JP2009203258A - Curable resin composition comprising epoxy silicone resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition that has low elasticity, strengths and transparency and is excellent in heat resistance and light resistance. <P>SOLUTION: The curable resin composition comprises as essential ingredients (A) an epoxy silicone resin which is represented by general formula (1) and has an epoxy equivalent of 150-2,000 g/eq, (B) an acid anhydride and (C) a curing accelerator. In the formula, R<SB>1</SB>is a 1-10C hydrocarbon group; R<SB>2</SB>is a 1-20C hydrocarbon group optionally containing an ether oxygen atom inside; E<SB>1</SB>is an epoxy group-containing group containing an epoxy group bonded via a group containing an isocyanuric ring skeleton; Z is a bivalent organic group optionally bearing a heteroatom inside; and m and n are each independently an integer of 0-100. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a thermosetting resin composition having an epoxy silicone resin having a linear siloxane bond as an essential component, excellent in optical properties, hardness, strength, low elasticity, deflection, and heat resistance. LED) It relates to a curable resin composition suitable for 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, if an epoxy resin composition containing an aromatic is used as a sealing material, the resin deteriorates due to 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 decreases.

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. 3523098 JP 2004-099751 A

  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. In Patent Document 5, an epoxy resin obtained by reacting a hydrogenated epoxy resin obtained by hydrogenating an aromatic epoxy resin with a polyvalent carboxylic acid and having an epoxy equivalent of 230 to 1000 g / eq. And a cyclic olefin are epoxidized. The obtained alicyclic epoxy resin is disclosed, and an epoxy resin composition for LED encapsulation containing the alicyclic epoxy resin and an acid anhydride curing agent or a cationic polymerization initiator is disclosed.

  On the other hand, Patent Document 6 discloses a resin composition using an epoxy compound having a silicone compound having excellent weather resistance in the main chain. 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 a silicone compound in which an isocyanuric acid compound having an epoxy group and a vinyl group and a silicone compound are added, and isocyanuric acid having an epoxy group is introduced into the side chain.

  As for the epoxy resin composition, the hardness of the cured product obtained from the epoxy resin composition is excellent, so it has excellent handling properties. In low-power white LED sealing applications, the required durability can be obtained. It is used. However, high-power LEDs are prone to 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 order to prevent discoloration due to an increase in calorific value, an epoxy resin that exhibits a high glass transition temperature is used, but such an epoxy resin is highly elastic and has lower strength and deflection than a normal epoxy resin and is lit off. There is also a problem that the sealing material is likely to be cracked due to a rapid temperature change due to. In addition, due to the recent shortening of the emission wavelength of LEDs, there are also problems such as the occurrence of discoloration and continuous reduction in light emission output when used continuously. For this reason, the sealing material is required to have high strength and toughness as well as further improvement in heat resistance and light resistance.

  In addition, electronic materials such as semiconductor encapsulants other than LEDs, printed wiring boards, and insulating materials are required to have thinner packages and larger areas. Resins used therefor also have heat resistance, toughness, and high strength. In some cases, low elasticity is also required.

  Recently, LED encapsulants based on silicone resins with excellent weather resistance have been developed in place of epoxy resins. Resin compositions based on 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, many epoxy resins having a silicone resin or silicone compound in the main chain have high flexibility derived from the silicone skeleton, but the hardness of the cured product is low and the surface tends to be sticky, and the strength is high. Has low 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 silicone skeleton having high hardness has improved handling properties, but has problems such as strength and deflection, and is prone to cracking due to a sudden temperature change during lighting and extinction. .

  Thus, even if a silicone resin having excellent weather resistance is used as a base, it has not been obtained that completely satisfies the physical properties required for LED encapsulants, and has sufficient hardness, strength, and deflection, There is a demand for materials that have excellent heat resistance and UV resistance, have mass productivity and handling properties similar to epoxy resins, and can be obtained at an economical price.

  In view of these current conditions, the present inventors have earnestly pursued a resin composition for an LED encapsulant that has a cured product with high hardness, no stickiness on the surface, excellent heat resistance and UV resistance, and has both strength and deflection. investigated. The inventors of the present invention have a linear siloxane bond as a structural unit that develops heat resistance, UV resistance and deflection, a ring structure composed of an organic group as a structural unit that develops hardness and strength, and handling that the epoxy resin has. Attention was focused on an epoxy silicone resin having an epoxy group at the terminal as a structural unit for developing the phenotype. As a result of repeated examination of materials, there is no stickiness at normal temperature when cured, low elasticity, strength and deflection, low cure shrinkage, transparency, excellent heat resistance and light resistance The present inventors have found a curable resin composition that is suitable for use in fastening and useful for other electronic materials such as semiconductor sealing materials and printed wiring boards, and has led to the present invention.

（式中、R₁は炭素数１〜１０の炭化水素基を表し、R₂は炭素数１〜２０の炭化水素基を表し、内部にエーテル性酸素原子を含んでいても良い。Ｅ₁はイソシアヌル環骨格を含む基を介して結合するエポキシ基を有するエポキシ基含有基であり、Ｚは内部にヘテロ原子を有していてもよい２価の有機基を表す。ｍ及びｎは独立に０〜１００の数を表す。）
（Ｂ） 酸無水物、及び
（Ｃ） 硬化促進剤
を含むことを特徴とする硬化性樹脂組成物である。 That is, the present invention includes the following components:
(A) Represented by the general formula (1), the epoxy equivalent is 150 to 2000 g / eq. Epoxy silicone resin, which is

(In the formula, R ₁ represents a hydrocarbon group having 1 to 10 carbon atoms, R ₂ represents a hydrocarbon group having 1 to 20 carbon atoms, and may contain an etheric oxygen atom therein. E ₁ represents An epoxy group-containing group having an epoxy group bonded through a group containing an isocyanuric ring skeleton, Z represents a divalent organic group which may have a hetero atom inside, and m and n are independently 0. Represents a number of ~ 100.)
A curable resin composition comprising (B) an acid anhydride and (C) a curing accelerator.

