JP6849971B2 - Silicone modified epoxy resin and its composition and cured product - Google Patents

Description

As an epoxy resin composition, it has been conventionally used for optical material applications (Patent Document 1). However, in the alicyclic epoxy resin, since the main skeleton is formed of an organic skeleton, sufficient heat resistance and weather resistance could not be imparted. Therefore, in the field of optical materials that require high transparency, it has been difficult to provide materials that can withstand exposure to harsh environments or under the influence of heat and light generated by optical members as optical materials. ..

As a solution to these problems, a technique for introducing an aromatic group between the silicone skeletons has been developed (Patent Documents 2 and 3). However, the skeletons described in Patent Documents 2 and 3 are colored, and it is difficult to ensure sufficient transparency. Further, with the progress of technology, there is an increasing demand for a material having excellent bendability and toughness in the field of organic EL and the like. Therefore, there has been a demand for the development of an epoxy resin having excellent transparency as well as heat resistance and toughness.

Japanese Unexamined Patent Publication No. 2006-282988 Japanese Unexamined Patent Publication No. 2001-122970 Japanese Unexamined Patent Publication No. 2001-261836

The present invention has been made in view of the above circumstances, and is a silicone-modified epoxy resin composition that gives a cured product having excellent transparency, heat resistance, and toughness, and an epoxy resin cured product obtained by curing the composition. The purpose is to provide.

（式中、Ｒ_２は水素原子、下記式（２Ａ）

（式中、Ｒ_１は直接結合又はエステル、エーテル結合を含有してもよい炭素数１〜６のアルキレン基を、＊は上記式（１）において隣接するケイ素原子への結合を示す。）、
下記式（２Ｂ）

（式中、Ｒ_１、＊は上記と同様の意味を表す。）、
炭素数１〜６の一価脂肪族炭化水素基又は炭素数６〜１２の一価芳香族炭化水素基を、Ａは炭素数１〜２０のヘテロ環骨格、環式炭化水素骨格又は芳香環骨格を有しても良い有機基を、ｎは平均値で０〜１０をそれぞれ表す。式中、複数存在するＲ_１〜Ｒ_２はそれぞれ同一であっても異なってもよい。但し、複数存在するＲ_２のうち少なくとも一つは上記式（２Ａ）又は（２Ｂ）を表す。）
（２）前記ヘテロ環骨格、環式炭化水素骨格、芳香環骨格が下記から選択される（１）に記載のシリコーン変性エポキシ樹脂。
ヘテロ環骨格：モルホリン骨格、テトラヒドロフラン骨格、オキサン骨格、ジオキサン骨格、トリオキサン骨格、トリアジン骨格、カルバゾール骨格、ピロリジン骨格、ピペリジン骨格
環式炭化水素骨格：ジシクロデカン骨格、トリシクロデカン骨格、アダマンタン骨格、シクロヘキサン骨格、シクロペンタン骨格、シクロヘプタン骨格
芳香環骨格：ベンゼン骨格、ナフタレン骨格、カルバゾール骨格
（３）前記式（１）において、複数存在するＲ_２のうち少なくとも一つは炭素数６〜１２の一価芳香族炭化水素基を表すことを特徴とする（１）又は（２）に記載のシリコーン変性エポキシ樹脂。
（４）前記式（１）において、Ａが炭素数１〜１０のアルキレン基、下記式（３）

（上記式中、Ｒ_３は炭素数１〜６のアルキレン基を、Ｒ_４は水素原子又は炭素数１〜３のアルキル基を、ｍは０又は１の整数を、ｋは１〜４の整数を表す。＊は上記式（１）において隣接する酸素原子への結合を表す。）
又は下記式（４）

（上記式中、Ｒ_３、Ｒ_４、ｋ、＊は前記と同様の意味を表す。）
のいずれかの有機基である（１）に記載のシリコーン変性エポキシ樹脂。
（５）前記シリコーン変性エポキシ樹脂が、下記式（５Ａ）

（式中、Ｒ_５は直接結合又はエステル、エーテル結合を含有してもよい炭素数１〜６のアルキレン基を表す。）
の末端アルケニル基を含有するエポキシ基含有化合物又は下記式（５Ｂ）

（式中、Ｒ_５は上記と同様の意味を表す。）
の末端水酸基を含有するエポキシ基含有化合物と、下記式（６）

（式中、Ｒは水素原子、炭素数１〜６の一価脂肪族炭化水素基又は炭素数６〜１２の一価芳香族炭化水素基を、Ａ及びｎは前記式（１）と同様の意味を表す。）
の反応物である（１）〜（４）のいずれか一項に記載のシリコーン変性エポキシ樹脂。
（６）（１）〜（５）のいずれか一項に記載の（Ａ）シリコーン変性エポキシ樹脂と（Ｂ）エポキシ樹脂硬化剤を含有するエポキシ樹脂組成物。
（７）さらに、（Ｃ）エポキシ樹脂硬化触媒を含有する（１）〜（６）のいずれか一項に記載のエポキシ樹脂組成物。
（８）（６）記載のエポキシ樹脂硬化剤がアミン系硬化剤、フェノール系硬化剤、酸無水物系硬化剤、多価カルボン酸樹脂のいずれかから選ばれることを特徴とするエポキシ樹脂組成物。
（９）（６）〜（８）のいずれか一項に記載のエポキシ樹脂組成物を硬化してなる硬化物。 The present invention relates to the following (1) to (9).
(1) A silicone-modified epoxy resin represented by the following formula (1).

(In the formula, R ₂ is a hydrogen atom, the following formula (2A)

(In the formula, R ₁ indicates an alkylene group having 1 to 6 carbon atoms which may contain a direct bond or an ester or ether bond, and * indicates a bond to an adjacent silicon atom in the above formula (1)).
The following formula (2B)

(In the formula, R ₁ , * represent the same meaning as above.),
A monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, A is a heterocyclic skeleton having 1 to 20 carbon atoms, a cyclic hydrocarbon skeleton or an aromatic ring skeleton. Each of the organic groups may have an average value of 0 to 10. In the formula, a plurality of R _{1 to} R ₂ existing may be the same or different from each other. Provided that at least one of _{R 2} existing in plural represents the above formula (2A) or (2B). )
(2) The silicone-modified epoxy resin according to (1), wherein the heterocyclic skeleton, the cyclic hydrocarbon skeleton, and the aromatic ring skeleton are selected from the following.
Heterocyclic skeleton: morpholin skeleton, tetrahydrofuran skeleton, oxane skeleton, dioxane skeleton, trioxane skeleton, triazine skeleton, carbazole skeleton, pyrrolidine skeleton, piperidine skeleton Cyclic hydrocarbon skeleton: dicyclodecane skeleton, tricyclodecane skeleton, adamantan skeleton, cyclohexane skeleton, Cyclopentane skeleton, cycloheptan skeleton Aromatic ring skeleton: benzene skeleton, naphthalene skeleton, carbazole skeleton (3) In the above formula (1), _{at least one of a plurality of R 2} is a monovalent aromatic having 6 to 12 carbon atoms. The silicone-modified epoxy resin according to (1) or (2), which represents a hydrocarbon group.
(4) In the above formula (1), A is an alkylene group having 1 to 10 carbon atoms, and the following formula (3)

(In the above formula, R ₃ is an alkylene group having 1 to 6 carbon atoms, R ₄ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m is an integer of 0 or 1, and k is an integer of 1 to 4. * Represents a bond to an adjacent oxygen atom in the above formula (1).)
Or the following formula (4)

(In the above formula, R ₃ , R ₄ , k, * represent the same meanings as described above.)
The silicone-modified epoxy resin according to (1), which is an organic group according to any one of the above.
(5) The silicone-modified epoxy resin has the following formula (5A).

(In the formula, R ₅ represents an alkylene group having 1 to 6 carbon atoms which may contain a direct bond or an ester or ether bond.)
Epoxy group-containing compound containing a terminal alkenyl group or the following formula (5B)

(In the formula, R ₅ has the same meaning as above.)
Epoxy group-containing compound containing the terminal hydroxyl group of, and the following formula (6)

(In the formula, R is a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and A and n are the same as in the above formula (1). Represents the meaning.)
The silicone-modified epoxy resin according to any one of (1) to (4), which is a reaction product of the above.
(6) An epoxy resin composition containing (A) a silicone-modified epoxy resin and (B) an epoxy resin curing agent according to any one of (1) to (5).
(7) The epoxy resin composition according to any one of (1) to (6), which further contains (C) an epoxy resin curing catalyst.
(8) An epoxy resin composition according to (6), wherein the epoxy resin curing agent is selected from any of an amine-based curing agent, a phenol-based curing agent, an acid anhydride-based curing agent, and a polyvalent carboxylic acid resin. ..
(9) A cured product obtained by curing the epoxy resin composition according to any one of (6) to (8).

（式中、Ｒ_５は直接結合又はエステル、エーテル結合を含有してもよい炭素数１〜６のアルキレン基を表す。）
の末端アルケニル基を含有するエポキシ基含有化合物又は下記式（５Ｂ）

（式中、Ｒ_５は上記と同じ基を表す。）
の末端水酸基を含有するエポキシ基含有化合物を、下記式（６）で表される化合物とそれぞれヒドロシリル化反応、脱水素カップリングすることで得られる。 The silicone-modified epoxy resin of the present invention has the following formula (5A).

