JP4969095B2 - Curable resin composition and method for producing the same - Google Patents

Description

  The present invention relates to a curable resin composition that is cured by light, heat, and the like. Specifically, the present invention relates to a curable resin composition that is excellent in transparency and flexibility, has little coloration due to deterioration, and is suitable as a sealing agent for optical semiconductor elements and the like. . Further, a polyol used in the curable resin composition, a transparent sealing material comprising the curable resin composition, an optical adhesive, a photocurable adhesive, a photocurable sealing material, a photocurable optical waveguide, and the The present invention relates to a cured resin obtained by curing a curable resin composition, a transparent sheet made of the cured resin, a composite material, and an optical semiconductor device. Furthermore, it is related with the manufacturing method of this curable resin composition, and the manufacturing method of this curable resin composition including the refinement | purification process of a coloring cause substance in detail.

  Curable resin compositions that are cured by light or heat are used in various applications such as adhesives, protective layers, and sealants because of their ease of handling. Among them, epoxy resins, oxetane resins, vinyl ether resins, benzoxazines, and the like are utilized as sealing agents for light emitting diodes (LEDs) and protective layers for recording layers of optical discs by taking advantage of their transparency and hardness (for example, Patent Documents 1 and 2). However, while the above resin has high hardness, it has a defect that it is inferior in toughness and easily broken under stress, and it has been a challenge to impart toughness.

JP-A-2005-068234 Japanese Patent Laid-Open No. 6-084203

  As a result of the study, the present inventors have found that by adding a flexible polyol to the above epoxy resin, oxetane resin, etc., toughness is imparted while maintaining transparency and hardness.

  However, at the same time, it was found that the resin composition to which the above polyol was added yellowed after compounding. Conventionally, the polyol itself often has a problem of coloring due to impurities, and the color tone of the polyol is improved by refining or the like (for example, JP-A Nos. 61-143428 and 4-277520). Gazette). However, the yellowing in the mixed system of the present polyol and epoxy resin occurs even when the coloring of the polyol itself is improved, unlike the above-mentioned coloring of the polyol which has been a problem. For this reason, it is estimated that it is a coloring mechanism different from the conventional one, and improvement has been a problem.

  An object of the present invention is to suppress coloring after mixing of a heat or photocurable resin composition comprising an epoxy resin or the like and a polyol, and to provide a curable resin composition suitable as a sealing agent for an optical semiconductor element and the like. Polyol used in the curable resin composition, a transparent sealing material comprising the curable resin composition, an optical adhesive, a photocurable adhesive, a photocurable sealing material, a photocurable optical waveguide, and the curable resin composition It is providing the resin cured | curing material which hardened | cured the thing, the transparent sheet which consists of this resin cured | curing material, a composite material, and an optical semiconductor device. Furthermore, it is providing the manufacturing method of this curable resin composition.

  As a result of intensive studies, the present inventor has found that, by performing a specific purification treatment, the coloring of the curable resin composition composed of the curable resin and the polyol is greatly reduced, and the above object is achieved. The present invention has been completed.

That is, the present invention
A method for producing a curable resin composition comprising an epoxy resin and a polyol B which is liquid at 40 ° C. having a number average molecular weight of 300 or more, and having an APHA of 50 or less,
Polyol B is
An oligomer having an ester skeleton in the molecule, a polyester polyol having two or more terminal hydroxyl groups and a caprolactone copolymer;
An oligomer having an ether skeleton in the molecule, a polyether polyol having two or more terminal hydroxyl groups, and
Other oligomers having a carbonate skeleton in the molecule, having two or more terminal hydroxyl groups and represented by 1,6-hexanediol and HO—R ¹ —OH (wherein R ¹ is the number of carbon atoms) 2 to 14, which may be linear or branched, may contain 1 to 3 cyclic structures, and may contain oxygen atoms in the molecule), and A polycarbonate polyol comprising a carbonate component and having a molar ratio of 1,6-hexanediol to other diol of 10: 1 to 2: 8 and a number average molecular weight of 300 to 3000,
At least one polyol selected from the group consisting of:
Provided is a method for producing a curable resin composition, characterized in that an epoxy resin and polyol B are mixed at a blending ratio (weight ratio) of 50:50 to 95: 5 and then purified by washing with water .
The present invention also provides:
A method for producing a curable resin composition comprising an epoxy resin and a polyol B which is liquid at 40 ° C. having a number average molecular weight of 300 or more, and having an APHA of 50 or less,
Polyol B is
An oligomer having an ester skeleton in the molecule, a polyester polyol having two or more terminal hydroxyl groups and a caprolactone copolymer;
An oligomer having an ether skeleton in the molecule, a polyether polyol having two or more terminal hydroxyl groups, and
Other oligomers having a carbonate skeleton in the molecule, having two or more terminal hydroxyl groups and represented by 1,6-hexanediol and HO—R ¹ —OH (wherein R ¹ is the number of carbon atoms) 2 to 14, which may be linear or branched, may contain 1 to 3 cyclic structures, and may contain oxygen atoms in the molecule), and A polycarbonate polyol comprising a carbonate component and having a molar ratio of 1,6-hexanediol to other diol of 10: 1 to 2: 8 and a number average molecular weight of 300 to 3000,
At least one polyol selected from the group consisting of:
Provided is a method for producing a curable resin composition, characterized in that an epoxy resin and polyol B are mixed at a blending ratio (weight ratio) of 50:50 to 95: 5 and then purified by an adsorbent.

Furthermore, the present invention, the adsorbent is provided activated clay, ion exchange resins, activated carbon, a method of manufacturing the curable resin composition is at least one adsorbent selected zeolite preparative or al.
Moreover, this invention provides the manufacturing method of said curable resin composition whose adsorbent is an inorganic synthetic adsorbent.

Furthermore, this invention provides the method of manufacturing a curable resin composition by the manufacturing method of said curable resin composition, and using this curable resin composition as a transparent sealing agent .

Furthermore, this invention provides the method of manufacturing a curable resin composition by the manufacturing method of said curable resin composition, and using this curable resin composition as an optical adhesive .

Furthermore, this invention provides the method of manufacturing a curable resin composition by said manufacturing method of curable resin composition, and using this curable resin composition as a photocurable adhesive agent .

Furthermore, this invention provides the method of manufacturing a curable resin composition by the manufacturing method of said curable resin composition, and using this curable resin composition as a photocurable sealing material .

Furthermore, the present invention provides a method for producing a curable resin composition by the above-described method for producing a curable resin composition, and producing a photocurable optical waveguide using the curable resin composition .

Furthermore, the present invention provides a method for producing a cured resin, which produces a curable resin composition by the above-described method for producing a curable resin composition, and further cures the curable resin composition into a cured resin product. .

Furthermore, this invention manufactures a curable resin composition by the manufacturing method of said curable resin composition, Furthermore, this curable resin composition is hardened | cured to a resin cured material, and a transparent sheet is obtained. A manufacturing method is provided.

Furthermore, the present invention provides a composite material in which a curable resin composition is produced by the above-described method for producing a curable resin composition, and the curable resin composition is further cured into a resin cured product to obtain a composite material. A manufacturing method is provided.

Furthermore, the present invention provides a resin composition for encapsulating an optical semiconductor by producing a curable resin composition by the above-described method for producing a curable resin composition, and further curing the curable resin composition into a resin cured product. The manufacturing method of the resin composition for optical semiconductor sealing which obtains is provided.

Furthermore, the present invention provides an optical semiconductor element sealed with a cured resin obtained by producing a curable resin composition by the method for producing a curable resin composition and further curing the curable resin composition. An optical semiconductor device manufacturing method is provided.
In this specification, in addition to the above invention,
It comprises at least one resin A selected from an epoxy resin, an oxetane resin, a vinyl ether resin, and a benzoxazine resin, a polyol B that is liquid at 40 ° C. having a number average molecular weight of 300 or more, and an APHA of 50 or less. The characteristic curable resin composition will also be described.
In addition to the above invention, in this specification,
A method for producing a curable resin composition, wherein the polyol B is purified by washing with water and then mixed with the resin A.
A method for producing a curable resin composition, wherein the resin A and the polyol B are mixed and then purified by washing with water,
A method for producing a curable resin composition, wherein the polyol B is purified by an adsorbent and then mixed with the resin A.
A method for producing a curable resin composition, wherein the resin A and the polyol B are mixed and then purified by an adsorbent, and
A liquid polyol having a number average molecular weight of 300 or more, wherein when mixed with at least one resin A selected from an epoxy resin, an oxetane resin, a vinyl ether resin, and a benzoxazine resin, the APHA is 50 or less. The polyol to be used is also described.

  Since the curable resin composition of the present invention uses a specific resin and a polyol and defines the color tone, it is excellent in hardness, transparency and toughness. Therefore, a transparent encapsulant made of the curable resin composition, an optical adhesive, a cured resin obtained by curing the curable resin composition, a transparent sheet made of the cured resin, a composite material, and an optical semiconductor Similarly, the sealing material is excellent in transparency, toughness, and the like. Furthermore, the production method of the present invention can remove substances that cause coloring when a resin such as epoxy and a polyol are mixed, and is effective in preventing coloring of the curable resin composition.

  The curable resin composition of the present invention is a bifunctional or higher functional liquid polyol (polyol) having a terminal hydroxyl group with a resin (referred to as resin A) that is curable by heat or light from the viewpoint of achieving both hardness, transparency and toughness. B)) as an essential component. In addition to the resin A and the polyol B, a curing agent, a curing accelerator, a curing catalyst, or the like is preferably added, although it varies depending on the curing method of the resin composition. Further, within the range not inhibiting the effect of the present invention, antioxidants, lubricants, antifoaming agents, silane coupling agents, flame retardants, acid diffusion control agents, reactive diluents, photosensitizers, dehydrating agents, interfaces. Various additives such as an activator, an antistatic agent, and a plasticizer may be added.

  The resin A of the present invention is a resin that exhibits curability by light, heat, or the like, and greatly affects transparency and strength after being cured. The resin A of the present invention is at least one resin selected from an epoxy resin, an oxetane resin, a vinyl ether resin, and a benzoxazine resin, and may be a mixture of two or more resins.

  When an epoxy resin is used as the resin A of the present invention, the epoxy resin is preferably liquid at normal temperature from the viewpoint of processability and ease of mixing with the polyol B. Here, “liquid” means that the viscosity measured at 25 ° C. is less than 50000 mPa · s. When the epoxy resin is in a solid state, due to poor mixing, shrinkage during curing increases, cracks, wrinkles, and the like occur, and productivity may be reduced.

  The epoxy resin is not particularly limited, but is preferably an alicyclic epoxy resin having a cyclic aliphatic skeleton and one or more, preferably two or more epoxy groups in the molecule. More preferably, it is a case where two epoxy groups are contained in one molecule. As an alicyclic epoxy resin containing two epoxy groups in one molecule, for example, (a) one having two epoxy groups formed containing two carbon atoms constituting a cyclic aliphatic skeleton, b) An epoxy group in which only one of two epoxy groups is formed to include two carbon atoms constituting a cycloaliphatic skeleton, and (c) carbon constituting an cycloaliphatic skeleton. An epoxy resin such as glycidyl ether containing no atoms is used.

Examples of the epoxy resin (a) include compounds having the following structural formula.

  The compound represented by the general formula (I) is produced by oxidizing a corresponding alicyclic olefin compound with an aliphatic percarboxylic acid or the like. Among these, those produced using substantially anhydrous aliphatic percarboxylic acid are preferable in that they have a high epoxidation rate (see, for example, JP-A-2002-275169).

