of the oxidation method include, but are not limited to, a method of oxidizing with a peracid such as peracetic acid, a method of oxidizing with a hydrogen peroxide solution, and a method of oxidizing with air (oxygen).

  Specific examples of the epoxidation method using peracid include the method described in Japanese Patent Application Laid-Open No. 2006-52187. Examples of peracid raw materials that can be used include organic acids such as formic acid, acetic acid, propionic acid, maleic acid, benzoic acid, m-chlorobenzoic acid, and phthalic acid, and acid anhydrides thereof. Among these, it is preferable to use formic acid, acetic acid, and phthalic anhydride from the viewpoint of the efficiency of reacting with hydrogen peroxide to produce an organic peracid, the reaction temperature, the ease of operation, and the economy. Formic acid or acetic acid is more preferably used from the viewpoint of simplicity of reaction operation.

  Various methods can be applied to the method of epoxidation with hydrogen peroxide solution. Specifically, Japanese Patent Application Laid-Open No. 59-108793, Japanese Patent Application Laid-Open No. 62-234550, Japanese Patent Application Laid-Open No. No. 5-291919, Japanese Patent Application Laid-Open No. 11-349579, Japanese Patent Publication No. 1-33341, Japanese Patent Publication No. 2001-17864, Japanese Patent Publication No. 3-57102, etc. Various methods can be applied.

  In addition, Non-Patent Document 1 (James V. Crivello and Ramesh Narayan, Novel Epoxynorbornane Monomers. 1. Synthesis and Characterization, Macromolecules 1996, 29, pp. 433-438) can also be described. . Specifically, it can be obtained by epoxidizing an alkenyl group using oxone.

  The olefinic compounds represented by the formulas (13) to (15) are subjected to an addition reaction between the hydrogen siloxanes represented by the formulas (8) to (10) and a cyclohexene compound having an alkenyl group (for example, vinylcyclohexene). Can be obtained.

  The epoxy equivalent (measured according to JIS K7236) of the silicone-modified epoxy resin (A) of the present invention is preferably 150 to 800 g / eq, more preferably 200 to 600. If the epoxy equivalent is less than 150, the hardness of the cured product becomes too high, for example, there is a concern that the reliability during moisture reflow is inferior, and if it exceeds 800, the mechanical strength may be inferior.

  Next, the polyvalent carboxylic acid compound (B) of the present invention will be described. The polyvalent carboxylic acid compound (B) of the present invention is a compound represented by the following formula (4).

In formula (4), specific examples of R ³ include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, isopropylene group, isobutylene group, isopentylene group, neopentylene group, isohexylene group, cyclohexyl group. Although a silene group etc. are mentioned, a methylene group, ethylene group, and a propylene group are preferable from a heat resistant transparency viewpoint of the hardened | cured material obtained, and an ethylene group is especially preferable.

In the formula (4), specific examples of the alkyl group having 1 to 6 carbon atoms in R ⁴ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, Examples thereof include an isopentyl group, a neopentyl group, a cyclopentyl group, a hexyl group, an isohexyl group, and a cyclohexyl group, and a methyl group is preferable from the viewpoint of heat resistance and transparency of the resulting cured product.

Among R ⁴ , a methyl group and a carboxyl group are preferable, and a methyl group is preferable from the viewpoint of transparency of the obtained cured product. From the viewpoint of gas barrier properties, high glass transition temperature (Tg), and hardness of the obtained cured product. Is particularly preferably a carboxyl group.

In the formula (4), a plurality of R ³ and R ⁴ may be the same or different.

  The polyvalent carboxylic acid compound (B) represented by the formula (4) is a trishydroxyalkyl compound isocyanurate represented by the following formula (16) and a carboxylic acid anhydride represented by the following formula (17). It can be obtained by addition reaction with a compound.

In the formula (16), R ³ represents the same meaning as described above, and in the formula, a plurality of R ³ may be the same or different.

  Among the compounds represented by the formula (16), compounds represented by the following formulas (18) to (20) are preferable from the viewpoints of transparency of the cured product and gas barrier properties.

In formula (17), R ⁴ represents the same meaning as described above.

  Of the compounds represented by the formula (17), the compounds represented by the following (5) to (7) are particularly preferred.

  The production of the polyvalent carboxylic acid compound (B) can be carried out in a solvent or without a solvent. As the solvent, any solvent that does not react with the trishydroxyalkyl compound of isocyanuric acid represented by the above formula (16) and the carboxylic acid anhydride compound represented by the formula (17) can be used without particular limitation. Examples of solvents that can be used include aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran and acetonitrile, ketones such as methyl ethyl ketone, cyclopentanone and methyl isobutyl ketone, toluene and xylene. An aromatic hydrocarbon etc. are mentioned, Among these, an aromatic hydrocarbon and ketones are preferable.

