JP2009114372A - Polyfunctional epoxy silicone resin, manufacturing method thereof, and resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyfunctional epoxy silicone resin liquid at room temperature, having excellent pot life and storage stability, small hardening shrinkage, high hardness of a hardened product, no sticky surface, excellent heat resistance and UV resistance and suitable as a LED sealing resin. <P>SOLUTION: The polyfunctional epoxy silicone resin is obtained by condensing 10-70 wt.% silane monomer having three OR groups and 30-90 wt.% silane monomer having one epoxy group and two OR groups in the presence of water and a basic catalyst comprising an alkali metal carbonate or an alkaline earth metal carbonate, and carrying out a sealing reaction of a terminal alkoxy group and a terminal silanol group under an acidic condition using 10-90 wt.% silane compound having one OR group as a terminator. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polyfunctional epoxy silicone resin, a method for producing the same, and a thermosetting resin composition excellent in optical properties, hardness, strength, deflection, and heat resistance, which comprises a polyfunctional epoxy silicone resin obtained therefrom as an essential component. The present invention relates to a curable resin composition suitable for light-emitting diode (LED) sealing.

  Epoxy resins are mainly used in many applications in the paint, civil engineering, and electrical fields because of their excellent electrical properties, adhesiveness, heat resistance, and the like. In particular, aromatic epoxy resins such as bisphenol A type diglycidyl ether, bisphenol F type diglycidyl ether, phenol novolac type epoxy resin, and cresol novolac type epoxy resin have water resistance, adhesiveness, mechanical properties, heat resistance, and electrical insulation. It is widely used in combination with various curing agents because of its excellent economic efficiency. However, since these resins contain an aromatic ring, they are easily deteriorated by ultraviolet rays or the like, and there are restrictions in use in fields where weather resistance and light resistance are required.

  In the field of blue and white LED devices, when an epoxy resin composition containing an aromatic is used as a sealing material, the resin is deteriorated by the light emitted from the LED element and the heat emitted from the LED element, and the yellow color changes over time. There is a problem that the luminance is lowered.

  Patent Document 1 discloses an epoxy resin composition for electrical / electronic materials containing a hydrogenated epoxy resin obtained by hydrogenating an aromatic epoxy resin and a curing agent. Patent Document 2 discloses a curable epoxy resin composition containing a hydrogenated epoxy resin obtained by hydrogenating an aromatic epoxy, a cycloaliphatic epoxy resin, and a curing agent. Patent Documents 3 and 4 disclose an epoxy resin composition containing an alicyclic epoxy resin obtained by oxidizing a cyclic olefin. Patent Document 5 discloses a hydrogenated epoxy resin having an epoxy equivalent of 230 to 1000 g / eq. Obtained by hydrogenating an aromatic epoxy resin, or an epoxy equivalent obtained by reacting this hydrogenated epoxy resin with a polyvalent carboxylic acid. Is proposed an epoxy resin composition for LED encapsulation containing an alicyclic epoxy resin obtained by epoxidizing an epoxy resin having a cyclic olefin of 230 to 1000 g / eq. And an acid anhydride curing agent or a cationic polymerization initiator. ing.

  On the other hand, Patent Document 6 discloses a resin composition using an epoxy compound having silicone with a main chain having excellent weather resistance. Patent Document 7 discloses a resin composition for LED encapsulation obtained by addition reaction and curing of a silicone compound having a hydrosilyl group and a silicone compound having a vinyl group. Patent Document 8 discloses an optical semiconductor encapsulant resin composition using an epoxy compound having a main chain of silicone having a molecular weight of 500 to 2100 and an epoxy equivalent of 180 to 230. However, these epoxy silicones have high flexibility derived from the silicone skeleton, but have the drawback that the hardness of the cured product is low and the surface tends to be sticky.

  Patent Document 9 discloses an epoxy group-containing polyhedral oligomeric silicate compound having a cage structure and a structure in which a part of the apex of the cage structure is cleaved. Patent Document 10 discloses a modified polysiloxane compound having an epoxy group in a side chain. Although these epoxy silicone resins have improved stickiness, they have not been sufficient in terms of long-term heat resistance and strength. Moreover, as a method for synthesizing these siloxane compounds containing an epoxy group, a method in which a silicone resin having a hydrosilyl group and an epoxy compound having a double bond are subjected to an addition reaction is disclosed, but this addition reaction is extremely exothermic. In addition, the reaction is difficult to control due to the disadvantage that it easily gels due to a side reaction between the hydrosilyl group and the epoxy group. Further, there has been a problem that the metal or metal compound used in the addition reaction grows into colloidal particles to easily cause a coloring phenomenon, and it is difficult to ensure transparency. Furthermore, the hydrosilyl oligomer used as a raw material tends to cause a disproportionation reaction with water and alcohol, and as a result, there is a problem that the generated hydrogen gas tends to be a problem of storage safety.

Japanese Patent No. 3537119 Japanese Patent No. 3415047 JP-A-9-213997 JP 2000-196151 A JP 2003-277473 A JP-A-10-110102 Japanese Patent No. 3523096 JP 2005-171021 A Special table 2003-510337 gazette JP 2004-289102 A

  As for the epoxy resin composition, since the hardness of the cured product is high, it is excellent in handling properties. In low-power white LED sealing applications, the required durability is obtained, so it is often used in low-power applications. Yes. However, high-power LEDs tend to cause discoloration due to an increase in light emission and heat generation, and thus have a disadvantage that it is difficult to obtain a sufficient lifetime. In addition, there is a problem that the sealing material is likely to crack due to a sudden temperature change caused by turning off and on. In addition, due to the recent shortening of the light emission wavelength of LEDs, there is a problem that the light emission output is likely to be lowered due to discoloration when continuously used, so further improvement in heat resistance and light resistance is required. Yes. Recently, LED encapsulants based on silicone resins with excellent weather resistance have been developed in place of epoxy resins. Resin compositions by addition reaction of hydrosilyl groups and olefins, and silicone resins having epoxy groups Has been reported on a resin composition obtained by curing using a curing agent.

  However, most of the silicone resins and epoxy resins having silicone as the main chain have high flexibility derived from the silicone skeleton, but the hardness of the cured product is low, the surface tends to be sticky, and the strength is low. Has disadvantages. For this reason, transparency deterioration due to adhesion of dust or the like is likely to occur, and handling at the time of LED manufacturing is difficult, and the manufacturing method, configuration, design, and use are limited. In addition, a resin having a high hardness silicone skeleton has improved handling properties, but has a disadvantage that cracks are likely to occur due to a sudden temperature change during lighting and extinction.

  As described above, even if a silicone resin having excellent weather resistance is used as a base, it is not possible to obtain a resin that completely satisfies both the economic properties and the physical properties required for the LED sealing material, and has sufficient hardness. There is a need for materials that have excellent UV resistance, such as potting and dispensing methods, mass productivity, handling properties, good pot life and storage stability similar to those of epoxy resins.