  Moreover, this invention is a hardened | cured material obtained by heat-hardening said curable resin composition.

3) 一般式（１）中のＺが、一般式（３）で表される上記の硬化性樹脂組成物。

A preferred embodiment of the present invention will be described below.
1) Said curable resin composition which is m = 0 in General formula (1).
2) The curable resin composition as described above, wherein E ₁ in the general formula (1) is represented by the general formula (2).

3) Said curable resin composition by which Z in General formula (1) is represented by General formula (3).

4) Furthermore, said curable resin composition containing the following component.
(D) Epoxy resin or epoxy compound having two or more epoxy groups
5) Component (D) is an epoxy resin derived from phenols, an epoxy compound derived from an olefin compound containing a ring structure, an epoxy compound having an isocyanuric skeleton, or a polyfunctional epoxy silicone represented by general formula (5) Said curable resin composition which is at least 1 type chosen from resin.
(R ₃ SiO _3/2 ) _k (R ₄ R ₅ SiO) _j (Me ₃ SiO _1/2 ) _i (5)
(In formula, R < ₃ > -R < ₅ > is a C1-C20 hydrocarbon group which may contain the epoxy group independently, and may have 1-3 etheric oxygen atoms inside. However, one or more of R _{3 to} R ₅ always contain an epoxy group, and R ₄ and R ₅ do not have an epoxy group at the same time, i to k represent a molar ratio, i + j + k = 1, (It is a number satisfying 0 <k <1, 0 <j <1, 0 <i <0.75.)
6) Said curable resin composition whose weight ratio of (A) component and (D) component is (A) :( D) = 1-95: 99-5.

  The thermosetting resin composition of the present invention has thermosetting properties, and the cured product is hard, has little curing shrinkage, has no stickiness on the surface of the cured product, is excellent in strength, deflection, and transparency, and has heat resistance. Excellent in light resistance and light resistance. Therefore, the thermosetting resin composition of the present invention is useful in the fields of electronic materials such as paints, coating agents, printing inks, resist inks, adhesives, semiconductor encapsulants, molding materials, casting materials, and electrical insulating materials. It is. In particular, it is useful in the LED field and is excellent as a thermosetting resin composition for LED encapsulation.

Hereinafter, embodiments of the present invention will be described in detail.
The curable resin composition of this invention contains the said (A) epoxy silicone resin, (B) acid anhydride, and (C) hardening accelerator as an essential component. Hereinafter, the epoxy silicone resin is also referred to as component (A), the acid anhydride as component (B), and the curing accelerator as component (C). In addition, it is understood that the epoxy resin and epoxy compound as used in this specification may have the same meaning. Therefore, an epoxy resin or an epoxy compound may be used in a meaning that represents both.

  The epoxy silicone resin that is an essential component of the curable resin composition of the present invention is represented by the above general formula (1), and has an epoxy equivalent of 150 to 2000 g / eq. It is.

  When the epoxy equivalent is in the above range, a cured product having sufficient hardness, strength and deflection and excellent in heat resistance and UV resistance can be obtained. Epoxy equivalent is 150 g / eq. If it is less than 1, the linear siloxane bond is not sufficiently present in the resin, and the effect of the present invention cannot be obtained in terms of the toughness of the cured product. Epoxy equivalent is 2000 g / eq. On the other hand, when the amount exceeds the above, there are too many linear siloxane bonds in the resin, and the cured product has a sticky surface, and the effect of the present invention cannot be obtained. A preferable epoxy equivalent is 170-1600 g / eq. , More preferably 170-1300 g / eq. It is.

  M and n in General formula (1) represent the number of 0-100, respectively. By being in the above range, a cured resin composition excellent in initial transmittance, low elastic modulus and deflection can be obtained. In particular, by setting m = 0, a cured resin composition excellent in heat resistance and strength. Can be obtained. When m and n exceed the above ranges, the effects of the present invention cannot be obtained in terms of heat resistance, hardness, and strength.

  The properties of the epoxy silicone resin are not particularly limited. However, when the properties at 25 ° C. are solid, the melting point or softening point is 30 ° C. to 180 ° C., more preferably 50 from the viewpoint of handling when used as a sealing material. It is preferable that it is 150 to 150 degreeC. When it is liquid at normal temperature, the viscosity at normal temperature is preferably 0.001 to 1000 Pa · s.

R ₁ in the general formula (1), a hydrocarbon group having 1 to 10 carbon atoms. 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 ₁ is a methyl group in view of the physical properties of the cured product and availability.

（式中、R₆は炭素数１〜１７の炭化水素基又は単結合である。） R ₂ in the general formula (1) represents a divalent hydrocarbon group having 1 to 20 carbon atoms, and may contain an etheric oxygen atom inside. Examples of such a hydrocarbon group include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, a decylene group, a dodecylene group, or a divalent group represented by the following general formula (6). It is not limited to these, and each may be the same or different. A preferred hydrocarbon group is a propylene group because of the physical properties of the cured product and availability.

(In the formula, R ₆ is a hydrocarbon group having 1 to 17 carbon atoms or a single bond.)