  These solvents may be used alone or in combination of two or more. When the solvent is used, the amount used is 0.1% relative to a total of 100 parts by mass of the trishydroxyalkyl compound isocyanurate represented by the above formula (16) and the carboxylic acid anhydride compound represented by the formula (17). 5-300 mass parts is preferable.

  Since the polyvalent carboxylic acid compound (B) is often a solid at room temperature (25 ° C.), synthesis in a solvent is preferable from the viewpoint of workability.

  The polyvalent carboxylic acid (B) of the present invention can be produced without a catalyst or with a catalyst. When a catalyst is used, usable catalysts are hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, nitric acid, trifluoroacetic acid, trichloroacetic acid and other acidic compounds, sodium hydroxide, potassium hydroxide, water Metal hydroxides such as calcium oxide and magnesium hydroxide, amine compounds such as triethylamine, tripropylamine and tributylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, Heterocyclic compounds such as imidazole, triazole, tetrazole, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium Roxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, trioctyl Quaternary ammonium salts such as methylammonium acetate, orthotitanic acid such as tetraethyl orthotitanate, tetramethyl orthotitanate, tin octylate, cobalt octylate, zinc octylate, manganese octylate, calcium octylate, sodium octylate, Examples include metal soaps such as potassium octylate.

  When using a catalyst, it can also be used 1 type or in mixture of 2 or more types.

  The amount used in the case of using a catalyst is 0.000 with respect to a total of 100 parts by mass of the trishydroxyalkyl compound isocyanurate represented by the above formula (16) and the carboxylic acid anhydride compound represented by the formula (17). 05-10 mass parts is preferable.

  As a method for adding the catalyst, it is added directly or used in a state dissolved in a soluble solvent or the like. At this time, it is preferable to avoid using an alcoholic solvent such as methanol or ethanol or water because it reacts with an unreacted carboxylic acid anhydride compound represented by the formula (17).

  The reaction temperature during the production of the polyvalent carboxylic acid compound (B) of the present invention is usually 20 to 160 ° C., preferably 50 to 150 ° C., particularly preferably 60 to 145 ° C., although it depends on the amount of catalyst and the solvent used. is there. The total reaction time is usually 1 to 20 hours, preferably 3 to 18 hours. The reaction may be carried out in two or more stages, for example, after reacting at 20 to 100 ° C. for 1 to 8 hours, it may be allowed to react at 100 to 160 ° C. for 1 to 12 hours. In particular, the carboxylic acid anhydride compound represented by the formula (16) is often highly volatile, and when such a compound is used, it is reacted at 20 to 100 ° C. and then reacted at 100 to 160 ° C. By doing so, volatilization can be suppressed. Thereby, not only can the diffusion of harmful substances into the atmosphere be suppressed, but also the polyvalent carboxylic acid compound (B) as designed can be obtained.

  In the case of production using a catalyst, the catalyst can be removed by quenching and / or washing with water as necessary, but it can be left as it is and used as a curing accelerator for the epoxy resin composition. .

  When performing a water washing process, it is preferable to add the solvent which can be isolate | separated from water depending on the kind of solvent currently used. Preferred solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone, esters such as ethyl acetate, butyl acetate, ethyl lactate and isopropyl butanoate, hydrocarbons such as hexane, cyclohexane, toluene and xylene. Can be illustrated.

  When a solvent is used for the reaction or washing with water, it can be removed by vacuum concentration or the like.

  The acid value (measured by the method described in JIS K2501) of the produced polycarboxylic acid compound (B) is preferably 150 to 415 mgKOH / g, more preferably 185 to 375 mgKOH / g, particularly 200 to 320 mgKOH. / G is preferred. If the acid value is 150 mgKOH / g or more, it is preferable because the mechanical properties of the cured product are improved, and if it is 415 mgKOH / g or less, the cured product does not become too hard and the elastic modulus becomes appropriate.

  The functional group (carboxylic acid) equivalent of the polyvalent carboxylic acid (B) is preferably 135 to 312 g / eq, more preferably 150 to 300 g / eq, and particularly preferably 180 to 280 g / eq.

  The epoxy resin composition of the present invention may contain a carboxylic acid anhydride compound (C) in addition to the above-described silicone-modified epoxy resin (A) and the polyvalent carboxylic acid compound (B). This is a preferred embodiment from the viewpoint.

  The carboxylic anhydride compound (C) is not limited as long as it contains a carboxylic anhydride group in the molecule. For example, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydro anhydride Phthalic acid, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, a mixture of 3-methyl-hexahydrophthalic anhydride and 4-methyl-hexahydrophthalic anhydride, tetrahydrophthalic anhydride, nadic anhydride , Methyl nadic acid anhydride, norbornane-2,3-dicarboxylic acid anhydride, methylnorbornane-2,3-dicarboxylic acid anhydride, 2,4-diethylglutaric acid anhydride, and the like. ) To (7) are preferred from the viewpoint of transparency of the cured product.

  Especially, when using an epoxy resin composition in liquid form at room temperature (25 degreeC), it is preferable from the viewpoint that the viscosity adjustment of an epoxy resin composition can be easily used to use the compound represented by the said Formula (6).

