JP5219872B2 - Modified resin composition, cured product thereof, sealing material containing them, and method for producing modified resin composition - Google Patents

Description

  The present invention relates to a modified resin composition, a cured product thereof, a sealing material containing them, and a method for producing the modified resin composition.

  In recent years, the LED (light emitting diode) -related market has shown rapid growth, and accordingly, demand for high-performance and inexpensive sealing materials is also increasing. Conventionally, an epoxy resin has been used as a material for a sealing material. However, since it is inferior in performance, particularly in light resistance, a field where it can be used is limited. Among these, this tendency is remarkable for epoxy resins having an aromatic ring such as bisphenol A glycidyl ether.

  As a material for the sealing material, a silicone resin has been studied, but the silicone resin is excellent in light resistance and heat resistance, but has many problems in hardness and adhesiveness of the cured product. Moreover, compared with an epoxy resin, it is inferior to practicality also including being very expensive.

  In recent years, in order to solve the above-described problems, a hybrid type resin of epoxy and silicone has been actively developed. However, the hybrid type resin of epoxy and silicone is inferior in storage stability and has a problem that the viscosity of the resin is remarkably increased during storage or is gelled, which is not practical. .

As others, Patent Documents 1 and 2 describe a composition in which an epoxy resin and a silicone resin condensed in advance are mixed.
Patent Documents 3 and 4 describe a resin composition obtained by mixing an epoxy resin and a methoxysilane condensate and performing a dealcoholization reaction.
Patent Documents 5 and 6 describe a resin composition obtained by mixing an epoxy resin and a tetramethoxysilane condensate and hydrolytic condensation.
Patent Document 7 describes a resin obtained by hydrolytic condensation of an alkoxysilane compound having an organic group having a cyclic ether group and an alkoxysilane compound having an organic group having an aryl group.
Patent Document 8 describes a modified phenoxy resin obtained by subjecting an epoxy resin and γ-glycidoxypropylmethoxysilane to a demethanol reaction.

JP 2006-241230 A JP 2006-225515 A JP 2005-179401 A JP 2003-246838 A International Publication No. 2005/081024 Pamphlet JP 2007-284621 A JP 2008-120443 A JP 2007-321130 A

  However, with the rapid progress of the LED (light emitting diode) related market in recent years, there has been a demand for development of a resin composition that can exhibit even higher performance, particularly as a sealing material. However, there are still many points to be improved in terms of performance.

  Accordingly, the present invention provides a composition that is excellent in fluidity and can exhibit light resistance, crack resistance, and surface tackiness when used as a cured product thereof, a cured product thereof, and a sealing material including them. With the goal.

  As a result of earnest research to solve the above problems, the present inventor contains a resin composition obtained by cohydrolytic condensation of an epoxy resin and a specific alkoxysilane compound, and an oxetane compound. It is found that a composition excellent in fluidity, a cured product excellent in light resistance, crack resistance, and surface tackiness using the same, and a sealing material containing them can be provided by making the present invention. It came to.