E ₁ in the general formula (1) is an epoxy group-containing group having an epoxy group bonded through a group containing an isocyanuric ring skeleton, preferably ^{-R 10 -R 11 - (R 12} -E) n Can be expressed as Here, R ¹¹ is a group having an isocyanuric ring skeleton, and R ¹⁰ and R ¹² are preferably a direct bond or a chain hydrocarbon group, but may contain a hetero atom. E is an epoxy group, and n is 1 to 3, preferably 2.

Z in the general formula (1) represents a divalent organic group. Such an organic group is represented by the above general formula (6) or the following general formulas (7) to (12) in addition to an ethylene group, a propylene group, a butylene group, a hexylene group, a decylene group, a dodecylene group, and the like. There are organic groups. However, it is not limited to these. Preferably, it is an organic group represented by General formula (3). This organic group is an organic group in which R ₆ is an ethylene group in the general formula (7).

（式中、Ｒ₆は炭素数１〜２０の炭化水素基を表し、内部に酸素原子を有していても良い。）

(In the formula, R ₆ represents a hydrocarbon group having 1 to 20 carbon atoms and may have an oxygen atom therein.)

（式中、Ｒ₇は炭素数１〜２０の炭化水素基を表し、内部に酸素原子を有していても良い。Ｘは炭素数１〜２０の炭化水素基、酸素原子、硫黄原子、カルボニル基、スルホニル基、スルフィニル基又は単結合を表す。）

(In the formula, R ₇ represents a hydrocarbon group having 1 to 20 carbon atoms, and may have an oxygen atom therein. X represents a hydrocarbon group having 1 to 20 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group. Represents a group, a sulfonyl group, a sulfinyl group or a single bond.)

（式中、Ｒ₈は炭素数１〜２０の炭化水素基を表し、内部に酸素原子を有していても良い。）

(In the formula, R ₈ represents a hydrocarbon group having 1 to 20 carbon atoms, and may have an oxygen atom therein.)

（式中、Ｒ₉は炭素数１〜２０の炭化水素基を表し、内部に酸素原子を有していても良い。Ｘは一般式（８）における説明と同義である。）

(In the formula, R ₉ represents a hydrocarbon group having 1 to 20 carbon atoms and may have an oxygen atom therein. X has the same meaning as in the general formula (8).)

（式中、Ｒ₁₀は炭素数１〜２０の炭化水素基を表し、内部に酸素原子を有していても良い。）

(In the formula, R ₁₀ represents a hydrocarbon group having 1 to 20 carbon atoms and may have an oxygen atom therein.)

（式中、Ｒ₁₁は炭素数１〜２０の炭化水素基を表し、内部に酸素原子を有していても良い。）

(In the formula, R ₁₁ represents a hydrocarbon group having 1 to 20 carbon atoms, and may have an oxygen atom therein.)

  In order to introduce these divalent organic groups into the structure of the general formula (1), for example, by using a compound in which both ends of the general formulas (6) to (12) are double bonds. Can be achieved.

  The epoxy silicone resin represented by the general formula (1) includes a silicone resin represented by the following general formula (4), an epoxy compound (Ea) arranged with a ring structure having one double bond in one molecule, and Or a reaction of the silicone resin represented by the following general formula (4), an organic compound having two double bonds in one molecule, and the epoxy compound (Ea). At this time, when an organic compound having two double bonds in one molecule is not used, a resin with m = 0 is obtained.

一般式（４）において、R₁、ｎは一般式（１）で表される説明と同義であり、好ましいR₁はメチル基である。

In the general formula (4), R ₁ and n have the same meanings as described in the general formula (1), and preferred R ₁ is a methyl group.

As the epoxy compound (Ea), a compound having an epoxy group, an isocyanurate ring structure and one carbon-carbon double bond is suitable. Since the epoxy compound (Ea) gives the above E ₁ , if E ₁ is represented by —R ¹⁰ —R ¹¹ — (R ¹² —E) _n , the portion corresponding to R ¹⁰ is carbon-carbon 2. It is preferable to have one double bond. However, it is not limited to the said manufacturing method. Preferred epoxy compounds (Ea) include, but are not limited to, epoxy compounds such as N-allyl-N ′, N ″ -diglycidyl isocyanurate. Moreover, you may use these epoxy compounds for reaction, using 2 or more types together. Among these, a particularly preferable epoxy compound (Ea) is N-allyl-N ′, N ″ -diglycidyl isocyanurate.

  As an organic compound having two double bonds in one molecule, a carbon-carbon double bond having an alicyclic or aromatic group in the molecule and having reactivity with Si-H group is contained in one molecule. The compound which has two in this is mentioned. These compounds are not particularly limited as long as they give an alkylene group or Z as in the above general formulas (6) to (12) by addition reaction with the Si—H group, and various compounds are used. it can. A preferred compound as an organic compound having two double bonds in one molecule is divinylbenzene because of availability, ease of reaction, and physical properties when cured.

  As the catalyst used in the addition reaction (hydrosilyl addition reaction), various precious metal catalysts or complex compounds thereof can be used as long as they are known. Examples of the noble metal catalyst include platinum, rhodium, palladium, ruthenium, and iridium, but are not limited thereto, and two or more kinds may be used as necessary. Further, a material in which these metals are immobilized on a particulate carrier material such as carbon, activated carbon, aluminum oxide, silica, or the like may be used.