(In the formula, R ₅ represents an alkylene group having 1 to 6 carbon atoms which may contain a direct bond or an ester or ether bond.)
Epoxy group-containing compound containing a terminal alkenyl group or the following formula (5B)

(In the formula, R ₅ represents the same group as above.)
It is obtained by hydrosilylation reaction and dehydrogenation coupling of the epoxy group-containing compound containing the terminal hydroxyl group of the above with the compound represented by the following formula (6), respectively.

で表される末端アルケニル基を含有するエポキシ基含有化合物を挙げることができる。 Here, R ₅ is an alkylene group having 1 to 6 carbon atoms which may contain a direct bond or an ester or ether bond, and specifically, a methylene group, an ethylene group, a propylene group, a butylene group or an isopropylene group. , Methyl ester group, methyl ether group, etc.
Examples of the compound represented by the formula (5A) include the following formulas (7) to (9).

Examples thereof include an epoxy group-containing compound containing a terminal alkenyl group represented by.

（式中、Ｒは水素原子、炭素数１〜６の一価脂肪族炭化水素基又は炭素数６〜１２の一価芳香族炭化水素基を、ｎは前記式（１）と同様の意味を表す。）
ここで、上記式（６）のＲについて少なくとも１つ以上がフェニル基等の炭素数６〜１２の一価芳香族炭化水素基であることが好ましい。
Ａは炭素数１〜２０のヘテロ環骨格、環式炭化水素骨格又は芳香環骨格を有しても良い有機基を表す。 To obtain the silicone-modified epoxy resin of the present invention, the compound of the following formula (6) is used in the reaction.

(In the formula, R is a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and n has the same meaning as in the above formula (1). Represent.)
Here, it is preferable that at least one or more of R in the above formula (6) is a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms such as a phenyl group.
A represents an organic group which may have a heterocyclic skeleton, a cyclic hydrocarbon skeleton or an aromatic ring skeleton having 1 to 20 carbon atoms.

In this case, the reaction ratio between the organic silicon compound having a SiH group at the terminal and the compound having a terminal alkenyl group or the compound having a terminal hydroxyl group is the molar ratio (H / Vi) of SiH group / (alkenyl group or hydroxyl group). It is preferable to react at a ratio of 0.1 to 3.0, particularly 0.5 to 1.5. The hydrosilylation reaction or the dehydrogenation coupling reaction may be carried out according to a conventionally known method.
Then, the organosilicon compound having a SiH group at the terminal represented by the above formula (6) and the compound having a terminal alkenyl group represented by the above formula (5A) or the terminal hydroxyl group represented by the above formula (5B) are added. The compound can be produced by a hydrosilylation reaction and a dehydrogenation coupling in the presence of a noble metal catalyst such as platinum, rhodium, or palladium.

Here, the compound represented by the above formula (6) will be described in detail.

（上記式中、Ｒ_３は炭素数１〜６のアルキレン基を、Ｒ_４は水素原子又は炭素数１〜３のアルキル基を、ｍは０又は１の整数を、ｋは１〜４の整数を表す。＊は上記式（１）において隣接する酸素原子への結合を表す。）
又は下記式（４）

（上記式中、Ｒ_３、Ｒ_４、ｋ、＊は前記式（３）と同様の意味を表す。）
のいずれかの有機基をそれぞれ表す。式中、複数存在するＲ_１〜Ｒ_３、はそれぞれ同一であっても異なってもよい。複数存在するＲ_２のうち少なくとも一つは炭素数６〜１２の一価芳香族炭化水素基を表す。）である。 In the compound represented by the above formula (6), A is an organic group such as an alkylene group which may have a heterocyclic skeleton having 1 to 20 carbon atoms, a cyclic hydrocarbon skeleton or an aromatic ring skeleton. Here, from the viewpoint of increasing the molecular weight, it is preferable to have a heterocyclic skeleton, a cyclic hydrocarbon skeleton or an aromatic skeleton. On the other hand, from the viewpoint of keeping the molecular weight small, a chain hydrocarbon group having a straight chain or a branched chain is preferable. Further, from the viewpoint of improving heat resistance, it is preferable to have a cyclic hydrocarbon skeleton, and from the viewpoint of improving toughness, it has a heterocyclic skeleton, or has a linear or branched chain. It is preferably a hydrocarbon group.
Examples of the heterocyclic skeleton include a morpholine skeleton, a tetrahydrofuran skeleton, an oxane skeleton, a dioxane skeleton, a trioxane skeleton, a triazine skeleton, a carbazole skeleton, a pyrrolidine skeleton, a piperidine skeleton and the like. Of these, an oxane skeleton, a dioxane skeleton, a trioxane skeleton, and a morpholine skeleton are preferable.
Examples of the cyclic hydrocarbon skeleton include a dicyclodecane skeleton, a tricyclodecane skeleton, an adamantane skeleton, a cyclohexane skeleton, a cyclopentane skeleton, and a cycloheptane skeleton. Of these, a tricyclodecane skeleton and a cyclohexane skeleton are preferable.
Examples of the aromatic skeleton include a benzene skeleton, a naphthalene skeleton, and a carbazole skeleton. Of these, the benzene skeleton is preferable.
Examples of the chain hydrocarbon group having a linear or branched chain include a methylene group, an ethylene group, a propylene group, a butylene group and the like. Of these, an ethylene group is preferable.
The number of carbon atoms constituting A is usually 1 to 20, preferably 1 to 15, and more preferably 2 to 12.
More specifically, the preferable organic group of A is an alkylene group having 1 to 10 carbon atoms, which is represented by the following formula (3).

(In the above formula, R ₃ is an alkylene group having 1 to 6 carbon atoms, R ₄ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m is an integer of 0 or 1, and k is an integer of 1 to 4. * Represents a bond to an adjacent oxygen atom in the above formula (1).)
Or the following formula (4)

(In the above formula, R ₃ , R ₄ , k, * represent the same meaning as the above formula (3).)
Represents any of the organic groups of. In the formula, a plurality of R _{1 to} R ₃ existing may be the same or different from each other. At least one of the plurality present R ₂ represents a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms. ).

In the monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or the monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms in R, specific examples of the monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms include. Saturated monovalent aliphatic hydrocarbons such as alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, heptyl group, 2-ethylhexyl group, heptyl group and octyl group. Examples thereof include unsaturated monovalent aliphatic hydrocarbon groups such as alkenyl groups such as groups, vinyl groups, allyl groups, isopropenyl groups and butenyl groups, preferably methyl group, ethyl group, n-propyl group, isopropyl group and the like. It is an n-butyl group, a t-butyl group, a heptyl group, and more preferably a methyl group. Specific examples of the monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms include an aryl group such as a phenyl group, a trill group, a xsilyl group and a naphthyl group, a benzyl group, a 2-phenylethyl group and a 2-phenylpropi group. It is an aralkyl group such as a ru group, preferably a phenyl group, a benzyl group, a 2-phenylethyl group, a 2-phenylpropyl group, and more preferably a phenyl group.

R ₃ is an alkylene group having 1 to 6 carbon atoms. Specifically, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, hexyl group, ethylene ester group, propylene ester group, butylene ester group, pentylene ester group, isopropylene ester. Examples thereof include a group, an isobutylene ester group, an ethylene ether group, a propylene ether group, a butylene ether group, a pentylene ether group, a hexylene ether group and the like. Among these alkylene groups, a methylene group and an isobutylene group are particularly preferable from the viewpoint of low gas permeability and strength of the cured product.

Is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms in R _4. Specific examples thereof include a methyl group, an ethyl group and a propyl group. Of these, an ethyl group is preferable.

n has an average value of 0 to 10, preferably 0 to 5, and more preferably 0 to 2. The average value of k is 1 to 10, and it is preferably 1 to 2 from the viewpoint of low gas permeability of the cured product.

（式中、Ａは炭素数１〜２０のヘテロ環骨格、環式炭化水素骨格又は芳香環骨格を有しても良い有機基を表す。）で表される多価アルコール類と、一般式（１１）

（式中、Ｒは前記式（６）と同様の意味を表し、複数あるＲは同一であっても異なっていても良い。）で表されるヒドロシラン類とを、パラジウム含有触媒の存在下、反応させることにより、上記一般式（６）で表される、前駆体ケイ素化合物が提供される。
ここで、炭素数１〜２０のヘテロ環骨格、環式炭化水素骨格又は芳香環骨格を有しても良い有機基の例として、ヘテロ環骨格、環式炭化水素骨格又は芳香環骨格としては上記骨格を挙げることができる。そして、例として、Ａは炭素数１〜１０のアルキレン基、下記式（３）

（上記式中、Ｒ_３は炭素数１〜６のアルキレン基を、Ｒ_４は水素原子又は炭素数１〜３のアルキル基を、ｍは０又は１の整数を、ｋは１〜４の整数を表す。＊は上記式（１）において隣接する酸素原子への結合を表す。）
又は下記式（４）

（上記式中、Ｒ_３、Ｒ_４、ｋ、＊は前記式（３）と同様の意味を表す。）
のいずれかの有機基をそれぞれ表す。式中、複数存在するＲ_３、Ｒ_４、はそれぞれ同一であっても異なってもよい。）を挙げることができる。 Here, the compound represented by the above formula (6) can be obtained by reacting a polyhydric alcohol with a silane compound.
That is, according to the present invention, the general formula (10)

(In the formula, A represents an organic group which may have a heterocyclic skeleton, a cyclic hydrocarbon skeleton or an aromatic ring skeleton having 1 to 20 carbon atoms), and polyvalent alcohols represented by the general formula ( 11)

(In the formula, R has the same meaning as that of the above formula (6), and a plurality of Rs may be the same or different.) In the presence of a palladium-containing catalyst, hydrosilanes represented by the above formula (6) may be used. By reacting, a precursor silicon compound represented by the above general formula (6) is provided.
Here, as an example of an organic group which may have a heterocyclic skeleton, a cyclic hydrocarbon skeleton or an aromatic ring skeleton having 1 to 20 carbon atoms, the heterocyclic skeleton, the cyclic hydrocarbon skeleton or the aromatic ring skeleton is described above. The skeleton can be mentioned. Then, as an example, A is an alkylene group having 1 to 10 carbon atoms, and the following formula (3)

(In the above formula, R ₃ is an alkylene group having 1 to 6 carbon atoms, R ₄ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m is an integer of 0 or 1, and k is an integer of 1 to 4. * Represents a bond to an adjacent oxygen atom in the above formula (1).)
Or the following formula (4)

(In the above formula, R ₃ , R ₄ , k, * represent the same meaning as the above formula (3).)
Represents any of the organic groups of. In the formula, a plurality of R ₃ and R ₄ may be the same or different from each other. ) Can be mentioned.

