JP2008274004A - Curable resin composition and its cured material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition capable of forming a cured material having both of light fast transparency and bonding reliability by curing a modified polyorganosiloxane compound having an epoxy group and/or oxetanyl group in one molecule. <P>SOLUTION: This curable resin composition contains (A) the modified polyorganosiloxane compound having ≥2 epoxy groups and/or oxetanyl groups in one molecule, which is a hydrosililation reaction material of the following compounds: (α1) an organic compound having 2 to 6 carbon-carbon double bonds having a reactivity with SiH group in one molecule, (α2) a linear and/or cyclic polyorganosiloxane compound having at least 2 SiH groups in one molecule and (α3) an organic compound having at least one epoxy or oxetanyl group and one carbon-carbon double bond having a reactivity with the SiH group, (B) an acid anhydride and (C)a curing accelerator, and its cured material is also provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a curable resin composition, and more specifically, a curable resin composition containing a modified polyorganosiloxane compound having two or more epoxy groups and / or oxetanyl groups in one molecule, and curing the composition. It relates to a cured product.

  Generally, an optical semiconductor device is configured by resin-sealing an optical semiconductor element such as a light emitting diode or a photodiode with an epoxy resin composition. In the case of blue LEDs and white LEDs that have been attracting attention in recent years, optical transparency, light resistance, and adhesion to members are strongly required for the sealing resin.

Therefore, a cation / acid anhydride combined curing system of an alicyclic epoxy resin has been studied as a resin having optical transparency, light transparency, and adhesion to a member. For example, Patent Document 1 is disclosed. For example, Patent Document 2 discloses a study using an epoxy group-containing silicone resin. However, although the epoxy resin and the epoxy group-containing silicone resin have light resistance and transparency, adhesion reliability is still insufficient, and development of a resin having both is strongly demanded.
JP 2003-176334 A Japanese Patent Laid-Open No. 2006-152088

  The present invention cures a modified polyorganosiloxane compound having two or more epoxy groups and / or oxetanyl groups in one molecule to provide a cured product having both light resistance and adhesion reliability, and curing capable of giving such a cured product. It aims at providing a conductive resin composition.

  As a result of intensive studies by the inventors, a modified polyorganosiloxane compound having two or more specific epoxy groups or oxetanyl groups having optical transparency, heat resistance, light resistance, and crack resistance can be used in combination with a cation / acid anhydride. It has been found that by curing, a cured product having not only excellent light resistance and transparency but also excellent adhesion reliability can be obtained, and the present invention has been completed.

That is, the present invention is (A) a hydrosilylation reaction product of the following compounds (α1) to (α3): a modified polyorganosiloxane compound having two or more epoxy groups and / or oxetanyl groups in one molecule:
(Α1) an organic compound having 2 to 6 carbon-carbon double bonds having reactivity with SiH groups in one molecule;
(Α2) a linear and / or cyclic polyorganosiloxane compound having at least two SiH groups in one molecule,
(Α3) In one molecule, an organic compound having at least one epoxy group or oxetanyl group and one carbon-carbon double bond having reactivity with a SiH group,
The present invention relates to a curable resin composition containing (B) an acid anhydride and (C) a curing accelerator.

  The compound (α1) is diallyl monoglycidyl isocyanurate, diallyl monobenzyl isocyanurate, 1,3-bis (allyloxy) adamantane, 1,3-bis (vinyloxy) adamantane, 1,4-cyclohexanedimethanol divinyl ether, Dicyclopentadiene, divinylbenzene, vinylcyclohexene, 1,5-hexadiene, 1,9-decadiene, diallyl ether, triallyl isocyanurate, triallyl cyanurate, 1,2,4-trivinylcyclohexane, trimethylolpropane tri At least one selected from the group consisting of allyl ether, 1,3,5-tris (allyloxy) adamantane, 1,3,5-tris (vinyloxy) adamantane, and pentaerythritol tetraallyl ether It is preferable that.

  The compound (α2) is represented by the following general formula (I)

（式中Ｒ¹は炭素数１〜６の有機基を表し、ｎは３〜１０の数を表す）で表されるＳｉＨ基を有する環状ポリオルガノシロキサン化合物であることが好ましい。
上記化合物（α３）は、１，２−エポキシ−４−ビニルシクロへキサン、３−エチル−３−アリルオキシメチルオキセタン、および、１−アリルオキシ−２，３−エポキシプロパンからなる群から選ばれる少なくとも一種であることが好ましい。

(Wherein R ¹ represents an organic group having 1 to 6 carbon atoms, and n represents a number of 3 to 10), and is preferably a cyclic polyorganosiloxane compound having a SiH group.
The compound (α3) is at least one selected from the group consisting of 1,2-epoxy-4-vinylcyclohexane, 3-ethyl-3-allyloxymethyloxetane, and 1-allyloxy-2,3-epoxypropane. It is preferable that

The SiH group value in the (A) modified polyorganosiloxane compound is preferably less than 3.0 mmol / g.
The (B) acid anhydride is preferably methylhexahydrophthalic anhydride, and the blending amount of the (B) acid anhydride is 1 to 100 weights per 100 parts by weight of the (A) modified polyorganosiloxane compound. Part.
The (C) curing accelerator is preferably a boron-based iodonium salt and / or an antimony-based sulfonium salt, and the blending amount of the (C) curing accelerator is 100 parts by weight of the (A) modified polyorganosiloxane compound. It is preferable to contain 0.001-5 weight part with respect to it.

  The cured product of the present invention is obtained by curing the curable resin composition.

  According to the curable resin composition of the present invention, a cured product having excellent light resistance and adhesion reliability can be provided.

  The present invention will be described in detail below.

  The curable resin composition of the present invention contains a modified polyorganosiloxane compound (A), an acid anhydride (B), and a curing accelerator (C), and cures the curable resin composition of the present invention. The cured product thus obtained has an excellent effect of being excellent in light resistance and adhesion reliability.

  Hereinafter, each component of the curable resin composition of the present invention will be described.

  The compound (α1) of the present invention will be described.

  The compound (α1) is not particularly limited as long as it is an organic compound containing 2 to 6 carbon-carbon double bonds having reactivity with the SiH group in one molecule. Organic compounds do not contain siloxane units (Si-O-Si) such as polysiloxane-organic block copolymers and polysiloxane-organic graft copolymers, but only C, H, N, O, S, and halogen as constituent elements It is preferable that it contains. Those containing siloxane units have gas permeability and repelling problems.

  The bonding position of the carbon-carbon double bond having reactivity with the SiH group is not particularly limited, and may be present anywhere in the molecule.

  The organic compound of the compound (α1) can be classified into an organic polymer compound and an organic monomer compound.

  Examples of organic polymer compounds include polyether, polyester, polyarylate, polycarbonate, saturated hydrocarbon, unsaturated hydrocarbon, polyacrylate ester, polyamide, phenol-formaldehyde (phenolic resin) ), Polyimide compounds can be used.

  Examples of organic monomer compounds include aromatic hydrocarbons such as phenols, bisphenols, benzene, and naphthalene: aliphatic hydrocarbons such as linear and alicyclics: heterocyclic compounds, and mixtures thereof. Etc.

