JP5330632B2 - Resin composition, optical member using the same, and method for producing the same - Google Patents

Description

  The present invention is a resin composition having a high optical transparency of the cured product and excellent in heat resistance, light resistance and mechanical properties, and a transparent substrate, lens, adhesive, optical waveguide, light-emitting diode using the cured product ( LED), a phototransistor, a photodiode, an optical member suitable for an optical semiconductor device application such as a solid-state imaging device, and a manufacturing method thereof.

  Conventionally, acrylic resins having excellent transparency and light resistance have been widely used as optical member resins. On the other hand, the resin for optical members used in the field of optical / electronic equipment is required to have a mounting process on an electronic substrate and the like, heat resistance and mechanical characteristics under high temperature operation, and epoxy resin is often used. However, in recent years, the use of high-intensity laser light, blue light, and near-ultraviolet light has expanded in the field of optical and electronic equipment, and a resin that is more excellent in transparency, heat resistance, and light resistance than ever is required.

  In general, epoxy resins have high transparency in the visible range, but sufficient transparency cannot be obtained in the ultraviolet to near ultraviolet range. Among them, epoxy resins using alicyclic bisphenol A diglycidyl ether have relatively high transparency, but have problems such as being easily colored by heat and light. For example, Patent Documents 1 and 2 disclose a method for reducing impurities that are one of the causes of coloring contained in alicyclic bisphenol A diglycidyl ether, but further improvement in heat resistance and ultraviolet coloring resistance is required. It has been.

  Silicone resin is highly transparent up to the near-ultraviolet region and has a large Si—O bond energy, and thus has excellent light resistance and is difficult to be colored by heat or light. In general, silicone resins are polymerized by dehydration condensation reaction between silanol groups, condensation reaction between silanol groups and hydrolyzable groups, reaction by organic peroxide of methylsilyl group and vinylsilyl group, addition reaction of vinylsilyl group and hydrosilyl group, etc. Is done. For example, Patent Document 3 discloses a silicone resin obtained by an addition reaction between a vinylsilyl group and a hydrosilyl group. However, the silicone resin obtained by utilizing these reactions also has problems such as the case where the curing does not proceed due to the influence of the catalyst poison due to the curing atmosphere and the thermal expansion coefficient of the cured product is large. Furthermore, although an epoxy resin composition containing a silicone resin modified with an epoxy group is disclosed in, for example, Patent Document 4, a silicone that can be contained due to a compatibility problem between the silicone resin and the epoxy resin or its curing agent. The amount of resin is limited.

  On the other hand, improvement of heat resistance, which is a drawback of acrylic resins having excellent optical properties, has been studied, and there is an example of introducing a crosslinked structure between acrylic main chains. For example, Patent Document 5 discloses a reaction product obtained by crosslinking with a (meth) acrylic polymer containing an epoxy group and a polyvalent carboxylic acid. However, as shown in the examples, since the (meth) acrylic polymer containing an epoxy group is insoluble in the polyvalent carboxylic acid of the curing agent, it can be dissolved in an organic solvent and molded and cured. Must not. Non-patent document 1 reports an example in which a low molecular weight (meth) acrylic polymer containing an epoxy group is dissolved in a liquid epoxy monomer and reacted with a curing agent. However, since this system also uses a liquid epoxy monomer that is inferior in heat resistance and light resistance as a solubilizer for the (meth) acrylic polymer, further improvement in properties is required.

  In addition, acrylic resins also have a drawback that the amount of cure shrinkage is large. This is because, unlike the ring-opening polymerization reaction of epoxy, in the case of acrylate, the Van de Waals distance of the monomer is reduced to the covalent bond distance by radical polymerization. Due to the curing shrinkage, a stress is generated in the cured product of the acrylic resin, and there is a problem that the adhesion to the adherend is inferior.

  Therefore, a resin composition suitable for an optical member, which is a solvent-free system, is liquid at room temperature, is easy to mold and cure, has excellent transparency, light resistance, heat resistance, mechanical properties, and has a small curing shrinkage. Is desired.

JP 2003-171439 A JP 2004-75894 A JP 2004-186168 A JP 2004-155865 A JP 2003-160640 A "Proceedings of the 53rd Network Polymer Lecture Meeting" p49-52 “Network Polymer” Vol. 24, N0.3 (2003) p148-155

  The present invention provides a resin composition in which the cured product has high optical transparency, excellent light resistance, heat resistance and mechanical properties, small curing shrinkage, and excellent storage stability. In addition, the present invention provides an optical member having high optical transparency, excellent light resistance, heat resistance, mechanical properties, small curing shrinkage using the resin composition, and further simplifying the optical member in a short time. The manufacturing method to produce is provided.