（式（１）中、ｎ＝０〜３であり、Ｒ^１は水素原子又は有機基を示す。また、複数のＲ^２は、同一又は異なっていてもよく、水素原子又は炭素数１〜８のアルキル基を示す。）
前記アルコキシシラン化合物は、
（Ｂ）ｎ＝１〜２であり、Ｒ^１として、少なくとも１つの環状エーテル基を有する、少なくとも１種のアルコキシシラン化合物と、
（Ｃ）ｎ＝１〜２であり、Ｒ^１として、少なくとも１つのアリール基を有する、少なくとも１種のアルコキシシラン化合物と、
を含み、かつ、下記式（２）で表される（Ｂ）及び（Ｃ）の混合指標αが、０．００１〜１９である樹脂組成物と、オキセタン化合物と、を含有する組成物；
混合指標α＝（αｃ）／（αｂ） （２）
（式（２）中、αｂ：前記（Ｂ）成分の含有量（ｍｏｌ％）、αｃ：前記（Ｃ）成分の含有量（ｍｏｌ％））。
［２］
前記アルコキシシラン化合物として、
（Ｄ）前記一般式（１）において、ｎ＝０である、少なくとも１種のアルコキシシラン化合物を、さらに含む［１］に記載の組成物。
［３］
下記式（３）で表される前記アルコキシシラン化合物の混合指標βが、０．０１〜１．４である、［１］又は［２］に記載の組成物；
混合指標β＝｛（β^ｎ２）／（β^ｎ０＋β^ｎ１）｝ （３）
（式（３）中、
β^ｎ２：前記一般式（１）において、ｎ＝２であるアルコキシシラン化合物の含有量（ｍｏｌ％）、
β^ｎ０：前記一般式（１）において、ｎ＝０であるアルコキシシラン化合物の含有量（ｍｏｌ％）、
β^ｎ１：前記一般式（１）において、ｎ＝１であるアルコキシシラン化合物の含有量（ｍｏｌ％）、
ここで、０≦｛（β^ｎ０）／（β^ｎ０＋β^ｎ１＋β^ｎ２）｝≦０．１である）。
［４］
下記式（４）で表される、前記（Ａ）エポキシ樹脂と前記アルコキシシラン化合物との混合指標γが、０．０２〜１５である、［１］〜［３］のいずれか一項に記載の組成物；
混合指標γ＝（γａ）／（γｓ） （４）
（式（４）中、
γａ：エポキシ樹脂の質量（ｇ）、
γｓ：一般式（１）において、ｎ＝０〜２であるアルコキシシラン化合物の質量（ｇ））
［５］
カチオン重合開始剤がさらに添加された、請求項［１］〜［４］のいずれか一項に記載の組成物。
［６］
［１］〜［５］のいずれか一項に記載の組成物を、熱により硬化させて得られる硬化物。
［７］
［６］記載の硬化物を含む封止材。
［８］
（Ａ）エポキシ樹脂と、下記一般式（１）で表されるアルコキシシラン化合物と、を共加水分解縮合させて得られうる樹脂組成物に、オキシラン化合物を添加することを少なくとも行う、組成物の製造方法；

（式（１）中、ｎ＝０〜３であり、Ｒ^１は、水素原子又は有機基を示す。また、複数のＲ^２は、同一又は異なっていてもよく、水素原子又は炭素数１〜８のアルキル基を示す。）
前記アルコキシシラン化合物は、
（Ｂ）ｎ＝１〜２であり、Ｒ^１として、少なくとも１つの環状エーテル基を有する、少なくとも１種のアルコキシシラン化合物と、
（Ｃ）ｎ＝１〜２であり、Ｒ^１として、少なくとも１つのアリール基を有する、少なくとも１種のアルコキシシラン化合物と、
を含み、かつ、下記式（２）で表される（Ｂ）及び（Ｃ）の混合指標αが、０．００１〜１９であり、
混合指標α＝（αｃ）／（αｂ） （２）
（式（２）中、αｂ：前記（Ｂ）成分の含有量（ｍｏｌ％）、αｃ：前記（Ｃ）成分の含有量（ｍｏｌ％））。 That is, the present invention is as follows.
[1]
(A) an epoxy resin;
An alkoxysilane compound represented by the following general formula (1):
A resin composition obtained by cohydrolyzing and condensing