Further, the polyhydric alcohols used in the present invention do not have to be one kind each, and a mixture of a plurality of kinds may be used. The dihydrosilanes represented by the general formula (11) do not have to be one type.

（上記式中、Ｒ_３は炭素数１〜６のアルキレン基を、Ｒ_４は水素原子又は炭素数１〜３のアルキル基を、ｍは０又は１の整数を、ｋは１〜４の整数を表す。＊は上記式（１）において隣接する酸素原子への結合を表す。）
で表されるジオール化合物、下記式（１３）

（上記式中、Ｒ_３、Ｒ_４、ｋ、＊は前記式（３）と同様の意味を表す。）
で表されるジオール化合物を挙げることができる。 As the polyhydric alcohols used in the production method of the present invention, alkylene glycols which may have a heterocyclic skeleton having 1 to 20 carbon atoms, a cyclic hydrocarbon skeleton or an aromatic ring skeleton can be used. Examples of the heterocyclic skeleton, the cyclic hydrocarbon skeleton, and the aromatic ring skeleton include the above-mentioned skeletons. Further, alkylene glycols having a linear or branched chain having 1 to 20 carbon atoms can also be used.
As an example, the following equation (12)

(In the above formula, R ₃ is an alkylene group having 1 to 6 carbon atoms, R ₄ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m is an integer of 0 or 1, and k is an integer of 1 to 4. * Represents a bond to an adjacent oxygen atom in the above formula (1).)
The diol compound represented by the following formula (13)

(In the above formula, R ₃ , R ₄ , k, * represent the same meaning as the above formula (3).)
Examples of the diol compound represented by.

Examples of alkylene glycols having a linear or branched chain having 1 to 20 carbon atoms include ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, decanediol, and 2,4-dimethylpentanediol. , 1,3-Propanediol, 1,4-butanediol, 1,3-butanediol and the like.

で表されるジオール化合物であることが好ましい。 The diol compound represented by the formula (12), R ₃ is a methylene group, an ethylene group, a propylene group, butylene group, isobutylene group, pentylene group, an isopentylene group, but hexene group, etc., is a methylene group Is preferable.
m is preferably 1 and R ₄ is preferably a hydrogen atom.
In particular, the following equation (14)

It is preferably a diol compound represented by.

で表されるジオール化合物であることが好ましい。 The diol compound represented by the formula (13), R ₃ is a methylene group, an ethylene group, a propylene group, butylene group, isobutylene group, t-butylene, pentylene, isopentylene, but hexene group, and the like , Methylene group, t-butylene group is preferable.
R ₄ is preferably a hydrogen atom.
In particular, the following equation (15)

It is preferably a diol compound represented by.

The hydrosilanes used in the production method of the present invention are not particularly limited, and examples thereof include dimethylsilane, propylmethylsilane, butylmethylsilane, hexylmethylsilane, dodecylmethylsilane, dibutylsilane, and dihexylsilane. Dicyclohexylsilane, phenylsilane, phenylmethylsilane, naphthylmethylsilane, benzylmethylsilane, trillmethylsilane, anisylmethylsilane, trifluoromethylphenylmethylsilane, diphenylsilane, ditrilsilane, dianicilsilane, bis (trifluoromethylphenyl) silane, Examples thereof include dinaphthylsilane and dibenzylsilane.
Of these, phenylsilane and diphenylsilane are preferable.

In the production method of the present invention, a palladium-containing catalyst is used. Various types of palladium-containing catalysts can be used. Examples thereof include bis (triphenylphosphine) dichloropalladium, bis (triethylphosphine) dichloropalladium, bis (tricyclohexylphosphine) palladium, and tetrakis (triphenyl). Phosphine) palladium, tris (triethylphosphine) palladium, (tetramethylethylenediamine) dichloropalladium, allylpalladium chloride dimer, bis (benzonitrile) dichloropalladium, (1,5-cyclooctadiene) dichloropalladium, tris (dibenziliden Examples thereof include acetone) dipalladium, bis (acetylacetonato) palladium, palladium acetate, palladium chloride, palladium black, palladium carbon, and nitrogen-containing heterocyclic carben palladium. Here, it is preferable to use palladium carbon because it is easy to control the molecular weight and suppress gelation.

The production method of the present invention is achieved by reacting polyhydric alcohols with hydrosilanes in the presence of a palladium-containing catalyst. The molar ratio of the organic diols to the hydrosilanes is not particularly limited, but a molar ratio in the range of 1: 5 to 5: 1, more preferably 1: 2 to 2: 1 is desirable. The molar ratio of hydrosilanes to palladium in the palladium-containing catalyst is not particularly limited, but this can be carried out at a molar ratio in the range of 10,000: 1 to 2: 1 in consideration of yield and the like. .. The reaction in the present invention can be carried out without using a solvent when one of the raw materials is a liquid, but a hydrocarbon solvent such as benzene, toluene or hexane, diethyl ether, THF, dioxane or the like can be used. A halogen-based solvent such as an ether solvent, methylene chloride, or chloroform can be used. The reaction temperature is also not particularly limited, but this can be carried out in the range of 0 ° C. to 150 ° C. in consideration of reactivity, stability of the raw material and the like.

（式中、Ｒ_５は直接結合又はエステル、エーテル結合を含有してもよい炭素数１〜４のアルキレン基を表す。）
で表されるオレフィン化合物を酸化して得ることができる。 Here, the compound represented by the above formula (5) can be obtained by oxidizing the compound having the terminal alkenyl group by the above-mentioned oxidation method of the diolefin resin.
That is, the following equation (16)

(In the formula, R ₅ represents an alkylene group having 1 to 4 carbon atoms which may contain a direct bond or an ester or ether bond.)
It can be obtained by oxidizing the olefin compound represented by.

In the above formula (16), R ₅ is a direct bond or an ester, an alkylene group having 1 to 4 carbon atoms which may contain an ether bond. Specific examples thereof include an ethylene group, a propylene group, an isopropylene group, a butylene group, an ethylene ester group, a propylene ester group, an ethylene ether group, a propylene ether group, a butylene ether group, a pentylene ether group and a hexylene ether group. Be done. Among these alkylene groups, an ethylene group and a propylene group are particularly preferable from the viewpoint of low gas permeability and strength of the cured product.

Examples of the oxidation method include, but are not limited to, a method of oxidizing with a peracid such as peracetic acid, a method of oxidizing with a hydrogen peroxide solution, and a method of oxidizing with air (oxygen).
Specific examples of the epoxidation method using peracid include the methods described in Japanese Patent Application Laid-Open No. 2006-52187. Peracids that can be used include, for example, organic acids such as formic acid, acetic acid, propionic acid, maleic acid, benzoic acid, m-chlorobenzoic acid, phthalic acid and their acid anhydrides. Among these, formic acid, acetic acid, and phthalic anhydride are preferably used from the viewpoints of efficiency of reacting with hydrogen peroxide to generate organic peracid, reaction temperature, convenience of operation, and economy. From the viewpoint of convenience of reaction operation, it is more preferable to use formic acid or acetic acid.
Various methods can be applied to the method of epoxidation with a hydrogen peroxide solution. Specifically, Japanese Patent Application Laid-Open No. 59-108793, Japanese Patent Application Laid-Open No. 62-234550, and Japanese Patent Application Laid-Open No. As mentioned in Japanese Patent Application Laid-Open No. 5-213919, Japanese Patent Application Laid-Open No. 11-349579, Japanese Japanese Patent Application Laid-Open No. 1-33471, Japanese Japanese Patent Application Laid-Open No. 2001-17864, Japanese Japanese Patent Application Laid-Open No. 3-57102, etc. Method can be applied.
In addition, Non-Patent Document 1 (James V. Crivello and Ramesh Narayan, Novell Epoxynorborne Monomers. 1. Synthesis and characterization, Macromolecules. .. Specifically, it can be obtained by epoxidizing an olefin group using oxone.

Hereinafter, a particularly preferable method for obtaining the compound represented by the formula (5) will be illustrated.
First, the diolefin compound represented by the formula (16), polyacids and quaternary ammonium salt are reacted in two layers of an organic solvent and a hydrogen peroxide solution.

