JP2006307088A - Resin composition, optical member using the same and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition whose cured product has high optical transparency and excellent lightfastness, heat resistance and mechanical characteristics and which excels in storage stability; to provide an optical member which, using the resin composition, has high optical transparency and excellent lightfastness, heat resistance and mechanical characteristics; and to provide a method for preparing the optical member in a short time and simply. <P>SOLUTION: The resin composition comprises a (meth)acrylate containing an epoxy group as a monomer component (A), a silicone oil modified with a (meth)acrylate on its one terminal as a monomer component (B), an epoxy-modified silicone as a monomer component (C), and an acid anhydride as a curing agent (D) for the epoxy. The composition is a liquid at 25°C and hardens by heating or irradiation of light. <P>COPYRIGHT: (C)2007,JPO&INPIT

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.

  Further, in order to further improve the heat resistance and light resistance coloring property of the acrylic resin, an acrylate resin obtained by copolymerization of a silicone-containing acrylate monomer and an acrylate monomer is disclosed in Non-Patent Document 2, for example. The fraction of silicone acrylate that can be introduced from is limited. Moreover, it is guessed that cured | curing material physical property also tends to fall.

  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 “Journal of Applied Polymer Science” Vol. 56, (1995) p317-324.

  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 provides [1] an epoxy group-containing (meth) acrylate as the monomer component (A), a one-end (meth) acryl-modified silicone oil as the monomer component (B), an epoxy-modified silicone as the monomer component (C), and epoxy curing. It is a resin composition that contains an acid anhydride as the agent (D), is a 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 (E) and an epoxy curing accelerator (F).

  The present invention also provides [3] both radical polymerization of the monomer component (A) and the monomer component (B) and ionic polymerization of the monomer component (A), the monomer component (C) and the epoxy curing agent (D). Is the resin composition according to the above [1] or [2], which proceeds by heating or light irradiation.

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

  The present invention also provides [5] a first liquid containing the monomer component (A), the monomer component (B), and the monomer component (C), and optionally containing the monomer component (G), and the epoxy. The curing agent (D), the radical polymerization initiator (E) and the second liquid containing the epoxy curing accelerator (F) are mixed and cured by heating or light irradiation. It is a resin composition as described in [1]-[4].

  The present invention also provides [6] an optical member produced by curing the resin composition according to any one of [1] to [5].

  Moreover, this invention uses [7] the resin composition in any one of said [1]-[5], a monomer component (A) and a monomer component (B), and the monomer component (G) depending on the case. Is a method of producing an optical member, wherein the radical polymerization is performed by light irradiation, and the ion polymerization of the monomer component (A), the monomer component (C), and the epoxy curing agent (D) is performed by subsequent heating. .

  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., 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 the monomer component (C). As an epoxy-modified silicone, and an acid anhydride as an epoxy curing agent (D). In addition to this, it is preferable to contain a radical polymerization initiator (E) and an epoxy curing accelerator (F). In addition to this, it is preferable to contain (meth) acrylate as the monomer component (G).

  The resin composition of the present invention has an acrylic main chain 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, an acryl side chain epoxy group and an epoxy modified silicone (monomer (C) component) and an acid anhydride (epoxy curing agent (D)) are ionically polymerized to crosslink within and between the acrylic main chains. Further, the resin is cured by forming a crosslink by a silicone chain, and as a result, it is possible to achieve both excellent optical properties of the acrylic resin and the silicone resin and excellent heat resistance and mechanical properties of the epoxy resin. Moreover, when the component (G) which is an arbitrary component is 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).

  The radical polymerization of acrylate and the ionic polymerization of an epoxy group and an acid anhydride and the modification of the epoxy resin with acrylate are described in, for example, “Network Polymer” Vol. 24, N0.3 (2003) p148-155. However, these use an acrylate monomer and an epoxy monomer to 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 radical polymerization of an epoxy group-containing (meth) acrylate and one-terminal (meth) acryl-modified silicone oil, and the acrylic main chain epoxy is further formed. A cross-linked structure is formed in and between the acrylic main chain and between the main chains by ionic polymerization of the group and epoxy-modified silicone and acid anhydride, so that a cured resin product having uniform and high transparency and excellent cured material properties can be obtained. Can do. This is because by introducing silicone into the ester side chain of the acrylic main chain, even if an epoxy-modified silicone coexists to form a crosslink with an acid anhydride, a uniform cured product can be obtained without phase separation. Inferred.