(In the formula (1), n = 0 to 3, and R ¹ represents a hydrogen atom or an organic group. The plurality of R ² may be the same or different, and may be a hydrogen atom or a carbon number of 1 to 8. Represents an alkyl group of
The alkoxysilane compound is
(B) n = 1-2, and as R ¹ , at least one alkoxysilane compound having at least one cyclic ether group;
(C) n = 1-2, and as R ¹ , at least one alkoxysilane compound having at least one aryl group;
And a composition containing a resin composition having a mixing index α of (B) and (C) represented by the following formula (2) of 0.001 to 19 and an oxetane compound;
Mixing index α = (αc) / (αb) (2)
(In formula (2), αb: content (mol%) of the component (B), αc: content (mol%) of the component (C)).
[2]
As the alkoxysilane compound,
(D) The composition according to [1], further including at least one alkoxysilane compound in which n = 0 in the general formula (1).
[3]
The composition according to [1] or [2], wherein a mixing index β of the alkoxysilane compound represented by the following formula (3) is 0.01 to 1.4;
Mixing index β = {(β ⁿ² ) / (β ⁿ⁰ + β ⁿ¹ )} (3)
(In formula (3),
β ⁿ² : content (mol%) of the alkoxysilane compound in which n = 2 in the general formula (1),
β ⁿ⁰ : the content (mol%) of the alkoxysilane compound in which n = 0 in the general formula (1),
β ⁿ¹ : content (mol%) of the alkoxysilane compound in which n = 1 in the general formula (1),
Here, 0 ≦ {(β ⁿ⁰ ) / (β ⁿ⁰ + β ⁿ¹ + β ⁿ² )} ≦ 0.1).
[4]
The mixing index γ represented by the following formula (4) between the (A) epoxy resin and the alkoxysilane compound is 0.02 to 15 and described in any one of [1] to [3]. A composition of;
Mixing index γ = (γa) / (γs) (4)
(In formula (4),
γa: mass of epoxy resin (g),
γs: mass (g) of alkoxysilane compound in which n = 0 to 2 in the general formula (1)
[5]
The composition according to any one of claims [1] to [4], wherein a cationic polymerization initiator is further added.
[6]
A cured product obtained by curing the composition according to any one of [1] to [5] with heat.
[7]
[6] A sealing material containing the cured product according to [6].
[8]
(A) An epoxy resin and an alkoxysilane compound represented by the following general formula (1) are at least added to an oxirane compound to a resin composition obtained by cohydrolysis condensation. Production method;

(In formula (1), n = 0 to 3, and R ¹ represents a hydrogen atom or an organic group. The plurality of R ² may be the same or different, and may be a hydrogen atom or a carbon number of 1 to 3. 8 represents an alkyl group.)
The alkoxysilane compound is
(B) n = 1-2, and as R ¹ , at least one alkoxysilane compound having at least one cyclic ether group;
(C) n = 1-2, and as R ¹ , at least one alkoxysilane compound having at least one aryl group;
And the mixture index α of (B) and (C) represented by the following formula (2) is 0.001 to 19,
Mixing index α = (αc) / (αb) (2)
(In formula (2), αb: content (mol%) of the component (B), αc: content (mol%) of the component (C)).

  According to the present invention, a composition having excellent fluidity and improved storage stability can be obtained. Moreover, the hardened | cured material of the said composition which has the outstanding light resistance, crack resistance, and surface tackiness, Furthermore, the sealing material containing the hardened | cured material of the said composition is obtained.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiment, and can be implemented with various modifications within the scope of the gist.

(Resin composition)
The composition of this embodiment is
(A) an epoxy resin;
An alkoxysilane compound represented by the following general formula (1):
Is a resin composition obtained by cohydrolysis condensation,

In formula (1), n = 0 to 3, and R ¹ represents a hydrogen atom or an organic group. Moreover, several R < ² > is the same or different and shows a hydrogen atom or a C1-C8 alkyl group.

The alkoxysilane compound represented by the general formula (1) is (B) n = 1-2, and R ¹ has at least one cyclic ether group, and (C) n = 1 to 2 and R ¹ having at least one aryl group and at least one alkoxysilane compound, and represented by the following formula (2) (B) and (C) Is obtained by mixing a resin composition having a mixing index α of 0.001 to 19 and an oxetane compound.
Mixing index α = (αc) / (αb) (2)
In formula (2), αb is mol% of the component (B), and αc is mol% of the component (C).

  The present inventor used a resin composition obtained by cohydrolyzing and condensing an epoxy resin and a specific alkoxysilane compound, a composition containing a cationic polymerization initiator, and having excellent fluidity, and used the same. It discovered that the hardened | cured material excellent in light resistance, crack resistance, and surface tack property, and the sealing material containing them are obtained.

((A) Epoxy resin)
The (A) epoxy resin in the present embodiment refers to a compound having an oxirane ring, usually two or more oxirane rings in the molecule, excluding an alkoxysilane compound and a condensate thereof described later, and satisfying the above requirements. If it is, it will not specifically limit. These may be used alone or in combination.

The epoxy equivalent (WPE) of the epoxy resin is preferably 100 to 600 g / eq, more preferably 100 to 500 g / eq, and still more preferably 100 to 300 g / eq.
Depending on the composition balance with the alkoxysilane compound represented by the general formula (1), when the epoxy equivalent (WPE) is less than 100 g / eq, the storage stability of the target resin composition may be lowered. If it exceeds 600 g / eq, the crack resistance of the cured product of the composition may be deteriorated.