  In view of these current conditions, the present inventors are liquids that are easy to handle at room temperature, have good pot life and storage stability, have little cure shrinkage, have high hardness of cured products, and have no stickiness on the surface, heat resistance We have intensively studied resins suitable for LED encapsulants with excellent UV resistance. The present inventors paid attention to alkoxysilane containing an epoxy ring in the molecule, and increased the molecular weight of alkoxysilane without opening the epoxy ring, and repeatedly studied materials that do not produce water or alcohol as a by-product during curing. As a result, dialkoxysilane containing an epoxy group in the molecule and trifunctional alkoxysilane having no epoxy group are allowed to coexist and polymerize without damaging the epoxy group using water and a basic catalyst, and an end-capping material is used. By inactivating the remaining alkoxy groups and silanol groups, the inventors have found a production method for obtaining a polyfunctional epoxy silicone resin having excellent storage stability and having substantially only an epoxy group as a crosslinkable substituent. And by using the resin obtained by the production method for the composition for LED sealing material, there is no stickiness at room temperature when it is made into a cured product, it is excellent in strength, has a relatively small linear expansion coefficient, and cure shrinkage. It has been found that it has little transparency, transparency, excellent heat resistance and light resistance, and has led to the present invention.

  That is, in the present invention, the silane monomer represented by the following general formula (1) is 10 to 70% by weight with respect to a total of 100% by weight of all monomers and terminal terminators, and the epoxy silane monomer represented by the general formula (2). 30-90% by weight is combined with 100% by weight of the total monomers and end terminators in the presence of water and a basic catalyst selected from alkali metal carbonates or alkaline earth metal carbonates, and then the general formula Using the terminal terminator represented by (3), the terminal alkoxy group and the terminal silanol group are subjected to a sealing reaction under acidic conditions using 10 to 90% by weight based on 100% by weight of all monomers and the terminal terminator. Is a method for producing a polyfunctional epoxy silicone resin.

（式中、R₁はそれぞれ独立に炭素数１〜３の炭化水素基を示し、R₂は炭素数１〜１０の鎖状若しくは環状の脂肪族炭化水素基又はフェニル基を示す。）

（式中、R₁はそれぞれ独立に炭素数１〜３の炭化水素基を示し、R₂は炭素数１〜１０の鎖状若しくは環状の脂肪族炭化水素基又はフェニル基を示し、E₁はエポキシ基を有する炭素数１〜２０のエポキシ基含有基を示し、エポキシ基を構成する酸素原子の他にエーテル結合性又はエステル結合性酸素原子を１〜２個有していてもよい。）

（式中、R₁は炭素数１〜３の炭化水素基を示し、R₂はそれぞれ独立に炭素数１〜１０の鎖状若しくは環状の脂肪族炭化水素基又はフェニル基を示す。）

(In the formula, each R ₁ independently represents a hydrocarbon group having 1 to 3 carbon atoms, and R ₂ represents a chain or cyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms or a phenyl group.)

(In the formula, each R ₁ independently represents a hydrocarbon group having 1 to 3 carbon atoms, R ₂ represents a chain or cyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms or a phenyl group, and E ₁ represents An epoxy group-containing group having 1 to 20 carbon atoms having an epoxy group is shown, and may have 1 to 2 ether-bonded or ester-bonded oxygen atoms in addition to the oxygen atom constituting the epoxy group.

(In the formula, R ₁ represents a hydrocarbon group having 1 to 3 carbon atoms, and R ₂ independently represents a chain or cyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms or a phenyl group.)

（式中、R₂はそれぞれ独立に炭素数１〜１０の鎖状若しくは環状の脂肪族炭化水素基、又はフェニル基を示す。E₁はエポキシ基を有する炭素数１〜２０のエポキシ基含有基を示し、エポキシ基を構成する酸素原子の他にエーテル結合性又はエステル結合性酸素原子を１〜２個有していてもよい。０．１≦ａ≦０．７、０．３≦ｂ≦０．９、０．１≦ｃ≦０．６である。ここで、ａ＋ｂ＋ｃは０．５〜１の範囲であることが好ましい。） It is preferable that the polyfunctional epoxy silicone resin obtained by the manufacturing method of the said polyfunctional epoxy silicone resin has each unit represented by following General formula (4).

(In the formula, each R ₂ independently represents a linear or cyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms or a phenyl group. E ₁ is an epoxy group-containing group having 1 to 20 carbon atoms having an epoxy group. In addition to the oxygen atom constituting the epoxy group, it may have 1 or 2 ether- or ester-bonded oxygen atoms: 0.1 ≦ a ≦ 0.7, 0.3 ≦ b ≦ 0.9 and 0.1 ≦ c ≦ 0.6, where a + b + c is preferably in the range of 0.5 to 1.)

In the method for producing the polyfunctional epoxy silicone resin, the terminal alkoxy group and the terminal silanol group are sealed using a phosphoric acid catalyst. In general formula (2), E ₁ is 2- (3,4- Epoxy cyclohexyl) ethyl group, or epoxy equivalent of 180 to 1000 (g / eq.), Polystyrene equivalent weight average molecular weight of 500 to 10,000, and ratio of weight average molecular weight to epoxy equivalent (weight molecular weight / epoxy equivalent). Satisfying one or more of 2 or more is an excellent method for producing a polyfunctional epoxy silicone resin.

  Moreover, this invention is a polyfunctional epoxy silicone resin obtained with the manufacturing method of the said polyfunctional epoxy silicone resin. Further, the present invention is a polyfunctional epoxy silicone resin composition comprising: a) an epoxy resin curing agent, a curing accelerator or a curing catalyst, and b) an antioxidant. It is.

  Hereinafter, embodiments of the present invention will be described in detail.

  In the production method of the present invention, the above silane monomer, epoxy silane monomer and terminal terminator are used as essential reaction raw materials. The monomers (total monomers) containing these silane monomers and the end terminator are collectively referred to as a reaction raw material.

Since the silane monomer (trifunctional silane monomer) represented by the general formula (1) used in the production method of the present invention contains three OR groups in one molecule and can form three bonds, condensation The molecule produced by Moreover, the epoxy silane monomer (bifunctional epoxy silane monomer) represented by the general formula (2) contains an epoxy group and two OR groups in the molecule, forms two bonds, and is formed by condensation. An epoxy group can be introduced therein. By using these two types of monomers, a branched polyfunctional epoxy silicone resin can be obtained. The degree of branching can be controlled by changing the use ratio of the silane monomer and the epoxy silane monomer, and the epoxy equivalent can be controlled by changing the use ratio of the epoxy silane monomer. If necessary, a silane monomer represented by Si (OR) ₄ (tetrafunctional silane monomer) can be used. In this case, four bonds can be formed. Can do. Further, a trifunctional epoxy silane monomer containing an epoxy group and three OR groups, a bifunctional alkoxysilane monomer having no epoxy group, and the like can be used as the silane monomer. The OR group is a hydrolyzable alkoxy group or the like.