The polyacids used in the present invention are not particularly limited as long as they are compounds having a polyacid structure, but polyacids containing tungsten or molybdenum are preferable, polyacids containing tungsten are more preferable, and tungstate salts are particularly preferable.
Specific polyacids and polyacidates contained in polyacids include tungsten-based acids selected from tungonic acid, 12-tangstophosphoric acid, 12-tangstoboric acid, 18-tangstophosphoric acid, 12-tangstosilicic acid and the like. Examples thereof include molybdenum-based acids selected from molybdic acid and phosphoric acid, and salts thereof.
Examples of the counter cations of these salts include ammonium ion, alkaline earth metal ion, alkali metal ion and the like.
Specific examples thereof include, but are not limited to, alkaline earth metal ions such as calcium ion and magnesium ion, and alkali metal ions such as sodium, potassium and cesium. Particularly preferable counter cations are sodium ion, potassium ion, calcium ion and ammonium ion.

The amount of polyacids used is 1.0 to 20 mmol in terms of metal element (tungsten atom for tangtenic acid, molar number of molybdenum atom for molybdenum acid) with respect to 1 mol (functional group equivalent) of olefin in the diolefin compound of the present invention. It is preferably 2.0 to 20 mmol, more preferably 2.5 to 10 mmol.

As the quaternary ammonium salt, a quaternary ammonium salt having a total carbon number of 10 or more, preferably 25 to 100, more preferably 25 to 55 can be preferably used, and particularly preferably one in which all the alkyl chains are aliphatic chains. ..
Specifically, tridecanyl methylammonium salt, dilauryldimethylammonium salt, trioctylmethylammonium salt, trialkylmethyl (mixed type of compound having an alkyl group as an octyl group and a compound having a decanyl group) ammonium salt, trihexa Examples thereof include decylmethylammonium salt, trimethylstearylammonium salt, tetrapentylammonium salt, cetyltrimethylammonium salt, benzyltributylammonium salt, disetyldimethylammonium salt, tricetylmethylammonium salt, and dihardened beef fat alkyldimethylammonium salt. Not limited to.
Moreover, carboxylic acid ion is used as an anion species of these salts. As the carboxylic acid ion, acetate ion, carbonate ion and formate ion are preferable. In addition, acetate ion is particularly preferable.
If the carbon number of the quaternary ammonium salt exceeds 100, the hydrophobicity may become too strong and the solubility in the organic layer may be deteriorated. On the other hand, when the quaternary ammonium salt has less than 10 carbon atoms, the hydrophilicity becomes strong, and the compatibility with the organic layer may also deteriorate.
Halogen generally remains in the quaternary ammonium salt. In the present invention, it is particularly 1% by mass or less, more preferably 1000 ppm or less, still more preferably 700 ppm or less. If the total amount of halogen exceeds 1% by mass, a large amount of halogen remains in the product, which is not preferable.
The amount of the tungsten acid and the quaternary ammonium carboxylate used is preferably 0.01 to 0.8 times equivalent, or 1.1 to 10 times equivalent, which is several times the valence of the tungsten acid used. More preferably, it is 0.05 to 0.7 times equivalent, or 1.2 to 6.0 times equivalent, and further preferably 0.05 to 0.5 times equivalent, or 1.3 to 4.5 times equivalent. is there.
For example, since tungstic acid is divalent in H2WO4, the quaternary ammonium carboxylate is preferably in the range of 0.02 to 1.6 mol or 2.2 to 20 mol with respect to 1 mol of tungstic acid. .. Similarly, if it is tongue tungstic acid, it is trivalent, so it is 0.03 to 2.4 mol, or 3.3 to 30 mol, and if it is silicotungstic acid, it is tetravalent, so it is 0.04 to 3.2. It is preferably mol or 4.4-40 mol.
When the amount of the quaternary ammonium carboxylate is lower than 1.1 times the equivalent of the valence of tungsten acids, the epoxidation reaction is difficult to proceed (in some cases, the reaction proceeds faster), and by-products are produced. The problem arises that things are easy to make. If it is more than 10 times equivalent, it is not preferable to treat the excess quaternary ammonium carboxylate because it has a function of suppressing the reaction.

As the quaternary ammonium salt having a carboxylic acid ion as an anion, a commercially available product may be used. For example, the raw material quaternary ammonium salt is treated with a metal hydroxide or an ion exchange resin and converted into a quaternary ammonium hydroxide. Further, it may be produced by a method such as reacting with various carboxylic acids. Examples of the raw material quaternary ammonium salt include halides of quaternary ammonium and various metal salts. Further, if there is a suitable quaternary ammonium hydrooxide, it may be used.

Any of them can be used as a buffer solution, but it is preferable to use an aqueous phosphate solution in this reaction. The pH is preferably adjusted between pH 4 and 10, and more preferably pH 5 to 9. When the pH is less than 4, the hydrolysis reaction and polymerization reaction of the epoxy group are likely to proceed. Further, when the pH exceeds 10, the reaction becomes extremely slow, and there arises a problem that the reaction time is too long.
In particular, in the present invention, a buffer solution adjusted so that the pH is between 5 and 9 when the catalytic tungsten acids are dissolved is preferable.
As for the method of using the buffer solution, for example, in the case of a phosphoric acid-phosphate aqueous solution which is a preferable buffer solution, 0.1 to 10 mol% equivalent of phosphoric acid (or phosphorus such as sodium dihydrogen phosphate) is used with respect to hydrogen peroxide. A method of adjusting the pH with a basic compound (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, etc.) using a phosphate) can be mentioned. Here, it is preferable that the pH is adjusted to the above-mentioned pH when hydrogen peroxide is added. It is also possible to adjust using sodium dihydrogen phosphate, disodium hydrogen phosphate, or the like. The preferred phosphate concentration is 0.1 to 60% by weight, preferably 5 to 45% by weight.
In addition, in this reaction, a buffer solution is not used, and a phosphate such as disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate or sodium tripolyphosphate (or its hydrate) is used without adjusting the pH. It may be added directly. In terms of simplifying the process, there is no hassle of pH adjustment, and direct addition is particularly preferable. The amount of phosphate used in this case is usually 0.1 to 5 mol% equivalent, preferably 0.2 to 4 mol% equivalent, more preferably 0.3 to 3 mol% equivalent, relative to hydrogen peroxide. Is. At this time, if the pH exceeds 5 mol% equivalent with respect to hydrogen peroxide, pH adjustment is required, and if it is less than 0.1 mol% equivalent, the hydrolyzate of the produced epoxy resin easily proceeds or the reaction is slow. There will be harmful effects such as becoming.

This reaction is epoxidized with hydrogen peroxide. As the hydrogen peroxide used in this reaction, an aqueous solution having a hydrogen peroxide concentration of 10 to 40% by mass is preferable because of its ease of handling. If the concentration exceeds 40% by mass, it becomes difficult to handle and the decomposition reaction of the produced epoxy resin easily proceeds, which is not preferable.

This reaction uses an organic solvent. The amount of the organic solvent used is 0.3 to 10 by mass ratio with respect to the diolefin compound 1 which is the reaction substrate, preferably 0.3 to 5, and more preferably 0.5 to 2.5. is there. If the mass ratio exceeds 10, the reaction progresses extremely slowly, which is not preferable. Specific examples of the organic solvent that can be used include alkanes such as hexane, cyclohexane and heptane, aromatic hydrocarbon compounds such as toluene and xylene, and alcohols such as methanol, ethanol, isopropanol, butanol, hexanol and cyclohexanol. Be done. In some cases, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and anone, ethers such as diethyl ether, tetrahydrofuran and dioxane, ester compounds such as ethyl acetate, butyl acetate and methyl formate, and nitriles such as acetonitrile. Compounds and the like can also be used.

As a specific reaction operation method, for example, when the reaction is carried out in a batch type reaction vessel, a diolefin compound, hydrogen peroxide (aqueous solution), polyacids (catalyst), a buffer solution, a quaternary ammonium salt and an organic solvent are used. In addition, stir in two layers. The stirring speed is not specified. Since heat is often generated when hydrogen peroxide is added, a method of gradually adding hydrogen peroxide after adding each component may be used.

The reaction temperature is not particularly limited, but is preferably 0 to 90 ° C, more preferably 0 to 75 ° C, and particularly preferably 15 ° C to 60 ° C. If the reaction temperature is too high, the hydrolysis reaction tends to proceed, and if the reaction temperature is low, the reaction rate becomes extremely slow.

The reaction time depends on the reaction temperature, the amount of catalyst, and the like, but from the viewpoint of industrial production, a long-term reaction consumes a large amount of energy, which is not preferable. The preferred range is 1 to 48 hours, preferably 3 to 36 hours, and even more preferably 4 to 24 hours.

After completion of the reaction, quench treatment with excess hydrogen peroxide is performed. The quenching treatment is preferably carried out using a basic compound. It is also preferable to use a reducing agent and a basic compound in combination. As a preferable treatment method, a method of neutralizing and adjusting the pH to 6 to 12 with a basic compound and then using a reducing agent to quench the remaining hydrogen peroxide can be mentioned. If the pH is less than 6, the heat generated when reducing excess hydrogen peroxide is large, and decomposition products may be generated.

Examples of the reducing agent include sodium sulfite, sodium thiosulfate, hydrazine, oxalic acid, vitamin C and the like. As for the amount of the reducing agent used, the excess amount of hydrogen peroxide is usually 0.01 to 20 times by mole, more preferably 0.05 to 10 times by mole, and further preferably 0.05 to 3 times by mole with respect to the number of moles. is there.