Noble metal complex compounds include platinum halogen compounds (PtCl ₄ , H ₂ PtCl ₆ .6H ₂ O, Na ₂ PtCl ₆ .4H ₂ O, etc.), platinum-olefin complexes, platinum-alcohol complexes, platinum-alcolate complexes, platinum -Ether complexes, platinum-carbonyl complexes, platinum-ketone complexes, platinum-vinylsiloxane complexes such as platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane, bis (γ-picoline) -platinum dichloride , Trimethylenedipyridine-platinum dichloride, dicyclopentadiene-platinum dichloride, cyclooctadiene-platinum dichloride, cyclopentadiene-platinum dichloride, bis (alkynyl) bis (triphenylphosphine) platinum complex, bis (alkynyl) (cyclooctadiene) ) Platinum complex, rhodium chloride, tri (Triphenylphosphine) rhodium chloride, although such tetrakis ammonium over rhodium chloride complex are mentioned not particularly limited, may be used two or more.

  The noble metal catalysts may be used alone or in advance in a solvent to be dissolved, and then charged into the reaction system. Although the use ratio of the noble metal catalyst is not particularly limited, it is in the range of 0.1 ppm to 100,000 ppm, preferably 1 ppm to 10,000 ppm, based on the weight of the epoxy compound (Ea) usually used in the reaction.

  The hydrosilylation reaction can be carried out without a solvent, but the reaction system may be diluted with an organic solvent as necessary, and is not particularly limited as long as it is a compound that does not adversely influence the reaction. For example, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, aliphatic ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, benzene, toluene, orthoxylene, Aromatics such as meta-xylene, para-xylene, chlorobenzene and dichlorobenzene, and ethers such as diethylene glycol dimethyl ether and triethylene glycol dimethyl ether can be mentioned. Two or more of these organic solvents may be selected and used as a mixed solvent.

  Although it does not specifically limit about the temperature conditions in hydrosilyl addition reaction, Usually, 0 to 200 degreeC, Preferably it is 30 to 180 degreeC. Below 0 ° C, the reaction takes time and is not economical. When the reaction is carried out at 200 ° C. or higher, the addition reaction between the epoxy group and the hydrosilyl moiety proceeds, making it difficult to control the reaction.

  When a compound having two double bonds in one molecule is used as a reaction raw material and Z of the general formula (1) is introduced, the molar ratio of the double bonds is equal to or less than the equivalent of Si—H groups, preferably 80 % Or less, and a mixing ratio in which Si—H groups always remain at the ends. Examples of the reaction method include a silicone resin of the general formula (4), a compound having two double bonds in one molecule, and an epoxy compound having one double bond and an isocyanuric acid ring structure ( The reaction may be carried out by simultaneously adding the three types of Ea), or by reacting the silicone resin of the general formula (4) with a compound having two double bonds in one molecule, and then remaining Si. A two-step reaction in which an epoxy compound (Ea) is added for the purpose of sealing the —H group may be performed. However, when a plurality of Z are introduced into the general formula (1), that is, when m ≧ 2, the latter two-stage reaction is preferably performed from the viewpoint of reaction control.

  Next, (B) acid anhydride and (C) curing accelerator, which are essential components of the resin composition of the present invention, will be described.

  As the acid anhydride, various compounds can be applied as long as they are known ones used as an epoxy resin curing agent. For example, succinic anhydride, maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylated hexahydrophthalic anhydride, nadic anhydride, hydrogenated nadic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. Two or more types may be used as necessary. In particular, preferred acid anhydride cured products for obtaining the effects of the present invention 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, and more preferred catalysts are organic phosphine compounds and salts thereof.

  The cured resin composition of the present invention is composed of the components (A), (B), and (C), and has a characteristic that is excellent in deflection. Further, as the component (D), two or more per molecule. By using an epoxy resin or epoxy compound having an epoxy group, a cured resin composition having excellent optical properties, hardness, strength, deflection, and heat resistance can be obtained. In addition, the epoxy silicone resin corresponding to the component (A) is not handled as the component (D).

  Component (D) is an epoxy resin derived from phenols, an epoxy compound derived from an olefin compound containing a ring structure, an epoxy compound having an isocyanuric skeleton, or a polyfunctional epoxy silicone represented by the above general formula (5) Of these, at least one may be selected.

In the general formula (5), R _{3 to} R ₅ are each a hydrocarbon group or aromatic group having 1 to 20 carbon atoms which may contain an epoxy group, and have 1 to 3 etheric oxygen atoms inside. You may do it. However, one or more of R _{3 to} R ₅ always contain an epoxy group. R ₄ and R ₅ do not have an epoxy group at the same time. i to k represent the existing molar ratio, i + j + k = 1, 0 <k <1, 0 <j <1, 0 <i <0.75.