  When the amount of the silane monomer represented by the general formula (1) is within the range of 10 to 70% by weight of the reaction raw material, it becomes a polyfunctional epoxy silicone whose main chain is developed in a branched shape, and has mechanical strength and heat resistance. A cured product can also be obtained. Preferably, it is 15 to 65% by weight. More preferably, it is 20 to 40% by weight. When the amount of the silane monomer used is less than 10%, the amount of linear epoxy silicone increases and the mechanical properties deteriorate. If it exceeds 70% by weight, the epoxy concentration in the resin is low, and it tends to be soft when cured, which is not preferable.

  The usage-amount of the epoxysilane monomer represented by General formula (2) is the range of 30 to 90 weight% of a reaction raw material. When the amount of the epoxy silane monomer used is less than 30% by weight, the epoxy concentration in the resin is low, and it tends to be soft when cured. On the other hand, if it exceeds 90% by weight, the resin linear structure increases and the mechanical strength and heat resistance are lowered. Preferably it is 35-85 weight%, More preferably, it is 40-80 weight%.

  The amount of the terminal terminator represented by the general formula (3) is 10 to 90% by weight of the reaction raw material, but the amount of the monomer represented by the general formulas (1) and (2) which is the first stage reaction. The amount actually consumed depends on the condensation state, and the excess end-stopper is removed by subsequent processing. When the amount of the terminal terminator used is less than 10% by weight, the terminal OR group remaining in the first stage reaction cannot be sufficiently sealed, and the storage stability is lowered. When it exceeds 90% by weight, the amount of the surplus end terminator that does not participate in end termination increases.

  Although the reaction raw material used as the basis of the calculation of the said usage amount consists of monomers and a terminal terminator as mentioned above, the silane monomer represented by General formula (1), the epoxysilane monomer represented by General formula (2) And the end terminator represented by General formula (3) is used as a reaction raw material, and it is good to make the sum total 100 weight%. However, as described above, other silane monomers such as a tetrafunctional silane monomer can be used as a reaction raw material. When other silane monomers are used as reaction raw materials, a silane monomer represented by the general formula (1), an epoxy silane monomer represented by the general formula (2), and a terminal stopper represented by the general formula (3) are used. It is preferable to use 50% by weight or more, preferably 80% by weight or more of the entire reaction raw material, and 50% by weight or less of other silane monomers.

R ₁ in the general formulas (1) to (3) is each independently a hydrocarbon group having 1 to 3 carbon atoms. Examples of such substituents include a methyl group, an ethyl group, a propyl group, and an isopropyl group. A methyl group is preferable from the viewpoint of reactivity.

R < ₂ > of General formula (1)-(3) shows the hydrocarbon group or phenyl group which may have a C1-C10 cyclic structure. Examples of such hydrocarbon groups include linear hydrocarbons such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, octyl group, isooctyl group, decyl group, cyclohexyl group, etc. An aromatic hydrocarbon group such as an aliphatic hydrocarbon group or a phenyl group is not limited to these, and they may be the same or different from each other. Preferred R ₂ is a methyl group or a phenyl group in view of physical properties of the cured product and availability.

E ₁ in the general formula (2) represents an epoxy group-containing group having 1 to 20 carbon atoms having an epoxy group inside, and has 1 to 2 ether-bonding or ester-bonding oxygen atoms inside. Also good. Examples of such an epoxy group-containing group include a propyl glycidyl ether group, an acryloyl glycidyl ether group, a methacryloyl glycidyl ether group, a 2- (3,4-epoxycyclohexyl) ethyl group, and a 4- (2-methylethynyl) cyclohexene oxide group. 2 or more types may be used as necessary. A preferred epoxy compound is a 2- (3,4-epoxycyclohexyl) ethyl group from the viewpoints of economy, availability, and physical properties when cured.

  Examples of the end-capping agent represented by the general formula (3) include trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triphenylsilanol, and the like. good. A preferred compound is trimethylmethoxysilane because of end-capping reactivity and availability.

  The silane monomer containing an epoxy group represented by the general formula (2) is obtained by a known method by adding a corresponding silane monomer having a Si-H group and an epoxy compound having a double bond by using a noble metal catalyst. Obtainable.

  Examples of the silane monomer having a Si-H group include methyldimethoxysilane, methyldiethoxysilane, ethyldimethoxysilane, ethyldiethoxysilane, propyldimethoxysilane, propyldiethoxysilane, butyldimethoxysilane, butyldiethoxysilane, and hexyldimethoxy. Examples include silane, hexyldiethoxysilane, cyclohexyldimethoxysilane, and phenyldiethoxysilane. Two or more types may be used as necessary. The preferred compound is methyldimethoxysilane from the viewpoints of economy, availability, and physical properties when cured.

  Examples of the epoxy compound having a double bond include allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, 4-vinylcyclohexene oxide, and 4- (2-methylethynyl) cyclohexene oxide. If necessary, two or more kinds are used. Also good. A preferred compound is 4-vinylcyclohexene oxide from the viewpoint of economy, availability, and physical properties when cured.

  The noble metal catalyst, catalyst addition amount, reaction solvent, concentration, temperature conditions, etc. used for this reaction are not particularly limited as long as they are known conditions, and the reaction can be carried out by methods preferred by those skilled in the art.

  In the production method of the present invention, the basic catalyst used for the condensation reaction is at least one selected from alkali metal carbonates and alkaline earth metal carbonates. By using these catalysts, the condensation reaction can be performed without the epoxy ring opening as described above.

  Examples of such basic catalysts include lithium carbonate, lithium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, rubidium carbonate, rubidium bicarbonate, cesium carbonate, cesium bicarbonate, magnesium carbonate, carbonate Examples include magnesium hydrogen carbonate, calcium carbonate, calcium hydrogen carbonate, strontium carbonate, strontium hydrogen carbonate anhydrides and hydrates thereof, and two or more of them may be used as necessary. Preferred compounds are sodium carbonate and potassium carbonate.

  The basic catalysts may be used alone or in advance in a solvent to be dissolved, and then charged into the reaction system. Although there is no restriction | limiting in particular about the usage-amount of a basic catalyst, Usually 0.0001-10 mol% with respect to a total of 100 mol% of the monomer represented by General formula (1) and (2), Preferably 0.001-1 mol %. In the production method of the present invention, it is possible to use other silane monomers other than the monomers represented by the general formulas (1) and (2). Calculated including monomer. In the following description, the total of monomers is understood as described above.

  In the method for producing a polyfunctional epoxy silicone resin of the present invention, the amount of water used in the condensation reaction is not particularly limited, but is usually based on the total mol of monomers represented by the general formulas (1) and (2). 0.001 to 10 times mol, preferably 0.01 to 5 times mol.

Many of the OR ₁ groups (typically referred to as alkoxy groups because they are alkoxy groups) by the condensation reaction (first stage reaction) become high molecular weight as -O- groups. However, some remain at the terminal as alkoxy groups or in the form of OH groups. Therefore, the condensation reaction is followed by the next reaction (second stage reaction).