Examples of the basic compound include metal hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide, metal carbonates such as sodium carbonate and potassium carbonate, and phosphorus such as sodium phosphate and sodium hydrogen phosphate. Examples include basic solids such as carbonates, ion exchange resins, and alumina.
The amount used is water, organic solvents (for example, aromatic hydrocarbons such as toluene and xylene, ketones such as methylisobutylketone and methylethylketone, hydrocarbons such as cyclohexane, heptane and octane, methanol, ethanol, isopropyl alcohol and the like. If it is soluble in various solvents such as alcohols), the amount used is usually 0.01 to 20 times, more preferably 0.05 to 10 times, the number of moles of excess hydrogen peroxide. The amount is mol, more preferably 0.05 to 3 times the molar amount. These may be added as water or a solution of the above-mentioned organic solvent, or may be added alone.
When a solid base that is insoluble in water or an organic solvent is used, it is preferable to use an amount of 1 to 1000 times by mass ratio with respect to the amount of hydrogen peroxide remaining in the system. It is more preferably 10 to 500 times, still more preferably 10 to 300 times. When a solid base that is insoluble in water or an organic solvent is used, the treatment may be performed after the aqueous layer and the organic layer described later are separated.

After quenching the hydrogen peroxide (or before quenching), at this time, if the organic layer and the aqueous layer are not separated, or if an organic solvent is not used, the above-mentioned organic solvent is added and the operation is performed to obtain water. The reaction product is extracted from the layer. The organic solvent used at this time is 0.5 to 10 times, preferably 0.5 to 5 times, the mass ratio of the raw material diolefin compound. After repeating this operation several times as necessary, the organic layer is separated, and if necessary, the organic layer is washed with water for purification.
The obtained organic layer may be an ion exchange resin, a metal oxide (particularly silica gel or alumina, etc.), activated carbon (particularly chemical-activated activated carbon is preferable), or a composite metal salt (particularly a basic composite metal salt), if necessary. (Preferably), viscous minerals (particularly, layered viscous minerals such as montmorillonite are preferable), and the like, and after further washing with water and filtration, the solvent is distilled off to obtain the desired epoxy compound. In some cases, it may be further purified by column chromatography or distillation.

（式中、Ｒ_２は水素原子、下記式（２Ａ）

（式中、Ｒ_１は直接結合又はエステル、エーテル結合を含有してもよい炭素数１〜６のアルキレン基を、＊は上記式（１）において隣接するケイ素原子への結合を示す。）
、下記式（２Ｂ）

（式中、Ｒ_１、＊は上記と同様の意味を表す。）
、炭素数１〜６の一価脂肪族炭化水素基又は炭素数６〜１２の一価芳香族炭化水素基を、Ａは炭素数１〜２０のヘテロ環骨格、環式炭化水素骨格又は芳香環骨格を有しても良い有機基を、ｎは平均値で０〜１０をそれぞれ表す。式中、複数存在するＲ_１〜Ｒ_４はそれぞれ同一であっても異なってもよい。但し、複数存在するＲ_２のうち少なくとも一つは上記式（２Ａ）又は（２Ｂ）を表す。）
このようにして得られた、上記シリコーン変性エポキシ樹脂において、分子量としては、各々下記の要件を満たすことが好適である。
数平均分子量（Ｍｎ）としては、２００〜３００００が好ましく、３００〜１００００が好ましく、３００〜５０００がより好ましい。
重量平均分子量（Ｍｗ）としては、２００〜５００００が好ましく、３００〜３００００が好ましく、３００〜１００００がより好ましい。この範囲にあることで、耐熱性、強靭性、操作性に優れたシリコーン変性エポキシ樹脂を得ることができる。
分子量分布（Ｍｗ／Ｍｎ）としては、１〜５０が好ましく、１〜３０が好ましく、１〜１０がより好ましい。 By going through the above-mentioned reaction, a silicone-modified epoxy resin represented by the following formula (1) can be obtained.

(In the formula, R ₂ is a hydrogen atom, the following formula (2A)

(In the formula, R ₁ indicates an alkylene group having 1 to 6 carbon atoms which may contain a direct bond or an ester or ether bond, and * indicates a bond to an adjacent silicon atom in the above formula (1).)
, The following formula (2B)

(In the formula, R ₁ , * represent the same meaning as above.)
, A monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and A is a heterocyclic skeleton having 1 to 20 carbon atoms, a cyclic hydrocarbon skeleton or an aromatic ring. An organic group that may have a skeleton is represented by n as an average value of 0 to 10, respectively. In the formula, a plurality of R _{1 to} R ₄ existing may be the same or different. Provided that at least one of _{R 2} existing in plural represents the above formula (2A) or (2B). )
In the silicone-modified epoxy resin thus obtained, it is preferable that the molecular weights of the silicone-modified epoxy resins satisfy the following requirements.
The number average molecular weight (Mn) is preferably 200 to 30,000, preferably 300 to 10,000, and more preferably 300 to 5,000.
The weight average molecular weight (Mw) is preferably 200 to 50,000, preferably 300 to 30,000, and more preferably 300 to 10,000. Within this range, a silicone-modified epoxy resin having excellent heat resistance, toughness, and operability can be obtained.
The molecular weight distribution (Mw / Mn) is preferably 1 to 50, preferably 1 to 30, and more preferably 1 to 10.

The above R ₁ is an alkylene group having 2 to 6 carbon atoms which may contain a direct bond, an ester or an ether bond. Specifically, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, hexyl group, ethylene ester group, propylene ester group, butylene ester group, pentylene ester group, isopropylene ester group, isobutylene. Examples thereof include an ester group, an ethylene ether group, a propylene ether group, a butylene ether group, a pentylene ether group and a hexylene ether group. Among these alkylene groups, an ethylene group and a propylene group are particularly preferable from the viewpoint of low gas permeability and strength of the cured product.

In monovalent aliphatic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms having 1 to 6 carbon atoms in R _2, specific examples of the monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms , Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, heptyl group, 2-ethylhexyl group, heptyl group, octyl group and other alkyl groups. Examples thereof include unsaturated monovalent aliphatic hydrocarbon groups such as alkenyl groups such as hydrogen group, vinyl group, allyl group, isopropenyl group and butenyl group, preferably methyl group, ethyl group, n-propyl group and isopropyl group. , N-Butyl group, t-Butyl group, heptyl group, more preferably methyl group. Specific examples of the monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms include an aryl group such as a phenyl group, a trill group, a xsilyl group and a naphthyl group, a benzyl group, a 2-phenylethyl group and a 2-phenylpropi group. It is an aralkyl group such as a ru group, preferably a phenyl group, a benzyl group, a 2-phenylethyl group, a 2-phenylpropyl group, and more preferably a phenyl group.

Further, as the obtained silicone-modified epoxy resin, the epoxy equivalent is preferably 500 to 20000 g / eq, more preferably 500 to 3000 g / eq, and particularly preferably 500 to 2000 g / eq. This is because high heat resistance can be ensured when the epoxy equivalent is in a suitable range.
Further, the residual amount of the solvent is preferably less than 5%, more preferably less than 2%. This is because if the residual amount of the solvent is large, there is a possibility that the cured product may volatilize during curing to cause a recess in the cured product.

In the compound represented by the above formula (1), A is an organic group such as an alkylene group which may have a heterocyclic skeleton having 1 to 20 carbon atoms, a cyclic hydrocarbon skeleton or an aromatic ring skeleton. From the viewpoint of improving heat resistance, it is preferable to have a cyclic hydrocarbon skeleton, and from the viewpoint of improving toughness, a chain hydrocarbon having a heterocyclic skeleton or a straight chain or a branched chain. It is preferably a group.
Examples of the heterocyclic skeleton include a morpholine skeleton, a tetrahydrofuran skeleton, an oxane skeleton, a dioxane skeleton, a trioxane skeleton, a triazine skeleton, a carbazole skeleton, a pyrrolidine skeleton, and a piperidine skeleton. Of these, an oxane skeleton, a dioxane skeleton, a trioxane skeleton, and a morpholine skeleton are preferable.
Examples of the cyclic hydrocarbon skeleton include a dicyclodecane skeleton, a tricyclodecane skeleton, an adamantane skeleton, a cyclohexane skeleton, a cyclopentane skeleton, and a cycloheptane skeleton. Of these, a tricyclodecane skeleton and a cyclohexane skeleton are preferable.
Examples of the aromatic skeleton include a benzene skeleton, a naphthalene skeleton, and a carbazole skeleton. Of these, the benzene skeleton is preferable.
Examples of the chain hydrocarbon group having a linear or branched chain include a methylene group, an ethylene group, a propylene group, a butylene group and the like. Of these, an ethylene group is preferable.
The number of carbon atoms constituting A is usually 1 to 20, preferably 1 to 15, and more preferably 2 to 12.

<(B) Hardener>
As the curing agent, a curing agent having a functional group reactive with an epoxy group is used. For example, an acid anhydride-based curing agent, a polyvalent carboxylic acid resin, a phenol-based curing agent, and an amine-based curing agent can be mentioned, and among them, an acid anhydride-based curing agent and a polyvalent carboxylic acid resin are preferable. Examples of the acid anhydride-based curing agent include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, phthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, and the like. A mixture of 3-methyl-hexahydrophthalic anhydride and 4-methyl-hexahydrophthalic anhydride, tetrahydrophthalic anhydride, nadicic anhydride, methylnadic anhydride, norbornan-2,3-dicarboxylic acid anhydride, methylnorbornan-2 , 3-Dicarboxylic anhydride, 2,4-diethylglutaric anhydride and the like, of which hexahydrophthalic anhydride and its derivatives are preferred.