  In the general formula (I), Y represents a linking group, and examples thereof include a single bond, a divalent hydrocarbon group, a carbonyl group, an ester bond, an amide bond, a carbonate bond, and a group in which a plurality of these are linked. It is done. The divalent hydrocarbon group is preferably a linear or branched alkylene group having 1 to 18 carbon atoms or a divalent alicyclic hydrocarbon group (particularly a divalent cycloalkylene group). Illustrated. Furthermore, examples of the linear or branched alkylene group include methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene groups. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, Examples include 1,4-cyclohexylene and cyclohexylidene groups.

Specific examples of the compound described above include the following compounds.

  In addition, said m is an integer of 1-30.

  Examples of the epoxy resin (b) include limonene diepoxide.

  Further, as the epoxy group of (c), cycloalkylene glycol diglycidyl ether having a low viscosity (for example, a viscosity at 25 ° C. of 100 cps or less), a glycidyl type epoxy resin such as liquid bisphenol A type or F type, or hydrogenated. A bisphenol A type epoxy resin, a glycidylamine type epoxy resin, or the like can be used. As said cycloalkylene glycol diglycidyl ether, the compound shown below can be used, for example.

  The epoxy resins (a) to (c) can be used alone or in combination, but preferably contain at least one of (a) or (b). In particular, (c) can also serve as a reactive diluent when used together with (a) or (b). When used as a reactive diluent, the amount of (c) is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, when (a) and / or (b) is 100 parts by weight. is there.

  Examples of the epoxy resin include “Celoxide 2021”, “Celoxide 3000”, “Celoxide 2081” manufactured by Daicel Chemical Industries, Ltd., “ERL-4221”, “UVR-6128”, “UVR-6128” manufactured by Dow Chemical Co., Ltd. “UVR-6105” and the like are commercially available.

  Further, the epoxy resin of the present invention is preferably in a liquid state, but even if it is a solid epoxy resin, the curable resin composition after blending each component has a viscosity at 25 ° C. of 40000 cp or less. It is possible to use it if it exists. Examples of usable solid epoxy resins include solid bisphenol-type epoxy resins, novolac-type epoxy resins, glycidyl esters, triglycidyl isocyanurate, epoxidized cyclohexane polyether, and the like. These may be used alone or in combination of two or more. In addition, for example, epoxidized cyclohexane polyether is available as “EHPE-3150” manufactured by Daicel Chemical Industries, Ltd.

  When the resin A of the present invention is an oxetane resin, the oxetane resin is not particularly limited as long as it is a curable compound having an oxetane ring in the molecule and is curable. For example, 3-ethyl-3- Hydroxymethyl oxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 3-ethyl-3- (phenoxymethyl) oxetane, di [1-ethyl (3-oxetanyl)] methyl Examples include ether, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane, oxetanylsilsesquioxane, and the like. As these compounds, for example, “OXT-101, 121, 211, 221, 212, 610” manufactured by Toagosei Co., Ltd. is commercially available.

  When the resin A of the present invention is a vinyl ether resin, the vinyl ether resin is not particularly limited as long as it is a curable vinyl ether compound. For example, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl Examples include vinyl ether. As these compounds, for example, “TOE-2000H” manufactured by Kyowa Hakko Chemical Co., Ltd. and Maruzen Petrochemical Co., Ltd. “HEVE, HBVE, DEGV” are available.

When the resin A of the present invention is a benzoxazine resin, the benzoxazine resin is not particularly limited as long as it is a curable compound having a benzoxazine skeleton. For example, the following compounds are exemplified. Is done. The benzoxazine resin is, for example, benzoxazine manufactured by Shikoku Kasei Kogyo Co., Ltd., “BXZ-1 (BS-BXZ9), BXZ-2 (BF-BXZ), BXZ-3 (BA—) manufactured by Konishi Chemical Co., Ltd. BXZ) "is commercially available.

  The polyol B of the present invention is a compound having at least a hydroxyl group at a terminal and having two or more hydroxyl groups in one molecule, and preferably the number of hydroxyl groups per molecule is two. Moreover, it is preferable to have two or more terminal hydroxyl groups, and more preferably, both ends are hydroxyl groups. Polyol B mainly plays a role of imparting toughness to the curable resin composition. By introducing the polyol B to the curable resin A, the distance between the cross-linking points is increased after being cured by heat, light or the like, so that toughness can be imparted to the cured product.

  The polyol B of the present invention is a liquid oligomer, and further includes a polyester polyol having an ester skeleton in the molecule, a polyether polyol having an ether skeleton, a polycarbonate polyol having a carbonate skeleton, and the above copolymer. , And the like are particularly preferable. Here, “liquid” means a transparent liquid at 40 ° C. When the polyol is solid, waxy or pasty, the resin A and polyol B are poorly dissolved, the strength of the cured product is lowered, and the cured product is clogged.

  When a polyester polyol is used as the polyol B of the present invention, the polyester polyol is composed of a polyol component and a carboxylic acid component, and can be synthesized by a dehydration esterification reaction, a transesterification reaction, a ring-opening polymerization of a lactone, or a combination thereof. it can.

  Examples of the polyol component of the polyester polyol include ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, and 1,5-pentane. Diol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2,6-hexanediol, 1,4-cyclohexanedimethanol, 1,12-dodecanediol, polybutadienediol, neopentyl glycol, tetra Methylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, 1,3-dihydroxyacetone, hexylene glycol, 1,2,6-hexanetriol, ditrimethylolpropane, pentaerythritol And the like. Moreover, polyether polyol and polycarbonate polyol may be used.

  The carboxylic acid component of the polyester polyol includes oxalic acid, adipic acid, sebacic acid, fumaric acid, malonic acid, succinic acid, glutaric acid, azelaic acid, citric acid, 2,6-naphthalenedicarboxylic acid, phthalic acid, and isophthalic acid. Acid, terephthalic acid, citralaconic acid, 1,10-decanedicarboxylic acid, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride Lactic acid, malic acid, glycolic acid, dimethylolpropionic acid, dimethylolbutanoic acid and the like. Examples of lactones include ε-caprolactone, δ-valerolactone, and γ-butyrolactone.

  The above polyester polyol is, for example, “Placcel series (205U, L205AL, L208AL, L212AL, L220AL, L230AL, 220ED, 220EC, 220EB, 303,305, L312AL, 320, 410, 410D, manufactured by Daicel Chemical Industries, Ltd., P3403, E227, DC2009, DC2016, DC2209) "and" Kurapol "manufactured by Kuraray Co., Ltd. are commercially available.

  When a polyether polyol is used as the polyol B of the present invention, examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and copolymers thereof. These are produced by ring-opening polymerization of cyclic ethers such as ethylene oxide, propylene oxide and tetrahydrofuran.

  As the polyether polyol, “P-400, P-700, P-1000, P-2000, P-3000, G-300, G-400, G-700, G-1500, manufactured by Asahi Denka Kogyo Co., Ltd. G-3000, G-4000, EDP-450, EDP-550, DG-500, DG-575, SP-600, SP-690SC-800, SC-1000, SC-1001, Quadrol ", Nippon Oil & Fat Co., Ltd. Polyethylene glycol “PEG # 200, 400, 600, 1000, 1500, 2000, 4000, 6000”, Bishool “2EN-6, 4EN, 10EN, 2P, 2PN, 3PN” manufactured by Toho Chemical Industry Co., Ltd., Asahi Glass Co., Ltd. ) “Poly-G 420P, 720PG, 1020P, 2020P, 3020P, 630PG, 1030PG” 1530PG, 2530PG, 3030PG, 4030PG, 5030PG, 210PG, 212PG, 448PG, 412PG, 439PG, 216PG, X-213, X-301, X-302, X-303, 400P, 415P, 419P, 423P, 443P, 427P, 441P, 442P, 610PG, 357SA, 465SA, 480SA, 530SA, X-71-531, X-71-532, 375S, 531S, RF-64, RF-66, "PEG200, PEG300" manufactured by Sanyo Chemical Industries , PEG400, PEG600, PEG1000, PEG1500, PEG1540, PEG2000, PEG4000S, PEG4000N, PEG6000S, PEG6000P ”,“ Sanix GP-200, GE-25 ” 0, TP-700, TE-700, EP-400, HE-400, HE-560, HE-600, RA-530, RX-401, RX-300, RX-403, RX-500, HR-460A " , “Sannicks triol GP-250, GP-400, GP-600, GP-1000, TP-400”, “Sannix polyol RP-410A, HR-450P, HS-209”, “Sannicks hexatriol SP- 750 "etc. are commercially available.

  When the polyol B of the present invention is a polycarbonate polyol, as the polycarbonate polyol, the carbonate exchange reaction using a phosgene method or a dialkyl carbonate such as dimethyl carbonate or diethyl carbonate, or diphenyl carbonate (similar to the method for producing a normal polycarbonate polyol) JP-A-62-187725, JP-A-2-175721, JP-A-2-49025, JP-A-3-220233, JP-A-3-252420 and the like.

  Examples of the polyol used in the carbonate exchange reaction together with the dialkyl carbonate include 1,6-hexanediol, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3- Butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, 1,12-dodecanediol, polybutadienediol, neopentyl glycol, tetramethylene glycol, propylene glycol, Dipropylene glycol, dipropylene glycol glycerin, trimethylolpropane, 1,3-dihydroxyacetone, hexylene glycol, 1,2,6-hexanetriol, ditrimethylolpropane, tri Chiroruetan, trimethylol octane, pentaerythritol. Also, ester glycol (manufactured by Mitsubishi Gas Chemical Co., Inc.), polyester polyol, and polyether polyol can be used.

  Examples of the polycarbonate polyol include “Placcel CD205, CD205PL, CD205HL, CD210, CD210PL, CD210HL, CD220, CD220PL, CD220HL, CD220EC, CD221T” manufactured by Daicel Chemical Industries, Ltd. and “UM-” manufactured by Ube Industries, Ltd. CARB90 (1/3), UM-CARB90 (1/1), UC-CARB100 ", etc. are commercially available.

In addition, among the above, the polycarbonate polyol is an oligomer composed of a 1,6-hexanediol component, another diol component represented by the chemical formula HO—R ¹ —OH, and a carbonate component. This is particularly preferable from the viewpoint of the balance between the flexibility and hardness of the object. In the above case, the molar ratio of the 1,6-hexanediol component to other diol components is preferably 10: 1 to 2: 8. In addition, carbon number of said R < ¹ > is 2-14, may be either linear form or branched form, and may contain 1-3 cyclic structures. Further, the molecule may contain oxygen, nitrogen and sulfur atoms.

  The number average molecular weight of the polyol B is 300 or more, preferably 500 to 3000, and more preferably 800 to 2500. In particular, in the case of polycarbonate polyol, the number average molecular weight is preferably 300 to 3000, more preferably 500 to 3000, and still more preferably 1000 to 2500. When the molecular weight is less than 300, the curing reaction is difficult to proceed, and adhesiveness remains even after curing, so that productivity may be reduced, or bending elastic modulus and bending strength may be reduced. On the other hand, when the molecular weight exceeds 3000, the viscosity is high and the handleability may be lowered.

  The polyol B of the present invention is preferably a polyol having an APHA of 50 or less when mixed with any one of the above epoxy resin, oxetane resin, vinyl ether resin, and benzoxazine resin.