  The carbon-carbon double bond having reactivity with the SiH group of the compound (α1) is not particularly limited, but the following general formula (II)

（式中Ｒ^２は水素原子あるいはメチル基を表す。）で示される基が反応性の点から好適である。また、原料の入手の容易さからは、

A group represented by the formula (wherein R ² represents a hydrogen atom or a methyl group) is preferred from the viewpoint of reactivity. In addition, from the availability of raw materials,

で示される基が特に好ましい。

Is particularly preferred.

  As the carbon-carbon double bond having reactivity with the SiH group of the compound (α1), an alicyclic group having a partial structure represented by the following general formula (III) in the ring is the heat resistance of the cured product. Is preferable from the viewpoint of high.

（式中Ｒ^３は水素原子あるいはメチル基を表す。）また、原料の入手の容易さからは、下記式で表される部分構造を環内に有する脂環式の基が好適である。

(In the formula, R ³ represents a hydrogen atom or a methyl group.) From the viewpoint of availability of raw materials, an alicyclic group having a partial structure represented by the following formula in the ring is preferable.

ＳｉＨ基と反応性を有する炭素−炭素二重結合は化合物（α１）の骨格部分に直接結合していてもよく、２価以上の置換基を介して共有結合していても良い。２価以上の置換基としては炭素数０〜１０の置換基であれば特に限定されないが、構成元素としてＣ、Ｈ、Ｎ、Ｏ、Ｓ、およびハロゲンのみを含むものが好ましい。これらの置換基の例としては、

The carbon-carbon double bond having reactivity with the SiH group may be directly bonded to the skeleton portion of the compound (α1), or may be covalently bonded through a divalent or higher valent substituent. The divalent or higher valent substituent is not particularly limited as long as it is a substituent having 0 to 10 carbon atoms, but preferably includes only C, H, N, O, S, and halogen as constituent elements. Examples of these substituents include

が挙げられる。また、これらの２価以上の置換基の２つ以上が共有結合によりつながって１つの２価以上の置換基を構成していてもよい。

Is mentioned. Moreover, two or more of these divalent or higher valent substituents may be connected by a covalent bond to constitute one divalent or higher valent substituent.

  Examples of the group covalently bonded to the skeleton as described above include vinyl group, allyl group, methallyl group, acrylic group, methacryl group, 2-hydroxy-3- (allyloxy) propyl group, 2-allylphenyl group, 3 -Allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group, 4- (allyloxy) phenyl group, 2- (allyloxy) ethyl group, 2,2-bis (allyl) Oxymethyl) butyl group, 3-allyloxy-2, 2-bis (allyloxymethyl) propyl group, vinyl ether group,

が挙げられる。

Is mentioned.

  Specific examples of the compound (α1) include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether. 1,1,2,2-tetraallyloxyethane, diarylidenepentaerythritol, triallyl cyanurate, triallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monobenzyl isocyanurate, 1,2,4-tri Vinylcyclohexane, 1,4-butanediol divinyl ether, nonanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, triethylene Recall divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, diallyl ether of bisphenol S, divinylbenzene, divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,3-bis (Allyloxy) adamantane, 1,3-bis (vinyloxy) adamantane, 1,3,5-tris (allyloxy) adamantane, 1,3,5-tris (vinyloxy) adamantane, dicyclopentadiene, vinylcyclohexene, 1,5 Hexadiene, 1,9-decadiene, diallyl ether, bisphenol A diallyl ether, tetraallyl bisphenol A, 2,5-diallylphenol allyl ether, and oligomers thereof 1,2-polybutadiene (1,2 ratio of 10 to 100%, preferably 1,2 ratio of 50 to 100%), allyl ether of novolak phenol, allylated polyphenylene oxide,

の他、従来公知のエポキシ樹脂のグルシジル基の一部または全部をアリル基に置き換えたもの等が挙げられる。

In addition, the glycidyl group of a conventionally known epoxy resin may be partially or wholly replaced with an allyl group.

  As the compound (α1), it is also possible to use a low molecular weight compound that is difficult to express by dividing into a skeleton portion and an alkenyl group (a carbon-carbon double bond having reactivity with a SiH group) as described above. Specific examples of these low molecular weight compounds include aliphatic chain polyene compound systems such as butadiene, isoprene, octadiene and decadiene, fats such as cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene and norbornadiene. Examples thereof include aromatic cyclic polyene compound systems and substituted aliphatic cyclic olefin compound systems such as vinylcyclopentene and vinylcyclohexene.

  The number of carbon-carbon double bonds having reactivity with the SiH group of the compound (α1) may be 2 to 6 per molecule on average. When the number of carbon-carbon double bonds having reactivity with the SiH group of the compound (α1) is 1 or less per molecule, even if it reacts with the compound (α2), only a graft structure is formed. Don't be. On the other hand, when the number of carbon-carbon double bonds having reactivity with the SiH group of the compound (α1) is more than 6 per molecule, it becomes easy to gel when synthesizing the modified polyorganosiloxane compound, Moreover, the storage stability of a curable composition will worsen.

  The compound (α1) preferably contains 3 or more carbon-carbon double bonds in one molecule from the viewpoint of good reactivity. Further, from the viewpoint that storage stability tends to be good, it is more preferable that one molecule contains 4 or less carbon-carbon double bonds.

  As the compound (α1), the molecular weight that can be calculated from the structural formula is less than 900 from the viewpoint of high mechanical heat resistance and from the viewpoint that the raw material liquid has little stringiness and good moldability, handleability, and coatability. Is preferably less than 700, more preferably less than 500. In order to obtain good workability, the compound (α1) preferably has a viscosity at 23 ° C. of less than 100 Pa · s, more preferably less than 30 Pa · s, and even more preferably less than 3 Pa · s. . The viscosity can be measured with an E-type viscometer.

  The compound (α1) is preferably a compound having a low content of a compound having a phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group from the viewpoint of suppression of coloring, particularly yellowing, and the phenolic hydroxyl group and / or phenolic hydroxyl group. Those not containing a compound having a derivative of In the present invention, the phenolic hydroxyl group means a hydroxyl group directly bonded to an aromatic hydrocarbon nucleus exemplified by a benzene ring, naphthalene ring, anthracene ring, etc., and a phenolic hydroxyl group derivative means a hydrogen atom of the above-mentioned phenolic hydroxyl group. A group substituted by an alkyl group such as a methyl group or an ethyl group, an alkenyl group such as a vinyl group or an allyl group, an acyl group such as an acetoxy group, or the like.

  From the viewpoint that the obtained cured product is less colored and has high light resistance, the compound (α1) is vinylcyclohexene, dicyclopentadiene, triallyl isocyanurate, diallyl of 2,2-bis (4-hydroxycyclohexyl) propane. Ether, 1,2,4-trivinylcyclohexane is preferred, triallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl ether of 2,2-bis (4-hydroxycyclohexyl) propane, 1,2,4-trivinylcyclohexane Is particularly preferred.

  The compound (α1) may have other reactive groups. Examples of the reactive group in this case include an epoxy group, an oxetanyl group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, and an alkoxysilyl group. When it has these functional groups, the adhesiveness of the resulting curable composition tends to be high, and the strength of the resulting cured product tends to be high. Of these functional groups, an epoxy group is preferable from the viewpoint that the adhesiveness can be further increased. Moreover, it is preferable to have 1 or more reactive groups in one molecule on average from the point that the heat resistance of the obtained cured product tends to be high.

  As the compound (α1), triallyl isocyanurate and diallyl monoglycidyl isocyanurate represented by the following general formula (IV) are particularly preferable from the viewpoint of high heat resistance and light resistance.