  The epoxy resin composition of the present invention is obtained by mixing at least one selected from the silicone-modified epoxy resins (A) represented by the formulas (1) to (3) and a polyvalent carboxylic acid compound (B). Can do.

  The epoxy resin composition of the present invention can be obtained by uniformly mixing the above components at room temperature or under heating. For example, mix thoroughly until uniform using a cartridge case, extruder, kneader, three rolls, universal mixer, planetary mixer, homomixer, homodisper, bead mill, etc., and if necessary, filter with SUS mesh etc. It is prepared by doing.

  When preparing, a carboxylic acid anhydride compound (C), an epoxy resin curing accelerator (D), a phosphorus antioxidant (E), a phenol antioxidant (F), an adhesion assistant, a light stabilizer, etc., which will be described later. May be mixed together.

  When the carboxylic acid anhydride compound (C) is added to the epoxy resin composition of the present invention, it may be added to the composition of the silicone-modified epoxy resin (A) and the polyvalent carboxylic acid compound (B). After the carboxylic acid compound (B) and the carboxylic acid anhydride compound (C) are mixed in advance to obtain a polyvalent carboxylic acid composition, the silicone-modified epoxy resin (A) is added, whereby the epoxy resin composition of the present invention. May be adjusted.

  In this case as well, for example, use a cartridge case, extruder, kneader, three rolls, universal mixer, planetary mixer, homomixer, homodisper, bead mill, etc. It can prepare by performing a filtration process by SUS mesh etc.

  When preparing, you may mix together the epoxy resin hardening accelerator (D) mentioned later, phosphorus antioxidant (E), phenolic antioxidant (F), an adhesion assistant, a light stabilizer, etc.

  When preparing the polyvalent carboxylic acid composition which is a mixture of the polyvalent carboxylic acid compound (B) and the carboxylic acid anhydride compound (C), the formula (17) ) And the carboxylic acid anhydride compound (C) in the polyvalent carboxylic acid composition are the same as those in formula (16) when the polyvalent carboxylic acid compound (B) is produced. When the reaction is performed in an excess of the carboxylic anhydride compound (C) with respect to the represented trishydroxyalkyl compound of isocyanuric acid and the production of the polyvalent carboxylic acid (B) is completed, the polyvalent carboxylic acid compound (B ) And a carboxylic acid anhydride (C).

  As the charging ratio of both in the reaction, 0.001 to 0.7 equivalent of the hydroxyl equivalent of the trishydroxyalkyl compound of isocyanuric acid with respect to 1 equivalent of the acid anhydride group in terms of the functional group equivalent, It is preferable to charge in the range of 0.01 to 0.5 equivalent.

  Adjusting the concentration of the polyvalent carboxylic acid compound (B) in the polyvalent carboxylic acid composition by further mixing the carboxylic acid anhydride (C) with the polyvalent carboxylic acid composition thus obtained. Can do.

  When an excess carboxylic acid anhydride compound (C) is charged and reacted during the production of the polyvalent carboxylic acid compound (B), the excess carboxylic acid anhydride compound (C) is hydrolyzed by water during the washing step. It is better to avoid the water washing process described above.

  In the epoxy resin of the present invention, the polycarboxylic acid (B) and the carboxylic acid anhydride compound (C) are present at a ratio of the carboxylic acid anhydride compound (C) to 100 parts by mass of the polyvalent carboxylic acid (B). 1-1000 mass parts is preferable, More preferably, it is 10-800 mass parts, Most preferably, it is 50-500 mass parts.

  From the viewpoint of obtaining a liquid epoxy resin composition at room temperature (25 ° C.), it is preferable to use a polyvalent carboxylic acid composition that is liquid at room temperature (25 ° C.). In this case, the carboxylic acid anhydride compound is 10 to 1900 parts by mass, preferably 100 to 400 parts by mass with respect to 100 parts by mass of the carboxylic acid compound. Here, it is preferable that the polyvalent carboxylic acid composition is in a liquid form because it can be applied to a field that is required to be used in a liquid form (for example, sealing of a surface-mounted LED).

  In addition to the silicone-modified epoxy resin (A), an epoxy resin can be mixed and used for the epoxy resin composition of the present invention. For example, epoxy resins that are glycidyl etherified products of phenolic compounds, epoxy resins that are glycidyl etherified products of various novolak resins, alicyclic epoxy resins, aliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester epoxy resins, glycidylamine And epoxy resins obtained by glycidylation of halogenated phenols, copolymers of polymerizable unsaturated compounds having an epoxy group and other polymerizable unsaturated compounds.

  When other epoxy resins are mixed and used, the amount used is mixed so that the silicone-modified epoxy resin (A) is 30% by mass or more in the whole epoxy resin, from the viewpoint of heat-resistant transparency of the cured product. Preferably, 50 mass% or more is more preferable.