  The blending ratio (weight ratio) of the resin A and the polyol B of the present invention is preferably 50:50 to 95: 5, more preferably 55:45 to 90:10, from the viewpoints of transparency, toughness, and heat resistance. More preferably, it is 60: 40-80: 20.

  The curable resin composition of the present invention varies depending on the curing method and the types of the resin A and polyol B used, and is not particularly limited, but from the viewpoint of increasing the curing reaction rate and improving the productivity, the resin A and the polyol It is preferable that a curing agent and a curing accelerator or a curing catalyst be included in addition to B (the two are called main agents).

  When the curable resin composition of this invention contains a hardening | curing agent, although it does not specifically limit as a hardening | curing agent, An acid anhydride is illustrated preferably. The acid anhydride can be selected from those generally used as curing agents for epoxy resins and is not particularly limited, but is preferably liquid at room temperature. As the acid anhydride, for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methylendomethylenetetrahydrophthalic anhydride and the like are preferable. However, within a range that does not adversely affect the fluidity (impregnation property when casting) of the curable resin composition of the present invention, acid anhydrides that are solid at room temperature, for example, phthalic anhydride, tetrahydrophthalic anhydride Hexahydrophthalic anhydride, methylcyclohexene dicarboxylic acid anhydride, and the like can be used. When an acid anhydride that is solid at room temperature is used, it is preferably dissolved in a liquid acid anhydride at room temperature and used as a liquid mixture at room temperature.

  The compounding quantity of a hardening | curing agent is 50-150 weight part with respect to 100 weight part of main agents (resin A and polyol B), Preferably it is 52-145 weight part, More preferably, it is 55-140 weight part. More specifically, an effective amount capable of exerting an effect as a curing agent, that is, a functional group usually involved in the curing reaction in the resin A (for example, an epoxy group if the resin A is an epoxy resin, an oxetanyl group if the resin A is an oxetane resin). Etc.) It is preferable to use the acid anhydride at a ratio of 0.5 to 1.5 times per equivalent.

  When the curable resin composition of the present invention contains a curing accelerator, the curing accelerator can be selected from those generally used, and is not particularly limited, but diazabicycloundecene-based curing acceleration. Agents are preferred. The diazabicycloundecene-based curing accelerator may be used alone or in combination with other curing accelerators such as phosphate esters, phosphines, tertiary or quaternary amines. In the present invention, the curing accelerator is a compound having a function of accelerating the curing reaction between the main agent and the curing agent.

  Preferred examples of the diazabicycloundecene-based curing accelerator include 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) and salts thereof, among which 1,8-diazabicyclo [5. 4.0] Undecen-7 octylate and sulfonate are particularly preferred. Examples of other curing accelerators include tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2- Preferred examples include imidazoles such as ethyl-4-methylimidazole, organic phosphine compounds such as triphenylphosphine, tertiary amine salts, quaternary ammonium salts, phosphonium salts, metal salts such as tin octylate, and the like. In addition, when a diazabicycloundecene-based curing accelerator and other curing accelerators are mixed, the content of the diazabicycloundecene-based curing accelerator is determined from the viewpoint of the color of the resin after curing. It is preferable that it is 50 weight% or more in a mixture, More preferably, it is 70 weight% or more.

  As for the compounding quantity of the hardening accelerator of this invention, 0.05-5 weight part is preferable with respect to 100 weight part of main agents, More preferably, it is 0.1-3 weight part, More preferably, it is 0.25-2. .5 parts by weight. When the blending amount is less than 0.05 parts by weight, the curing accelerating effect may be insufficient, and when it exceeds 5 parts by weight, the hue of the cured product is deteriorated.

  When the curable resin composition of the present invention includes a curing catalyst, the curing catalyst is not particularly limited as long as it is a catalyst that generates protons, radicals, and the like by active energy rays such as heat and light, and a cationic polymerization initiator, Although it may be a radical polymerization initiator or an anionic polymerization initiator, it is preferably a cationic polymerization initiator, particularly a thermal cationic polymerization initiator. Specific examples of the curing catalyst vary depending on the combination of the resin A and the polyol B. For example, onium salts having hydrocarbon groups, allene-ion complexes, silanols or phenols / chelates, sulfonic acid esters, imides Examples thereof include sulfonates. The onium salt having a hydrocarbon group is preferably an aryldiazonium salt, aryliodonium salt, arylsulfonium salt or the like, and “PP-33, CP-66, CP-77” manufactured by Asahi Denka Kogyo Co., Ltd. "FC-509, FC-520", manufactured by 3M Co., Ltd. E. "UVE1014" manufactured by Corporation, "SI-60L, SI-80L, SI-100L, SI-110L" manufactured by Sanshin Chemical Industry Co., Ltd. are commercially available. As the allene-ion complex, “CG-24-61” manufactured by Ciba Geigy Co., Ltd. is available. Furthermore, as the chelate compound, it is possible to use aluminum trisacetylacetonate, aluminum trisacetoacetate ethyl, etc., silanol, and phenols such as triphenylsilanol and bisphenol S.

  As the curing catalyst of the present invention, a photocationic polymerization initiator that causes cationic polymerization by irradiation with ultraviolet rays or electron beams may be used. The cationic photopolymerization initiator is a compound that initiates polymerization by generating cationic species upon irradiation with ultraviolet rays. For example, a hexafluoroantimonate salt or a pentafluorohydroxyantimonate salt represented by the following formulas (II) to (XVI): , Hexafluorophosphate salts, hexafluoroarsenate salts and other cationic polymerization initiators.

(In the above formula, Ar represents an aryl group, for example, a phenyl group, and X ⁻ represents PF ₆ ⁻ , SbF ₆ ⁻ or AsF ₆ ⁻ ).

(In the above formula, R ¹ represents an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, and r represents an integer of 0 to 3. X ⁻ represents PF ₆ ⁻ , SbF ₆ ⁻ or AsF. ₆ ^- represents a).

(In the above formula, Y ⁻ represents PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ or SbF ₅ (OH) ⁻ ).

(In the above formula, X ⁻ represents PF ₆ ⁻ , SbF ₆ ⁻ or AsF ₆ ⁻ .)

(In the above formula, X ⁻ represents PF ₆ ⁻ , SbF ₆ ⁻ or AsF ₆ ⁻ .)

（上記式中、Ｘ^-はＰＦ₆ ^-、ＳｂＦ₆ ^- 又はＡｓＦ₆ ^-を表す。）

(In the above formula, X ⁻ represents PF ₆ ⁻ , SbF ₆ ⁻ or AsF ₆ ⁻ .)

(In the above formula, R ² represents an aralkyl group having 7 to 15 carbon atoms or an alkenyl group having 3 to 9 carbon atoms, R ³ represents a hydrocarbon group or hydroxyphenyl group having 1 to 7 carbon atoms, R ⁴ represents an alkyl group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom,
X ⁻ represents PF ₆ ⁻ , SbF ₆ ⁻ or AsF ₆ ⁻ . )

(In the above formula, R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.)

(In the above formula, R ⁷ and R ⁸ each independently represents an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.)

  A commercial item can also be used as a cationic polymerization initiator. Examples of commercially available products include UVACURE1591 (manufactured by Daicel-Cytec), Irgacure 264 (manufactured by Ciba-Geigy), CIT-1682 (manufactured by Nippon Soda Co., Ltd.), Cyracure UVI-6970, UVI-6974, UVI-6990 (all manufactured by Union Carbide, USA), SI-60L, SI-100L (all manufactured by Sanshin Chemical Industry), Optomer SP-150, SP-170, SP-152, SP-172, R-gen-BF1172 (manufactured by Double Bond Chemical), Irgacure 250 (manufactured by Ciba Specialty Chemical), UV1240, UV1241, UV2257 (manufactured by Doitron) and the like can be mentioned.

  The blending amount of the curing catalyst of the present invention is preferably from 0.01 to 15 parts by weight, more preferably from 0.1 to 15 parts by weight, based on 100 parts by weight of the main agent, from the viewpoints of heat resistance, transparency, weather resistance and the like of the cured resin. 01 to 12 parts by weight, more preferably 0.05 to 10 parts by weight, and most preferably 0.1 to 10 parts by weight.

  Furthermore, a compound having a hydroxyl group having a number average molecular weight of less than 300 may be added to the curable resin composition of the present invention as necessary for the purpose of slowly adjusting the reaction and adjusting the reaction rate. In that case, examples of the compound having a hydroxyl group include ethylene glycol, diethylene glycol, and glycerin.

  The curable resin composition of the present invention has an antioxidant, a lubricant, an antifoaming agent, a silane coupling agent, a flame retardant, an acid diffusion control agent, a reactive dilution, as long as it does not inhibit the curing of the present invention. Various additives such as an agent, a photosensitizer, a dehydrating agent, a surfactant, an antistatic agent, and a plasticizer can be blended. Examples thereof include silicone-based and fluorine-based antifoaming agents, and silane coupling agents such as γ-glycidoxypropyltrimethoxysilane. The amount of the additive is preferably 5% by weight or less based on the resin composition.

  APHA of the curable resin composition of this invention is 50 or less, Preferably, it is 30 or less, More preferably, it is 10 or less. APHA is an index of the degree of coloring, and when APHA exceeds 50, coloring is recognized. For example, in applications where colorless transparency such as a sealing agent for optical semiconductor elements, an optical lens, a panel substrate, etc. is required. Cannot be used.

  The viscosity (25 ° C.) of the curable resin composition of the present invention is preferably 100 to 40000 mPa · s, more preferably 200 to 25000 mPa · s, from the viewpoint of processability.

  The glass transition temperature (Tg) of the cured resin product of the present invention is preferably 100 ° C. or higher, more preferably 120 ° C. or higher. When Tg after curing is less than 100 ° C., for example, when used as a sealant for an optical semiconductor element, deformation may occur when exposed to a high temperature environment.

  The bending elastic modulus (based on JIS K 6911) of the cured resin of the present invention is 1900 to 2850 MPa, more preferably 1950 to 2800 MPa, and still more preferably 2000 to 2800 MPa. Moreover, bending strength is 55-105 MPa, More preferably, it is 60-100 MPa, More preferably, it is 65-95 MPa. When the flexural modulus and flexural strength are less than the above ranges, the cured product is brittle, and when used as a manufacturing process or product, damage such as "cracking" occurs just by applying a small deformation. And handling properties may be reduced, or complaints may be caused. Moreover, when exceeding the said range, it may be difficult to manufacture industrially cheaply.

  The light transmittance of the resin cured product of the present invention with respect to light having a wavelength of 400 nm (manufactured by Shimadzu Corporation, spectrophotometer “UV-2450”, thickness of cured product 3 mm) is preferably 80 T% or more, more preferably 82 T. % Or more, more preferably 83 T% or more. The light transmittance of the cured resin of the present invention with respect to light having a wavelength of 380 nm is preferably 78 T% or more. When the light transmittance is less than the above specified range, the cured product is colored, so that it cannot be used because the quality of the product is inferior, particularly in applications where colorless transparency is required.

  The water absorption of the cured resin of the present invention (according to JIS K 6911: 23 ° C., 24 hours) is preferably 0.65% or less, more preferably 0.6% or less. If the water absorption exceeds 0.7%, the cured product will hydrolyze when the illuminant, phosphor, and optical waveguide are exposed to a high humidity environment, resulting in reduced strength and long-term use. It may not be tolerable.

  The light transmittance for light having a wavelength of 400 nm after heat-treating the cured resin of the present invention at 150 ° C. for 24 hours is preferably 70 T% or more, more preferably 72 T% or more, and further preferably 74 T% or more. When the light transmittance after the heat treatment is out of the above range, coloring may progress when used for a long time, and the product life may be shortened.