  When the terminal alkoxy group or terminal silanol group after the condensation reaction is sealed, a resin excellent in storage stability can be obtained by performing the terminal blocking reaction under acidic conditions using an acidic catalyst. In particular, by using a phosphoric acid catalyst (including a phosphoric acid derivative) as an acidic catalyst, the end-capping reaction can be performed without opening the epoxy ring as described above, and the resin has excellent storage stability. Can be obtained.

  Examples of the phosphoric acid catalyst include hypophosphorous acid, phosphorous acid, pyrophosphoric acid, fluorophosphoric acid, orthophosphoric acid, metaphosphoric acid, polyphosphoric acid, ultrapolyphosphoric acid, and a part of hydrogen is alkali metal, alkaline earth metal, ammonium Examples include acidic compounds that are salts with ions and the like, and two or more of them may be used as necessary. Preferred compounds are phosphoric acid, metaphosphoric acid, and polyphosphoric acid.

  Each of the above catalysts may be dissolved alone or in advance in a solvent to be dissolved, and then charged into the reaction system. If the inside of the reaction system becomes acidic, the use ratio of the above catalyst is not particularly limited, but in addition to the amount of acid neutralizing the basic catalyst added during the condensation reaction, 0.0001 to 1 mol%, preferably 0.001 to 0.5 mol% is used.

  The timing at which the end-capping agent is added is not particularly limited as long as the scope and effect of the present invention are not impaired. The end-capping agent may be charged into the system after performing a condensation reaction until it reaches a viscosity and molecular weight that is preferable to those skilled in the art, or after adding a part during the condensation reaction for the purpose of adjusting the molecular weight, acidic conditions You may take the form which throws in the rest after making it lower.

  In the end capping reaction, the end capping reaction proceeds even if it is added alone, but it is preferable to add additional water in order to promote the reaction. At this time, the ratio of water used is in the range of 0.01 to 10 mol, preferably 0.1 to 3 mol, relative to 1 mol of the end-capping agent.

  In the method for producing a polyfunctional epoxysilicone resin of the present invention, the condensation reaction and end-capping reaction can be carried out without solvent, but from the viewpoint of reaction control, it is preferable to use a diluting solvent that does not adversely influence the reaction. Examples of the diluting solvent include aliphatic hydrocarbons such as hexane, heptane, cyclohexane, methylcyclohexane, and ethylcyclohexane, aliphatic ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone, benzene, and toluene. , Aromatics such as ortho-xylene, meta-xylene, para-xylene, chlorobenzene, dichlorobenzene, aliphatic amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, dioxane, diethylene glycol Examples include ethers such as dimethyl ether and triethylene glycol dimethyl ether. Two or more of these organic solvents may be selected and used as a mixed solvent.

  The reaction temperature in the condensation reaction and the end-capping reaction is not particularly limited, but is usually 20 ° C to 150 ° C, preferably 30 ° C to 90 ° C. Below 20 ° C, the reaction is very slow and not economical. Moreover, when it becomes 150 degreeC or more, reaction control will become difficult, such as gelatinizing.

  Moreover, if it is a grade which does not impair the effect of this invention, after performing a condensation reaction using together the trifunctional alkoxysilane which has an epoxy group, and the tetrafunctional or bifunctional alkoxysilane which does not have an epoxy group, it is terminal. A sealing reaction may be performed. These monomers also serve as reaction raw materials. When these monomers are used as reaction raw materials, they are used as reaction raw materials for condensation reactions. The amount used is preferably in the above-described range.

  Examples of the trifunctional alkoxysilane having an epoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- Examples include (3,4-epoxycyclohexyl) ethyltriethoxysilane, but are not limited thereto.

  Examples of the tetrafunctional alkoxysilane include tetraethoxysilane.

  Examples of the bifunctional alkoxysilane having no epoxy group include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, di-n-butyldimethoxysilane, and di-n. -Bifunctional alkoxysilane monomers such as butyldiethoxysilane, di-i-butyldimethoxysilane, di-i-butyldimethoxysilane, dihexyldimethoxysilane, cyclohexylmethyldimethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane and the like are necessary. Two or more kinds may be used depending on the case.

  As for the epoxy equivalent of the polyfunctional epoxy resin to manufacture, it is good that an epoxy equivalent is 180-1000 (g / eq.). A polyfunctional epoxy silicone resin having an epoxy equivalent of less than 180 is practically difficult to obtain, and a resin of 1000 or more is not preferred because the number of epoxy groups in the resin is low, and it tends to be soft when cured. The epoxy equivalent is preferably in the range of 200 to 900, more preferably 220 to 600. The polyfunctional epoxy silicone resin is required to have a weight average molecular weight (weight average molecular weight in terms of polystyrene, expressed as Mw) of 500 to 10,000, and particularly preferably 1,000 to 6,000. When Mw is less than 500, the degree of condensation is small, and the effect of the present invention cannot be obtained when a cured product is obtained. On the other hand, when it exceeds 10,000, the resulting resin has a high viscosity and is difficult to handle. Further, it is not preferable because it is difficult to obtain the effects of the present invention, such as being very easily broken even when cured.

  After completion of the second stage reaction, it may be purified by performing treatments such as solvent removal, water washing, and drying as necessary. Although the polyfunctional epoxy silicone resin of this invention is obtained by the said manufacturing method, a manufacturing method is not limited.

The polyfunctional epoxy silicone resin of the present invention includes a silane monomer represented by the general formula (1), an epoxy silane monomer represented by the general formula (2) and a terminal stopper represented by the general formula (3) as raw materials. When used, it becomes a polyfunctional epoxy silicone resin having each unit represented by the following general formula (4).

Wherein, R ₂ has the same meaning as R ₂ in formula (1) and (2), E ₁ has the same meaning as E ₁ of the general formula (2). Each unit is generated in turn from a silane monomer represented by the general formula (1), an epoxysilane monomer represented by the general formula (2), and an end-stopper represented by the general formula (3). Therefore, the amount (weight ratio) a, b and c of each unit is represented by the silane monomer represented by the general formula (1), the epoxysilane monomer represented by the general formula (2) and the general formula (3), respectively. Although the total amount of the end terminator often does not react, it often takes a value less than the amount used. When the above three components are used as reaction raw materials and the amount is the above, a + b + c = 1, 0.1 ≦ a ≦ 0.7, 0.3 ≦ b ≦ 0.9, 0.1 ≦ c ≦ 0.6 It is good to become.