（式中Ｒ^４は炭素数１〜５０の一価の有機基を表し、それぞれのＲ^４は異なっていても同一であってもよく、少なくとも２個のＲ^４はＳｉＨ基との反応性を有する炭素−炭素二重結合を含む）で表される化合物が好ましい。

(Wherein R ⁴ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ⁴ may be different or the same, and at least two R ⁴ have reactivity with SiH group. The compound represented by the carbon-carbon double bond which has) is preferable.

R ^{4 in the} general formula (IV) is preferably a monovalent organic group having 1 to 20 carbon atoms from the viewpoint that the heat resistance of the obtained cured product can be further increased. 10 monovalent organic groups are more preferable, and monovalent organic groups having 1 to 4 carbon atoms are more preferable. Examples of these preferable R ⁴ are methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group,

等が挙げられる。

Etc.

R ^{4 in the} general formula (IV) is a carbon in which at least one of the three R ^{4 s} contains one or more epoxy groups from the viewpoint that adhesion of the obtained cured product to various materials can be improved. A monovalent organic group of 1 to 50 is preferable,

で表されるエポキシ基を１個以上含む炭素数１〜５０の一価の有機基であることがより好ましい。これらの好ましいＲ^４の例としては、グリシジル基、

It is more preferable that it is a C1-C50 monovalent organic group containing 1 or more of epoxy groups represented by these. Examples of these preferred R ⁴ include glycidyl group,

等が挙げられる。

Etc.

As R ^{4 in the} general formula (IV), at least one of the three R ⁴ groups is from the viewpoint of improving the reactivity.

で表される基を１個以上含む炭素数１〜５０の一価の有機基であることが好ましく、下記一般式（Ｖ）

It is preferable that it is a C1-C50 monovalent organic group containing 1 or more groups represented by general formula (V) below.

（式中Ｒ^５は水素原子あるいはメチル基を表す。）で表される基を１個以上含む炭素数１〜５０の一価の有機基であることがより好ましく、
３つのＲ^４のうち少なくとも２つが下記一般式（ＶＩ）

(Wherein R ⁵ represents a hydrogen atom or a methyl group), and more preferably a monovalent organic group having 1 to 50 carbon atoms and containing at least one group represented by:
At least two of the three R ⁴ are represented by the following general formula (VI)

（式中Ｒ⁶は直接結合あるいは炭素数１〜４８の二価の有機基を表し、Ｒ⁷は水素原子あるいはメチル基を表す。）で表される有機化合物（複数のＲ⁶およびＲ⁷はそれぞれ異なっていても同一であってもよい。）であることがさらに好ましい。

(Wherein R ⁶ represents a direct bond or a divalent organic group having 1 to 48 carbon atoms, and R ⁷ represents a hydrogen atom or a methyl group) (a plurality of R ⁶ and R ⁷ are More preferably, they may be the same or different.

R ^{6 in the} general formula (VI) is a direct bond or a divalent organic group having 1 to 48 carbon atoms. From the viewpoint that the heat resistance of the resulting cured product can be further increased, the direct bond or carbon It is preferably a divalent organic group having 1 to 20 carbon atoms, more preferably a direct bond or a divalent organic group having 1 to 10 carbon atoms, and a direct bond or a divalent organic group having 1 to 4 carbon atoms. More preferably, it is a group. Examples of these preferred R ⁶ include

等が挙げられる。

Etc.

As R ^{6 in the} general formula (VI), from the viewpoint that the chemical thermal stability of the resulting cured product can be improved, it is a direct bond or contains two or less oxygen atoms and contains C as a constituent element. It is preferably a C1-C48 divalent organic group containing only H and O, more preferably a direct bond or a C1-C48 divalent hydrocarbon group. Examples of these preferred R ⁶ include

が挙げられる。

Is mentioned.

R ^{7 in the} general formula (VI) is a hydrogen atom or a methyl group, and a hydrogen atom is preferable from the viewpoint of good reactivity.

  However, in the preferred examples of the organic compound represented by the general formula (IV) as described above, it is necessary to contain 2 to 6 carbon-carbon double bonds having reactivity with the SiH group in one molecule. It is. From the viewpoint that heat resistance can be further improved, an organic compound containing three or more carbon-carbon double bonds having reactivity with SiH groups in one molecule is more preferable.

  Preferable specific examples of the organic compound represented by the general formula (IV) include triallyl isocyanurate.

  In order to improve the adhesiveness of the cured product, diallyl monoglycidyl isocyanurate is preferable as the compound (α1).

  The various compounds (α1) described above can be used alone or in admixture of two or more.

Next, the compound (α2) will be described.
The compound (α2) is not particularly limited as long as it is a linear and / or cyclic organopolysiloxane compound having at least two SiH groups in one molecule. For example, it is a compound described in International Publication WO 96/15194, Those having at least two SiH groups in one molecule can be used.

  Of these, from the viewpoint of availability and good reactivity with the compound (α1), the following general formula (I)

（式中、Ｒ^１は炭素数１〜６の有機基を表し、ｎは３〜１０の数を表す。）で表される、１分子中に少なくとも３個のＳｉＨ基を有する環状オルガノポリシロキサンが好ましい。

(Wherein R ¹ represents an organic group having 1 to 6 carbon atoms, and n represents a number of 3 to 10). Cyclic organopolysiloxane having at least three SiH groups in one molecule. Is preferred.

The substituent R ¹ in the compound represented by the general formula (I) is preferably composed of C, H, and O, more preferably a hydrocarbon group, and a methyl group. Further preferred.

  The compound represented by the general formula (I) is preferably 1,3,5,7-tetramethylcyclotetrasiloxane from the viewpoint of availability and reactivity.

The various compounds (α2) described above can be used alone or in admixture of two or more.
(Compound (α3))
Next, the compound (α3) will be described.

  The compound (α3) is not particularly limited as long as it is an organic compound having at least one epoxy group or oxetanyl group and one carbon-carbon double bond having reactivity with a SiH group in one molecule.

  The carbon-carbon double bond having reactivity with the SiH group is preferably the same as the carbon-carbon double bond having reactivity with the SiH group of the compound (α1).

  As an epoxy group, the following general formula (VII)

（但し、Ｒ^８は炭素数が１〜１０、酸素数が０〜２の２価の有機基）が挙げられる。

(However, R ⁸ is a divalent organic group having 1 to 10 carbon atoms and 0 to 2 oxygen atoms).

  As the oxetanyl group, the following general formula (VIII)

（但し、Ｒ⁹は炭素数が１〜１０、酸素数が０〜２の２価の有機基）が挙げられる。

(However, R ⁹ is a divalent organic group having 1 to 10 carbon atoms and 0 to 2 oxygen atoms).

  Specific examples of the compound (α3) include 1,2-epoxy-4-vinylcyclohexane, 3-ethyl-3-, from the viewpoint that the hydrosilylation reactivity with the SiH group of the compound (α2) is good. Allyloxymethyloxetane and 1-allyloxy-2,3-epoxypropane are preferred.