  The yellow index (YI) of the cured resin of the present invention is preferably 2.5 or less, more preferably 2.0 or less. When YI exceeds 2.5, it becomes yellowish, so that it may be difficult to use when colorless transparency is required such as when an LED is sealed.

  The curable resin composition of the present invention is preferably used as a transparent sealant, and particularly preferably used as a sealant for optical elements such as LEDs. The transparent encapsulant of the present invention is preferable because it has high transparency and therefore has little absorption of light generated from the element, so that there is no decrease in light amount or color change. Furthermore, shrinkage at the time of curing is small, and damage to elements in the production process can be greatly reduced, and productivity is improved. In addition, even when used for a long time, there is little quality deterioration due to coloring.

  The curable resin composition of the present invention has high transparency and low light loss, can reduce the curing shrinkage and the optical component is less distorted, and has no deterioration or coloring during long-term use. It is also preferably used as an optical adhesive. The optical adhesive is preferably used for, for example, assembly and connection of optical communication devices such as liquid crystal panel components and optical fibers, fixation of various optical components such as optical sensors and optical lenses, and bonding of optical components such as optical lenses and prisms, etc. It is done.

  Furthermore, when the curable resin composition of the present invention is photocurable, it is preferably used for photocurable adhesives, photocurable sealing materials, photocurable optical waveguide applications, and the like.

  The cured resin of the present invention is preferably used as a transparent sheet for protecting optical parts such as liquid crystal panels. Since the transparency is high, there is no deterioration in image quality, and the high hardness is preferable because the scratch resistance of the surface is improved. Furthermore, since it has flexibility, processing is easy.

  Further, the cured resin of the present invention can be easily combined with other materials due to high adhesiveness, small curing shrinkage, and flexibility, and can be used as a composite material. Examples of the composite material include nano-sized inorganic fillers (silica, alumina, clay minerals, etc.), glass powder, glass filler, composite materials with glass fibers, and the like.

  Moreover, since the resin cured product of the present invention has high transparency and high bending strength and low bending elastic modulus as described above, it is excellent in bending resistance and heat resistance. Therefore, the cured product of the curable resin composition of the present invention is an optical sheet (transparent) such as a liquid crystal display substrate including an active matrix type, an organic EL display element substrate, a color filter substrate, a touch panel substrate, and a solar cell substrate. Sheet or transparent plate), optical lenses, optical waveguides, optical elements, LED sealing materials, optical semiconductor sealing resin compositions, and the like.

  The optical semiconductor device of the present invention is formed by sealing an optical semiconductor element with a cured resin of the curable epoxy resin composition of the present invention used for optical semiconductor sealing.

[Method for producing curable resin composition]
Although the example of the manufacturing method of the curable resin composition of this invention is shown below, a manufacturing method is not limited to the method quoted here.

  Resin A, polyol B and, if necessary, a predetermined amount of a curing agent, a curing accelerator, a curing catalyst, and other additives, and a uniaxial or multiaxial extruder or kneader equipped with a decompression device, Using a general-purpose device such as a dissolver, a curable resin composition is prepared by stirring and mixing while excluding bubbles under vacuum heating. At this time, the temperature of stirring and mixing is preferably set to 10 to 60 ° C. When the temperature is less than 10 ° C., the viscosity of the mixture becomes high and uniform mixing becomes difficult, and the transparency of the resin composition and its cured product is lowered, or the temperature is locally increased by shearing heat generation. As a result, deterioration or coloring due to heat may occur. Further, when the temperature exceeds 60 ° C., a curing reaction may occur or coloring due to thermal deterioration may occur. The residence time in the stirring / mixing step is preferably 15 to 180 minutes. If the residence time is less than 15 minutes, the mixture is not sufficiently mixed, resulting in a non-uniform resin composition, and transparency may be lowered. In addition, when the residence time exceeds 180 minutes, a long thermal history may be received, resulting in thermal degradation and coloring.

  In order to achieve transparency and APHA of the curable resin composition of the present invention, purification is preferably performed in the production process. In addition, although the order of a refinement | purification process and the said mixing process is not specifically limited, (1) It mixes, after refine | purifying polyol B or (2) The refinement | purification process of a mixture is performed after mixing resin A and polyol B It is preferable to include at least one of these steps. When mixing after purification of both resin A and polyol B, the treatments (1) and (2) may be performed together. For example, the purification step of polyol B may be repeated a plurality of times. For example, when only the resin A is purified and the curable resin composition is produced by mixing without purifying the polyol B, the APHA of the present invention may not be controlled. This is presumably because the interaction between the substance contained in polyol B and resin A is one of the factors of coloring.

  As the above purification method, a known purification method can be used, and it is not particularly limited, but a purification method using water washing and a purification method using an adsorbent are particularly preferably exemplified. As the adsorbent, an existing adsorbent can be used, and is not particularly limited. However, activated clay, ion exchange resin, activated carbon, zeolite, and organic / inorganic synthetic adsorbent are preferable.

  Examples of the activated clay used as the adsorbent of the present invention include “activated clay SA35, SA1, T, R-15, E”, “Nikkanite G-36, G-153, G” manufactured by Toshin Kasei Co., Ltd. -168 "and" Galleon Earth "manufactured by Mizusawa Chemical Industry Co., Ltd. are commercially available.

  As the ion exchange resin used as the adsorbent of the present invention, “Diaion PK220, PK228, PK228L, PA316, SA20, SA12A, WA20, WA21, WA30, WK40, CR11, CR20, CRB02” manufactured by Mitsubishi Chemical Corporation, “Hokuetsu PF, HS, KS” manufactured by Ajinomoto Fine Techno Co., Ltd. “Amberlite IR120B, IR124Na, 200CT, IRA67, IRA402, IRA402BL Cl, IRA400J, IRA400J Cl, IRA410J Cl, IRA96J, IRA96SB, manufactured by Rohm and Haas Co., Ltd. , IRC50, IRC76, Amberlyst 15JWET ”and“ Dowex 66, HCR-S, HCR-W2, MAC-3, Marathon ”manufactured by Dow Chemical Co., Ltd. , Such as the WBA "is available as a commercial product.

  As the activated carbon used as the adsorbent of the present invention, “CL-H, Y-10S, Y-10SF” manufactured by Ajinomoto Fine Techno Co., Ltd., “S, FC, K, A, AP, manufactured by Phutamura Chemical Co., Ltd., RC, P, CG48A, CW130B, GC830A, SG, SGA "," Sunprif M-YC, M-AC, M-YC-P "manufactured by Suntex Co., Ltd. Brocol A, Brocol B, Brocol C "and the like are commercially available.

  As the zeolite used as the adsorbent of the present invention, “Molecular sieve 3A, 4A, 5A, 13X” manufactured by Union Showa Co., Ltd. is commercially available.

  Examples of the synthetic adsorbent used as the adsorbent of the present invention include organic and inorganic substances such as activated silicic acid, activated alumina, magnesium oxide, chitosan, styrene resin, acrylic resin, and “Sylphonite” manufactured by Mizusawa Chemical Industry Co., Ltd. "Kyoward 100, 200, 300, 400, 500, 600, 700, 1000, 2000" manufactured by Kyowa Chemical Co., Ltd., "Amberlite XAD2, XAD4, XAD7HP, XAD16HP" manufactured by Rohm and Haas Co., Ltd. Etc. are available as commercial products.

  An example of the purification method using the above-described water washing and adsorbent is shown below, but the purification method is not limited to the methods listed here. Moreover, although it shows about the case where the polyol B is refine | purified, the mixture after mixing the resin A and the resin A, the polyol B, etc. can be refine | purified similarly.

[Purification by washing with water]
Polyol B alone or polyol B dissolved in an organic solvent is mixed and stirred with a predetermined amount of water to extract impurities having a high affinity for water into the aqueous phase. The purification may be performed by any of a batch method in which treatment is performed in a tank equipped with a stirrer and a circulation pump, and a continuous method using a static mixer. The amount of water used for purification is not particularly limited, but is preferably 10 to 300 parts by weight with respect to 100 parts by weight of polyol B. The purification temperature is preferably 10 to 80 ° C. and the time is preferably 10 to 180 minutes. When an organic solvent is used, examples of the organic solvent include hydrocarbon solvents such as hexane and heptane, ester solvents such as butyl acetate and ethyl acetate, aromatic solvents such as toluene, xylene and benzene, and liquids such as octanol. A long-chain alcohol or the like can be used, and the amount of the organic solvent used is preferably 20 to 300 parts by weight with respect to 100 parts by weight of polyol B. In addition, when refine | purifying after melt | dissolving polyol B in a solvent above, since a liquid separation becomes favorable and operation time can be shortened, it is preferable.

  Thereafter, water and polyol B (simple substance or solution) are separated again (liquid separation step). For the liquid separation, a device that increases the separation efficiency of water and solvent, such as a coalescer (manufactured by Nippon Pole Co., Ltd.), may be used. Further, when a solvent is used, the solvent is removed in a heated or non-heated state.

[Purification with adsorbent]
Impurities are adsorbed by bringing polyol B alone or polyol B dissolved in an organic solvent into contact with a predetermined amount of adsorbent. The above purification is performed by any of a column method in which polyol B (single or solution) is passed through a column filled with an adsorbent and a batch method in which processing is performed in a tank equipped with a stirrer and a circulation pump. May be. In the case of the batch method, the adsorbent is removed using an appropriate filter medium. Further, when a solvent is used, the solvent is removed in a heated or non-heated state. In addition, as an organic solvent, it is possible to use the solvent similar to the case of the said water washing.

  The amount of the adsorbent used for the purification is not particularly limited, but is preferably 10 to 300 parts by weight with respect to 100 parts by weight of polyol B. From the viewpoint of suppressing work efficiency and denaturation of the resin, the purification temperature is preferably 10 to 80 ° C. and the time is preferably 10 to 300 minutes. Among the above conditions, when an organic solvent is used, the viscosity is low, so that the process can be performed at a relatively low temperature. However, when an organic solvent is not used, the viscosity of polyol B is set as a relatively high processing temperature. It is preferable to reduce it from the viewpoint of work efficiency. Moreover, when refine | purifying after mixing of resin A and polyol B, you may heat a mixture previously from a viewpoint of work efficiency. In that case, the heating time is preferably within 36 hours from the viewpoint of preventing the mixture from denaturing.

  The cured product of the curable resin composition of the present invention is produced by forming a curable resin composition into a predetermined shape and then performing a curing treatment. As a molding method, various methods can be used depending on the application. For example, a method of injecting into a mold, a method of extruding into a sheet, a spin coating method, a spray method, a roll coating method, an ink jet method. For example, a method of coating on a substrate is used.

  As a curing method, a known method can be used, and a curing method by heating or a curing method by irradiation with active energy rays such as light can be used. For example, in the case of thermosetting, the treatment temperature is preferably 100 to 200 ° C, more preferably 100 to 190 ° C, and still more preferably 100 to 180 ° C. The treatment time is preferably 30 to 600 minutes, more preferably 45 to 540 minutes, and still more preferably 60 to 480 minutes. If the treatment temperature and treatment time are less than the above ranges, curing may be insufficient, and if the treatment temperature and treatment time exceed the above ranges, decomposition of the resin may occur. Even within the above range, the treatment time may be relatively short when the treatment temperature is high, and the treatment time is preferably relatively long when the treatment temperature is low.