  The use of the composition and the cured product of the present embodiment is not particularly limited, but when used as a sealing material, the epoxy equivalent of the epoxy resin is preferably 100 to 300 g / eq.

The epoxy resin is preferably a liquid having a viscosity at 25 ° C. of 1000 Pa · s or less, more preferably 500 Pa · s or less, and still more preferably 100 Pa · s or less.
When the viscosity at 25 ° C. exceeds 1000 Pa · s, the fluidity as a liquid is lost, and the compatibility with the alkoxysilane compound described later tends to deteriorate.
In addition, when the viscosity at 25 ° C. is more than 500 Pa · s and 1000 Pa · s or less (500 Pa · s <viscosity ≦ 1000 Pa · s), it can be used by adjusting the temperature at the time of production, selecting a solvent, etc. Since manufacturing conditions tend to be somewhat limited, it is preferably 500 Pa · s or less.

The type of epoxy resin is not particularly limited, and specific examples include alicyclic epoxy resins, aliphatic epoxy resins, polyfunctional epoxy resins that are glycidyl ethers of polyphenol compounds, and glycidyl ethers of various novolac resins. Polyfunctional epoxy resin, aromatic epoxy resin nuclear hydride, aliphatic epoxy resin, heterocyclic epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, epoxy glycidylated from halogenated phenols Examples thereof include resins.
Among these, alicyclic epoxy resins and aliphatic epoxy resins are preferable from the viewpoint of being readily available and having good physical properties when the intended composition of the present embodiment is cured. A cyclic epoxy resin is more preferable. These epoxy resins may be used alone or in combination.

(Alicyclic epoxy resin)
The alicyclic epoxy resin is not particularly limited as long as it is an epoxy resin having an alicyclic epoxy group, and examples thereof include an epoxy resin having a cyclohexene oxide group, a tricyclodecene oxide group, a cyclopentene oxide group, and the like. Can be mentioned.
Specific examples of the alicyclic epoxy resin include 4-vinyl epoxycyclohexane, dioctyl epoxyhexahydrophthalate, and di-2-ethylhexyl epoxyhexahydrophthalate as monofunctional alicyclic epoxy compounds. Examples of the bifunctional alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloctyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4 -Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, bis (3,4-epoxy-6-methyl) (Cyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethyl Glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexane carboxylate), 1,2,8,9- diepoxylimonene, and the like. Examples of the polyfunctional alicyclic epoxy compound include 1,2-epoxy-4- (2-oxiranyl) cyclohexene adduct of 2,2-bis (hydroxymethyl) -1-butanol. Examples of the polyfunctional alicyclic epoxy compound include Epolide GT401, EHPE3150 (manufactured by Daicel Chemical Industries, Ltd.), and the like.
Typical examples of the alicyclic epoxy resin are shown below.

(Aliphatic epoxy resin)
The aliphatic epoxy resin is not particularly limited, and specifically, 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, pentaerythritol, xylylene glycol derivatives, etc. Examples thereof include glycidyl ethers of polyhydric alcohols. Typical examples of the aliphatic epoxy resin are shown below.

(Polyfunctional epoxy resin)
The polyfunctional epoxy resin which is a glycidyl etherified product of a polyphenol compound is not particularly limited, and specifically, bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, tetramethylbisphenol A, dimethyl Bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S, dimethyl bisphenol S, tetramethyl-4,4′-biphenol, dimethyl-4,4′-biphenylphenol, 1- (4-hydroxyphenyl)- 2- [4- (1,1-bis- (4-hydroxyphenyl) ethyl) phenyl] propane, 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene -Bis (3-methyl-6-tert-butyl) Ruphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, 2,6-di (t-butyl) hydroquinone, pyrogallol, phenols having a diisopropylidene skeleton, 1,1-di (4-hydroxyphenyl) fluorene, etc. Examples thereof include phenols having a fluorene skeleton, polyfunctional epoxy resins which are glycidyl etherified products of polyphenol compounds of phenolized polybutadiene.
Among the above, many of the types that are excellent in transparency and fluidity are commercially available and can be obtained at a low price, and tend to be excellent in crack resistance when the intended composition of the present embodiment is a cured product. Therefore, a polyfunctional epoxy resin which is a glycidyl etherified product of phenols having a bisphenol A skeleton is preferable.