  In the general formula (4), when a is 0.1 to 0.7, a polyfunctional epoxy silicone having a branched main chain is obtained, and a sufficient cross-linked structure is obtained. High light resistance, mechanical strength and heat resistance Can be obtained. When a is smaller than 0.1, many linear or cyclic polyfunctional epoxy silicone resins are obtained, and the cured product tends to be inferior in heat resistance and mechanical strength. On the other hand, when a is larger than 0.7, the epoxy concentration in the resin becomes low, and when it is made into a cured product, it tends to be soft. Preferably, 0.15 ≦ a ≦ 0.6. More preferably, 0.2 ≦ a ≦ 0.4. Further, b is preferably 0.3 to 0.8. Even when b is smaller than 0.3, the epoxy concentration in the resin is low, and it tends to be soft when cured. On the other hand, when b is larger than 0.9, the resin linear structure is increased and the mechanical strength and heat resistance are likely to be lowered. Preferably 0.4 ≦ b ≦ 0.7. c is preferably from 0.1 to 0.6. If c is less than 0.1, the storage stability tends to be poor, and if c is 0.6 or more, the epoxy functional group density tends to decrease and mechanical properties tend to decrease. More preferably, 0.1 ≦ c ≦ 0.5. In addition, also when using another monomer etc. as a reaction raw material, it is good that the range of said a, b, and c exists in the said range. When a reaction raw material such as another monomer is used, it has a corresponding unit, and if the amount is d (may be the sum of a plurality of units), a + b + c + d = 1. .

  Next, the resin composition using the polyfunctional epoxy silicone resin of the present invention will be described.

  The polyfunctional epoxy silicone resin composition of the present invention comprises a polyfunctional epoxy silicone resin, a curing agent having reactivity with an epoxy group, and a curing accelerator or a curing catalyst effective for reaction with a curing agent, if necessary. An inhibitor and other additives can be blended to form a thermosetting resin composition. This polyfunctional epoxy silicone resin composition gives a cured resin having excellent transparency by heat treatment.

  As the curing agent, various compounds can be applied as long as they are known as curing agents for epoxy resins. For example, organic amine compounds, dicyandiamide and derivatives thereof, imidazoles and derivatives thereof such as 2-methylimidazole and 2-ethyl-4-methylimidazole, bisphenol A, bisphenol F, brominated bisphenol A, naphthalenediol, 4,4′- Dihydric phenol compounds such as biphenol, novolak resin or aralkylphenol resin obtained by condensation reaction of phenol or naphthols with formaldehyde or xylylene glycols, succinic anhydride, maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride Hydrazide such as methylated hexahydrophthalic anhydride, nadic anhydride, hydrogenated nadic anhydride, trimellitic anhydride, pyromellitic anhydride and other acid anhydride compounds, and adipic hydrazide Can apply things, it may be used two or more, if necessary. Particularly preferred curing agents for obtaining the effects of the present invention are acid anhydride cured products, and more preferred are hexahydrophthalic anhydride, methylated hexahydrophthalic anhydride, and hydrogenated nadic anhydride.

  As the curing accelerator, various compounds can be applied as long as they are known as curing accelerators for epoxy resins. Examples include tertiary amines and salts thereof, imidazoles and salts thereof, organic phosphine compounds and salts thereof, and organic metal salts such as zinc octylate and tin octylate. Two or more kinds may be used as necessary. . In particular, preferred curing accelerators for obtaining the effects of the present invention are tertiary amines and salts thereof, organic phosphine compounds and salts thereof, more preferably organic phosphine compounds and salts thereof.

  The polyfunctional epoxy silicone resin composition of the present invention can provide a thermosetting resin composition having excellent transparency and hardness even when a cationic curing catalyst, particularly a thermocationic curing catalyst, is used.

  As the thermal cationic curing catalyst, various compounds can be applied as long as they are known. For example, an onium salt compound composed of an organic cation molecule having a sulfonium cation, an iodonium cation, and an anionic species having Lewis acidity such as a tetrafluoroboron anion, a hexafluorophosphorus anion, a hexafluoroarsenic anion, and a hexafluoroantimony anion. Etc. Among these, it is desirable to use an onium salt composed of an organic cation molecule having a sulfonium cation and a hexafluoroantimony anion.

  The resin composition is characterized by adding a hindered phenol compound as an essential component as an antioxidant. By adding this compound, the thermal coloring of the cured product can be reduced even when exposed to a high temperature environment for a long time.

  As the antioxidant, various compounds can be applied as long as they are known. For example, 2,6-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-tert-butyl-p-ethylphenol, stearyl-β- (3,5-di-tert-butyl-4-4 Monophenols such as -hydroxyphenyl) propionate, 2,2-methylenebis (4-methyl-6-tert-butylphenol), 2,2-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'- Bisphenols such as thiobis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl- 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydro Shifeniru) propionate] polymer phenols such as methane and the like, may be used two or more.

Among these, it is possible to improve the thermal coloring of the polyfunctional epoxy silicone resin composition of the present invention by adding a hindered phenol compound containing a spiroglycol skeleton, for example, a compound represented by the formula (5). It becomes.

  In addition, the spiroglycol skeleton containing hindered phenol compound is available, for example with the name of Sumilizer GA-80 (made by Sumitomo Chemical Co., Ltd.) and Adeka Stub AO-80 (made by ADEKA Co., Ltd.).

  Although the amount of the hindered phenol added is not particularly limited, it can be added by adding 0.001% to 20%, preferably 0.01% to 5% to the polyfunctional epoxy silicone resin composition. Thermal coloring of the polyfunctional epoxy silicone resin composition of the invention can be improved.

  In the polyfunctional epoxy silicone resin composition, it is also advantageous to use an ester skeleton-containing thioether compound antioxidant together with a spiroglycol skeleton-containing hindered phenol compound. By using these two kinds of antioxidants in combination, thermal coloring of a cured product obtained by further curing a polyfunctional epoxy silicone resin composition than when a spiroglycol type hindered phenol type antioxidant is used alone. Can be reduced.

  As the ester skeleton-containing thioether compound-based antioxidant, various compounds can be selected as long as they are known. For example, dilauryl 3,3′-dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-dilauryl 3,3′-thiodipropionate, distearyl 3,3′-dilauryl 3,3′-thio Examples include dipropionate and pentaerythrityltetrakis (3-laurylthiopropionate), and two or more kinds may be used as necessary. A preferred ester skeleton-containing thioether compound-based antioxidant is pentaerythrityl tetrakis (3-lauryl thiopropionate), which is available under the name Sumilizer TP-D (Sumitomo Chemical Co., Ltd.).

  The addition amount of the ester skeleton-containing thioether compound-based antioxidant is not particularly limited, but is 0.001% to 20%, preferably 0.01% to 5% with respect to the polyfunctional epoxy silicone resin composition. By adding, the thermal coloring of the polyfunctional epoxy silicone resin composition can be improved.

  In addition, an antioxidant containing a phosphorus atom may be used in combination as long as the effects of the present invention, such as handling at room temperature, storage stability, low curing shrinkage, high hardness, heat resistance, and UV resistance, are not impaired. Various compounds can be applied as long as they are known. For example, triphenyl phosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-tert-butyl 4-hydroxybenzyl) -9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the like. Two or more of these antioxidants may be used as necessary.