The various compounds (α3) described above can be used alone or in admixture of two or more.
(Hydrosilylation catalyst)
As a catalyst for the hydrosilylation reaction of the compound (α1), the compound (α2), and the compound (α3), for example, the following can be used. Platinum simple substance, alumina, silica, carbon black or the like supported on solid platinum, chloroplatinic acid, a complex of chloroplatinic acid and alcohol, aldehyde, ketone or the like, platinum-olefin complex (for example, Pt (CH ₂ = CH ₂ ) ₂ (PPh ₃ ) ₂ , Pt (CH ₂ = CH ₂ ) ₂ Cl ₂ ), platinum-vinylsiloxane complex (for example, Pt (ViMe ₂ SiOSiMe ₂ Vi) _n , Pt [(MeViSiO) ₄ ]) _m ), platinum-phosphine complexes (eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ), platinum-phosphite complexes (eg, Pt [P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄₎ (in the formula, Me represents a methyl group, Bu a butyl group, Vi is vinyl group, Ph represents a phenyl group, n, m is an integer.), dicarbonyl dichloroplatinum, Karushuteto Karstedt catalyst, as well as the platinum-hydrocarbon complexes described in Ashby US Pat. Nos. 3,159,601 and 3,159,622, and Lamoreaux, US Pat. No. 3,220,972. And platinum alcoholate catalysts. In addition, platinum chloride-olefin complexes described in Modic US Pat. No. 3,516,946 are also useful in the present invention.

Examples of catalysts other than platinum compounds include RhCl (PPh) ₃ , RhCl ₃ , RhAl ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , TiCl _4. , Etc.

  Of these, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes and the like are preferable from the viewpoint of catalytic activity. Moreover, these catalysts may be used independently and may be used together 2 or more types.

Although the addition amount of the catalyst is not particularly limited, the lower limit of the preferable addition amount is sufficient with respect to 1 mol of SiH groups of the compound (α2) in order to have sufficient curability and keep the cost of the curable composition relatively low. 10 ^-8 mol, more preferably 10 ^-6 moles, the upper limit of the preferable amount is 10 ^-1 mol per mole of the SiH group in the compound ([alpha] 2), more preferably 10 ^-2 moles.

In addition, a cocatalyst can be used in combination with the above catalyst. Examples thereof include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl malate, 2-hydroxy-2-methyl-1 Examples include acetylene alcohol compounds such as butyne and 1-ethynyl-1-cyclohexanol, and sulfur compounds such as simple sulfur. The addition amount of the cocatalyst is not particularly limited, but the lower limit of the preferable addition amount with respect to 1 mol of the hydrosilylation catalyst is 10 ⁻² mol, more preferably 10 ⁻¹ mol, and the upper limit of the preferable addition amount is 10 ^2. Mol, more preferably 10 mol.
(Reaction of Compound (α1), Compound (α2), and Compound (α3))
A modified polyorganosiloxane compound having two or more epoxy groups and / or oxetanyl groups in one molecule is an organic compound having 2 to 6 carbon-carbon double bonds having reactivity with SiH groups in one molecule. Compound (compound (α1)), a chain and / or cyclic polyorganosiloxane compound (compound (α2)) having at least two SiH groups in one molecule, and at least an epoxy group or oxetanyl group in one molecule It is a compound obtained by reacting an organic compound (compound (α3)) having one carbon-carbon double bond having a reactivity with one SiH group in the presence of a hydrosilylation catalyst.

  There are various reaction methods for the compound (α1), the compound (α2), and the compound (α3), and two preferred synthesis methods are shown.

  One is that after an excess compound (α2) and a compound (α1) are subjected to a hydrosilylation reaction, the unreacted compound (α2) is once removed, and the obtained compound (α2) and the compound (α1) This is a synthesis method (A) in which a reaction product is subjected to a hydrosilylation reaction of the compound (α3).

  One is a synthesis method (B) in which the compound (α2) and the compound (α3) are hydrosilylated and then the compound (α1) is hydrosilylated to remove unreacted compounds.

  As a synthesis method, the synthesis method (A) is preferable from the viewpoint that the reactivity is good because the low molecular weight material is small and the heat resistance and light resistance of the cured product is improved.

  As a synthesis method, synthesis method (B) is preferable from the viewpoint that synthesis in one pot is possible and manufacturing cost is excellent.

  As a synthesis method, various methods can be used as a method of mixing the compound (α1), the compound (α2), and the compound (α3). A catalyst is mixed with the compound (α1) and / or the compound (α3). A method of mixing the compound with the compound (α2) is preferable. It is difficult to control the reaction when the catalyst is mixed with the compound (α1) and / or the mixture of the compound (α3) and the compound (α2). When the method of mixing the compound (α1) and / or the compound (α3) with the mixture of the compound (α2) and the catalyst is used, the compound (α2) is reactive with moisture mixed in by the catalyst. May be altered.

  The reaction temperature can be variously set. In this case, the lower limit of the preferable temperature range is 30 ° C., more preferably 50 ° C., and the upper limit of the preferable temperature range is 200 ° C., more preferably 150 ° C. If the reaction temperature is low, the reaction time for sufficiently reacting becomes long, and if the reaction temperature is high, it is not practical. The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as required.

  Various reaction times and pressures during the reaction can be set as required.

  Oxygen can be used during the hydrosilylation reaction. The hydrosilylation reaction can be promoted by adding oxygen to the gas phase portion of the reaction vessel. From the point of setting the amount of oxygen to be below the lower limit of explosion limit, the oxygen volume concentration in the gas phase must be controlled to 3% or less. In view of promoting the hydrosilylation reaction effect by the addition of oxygen, the oxygen volume concentration in the gas phase is preferably at least 0.1%, more preferably at least 1%.

  A solvent may be used during the hydrosilylation reaction. Solvents that can be used are not particularly limited as long as they do not inhibit the hydrosilylation reaction. Specific examples include hydrocarbon solvents such as benzene, toluene, hexane, heptane, tetrahydrofuran, 1,4-dioxane, 1, Ether solvents such as 3-dioxolane and diethyl ether, ketone solvents such as acetone and methyl ethyl ketone, and halogen solvents such as chloroform, methylene chloride and 1,2-dichloroethane can be preferably used. The solvent can also be used as a mixed solvent of two or more types. As the solvent, toluene, tetrahydrofuran, 1,3-dioxolane and chloroform are preferable. The amount of solvent to be used can also be set as appropriate.

  After the compound (α1), the compound (α2) and the compound (α3) are hydrosilylated, the solvent and / or the unreacted compound can be removed. By removing these volatile components, the reaction product obtained does not have volatile components. Therefore, when creating a cured product using the reaction product, problems of voids and cracks due to volatilization of volatile components are unlikely to occur. . Examples of the removal method include vacuum devolatilization. When devolatilizing under reduced pressure, it is preferable to treat at a low temperature. The upper limit of the preferable temperature in this case is 100 ° C, more preferably 80 ° C. When treated at high temperatures, it tends to be accompanied by alterations such as thickening.

In the production method of the present invention, various additives can be used depending on the purpose.
(Geling inhibitor)
For the purpose of improving the storage stability of the resulting reaction product, or after hydrosilylating the compound (α1), the compound (α2) and the compound (α3), the solvent and / or the unreacted compound is removed by devolatilization under reduced pressure. A gelation inhibitor can be used for the purpose of suppressing alteration such as thickening due to heat treatment in the case of removal. Examples of the gelation inhibitor include a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin-based compound, and an organic peroxide, and these may be used in combination. .

  Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols such as 3-hydroxy-3-methyl-1-butyne, 3-hydroxy-3-phenyl-1-butyne and 1-ethynyl-1-cyclohexanol. And maleate esters such as ene-yne compounds and dimethyl malate. Examples of the organophosphorus compounds include triorganophosphines, diorganophosphines, organophosphines, triorganophosphites and the like. Examples of organic sulfur compounds include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, benzothiazole disulfide and the like. Examples of tin compounds include stannous halide dihydrate and stannous carboxylate. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

  Among these gelation inhibitors, benzothiazole, thiazole, dimethyl malate, 3-hydroxy-3-methyl-1-butyne, 1-ethynyl-1 are preferred from the viewpoint of good delayed activity and good raw material availability. -Cyclohexanol and triphenylphosphine are preferable.

Although the addition amount of the gelation inhibitor can be variously set, the lower limit of the preferable addition amount with respect to 1 mol of the hydrosilylation catalyst to be used is 10 ⁻¹ mol, more preferably 1 mol, and the upper limit of the preferable addition amount is 10 ³ mol. More preferably, it is 10 ² mol. When there is little addition amount, the desired storage stability and the gelatinization inhibitory effect at the time of vacuum devolatilization will not be acquired. If the amount added is large, it can be a curing inhibitor during the curing reaction.

  Moreover, these gelation inhibitors may be used alone or in combination of two or more.

Examples of the modified polyorganosiloxane compounds which are hydrosilylation reaction products of the compound (α1), the compound (α2) and the compound (α3) as described above include triallyl isocyanurate and 1,3,5,7- Reaction product of tetramethylcyclotetrasiloxane and 1,2-epoxy-4-vinylcyclohexane, triallyl isocyanurate, 1,3,5,7-tetramethylcyclotetrasiloxane and 1-allyloxy-2,3-epoxypropane A reaction product of triallyl isocyanurate, 1,3,5,7-tetramethylcyclotetrasiloxane and 3-ethyl-3-allyloxymethyloxetane,
Reaction product of diallyl monoglycidyl isocyanurate, 1,3,5,7-tetramethylcyclotetrasiloxane and 1,2-epoxy-4-vinylcyclohexane, diallyl monoglycidyl isocyanurate and 1,3,5,7-tetra A reaction product of methylcyclotetrasiloxane and 1-allyloxy-2,3-epoxypropane, diallyl monoglycidyl isocyanurate, 1,3,5,7-tetramethylcyclotetrasiloxane and 3-ethyl-3-allyloxymethyloxetane Reactants,
Reaction product of divinylbenzene, 1,3,5,7-tetramethylcyclotetrasiloxane and 1,2-epoxy-4-vinylcyclohexane, divinylbenzene and 1,3,5,7-tetramethylcyclotetrasiloxane and 1 -A reaction product of allyloxy-2,3-epoxypropane, a reaction product of divinylbenzene, 1,3,5,7-tetramethylcyclotetrasiloxane and 3-ethyl-3-allyloxymethyloxetane, and the like.

  These reactants can be used alone or in admixture of two or more.

In the present invention, the SiH group value of the modified polyorganosiloxane compound (A) obtained through the hydrosilylation reaction is preferably less than 3.0 mmol / g. If the SiH value is 3.0 mmol / g or more, the physical properties and shape after curing may be adversely affected.
(Acid anhydride)
The curable resin composition of the present invention contains an acid anhydride (B) as an essential component. By adding the acid anhydride (B), the resulting cured product has not only a general effect of improving and / or stabilizing adhesion, but also high light resistance and adhesion reliability. An excellent effect such as superiority can be achieved.

  The acid anhydride (B) is not particularly limited, but an acid anhydride having no carbon-carbon double bond in the molecule is preferable. Specific examples include hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, hydrogenated nadic anhydride, hydrogenated methyl nadic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride. Among the acid anhydrides, methylhexahydrophthalic anhydride is particularly preferable from the viewpoints of maintaining heat and light resistance and transparency and improving adhesion and / or stabilization.

  Although the usage-amount of an acid anhydride can be set variously, 1-100 weight part is preferable with respect to 100 weight part of modified polyorganosiloxane compounds (A), and it is more preferable to contain 1-20 weight part. When the addition amount is small, the effect of improving the adhesiveness does not appear, and when the addition amount is large, the physical properties of the cured product may be adversely affected.

(Curing accelerator)
In the present invention, the curing accelerator (C) is an essential component and acts as a cationic polymerization initiator for the modified polyorganosiloxane compound (A) having two or more epoxy groups and / or oxetanyl groups in one molecule. The curing accelerator (C) is not particularly limited, but it is desirable to use a thermal cationic polymerization initiator and an active energy ray cationic polymerization initiator.

  Cationic or protonic acid catalysts such as sulfonium salts, ammonium salts, pyridinium salts, phosphonium salts, iodonium salts, triflate salts, boron trifluoride ether complex compounds, boron trifluoride, etc. Can be used. In addition, it is known that specific phenol compounds such as an aluminum complex and a silanol compound, and an aluminum complex and bisphenol S serve as a cationic polymerization catalyst. Specific examples include Adeka Opton CP-77 (ADEKA).

  Among the aromatic onium salts used as active energy ray cationic polymerization initiators, there are those that generate cationic species by heat, and these can also be used as curing accelerators. Examples include Sun-Aid SI-60L, SI-80L and SI-100L (Sanshin Chemical Industry Co., Ltd.), WPI116 (Wako Pure Chemical Industries, Ltd.), RHODORSIL PI2074 (Rhodia Inc.), and the like.

  Among the above cationic polymerization initiators, boron-based aromatic iodonium salts or antimony-based sulfonium salts are preferable in that they have excellent compatibility and curability with the modified polyorganosiloxane compound (A) having an epoxy group and / or oxetanyl group. Among the boron-based aromatic iodonium salts, RHODORSIL PI2074 (Rhodia) is preferable, and among the antimony-based sulfonium salts, CP-77 (ADEKA) is preferable.

Although the usage-amount of the said hardening accelerator (C) can be variously set, 0.001-5 weight part is preferable with respect to 100 weight part of modified polyorganosiloxane compounds (A), and 0.01-1 weight part is more preferable. . When the amount of the curing accelerator is small, there is a tendency that it takes a long time for curing or a cured product that is sufficiently cured cannot be obtained. If the amount of the curing accelerator is large, the color of the accelerator remains in the cured product, or coloring or bulging due to rapid curing, or the heat and light resistance of the cured product tends to be impaired, which is not preferable.
(Various additives)
In the range which does not impair the objective and effect of this invention other than said (A) modified polyorganosiloxane compound, said (B) acid anhydride, and said (C) hardening accelerator, the curable resin composition of this invention. Various additives can be contained.
(Anti-aging agent)
An anti-aging agent can be used in the curable resin composition of the present invention for the purpose of improving heat and light resistance. Examples of the anti-aging agent include phosphorus-based, sulfur-based, hindered phenol-based anti-aging agents such as citric acid and phosphoric acid.