  A typical example of a polyfunctional epoxy resin which is a glycidyl etherified product of phenols having a bisphenol skeleton is shown below.

When a polyfunctional epoxy resin that is a glycidyl etherified product of a polyphenol compound is used as the epoxy resin, these repeating units (n in the chemical formula showing the above representative examples) are not particularly limited, but preferably Is less than 50, more preferably 0.001 to 10, and still more preferably 0.01 to 2.
When the repeating unit is less than 0.001, the reactivity with the alkoxysilane compound may be deteriorated, and when it exceeds 50, the fluidity is lowered, which may cause a practical problem. From the viewpoint of the balance between the above-described reactivity and fluidity, the repeating unit is particularly preferably from 0.01 to 2.

(Polyfunctional epoxy resin that is glycidyl etherified product of novolak resin)
The polyfunctional epoxy resin that is a glycidyl etherified product of novolak resin is not particularly limited, and examples thereof include phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, and naphthol. Glycidyl etherification products of various novolac resins such as novolak resins made from various phenols such as phenols, xylylene skeleton-containing phenol novolak resins, dicyclopentadiene skeleton-containing phenol novolak resins, biphenyl skeleton-containing phenol novolak resins, and fluorene skeleton-containing phenol novolak resins. Etc.
A typical example of a polyfunctional epoxy resin which is a glycidyl etherified product of a novolak resin is shown below.

(Nuclear hydride of aromatic epoxy resin)
The nuclear hydride of the aromatic epoxy resin is not particularly limited. For example, glycidyl etherified products of phenol compounds (bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, etc.) or various phenols (phenols) , Cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, naphthols, etc.) and hydrides of glycidyl ethers of novolac resins Can be mentioned.

(Heterocyclic epoxy resin)
The heterocyclic epoxy resin is not particularly limited, and examples thereof include heterocyclic epoxy resins having a heterocyclic ring such as an isocyanuric ring and a hydantoin ring.

(Glycidyl ester epoxy resin)
The glycidyl ester-based epoxy resin is not particularly limited, and examples thereof include epoxy resins composed of carboxylic acids such as hexahydrophthalic acid diglycidyl ester and tetrahydrophthalic acid diglycidyl ester.
The glycidylamine epoxy resin is not particularly limited. For example, an epoxy resin obtained by glycidylating amines such as aniline, toluidine, p-phenylenediamine, m-phenylenediamine, diaminodiphenylmethane derivative, and diaminomethylbenzene derivative. Etc.

(Epoxy resin obtained by glycidylation of halogenated phenols)
Epoxy resins obtained by glycidylation of halogenated phenols are not particularly limited. For example, brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolac, chlorinated Examples thereof include epoxy resins obtained by glycidyl etherification of halogenated phenols such as bisphenol S and chlorinated bisphenol A.

The epoxy resin mentioned above can use a polyol together.
The polyol is not particularly limited as long as it is a compound having two or more hydroxyl groups in the molecule. For example, ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,2-hexanediol, 1,6- Examples include hexanediol.

(Alkoxysilane compound)
The alkoxysilane compound in this embodiment shows the silicon compound which has 1-4 alkoxyl groups, and is represented by following General formula (1).

In formula (1), n = 0 to 3, and R ¹ represents a hydrogen atom or an organic group.
Moreover, several R < ² > is the same or different and shows a hydrogen atom or a C1-C8 alkyl group.

R ¹ in the general formula (1) represents a hydrogen atom or an organic group and is not particularly limited. Examples of the organic group include an organic group having a cyclic ether group and an organic group having an aryl group, which will be described later. Examples include an organic group having an alkyl group, a vinyl group, a methacryl group, a mercapto group, and an isocyanate group, and among them, an alkyl group is preferable.

  Here, examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a butyl group (n-butyl, i-butyl, t-butyl, sec-butyl), and a pentyl group (n -Pentyl, i-pentyl, neopentyl, etc.), hexyl group (n-hexyl, i-hexyl, etc.), heptyl (n-heptyl, i-heptyl, etc.), octyl group (n-octyl, i-octyl, t-octyl) Etc.), nonyl (n-nonyl, i-nonyl etc.), decyl group (n-decyl, i-decyl etc.), dodecyl group (n-dodecyl, i-dodecyl etc.), and these are linear or Any of a branched alkyl group may be used.