As epoxy resins derived from phenols, epoxy resins derived from monocyclic dihydric phenols such as resorcinol, hydroquinone, 2,5-ditertiarybutyl hydroquinone, and those obtained by nuclear hydrogenation of the aromatic ring, Epoxy resins derived from naphthalenediols such as 1,3-naphthalenediol, 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 2,7-naphthalenediol, and aromatic rings thereof 4,4′-isopropylidenediphenol, 4,4′-isopropylidenebis (2-methylphenol), 4,4′-isopropylidenebis (2,6-dimethylphenol), 4 , 4'-dihydroxydiphenylmethane, 4,4'-dihydroxy-3,3'-dimethyl Rudiphenylmethane, 4,4′-dihydroxy-3,3 ′, 5,5′-tetramethyldiphenylmethane, 4,4′-secondary butylidenebisphenol, 4,4′-isopropylidenebis (2-tertiarybutylphenol), 4,4′-cyclohexylidenediphenol, 4,4′-butylidenebis (6-tertiarybutyl-2-methyl) phenol, 4,4 ′-(1-α-methylbenzylidene) bisphenol, 4,4′-dihydroxy Tetraphenylmethane, α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene, α, α′-bis (4-hydroxy-3-methylphenyl) -1,4-diisopropylbenzene, α, α′-bis (4-hydroxy-3,5-dimethylphenyl) -1,3-dimethylbenzene, α, α′-bis (4 -Hydroxy-3,5-dimethylphenyl) -1,4-dimethylbenzene, 4,4'-dihydroxydiphenyl ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxy-3-methylphenyl) sulfide, 4, Derived from bisphenols such as 4'-thiobis (2-tertiarybutyl-5-methylphenol), 4,4'-biphenol, 4,4'-dihydroxy-3,3 ', 5,5'-tetramethyldiphenyl However, it is not limited to those obtained by nuclear hydrogenation of the epoxy resin or the aromatic ring thereof.
Two or more of these epoxy resins may be used in combination.

Examples of the epoxy compound derived from an olefin compound containing a ring structure include, but are not limited to, an epoxy compound represented by the following general formula (13) or general formula (14). Two or more of these epoxy compounds may be used in combination. A particularly preferred compound is a compound in which R ₁₂ or R ₁₃ is a methylene group from the standpoint of availability and physical properties when cured.

（式中、R₁₂、R₁₃は炭素数１〜２０の直鎖状炭化水素基を表す。）

(In the formula, R ₁₂ and R ₁₃ each represent a linear hydrocarbon group having 1 to 20 carbon atoms.)

  Examples of the epoxy compound having an isocyanuric skeleton include triglycidyl isocyanurate, N, N′-diglycidyl isocyanuric acid, N-allyl-N ′, N ″ -diglycidyl isocyanurate, and these epoxy compounds are 2 More than one species may be used in combination. A particularly preferred compound is triglycidyl isocyanurate because of its availability and physical properties when cured.

R _{3 to} R ₅ in the general formula (5) are each independently a hydrocarbon group or aromatic group having 1 to 20 carbon atoms which may contain an epoxy group, and an etheric oxygen atom in the interior of 1 to You may have three. Examples of such R _{3 to} R ₅ include a straight chain hydrocarbon such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, octyl group, isooctyl group, decyl group, and cyclohexyl group. Hydrocarbon groups containing an epoxy group such as an aliphatic hydrocarbon group such as phenyl group, an aromatic hydrocarbon group such as phenyl group, γ-glycidoxypropyl group, 2,-(3,4-epoxycyclohexyl) ethyl group, etc. However, it is not limited to these, and they may be the same or different. However, R ₄ and R ₅ do not have an epoxy group at the same time. Preferred R _{3 to} R ₅ are a methyl group and a phenyl group when an epoxy group is not included, and 2,-(3,4) when an epoxy group is included, because of the physical properties of the cured product and availability. -Epoxycyclohexyl) ethyl group.

  The polyfunctional epoxy silicone resin represented by the general formula (5) hydrolyzes alkoxysilanes represented by the following general formulas (9) to (11) in the presence of water and an acidic compound or a basic compound. It can be obtained by conducting a condensation reaction. The amount of water to be used, acidic compound, basic compound, reaction temperature, reaction solvent and the like are not particularly limited, and the reaction may be performed in a form preferable to those skilled in the art.

（式中、R₁は炭素数１〜１０の炭化水素基を表し、R₃〜R₅はそれぞれ一般式（５）における説明と同義である。）

(In the formula, R ₁ represents a hydrocarbon group having 1 to 10 carbon atoms, and R _{3 to} R ₅ have the same meanings as described in the general formula (5).)

The polyfunctional epoxy silicone resin represented by the general formula (5) is a precursor of a silicone resin having a hydrosilyl group in which at least one of R _{3 to} R _{5 in} the general formula (5) is substituted with a hydrogen atom. A compound having at least one carbon-carbon double bond and an epoxy group in the molecule can also be obtained by a hydrosilyl addition reaction using a noble metal catalyst. The noble metal catalyst, reaction temperature, and reaction solvent used at this time are not particularly limited, and the reaction may be carried out in a form preferable to those skilled in the art.

  The structure of the polyfunctional epoxy silicone resin represented by the general formula (5) is not particularly limited. For example, a polyhedral oligosilsesquioxane structure in which the Si—O bond is similar to a polyhedron, an incompletely condensed structure in which the vertex of the polyhedron is partially cleaved or missing, and a linear or cyclic Si—O bond It may have a siloxane structure forming a structure, a random structure developed in a branched shape, or the like.

  Although it does not specifically limit about the epoxy equivalent of the polyfunctional epoxy silicone resin represented by General formula (5), Usually, 180-1000 g / eq. It is. When the epoxy equivalent is in this range, the cured product obtained from the resin composition of the present invention has excellent optical properties, hardness, strength, deflection, and heat resistance. Epoxy equivalent is 180 g / eq. It is virtually impossible to obtain a polyfunctional epoxy silicone resin of less than 1000 g / eq. If it exceeds 1, the hardness and heat resistance of the cured product may be lost.

  (D) When mix | blending a component, it is good for the structural ratio with (A) component to satisfy | fill (A) :( D) = 1-95: 99-5 by weight conversion. By being in this ratio, the cured product when cured resin composition is hard, there is little cure shrinkage, there is no stickiness on the surface, it is excellent in strength, deflection, transparency, heat resistance, light resistance Can be obtained. When the component (A) is less than 1, it is difficult to obtain a sufficient effect from the viewpoint of strength, low elasticity and deflection, and when it exceeds 95, the effect of the present invention is difficult to obtain from the viewpoint of heat resistance. A preferred ratio is (A) :( D) = 10-80: 90-20, more preferably 20-70: 80-30.