As the phosphorus-based anti-aging agent, various types including Irgafos 38 available from Ciba Specialty Chemicals are used. Sulfur-based antioxidants include mercaptans, mercaptan salts, sulfide carboxylates, sulfides including hindered phenol sulfides, polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium Examples thereof include compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothioacids, polythioacids, thioamides, and sulfoxides.
Moreover, these anti-aging agents may be used independently and may be used together 2 or more types.
(Radical inhibitor)
A radical inhibitor may be added to the curable resin composition obtained in the present invention. Examples of the radical inhibitor include 2,6-di-t-butyl-3-methylphenol (BHT), 2,2′-methylene-bis (4-methyl-6-t-butylphenol), tetrakis (methylene- Phenol radical inhibitors such as 3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate) methane, phenyl-β-naphthylamine, α-naphthylamine, N, N′-secondary butyl-p- Examples include amine radical inhibitors such as phenylenediamine, phenothiazine, N, N′-diphenyl-p-phenylenediamine, and the like.
Moreover, these radical inhibitors may be used alone or in combination of two or more.
(Adhesion improver)
In the present invention, an adhesion improver may be added to the curable resin composition to improve adhesion. Examples of the adhesion improver include commonly used adhesives, for example, various coupling agents, phenol resins, coumarone-indene resins, rosin ester resins, terpene-phenol resins, α-methylstyrene-vinyltoluene copolymer. Examples include coalesced polymers, polyethylmethylstyrene, and aromatic polyisocyanates.

An example of the coupling agent is a silane coupling agent. The silane coupling agent is not particularly limited as long as it is a compound having at least one functional group reactive with an organic group and one hydrolyzable silicon group in the molecule. The group reactive with the organic group is preferably at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group from the viewpoint of handleability. From the viewpoints of adhesiveness and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable.
As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.

  Preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- Epoxycyclohexyl) alkoxysilanes having an epoxy functional group such as ethyltriethoxysilane: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Methacrylic or acrylic groups such as triethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane Alkoxysilanes which can be exemplified.

Moreover, these coupling agents, silane coupling agents, etc. may be used independently and may be used together 2 types or more.
(Reactive diluent)
A reactive diluent can be used in the curable resin composition of the present invention. Examples of the reactive diluent include various epoxy compounds, oxetane compounds, and vinyl ether compounds.

  Preferred reactive diluents include, for example, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, 2,2′-bis (4-glycidyloxycyclohexyl) propane, 3,4-epoxycyclohexylmethyl-3 ′, 4 ′. -Epoxycyclohexanecarboxylate, vinylcyclohexene dioxide, 1-methyl-4- (2-methyloxiranyl) -7-oxabicyclo [4.1.0] heptane, 2- (3,4-epoxycyclohexyl) ) -5,5-spiro- (3,4-epoxycyclohexane) -1,3-dioxane, bis (3,4-epoxycyclohexyl) adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate , Monoallyl diglycidyl isocyanate Nurate, diallyl monoglycidyl isocyanurate, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, bis [1-ethyl (3-oxetanyl)] methyl ether, 3-ethyl-3- (Phenoxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, cyclohexyl vinyl ether, 1,4-butanediol divinyl ether, nonanediol divinyl ether, cyclohexanediol divinyl ether, cyclohexanedimethanol A divinyl ether etc. can be mentioned.

These reactive diluents may be used alone or in combination of two or more.
(solvent)
When the obtained reaction product has a high viscosity, it can be used by dissolving in a solvent. Solvents that can be used are not particularly limited, and specific examples include hydrocarbon solvents such as benzene, toluene, hexane, heptane, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, diethyl ether, and the like. Ether solvents, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, glycol solvents such as propylene glycol-1-monomethyl ether-2-acetate (PGMEA), ethylene glycol diethyl ether, chloroform, methylene chloride, A halogen-based solvent such as 1,2-dichloroethane can be preferably used. These solvents may be used alone or as a mixed solvent of two or more.
(Other additives)
The curable composition of the present invention includes other ion traps such as fillers, colorants, flame retardants, flame retardant aids, surfactants, antifoaming agents, emulsifiers, leveling agents, anti-fogging agents, and antimony-bismuth. Agent, thixotropic agent, tackifier, storage stability improver, ozone degradation inhibitor, light stabilizer, thickener, plasticizer, reactive diluent, antioxidant, thermal stabilizer, conductivity imparting Agents, antistatic agents, radiation blocking agents, nucleating agents, phosphorus peroxide decomposing agents, lubricants, pigments, metal deactivators, thermal conductivity imparting agents, physical property modifiers, etc. It can be added in a range not present.
(Method for preparing curable resin composition and curing method)
The method for preparing the curable resin composition is not particularly limited, and can be prepared by various methods. Various components may be mixed and prepared immediately before curing, or all components may be mixed and prepared in advance and stored at a low temperature. In addition to the modified polyorganosiloxane compound, acid anhydride and curing accelerator, when various additives are used for the purpose of improving physical properties, these additives and the cationic polymerization initiator are mixed and stored in advance. Alternatively, the respective predetermined amounts may be mixed immediately before curing. By previously dissolving the cationic polymerization initiator in various additives, the mixing time can be shortened, and it is not necessary to dissolve the cationic polymerization initiator in a volatile solvent. In the case where a cationic polymerization initiator is mixed with a modified polyorganosiloxane compound and stored, the epoxy group or oxetanyl group has reactivity, and thus may be altered during storage.

  The thermosetting temperature can be variously set, but the lower limit of the preferable temperature is 30 ° C, more preferably 50 ° C, and further preferably 70 ° C. The upper limit of the preferable temperature is 250 ° C, more preferably 200 ° C, and still more preferably 150 ° C. When reaction temperature is low, reaction time for making it fully react may become long. If the reaction temperature is high, coloring or bulging may occur.

Curing may be performed at a constant temperature, but the temperature may be changed in multiple steps or continuously as required. It is preferable to carry out the reaction while raising the temperature in a multistage manner or continuously, rather than at a constant temperature, in that a cured product with less coloring and less distortion can be easily obtained.
(Use)
The curable resin composition or cured product of the present invention can be used for various applications. It can be applied to various uses in which a conventional epoxy resin adhesive is used.

For example, transparent materials, optical materials, optical lenses, optical films, optical sheets, optical component adhesives, optical waveguide coupling optical adhesives, optical waveguide peripheral member fixing adhesives, DVD bonding adhesives, adhesives, Dicing tape, electronic materials, insulating materials (including printed circuit boards, wire coatings, etc.), high voltage insulating materials, interlayer insulating films, insulating packings, insulating coating materials, adhesives, high heat resistant adhesives, high heat dissipation adhesives , Optical adhesives, LED element adhesives, various substrate adhesives, heat sink adhesives, paints, UV powder paints, inks, colored inks, UV inkjet inks, coating materials (hard coats, sheets, films, peeling Paper coating, optical disk coating, optical fiber coating, etc.), molding materials (including sheets, films, FRP, etc.), sealing materials, pottes Sealing material, sealing material, light-emitting diode sealing material, optical semiconductor sealing material, liquid crystal sealant, display device sealant, electrical material sealant, solar cell sealant, high heat-resistant sealant, resist Materials, liquid resist materials, colored resists, dry film resist materials, solder resist materials, color filter materials, stereolithography, electronic paper materials, hologram materials, solar cell materials, fuel cell materials, display materials, recording materials It can be applied to anti-vibration materials, waterproof materials, moisture-proof materials, heat-shrinkable rubber tubes, O-rings, photosensitive drums for copying machines, solid electrolytes for batteries, and gas separation membranes. In addition, concrete protective materials, linings, soil injection agents, cold storage heat materials, sealing materials for sterilization treatment devices, contact lenses, oxygen-enriched films, additives to other resins, and the like can be mentioned.