  Moreover, the polyfunctional epoxy silicone resin of this invention can also be mix | blended with another thermosetting resin, and can also be set as a composition. As a resin used together with the polyfunctional epoxy silicone resin of the present invention as a thermosetting resin, an unsaturated polyester resin, a thermosetting acrylic resin, a thermosetting amino resin, a thermosetting melamine resin, a thermosetting urea resin, Examples include, but are not limited to, thermosetting urethane resins, thermosetting oxetane resins, thermosetting epoxy / oxetane composite resins, and the like.

  The polyfunctional epoxy silicone resin obtained by the production method of the present invention is a liquid that is easy to handle at room temperature, has good storage stability, the cured product is hard, has little curing shrinkage, and has no stickiness on the surface of the cured product. Excellent in strength, deflection and transparency, heat resistance and UV resistance. Accordingly, the polyfunctional epoxy silicone resin and thermosetting resin composition of the present invention are used in the fields of electronic materials such as paints, coating agents, printing inks, resist inks, adhesives, semiconductor encapsulants, molding materials, casting materials, and the like. Useful in the field of electrical insulation materials. In particular, it is useful in the LED field and is excellent as a thermosetting resin composition for LED encapsulation.

Next, the present invention will be specifically described based on examples, but the present invention is not limited to the following examples unless it exceeds the gist.
A method for measuring physical properties of the cured product is shown below.

1) Measurement of glass transition temperature (Tg) of cured product The glass transition temperature of the cured product was measured in the range of 30 ° C to 270 ° C using a thermal stress strain measuring device TMA / SS120U manufactured by Seiko Denshi Kogyo Co., Ltd. The temperature at which the expansion coefficient changed was defined as the glass transition temperature. The heating rate was 5 ° C./min.

2) Measurement of linear expansion coefficient below the glass transition point.
Measured in the range of 30 ° C to 270 ° C using a thermal stress strain measuring device TMA / SS120U manufactured by Seiko Electronics Industry Co., Ltd., and the linear expansion coefficient was calculated from the slope of a straight line connected at two points of 40 ° C and 60 ° C. did. The heating rate was 5 ° C./min.

3) Initial transmittance of cured product Using a self-recording spectrophotometer U-3410 manufactured by Hitachi, Ltd., a transmittance of 400 nm of a cured product having a thickness of 1 mm was measured.

4) Measurement of UV resistance Using a weather resistance tester QUV manufactured by Q Panel Co., Ltd., a 4 mm thick cured product, the transmittance at 400 nm after UV irradiation for 600 hours was measured in the same manner as the initial transmittance. A UVA of 340 nm was used for the QUV lamp, and the black panel temperature was 55 ° C.

5) Measurement of initial heat resistance The cured product was exposed to an environment of 150 ° C., and the transmittance at 400 nm after 72 hours was measured in the same manner as the initial transmittance.

6) Measurement of long-term heat resistance The cured product was exposed to an environment of 150 ° C., and the transmittance at 400 nm after 400 hours was measured in the same manner as the initial transmittance.

7) Surface stickiness When the cured product was placed in a polyethylene bag at room temperature and brought into contact with the surface, the cured product was judged to be sticky if it adhered to the polyethylene bag.

8) Measurement of hardness The surface hardness of the cured product at room temperature was measured using a hardness meter TYPE-D manufactured by Teclock Co., Ltd.

9) Cured product after removing the mold When the mold was removed, the uniformity of the cured product and cracking of the cured product due to curing shrinkage were visually determined. ○: Uniform cured product. (Triangle | delta): Although the shape of a metal mold | die is maintained, the crack has arisen in hardened | cured material. X: The shape of the mold was not maintained and the resin was cracked.

10) Bending and deflection characteristic test In accordance with JIS-7171, 80 mm × 10 mm × 4 mm test pieces were used to measure bending elastic modulus, bending strength, and bending deflection by an autograph (manufactured by Shimadzu Corporation).

Synthesis example 1
156 parts by weight (1.25 mol) of 4-vinylcyclohexene oxide and 0.18 part by weight of platinum catalyst supported on carbon (3% supported product) were added to four 500 mL units equipped with a thermometer, a cooling pipe, a nitrogen introducing pipe and a stirring blade. It put into the mouth separable flask. After heating up to 80 degreeC, 115 weight part of methyldimethoxysilane was dripped over 3 hours. After completion of the dropping, stirring was continued for 3 hours. The reaction solution was added dropwise to a 0.1 N sodium hydroxide / methanol solution, and after confirming that no gas was generated, the obtained brown filtrate was distilled under reduced pressure, under reduced pressure of 135 ° C. and 1 mmHg. The component to be distilled out was taken out by fractional distillation. In this way, 135 parts by weight of a colorless and transparent epoxy silane monomer in which E ₁ of the general formula (2) is represented by a 2- (3,4-epoxycyclohexyl) ethyl group was obtained. The epoxy equivalent of this epoxy silane monomer is 232 g / eq. Met.

Example 1
100 parts by weight (0.435 mol) of the epoxysilane monomer obtained in Synthesis Example 1, 86 parts by weight of phenyltrimethoxysilane (0.435 mol), 79 parts by weight of dioxane, 7 parts by weight of water, 9.67 parts by weight of 5% sodium carbonate Parts (amount of water added, 0.926 mol in total) were charged into a 1 L four-necked separable flask equipped with a thermometer, a cooling tube, a nitrogen introducing tube, and a stirring blade. This solution was heated to 80 ° C. while stirring, and the reaction was continued for 3 hours while refluxing methanol as a by-product. After confirming the disappearance of the raw material on GPC, 19.1 parts by weight of a 20% phosphoric acid aqueous solution and 136 parts by weight (1.30 mol) of trimethylmethoxysilane were added, and the reaction was continued at 55 ° C. for 3 hours. After 200 parts by weight of toluene was added for dilution, washing with water was repeated using 120 parts by weight of water until the aqueous layer became neutral. The organic layer was taken out, and the solvent was distilled off using an evaporator under a reduced pressure of 65 ° C. and 80 mmHg, followed by vacuum drying for 30 minutes under a reduced pressure of 5 mmHg with a vacuum pump while maintaining the internal temperature. In this way, 81 parts by weight of a colorless and transparent polyfunctional epoxy silicone resin (ES1) into which 2- (3,4-epoxycyclohexyl) ethyl group was introduced was obtained. The epoxy equivalent of this resin is 373 g / eq. Met.

Example 2
100 parts by weight (0.435 mol) of the epoxysilane monomer obtained in Synthesis Example 1, 21.5 parts by weight (0.109 mol) of phenyltrimethoxysilane, 52 parts by weight of dioxane, 2.7 parts by weight of water, 5% potassium carbonate The same as in Example 1 except that 8.72 parts by weight (amount of water added, 0.634 mol in total), 13.4 parts by weight of 5% phosphoric acid aqueous solution, and 103 parts by weight (0.992 mol) of trimethylmethoxysilane were used. The operation was performed to obtain 77 parts by weight of a colorless and transparent polyfunctional epoxy silicone resin (ES2) into which 2- (3,4-epoxycyclohexyl) ethyl group was introduced. The epoxy equivalent of this resin is 275 g / eq. Met.