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

  In addition, by including an epoxy group-containing (meth) acrylic copolymer in the composition of the present invention, 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 a uniform and high transparency can be obtained.

  Further, by including a polymerization-reactive acrylic oligomer in the composition of the present invention, an acrylic side chain can be further formed on the acrylic main chain, and a cured resin product having a uniform and high transparency with small curing shrinkage can be obtained.

  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).

  Although it does not specifically limit as a one terminal (meth) acryl modified silicone oil which is a monomer component (B) used by this invention, For example, (2-acryloxyethoxy) trimethylsilane, (3-acryloxypropyl) trimethoxysilane , (3-acryloxypropyl) trimethylsilane, (3-acryloxypropyl) dimethylmethoxysilane, (3-acryloxypropyl) methyldimethoxysilane, (3-acryloxypropyl) methylbis (trimethylsiloxy) silane, (2- (Methacryloxyethoxy) trimethylsilane, (3-methacryloxypropyl) trimethoxysilane, (3-methacryloxypropyl) trimethylsilane, (3-methacryloxypropyl) dimethylmethoxysilane, (3-methacryloxypropyl) methyl Silane, (3-methacryloxypropyl) methyl bis (trimethylsiloxy) silane, and among them (3-acryloxypropyl) trimethoxysilane, (3-methacryloxypropyl) trimethoxysilane are preferred.

  Although it does not specifically limit as an epoxy modified silicone which is a monomer component (C) used by this invention, For example, it is preferable that it is the polydimethylsiloxane of both terminal epoxy modification. Moreover, it is preferable that the epoxy equivalent of epoxy-modified silicone is not too large in view of compatibility with acrylates and acid anhydrides, and it is particularly preferably 1000 or less.

  The epoxy curing agent (D) used in the present invention is not particularly limited, but is an acid anhydride which is liquid at 25 ° C., for example, 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 (E) used in the present invention, any one that can be used for normal 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 photo radical polymerization, a radical photopolymerization initiator (H) is used instead of a radical thermal polymerization initiator such as the above-mentioned azo initiator or peroxide initiator. 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 (F) 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. .

  The (meth) acrylate that is the monomer component (G) used in the present invention is not particularly limited. 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 (G) may contain polyfunctional (meth) acrylate. Examples of the polyfunctional (meth) acrylate 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.

  Examples of the epoxy group-containing (meth) acrylic copolymer that can be used in the present invention include an epoxy group-containing (meth) acrylate listed as the monomer component (A) and a single terminal (meth) listed as the monomer component (B). ) Acrylic modified silicone oil, and in some cases, a copolymer of (meth) acrylate which is the monomer component (G). Therefore, the epoxy group-containing (meth) acrylic copolymer is a copolymer consisting of 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. It may be a coalescence 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 is soluble in the monomer components (A) and (B) and the epoxy curing agent (D), the molecular weight is preferably low, and the weight average molecular weight is It 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. In the epoxy group-containing (meth) acrylic copolymer, other monomers may be blended and copolymerized within a range not impairing the object of the present invention.

  The polymerization-reactive acrylic oligomer that can be used in the present invention is not particularly limited, but is preferably an acrylic oligomer containing one or more (meth) acryloyl groups. Monomer) 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 desirably 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 (E) used and the gelation temperature of the epoxy curing accelerator (F). Generally, since the half-life temperature of the radical polymerization initiator is lower than the gelation temperature of the epoxy curing accelerator, first, radical polymerization of (meth) acrylate proceeds, and (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) = 10: 90 to 60:40, 15:85 It is particularly preferable to blend so as to be ˜40: 60. When the ratio of the component (A) is less than 10, the crosslink density becomes too small, so that the heat resistance is lowered and tends to be brittle. On the other hand, when the ratio of the component (A) exceeds 60, the effect of the component (B) tends to be small.

  The blending amounts of the component (A) and the component (C) in the present invention are preferably blended so that the respective weight ratios are (A) :( C) = 90: 10 to 30:70, 90:10 It is particularly preferable to blend so as to be ˜50: 50. When the ratio of the component (A) is less than 30, the crosslink density becomes too small, so that the heat resistance 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 (C) tends to be small.