  The present invention includes [1] an epoxy group-containing (meth) acrylate as the monomer component (A), a one-terminal (meth) acryl-modified silicone oil as the monomer component (B), and an acid anhydride as the epoxy curing agent (C). It is a resin composition that is liquid at 25 ° C. and is cured by heating or light irradiation.

  Moreover, the present invention is [2] the resin composition according to [1], further comprising a radical polymerization initiator (D) and an epoxy curing accelerator (E).

  In the present invention, [3] both radical polymerization of the monomer component (A) and the monomer component (B) and ion polymerization of the monomer component (A) and the epoxy curing agent (C) proceed by heating or light irradiation. The resin composition according to [1] or [2].

  Moreover, this invention is [4] Furthermore, it is a resin composition of said [1]-[3] description which contains (meth) acrylate as a monomer component (F).

  Moreover, this invention is [5] Furthermore, the said (1)-[4] description which contains the epoxy group containing (meth) acryl copolymer whose weight average molecular weight is 20,000 or less as a component (G). It is a resin composition.

  Moreover, this invention is [6] Furthermore, it is a resin composition of the said [1]-[5] description containing a polymerization reactive acrylic oligomer as a component (H).

  The present invention also includes [7] the monomer component (A) and the monomer component (B), and in some cases, one of the monomer component (F), the component (G), and the component (H). The first liquid that can contain the above and the second liquid containing the epoxy curing agent (C), the radical polymerization initiator (D), and the epoxy curing accelerator (E) are mixed and heated. Or it is a resin composition as described in said [1]-[6] hardened | cured by light irradiation.

  The present invention also provides [8] an optical member produced by curing the resin composition according to any one of [1] to [7].

  [9] The present invention uses [9] the resin composition according to any one of [1] to [7] above, the monomer component (A) and the monomer component (B), and optionally the monomer component (F). And / or radical polymerization with the component (H) by light irradiation, and ion polymerization between the monomer component (A) and the epoxy curing agent (C), and optionally the component (G), by subsequent heating. This is a method for manufacturing an optical member.

  The resin composition of the present invention has a high optical transparency of the cured product, a decrease in transmittance after storage at high temperature, a high bending strength, excellent heat resistance and mechanical properties, and a small shrinkage in curing. It is suitable as a resin composition for electronic materials such as a sealing resin for optical semiconductors. Moreover, the resin composition of this invention is excellent also in storage stability. And the lifetime and reliability of an optical element improve by applying the resin composition of this invention excellent in heat resistance, light resistance, and mechanical strength to an optical member. Moreover, the manufacturing method of the optical member of this invention can obtain hardened | cured material easily in a short time.

  The resin composition of the present invention is liquid at 25 ° C., the monomer component (A) is an epoxy group-containing (meth) acrylate, the monomer component (B) is a one-terminal (meth) acryl-modified silicone oil, an epoxy curing agent ( C) contains an acid anhydride. In addition to this, it is preferable to contain a radical polymerization initiator (D) and an epoxy curing accelerator (E). Further, in addition to this, (meth) acrylate as the monomer component (F), epoxy group-containing (meth) acrylic copolymer having a weight average molecular weight of 20,000 or less as the component (G), and polymerization reaction as the component (H) It is preferable to contain 1 or more types of a functional acrylic oligomer.

  In the resin composition of the present invention, an acrylic main chain is formed by radical polymerization of an epoxy group-containing (meth) acrylate (monomer (A) component) and one terminal (meth) acryl-modified silicone oil (monomer (B) component). In addition, crosslinks in the acrylic main chain and between the main chains are formed by ionic polymerization of the epoxy group of the acrylic side chain of component (A) and an acid anhydride (epoxy curing agent (C)), and cured. As a result, it is possible to achieve both the excellent optical properties of the acrylic resin and the silicone resin and the excellent heat resistance properties and mechanical properties of the epoxy resin. Moreover, when the component (F) and the component (H) which are optional components are contained in the resin composition, an acrylic main chain is formed by radical polymerization of these components with the component (A) and the component (B), When component (G), which is an optional component, is contained in the resin composition, cross-linking is formed between the acrylic main chains by ionic polymerization of component (G) and component (C).

  Performing radical polymerization of acrylate and ionic polymerization of an epoxy group and an acid anhydride and modifying an epoxy resin with acrylate is described in, for example, “Network Polymer” Vol. 24, N0.3 (2003) p148-155. However, these use an acrylate monomer and an epoxy monomer, and form an interpenetrating polymer network structure that is separately cross-linked, so that there is a problem that properties such as transparency of the cured product are deteriorated.

  In addition, introduction of modified silicone into the resin skeleton is effective in improving light resistance, and therefore epoxy-modified silicone has been studied. However, these are limited in the type and amount of silicone segments that can be introduced in terms of compatibility with silicone.