Example 3
100 parts by weight (0.435 mol) of the epoxysilane monomer obtained in Synthesis Example 1 as a reaction raw material, 21.5 parts by weight (0.109 mol) of phenyltrimethoxysilane, and 14.8 parts by weight of methyltrimethoxysilane (0. 109 mol) and using 50 parts by weight of dioxane as a solvent, the same operation as in Example 2 was performed to obtain 84 parts by weight of a colorless and transparent polyfunctional epoxy silicone resin (ES3). The epoxy equivalent of this resin is 242 g / eq. Met.

Comparative Example 1
100 parts by weight (0.435 mol) of the epoxysilane monomer obtained in Synthesis Example 1, 43 parts by weight of dioxane, 1.5 parts by weight of water, 9.7 parts by weight of 5% sodium carbonate (amount of water added, 0.623 mol in total) Was charged into a separable flask. This solution was heated to 80 ° C. while stirring, and the reaction was continued for 3 hours while refluxing methanol as a by-product. After confirming the disappearance of the raw material on GPC, 4.3 parts by weight of a 20% phosphoric acid aqueous solution and 81 parts by weight (0.78 mol) of trimethylmethoxysilane were added, and the reaction was continued at 55 ° C. for 3 hours. The following was processed in the same manner as in Example 1 to obtain 81 parts by weight of a linear, colorless and transparent polyfunctional epoxy silicone resin (ES4). The epoxy equivalent of this resin is 251 g / eq. Met.

Comparative Example 2
130 parts by weight (1.05 mol) of 4-vinylcyclohexene oxide, 0.213 parts by weight of a carbon-supported platinum catalyst (3% supported product, manufactured by NP Chemcat Co., Ltd.), thermometer, cooling pipe, nitrogen introduction pipe And put into a 500 mL four-necked separable flask equipped with a stirring blade. To this solution, methyl hydrogen silicone oil (theoretical Si-H equivalent 64 g / eq.) Was added dropwise over 3 hours. When the internal temperature was raised from room temperature to 40 ° C., the reaction solution turned into a soft gel.

Comparative Example 3
37 parts by weight (0.30 mol) of 4-vinylcyclohexene oxide, 0.1 parts by weight of a carbon-supported platinum catalyst (3% supported product, manufactured by N.E. Chemcat Co., Ltd.), thermometer, cooling pipe, nitrogen introduction pipe, It was put into a 500 mL 4-neck separable flask equipped with a stirring blade. When this solution was heated to 50 ° C. and methylhydrogen-dimethylsilicone oligomer (theoretical Si—H equivalent 245 g / eq.) Was added dropwise, the reaction solution turned into a soft gel when 13 parts by weight of the solution was added dropwise. .

Comparative Example 4
100 parts by weight (0.435 mol) of the epoxysilane monomer obtained in Synthesis Example 1, 43 parts by weight of dioxane, 10.8 parts by weight of water, 0.37 parts by weight of 35% concentrated hydrochloric acid (the amount of water added, 0.623 mol in total) Was introduced into a 1 L four-necked separable flask equipped with a thermometer, a cooling tube, a nitrogen introducing tube, and a stirring blade. When this solution was heated to 80 ° C. and stirred for 3 hours and subjected to GPC measurement, the raw material silane monomer hardly caused a condensation reaction.

Comparative Example 5
In Example 1, except that 2.8 parts by weight of 5% aqueous sodium hydroxide solution was used instead of 9.67 parts by weight of 5% sodium carbonate and the total amount of water was 0.926 mol, Example 1 The reaction (first stage reaction) was carried out in the same manner as described above, and after 3 hours, the reaction product became a sticky amorphous product. Since this amorphous product was insoluble in trimethylmethoxysilane and toluene, the desired polyfunctional epoxy silicone resin could not be obtained.

Comparative Example 6
100 parts by weight (0.435 mol) of the epoxysilane monomer obtained in Synthesis Example 1, 86 parts by weight of phenyltrimethoxysilane (0.435 mol), 79 parts by weight of dioxane, 7 parts by weight of water, 9.67 parts by weight of 5% sodium carbonate Parts (amount of water added, 0.926 mol in total) were charged into a 1 L four-necked separable flask equipped with a thermometer, a cooling tube, a nitrogen introducing tube, and a stirring blade. The solution was heated to 80 ° C. while stirring, and the reaction was continued for 6 hours while refluxing methanol as a by-product. After 200 parts by weight of toluene was added for dilution, washing with water was repeated using 120 parts by weight of water until the aqueous layer became neutral. The organic layer was taken out, and the solvent was distilled off using an evaporator under a reduced pressure of 65 ° C. and 80 mmHg, followed by vacuum drying for 30 minutes under a reduced pressure of 5 mmHg with a vacuum pump while maintaining the internal temperature. In this way, 80 parts by weight of a colorless and transparent polyfunctional epoxy silicone resin (ES5) into which 2- (3,4-epoxycyclohexyl) ethyl group was introduced was obtained. The epoxy equivalent of this resin is 240 g / eq. Met.

Viscosity η, epoxy equivalent, number average molecular weight Mn, weight average molecular weight Mw (all in terms of polystyrene) of polyfunctional epoxy silicone resins ES1 to ES5 obtained in Examples 1 to 3 and Comparative Examples 1 and 6, Table 1 shows the nonvolatile content and 25 ° C. viscosity η, epoxy equivalent, number average molecular weight Mn, and weight average molecular weight Mw of the resin after standing for 1 hour in an environment of 125 ° C. at atmospheric pressure as a storage stability determination means. . Note that EEW is an abbreviation for epoxy equivalent. Except for ES5 which was not subjected to ES5 terminal termination treatment in Comparative Example 6, there was no significant difference in molecular weight and EEW before and after treatment at 125 ° C.

Examples 4-7
The polyfunctional epoxy silicone resins (ES1 to 3) obtained in Examples 1 to 3 were subjected to a ratio of epoxy equivalent to acid anhydride equivalent using methylated hexahydrophthalic anhydride (acid anhydride equivalent 168 g / eq.). = 1: 1, mixed well, and then added 0.5 wt% of the composition as a curing accelerator, tetra-n-butylphosphonium o, o'-diethyl phosphorodithionate, to give a polyfunctional epoxy silicone A resin composition was obtained. This composition was vacuum degassed and cured in a mold at 100 ° C. for 4 hours and further at 140 ° C. for 12 hours to prepare a resin plate having a thickness of 1 mm.

Example 8
A polyfunctional epoxy was prepared in the same manner as in Example 4 except that 0.5% of the composition was added as an antioxidant, spiroglycol skeleton-containing hindered phenolic compound Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.). A silicone resin composition was obtained, and then a resin plate having a thickness of 1 mm was prepared.