  When the curable resin composition of the present invention is used as an LED sealing application, it is preferable to add an antioxidant to prevent oxidative deterioration during heating and to obtain a cured product with little coloring.

  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 Ciphenyl) propionate] high molecular phenols such as methane, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-tert-butyl 4-hydroxybenzyl) Oxaphosphaphenanthrenes such as -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Oxides, dilauryl 3,3'-dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-dilauryl 3,3'-thiodipropionate, distearyl 3,3'-dilauryl 3,3'- Thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropione) G) ester skeleton-containing thioether compounds based antioxidants and the like. Two or more of these antioxidants may be used as necessary.

  The curable resin composition of the present invention can contain a filler, a colorant and the like as necessary. The curable resin composition of the present invention gives a cured product by thermally curing it.

  Although the curable resin composition of the present invention comprises the above components (A) to (C) as essential components, the resin component (in addition to the resin, a component that is cured to become a part of the resin, for example, a monomer, a cure) 60 wt% or more, preferably 80 wt% or more, more preferably 90 wt% or more of the component (A) to the component (B). In addition, the blending ratio of the component (A), the component (B), and the component (C) may be determined as follows.

  It is preferable that the epoxy group of (A) component and the functional group in the hardening | curing agent of (B) component are the range of 0.8-1.5 by an equivalent ratio. Outside this range, an unreacted epoxy group or a functional group in the curing agent remains after curing, and functions such as hardness and heat resistance when cured are reduced, which is not preferable. Moreover, as a mixture ratio of (C) component which is an effect promoter, the range of 0.1 wt%-5 wt% is preferable with respect to the sum total of (A) component and (B) component. If it is less than 0.1 wt%, the gelation time is delayed, resulting in a decrease in workability due to a decrease in rigidity at the time of curing. Conversely, if it exceeds 5.0 wt%, curing proceeds during molding and unfilling is likely to occur. Become.

  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.

Synthesis example 1
In the general formula (4), 184 parts by weight of polysiloxane (Si-H equivalent 363 g / eq.) Having a terminal Si-H group in which the average value of n is about 8, and R ₁ is a methyl group, and 250 parts by weight of dioxane Then, 0.27 parts by weight of platinum catalyst (platinum concentration 5%) supported on carbon powder was put into a 1 L four-necked separable flask equipped with a thermometer, a cooling tube, a nitrogen introduction tube, and a stirring blade. After raising the internal temperature to 90 ° C., 150 parts by weight of N-allyl-N ′, N ″ -diglycidyl isocyanurate was added over 3 hours. After completion of the addition, the internal temperature was raised to 110 ° C., and the reaction was carried out while refluxing dioxane. The reaction solution was dropped into a 0.1N potassium hydroxide / methanol solution, and it was confirmed that hydrogen gas was not generated. The remaining platinum catalyst was filtered using celite. The solvent of the filtrate was distilled off using an evaporator to obtain 320 parts by weight of an epoxy silicone resin (ES1). This epoxy silicone resin (ES1) is composed of a linear siloxane bond and an isocyanuric ring in the general formula (1) where R ₂ is a propylene group, E ₁ is a group of the general formula (2), and m = 0. And has an epoxy group at the end. The epoxy equivalent of this epoxy silicone resin (ES1) is 317 g / eq. The viscosity at 25 ° C. was 4.5 Pa · s.

Synthesis example 2
In the general formula (4), 38 parts by weight of polysiloxane (Si-H equivalent 215 g / eq.) Having a terminal Si—H group in which the average value of n is about 4, R ₁ is a methyl group, and 38 parts by weight of dioxane Parts, platinum catalyst supported on carbon powder (platinum concentration 5%) 0.09 parts by weight, N-allyl-N ′, N ″ -diglycidyl isocyanurate 50 parts by weight Then, 81 parts by weight of an epoxy silicone resin (ES2) was obtained. This epoxy silicone resin (ES2) is composed of a linear siloxane bond and an isocyanuric ring in the general formula (1) where R ₂ is a propylene group, E ₁ is a group of the general formula (2), and m = 0. And has an epoxy group at the end. The epoxy equivalent of this resin is 237 g / eq. The melting point was about 55 ° C. and the viscosity at 75 ° C. was 0.34 Pa · s.

Synthesis example 3
In general formula (4), n = 0, polysiloxane having a terminal Si—H group in which R ₁ is a methyl group (Si—H equivalent 67 g / eq.) 34 parts by weight, dioxane 38 parts by weight, carbon powder Except that 0.09 part by weight of a platinum catalyst (platinum concentration 5%) supported on the catalyst, 140 parts by weight of N-allyl-N ′, N ″ -diglycidyl isocyanurate, and a 500 ml autoclave as a reaction vessel were used. The same operation as in Example 1 was performed. Thus, R ₂ represented by the general formula (1) is a propylene group, E ₁ is a group of the general formula (2), and m = 0, a structure composed of a linear siloxane bond and an isocyanuric ring inside And 148 parts by weight of an epoxy silicone resin (ES3) having an epoxy group at the end was obtained. The epoxy equivalent of this resin is 177 g / eq. The properties at 25 ° C. were solid and the melting point was 133 ° C.