  In the present invention, the polyvalent carboxylic acid compound (B) or the mixture of the polyvalent carboxylic acid compound (B) and the carboxylic acid anhydride compound (C) functions as a curing agent for the epoxy resin. A curing agent can also be contained. For example, an amine type hardening | curing agent, a phenol type hardening | curing agent, and polyhydric carboxylic acid resin are mentioned.

  The polycarboxylic acid resin is a compound having at least two or more carboxyl groups and having an aliphatic hydrocarbon group or a siloxane skeleton as a main skeleton. In the present invention, the polyvalent carboxylic acid resin is not only a polyvalent carboxylic acid compound having a single structure, but also a mixture of a plurality of compounds having different substituent positions or different substituents, that is, a polyvalent carboxylic acid. A composition is also included, and in the present invention, they are collectively referred to as a polyvalent carboxylic acid resin.

  The polycarboxylic acid resin is particularly preferably a bifunctional to hexafunctional carboxylic acid, which is obtained by reacting a polyhydric alcohol having 5 or more carbon atoms or a polyhydric alcohol having a siloxane structure with an acid anhydride. More preferred are the compounds. Furthermore, the polycarboxylic acid whose said acid anhydride is a saturated aliphatic cyclic acid anhydride is preferable.

  As the 2- to 6-functional polyhydric alcohol, the alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1, 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1.3-propanediol, neopentyl glycol, Diols such as tricyclodecane dimethanol and norbornene diol, triols such as glycerin, trimethylol ethane, trimethylol propane, trimethylol butane, 2-hydroxymethyl-1,4-butanediol, pentaerythritol, ditrimethylol group Tetraols such as bread, hexaol such as dipentaerythritol and the like.

  Particularly preferred alcohols are alcohols having 5 or more carbon atoms, particularly 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 2, Examples include 4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornene diol, among others 2-ethyl-2-butyl-1 , 3-propanediol, neopentyl glycol, 2,4-diethylpentanediol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, norbornenediol, and other alcohols having a branched chain structure or a cyclic structure are more preferable. . From the viewpoint of imparting a high illuminance retention rate, 2,4-diethylpentanediol and tricyclodecane dimethanol are particularly preferable.

  As acid anhydrides added to 2-6 functional polyhydric alcohols, especially methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride Bicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid -3,4-anhydride is preferable, and methylhexahydrophthalic anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride are particularly preferable. Here, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride is preferable for increasing the hardness, and methylhexahydrophthalic anhydride is preferable for increasing the illuminance retention.

  Although there is no particular designation as a condition for the addition reaction, one specific reaction condition is that the acid anhydride and polyhydric alcohol are reacted in a non-catalytic and solvent-free condition at 40 to 150 ° C. and heated to react. After completion, take it out as it is. It is a technique. However, it is not limited to this reaction condition.

  The compounding quantity of the epoxy resin hardening | curing agent in the epoxy resin composition of this invention is a functional group (reactive with an epoxy group with respect to 1 mol in total of the epoxy group in the epoxy resin containing a silicone modified epoxy resin (A)). In the case of an acid anhydride-based curing agent, the amount of acid anhydride group represented by -CO-O-CO- is 0.3 to 1.0 mol, preferably 0.4 to 0.8 mol. Is the amount. If the functional group having reactivity with the epoxy group is 0.3 mol or more, the heat resistance and transparency of the cured product are improved, and if it is 1.0 mol or less, the mechanical properties of the cured product are improved. Therefore, it is preferable. Here, “functional group having reactivity with epoxy group” means an amino group possessed by an amine curing agent, a phenolic hydroxyl group possessed by a phenol curing agent, an acid anhydride group possessed by an acid anhydride curing agent, It is a carboxyl group possessed by a polyvalent carboxylic acid resin.

  When other epoxy resin curing agents are contained, the amount used is mixed in the entire epoxy resin curing agent so that the polyvalent carboxylic acid (B) is 10% by mass or more. From a viewpoint, 15 mass% or more is more preferable.

  The epoxy resin composition of the present invention contains a silicone-modified epoxy resin (A), a polyvalent carboxylic acid compound (B), and an epoxy resin curing accelerator (D).

  From here, the epoxy resin curing accelerator (D) will be described.

  Examples of the epoxy resin curing accelerator (D) include quaternary phosphonium salts such as tetrabutylphosphonium / O, O-diethyl phosphorodithioate and tetraphenylphosphonium tetraphenylborate, and organic materials such as triphenylphosphine and diphenylphosphine. Phosphine curing catalyst, tertiary amine curing catalyst such as 1,8-diazabicyclo (5,4,0) undecene-7, triethanolamine, benzyldimethylamine, 1,8-diazabicyclo (5,4,0) undecene -7 Phenol salt, 1,8-diazabicyclo (5,4,0) undecene-7 octylate, 1,8-diazabicyclo (5,4,0) undecene-7 p-toluenesulfonate, 1,8- Quaternary ammonia such as diazabicyclo (5,4,0) undecene-7 formate Salts, organic carboxylates such as zinc octylate and zinc naphthylate, aluminum chelate compounds such as aluminum bisethyl acetoacetate monoacetylacetonate, aluminum ethyl acetoacetate diisopropylate, 2-methylimidazole, 2-phenyl- Examples include imidazoles such as 4-methylimidazole, thermal cation curing accelerators such as aromatic sulfonium salts, aromatic iodonium salts, and antimony sulfonium salts, and photocation curing accelerators such as antimony sulfonium salts and phosphorus sulfonium salts. It is done.