  On the other hand, in the material system of the resin composition of the present invention, an acrylic main chain is formed by using an epoxy group-containing (meth) acrylate, one-end (meth) acryl-modified silicone oil, and an acid anhydride, and further Since a cross-linked structure of an epoxy group and an acid anhydride is formed in the acrylic main chain and between the main chains, a cured resin product having a uniform and high transparency can be obtained.

  Also, by containing (meth) acrylate (component (F)), epoxy group concentration in the acrylic main chain formed from epoxy group-containing (meth) acrylate, (meth) acryl-modified silicone oil, (meth) acrylate In addition, the silicone concentration can be adjusted, and optimal cured product properties can be obtained.

  Moreover, by containing an epoxy group-containing (meth) acrylic copolymer (component (G)), a crosslinked structure of an epoxy group and an acid anhydride can be formed in the acrylic main chain and between the main chains, and the curing shrinkage is small. A cured resin having uniform and high transparency can be obtained.

  In addition, by containing a polymerization-reactive acrylic oligomer (component (H)), an acrylic side chain can be further formed in the acrylic main chain, and a cured resin having a uniform and high transparency can be obtained with a small curing shrinkage. it can.

  Although it does not specifically limit as an epoxy-group containing (meth) acrylate which is a monomer component (A) used by this invention, For example, glycidyl methacrylate, 3,4-epoxy cyclohexyl methyl acrylate, 3,4-epoxy cyclohexyl methyl methacrylate, Examples include 1,4-hydroxybutyl acrylate glycidyl ether, and glycidyl methacrylate is particularly preferable. Here, “(meth) acrylate” used in the present invention means acrylate or methacrylate, and “(meth) acryl” means acryl or methacryl ”(the same applies hereinafter).

The one-terminal (meth) acryl-modified silicone oil that is the monomer component (B) used in the present invention is not particularly limited, and examples thereof include ( 3-acryloxypropyl) methylbis (trimethylsiloxy) silane and ( 3-methacryloxypropyl). ) methylbis (trimethylsiloxy) silane, (3-methacryloxypropyl) include tris (trimethylsiloxy) silane and the like, with even (3-methacryloxypropyl) tris (trimethylsiloxy) silane is preferred in.

  The epoxy curing agent (C) used in the present invention is not particularly limited, but is an acid anhydride that is liquid at 25 ° C., such as methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, hydrogen. Methyl nadic acid anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, and the like. Among them, alicyclic acid anhydride is preferable, and methylhexahydrophthalic anhydride and hydrogenated methyl nadic acid anhydride are particularly preferable. .

  As the radical polymerization initiator (D) used in the present invention, any one that can be used for ordinary radical polymerization, such as an azo initiator and a peroxide initiator, can be used. Examples of the azo initiator include azobisisobutyronitrile, azobis-4-methoxy-2,4-dimethylvaleronitrile, azobiscyclohexanone-1-carbonitrile, azodibenzoyl, and the like. Initiators include benzoyl peroxide, lauroyl peroxide, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-2-ethylhexanoate, 1,1-t-butylperoxy-3,3 , 5-trimethylcyclohexane, t-butylperoxyisopropyl carbonate, and the like.

  When radical polymerization is carried out by radical photopolymerization, a radical photopolymerization initiator (D) is used instead of radical thermal polymerization initiators such as the above-mentioned azo initiators and peroxide initiators. Can be used. The radical photopolymerization initiator is not particularly limited as long as it efficiently absorbs and activates ultraviolet rays of an industrial UV irradiation apparatus and does not yellow the cured resin. For example, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-methyl-1-phenyl-propan-1-one, oligo (2-hydroxy-2-methyl-1- (4- (1 -Methylvinyl) phenyl) propanone, a mixture of oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone and tripropylene glycol diacrylate, and oxy-phenyl-acetic acid -2- (2-Oxo-2-phenyl-acetoxy-ethoxy) -ethyl ester and oxy-phenyl Acetate tic acid 2- (2-hydroxy - ethoxy) - mixture of ethyl esters.

  Although it does not specifically limit as an epoxy hardening accelerator (E) used by this invention, For example, quaternary phosphonium salt type | system | group, quaternary ammonium salt type | system | group, imidazole type | system | group, DBU (1,8-diaza-bicyclo- (5,4) , 0) -undecene-7) fatty acid salt system, metal salt system, triphenylphosphine system and the like. Examples of the quaternary phosphonium salt system include tetrabutylphosphonium diethylphosphodithionate, tetraphenylphosphonium bromide, and tetrabutylphosphonium bromide. Examples of the quaternary ammonium salt system include tetraethylammonium bromide and tetrabutylammonium bromide are imidazole. Examples of the system include 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2,4-diamino-6- [2-methylimidazolyl- ( 1)] Ethyl-s-triazine, 2-phenylimidazoline, etc., DBU fatty acid salt system is DBU 2-ethylhexanoate, and metal salt system is zinc octylate, tin octylate, etc. .