  Examples and Comparative Examples of the present invention are shown below, but the present invention is not limited to the following.

  The SiH group value and residual allyl group value of the intermediate reaction product of the modified polyorganosiloxane compound and the residual SiH group value and epoxy group value of the modified polyorganosiloxane compound prepared in the examples and comparative examples of the present invention are as follows. Measured.

(NMR)
A 300 MHz NMR apparatus manufactured by Varian Technologies Japan Limited was used.
(B) The reaction rate of the allyl group in the component synthesis was measured by adding the reaction solution diluted to about 1% with deuterated chloroform to the NMR tube, the peak of the methylene group derived from the unreacted allyl group, and the reaction. It calculated | required from the peak of the methylene group derived from an allyl group. As the functional group value of the modified polyorganosiloxane compound, the epoxy group value (mmol / g) and the SiH group value (mmol / g) in terms of dibromoethane were determined.

(Synthesis Example 1)
In a 2 L autoclave, 419 g of toluene, 714 g of 1,3,5,7-tetramethylcyclotetrasiloxane and the gas phase portion were replaced with nitrogen, and then heated and stirred at an external temperature of 103 degrees. A mixed liquid of 150 g of diallyl monoglycidyl isocyanurate, 128 g of toluene and 0.22 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 100 minutes. The reaction was terminated by cooling the reaction solution 60 minutes after the completion of dropping. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain a colorless and transparent liquid “Reaction product 1”. “Reactant 1” was found to have an SiH group value of 7.2 mmol / g from ¹ H-NMR measurement.
Further, 300 g of toluene and 150 g of “Reactant 1” were placed in a 1 L flask, and the gas phase portion was purged with nitrogen, and then heated and stirred at an internal temperature of 100 ° C. 110 minutes of a mixture of 57.6 g of 1,2-epoxy-4-vinylcyclohexane, 106.0 g of allyl glycidyl ether, 59.9 g of toluene and 0.0090 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) It was dripped over. The reaction liquid was cooled 60 minutes after completion | finish of dripping. By devolatilizing this reaction solution, a colorless and transparent modified polyorganosiloxane compound was obtained. The obtained modified polyorganosiloxane compound was found to have an epoxy group value of 4.7 mmol / g and a residual SiH group value of 0.1 mmol / g from ¹ H-NMR measurement.

(Synthesis Example 2)
300 g of toluene and 200 g of “Reactant 1” were placed in a 1 L flask, and the gas phase portion was purged with nitrogen, and then heated and stirred at an internal temperature of 100 ° C. A mixed solution of 100.0 g of 1,2-epoxy-4-vinylcyclohexane, 60.0 g of toluene and 0.0090 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 120 minutes. 30 minutes after the completion of dropping, 0.0036 g of triphenylphosphine was added as a gelation inhibitor in a 100-fold diluted solution of toluene, and then the reaction solution was cooled. By devolatilizing this reaction solution, a colorless and transparent modified polyorganosiloxane compound was obtained. The obtained modified polyorganosiloxane compound was found to have an epoxy group value of 2.7 mmol / g and a residual SiH group value of 2.4 mmol / g from ¹ H-NMR measurement.

(Synthesis Example 3)
300 g of toluene and 200 g of “Reactant 1” were placed in a 1 L flask, and the gas phase portion was purged with nitrogen, and then heated and stirred at an internal temperature of 100 ° C. Mixture of 49.9 g of 1,2-epoxy-4-vinylcyclohexane, 45.9 g of allyl glycidyl ether, 60.0 g of toluene and 0.0110 g of platinum vinylsiloxane complex in xylene solution (containing 3 wt% as platinum) for 60 minutes It was dripped over. Sixty minutes after the completion of the dropwise addition, 0.0043 g of triphenylphosphine was added as a gelation inhibitor in a 100-fold diluted solution of toluene, and then the reaction solution was cooled. By devolatilizing this reaction solution, a colorless and transparent modified polyorganosiloxane compound was obtained. The obtained modified polyorganosiloxane compound was found to have an epoxy group value of 2.4 mmol / g and a residual SiH group value of 2.4 mmol / g from ¹ H-NMR measurement.

(Synthesis Comparative Example 1)
Into a 2 L autoclave, 719 g of toluene and 153 g of 1,3,5,7-tetramethylcyclotetrasiloxane were added, and the gas phase portion was purged with nitrogen, and then the internal temperature was stabilized and stirred at 60 ° C. A mixed liquid of 315 g of 1,2-epoxy-4-vinylcyclohexane, 315 g of toluene, and 0.0330 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 100 minutes. After completion of dropping, the internal temperature was raised to 80 ° C. 180 minutes after completion of the dropwise addition, 0.133 g of triphenylphosphine was added as a gelation inhibitor in a 100-fold dilution with toluene, and then cooled. The reaction solution was devolatilized to obtain a slightly yellow transparent modified polyorganosiloxane compound. The obtained modified polyorganosiloxane compound was found to have an epoxy group value of 6.0 mmol / g and a residual SiH group value of 0.2 mmol / g from ¹ H-NMR measurement.

Example 1
Modified polyorganosiloxane compound obtained in Synthesis Examples 1 to 3 as a modified organosiloxane compound having an epoxy group, 4-methylhexahydrophthalic anhydride (Ricacid MH-700, Shin Nippon Rika Co.) as an acid anhydride, curing acceleration 3-methyl-2-butenyltetramethylenesulfonium hexafluoroantimonate (Adeka Opton CP-77, ADEKA) as an agent and Irgafos 38 (Ciba Specialty Chemicals) as an anti-aging agent are cured at the blending ratio shown in Table 1. A sex composition was prepared. About the compounding method, the compound which has an epoxy group, an acid anhydride, anti-aging agent, and the hardening accelerator was mixed for a predetermined amount, and what was stirred and deaerated was made into the curable composition.
The curable composition was poured into a cell prepared by sandwiching a 3 mm thick silicone rubber sheet as a spacer between two glass plates, heated at 80 ° C. for 2 hours, 100 ° C. for 2 hours, 120 ° C. for 2 hours, and 150 ° C. for 2 hours, Slow cooling to obtain a cured product.

(Examples 2 and 3)
Modified polyorganosiloxane compound obtained in Synthesis Examples 2 and 3 as a modified organosiloxane compound having an epoxy group, Ricacid MH-700 as an acid anhydride, and tricumyliodonium tetrakispentafluorophenylborate (Rhodia, Inc.) as a curing accelerator A curable composition was prepared at a blending ratio shown in Table 1 with a 50 wt% PGMEA solution of trade name RHODORSIL PI2074). Regarding the blending method, a compound having an epoxy group, an acid anhydride and a curing accelerator were mixed in a predetermined amount, stirred and degassed to obtain a curable composition.
The curable composition was poured into a cell prepared by sandwiching a 1 mm-thick silicone rubber sheet between two glass plates as a spacer, heated at 70 ° C. for 2 hours, 90 ° C. for 2 hours, 120 ° C. for 2 hours, then gradually cooled and cured. I got a thing.