In the case of curing with active energy rays, visible light, infrared rays, ultraviolet rays, X rays, α rays, β rays, γ rays, electron rays, and the like can be used as the active energy rays to be irradiated. Among these, ultraviolet rays having a wavelength of 200 to 400 nm are preferably used from the viewpoint of industrial properties such as safety and reaction efficiency. Preferable irradiation conditions include, for example, irradiation with an illuminance of 1 to 1000 mW / cm ² and an irradiation amount of 0.01 to 5000 mJ / cm ² . As an active energy ray irradiation device, for example, a lamp light source such as a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, or an excimer lamp, a pulse such as an argon ion laser or a helium neon laser, or a continuous laser light source can be used. It is. In the above case, a photomask can be used in combination.

[Methods for measuring physical properties and methods for evaluating effects]
Below, the measuring method used by this application and the evaluation method of an effect are illustrated.

(1) APHA
The hue (APHA) of the resin composition (mixture of resin A and polyol B) in Examples and Comparative Examples was measured in accordance with ASTM D 1209 and compared with an APHA standard colorimetric tube.

(2) Glass transition temperature (Tg)
The thermosetting resin composition was thermally cured under conditions of 110 ° C. for 2 hours and 180 ° C. for 2 hours (Examples 7 and 8 and Comparative Example 2 were conditions of 100 ° C. for 2 hours and 150 ° C. for 3 hours). A test piece of a cured product of the thermosetting resin composition was obtained. Measurement was performed under the following conditions to determine the glass transition temperature (Tg).
Test piece: length 10 mm x width 5 mm x thickness 5 mm
Measuring apparatus: Thermomechanical measuring apparatus (TMA) "TMA / SS6000" manufactured by Seiko Instruments Inc.
Measurement mode: Compression (needle penetration), constant load measurement heating rate: 5 ° C / min

(3) Bending elastic modulus and bending strength In the same manner as in (2), a cured product of a thermosetting resin composition was prepared, and the bending elastic modulus and bending strength were measured according to JIS K 6911 under the following conditions. .
Atmosphere: 23 ° C, 50% RH
Measuring device: Orientec Tensilon "(RTC-1350A)"
Test piece: length 80 mm x width 10 mm x thickness 5 mm
Test speed: 1mm / min

(4) Light transmittance (Examples 1-19, Comparative Examples 1-6)
In the same manner as (2), a cured product of the thermosetting resin composition was produced and used as a test piece. Each light transmittance (T%) with respect to incident light with a wavelength of 380 nm and 400 nm was measured under the following conditions.
Test piece: Thickness 3mm
Apparatus: Shimadzu Corporation spectrophotometer "UV-2450"
Wavelength: 380nm, 400nm

(5) Water absorption rate In the same manner as in (2), a cured product of a thermosetting resin composition was prepared and used as a test piece (diameter 5 cm × thickness 3 mm). In accordance with JIS K 6991, the sample was left in water at 23 ° C. for 24 hours, and the water absorption was measured from the weight difference before and after the test.

(6) Heat resistant color stability (Examples 1-19, Comparative Examples 1-6)
In (4), the test piece whose light transmittance was measured was left in an oven at 150 ° C. for 24 hours to obtain a test piece. In the same manner as (4), the light transmittance of the test piece at a wavelength of 400 nm was measured.

(7) Viscosity The viscosity was measured at 25 ° C. using an E-type viscometer.

(8) Number average molecular weight HLC-8220GPC (manufactured by Tosoh Corporation) was used to determine the number average molecular weight by comparison with polystyrene standards.

(9) Yellow index (YI)
In the same manner as (2), a cured product of the thermosetting resin composition was produced and used as a test piece having a thickness of 3 mm. Using a color difference meter “Σ90” manufactured by Nippon Denshoku Industries Co., Ltd., YI value was measured according to JIS K 7103.

(10) Adhesive strength As test pieces, an aluminum plate (width 15 mm, thickness 0.5 mm) and a polyethylene terephthalate film (width 15 mm, thickness 200 μm) were used. The test piece and the test piece are overlapped length 5 mm (length 5 mm x width 15 mm), and the curable resin composition is applied to the overlapped portion, bonded and fixed while removing bubbles, and irradiated with a high-pressure mercury lamp. Irradiation was performed so that the amount was 900 mJ.
Thereafter, the adhesive strength (kg / 15 mm) was measured using a tensile tester. The test was conducted for two combinations of a polyethylene terephthalate film and a polyethylene terephthalate film, and an aluminum plate and a polyethylene terephthalate film. The obtained adhesive strengths were determined as “adhesive strength (PET / PET)” and “adhesive strength (Al Plate / PET) ”.

(11) Light transmittance (Examples 20 to 23, Comparative Example 7)
A curable resin composition was poured into a mold formed so as to have a film thickness of 0.5 mm, and irradiated with a high-pressure mercury lamp so that the irradiation amount was 1800 mJ. The light transmittance (wavelength 400 nm) of the obtained cured product was measured using a spectrophotometer (Spectrophotometer “UV-2450” manufactured by Shimadzu Corporation).

(12) Heat resistance degradation (Examples 20 to 23, Comparative Example 7)
The cured product, whose light transmittance was measured in (11), was put in a thermostat at 120 ° C. and subjected to a thermal degradation test for 168 hours. After the test, the light transmittance (400 nm) was measured in the same manner as (11). did. The light transmittance after the test with the light transmittance before the heat degradation test as 100% was determined and defined as heat resistance degradation (%).

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited by these Examples. In addition, Examples 1-4, 6-12, 14, 18, 20, and 22 are described as reference examples.

Example 1
Polycaprolactone diol (manufactured by Daicel Chemical Industries, Ltd., trade name “Placcel L212AL”, number average molecular weight: 1250, liquid) (B1) 100 parts by weight and toluene 100 parts by weight in a jacketed flask equipped with a stirrer The mixture was stirred and mixed at 40 ° C. for 30 minutes to completely dissolve both. Next, 100 parts by weight of ion-exchanged water was added to the flask, and the mixture was stirred and mixed at 60 ° C. for 90 minutes (the liquid was cloudy). After stirring, the mixture was allowed to stand for 60 minutes and separated. After removing the separated lower layer (aqueous layer), the upper layer was desolvated using an evaporator at 80 ° C. and 10 torr (about 1330 Pa) to obtain a polyol (B1 ′).
As the resin A, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (manufactured by Daicel Chemical Industries, Ltd., trade name “Celoxide 2021P”, alicyclic epoxy resin, liquid (25 ° C.), 75 parts by weight of epoxy equivalent 134) (A1) and 25 parts by weight of B1 ′ as polyol B were mixed. The resin composition obtained by mixing the epoxy A1 and the polyol B1 ′ had an APHA of 30, and satisfied the APHA defined in the present invention.
Next, 96.2 parts by weight of methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., trade name “Rikacid MH-700” (C1) as a curing agent, and benzyldimethylamine (Japanese A curable resin composition was obtained by mixing and stirring for 20 minutes at room temperature using 0.93 parts by weight of Kodoku Pharmaceutical Co., Ltd. (D1) and “Bubble Nertaro” manufactured by Shinky Corporation.
Subsequently, a cured product of the resin composition was produced. After the obtained curable resin composition is poured into a mold having a predetermined size, the cured product is subjected to a thermosetting treatment at 110 ° C. for 2 hours and then at 180 ° C. for 2 hours using a curing oven. A cured product of the curable resin composition was obtained.
The obtained cured product has a glass transition temperature: 169 ° C., light transmittance (400 nm): 87.5 T%, light transmittance (heat-resistant coloring stability test: after 24 hours heat treatment): 75.6 T%, light transmittance (380 nm): 82.3 T%, flexural modulus: 2701 MPa, flexural strength: 70.5 MPa, water absorption: 0.37%, excellent heat resistance, transparency, toughness, etc. Even when subjected to the heat history of time, it was an excellent cured product with little coloring.

Example 2
Example 1 except that polycaprolactone triol (trade name “Placcel 308”, number average molecular weight: 850, liquid) (B2) (B2) manufactured by Daicel Chemical Industries, Ltd. (B2) is used as the polyol, and toluene is changed to ethyl acetate. Similarly, a polyol (B2 ′) was obtained.
70 parts by weight of A1 as resin A, 30 parts by weight of B2 ′ as polyol B, 87.6 parts by weight of C1 as a curing agent, a special amine-based curing accelerator (trade name, manufactured by San Apro Co., Ltd.) “U-CAT 18X”) (D2) A curable resin composition was obtained in the same manner as in Example 1 using 0.66 parts by weight.
The resin composition (mixture of A1 and B2 ′) had an APHA of 35 and satisfied the APHA defined in the present invention.
Subsequently, a cured product of the curable resin composition was obtained in the same manner as in Example 1. The obtained cured product has a glass transition temperature: 153 ° C., light transmittance (400 nm): 88.2 T%, light transmittance (heat-resistant coloring stability test: after 24 hours heat treatment): 76.3 T%, light transmittance (380 nm): 81.7 T%, flexural modulus: 2320 MPa, flexural strength: 76.3 MPa, water absorption: 0.40%, excellent heat resistance, transparency, toughness, etc. Even when subjected to the heat history of time, it was an excellent cured product with little coloring.

Example 3
The polyol (B3 ′) was the same as in Example 1 except that polycaprolactone diol (manufactured by Daicel Chemical Industries, Ltd., trade name “Placcel 205H”, number average molecular weight: 530, liquid) (B3) was used as the polyol. )
As in Example 1, 60 parts by weight of A1 as resin A, 40 parts by weight of B3 ′ as polyol B, 78.2 parts by weight of C1 as a curing agent, and 0.75 parts by weight of D1 as a curing accelerator were used. Thus, a curable resin composition was obtained.
The resin composition (mixture of A1 and B3 ′) had an APHA of 40 and satisfied the APHA defined in the present invention.
Subsequently, a cured product of the curable resin composition was obtained in the same manner as in Example 1. The obtained cured product has a glass transition temperature: 177 ° C., light transmittance (400 nm): 88.4 T%, light transmittance (heat-resistant coloring stability test: after 24 hours heat treatment): 76.2 T%, light transmittance (380 nm): 82.2 T%, flexural modulus: 2640 MPa, flexural strength: 71.7 MPa, water absorption: 0.33%, and has excellent heat resistance, transparency, toughness, etc. Even when subjected to the heat history of time, it was an excellent cured product with little coloring.

Example 4
The polyol is the same as in Example 1 except that the polyfunctional polycaprolactone polyol (trade name “Placcel 410D”, number average molecular weight: 1000, liquid) (B4) manufactured by Daicel Chemical Industries, Ltd. is used as the polyol. (B4 ′) was obtained.
As in Example 1, 75 parts by weight of A1 as resin A, 25 parts by weight of B4 ′ as polyol B, 91.6 parts by weight of C1 as a curing agent, and 0.69 parts by weight of D2 as a curing accelerator were used. Thus, a curable resin composition was obtained.
The resin composition (mixture of A1 and B4 ′) had an APHA of 35 and satisfied the APHA defined in the present invention.
Subsequently, a cured product of the curable resin composition was obtained in the same manner as in Example 1. The obtained cured product has a glass transition temperature: 162 ° C., light transmittance (400 nm): 87.6 T%, light transmittance (heat-resistant coloring stability test: after 24 hours heat treatment): 75.4 T%, light transmittance (380 nm): 81.7 T%, flexural modulus: 2550 MPa, flexural strength: 68.6 MPa, water absorption: 0.46%, excellent heat resistance, transparency, toughness, etc. Even when subjected to the heat history of time, it was an excellent cured product with little coloring.