  Although it does not specifically limit as (meth) acrylate which is a monomer component (F) used by this invention, For example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl Methacrylate, benzyl methacrylate, isobornyl methacrylate, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, benzyl acrylate, isobornyl acrylate, etc. may be mentioned. These may be used alone or in combination of two or more. Can be used. Moreover, the monomer component (F) may contain polyfunctional (meth) acrylate. Examples of polyfunctional (meth) acrylates include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and 1,9-nonanediol. Dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane dimethacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol Diacrylate, 1,10-decanediol diacrylate, neopentyl glycol diacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6- Hexanediol diacrylate 2-butyl-2-ethyl-1,3-propanediol diacrylate, 1,9-nonanediol diacrylate, dimethylol - diacrylate, and the like ethoxylated isocyanuric acid triacrylate.

  As the epoxy group-containing (meth) acrylic copolymer that is the component (G) used in the present invention, for example, the epoxy group-containing (meth) acrylate listed as the monomer component (A) and the piece listed as the monomer component (B) A terminal (meth) acryl-modified silicone oil and, in some cases, a copolymer of (meth) acrylate as the monomer component (F) may be mentioned. Accordingly, the epoxy group-containing (meth) acrylic copolymer (G) is the same as the monomer component (A) and the monomer component (B) having the same epoxy group-containing (meth) acrylate and one-terminal (meth) acryl-modified silicone oil monomer. Or a copolymer of an epoxy group-containing (meth) acrylate different from the monomer component (A) and a one-terminal (meth) acryl-modified silicone oil different from the monomer component (B). However, since the epoxy group-containing (meth) acrylic copolymer (G) is soluble in the monomer components (A) and (B) and the epoxy curing agent (D), its molecular weight is preferably low, and the weight The average molecular weight is particularly preferably 20,000 or less (the weight average molecular weight is measured by gel permeation chromatography (GPC) and converted to standard polystyrene). In the case of solution polymerization, such a low molecular weight copolymer can be obtained by performing polymerization conditions at a high temperature or adding a chain transfer agent. The epoxy group-containing (meth) acrylic copolymer of component (G) may be blended with other monomers as long as the object of the present invention is not impaired.

  Although it does not specifically limit as a polymerization reaction acrylic oligomer which is the component (H) in this invention, It is preferable that it is an acrylic oligomer containing 1 or more of (meth) acryloyl groups, and the acrylic oligomer of the (meth) acryloyl group terminal end (Macromonomer) is more preferable. Examples of the acrylic oligomer segment include methyl methacrylate, butyl acrylate, and isobutyl acrylate. From the viewpoint of solubility, the number average molecular weight is preferably 10,000 or less (the number average molecular weight is measured by GPC and converted to standard polystyrene).

  The crosslinked structure of the cured product depends on the relationship between the half-life temperature of the radical polymerization initiator (D) used and the gelation temperature of the epoxy curing accelerator (E). Generally, since the half-life temperature of the radical polymerization initiator is lower than the gelation temperature of the epoxy curing accelerator, the radical polymerization of (meth) acrylate proceeds first, and the (meth) acryl main chain is formed. The ionic polymerization of the epoxy group and the acid anhydride proceeds, and a crosslinked structure is formed in the acrylic main chain and between the main chains. However, by selecting a combination in which the half-life temperature of the radical polymerization initiator and the gelation temperature of the epoxy curing accelerator are close, there is no steric restriction of the acrylic main chain, and a denser cross-linked structure can be obtained. Conceivable.

  In the present invention, the blending amounts of the component (A) and the component (B) are preferably blended so that the respective weight ratios are (A) :( B) = 30: 70 to 90:10, and 40:60 It is particularly preferable to blend so as to be ˜60: 40. When the ratio of the component (A) is less than 30, the crosslinking density becomes too small, so that the heat resistance of the cured resin is lowered and tends to be brittle. On the other hand, when the ratio of the component (A) exceeds 90, the effect of the component (B) tends to be small.

  The compounding amount of the epoxy curing agent (C) component in the present invention is 0.5 to 1.2 in terms of an equivalent ratio (acid anhydride group / epoxy group) of the acid anhydride group and the epoxy group of the component (A). It is preferable that When this equivalent ratio is larger than 1.2, the cured product is easily colored by heat or ultraviolet rays. On the other hand, if the equivalent ratio is less than 0.5, the heat resistance of the resin cured product tends to decrease.

  The blending amount of the radical polymerization initiator (D) component in the present invention is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the total amount of the component (A) and the component (B). It is particularly preferable that the content be ˜1 part by weight. If this amount exceeds 5 parts by weight, the cured product tends to be colored by heat or ultraviolet rays, and if it is less than 0.01 part by weight, the resin composition tends to be difficult to cure.