Synthesis example 4
In the general formula (4), polysiloxane (Si-H equivalent 363 g / eq.) 161 parts by weight, divinylbenzene 23 parts by weight, wherein the average value of n is about 8, and R ₁ is a methyl group. , N-allyl-N ′, N ″ -diglycidyl isocyanurate 25 parts by weight, dioxane 260 parts by weight, platinum catalyst supported on carbon powder (platinum concentration 5%) 0.17 parts by weight The same operation as in Example 1 was performed. Thus, R ₂ represented by the general formula (1) is a propylene group, E ₁ is a group of the general formula (2), Z is a group of the general formula (3), and an average value of m is 8. 200 parts by weight of an epoxy silicone resin (ES4) having a structure composed of a linear siloxane bond and an isocyanuric ring inside and having an epoxy group at the terminal was obtained. The epoxy equivalent of this resin is 1146 g / eq. The viscosity at 25 ° C. was 740 cPs.

Examples 1-4
Epoxy silicone resins (ES1 to ES4) obtained in Synthesis Examples 1 to 4 and methylated hexahydrophthalic anhydride (MH: acid anhydride equivalent 168 g / eq.), Ratio of epoxy equivalent to acid anhydride equivalent = 1 : 1, add well, and add 0.5% by weight of tetra-n-butylphosphonium o, o'-diethyl phosphorodithionate as a curing accelerator. In the mold, a resin plate having a thickness of 1 mm was prepared by curing at 120 ° C. for 4 hours and further at 160 ° C. for 12 hours.

Example 5
The same operation as in Example 1 was performed using a mixture in which bisphenol A liquid epoxy resin (EpA: epoxy equivalent 187 g / eq.) Was used as component (D) and the weight ratio with ES1 was 1: 1, A resin plate having a thickness of 1 mm was prepared.

Example 6
3,4-epoxycyclohexenylmethyl-3, '4'-epoxycyclohexenecarboxylate (EpC: epoxy equivalent 130 g / eq.) Was used as component (D), and a mixture with a weight ratio of ES1 of 1: 1 was used. Then, the same operation as in Example 5 was performed to prepare a resin plate having a thickness of 1 mm.

Example 7
Using a mixture having triglycidyl isocyanurate (EpT: epoxy equivalent 100 g / eq.) As component (D) and having a weight ratio with ES1 of 1: 1, the same operation as in Example 5 was performed, and the thickness was 1 mm. A resin plate was created.

Example 8
Polyfunctionality obtained by performing hydrolysis and condensation reaction using 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, dimethyldimethoxysilane, and trimethylmethoxysilane in a molar ratio of 1: 1: 3 Resin having a thickness of 1 mm by performing the same operation as in Example 5 using a mixture in which epoxy silicone resin (EpS: epoxy equivalent 273 g / eq.) Is used as component (D) and weight ratio with ES1 is 1: 1. A board was created.

Example 9
3,4-epoxycyclohexenylmethyl-3, '4'-epoxycyclohexenecarboxylate (EpC: epoxy equivalent 130 g / eq.) Was used as component (D), and a mixture with a weight ratio of ES4 of 1: 1 was used. Then, the same operation as in Example 5 was performed to prepare a resin plate having a thickness of 1 mm.

Comparative Example 1
Except not using the epoxy silicone resin (ES1), the same operation as in Example 5 was performed to prepare a resin plate having a thickness of 1 mm.

Comparative Example 2
Except that EpC was used instead of EpA, the same operation as in Comparative Example 1 was performed to prepare a resin plate having a thickness of 1 mm.

Comparative Example 3
A resin plate having a thickness of 1 mm was prepared by performing the same operation as in Comparative Example 1 except that EpT was used instead of EpA.

Comparative Example 4
A resin plate having a thickness of 1 mm was prepared by performing the same operation as in Comparative Example 1 except that EpS was used instead of EpA.

Comparative Example 5
14 parts by weight of a dimethylsiloxane-methylhydrogensiloxane copolymer having an end of a trimethylsilyl group and having a hydrosilyl group in the chain (average molecular weight of about 700, Si—H equivalent: about 140 g / eq.) And N-allyl- The same as in Synthesis Example 1 except that 28 parts by weight of N ′, N ″ -diglycidyl isocyanurate, 150 parts by weight of dioxane, and 0.28 parts by weight of platinum catalyst (platinum concentration 5%) supported on carbon powder were used. The operation was performed. In this way, 35 parts by weight of dimethylsiloxane resin (PnES1) having an epoxy group and an isocyanuric group in the side chain was obtained. The epoxy equivalent of this resin is 232 g / eq. The properties at room temperature were solid.
A resin plate having a thickness of 1 mm was prepared in the same manner as in Example 1 except that the obtained dimethylsiloxane resin (PnES1) was used instead of the epoxy silicone resin (ES1).

Comparative Example 6
43 parts by weight of dimethylsiloxane resin having an Si—H group at one end (average molecular weight of about 4300, degree of polymerization of about 60), 3 parts by weight of N-allyl-N ′, N ″ -diglycidyl isocyanurate, about 170 parts by weight of dioxane The same operation as in Synthesis Example 1 was performed except that 0.3 parts by weight of platinum catalyst (platinum concentration 5%) supported on carbon powder was used. In this way, 40 parts by weight of an epoxy silicone resin (ES5) having a structure composed of a linear siloxane bond and an isocyanuric ring at one end and having an epoxy group at the end was obtained. The epoxy equivalent of this resin is 2230 g / eq. The viscosity at 25 ° C. was 20000 cPs.
The same operation as in Example 1 was performed except that the obtained epoxy silicone resin (ES5) was used instead of the epoxy silicone resin (ES1), but the obtained cured product was gel-like and used as a resin plate. I couldn't get it out.