Example 5
70 parts by weight of A1 as resin A, 30 parts by weight of B3 as polyol B, and 100 parts by weight of toluene were stirred and mixed at 40 ° C. for 30 minutes in a jacketed flask equipped with a stirrer. I let you. Next, 100 parts by weight of ion-exchanged water was added to the flask, and the mixture was stirred and mixed at 60 ° C. for 90 minutes (the liquid was cloudy). After stirring, the mixture was allowed to stand for 60 minutes and separated. The separated lower layer (aqueous layer) was removed, and the upper layer was desolvated using an evaporator at 80 ° C. and 10 torr to obtain a resin composition. The obtained resin composition (purified product of a mixture of A1 and B3) had an APHA of 50 and satisfied the APHA defined in the present invention.
This resin composition was blended with 77.4 parts by weight of C1 as a curing agent and 0.59 parts by weight of D2 as a curing accelerator to obtain a curable resin composition.
Subsequently, a cured product of the curable resin composition was obtained in the same manner as in Example 1. The obtained cured product has a glass transition temperature of 179 ° C., light transmittance (400 nm): 87.1 T%, light transmittance (heat-resistant coloring stability test: after 24 hours heat treatment): 76.0 T%, light transmittance (380 nm): 80.4 T%, flexural modulus: 2680 MPa, flexural strength: 70.4 MPa, water absorption: 0.38%, excellent heat resistance, transparency, toughness, etc. Even when subjected to the heat history of time, it was an excellent cured product with little coloring.

Example 6
100 parts by weight of polyol B2 and 30 parts by weight of ethyl acetate were stirred and mixed at 40 ° C. for 60 minutes in a jacketed flask equipped with a stirrer to completely dissolve both. Next, 3 parts by weight of ion exchange resin (manufactured by Mitsubishi Chemical Corporation, trade name “Diaion WA20”) was added to the flask, and the mixture was stirred and mixed at 80 ° C. for 120 minutes (the liquid was suspended). After that, it was filtered using a pressure filter and filter paper (trade name “5C”, manufactured by Advantech Co., Ltd.) to remove the ion exchange resin, using an evaporator at 80 ° C. and 10 torr (about 1330 Pa). Thereafter, the solvent was removed to obtain a polyol (B2 ″).
80 parts by weight of A1, 20 parts by weight of B2 ″, 89.1 parts by weight of C1, and 0.60 parts by weight of D2 were blended in the same manner as in Example 1 to obtain a curable resin composition. Moreover, it carried out similarly to Example 1, and obtained the hardened | cured material of the said curable resin composition.
The resin composition (mixture of A1 and B2 ″) had an APHA of 25 and satisfied the APHA defined in the present invention. The obtained cured product has a glass transition temperature: 159 ° C., light transmittance (400 nm): 88.9 T%, light transmittance (heat-resistant coloring stability test: after 24 hours heat treatment): 76.5 T%, light Transmittance (380 nm): 81.9 T%, flexural modulus: 2490 MPa, bending strength: 69.2 MPa, water absorption: 0.30%, excellent heat resistance, transparency, toughness, etc. Even when subjected to a long thermal history, it was an excellent cured product with little coloring.

Example 7
As polyol, polyether polyol (Asahi Denka Kogyo Co., Ltd., trade name "ADEKA Polyether P-1000"; propylene glycol added with propylene oxide (PO)) (B5) (100 parts by weight) and toluene 80 The parts by weight were stirred and mixed at 40 ° C. for 30 minutes in a jacketed flask equipped with a stirrer, so that both were completely compatible. Next, 5 parts by weight of an ion exchange resin (manufactured by Rohm and Haas Co., Ltd., trade name “Amberlite XAD7HP”) was added to the flask, and stirred and mixed at 60 ° C. for 90 minutes (the liquid was suspended). After stirring, the mixture was filtered using a pressure filter and filter paper (trade name “5C”, manufactured by Advantech Co., Ltd.) to remove the ion exchange resin, and removed using an evaporator at 80 ° C. and 10 torr. Solvent was used to obtain polyol (B5 ′).
70 parts by weight of A1, 30 parts by weight of B5 ′, 77.1 parts by weight of methyl hymic acid anhydride (manufactured by Hitachi Chemical Co., Ltd., trade name “HN5500E”) (C2) as a curing agent, curing accelerator As in Example 1, a curable resin composition was obtained using 0.58 parts by weight of tetrabutylammonium bromide (manufactured by Wako Pure Chemical Industries, Ltd.) (D3). Further, a cured product of the curable resin composition was obtained in the same manner as in Example 1 except that the curing conditions were changed to 100 ° C. for 1 hour and subsequently 160 ° C. for 3 hours.
The resin composition (mixture of A1 and B5 ′) had an APHA of 30, and satisfied the APHA defined in the present invention. The obtained cured product has a glass transition temperature: 159 ° C., light transmittance (400 nm): 86.7 T%, light transmittance (heat-resistant coloring stability test: after 24 hours heat treatment): 75.1 T%, light Transmittance (380 nm): 80.1 T%, flexural modulus: 2670 MPa, flexural strength: 71.8 MPa, water absorption: 0.34%, excellent heat resistance, transparency, toughness, etc. Even when subjected to a long thermal history, it was an excellent cured product with little coloring.

Example 8
As the polyol, polycarbonate diol (manufactured by Daicel Chemical Industries, Ltd., trade name “Placcel CD-210HL”, number average molecular weight: 1000, liquid) (B6) was purified by washing in the same manner as in Example 1, and the polyol (B6 ') Got.
Implemented using 80 parts by weight of A1, 20 parts by weight of B6 ′, and 0.7 parts by weight of a sulfonium salt cationic curing catalyst (trade name “SI-100L” manufactured by Sanshin Chemical Industry Co., Ltd.) In the same manner as in Example 1, a curable resin composition was obtained. Moreover, it carried out similarly to Example 7, and obtained the hardened | cured material of the said curable resin composition.
The resin composition (mixture of A1 and B6 ′) had an APHA of 40 and satisfied the APHA defined in the present invention. The obtained cured product has a glass transition temperature: 152 ° C., light transmittance (400 nm): 83.1 T%, light transmittance (heat-resistant coloring stability test: after 24 hours heat treatment): 74.0 T%, light Transmittance (380 nm): 78.5 T%, flexural modulus: 2640 MPa, flexural strength: 83.2 MPa, water absorption: 0.48%, excellent heat resistance, transparency, toughness, etc. Even when subjected to a long thermal history, it was an excellent cured product with little coloring.

Example 9
Polycarbonate diol (manufactured by Daicel Chemical Industries, Ltd., trade name “Placcel CD-220HL”, number average molecular weight: 2000, liquid) (B7) 100 parts by weight as a polyol, 150 parts by weight of hexane as an organic solvent, and equipped with a stirrer The mixture was stirred and mixed at 50 ° C. in a jacketed flask so that both were completely compatible. Next, a column packed with 10 parts by weight of an ion exchange resin (manufactured by Mitsubishi Chemical Corporation, trade name “Diaion UBK535”) was filled with the solution, and then pressure filtered at 0.2 kg / cm ² . . Further, the solvent was removed from the filtrate using an evaporator at 80 ° C. and 10 torr to obtain a polyol (B7 ′).
As resin A, 60 parts by weight of A1 and limonene diepoxide (manufactured by Daicel Chemical Industries, Ltd., trade name “Sexaloid 3000”; number average molecular weight 168) (A2) 10 parts by weight, B7 ′ 30 parts by weight, C2 Was used in the same manner as in Example 1 except that 65.9 parts by weight and 0.32 parts by weight of D2 were used. Moreover, it carried out similarly to Example 1, and obtained the hardened | cured material of the said curable resin composition.
The resin composition (mixture of A1 and B7 ′) had an APHA of 50 and satisfied the APHA defined in the present invention. The obtained cured product has a glass transition temperature: 169 ° C., light transmittance (400 nm): 86.8 T%, light transmittance (heat-resistant coloring stability test: after 24 hours heat treatment): 75.4 T%, light Transmittance (380 nm): 80.8 T%, flexural modulus: 2610 MPa, flexural strength: 94.7 MPa, water absorption: 0.49%, excellent heat resistance, transparency, toughness, etc. Even when subjected to a long thermal history, it was an excellent cured product with little coloring.

Example 10
Polycaprolactone diol (manufactured by Daicel Chemical Industries, Ltd., trade name “Placcel 220N”: number average molecular weight 2000) (B8) 100 parts by weight as the polyol, 180 parts by weight of ethyl acetate as the organic solvent, and ion exchange resin (Mitsubishi Chemical Co., Ltd., trade name “Diaion UBK535”) A polyol (B8 ′) was obtained in the same manner as in Example 9, except that the amount was changed to 15 parts by weight.
As shown in Table 1, a curable resin composition was obtained using 70 parts by weight of A1, 30 parts by weight of B8 ′, 90.4 parts by weight of C2, and 0.55 parts by weight of D3. Moreover, it carried out similarly to Example 1, and obtained the hardened | cured material of the said curable resin composition.
The resin composition (mixture of A1 and B8 ′) had an APHA of 45 and satisfied the APHA defined in the present invention. The obtained cured product has a glass transition temperature: 147 ° C., light transmittance (400 nm): 86.5 T%, light transmittance (heat-resistant coloring stability test: after 24 hours heat treatment): 75.7 T%, light Transmittance (380 nm): 81.0 T%, flexural modulus: 2580 MPa, flexural strength: 83.6 MPa, water absorption: 0.52%, excellent heat resistance, transparency, toughness, etc. Even when subjected to a long thermal history, it was an excellent cured product with little coloring.

Example 11
100 parts by weight of B7 as a polyol and 100 parts by weight of ethyl acetate as an organic solvent, instead of an ion exchange resin, 0.5 parts by weight of activated carbon (manufactured by Ajinomoto Fine Techno Co., Ltd., trade name “Hokuetsu GS-B”) The stirring conditions were changed to 60 ° C. for 90 minutes, and the same operation as in Example 6 was performed. The filtrate was desolvated using an evaporator at 80 ° C. and 10 torr to obtain a polyol (B7 ″).
A curable resin composition was obtained using 45 parts by weight of A1, 10 parts by weight of A2, 40 parts by weight of B7 ″, 74.6 parts by weight of C2, and 0.38 parts by weight of D3. Moreover, it carried out similarly to Example 1, and obtained the hardened | cured material of the said curable resin composition.
The resin composition (mixture of A1, A2 and B7 ″) had an APHA of 30, and satisfied the APHA defined in the present invention. The obtained cured product has a glass transition temperature of 162 ° C., light transmittance (400 nm): 88.2 T%, light transmittance (heat-resistant coloring stability test: after 24 hours heat treatment): 76.8 T%, light Transmittance (380 nm): 81.3 T%, flexural modulus: 2385 MPa, flexural strength: 93.2 MPa, water absorption: 0.61%, excellent heat resistance, transparency, toughness, etc. Even when subjected to a long thermal history, it was an excellent cured product with little coloring.