  The compounding amount of the epoxy curing accelerator (E) component in the present invention is 0.01 to 5 parts by weight with respect to 100 parts by weight of the total amount of the component (A), the component (B) and the component (C). The content is preferably 0.1 to 1 part by weight. If the blending amount exceeds 5 parts by weight, the cured product tends to be colored by heat or near ultraviolet rays, and if it is less than 0.01 part by weight, the resin composition tends to be difficult to cure.

  The compounding quantity of (F) component in this invention is the weight ratio of the said (F) component, (A) component, and (B) component, (F) :( A) + (B) = 10: 90- It is preferable to mix | blend so that it may become 50:50, and it is especially preferable to mix | blend so that it may become 10: 80-40: 60. Here, when the ratio of the component (F) is less than 10, the effect of the component (F) is small. On the other hand, when the ratio of the component (F) is greater than 50, the crosslink density becomes too small and the heat resistance is lowered, and the effect of the component (B) tends to be reduced.

  The compounding quantity of (G) component in this invention is the weight ratio of the said (G) component, (A) component, and (B) component, (G) :( A) + (B) = 10: 90- It is preferable to mix | blend so that it may become 50:50, and it is especially preferable to mix | blend so that it may become 20: 80-40: 60. Here, when the ratio of the component (G) is less than 10, the effect of reducing curing shrinkage is small. On the other hand, when the ratio of the (G) component is greater than 50, the (G) component tends to be difficult to dissolve with respect to the (A) component, the (B) component, and the (D) component.

  The compounding quantity of (H) component in this invention is the weight ratio of the said (H) component, (A) component, and (B) component, (G) :( A) + (B) = 10: 90- It is preferable to mix | blend so that it may become 50:50, and it is especially preferable to mix | blend so that it may become 20: 80-40: 60. Here, when the ratio of the component (H) is less than 10, the effect of reducing curing shrinkage is small. On the other hand, if the ratio of the (H) component is greater than 50, the (H) component is difficult to dissolve in the (A), (B) and (D) components, and the crosslinking density is too small. Therefore, the heat resistance of the cured product tends to decrease.

  In addition to the above components, the resin composition of the present invention includes hindered amine light stabilizers, phenolic and phosphorus antioxidants, ultraviolet absorbers, inorganic fillers, organic fillers, coupling agents, and polymerization inhibition. An agent or the like can be added. Moreover, a mold release agent, a plasticizer, an antistatic agent, a flame retardant, etc. may be added from the viewpoint of moldability. These are preferably liquid from the viewpoint of ensuring the light transmittance of the cured resin, but in the case of a solid, it is desirable to have a particle size equal to or smaller than the wavelength used.

  The method for producing an optical member using the resin composition of the present invention comprises an epoxy group-containing (meth) acrylate as the monomer component (A), a one-terminal (meth) acryl-modified silicone oil and an epoxy curing agent as the monomer component (B). (C) an acid anhydride, optionally containing a radical polymerization initiator (D) and an epoxy curing accelerator (E), and a resin composition that is liquid at room temperature (25 ° C.) by heating or light irradiation. The radical polymerization of the components (A) and (B) and the ionic polymerization of the components (A) and (C) are advanced and cured. The resin composition may contain (meth) acrylate as the monomer component (F), an epoxy group-containing (meth) acrylic copolymer as the component (G), and a polymerizable reactive acrylic oligomer as the component (H). Good.

  As the form of the resin composition, (A) component, (B) component and (C) component, (D) component added as necessary, (E) component, (F) component, (G) component, The resin solution prepared by mixing and preparing the component (H) may contain the component (A) and the component (B), and may optionally contain one or more components (F), (G), and (H). By separating the first liquid and the second liquid containing the component (C), the component (D) and the component (E), the storage stability of each can be improved. And the second liquid are mixed to obtain the resin composition of the present invention.

  In the method for producing an optical member using the resin composition of the present invention, a resin solution is poured into a desired portion, poured, potted, or poured into a mold and cured by heating or light irradiation. Moreover, it is desirable to reduce the oxygen concentration in the resin composition in advance by nitrogen bubbling in order to inhibit curing and prevent coloring.

  The curing conditions in the case of thermosetting depend on the type, combination, and amount of each component, but are not particularly limited as long as the temperature and time are finally completed for both radical polymerization and ionic polymerization. Is about 1 to 5 hours at 60 to 150 ° C. Moreover, in order to reduce the internal stress generated by the rapid curing reaction, it is desirable to raise the curing temperature stepwise. Furthermore, in order to easily obtain a cured product in a shorter time, first, photoradical polymerization of the component (A) and the component (B) is performed by light irradiation, and then this is heated to thereby heat the component (A) and the component (C). It is also possible to carry out ionic polymerization of the components.