Example 9
As an antioxidant, 0.1% of GA-80 and 0.3% of an ester skeleton-containing thioether compound lyzer TP-D (manufactured by Sumitomo Chemical Co., Ltd.) were added to the composition as in Example 4. Thus, a polyfunctional epoxy silicone resin composition was obtained, and then a 1 mm thick resin plate was prepared.

Comparative Example 7
Using the polyfunctional epoxy silicone resin (ES4) obtained in Comparative Example 1, the same operation as in Examples 4 to 7 was performed to obtain a polyfunctional epoxy silicone resin composition, and then a 1 mm thick resin plate was obtained. Created.

Comparative Example 8
Except for using 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (epoxy resin C), which is an alicyclic epoxy resin, in place of the polyfunctional epoxy silicone resin, the same as Example 4 Work was performed to obtain an epoxy resin composition, and then a resin plate having a thickness of 1 mm was prepared.

Comparative Example 9
An epoxy resin composition was obtained in the same manner as in Example 4 except that a diglycidyl ether compound (epoxy resin H) of hydrogenated bisphenol A was used instead of the polyfunctional epoxy silicone resin, and then a 1 mm thick resin plate It was created.

Comparative Example 10
An epoxy resin composition was prepared in the same manner as in Example 4 except that a cage-type silsesquioxane compound having an alicyclic epoxy group at the apex (EP0408: manufactured by Hybrid Plastics) was used instead of the polyfunctional epoxy silicone resin. Then, a resin plate having a thickness of 1 mm was prepared.

Comparative Example 11
Instead of a polyfunctional epoxy silicone resin, an epoxy equivalent obtained by addition reaction of methylhydrogen-dimethylsiloxane copolymer (Si-H equivalent: 92 g / eq.) And 4-vinylcyclohexene oxide is 217 g / eq. An epoxy resin composition was obtained in the same manner as in Example 4 except that an epoxy-modified polysiloxane resin (ESP1) containing about 20 alicyclic epoxies in one molecule was used. A 1 mm resin plate was produced.

  72 hours in the glass transition temperature, initial transmittance, UV resistance, surface stickiness, hardness (Shore D), shape of the cured product after removing the mold, and 150 ° C. environment. Table 2 shows changes in the shape of the cured product after being left standing.

Examples 9-11
3-methyl-2-butyltetramethylene sulfonium hexafluoroantimonate, which is a thermal cationic curing catalyst, with respect to 100 parts by weight of the polyfunctional epoxy silicone resins (ES1 to 3) obtained in Examples 1 to 3. (Product name: Adeka Opton CP-77 manufactured by Asahi Denka Kogyo Co., Ltd.) 0.5 part was added and mixed well to obtain a polyfunctional epoxy silicone resin composition. This composition was vacuum degassed and cured in a mold at 65 ° C. for 2 hours, at 100 ° C. for 4 hours, and further at 140 ° C. for 12 hours to prepare a resin plate having a thickness of 4 mm.

Comparative Example 12
An epoxy resin composition was obtained in the same manner as in Example 9 except that 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (epoxy resin C) was used instead of the polyfunctional epoxy silicone resin. Then, a resin plate having a thickness of 4 mm was prepared.

Comparative Example 13
An epoxy resin composition was obtained in the same manner as in Example 9 except that a diglycidyl ether compound of hydrogenated bisphenol A (epoxy resin H) was used instead of the polyfunctional epoxy silicone resin, and then a resin plate having a thickness of 4 mm was obtained. Created.

Comparative Example 14
Thermal cationic curing catalyst in the same manner as in Example 9 except that a cage-type silsesquioxane compound having an alicyclic epoxy group at the apex (EP0408: manufactured by Hybrid Plastics) was used instead of the polyfunctional epoxy silicone resin. However, the viscosity was high and could not be mixed.

  Table 3 shows the initial transmittance, light resistance, hardness (Shore D), and the shape of the cured product after removal of the mold of the resin plate-shaped cured products obtained in Examples 9 to 11 and Comparative Examples 12 and 13.

Claims (7)

Formula (1),

(In the formula, each R ₁ independently represents a hydrocarbon group having 1 to 3 carbon atoms, and R ₂ represents a chain or cyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms or a phenyl group.)
10 to 70% by weight of the silane monomer represented by general formula (2) with respect to a total of 100% by weight of all monomers and terminal terminators,

(In the formula, each R ₁ independently represents a hydrocarbon group having 1 to 3 carbon atoms, R ₂ represents a chain or cyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms or a phenyl group, and E ₁ represents An epoxy group-containing group having 1 to 20 carbon atoms having an epoxy group is shown, and may have 1 to 2 ether-bonded or ester-bonded oxygen atoms in addition to the oxygen atom constituting the epoxy group.
The presence of a basic catalyst selected from water and alkali metal carbonate or alkaline earth metal carbonate, with the epoxysilane monomer represented by the formula: Condensation under, then general formula (3),

(In the formula, R ₁ represents a hydrocarbon group having 1 to 3 carbon atoms, and R ₂ independently represents a chain or cyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms or a phenyl group.)
A terminal alkoxy group and a terminal silanol group are subjected to a sealing reaction under acidic conditions using 10 to 90% by weight of a terminal stopper represented by To produce a polyfunctional epoxy silicone resin. Multifunctional epoxy silicone resin is represented by the general formula (4)

(In the formula, each R ₂ independently represents a linear or cyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms or a phenyl group. E ₁ is an epoxy group-containing group having 1 to 20 carbon atoms having an epoxy group. In addition to the oxygen atom constituting the epoxy group, it may have 1 or 2 ether- or ester-bonded oxygen atoms: 0.1 ≦ a ≦ 0.7, 0.3 ≦ b ≦ The manufacturing method of the polyfunctional epoxy silicone resin of Claim 1 which has a unit represented by 0.9 and 0.1 <= c <= 0.6.).   The manufacturing method of the polyfunctional epoxy silicone resin of Claim 1 which performs sealing reaction of a terminal alkoxy group and a terminal silanol group using a phosphoric acid catalyst. The method for producing a polyfunctional epoxy silicone resin according to claim 1 or 2, wherein in the general formula (2), E ₁ is a 2- (3,4-epoxycyclohexyl) ethyl group.   The epoxy equivalent is 180 to 1000 (g / eq.), The weight average molecular weight in terms of polystyrene is 500 to 10,000, and the ratio of weight average molecular weight to epoxy equivalent (weight molecular weight / epoxy equivalent) is 2 or more. The manufacturing method of the polyfunctional epoxy silicone resin in any one.   The polyfunctional epoxy silicone resin obtained by the manufacturing method of the polyfunctional epoxy silicone resin in any one of Claims 1-4.   A polyfunctional epoxy silicone resin composition comprising: a) an epoxy resin curing agent, a curing accelerator or a curing catalyst, and b) an antioxidant in the polyfunctional epoxy silicone resin according to claim 5. .