  The compounding amount of the epoxy curing agent (D) component in the present invention is 0.00 by the equivalent ratio (acid anhydride group / epoxy group) of the acid anhydride group to the epoxy group of the component (A) and the component (C). It is preferable to set it as 5-1.2. 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 tends to decrease.

  The blending amount of the radical polymerization initiator (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 in some cases the component (G). The content is preferably 0.1 to 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, it tends to be difficult to cure.

  The compounding amount of the epoxy curing accelerator (F) 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 this 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 parts by weight, it tends to be difficult to cure.

  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 10: 80-40: 60. Here, when the ratio of the component (G) is less than 10, the effect of the component (G) is small. On the other hand, if the ratio of the component (G) is greater than 50, the crosslinking density becomes too small and the heat resistance is lowered, and the effect of the component (B) tends to be reduced.

  In the present invention, the amount of the epoxy group-containing (meth) acrylic copolymer or the polymerization-reactive acrylic oligomer is preferably as it is large because curing shrinkage can be reduced. Less than parts by weight are appropriate.

  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 as the monomer component (B), and a monomer component (C ) An epoxy-modified silicone and an epoxy curing agent (D) as an acid anhydride, and optionally a radical polymerization initiator (E) and an epoxy curing accelerator (F), which are liquid at room temperature (25 ° C.) By curing or heating the resin composition, both radical polymerization of the component (A) and the component (B) and ionic polymerization of the component (A), the component (C), and the component (D) are advanced and cured. It is characterized by that. In addition, the resin composition may contain (meth) acrylate as the monomer component (G).

  As a form of a resin composition, (A) component, (B) component, (C) component, and (D) component, (E) component added as needed, (F) component, and (G) A resin solution in which components are mixed and prepared may be used, but the first solution may contain (A) component, (B) component, and (C) component, and may further contain (G) component, and (D) component. , (E) and the second liquid containing the component (F) can be separated to improve the storage stability of each, and by mixing the first liquid and the second liquid at the time of use. The resin composition of the present invention is obtained.

  In the method for producing an optical member using the resin composition of the present invention, the 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), and in some cases, the component (G) is performed by light irradiation, and then heated. It is also possible to carry out ionic polymerization of the component (A), the component (C) and the component (D).

  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
18 parts by weight of glycidyl methacrylate (Light Ester G, manufactured by Kyoeisha Chemical Co., Ltd.) as an epoxy group-containing (meth) acrylate of the monomer component (A), (3) as a one-terminal (meth) acrylate-modified silicone oil of the monomer component (B) -Methacryloxypropyl) trimethylsilane (Silane Plane TM-0701T manufactured by Chisso Corporation) 18 parts by weight, epoxy component-modified polydimethylsiloxane having an epoxy equivalent of 490 as an epoxy-modified silicone of monomer component (C) (KF-105 Shin-Etsu) Chemical Industry Co., Ltd.) 18 parts by weight, 28 parts by weight of methylhexahydrophthalic anhydride (HN-5500, manufactured by Hitachi Chemical Co., Ltd.) as an acid anhydride of epoxy curing agent (D), radical polymerization initiator (E ) As azobisisobutyronitrile (Wako) 0.3 parts by weight of Yaku Kogyo Co., Ltd., 0.3 parts by weight of tetrabutylphosphonium diethyl phosphodithionate (Hishicolin PX-4ET, manufactured by Nippon Chemical Industry Co., Ltd.) as an epoxy curing accelerator (F), monomer component (G 18 parts by weight of isobornyl acrylate (Osaka Organic Chemical Co., Ltd.) as a (meth) acrylate 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)
21 parts by weight of glycidyl methacrylate (light ester G, manufactured by Kyoeisha Chemical Co., Ltd.) as an epoxy group-containing (meth) acrylate of the monomer component (A), (3) as a one-terminal (meth) acrylate-modified silicone oil of the monomer component (B) -Methacryloxypropyl) trimethylsilane (Silaplane TM-0701T manufactured by Chisso Corporation) 21 parts by weight, epoxy-modified silicone of the monomer component (C) having an epoxy equivalent of 490, both ends epoxy-modified polydimethylsiloxane (KF-105 Shin-Etsu) Chemical Industry Co., Ltd.) 10 parts by weight, 27 parts by weight of methylhexahydrophthalic anhydride (HN-5500, manufactured by Hitachi Chemical Co., Ltd.) as an acid anhydride of epoxy curing agent (D), radical polymerization initiator (E ) As azobisisobutyronitrile (Wako) 0.3 parts by weight of Yaku Kogyo Co., Ltd., 0.3 parts by weight of tetrabutylphosphonium diethyl phosphodithionate (Hishicolin PX-4ET, manufactured by Nippon Chemical Industry Co., Ltd.) as an epoxy curing accelerator (F), monomer component (G ) Was mixed with 21 parts by weight of isobornyl acrylate (produced by Osaka Organic Chemical Co., Ltd.) 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.