Comparative Example 7
In the general formula (4), polysiloxane having a terminal Si—H group (Si—H equivalent 363 g / eq.) In which the average value of n is about 8 and R ₁ is represented by a methyl group, 16 parts by weight of allyl isocyanurate, 250 parts by weight of dioxane, 0.4 part by weight of platinum catalyst (platinum concentration 5%) supported on carbon powder, 4 liters of 1 L with a thermometer, a cooling pipe, a nitrogen introduction pipe and a stirring blade It was put into a one-necked separable flask. The internal temperature was raised to 110 ° C. and stirred for 10 hours. After confirming disappearance of the carbon-carbon double bond by proton NMR, 50 parts by weight of 4-vinylcyclohexene oxide was added, and the mixture was further stirred at 110 ° C. for 20 hours. The reaction solution was dropped into a 0.1 N potassium hydroxide / methanol solution, and it was confirmed that generation of hydrogen gas ceased, and the platinum catalyst was filtered using celite. The solvent of the filtrate was distilled off using an evaporator. In this manner, 230 parts by weight of an epoxy silicone resin (ES6) having an epoxycyclohexyl group at the terminal and a dimethylsiloxane structure between the isocyanuric skeleton in the chain and the terminal epoxycyclohexyl group was obtained. The epoxy equivalent of this resin is 720 g / eq. The viscosity at 25 ° C. was 53000 cPs.
Using the obtained epoxy silicone resin (ES6), the same operation as in Example 1 was performed to prepare a resin plate having a thickness of 1 mm.

Comparative Example 8
The same as Example 1 except that the epoxy silicone resin (ES1) obtained in Synthesis Example 1 and a novolac type phenol resin (phenolic hydroxyl group equivalent of 105 g / eq.) Were used instead of methylated hexahydrophthalic anhydride. Thus, a 1 mm thick resin plate was prepared.

Measurement of glass transition temperature (Tg) of cured product 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. It was temperature. The heating rate was 5 ° C./min.

Measurement of linear expansion coefficient.
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.

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

Measurement of UV resistance 400 nm transmittance after UV irradiation of a 4 mm thick cured product using a Q panel company weather resistance tester QUV 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.

Measurement of initial heat resistance A cured product having a thickness of 1 mm 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.

Measurement of long-term heat resistance A cured product having a thickness of 1 mm 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.

Surface stickiness When the cured product was put 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 even to the polyethylene bag.

Measurement of hardness The surface hardness of the cured product at room temperature was measured using a TECKLOCK Co., Ltd. hardness meter TYPE-D.

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.

Bending and Deflection Characteristic Tests Based on JIS-7171, bending elastic modulus, bending strength and bending deflection were measured by an autograph (manufactured by Shimadzu Corporation) using a test piece of 80 mm × 10 mm × 4 mm. A test piece that did not break and fell off between the fulcrums was described as “no breakage”.

  Tables 1 and 2 show the measurement results of each test of the cured products obtained in Examples 1 to 9. Tables 3 and 4 show the measurement results of each test of the cured products obtained in Comparative Examples 1 to 9. In addition, Tables 1 to 4 show types of the component (A), the component (B), and the component (D) used in Examples and Comparative Examples.

Claims (8)

The following ingredients,
(A) Represented by the general formula (1), the epoxy equivalent is 150 to 2000 g / eq. Epoxy silicone resin, which is

(In the formula, R ₁ represents a hydrocarbon group having 1 to 10 carbon atoms, R ₂ represents a hydrocarbon group having 1 to 20 carbon atoms, and may contain an etheric oxygen atom therein. E ₁ represents An epoxy group-containing group having an epoxy group bonded through a group containing an isocyanuric ring skeleton, Z represents a divalent organic group which may have a hetero atom inside, and m and n are independently 0. Represents a number of ~ 100.)
A curable resin composition comprising (B) an acid anhydride and (C) a curing accelerator.   The curable resin composition according to claim 1, wherein in general formula (1), m = 0. E ₁ in the general formula (1) is the general formula (2)

The curable resin composition of Claim 1 or 2 represented by these. Z in the general formula (1) is the general formula (3).

The curable resin composition of Claim 1 or 3 represented by these. Furthermore, the following component (D) The curable resin composition in any one of Claims 1-4 containing the epoxy resin or epoxy compound which has a 2 or more epoxy group. Component (D) is an epoxy resin derived from phenols, an epoxy compound derived from an olefin compound containing a ring structure, an epoxy compound having an isocyanuric skeleton, or general formula (5)
(R ₃ SiO _3/2 ) _k (R ₄ R ₅ SiO) _j (Me ₃ SiO _1/2 ) _i (5)
(In formula, R < ₃ > -R < ₅ > is a C1-C20 hydrocarbon group which may contain the epoxy group independently, and may have 1-3 etheric oxygen atoms inside. However, one or more of R _{3 to} R ₅ must always contain an epoxy group, and R ₄ and R ₅ do not have an epoxy group at the same time, i to k represent a molar ratio, i + j + k = 1, (It is a number satisfying 0 <k <1, 0 <j <1, 0 <i <0.75.)
The curable resin composition according to claim 5, which is at least one selected from polyfunctional epoxy silicone resins represented by the formula:   The weight ratio of (A) component and (D) component is (A) :( D) = 1-95: 99-5, The curable resin composition of Claim 6.   A cured product obtained by heating and curing the curable resin composition according to claim 1.