（式中、Ａ_１はエーテル結合を介しても良い炭素総数１〜１０アルキレン基を表し、Ａ_２はメチル基又はフェニル基を表す。また、ｎは繰り返し数であり平均値を意味し、１〜１００である。）
酸無水物としては特にメチルテトラヒドロ無水フタル酸、無水メチルナジック酸、無水ナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、ブタンテトラカルボン酸無水物、ビシクロ［２，２，１］ヘプタン−２，３−ジカルボン酸無水物、メチルビシクロ［２，２，１］ヘプタン−２，３−ジカルボン酸無水物、シクロヘキサン−１，３，４−トリカルボン酸−３，４−無水物等が好ましく、中でもメチルヘキサヒドロ無水フタル酸、シクロヘキサン−１，３，４−トリカルボン酸−３，４−無水物が好ましい。ここで、硬度を上げるためには、シクロヘキサン−１，３，４−トリカルボン酸−３，４−無水物が好ましく、照度保持率を上げるためにはメチルヘキサヒドロ無水フタル酸無水物が好ましい。
付加反応の条件としては特に指定はないが、具体的な反応条件の１つとしては酸無水物、多価アルコールを無触媒、無溶剤の条件下、４０〜１５０℃で反応させ加熱し、反応終了後、そのまま取り出す。という手法である。ただし、本反応条件に限定されない。 Next, the multivalent carboxylic acid resin will be described.
The polyvalent carboxylic acid resin (B) is a compound having at least two or more carboxy groups and having an aliphatic hydrocarbon group or a siloxane skeleton as a main skeleton. In the present invention, the polyvalent carboxylic acid resin is not only a polyvalent carboxylic acid compound having a single structure, but also a mixture of a plurality of compounds having different substituent positions or different substituents, that is, a polyvalent carboxylic acid. The compositions are also included, and in the present invention, they are collectively referred to as a polyvalent carboxylic acid resin.
The polyvalent carboxylic acid resin (B) is particularly preferably a 2 to 6-functional carboxylic acid, and is a reaction between a 2 to 6-functional polyhydric alcohol having 5 or more carbon atoms or a polyhydric alcohol having a siloxane structure and an acid anhydride. The compound obtained by the above is more preferable. Further, a polycarboxylic acid in which the acid anhydride is a saturated aliphatic cyclic acid anhydride is preferable.
The alcohols having 2 to 6 functional polyhydric alcohols are not particularly limited as long as they are compounds having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1, 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1.3-propanediol, neopentylglycol, Diols such as tricyclodecanedimethanol and norbornenediol, triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1,4-butanediol, pentaerythritol, ditrimethylolpropane and the like. Tetraols, hexaols such as dipentaerythritol, etc. can be mentioned.
Particularly preferable alcohols are alcohols having 5 or more carbon atoms, and particularly 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 2, Examples thereof include compounds such as 4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecanedimethanol, norbornenediol, among which 2-ethyl-2-butyl-1 is used. , 3-Propanediol, neopentyl glycol, 2,4-diethylpentanediol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, norbornenediol and other alcohols having a branched chain structure or cyclic structure are more preferable. .. From the viewpoint of imparting a high illuminance retention rate, 2,4-diethylpentanediol and tricyclodecanedimethanol are particularly preferable.
The polyhydric alcohol having a siloxane structure is not particularly limited, and for example, a silicone oil represented by the following formula can be used.

(In the formula, A ₁ represents a total number of carbons of 1 to 10 alkylene groups which may be via an ether bond, A ₂ represents a methyl group or a phenyl group, and n is a number of repetitions and means an average value. ~ 100.)
Acid anhydrides include methyltetrahydrophthalic anhydride, methylnadic anhydride, nadicic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic acid anhydride, and bicyclo [2,2,1] heptane-. 2,3-Dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride and the like are preferable. Of these, methylhexahydrophthalic anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride are preferable. Here, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride is preferable in order to increase the hardness, and methylhexahydrophthalic anhydride anhydride is preferable in order to increase the illuminance retention rate.
The conditions for the addition reaction are not particularly specified, but as one of the specific reaction conditions, acid anhydride and polyhydric alcohol are reacted at 40 to 150 ° C. under the conditions of no catalyst and no solvent, and the reaction is carried out. After finishing, take it out as it is. It is a method called. However, the reaction conditions are not limited to this.

The polycarboxylic acid thus obtained has the following formula.

（式中、複数存在するＱは、水素原子、メチル基、カルボキシ基の少なくとも１種を表す。Ｐは前述の多価アルコール由来の炭素数２〜２０の鎖状、環状の脂肪族基である。ｍは２〜４である。）
で表される化合物が好ましい。

(In the formula, a plurality of Qs represent at least one of a hydrogen atom, a methyl group, and a carboxy group. P is a chain-like, cyclic aliphatic group having 2 to 20 carbon atoms derived from the above-mentioned polyhydric alcohol. . M is 2-4.)
The compound represented by is preferable.

The epoxy resin composition of the present invention preferably contains an acid anhydride. Specific examples of acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, nadicic anhydride, and hexahydrophthalic anhydride. Acid, methylhexahydrophthalic anhydride, butanetetracarboxylic acid anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3- Examples thereof include acid anhydrides such as dicarboxylic acid anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride.
In particular, methyltetrahydrophthalic anhydride, methylnadic anhydride, nadicic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic acid anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic Acid anhydrides, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydrides, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydrides and the like are preferred.
Especially preferably the following formula

（式中、存在するＳは、水素原子、メチル基、カルボキシ基の少なくとも１種以上を表す。）
で表されるヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、シクロヘキサン−１，３，４−トリカルボン酸−３，４−無水物が好ましく、中でもメチルヘキサヒドロ無水フタル酸、シクロヘキサン−１，３，４−トリカルボン酸−３，４−無水物が好ましい。

(In the formula, S present represents at least one of a hydrogen atom, a methyl group, and a carboxy group.)
Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride represented by, are preferable, and among them, methylhexahydrophthalic anhydride, cyclohexane-1,3, 4-Tricarboxylic acid-3,4-anhydride is preferred.

The polyvalent carboxylic acid resin (B) and the acid anhydride are preferably used in combination, and when used in combination, the ratio of use thereof is preferably in the following range.

W1 / (W1 + W2) = 0.05 to 0.70

However, W1 indicates the compounding mass portion of the polyvalent carboxylic acid resin (B), and W2 indicates the compounding mass portion of the acid anhydride. The range of W1 / (W1 + W2) is more preferably 0.05 to 0.60, still more preferably 0.10 to 0.55, and particularly preferably 0.15 to 0.4. If it is less than 0.05, the volatilization of the acid anhydride tends to increase during curing, which is not preferable. If it exceeds 0.70, the viscosity becomes high and handling becomes difficult. When no acid anhydride is contained (except when a small amount remains), the shape is solid or close to solid, or crystallized, so that there is no problem.
When the polyvalent carboxylic acid resin (B) and the acid anhydride are used in combination, the polyvalent carboxylic acid resin (B) is produced in excess of the acid anhydride when the polyvalent carboxylic acid resin (B) is produced, and the polyvalent carboxylic acid (B) and the acid anhydride are produced. The method of making a mixture of the above is also preferable from the viewpoint of ease of operation.

Specific examples of the phenol-based curing agent, amine-based curing agent, and amide-based curing agent include the following compounds.
Phenolic curing agents; bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpendiphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3', 5,5'-tetramethyl- [1 , 1'-biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene , Furfural, 4,4'-bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1,4'-bis (chloromethyl) benzene , 1,4'-bis (methoxymethyl) benzene and other polycondensates and modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, and polyphenols such as terpene and phenol condensates. , Not limited to these. These may be used alone or two or more kinds may be used.
Amine-based curing agents, amide-based curing agents; nitrogen-containing compounds such as polyamide resins synthesized from diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, linolenic acid dimer and ethylenediamine.

The blending amount of the curing agent for the component (B) is a functional group (-CO in the case of an acid anhydride-based curing agent) that is reactive with the epoxy group with respect to a total of 1 mol of the epoxy group in the component (A). The amount of the acid anhydride group represented by —O—CO− is 0.3 to 1.0 mol, preferably 0.4 to 0.8 mol. If the functional group having reactivity with the epoxy group is 0.3 mol or more, the heat resistance and transparency of the cured product are improved. Therefore, if it is 1.0 mol or less, the mechanical properties of the cured product are improved. Therefore, it is preferable. Here, the "functional group having reactivity with an epoxy group" refers to an amino group possessed by an amine-based curing agent, a phenolic hydroxyl group possessed by a phenol-based curing agent, an acid anhydride group possessed by an acid anhydride-based curing agent, and many. It is a carboxy group contained in a valent carboxylic acid resin.

<(C) Curing catalyst>
Examples of the curing catalyst include quaternary phosphonium salts such as tetrabutylphosphonium O, O-diethylphosphologithioate and tetraphenylphosphonium tetraphenylborate, and organic phosphine-based curing catalysts such as triphenylphosphine and diphenylphosphine, 1. , 8-diazabicyclo (5,4,5) undecene-7, tertiary amine-based curing catalysts such as triethanolamine and benzyldimethylamine, 1,8-diazabicyclo (5,4,0) undecene-7 phenol salt, 1 , 8-diazabicyclo (5,4,5) undecene-7 octylate, 1,8-diazabicyclo (5,4,5) undecene-7 p-toluenesulfonate, 1,8-diazabicyclo (5,4) 0) Quaternary ammonium salts such as undecene-7 formate, organic carboxylates such as zinc octylate and zinc naphthylate, aluminum bisethylacetate / monoacetylacetonate, aluminum ethylacetate acetate / diisopropyrate, etc. Examples thereof include imidazoles such as aluminum chelate compounds, 2-methylimidazole, 2-phenyl-4-methylimidazole and 2-ethyl-4-methylimidazole, preferably quaternary phosphonium salts and quaternary ammonium salts. ..