(Example 3)
As the epoxy group-containing (meth) acrylate of the monomer component (A), 18 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate (Cyclomer M100, manufactured by Daicel Chemical Industries, Ltd.) and one terminal (meth) acrylate of the monomer component (B) 18-part by weight of (3-methacryloxypropyl) trimethylsilane (manufactured by Silaplane TM-0701T Chisso Co., Ltd.) as the modified silicone oil, and epoxy-modified polydimethyl at both ends having an epoxy equivalent of 490 as the epoxy-modified silicone of the monomer component (C) 18 parts by weight of siloxane (KF-105 Shin-Etsu Chemical Co., Ltd.), 28 parts by weight of methylhexahydrophthalic anhydride (HN-5500, manufactured by Hitachi Chemical Co., Ltd.) as an acid anhydride of epoxy curing agent (D), As radical polymerization initiator (E) 0.3 parts by weight of zobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.), tetrabutylphosphonium diethylphosphodithionate (Hishicolin PX-4ET, manufactured by Nippon Chemical Industry Co., Ltd.) as an epoxy curing accelerator (F) 0 .3 parts by weight, 18 parts by weight of isobornyl acrylate (manufactured by Osaka Organic Chemical Co., Ltd.) as the (meth) acrylate of the monomer component (G) are mixed at room temperature (25 ° C.), and a liquid resin composition solution is prepared. It 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 4
18 parts by weight of glycidyl methacrylate (Light Ester G, manufactured by Kyoeisha Chemical Co., Ltd.) as an epoxy group-containing (meth) acrylate of the monomer component (A), (3) as a one-terminal (meth) acrylate-modified silicone oil of the monomer component (B) -Methacryloxypropyl) trimethylsilane (Silane Plane TM-0701T manufactured by Chisso Corporation) 18 parts by weight, epoxy component-modified polydimethylsiloxane having an epoxy equivalent of 490 as an epoxy-modified silicone of monomer component (C) (KF-105 Shin-Etsu) Chemical Industry Co., Ltd.) 18 parts by weight, 28 parts by weight of methylhexahydrophthalic anhydride (HN-5500, manufactured by Hitachi Chemical Co., Ltd.) as an acid anhydride of epoxy curing agent (D), as a radical photopolymerization initiator 1-hydroxycyclohexylphenyl Ton (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.), tetrabutylphosphonium diethylphosphodithionate (Hishicolin PX-4ET, manufactured by Nippon Chemical Industry Co., Ltd.) as an epoxy curing accelerator (F) 0.3 weight Part, 18 parts by weight of isobornyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) as the (meth) acrylate of the monomer component (G) 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)
24 parts by weight of glycidyl methacrylate (light ester G, manufactured by Kyoeisha Chemical Co., Ltd.) as an epoxy group-containing (meth) acrylate of the monomer component (A), (3) as a one-terminal (meth) acrylate-modified silicone oil of the monomer component (B) -Methacryloxypropyl) trimethylsilane (Silaplane TM-0701T manufactured by Chisso Corporation) 24 parts by weight, methylhexahydrophthalic anhydride (HN-5500, Hitachi Chemical Co., Ltd.) as an acid anhydride of epoxy curing agent (D) 28 parts by weight, 0.3 parts by weight of azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) as radical polymerization initiator (E), and tetrabutylphosphonium diethylphosphodithionate as epoxy curing accelerator (F) (Hishicolin PX-4ET, Nippon Chemical Industry Co., Ltd. Product) 0.3 parts by weight, 24 parts by weight of isobornyl acrylate (manufactured by Osaka Organic Chemical Co., Ltd.) as the (meth) acrylate of the monomer component (G) is mixed at room temperature (25 ° C.) to obtain a liquid resin composition The product 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)
Both ends of 490 glycidyl methacrylate (light ester G, manufactured by Kyoeisha Chemical Co., Ltd.) as the epoxy group-containing (meth) acrylate of the monomer component (A) and 490 epoxy equivalents as the epoxy-modified silicone of the monomer component (C) 22 parts by weight of epoxy-modified polydimethylsiloxane (KF-105 Shin-Etsu Chemical Co., Ltd.) and methylhexahydrophthalic anhydride (HN-5500, manufactured by Hitachi Chemical Co., Ltd.) as an acid anhydride of epoxy curing agent (D) 34 parts by weight, 0.3 parts by weight of azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) as the radical polymerization initiator (E), tetrabutylphosphonium diethylphosphodithionate (Hishicolin) as the epoxy curing accelerator (F) PX-4ET, manufactured by Nippon Chemical Industry Co., Ltd.) 0.3 parts by weight, 22 parts by weight of isobornyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) as the (meth) acrylate of the nomer component (G) was 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 4 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, B: (3-methacryloxypropyl) trimethylsilane, C1: epoxy-modified silicone (epoxy equivalent = 490) , C2: epoxy-modified silicone (epoxy equivalent = 1750), D: methylhexahydrophthalic anhydride, E: azobisisobutyronitrile, F: tetrabutylphosphonium diethylphosphodithionate, G: isobornyl acrylate, H : 1-hydroxycyclohexyl phenyl ketone.