Example 12
As a polyol, 100 parts by weight of polyethylene glycol (manufactured by Sanyo Chemical Industries, trade name “PEG 1500”) (B9) and 100 parts by weight of methyl isobutyl ketone were stirred and mixed at 30 ° C. to make them compatible. Thereafter, 2.5 parts by weight of activated carbon (trade name “FCS”, manufactured by Phthamura Chemical Co., Ltd.) was added, and a polyol (B9 ′) was obtained in the same manner as in Example 11.
As the resin A, 55 parts by weight of the following epoxy resin (trade name “B0018” manufactured by Daicel Chemical Industries, Ltd.) (A3), 45 parts by weight of B9 ′, 55.4 parts by weight of C2, and 0 of D2 A curable resin composition was obtained using 0.52 parts by weight. Moreover, it carried out similarly to Example 1, and obtained the hardened | cured material of the said curable resin composition.
The resin composition (mixture of A3 and B9 ′) had an APHA of 50 and satisfied the APHA defined in the present invention. The obtained cured product has a glass transition temperature: 159 ° C., light transmittance (400 nm): 86.9 T%, light transmittance (heat-resistant coloring stability test: after 24 hours heat treatment): 76.2 T%, light Transmittance (380 nm): 79.2 T%, flexural modulus: 2450 MPa, bending strength: 86.2 MPa, water absorption: 0.50%, excellent heat resistance, transparency, toughness, etc. Even when subjected to a long thermal history, it was an excellent cured product with little coloring.

Example 13
Using a jacketed flask equipped with a stirrer, 65 parts by weight of A1 and 35 parts by weight of B7 are mixed and stirred at 40 ° C. Thereafter, 0.8 part by weight of a zeolite adsorbent (manufactured by Showa Union Co., Ltd., trade name “Molecular Sieve 13X”) was added, and the mixture was stirred and mixed at 60 ° C. for 90 minutes. A composition was obtained. Note that no organic solvent was used. The obtained resin composition (purified product of a mixture of A1 and B7) had an APHA of 50 and satisfied the APHA defined in the present invention.
This resin composition was mixed with 83.5 parts by weight of C1 and 0.4 parts by weight of D2 to obtain a curable resin composition. Moreover, it carried out similarly to Example 1, and obtained the hardened | cured material of the said curable resin composition.
The obtained cured product has a glass transition temperature: 158 ° C., light transmittance (400 nm): 88.5 T%, light transmittance (heat-resistant coloring stability test: after 24 hours heat treatment): 76.9 T%, light transmittance (380 nm): 81.4 T%, flexural modulus: 2520 MPa, flexural strength: 83.6 MPa, water absorption: 0.36%, excellent heat resistance, transparency, toughness, etc. Even when subjected to the heat history of time, it was an excellent cured product with little coloring.

Example 14
Polycarbonate polyol (trade name “UH-CARB100”) (B10) (B10) (B10) is used as a polyol, 100 parts by weight of toluene as a solvent, and a zeolite-based adsorbent (instead of activated carbon as an adsorbent) A polyol (B10 ′) was obtained in the same manner as in Example 11 using 0.5 parts by weight of Showa Union Co., Ltd. (trade name “Molecular Sieve 4A”).
A curable resin composition was obtained using 60 parts by weight of A1, 40 parts by weight of B10 ′, 77.5 parts by weight of C1, and 0.38 parts by weight of D2. Moreover, it carried out similarly to Example 1, and obtained the hardened | cured material of the said curable resin composition.
The resin composition (mixture of A1 and B10 ′) had an APHA of 40 and satisfied the APHA defined in the present invention. The obtained cured product has a glass transition temperature: 151 ° C., light transmittance (400 nm): 86.2 T%, light transmittance (heat-resistant coloring stability test: after 24 hours heat treatment): 76.2 T%, light Transmittance (380 nm): 80.6 T%, flexural modulus: 2290 MPa, flexural strength: 82.1 MPa, water absorption: 0.44%, excellent heat resistance, transparency, toughness, etc. Even when subjected to a long thermal history, it was an excellent cured product with little coloring.

Example 15
Using a jacketed flask equipped with a stirrer, 65 parts by weight of A1 as the resin A and 35 parts by weight of B7 as the polyol are stirred and mixed at 40 ° C. for 60 minutes to be compatible. Note that no organic solvent was used. Thereafter, an inorganic synthetic adsorbent (manufactured by Kyowa Chemical Industry Co., Ltd., trade name “KYOWARD 500”: Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O) was added in an amount of 0.3 parts by weight. The mixture was stirred and mixed at 90 ° C. for 90 minutes with the adsorbent sufficiently dispersed. After stirring, filtration and removal of the adsorbent were performed using a pressure filter and filter paper (trade name “5C” manufactured by Advantech Co., Ltd.) to obtain a resin composition. The obtained resin composition (purified product of a mixture of A1 and B7) had an APHA of 30, and satisfied the APHA defined in the present invention.
To this resin composition, 75.6 parts by weight of C1 as a curing agent and 0.36 parts by weight of D2 as a curing accelerator were added, and a cured product of the curable resin composition was obtained in the same manner as in Example 1. . The obtained cured product has a glass transition temperature: 150 ° C., light transmittance (400 nm): 85.5 T%, light transmittance (heat-resistant coloring stability test: after 24 hours heat treatment): 75.8 T%, light transmittance (380 nm): 79.4 T%, flexural modulus: 2047 MPa, flexural strength: 83.6 MPa, water absorption: 0.39%, excellent heat resistance, transparency, toughness, etc. Even when subjected to the heat history of time, it was an excellent cured product with little coloring.

Example 16
A1 was changed to 65 parts by weight, B7 was changed to 35 parts by weight, C1 was changed to 71.4 parts by weight, and D2 was changed to 0.36 parts by weight. The adsorbent was changed to zeolite adsorbent (made by Showa Union Co., Ltd. Molecular sieve 13X ") A curable resin composition was obtained in the same manner as in Example 15 except that the content was changed to 0.8 part by weight. Moreover, it carried out similarly to Example 1, and obtained the hardened | cured material of the said curable resin composition.
The resin composition (purified product of a mixture of A1 and B7) had an APHA of 40 and satisfied the APHA defined in the present invention. The obtained cured product has a glass transition temperature of 148 ° C., light transmittance (400 nm): 85.1 T%, light transmittance (heat-resistant coloring stability test: after 24 hours heat treatment): 75.0 T%, light Transmittance (380 nm): 78.6 T%, flexural modulus: 2235 MPa, flexural strength: 78.6 MPa, water absorption: 0.49%, excellent heat resistance, transparency, toughness, etc. Even when subjected to a long thermal history, it was an excellent cured product with little coloring.

Example 17
30 parts by weight of polycarbonate diol (manufactured by Daicel Chemical Industries, Ltd., trade name “Placcel CD-220PL”: number average molecular weight 2000, liquid) (B11) and 70 parts by weight of A3 were mixed and mixed. Thereafter, using a column packed with 15 parts by weight of an adsorbent (Rohm and Haas Co., Ltd., trade name “Amberlite XAD2”), pressure filtration is performed at a pressure of 0.2 kg / cm ^{2 to} obtain a resin composition. Got.
The obtained resin composition (purified product of a mixture of A3 and B11) had an APHA of 35 and satisfied the APHA defined in the present invention.
Into this resin composition, 52.9 parts by weight of C1 and 0.7 parts by weight of E1 were blended to obtain a curable resin composition. Moreover, it carried out similarly to Example 1, and obtained the hardened | cured material of the said curable resin composition.
The obtained cured product has a glass transition temperature: 168 ° C., light transmittance (400 nm): 83.5 T%, light transmittance (heat-resistant coloring stability test: after 24 hours heat treatment): 74.2 T%, light transmittance (380 nm): 79.1 T%, flexural modulus: 2590 MPa, flexural strength: 65.4 MPa, water absorption: 0.60%, excellent heat resistance, transparency, toughness, etc. Even when subjected to the heat history of time, it was an excellent cured product with little coloring.

Example 18
As a polyol, 100 parts by weight of polyether polyol (Asahi Denka Kogyo Co., Ltd., trade name “ADEKA POLYETHER P-2000”; propylene oxide added with propylene oxide (PO)) (B12), and ethyl acetate A polyol (B12 ′) was prepared in the same manner as in Example 9, using a column packed with 200 parts by weight of an adsorbent and 15 parts by weight of a zeolite adsorbent (manufactured by Showa Union Co., Ltd., trade name “Molecular Sieve 13X”). )
60 parts by weight of A1, 40 parts by weight of B12 ′, 67.8 parts by weight of C1, and 0.33 parts by weight of D2 were blended, and a curable resin composition was obtained in the same manner as in Example 1. Moreover, it carried out similarly to Example 1, and obtained the hardened | cured material of the said resin composition.
The obtained resin composition (mixture of A1 and B12 ′) had an APHA of 50 and satisfied the APHA defined in the present invention. The obtained cured product has a glass transition temperature: 164 ° C., light transmittance (400 nm): 87.2 T%, light transmittance (heat-resistant coloring stability test: after 24 hours heat treatment): 75.7 T%, light Transmittance (380 nm): 81.0 T%, flexural modulus: 2260 MPa, flexural strength: 87.1 MPa, water absorption: 0.56%, excellent heat resistance, transparency, toughness, etc. Even when subjected to a long thermal history, it was an excellent cured product with little coloring.

Example 19
It implemented by the raw material composition similar to Example 18, and changed the processing method. A curable resin composition was obtained using a column in the same manner as in Example 17 except that an organic solvent was not used and 0.3 parts by weight of an inorganic synthetic adsorbent “KYOWARD 500” was used as the adsorbent.
The obtained resin composition (purified product of a mixture of A1 and B12) had an APHA of 40 and satisfied the APHA defined in the present invention. The obtained cured product has a glass transition temperature of 141 ° C., a light transmittance (400 nm): 87.2 T%, a light transmittance (heat-resistant coloring stability test: after 24 hours heat treatment): 75.7 T%, light Transmittance (380 nm): 81.0 T%, flexural modulus: 2260 MPa, flexural strength: 87.1 MPa, water absorption: 0.56%, excellent heat resistance, transparency, toughness, etc. Even when subjected to a long thermal history, it was an excellent cured product with little coloring.

Comparative Example 1
A curable resin composition and a cured product thereof were obtained in exactly the same manner as in Example 1 except that the polyol was not purified.
The resin composition (mixture of A1 and B1) had an APHA of 120 and did not satisfy the APHA defined in the present invention. The obtained cured product has a glass transition temperature of 161 ° C., light transmittance (400 nm): 80.2 T%, light transmittance (heat-resistant coloring stability test: after 24 hours heat treatment): 64.8 T%, light Transmittance (380 nm): 76.2 T%, flexural modulus: 2620 MPa, flexural strength: 72.2 MPa, water absorption: 0.31%, light transmittance is reduced, and long-term thermal history Coloring was also seen when receiving.

Comparative Example 2
A curable resin composition and a cured product thereof were obtained in exactly the same manner as in Example 2 except that the polyol was not purified.
The resin composition (mixture of A1 and B2) had an APHA of 150 and did not satisfy the APHA defined in the present invention. The obtained cured product has a glass transition temperature of 153 ° C., light transmittance (400 nm): 81.3 T%, light transmittance (heat-resistant coloring stability test: after 24 hours heat treatment): 67.8 T%, light Transmittance (380 nm): 76.8 T%, flexural modulus: 2360 MPa, flexural strength: 75.6 MPa, water absorption: 0.41%, light transmittance is reduced, and long-term thermal history Coloring was also seen when receiving.