  The resin composition of the present invention described above is a resin composition having high optical transparency of the cured product and excellent heat resistance, light resistance, and mechanical properties. The cured product is a transparent substrate, a lens, and an adhesive. It is suitable as an optical member for use in optical semiconductor elements such as an agent, an optical waveguide, a light emitting diode (LED), a phototransistor, a photodiode, and a solid-state imaging device.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1
As an epoxy group-containing (meth) acrylate of the monomer component (A), 35 parts by weight of glycidyl methacrylate (Light Ester G, manufactured by Kyoeisha Chemical Co., Ltd.), as a one-terminal (meth) acrylate-modified silicone oil of the monomer component (B) (3 -Methacryloxypropyl ) tris (trimethylsiloxy) silane (Silaplane TM-0701T manufactured by Chisso Corporation) 35 parts by weight, methylhexahydrophthalic anhydride (HN-5500, Hitachi as acid anhydride of epoxy curing agent (C) Kasei Kogyo Co., Ltd.) 30 parts by weight, radical polymerization initiator (D) as azobisisobutyronitrile (Wako Pure Chemical Industries, Ltd.) 0.3 part by weight, epoxy curing accelerator (E) as tetrabutylphosphonium Diethylphosphodithionate (Hishicolin PX-4ET, JP 0.3 parts by weight of Nippon Kagaku Kogyo Co., Ltd.) was mixed at room temperature (25 ° C.) to prepare a liquid resin composition solution. This resin solution is poured into a mold in which 3 mm and 1 mm thick silicone spacers are sandwiched between glass plates, and heated in an oven at 80 ° C., 100 ° C., 125 ° C., and 150 ° C. for 1 hour each. A cured product having a thickness of 3 mm and 1 mm was obtained.

(Example 2)
24 parts by weight of glycidyl methacrylate (Light Ester G, manufactured by Kyoeisha Chemical Co., Ltd.), 16 parts by weight of (3-methacryloxypropyl) tris (trimethylsiloxy) silane (Silaplane TM-0701T manufactured by Chisso Corporation), methyl hexahydro anhydride Phthalic acid (HN-5500, manufactured by Hitachi Chemical Co., Ltd.) 28 parts by weight, Azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) 0.3 parts by weight, Tetrabutylphosphonium diethylphosphodithionate (Hishicolin PX- 4ET, manufactured by Nippon Chemical Industry Co., Ltd.) 0.3 parts by weight, and as a monomer component (F) (meth) acrylate, 32 parts by weight of isobornyl acrylate (produced by Osaka Organic Chemical Co., Ltd.) at room temperature (25 ° C.). Mixing was performed to prepare a liquid resin composition solution. Using this resin solution, cured products having thicknesses of 3 mm and 1 mm were obtained in the same manner as in Example 1.

(Example 3)
18 parts by weight of glycidyl methacrylate (light ester G, manufactured by Kyoeisha Chemical Co., Ltd.), 18 parts by weight of (3-methacryloxypropyl) tris (trimethylsiloxy) silane (Silaplane TM-0701T manufactured by Chisso Corporation), methyl hexahydro anhydride 29 parts by weight of phthalic acid (HN-5500, manufactured by Hitachi Chemical Co., Ltd.), 0.2 parts by weight of azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.), tetrabutylphosphonium diethylphosphodithionate (Hishicolin PX- 4ET, manufactured by Nippon Chemical Industry Co., Ltd.) 0.3 parts by weight of glycidyl methacrylate (GMA) and (3-methacryloxypropyl) trimethylsilane (TRIS) as an epoxy group-containing (meth) acrylic copolymer of component (G) Copolymer (weight average molecular weight 10,000, Carboxymethyl equivalent 286, composition ratio of GMA and TRIS (weight) 1: 1) 35 parts by weight, were mixed at room temperature (25 ° C.), to prepare a resin composition solution of the liquid. Using this resin solution, cured products having thicknesses of 3 mm and 1 mm were obtained in the same manner as in Example 1.

Example 4
To 32 parts by weight of glycidyl methacrylate (Light Ester G, manufactured by Kyoeisha Chemical Co., Ltd.), 21 parts by weight of (3-methacryloxypropyl) tris (trimethylsiloxy) silane (Silaplane TM-0701T manufactured by Chisso Corporation), methyl hexahydro anhydride 36 parts by weight of phthalic acid (HN-5500, manufactured by Hitachi Chemical Co., Ltd.), 0.3 parts by weight of azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.), tetrabutylphosphonium diethylphosphodithionate (Hishicolin PX- 4ET, manufactured by Nippon Chemical Industry Co., Ltd.) 0.3 parts by weight, an acrylic reaction having a number average molecular weight of 6,000, having a methacryloyl group at one end and a main chain segment of methyl methacrylate as a polymerization reactive acrylic oligomer of component (H) Oligomer (AA6, manufactured by Toa Gosei Co., Ltd.) 11 parts by weight at room temperature (25 ° C.), to prepare a resin composition solution of the liquid. Using this resin solution, cured products having thicknesses of 3 mm and 1 mm were obtained in the same manner as in Example 1.