  The compounding quantity of an epoxy resin hardening accelerator (D) is 0.01-3 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, Preferably it is 0.05-1.5 mass part. . If the amount of the epoxy resin curing accelerator (D) is less than the lower limit, the effect of promoting the reaction between the epoxy resin and the curing agent may not be sufficient. On the contrary, when the compounding quantity of an epoxy resin hardening accelerator is more than the said upper limit, there exists a possibility of causing the discoloration at the time of hardening or a reflow test.

  The epoxy resin composition of the present invention contains a silicone-modified epoxy resin (A), a polyvalent carboxylic acid compound (B), and a phosphorus antioxidant (E).

  The phosphorus-based antioxidant (E) is not particularly limited as long as it contains a phosphorus atom in the structure and has a function of preventing oxidation of the resin and / or cured product. For example, 1, 1, 3 -Tris (2-methyl-4-ditridecyl phosphite-5-tert-butylphenyl) butane, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite, tris (diethylphenyl) phosphite, tris (di -Isopropylphenyl) phosphite, Tris Di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, tris (2,6-di-) tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4 6-di-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4) -Methylphenyl) phosphite, 2,2'-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl- -Methylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'- Biphenylene diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenedi Phosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite Bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)- 4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4, 4′-biphenylene diphosphonite, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trifluorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate , Dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, etc. 9,10-dihydro-9-oxa-10-phosphatonin phenanthrene-10-oxide.

  A commercial item can also be used for the said phosphorus antioxidant (E). The commercially available phosphorus compound is not particularly limited. For example, as HCA, manufactured by ADEKA, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, HCA is a preferred example of ADK STAB 260, ADK STAB 522A, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 135A, and Sanko Co., Ltd.

  The compounding quantity of phosphorus antioxidant (E) is 0.01-3 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, Preferably it is 0.02-1.5 mass part. . When the compounding quantity of phosphorus antioxidant (E) is less than the said lower limit, there exists a possibility that the heat resistant transparency of hardened | cured material may be inferior. On the contrary, if the blending amount of the phosphorus-based antioxidant (E) is more than the upper limit value, it may cause discoloration during curing or reflow test.

  The epoxy resin composition of the present invention contains a silicone-modified epoxy resin (A), a polyvalent carboxylic acid compound (B), and a phenolic antioxidant (F).

  The phenolic antioxidant (F) is not particularly limited as long as it contains a phenolic hydroxyl group in the structure and has a function of preventing oxidation of a resin and / or a cured product. -Tert-butyl-4-methylphenol, n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-tert-butyl -4-hydroxyphenyl) propionate] methane, 2,4-di-tert-butyl-6-methylphenol, 1,6-hexanediol-bis- [3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionate], tris (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-trime 2,4-6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate], 3,9-bis- [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8 , 10-tetraoxaspiro [5,5] undecane, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 2,2′-butylidenebis (4,6 -Di-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl) 6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) ) -4-methylphenol acrylate, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 2-tert-butyl-4-methylphenol, 2,4-di-tert-butylphenol 2,4-di-tert-pentylphenol, 4,4′-thiobis (3-methyl-6-ter -Butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), bis- [3,3-bis- (4'-hydroxy-3'-tert-butylphenyl) -butanoic acid ] -Glycol ester, 2,4-di-tert-butylphenol, 2,4-di-tert-pentylphenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl]- 4,6-di-tert-pentylphenyl acrylate, bis- [3,3-bis- (4′-hydroxy-3′-tert-butylphenyl) -butanoic acid] -glycol ester, and the like.

  A commercial item can also be used for the said phenolic antioxidant (F). There are no particular limitations on the commercially available phenolic compounds. For example, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, IRGANOX 295, IRGANOX 3114, IRGANOX 1098, AGANOX 1520L, Adeka 1520L, and AGANOX 1520L manufactured by Ciba Specialty Chemicals , ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-90, ADK STAB AO-330, Sumitizer GA-80 , Sumilizer MDP-S, Sumili zer BBM-S, Sumilizer GM, Sumilizer GS (F), Sumilizer GP, etc. are mentioned.

  The compounding quantity of a phenolic antioxidant (F) is 0.01-3 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, Preferably it is 0.02-1.5 mass parts. . If the blending amount of the phenolic antioxidant (F) is less than the lower limit, the heat-resistant transparency of the cured product may be inferior. On the other hand, when the blending amount of the phenolic antioxidant (F) is more than the upper limit value, it may cause discoloration during curing or a reflow test.