(Comparative Examples 1 and 2)
Modified polyorganosiloxane compound obtained in Synthesis Comparative Example 1 as a modified siloxane compound having an epoxy group, Celoxide 2021P (manufactured by Daicel Chemical Industries) as an alicyclic epoxy compound, Ricacid MH-700 as an acid anhydride, and a curing accelerator A curable composition was prepared with a blending ratio of Adeka Opton CP-77 (ADEKA) shown in Table 1. Regarding the blending method, a compound having an epoxy group, an acid anhydride and a curing accelerator were mixed in a predetermined amount, stirred and degassed to obtain a curable composition.
The curable composition was poured into a cell prepared by sandwiching a 3 mm thick silicone rubber sheet as a spacer between two glass plates, heated at 80 ° C. for 2 hours, 100 ° C. for 2 hours, 120 ° C. for 2 hours, and 150 ° C. for 2 hours, Slow cooling to obtain a cured product.

  Each cured product obtained in the above Examples and Comparative Examples was subjected to light transmittance measurement, light resistance test, and adhesion test using each curable composition obtained in the above Examples and Comparative Examples as follows. . These results are shown in Table 1.

(Light transmittance)
A 3 mm × 10 mm × 30 mm test piece was cut out from the obtained cured product, and the light transmittance of the test piece at 470 nm was measured under the condition of a scan speed of 300 nm / min using U-3300 manufactured by Hitachi, Ltd. . The light transmittance here is determined according to the following criteria and is shown in Table 1 as the initial transmittance.
A: Light transmittance is 90% or more. B: Light transmittance is 80 to 89%.
X: Light transmittance is less than 80% (adhesion strength test)
A 50 μm-thick coating film was prepared using the obtained curable composition, a 2 × 2 × 0.1 mm glass plate was stamped thereon, and the curable composition was adhered to the glass plate. This glass plate was placed on an aluminum plate whose surface was degreased with acetone in advance, and Example 1, Comparative Example 1 and Comparative Example 2 were 80 ° C. for 2 hours, 100 ° C. for 2 hours, 120 ° C. for 2 hours, and 150 ° C. for 2 hours. And a die shear test piece was prepared. In addition, Examples 2 and 3 were cured at 70 ° C. for 2 hours, 90 ° C. for 2 hours, and 120 ° C. for 2 hours to prepare die shear test pieces. About this die shear test piece, die shear strength was measured using the die shear tester 4000-DS100KG made from Dage.

(Light resistance test)
A 3 mm × 10 mm × 30 mm test piece and a die shear test piece cut out from the obtained cured product were used with a metering weather meter type M6T manufactured by Suga Test Instruments Co., Ltd., a premises temperature of 105 ° C., and an irradiance of 0.5. Irradiation was performed at 53 kW / m ² to an integrated irradiance of 50 MJ / m ² .
The light transmittance at 470 nm (equipment: U-3300 manufactured by Hitachi, Ltd., condition: scan speed 300 nm / min) was measured for the test piece after irradiation. The measured light transmittance is judged based on the same standard as the light transmittance, and the result is shown in Table 1 as the transmittance after the light resistance test.
About the die shear test piece after irradiation, the die shear strength was measured in the same manner as the adhesive strength test. The results are shown in Table 1 as glass / aluminum adhesion after the light resistance test.

表１から明らかなとおり、本発明の変性ポリオルガノシロキサン化合物（Ａ）、酸無水物（Ｂ）及び硬化促進剤（Ｃ）を使用して得られた透明性樹脂硬化物は、比較例で作製された硬化物に対して、耐光試験後においても光線透過率が良好で、かつ、優れたダイシェア強度を維持したことがわかる。したがって、本願発明の硬化性組成物から得られる硬化物は、耐光透明性、かつ接着信頼性に優れることが理解できる。

As is apparent from Table 1, the transparent resin cured product obtained using the modified polyorganosiloxane compound (A), acid anhydride (B) and curing accelerator (C) of the present invention was prepared in a comparative example. It can be seen that the cured product has good light transmittance and excellent die shear strength even after the light resistance test. Therefore, it can be understood that the cured product obtained from the curable composition of the present invention is excellent in light resistance and adhesion reliability.

  As described above, according to the present invention, an organic compound having a carbon-carbon double bond, a SiH group-containing polyorganosiloxane compound capable of giving a cured product excellent in light resistance and adhesion reliability, and , A modified polyorganosiloxane compound (A) that is a hydrosilylation reaction product of an organic compound having an epoxy group or oxetanyl group and a carbon-carbon double bond, an acid anhydride (B), and a curing accelerator (C) The transparent resin cured product obtained by curing the resin composition and the resin composition can provide a transparent resin excellent in light resistance and adhesion reliability. The obtained transparent cured product can be applied to various uses in which a conventional epoxy resin adhesive is used, including a sealing resin for a light emitting device, and its industrial value is extremely large.

Claims (10)

(A) A modified polyorganosiloxane compound having two or more epoxy groups and / or oxetanyl groups in one molecule, which is a hydrosilylation reaction product of the following compounds (α1) to (α3):
(Α1) an organic compound having 2 to 6 carbon-carbon double bonds having reactivity with SiH groups in one molecule;
(Α2) a linear and / or cyclic polyorganosiloxane compound having at least two SiH groups in one molecule,
(Α3) In one molecule, an organic compound having at least one epoxy group or oxetanyl group and one carbon-carbon double bond having reactivity with a SiH group,
(B) an acid anhydride, and
(C) A curable resin composition containing a curing accelerator.   The compound (α1) is diallyl monoglycidyl isocyanurate, diallyl monobenzyl isocyanurate, 1,3-bis (allyloxy) adamantane, 1,3-bis (vinyloxy) adamantane, 1,4-cyclohexanedimethanol divinyl ether, Dicyclopentadiene, divinylbenzene, vinylcyclohexene, 1,5-hexadiene, 1,9-decadiene, diallyl ether, triallyl isocyanurate, triallyl cyanurate, 1,2,4-trivinylcyclohexane, trimethylolpropane tri At least one selected from the group consisting of allyl ether, 1,3,5-tris (allyloxy) adamantane, 1,3,5-tris (vinyloxy) adamantane, and pentaerythritol tetraallyl ether In it, the curable resin composition according to claim 1. The compound (α2) has the following general formula (I)

(Wherein R ¹ represents an organic group having 1 to 6 carbon atoms and n represents a number of 3 to 10), and is a cyclic polyorganosiloxane compound having a SiH group. Curable resin composition. The compound (α3) is at least one selected from the group consisting of 1,2-epoxy-4-vinylcyclohexane, 3-ethyl-3-allyloxymethyloxetane, and 1-allyloxy-2,3-epoxypropane. The curable resin composition according to any one of claims 1 to 3.   The curable resin composition according to any one of claims 1 to 4, wherein the SiH group value in the (A) modified polyorganosiloxane compound is less than 3.0 mmol / g.   The curable resin composition according to any one of claims 1 to 5, wherein the (B) acid anhydride is methylhexahydrophthalic anhydride.   The curable resin according to any one of claims 1 to 6, wherein the blending amount of the (B) acid anhydride is 1 to 100 parts by weight with respect to 100 parts by weight of the (A) modified polyorganosiloxane compound. Composition.   The curable resin composition according to any one of claims 1 to 7, wherein the (C) curing accelerator is a boron-based iodonium salt and / or an antimony-based sulfonium salt.   The curable resin composition according to any one of claims 1 to 8, wherein the (C) curing accelerator is contained in an amount of 0.001 to 5 parts by weight with respect to 100 parts by weight of the (A) modified polyorganosiloxane compound. object.   A cured product obtained by curing the curable resin composition according to any one of claims 1 to 9.