(Example 5)
As an epoxy group-containing (meth) acrylate of the monomer component (A), 30 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate (Cyclomer M100, manufactured by Daicel Chemical Industries, Ltd.), (3-methacryloxypropyl) tris (trimethylsiloxy) Silane (Silaplane TM-0701T manufactured by Chisso Corporation) 30 parts by weight, Methylhexahydrophthalic anhydride (HN-5500, manufactured by Hitachi Chemical Co., Ltd.) 25 parts by weight, Azobisisobutyronitrile (Wako Pure Chemical Industries, Ltd.) 0.3 parts by weight of tetrabutylphosphonium diethylphosphodithionate (Hishicolin PX-4ET, manufactured by Nippon Chemical Industry Co., Ltd.), 15 parts by weight of isobornyl acrylate (produced by Osaka Organic Chemical Industry Co., Ltd.) Parts at room temperature (25 ° C) Composition solution was adjusted. Using this resin solution, cured products having thicknesses of 3 mm and 1 mm were obtained in the same manner as in Example 1.

(Example 7)
35 parts by weight of glycidyl methacrylate (Light Ester G, manufactured by Kyoeisha Chemical Co., Ltd.), 35 parts by weight of (3-methacryloxypropyl) tris (trimethylsiloxy) silane (Silaplane TM-0701T manufactured by Chisso Corporation), methyl hexahydro anhydride 29 parts by weight of phthalic acid (HN-5500, manufactured by Hitachi Chemical Co., Ltd.), 1 part by weight of 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals) as a photo radical polymerization initiator, tetrabutylphosphonium 0.3 parts by weight of diethylphosphodithionate (Hishicolin PX-4ET, manufactured by Nippon Chemical Industry Co., Ltd.) was mixed at room temperature (25 ° C.) to prepare a liquid resin composition solution. The resin solution, a 3mm Atsuoyobi 1mm thick silicone spacer poured into a mold sandwiched by glass plates, using an extra-high pressure mercury lamp, irradiance 11.6 mW / cm ^2, an accumulated exposure amount 3000 mJ / cm ² Radical polymerization was performed. Furthermore, it heated at 100 degreeC, 125 degreeC, 150 degreeC, and the conditions for 1 hour each in oven, and obtained the resin cured material of 3 mm thickness and 1 mm thickness.

(Comparative Example 1)
47 parts by weight of glycidyl methacrylate (light ester G, manufactured by Kyoeisha Chemical Co., Ltd.), 53 parts by weight of methylhexahydrophthalic anhydride (HN-5500, manufactured by Hitachi Chemical Co., Ltd.), azobisisobutyronitrile (Wako Pure Chemical Industries, Ltd.) 0.4 parts by weight manufactured by Kogyo Co., Ltd. and 0.5 parts by weight of tetrabutylphosphonium diethyl phosphodithionate (Hishicolin PX-4ET, manufactured by Nippon Chemical Industry Co., Ltd.) are mixed at room temperature (25 ° C.) to obtain a liquid resin. A composition solution was prepared. Using this resin solution, cured products having thicknesses of 3 mm and 1 mm were obtained in the same manner as in Example 1.

(Comparative Example 2)
32 parts by weight of glycidyl methacrylate (light ester G, manufactured by Kyoeisha Chemical Co., Ltd.), 36 parts by weight of methylhexahydrophthalic anhydride (HN-5500, manufactured by Hitachi Chemical Co., Ltd.), azobisisobutyronitrile (Wako Pure Chemical Industries, Ltd.) Kogyo Co., Ltd.) 0.3 parts by weight, tetrabutylphosphonium diethyl phosphodithionate (Hishicolin PX-4ET, Nippon Chemical Industry Co., Ltd.) 0.4 parts by weight, isobornyl acrylate (Osaka Organic Chemical Co., Ltd.) 32 parts by weight were mixed at room temperature (25 ° C.) to prepare a liquid resin composition solution. Using this resin solution, cured products having thicknesses of 3 mm and 1 mm were obtained in the same manner as in Example 1.

  The compositions of Examples 1 to 7 and Comparative Examples 1 and 2 are summarized in Table 1.

The numbers in Table 1 are parts by weight, A1: glycidyl methacrylate, A2: 3,4-epoxycyclohexylmethyl methacrylate, B1: (3-methacryloxypropyl) trimethylsilane, B2: (3-acryloxypropyl) trimethylsilane, C: methylhexahydrophthalic anhydride, D1: azobisisobutyronitrile, E1: tetrabutylphosphonium diethylphosphodithionate, F: isobornyl acrylate, G: copolymer of MMA and TRIS, H: terminal of methacryloyl group An oligomer composed of methyl methacrylate segments of I: 1-hydroxycyclohexyl phenyl ketone.