<Other ingredients>
In addition to the above components, conventional additives such as ultraviolet absorbers, deterioration inhibitors, phosphors, thermoplastic agents, diluents and the like may be used together as necessary.

  The epoxy resin composition of this invention can be manufactured by mix | blending said each component and various additives as needed, and melt | dissolving or melt-mixing. Melt mixing may be a known method. For example, the above components may be charged into a reactor and melt-mixed in a batch manner, or each of the above components may be charged into a kneader such as a kneader or a heat triple roll. And can be continuously melt-mixed. The epoxy resin curing accelerator (D) is heated and dissolved in advance in a polyvalent carboxylic acid composition which is a polyvalent carboxylic acid compound (B) or a mixture of a polyvalent carboxylic acid compound (B) and a carboxylic acid anhydride compound (C). It is preferable to mix and disperse and mix with the silicone-modified epoxy resin (A) component at the final stage of mixing.

Hereinafter, the present invention will be described in more detail with reference to synthesis examples and examples. The present invention is not limited to these synthesis examples and examples. In addition, each physical-property value in a synthesis example and an Example was measured with the following method. Here, a part represents a mass part unless otherwise specified.
○ GPC: GPC (gel permeation chromatography) was measured under the following conditions.
Manufacturer: Waters Column: SHODEX GPC LF-G (guard column), KF-603, KF-602.5, KF-602, KF-601 (2)
Flow rate: 0.4 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)
○ Epoxy equivalent: Measured by the method described in JIS K7236.
○ Functional group equivalent: Measured by the following method.
About 0.15 g of the polyvalent carboxylic acid composition was weighed and dissolved in 40 ml of methanol (special grade reagent), and then stirred at 20 to 28 ° C. for 10 minutes to obtain a measurement sample. The measurement sample was titrated with a 0.1N sodium hydroxide solution using a titrator AT-610 manufactured by Kyoto Electronics Industry Co., Ltd., and the value obtained as the acid value was calculated as the functional group equivalent.

[Synthesis Example 1] Synthesis of organopolysiloxane 1 having SiH group Phenyltrimethoxysilane (1 mol, 198.44 g), acetonitrile 30
g was mixed, and the internal temperature was cooled to 10 ° C. or lower. And 16 g of concentrated sulfuric acid was dropped over 30 minutes,
Thereafter, 81 g of water was added dropwise over 1 hour. Next, 1,1,3,3-tetramethyl-1,3
-Disiloxane (1.5 mol, 201.48 g) was added dropwise over 30 minutes and stirred overnight. After separation of the waste acid, 500 g of toluene was added and washed 3 times with hot water and 2 times with hot pure water. The obtained toluene solution was distilled under reduced pressure to obtain organopolysiloxane 1 having a compound represented by the following formula (8) as a main component. The purity of the obtained organopolysiloxane 1 was 97% (calculated from the peak area of the main component in the molecular weight distribution of GPC).

[Synthesis Example 2] Synthesis of organopolysiloxane 2 having SiH group Diphenyldimethoxysilane (1 mol, 244.36 g) and 10 g of acetonitrile were mixed, and the internal temperature was cooled to 10 ° C or lower. And 19 g of sulfuric acid was added dropwise over 30 minutes, and then 43 g of water was added dropwise over 1 hour. Next, 1,1,3,3-tetramethyl-1,3-disiloxane (3 mole, 402.96 g) was added dropwise over 30 minutes and stirred overnight. After separation of the waste acid, 500 g of toluene was added and washed 3 times with hot water and 2 times with hot pure water. The obtained toluene solution was distilled under reduced pressure to obtain organopolysiloxane 2 containing as a main component a compound represented by the following formula (9). The purity of the obtained organopolysiloxane 2 was 97% (calculated from the peak area of the main component in the molecular weight distribution of GPC).

[Synthesis Example 3] Synthesis of organopolysiloxane 3 having SiH groups Diphenyldimethoxysilane (1.0 mol, 244.36 g) and 7 g of acetonitrile were mixed, and the internal temperature was cooled to 10 ° C or lower. And 14 g of sulfuric acid was added dropwise over 30 minutes, and then 43 g of water was added dropwise over 1 hour. Next, 1,1,3,3-tetramethyl-1,3-disiloxane (0.75 mol, 100.73 g) was added dropwise over 30 minutes and stirred overnight. After separation of the waste acid, 500 g of toluene was added and washed 3 times with hot water and 2 times with hot pure water. The obtained toluene solution was distilled under reduced pressure to obtain organopolysiloxane 3 mainly composed of a compound represented by the following formula (10).