  About the resin hardened | cured material obtained in the said Examples 1-4 and Comparative Examples 1-2, the glass transition temperature, bending strength, the light transmittance, and the 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 temperatures were room temperature (25 ° C.) and high temperature (250 ° C.). When the displacement in the three-point bending test did not break even when the sample thickness was 40% or more of the sample thickness, it was evaluated as “no break”.

（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 4 and Comparative Examples 1 and 2, that is, glass transition temperature, bending strength at room temperature (25 ° C.) and 250 ° C., and optical properties, that is, after curing (initial) and after standing at high temperature. Table 2 shows light transmittance and yellowing degree at a wavelength of 400 nm.

  From Table 2, it can be seen that all of the cured resin products of Examples 1 to 4 have a glass transition temperature of 170 ° C. or higher, excellent heat resistance, and excellent bending strength under conditions of room temperature and high temperature. Further, with regard to the optical characteristics, it can be seen that the initial transmittance is high, the yellowing degree is small, the decrease in transmittance after leaving at high temperature is small, and the amount of change in yellowing degree is small. On the other hand, when the crosslinked structure by epoxy-modified silicone is not introduced as in Comparative Example 1, it can be seen that the strength at high temperature is inferior. Further, as in Comparative Example 2, if the silicone main chain does not contain silicone by the one-terminal (meth) acrylate-modified silicone oil, the epoxy-modified silicone is not compatible and a transparent cured product cannot be obtained.

Claims (7)

  Epoxy group-containing (meth) acrylate as monomer component (A), single-end (meth) acryl-modified silicone oil as monomer component (B), epoxy-modified silicone as monomer component (C), acid anhydride as epoxy curing agent (D) A resin composition comprising a product, liquid at 25 ° C., and cured by heating or light irradiation.   The resin composition according to claim 1, further comprising a radical polymerization initiator (E) and an epoxy curing accelerator (F).   Both radical polymerization of the monomer component (A) and the monomer component (B) and ion polymerization of the monomer component (A), the monomer component (C) and the epoxy curing agent (D) are heated or irradiated. The resin composition according to claim 1, which proceeds by   Furthermore, the resin composition of any one of Claims 1-3 formed by containing (meth) acrylate as a monomer component (G).   A first liquid containing the monomer component (A), the monomer component (B), the monomer component (C), and optionally the monomer component (G), and the epoxy curing agent (D). The said radical polymerization initiator (E) and the 2nd liquid containing the said epoxy hardening accelerator (F) are mixed, and it hardens | cures by heating or light irradiation of any one of Claims 1-4. Resin composition.   The optical member produced by hardening | curing the resin composition of any one of Claims 1-5.   Using the resin composition according to any one of claims 1 to 5, the monomer component (A) and the monomer component (B), and optionally radical polymerization of the monomer component (G) is performed by light irradiation, The manufacturing method of the optical member which performs ion polymerization of a monomer component (A), a monomer component (C), and the epoxy hardening | curing agent (D) by subsequent heating.