The blending amount of the curing catalyst (C) is 0.01 to 3 parts by mass, preferably 0.05 to 1.5 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). If the blending amount of the curing catalyst is less than the lower limit, the effect of promoting the reaction between the epoxy resin and the curing agent may not be sufficient. On the contrary, if the blending amount of the curing catalyst is larger than the upper limit value, it may cause discoloration during curing or reflow test.

<(D) Antioxidant>
Examples of the antioxidant include a phosphorous acid compound, a hindered phenol-based antioxidant, a phenol-based, sulfur-based, and a phosphorus-based antioxidant, and a hindered phenol-based antioxidant is preferable. The antioxidants can be used alone or in combination of two or more.
Further, as the ultraviolet absorber, a hindered amine-based ultraviolet absorber is preferable.

Specific examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisol, 2,6-di-t-butyl-p-ethylphenol, and stearyl-β- (3). , 5-Di-t-Butyl-4-hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,4-bis- (n-octylthio)- Monophenols such as 6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,4-bis [(octylthio) methyl] -o-cresol; 2'-Methylenebis (4-methyl-6-t-butylphenol), 2,2'-Methylenebis (4-ethyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol) ), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6 -Hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-) Hydrocinnamamide), 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,5-di-t-butyl-4-hydroxybenzyl Phosphonate-diethyl ester, 3,9-bis [1,1-dimethyl-2-{β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4,8 , 10-Tetraoxaspiro [5,5] undecane, bisphenols such as bis (3,5-di-t-butyl-4-hydroxybenzylsulfonate ethyl) calcium; 1,1,3-tris (2-methyl) -4-Hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [ Methyl-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] Methyl, bis [3,3'-bis- (4'-hydroxy-3'-t-butylphenyl) Butylic acid] glycol ester, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -iso Cyanurate, 1,3,5-tris (3', 5'-di-t-butyl-4'-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocopherol Such as high molecular weight phenols are exemplified.

Specific examples of the sulfur-based antioxidant include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyll-3,3'-thiodipropionate and the like. ..

Specific examples of phosphorus-based antioxidants include triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, and tris (2,4-di-t-). Butylphenyl) phosphite, cyclic neopentanetetraylbis (octadecyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbi (2,4) Phenyl phosphites such as −di-t-butyl-4-methylphenyl) phosphite, bis [2-t-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa- Examples thereof include oxaphosphaphenanthrene oxides such as 10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

The blending amount of the component (D) is 0.1 to 0.5 parts by mass, preferably 0.1 to 0.3 parts by mass with respect to 100 parts by mass of the component (A). If the blending amount of the antioxidant exceeds the upper limit of the previous term, the remaining antioxidant is deposited on the surface of the cured resin, which is not preferable. If the amount is less than the lower limit of the previous term, the heat resistance and transparency are lowered.

<Other ingredients>
In addition to each of the above components, conventional additives such as ultraviolet absorbers, deterioration inhibitors, phosphors, thermoplastics, diluents and the like may be used in combination as necessary.

Further, a light stabilizer may be added to the epoxy resin composition of the present invention, if necessary.
As the light stabilizer, a hindered amine-based light stabilizer, particularly HALS and the like, is suitable. The HALS is not particularly limited, but typical ones are dibutylamine, 1,3,5-triazine, N, N'-bis (2,2,6,6-tetramethyl-4-). A polycondensate of piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, dimethyl-1- (2-hydroxyethyl) -4-hydroxy succinate -2,2,6,6-tetramethylpiperidine polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], bis (1,2,2, 6,6-Pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydrideiphenyl] methyl] Butylmalonate, bis (2,2,6,6-tetramethyl) -4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, Examples thereof include 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalate bis (1,2,2,6,6-pentamethyl-4-piperidyl). Only one type of HALS may be used, or two or more types may be used in combination.

Further, a binder resin can be added to the epoxy resin composition of the present invention, if necessary. Examples of the binder resin include butyral resin, acetal resin, acrylic resin, epoxy-nylon resin, NBR-phenol resin, epoxy-NBR resin, polyamide resin, polyimide resin, silicone resin and the like. , Not limited to these. The blending amount of the binder resin is preferably in a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by mass, preferably 0.05 to 20 parts by mass with respect to 100 parts by mass of the resin component. Parts by mass are used as needed.

Further, the epoxy resin composition of the present invention can be added with an inorganic filler, a pigment, a mold release agent, a silane coupling agent, a softening agent and the like, if necessary. In particular, the addition of a nonflammable inorganic filler has the effect of further improving the flame retardancy of the present composition, and as long as there is no problem in workability and physical properties after curing, a large amount should be added in terms of flame retardancy. Is desirable. Hydroxides such as aluminum hydroxide, magnesium hydroxide, and iron hydroxide are used as nonflammable inorganic fillers. Examples thereof include zinc nitrate, silica, alumina, calcium carbonate, aluminum nitride, silicon nitride and the like.

The epoxy resin composition of the present invention can be produced by blending each of the above components and, if necessary, various additives, and dissolving or melt-mixing them. The melt-mixing may be carried out by a known method. For example, the above components may be charged into a reactor and melt-mixed in a batch manner, or each of the above components may be charged into a kneader such as a kneader or a hot triple roll. It can be continuously melt-mixed. It is preferable that the curing catalyst (C) is previously heated, dissolved and mixed with the curing agent (B), and dispersed and mixed with the components (A), (D) and the like at the final stage of mixing.

In the epoxy resin composition of the present invention, for example, the epoxy resin and the curing agent are preheated to 100 to 200 ° C. to melt at least one of the epoxy resin and the curing agent, and the other is dissolved in this melt. After that, it can be obtained by adding and mixing an inorganic filler, a pigment, a mold release agent, a flame retardant, a silane coupling agent and the like and a curing accelerator, if necessary, with an extruder, a roll, a kneader or the like. Further, in some cases, each of the above components may be mixed by an extruder, roll, kneader or the like without going through the melting step. The obtained epoxy resin composition is usually molded using a transfer molding machine or the like and cured, but further curing at 80 to 200 ° C. for 2 to 10 hours improves the performance. Further, when the liquid encapsulant is used, a liquid epoxy resin can be used, and the epoxy resin composition of the present invention can be mixed and produced at room temperature.

The glass transition temperature of the cured product of the epoxy resin composition of the present invention is preferably 40 to 100 ° C. in DSC. The temperature (Td10) when the mass of the cured resin composition is reduced by 10% is preferably 380 ° C. or higher, more preferably 400 ° C. or higher, and particularly preferably 420 ° C. or higher. The upper limit is not particularly limited, but is usually 2000 ° C. or lower.

The cured product of the present invention can be used for various purposes such as molding materials, adhesives, composite materials, and paints. In addition, it is useful in the electrical and electronic fields such as IC encapsulation materials, laminated materials, and electrically insulating materials.

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples and Examples. The present invention is not limited to these synthetic examples and examples. The physical property values in the synthetic examples and the examples were measured by the following methods. Here, the part represents a mass part unless otherwise specified.
○ GPC: GPC was measured under the following conditions.
Various conditions of GPC Manufacturer: Waters column: SHODEX GPC LF-G (guard column), KF-603, KF-602.5, KF-602, KF-601 (2)
Flow velocity: 0.4 ml / min.
Column temperature: 40 ° C
Solvent used: THF (tetrahydrofuran)
Detector: RI (Differential Refractometer)
○ NMR: Measurement was performed with a deuterated chloroform solvent using JNM-ECS400 manufactured by JEOL Ltd.
Epoxy equivalent: Measured by the method described in JIS K-7236.

Example 1: Synthesis of silicone-modified epoxy resin 1 Tricyclodecanedimethanol (20 mmоl, 3.93 g), xylene 200 g, phenylsilane (24 mmоl, 3.00 ml), 10% in a flask equipped with a stirrer and a reflux condenser. 0.51 g of supported palladium carbon was added, and the mixture was reacted at 140 ° C. for 24 hours. After lowering to room temperature, 1,2-epoxy-4-vinylcyclohexane (64 mmоl, 8.35 ml) and tris (triphenylphosphine) rhodium (I) chloride (5 μmоl, 4.63 mg) were added, and the temperature was raised to 140 ° C. again. The temperature was raised and the mixture was stirred for 24 hours. After completion of the reaction, 10% supported palladium carbon was removed by filtration, and the reaction solution was reprecipitated with toluene-hexane. Further, it was concentrated to obtain a silicone-modified epoxy resin. When the epoxy equivalent of the obtained silicone-modified epoxy resin 1 was confirmed, it was 616 g / eq.

Example 2: Synthesis of silicone-modified epoxy resin 2 Tricyclodecanedimethanol (20 mmоl, 3.93 g), xylene 200 g, phenylsilane (24 mmоl, 3.00 ml), 10% in a flask equipped with a stirrer and a reflux condenser. 0.51 g of supported palladium carbon was added, and the mixture was reacted at 140 ° C. for 24 hours. After the temperature was lowered to room temperature, glycidol (64 mmоl, 4.27 ml) was added, the temperature was raised to 140 ° C. again, and the mixture was stirred for 24 hours. After completion of the reaction, 10% supported palladium carbon was removed by filtration, and the reaction solution was reprecipitated with toluene-hexane. Further, it was concentrated to obtain a silicone-modified epoxy resin. When the epoxy equivalent of the obtained silicone-modified epoxy resin 2 was confirmed, it was 705 g / eq.