[Synthesis Example 4] Synthesis of silicone-modified epoxy resin (1) In a 2 L separable flask, 0.38 g of 0.5 mass% toluene chloroplatinate solution, 200 g of toluene, 1,2-epoxy-4-vinylcyclohexane (3. 6 mol, 447 g) was added and stirred, and the internal temperature was raised to 80 ° C. Thereafter, the organopolysiloxane 1 (1 mol, 331.76 g) obtained above was added dropwise over 1 hour and reacted at 100 ° C. for 2 hours. The obtained toluene solution was distilled under reduced pressure to obtain a silicone-modified epoxy resin (A-1) mainly comprising the following compound (11). The epoxy equivalent of the silicone-modified epoxy resin (A-1) was 237 g / eq.

[Synthesis Example 5] Synthesis of Silicone Modified Epoxy Resin (2) In a 2 L separable flask, 0.26 g of 0.5 mass% toluene chloroplatinate solution, 200 g of toluene, 1,2-epoxy-4-vinylcyclohexane (2. 4 mol, 298.03 g) was added and stirred, and then the internal temperature was raised to 80 ° C. Thereafter, the organopolysiloxane 2 (1 mol, 332.61 g) obtained above was added dropwise over 1 hour and reacted at 100 ° C. for 2 hours. The obtained toluene solution was distilled under reduced pressure to obtain a silicone-modified epoxy resin (A-2) mainly comprising the following compound (12). The epoxy equivalent of the silicone-modified epoxy resin (A-2) was 296 g / eq.

[Synthesis Example 6] Synthesis of silicone-modified epoxy resin (3) In a 2 L separable flask, 0.78 g of 0.5 mass% chloroplatinic acid toluene solution, 200 g of toluene, 1,2-epoxy-4-vinylcyclohexane (2. 4 mol, 298.03 g) was added and stirred, and then the internal temperature was raised to 80 ° C. Thereafter, the organopolysiloxane 3 (1 mol, 530.91 g) obtained above was added dropwise over 1 hour and reacted at 100 ° C. for 2 hours. The obtained toluene solution was distilled under reduced pressure to obtain a silicone-modified epoxy resin (A-3) mainly comprising the following compound (13). The epoxy equivalent of the silicone-modified epoxy resin (A-3) was 400 g / eq.

[Synthesis Example 7] Synthesis of Silicone Modified Epoxy Resin (4) In a 2 L separable flask, 1.68 g of 0.5 mass% chloroplatinic acid toluene solution, 200 g of toluene, 1,2-epoxy-4-vinylcyclohexane (2. 4 mol, 596.06 g) was added and stirred, and the internal temperature was raised to 80 ° C. Thereafter, 2,4,6,8-tetramethylcyclotetrasiloxane (1 mol, 240.51 g) was added dropwise over 1 hour and reacted at 100 ° C. for 2 hours. The resulting toluene solution was distilled under reduced pressure to obtain a silicone-modified epoxy resin (A-4) mainly composed of the following compound (14). The epoxy equivalent of the silicone-modified epoxy resin (A-4) was 200 g / eq.

[Synthesis Example 8] [Synthesis of mixture of polyvalent carboxylic acid compound and acid anhydride compound (1)]
A glass 500 ml separable flask was charged with 43.9 g of tris (2-hydroxyethyl) isocyanurate and 213.4 g of Ricacid MH-T (4-methylhexahydrophthalic anhydride made by Shikoku Chemicals) while purging with nitrogen. A Dimroth condenser, a stirrer, and a thermometer were installed, and the flask was immersed in an oil bath. The oil bath was heated and the reaction was continued for 2 hours while maintaining the internal temperature at 65 ° C, followed by reaction at 70 ° C for 1 hour, 75 ° C for 1.5 hours, and 80 ° C for 1.5 hours. A peak of 1 area% or less of tris (2-hydroxyethyl) isocyanurate was confirmed by GPC, and 257 g of a polyvalent carboxylic acid composition (C-1) which is a mixture of a polyvalent carboxylic acid and a carboxylic anhydride compound was obtained. It was. The obtained mixture was a colorless and transparent liquid, and the purity by GPC was 58.2 area% of polyvalent carboxylic acid represented by the following formula (15), and 4-methylhexahydro represented by the following formula (16). Phthalic acid was 0.8 area%, and 4-methylhexahydrophthalic anhydride was 40.7 area%. The appearance was a colorless transparent liquid. The functional group equivalent was 188.3 g / eq.

[Synthesis Example 9] [Synthesis of mixture of polyvalent carboxylic acid compound and acid anhydride compound (2)]
A glass 500 ml separable flask was charged with 41.2 g of tricyclodecane dimethanol and 182.5 g of Ricacid MH-T (4-methylhexahydrophthalic anhydride manufactured by Shikoku Kasei Kogyo) while purging with nitrogen, and a Dimroth condenser, A stirrer and a thermometer were installed, and the flask was immersed in an oil bath. The oil bath was heated, and the internal temperature was kept at 40 ° C. for 2 hours, followed by reaction at 50 ° C. for 3 hours and 60 ° C. for 1.5 hours. The peak of 1% by area or less of tricyclodecane dimethanol was confirmed by GPC, and 223 g of a polyvalent carboxylic acid composition (C-3) that was a mixture of a polyvalent carboxylic acid and a carboxylic acid anhydride compound was obtained. The obtained mixture is a colorless and transparent liquid, and the purity by GPC is 59.9 area% for polyvalent carboxylic acid represented by the following formula (17), 0.7 area% for 4-methylhexahydrophthalic acid, 4-methylhexahydrophthalic anhydride was 39.4 area%. The appearance was a colorless transparent liquid. The functional group equivalent was 190 g / eq.