  About the resin hardened | cured material obtained in the said Examples 1-7 and Comparative Examples 1 and 2, glass transition temperature, bending strength, light transmittance, and yellowing degree were measured by the method shown below.

  The glass transition temperature (Tg) was measured using a differential thermomechanical analyzer (TAS100 model manufactured by Rigak) by cutting out a 3 × 3 × 20 mm test piece from a 3 mm thick resin cured product. The thermal expansion of the sample was measured at a temperature elevation rate of 5 ° C./min, and Tg was determined from the inflection point of the thermal expansion curve.

  The bending strength was determined by cutting a 3 × 20 × 50 mm test piece and performing a bending test with a three-point support according to JIS-K-6911 using a three-point bending test apparatus (Instron 5548 type). The bending strength was calculated from 1). The distance between fulcrums was 24 mm, the crosshead moving speed was 0.5 mm / min, and the measurement temperature was room temperature (25 ° C.).

（式（１）中、σｆＢ：曲げ強さ（ＭＰａ）、Ｐ’：試験片が折れた時の加重（Ｎ）であ
り、Ｌ：支点間距離、Ｗ：試験片の幅、ｈ：試験片の厚さである。）

(In formula (1), σfB: bending strength (MPa), P ′: weight (N) when the test piece is broken, L: distance between fulcrums, W: width of test piece, h: test piece Is the thickness of.)

  The light transmittance and the yellowing degree were measured with a 1 mm-thick test piece using a spectrophotometer (Hitachi spectrophotometer V-3310). The transmittance was measured after curing (initial stage) and after standing at high temperature for 72 hours at 150 ° C. as an evaluation of heat discoloration. The yellowing degree (YI) indicating yellowishness was determined from the following equation (2) by determining the tristimulus value XYZ in the case of the standard light C using the measured transmission spectrum.

Mechanical properties of Examples 1 to 7 and Comparative Examples 1 and 2, that is, glass transition temperature, room temperature (25 ° C.
Table 2 shows the bending strength and optical characteristics, i.e., the light transmittance at a wavelength of 400 nm and the degree of yellowing after curing (initial) and after standing at high temperature.

  In each of Examples 1 to 7, the glass transition temperature is 140 ° C. or higher, excellent heat resistance, and the bending strength is as high as 60 MPa or more. Furthermore, it can be seen that the optical characteristics have high initial transmittance, small yellowing, little decrease in transmittance after standing at high temperature, and small change in yellowing. On the other hand, it can be seen that the optical properties after high-temperature treatment are inferior when silicone is not contained in the acrylic main chain by one-terminal (meth) acrylate-modified silicone oil as in Comparative Example 1 and Comparative Example 2.

Claims (9)

(Meth) acrylate containing an epoxy group as the monomer component (A), (3-acryloxypropyl) methylbis (trimethylsiloxy) silane, (3-methacryloxypropyl) methylbis (trimethylsiloxy) silane as the monomer component (B) , and ( 3-methacryloxypropyl) tris (trimethylsiloxy) silane selected from the group consisting of at least one (meth) acryl-modified silicone , containing an acid anhydride as an epoxy curing agent (C), and liquid at 25 ° C. Yes, a resin composition that cures by heating or light irradiation.   Furthermore, the resin composition of Claim 1 formed by containing a radical polymerization initiator (D) and an epoxy hardening accelerator (E).   The radical polymerization of the monomer component (A) and the monomer component (B) and the ionic polymerization of the monomer component (A) and the epoxy curing agent (C) both proceed by heating or light irradiation. 2. The resin composition according to 2.   Furthermore, the resin composition of any one of Claims 1-3 formed by containing (meth) acrylate as a monomer component (F).   Furthermore, the resin composition of any one of Claims 1-4 formed by containing the epoxy group containing (meth) acryl copolymer whose weight average molecular weight is 20,000 or less as a component (G).   Furthermore, the resin composition of any one of Claims 1-5 formed by containing a polymerization reactive acrylic oligomer as a component (H). A first liquid containing the monomer component (A) and the monomer component (B), and optionally containing one or more of the monomer component (F), the component (G) and the component (H); , curing agent for the epoxy (C), made by mixing the second solution containing the radical polymerization initiator (D) and the epoxy curing accelerator (E), according to claim cured by heating or light irradiation 2 The resin composition of any one of -6.   The optical member produced by hardening | curing the resin composition of any one of Claims 1-7.   Radical polymerization of the monomer component (A) and the monomer component (B), and optionally the monomer component (F) and / or the component (H) using the resin composition according to any one of claims 1 to 7. A method for producing an optical member, wherein the monomer component (A) and an epoxy curing agent (C), and optionally, component (G) are further ionically polymerized by subsequent heating.