Example 3: Synthesis of Silicone Modified Epoxy Resin 3 Tricyclodecanedimethanol (20 mmоl, 3.93 g), xylene 200 g, diphenylsilane (24 mmоl, 4.46 ml), 10% in a flask equipped with a stirrer and a reflux condenser. 0.51 g of supported palladium carbon was added, and the mixture was reacted at 140 ° C. for 24 hours. After lowering to room temperature, 1,2-epoxy-4-vinylcyclohexane (8 mmоl, 1.04 ml) and tris (triphenylphosphine) rhodium (I) chloride (5 μmоl, 4.63 mg) were added, and the temperature was raised to 140 ° C. again. The temperature was raised and the mixture was stirred for 24 hours. After completion of the reaction, 10% supported palladium carbon was removed by filtration, and the reaction solution was reprecipitated with toluene-hexane. Further, it was concentrated to obtain a silicone-modified epoxy resin. When the epoxy equivalent of the obtained silicone-modified epoxy resin 1 was confirmed, it was 1531 g / eq.

Example 4: Synthesis of Silicone Modified Epoxy Resin 4 Dioxane glycol (20 mmоl, 4.36 g), xylene 200 g, diphenylsilane (24 mmоl, 4.46 ml), 10% supported palladium carbon in a flask equipped with a stirrer and a reflux condenser. 0.51 g was added and the mixture was reacted at 140 ° C. for 24 hours. After lowering to room temperature, 1,2-epoxy-4-vinylcyclohexane (8 mmоl, 1.04 ml) and tris (triphenylphosphine) rhodium (I) chloride (5 μmоl, 4.63 mg) were added, and the temperature was raised to 140 ° C. again. The temperature was raised and the mixture was stirred for 24 hours. After completion of the reaction, 10% supported palladium carbon was removed by filtration, and the reaction solution was reprecipitated with toluene-hexane. Further, it was concentrated to obtain a silicone-modified epoxy resin. When the epoxy equivalent of the obtained silicone-modified epoxy resin 1 was confirmed, it was 1666 g / eq.

Example 5: Synthesis of Silicone Modified Epoxy Resin 5 Ethylene glycol (20 mmоl, 1.24 g), xylene 200 g, diphenylsilane (24 mmоl, 4.46 ml), 10% supported palladium carbon in a flask equipped with a stirrer and a reflux condenser. 0.51 g was added and the mixture was reacted at 140 ° C. for 24 hours. After lowering to room temperature, 1,2-epoxy-4-vinylcyclohexane (8 mmоl, 1.04 ml) and tris (triphenylphosphine) rhodium (I) chloride (5 μmоl, 4.63 mg) were added, and the temperature was raised to 140 ° C. again. The temperature was raised and the mixture was stirred for 24 hours. After completion of the reaction, 10% supported palladium carbon was removed by filtration, and the reaction solution was reprecipitated with toluene-hexane. Further, it was concentrated to obtain a silicone-modified epoxy resin. When the epoxy equivalent of the obtained silicone-modified epoxy resin 1 was confirmed, it was 2343 g / eq.

The epoxy resin used in the comparative example is as follows.
[Comparative Example 1]
3'-4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Chemical Industries, Ltd., celloxide 2021P)
[Comparative Example 2]
Epoxy-modified silicone resin (manufactured by Toray Dow Corning Co., Ltd., BY16839).

-Characteristic evaluation of composition and cured product-
A cationic catalyst (Sun Aid SI-150, manufactured by Sanshin Chemical Industry Co., Ltd.) was added to the resins obtained in Examples 1, 3 to 5 and Comparative Examples 1 and 2 so as to be 1% by mass, and Example 2 was added. 2-Ethyl-4-methylimidazole) was added in an amount of 1% by mass. A 40 mm × 25 mm × 1 mm mold was prepared on a glass substrate with a heat-resistant release tape, and the curable resin composition of the present invention and the curable resin composition of Comparative Example were cast to a thickness of about 800 μm, respectively, and 80 The cured product of the present invention was obtained by curing at ° C. for 1 hour and then in a dryer at 150 ° C. for 3 hours. Heat resistance, toughness, color resistance, and dimensional stability were measured for each of the obtained cured products.
The characteristics of the obtained composition and cured product were evaluated by the following methods. Curing was performed by heating the composition at 100 ° C. for 1 hour and then at 150 ° C. for 4 hours. The results are shown in Table 1.

The evaluation methods and evaluation criteria for the fat composition and the cured film were as follows.
(1) Heat resistance: The temperature (Td10) when the mass of the cured resin composition is reduced by 10% is measured at 10 ° C./min in a nitrogen atmosphere with a thermogravimetric analyzer (TGADTA: manufactured by METTLER CORPORATION). did. The judgment criteria are as follows.
⊚: Td10 is 420 ° C. or higher ◯: Td10 is 400 ° C. or higher and 419 ° C. or lower Δ: Td10 is 380 ° C. or higher and 399 ° C. or lower ×: Td10 is 379 ° C. or lower (2) Toughness: Both ends of the cured film of the cured resin composition Was fixed by hand, and the state of the cured film when the central part was pressed was observed. The judgment criteria are as follows.
◎: Even if pressed strongly, it will not crack and will not crack.
◯: Even if it is pressed lightly, it will not crack and will not crack, but if it is pressed strongly, it will crack.
Δ: When pressed lightly, it cracks, and when pressed strongly, it cracks.
×: It breaks when pressed lightly.

As is clear from the results in Table 1, the compositions of Examples 1 to 5 are excellent in heat resistance and toughness. On the other hand, the composition of Comparative Example 1 is inferior in toughness and heat resistance. Further, although the epoxy-modified silicone resin of Comparative Example 2 has excellent heat resistance, it is inferior in toughness.

In addition, the moisture resistance of the silicone-modified epoxy resin of the present invention was evaluated. The evaluation method and evaluation criteria were as follows.
After leaving at 30 ° C. and 70% RH for 6 hours, the retention time of the peak top before and after leaving was examined by GPC.

As is clear from the results, the silicone-modified epoxy resin of the present invention has excellent moisture resistance.

Claims (8)

A silicone-modified epoxy resin represented by the following formula (1).

(In the formula, R ₂ is a hydrogen atom, the following formula (2A)

(In the formula, R ₁ indicates an alkylene group having 1 to 6 carbon atoms which may contain a direct bond or an ester or ether bond, and * indicates a bond to an adjacent silicon atom in the above formula (1)). The following formula (2B)

(Wherein, R _{1, *} represent the same meanings as above.), A monovalent aromatic hydrocarbon radical of monovalent aliphatic hydrocarbon group or a C6-12 having 1 to 6 carbon atoms, A is An organic group which may have a heterocyclic skeleton having 1 to 20 carbon atoms, a cyclic hydrocarbon skeleton or an aromatic ring skeleton, and n represents 1 to 10 on average. In the formula, a plurality of R _{1 to} R ₂ existing may be the same or different from each other. Provided that at least one of _{R 2} existing in plural represents the above formula (2A) or (2B). )
The silicone-modified epoxy resin has the following formula (5A).

(In the formula, R ₅ represents an alkylene group having 1 to 6 carbon atoms which may contain a direct bond or an ester or ether bond.)
Epoxy group-containing compound containing a terminal alkenyl group or the following formula (5B)

(In the formula, R ₅ has the same meaning as above.)
Epoxy group-containing compound containing the terminal hydroxyl group of, and the following formula (6)

(In the formula, R is a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and A and n are the same as in the above formula (1). Represents the meaning.)
Silicone modified epoxy resin which is a reaction product of.
The silicone-modified epoxy resin according to claim 1, wherein the heterocyclic skeleton, the cyclic hydrocarbon skeleton, and the aromatic ring skeleton are selected from the following.
Heterocyclic skeleton: morpholin skeleton, tetrahydrofuran skeleton, oxane skeleton, dioxane skeleton, trioxane skeleton, triazine skeleton, carbazole skeleton, pyrrolidine skeleton, piperidine skeleton cyclic hydrocarbon skeleton: dicyclodecane skeleton, tricyclodecane skeleton, adamantan skeleton, cyclohexane skeleton Cyclopentane skeleton, cycloheptane skeleton Aromatic ring skeleton: benzene skeleton, naphthalene skeleton, carbazole skeleton
The silicone modification according to claim 1 or 2, wherein at least one _{of a plurality of R 2} existing in the formula (1) represents a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms. Epoxy resin.
In the above formula (1), A is an alkylene group having 1 to 10 carbon atoms, and the following formula (3)

(In the above formula, R ₃ is an alkylene group having 1 to 6 carbon atoms, R ₄ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m is an integer of 0 or 1, and k is an integer of 1 to 4. * Represents a bond to an adjacent oxygen atom in the above formula (1).)
Or the following formula (4)

(In the above formula, R ₃ , R ₄ , k, * represent the same meanings as described above.)
The silicone-modified epoxy resin according to claim 1, wherein the silicone-modified epoxy resin represents any one of the organic groups.
An epoxy resin composition containing (A) a silicone-modified epoxy resin and (B) an epoxy resin curing agent according to any one of claims 1 to 4.
The epoxy resin composition according to claim 5 , further comprising (C) an epoxy resin curing catalyst.
The epoxy resin composition according to claim 5, wherein the epoxy resin curing agent is selected from any of an amine-based curing agent, a phenol-based curing agent, an acid anhydride-based curing agent, and a polyvalent carboxylic acid resin.
A cured product obtained by curing the epoxy resin composition according to any one of claims 5 to 7.