[Synthesis Example 10]
[Synthesis of Mixture of Polycarboxylic Acid Resin and Acid Anhydride Compound Used as Curing Agent (3)]
A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen, while 15 g of tricyclodecane dimethanol, 70 g of methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid MH), 15 g of 1,2,4-tricarboxylic acid-1,2-anhydride (Mitsubishi Gas Chemical Co., Ltd., H-TMAn) was added, reacted at 40 ° C. for 3 hours, and then heated and stirred at 70 ° C. for 1 hour. 1 g or less of tricyclodecane dimethanol was confirmed by GPC, and 100 g of a mixture (C-3) of a polyvalent carboxylic acid resin and a carboxylic acid anhydride compound was obtained. This is a colorless liquid resin obtained, and the purity by GPC is 37 area% of polyvalent carboxylic acid resin represented by the following formula (18), cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride. Was 11 area%, and methylhexahydrophthalic anhydride was 52 area%. The functional group equivalent was 171 g / eq. Met.

-Preparation of composition-
A resin composition was prepared with the formulation (parts by mass) shown in Table 1 below. Each component in these tables is as follows. In the table, a blank column means “0”.
(D) Curing accelerator: quaternary phosphonium salt (manufactured by Sun Apro, U-CAT5003)
(E) Phosphorous antioxidant: Isodecyl diphenyl phosphite (manufactured by ADEKA Corporation, Adeka Stub 135A)
(F) Phenol-based antioxidant: pentaerythritol tetrakis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] (manufactured by ADEKA, Adeka Stub AO-60)

-Characterization of composition and cured product-
The characteristics evaluation of the obtained composition and hardened | cured material was performed with the following method. Curing was performed by heating the composition at 100 ° C. for 1 hour and then at 150 ° C. for 4 hours. The results are shown in Table 1.

(1) Viscosity The viscosity was measured at 23 ° C. with a Toki Sangyo B-type rotational viscometer (product name: TVB-15M).

(2) Flexural strength, flexural modulus 80 mm × 10 mm × 4 mm rod-shaped cured product was prepared and measured according to JIS K7171 using an autograph (product name: AG-IS) manufactured by Shimadzu Corporation.

(3) Heat resistance The light transmittance (T ₀ ) at a wavelength of 450 nm of a 1 mm thick sheet-like cured product was measured with a spectrophotometer U-4100 (manufactured by Hitachi High-Tech). The cured product was measured for light transmittance (T ₁ ) after heating at 150 ° C. for 500 hours in the same manner, and T ₁ / T ₀ (%) was determined.

(4) Water vapor transmission rate The water vapor transmission rate of each cured product having a thickness of 0.5 mm was measured according to JIS K 7129.

(5) Hardness It measured about the rod-shaped hardened | cured material based on JISK6301 (type D).

  As is apparent from the results in Table 1, the compositions of Examples 1 to 3 are excellent in strength, heat resistance, and low gas permeability. On the other hand, although the composition of the comparative example is excellent in low gas permeability, it is inferior in strength and heat resistance.

Claims (6)

An epoxy resin containing at least one selected from silicone-modified epoxy resins (A) represented by the following formulas (1) and (3) and a polyvalent carboxylic acid compound (B) represented by the following formula (4) Composition.

(In the formula (1), R ¹ represents a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, R ² represents an oxygen atom or a phenylene group, X Is 3,4-epoxycyclohexylethyl group or 3-glycidoxypropyl group , m is an average value of 1 to 10, and a plurality of R ¹ and R ² may be the same or different. I do not care.)

(In the formula (3), R ¹ and X each have the same meaning as described above. In the formula, a plurality of R ¹ and X may be the same or different.)

(In Formula (4), R ³ represents an alkylene group having 1 to 6 carbon atoms, and R ⁴ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group. R ³ and R ⁴ may be the same or different.)   Furthermore, the epoxy resin composition of Claim 1 containing a carboxylic anhydride compound (C). The epoxy resin composition according to claim 2 , wherein the carboxylic acid anhydride compound (C) is selected from one or more of the following formulas (5) to (7).

  Furthermore, the epoxy resin composition as described in any one of Claims 1-3 containing an epoxy resin hardening accelerator (D).   Furthermore, the epoxy resin composition as described in any one of Claims 1-4 containing a phosphorus antioxidant (E) and / or a phenolic antioxidant (F).   Hardened | cured material formed by hardening | curing the epoxy resin composition as described in any one of Claims 1-5.