Comparative Example 3
A curable resin composition and a cured product thereof were obtained in the same manner as in Example 3 except that the polyol was not purified.
The resin composition (mixture of A1 and B3) had an APHA of 140 and did not satisfy the APHA defined in the present invention. The obtained cured product has a glass transition temperature of 181 ° C., light transmittance (400 nm): 82.4 T%, light transmittance (heat-resistant coloring stability test: after 24 hours heat treatment): 69.5 T%, light Transmittance (380 nm): 74.1 T%, flexural modulus: 2700 MPa, flexural strength: 69.6 MPa, water absorption: 0.55%, light transmittance is reduced, and long-term thermal history Coloring was also seen when receiving.

  The APHA of the raw material alicyclic epoxy (A1) used in Comparative Examples 1 to 3 was 5 and the APHA of the polycaprolactone diols B1 to B3 was 60 or less, but the APHA after mixing was 100 or more. It was.

Comparative Example 4
Polycaprolactone diol (manufactured by Daicel Chemical Industries, trade name “Placcel 220”: number average molecular weight 2000) (B13) as a polyol, and 1,8-diazabicyclo [5.4.0] undecene as a curing accelerator 7 octylate (manufactured by San Apro Co., Ltd., trade name “U-CAT SA-102”) (D4) was used. Was used. A curable resin composition as in Example 1 except that 60 parts by weight of A1, 40 parts by weight of B13, 78.2 parts by weight of C1, and 0.4 parts by weight of D4 are blended and no purification is performed. And a cured product thereof.
The resin composition (mixture of A1 and B13) had an APHA of 160 and did not satisfy the APHA defined in the present invention. Further, the obtained cured product has a glass transition temperature: 144 ° C., light transmittance (400 nm): 80.0 T%, light transmittance (heat-resistant coloring stability test: after 24 hours heat treatment): 62.1 T%, light Transmittance (380 nm): 72.7 T%, flexural modulus: 2180 MPa, bending strength: 71.1 MPa, water absorption: 0.51%, light transmittance is reduced, and long-term thermal history Coloring was also seen when receiving.

Comparative Example 5
A curable resin composition in the same manner as in Example 1 except that 70 parts by weight of A1, 30 parts by weight of B12, 85.9 parts by weight of C1, and 0.45 parts by weight of D4 are blended and purification is not performed. And a cured product thereof.
The resin composition (mixture of A1 and B12) had an APHA of 130 and did not satisfy the APHA defined in the present invention. The obtained cured product has a glass transition temperature: 136 ° C., light transmittance (400 nm): 80.6 T%, light transmittance (heat-resistant coloring stability test: after 24 hours heat treatment): 63.5 T%, light Transmittance (380 nm): 73.6 T%, flexural modulus: 2250 MPa, bending strength: 75.6 MPa, water absorption: 0.46%, light transmittance is reduced, and long-term thermal history Coloring was also seen when receiving.

Comparative Example 6
A curable resin composition as in Example 1 except that 70 parts by weight of A1, 30 parts by weight of B13, 0.5 parts by weight of E1, and 0.45 parts by weight of D4 are blended and purification is not performed. And a cured product thereof.
The resin composition (mixture of A1 and B13) had an APHA of 170 and did not satisfy the APHA defined in the present invention. The obtained cured product has a glass transition temperature of 129 ° C., light transmittance (400 nm): 78.9 T%, light transmittance (heat-resistant coloring stability test: after 24 hours heat treatment): 60.6 T%, light Transmittance (380 nm): 71.3 T%, flexural modulus: 2210 MPa, bending strength: 79.6 MPa, water absorption: 0.38%, light transmittance is reduced, and long-term thermal history Coloring was also seen when receiving.

  Furthermore, an additional characteristic at the time of using the curable resin composition of this invention as a photocurable resin composition is demonstrated using an Example. However, the present invention is not limited to these examples.

Example 20
For 100 parts by weight of the resin composition (a mixture of 60 parts by weight of A1 and 40 parts by weight of B3 ′) obtained in the same manner as in Example 3, a sulfonium salt photocation initiator (Daicel Cytec Co., Ltd.) And 4 parts by weight of a trade name “UVACURE1591”) and 0.3 parts by weight of a fluorosurfactant (trade name “FC430” manufactured by 3M Co., Ltd.) are blended in the same manner as in Example 1. A composition was obtained.
The obtained curable resin composition has adhesive strength (PET / PET): 11.5 (kg / 15 mm), adhesive strength (Al plate / PET): 14.2 (kg / 15 mm), and light transmittance (400 nm). ) 93.3T%, heat deterioration resistance: 82.4%, excellent adhesiveness, transparency, etc., and an excellent composition that hardly deteriorates even with a long-term heat history. .

Example 21
A curable resin composition was obtained in the same manner as in Example 20, except that the resin composition obtained in the same manner as in Example 5 (purified product of 70 parts by weight of A1 and 30 parts by weight of B3) was used. I got a thing.
The obtained curable resin composition has an adhesive strength (PET / PET): 11.6 (kg / 15 mm), an adhesive strength (Al plate / PET): 13.8 (kg / 15 mm), and a light transmittance (400 nm). ) 94.5 T%, heat deterioration resistance: 81.5%, excellent adhesiveness, transparency, etc., and an excellent composition that hardly deteriorates even with a long-term heat history. .

Example 22
A curable resin composition was prepared in exactly the same manner as in Example 20, except that the resin composition obtained in the same manner as in Example 14 (a mixture of 60 parts by weight of A1 and 40 parts by weight of B10 ′) was used. Obtained.
The obtained curable resin composition has adhesive strength (PET / PET): 12.2 (kg / 15 mm), adhesive strength (Al plate / PET): 14.3 (kg / 15 mm), and light transmittance (400 nm). ) 92.9T%, heat deterioration resistance: 79.3%, excellent adhesiveness, transparency, etc., and an excellent composition that hardly deteriorates even with a long-term heat history. .

Example 23
The curable resin composition was exactly the same as in Example 20, except that the resin composition obtained in the same manner as in Example 17 (purified product of 70 parts by weight of A3 and 30 parts by weight of B11) was used. I got a thing.
The obtained curable resin composition has an adhesive strength (PET / PET): 10.9 (kg / 15 mm), an adhesive strength (Al plate / PET): 13.9 (kg / 15 mm), and a light transmittance (400 nm). ) 93.7T%, heat deterioration resistance: 81.6%, excellent adhesiveness, transparency and the like, and an excellent composition that hardly deteriorates even with a long-term heat history. .

Comparative Example 7
A curable resin composition was obtained in exactly the same manner as in Example 20, except that the resin composition (a mixture of 60 parts by weight of A1 and 40 parts by weight of B3) obtained in the same manner as in Comparative Example 3 was used. It was.
The obtained curable resin composition has an adhesive strength (PET / PET): 6.1 (kg / 15 mm), an adhesive strength (Al plate / PET): 8.5 (kg / 15 mm), and a light transmittance (400 nm). ) 94.1 T%, heat deterioration resistance: 67.2%, inferior in adhesiveness, and easily deteriorated even with a long thermal history.

  As shown above, it was found that the curable resin composition of the present invention exhibits excellent properties such as adhesiveness by photocuring even when used as a photocurable resin composition.

Claims (14)

A method for producing a curable resin composition comprising an epoxy resin and a polyol B which is liquid at 40 ° C. having a number average molecular weight of 300 or more, and having an APHA of 50 or less ,
Polyol B is
An oligomer having an ester skeleton in the molecule, a polyester polyol having two or more terminal hydroxyl groups and a caprolactone copolymer;
An oligomer having an ether skeleton in the molecule, a polyether polyol having two or more terminal hydroxyl groups, and
Other oligomers having a carbonate skeleton in the molecule, having two or more terminal hydroxyl groups and represented by 1,6-hexanediol and HO—R ¹ —OH (wherein R ¹ is the number of carbon atoms) 2 to 14, which may be linear or branched, may contain 1 to 3 cyclic structures, and may contain oxygen atoms in the molecule), and A polycarbonate polyol comprising a carbonate component and having a molar ratio of 1,6-hexanediol to other diol of 10: 1 to 2: 8 and a number average molecular weight of 300 to 3000,
At least one polyol selected from the group consisting of:
A method for producing a curable resin composition , comprising mixing an epoxy resin and a polyol B at a blending ratio (weight ratio) of 50:50 to 95: 5 and then purifying by washing with water. A method for producing a curable resin composition comprising an epoxy resin and a polyol B which is liquid at 40 ° C. having a number average molecular weight of 300 or more, and having an APHA of 50 or less ,
Polyol B is
An oligomer having an ester skeleton in the molecule, a polyester polyol having two or more terminal hydroxyl groups and a caprolactone copolymer;
An oligomer having an ether skeleton in the molecule, a polyether polyol having two or more terminal hydroxyl groups, and
Other oligomers having a carbonate skeleton in the molecule, having two or more terminal hydroxyl groups and represented by 1,6-hexanediol and HO—R ¹ —OH (wherein R ¹ is the number of carbon atoms) 2 to 14, which may be linear or branched, may contain 1 to 3 cyclic structures, and may contain oxygen atoms in the molecule), and A polycarbonate polyol comprising a carbonate component and having a molar ratio of 1,6-hexanediol to other diol of 10: 1 to 2: 8 and a number average molecular weight of 300 to 3000,
At least one polyol selected from the group consisting of:
A method for producing a curable resin composition, comprising : mixing an epoxy resin and polyol B at a blending ratio (weight ratio) of 50:50 to 95: 5, and then purifying with an adsorbent. Manufacturing method of adsorbent, the activated clay, ion exchange resins, activated carbon, curable resin composition according to claim 2, wherein at least one adsorbent selected zeolite preparative or al. Method for producing a curable resin composition according to claim 2 adsorbent is a non-machine synthetic adsorbent. Method claimed by the production method of the curable resin composition according to any one of the paragraphs in claim 1-4, to produce a curable resin composition, using this curable resin composition as a transparent sealant. Method claimed by the production method of the curable resin composition according to any one of the paragraphs in claim 1-4, to produce a curable resin composition, using this curable resin composition as an optical adhesive. Method claimed by the production method of the curable resin composition according to any one of the paragraphs in claim 1-4, to produce a curable resin composition, using this curable resin composition as a photocurable adhesive. Method by the method for producing a curable resin composition according to any one of claims 1-4, to produce a curable resin composition, using this curable resin composition as a photocurable sealing material. A method for producing a photocurable optical waveguide by producing a curable resin composition by the method for producing a curable resin composition according to any one of claims 1 to 4 , and using the curable resin composition. . A curable resin composition is produced by the method for producing a curable resin composition according to any one of claims 1 to 4 , and further the resin cured product obtained by curing the curable resin composition into a resin cured product . Manufacturing method . A curable resin composition is produced by the method for producing a curable resin composition according to any one of claims 1 to 4 , and the curable resin composition is further cured into a resin cured product to obtain a transparent sheet. A method for producing a transparent sheet. A curable resin composition is produced by the method for producing a curable resin composition according to any one of claims 1 to 4 , and the curable resin composition is further cured into a resin cured product to obtain a composite material. A method for producing a composite material. A curable resin composition is produced by the method for producing a curable resin composition according to any one of claims 1 to 4 , and the curable resin composition is further cured into a resin cured product to thereby seal an optical semiconductor. The manufacturing method of the resin composition for optical semiconductor sealing which obtains the resin composition for stop. By the method for producing a curable resin composition according to any one of claims 1 to 4 , a curable resin composition is produced, and further a cured resin obtained by curing the curable resin composition , An optical semiconductor device manufacturing method for sealing an optical semiconductor element.