Among these, an alkyl group having 10 or less carbon atoms is preferable, and a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, and n-hexyl group are more preferable. In addition, hydrogen atoms or a part or all of the main chain skeleton of these alkyl groups are ether groups, ester groups, carbonyl groups, siloxane groups, halogen atoms such as fluorine, methacryl groups, acrylic groups, mercapto groups, amino groups, It may be substituted with at least one group selected from the group consisting of hydroxyl groups.
Moreover, several R < ² > in the above-mentioned general formula (1) is the same or different, respectively, and shows a hydrogen atom or a C1-C8 alkyl group. R ² is not particularly limited as long as it satisfies the above requirements, but is preferably a methyl group or an ethyl group.

((B) component)
The component (B) of the alkoxysilane compound represented by the general formula (1) is at least one kind in the general formula (1), where n = 1 to 2 and R ¹ has at least one cyclic ether group. This is an alkoxysilane compound.

  The cyclic ether group refers to an organic group having an ether in which carbon of a cyclic hydrocarbon is substituted with oxygen, and usually means a cyclic ether group having a 3- to 6-membered ring structure. Among them, a 3-membered or 4-membered cyclic ether group having a large ring strain energy and high reactivity is preferable, and a 3-membered ether group is particularly preferable.

  Specific examples of the cyclic ether group include, for example, a glycidoxyalkyl group having oxyglycidyl groups having 4 or less carbon atoms such as β-glycidoxyethyl, γ-glycidoxypropyl, γ-glycidoxybutyl, and the like, glycidyl Group, β- (3,4-epoxycyclohexyl) ethyl group, γ- (3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycycloheptyl) ethyl group, β- (3,4 epoxyepoxycyclohexyl) ) Alkyl substituted with a cycloalkyl group having 5 to 8 carbon atoms having an oxirane group such as propyl group, β- (3,4-epoxycyclohexyl) butyl group, β- (3,4-epoxycyclohexyl) pentyl group Groups and the like.

Among the above, glycidoxy in which an oxyglycidyl group is bonded to a C1-C3 alkyl group such as β-glycidoxyethyl group, γ-glycidoxypropyl group, β- (3,4-epoxycyclohexyl) ethyl group, etc. An alkyl group having 3 or less carbon atoms substituted with a C5-C8 cycloalkyl group having an alkyl group or an oxirane group is preferred.
Specific examples of the component (B) include, for example, 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, 3-glycidoxypropyl (methyl) dibutoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) diethoxysilane, 2,3-epoxypropyl (methyl) dimethoxysilane, 2,3 -Epoxypropyl (phenyl) dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltributoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, 2- (3,4-epoxy Hexyl) ethyl triethoxysilane, 2,3-epoxypropyl trimethoxysilane, 2,3-epoxy propyl triethoxy silane, and the like. These may be used alone or in combination.

((C) component)
The component (C) of the alkoxysilane compound represented by the general formula (1) is n = 1 to 2 in the general formula (1), and R ¹ has at least one aryl group. It is an alkoxysilane compound.

  An aryl group refers to a functional group or substituent derived from an aromatic hydrocarbon (simple aromatic ring or polycyclic aromatic hydrocarbon). The aryl group is not particularly limited as long as it matches this, but in consideration of steric hindrance in the higher order structure, a phenyl group, a benzyl group, and the like are preferable.

  Specific examples of the component (C) include, for example, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, phenyltriethoxysilane, trimethoxy [3- (phenylamino) propyl] silane, dimethoxydiphenylsilane, diphenyldiethoxysilane, phenyl Examples include trimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane. These may be used alone or in combination.

“(B) at least one alkoxysilane compound having general formula (1) where n = 1 to 2 and R ¹ having at least one cyclic ether group”, and “(C) general formula In (1), n = 1 to 2 and R ¹ has at least one aryl group, and the mixing ratio of “at least one alkoxysilane compound” is a mixing index calculated by the following formula (2): It is represented by α.
Mixing index α = (αc) / (αb) (2)
(Wherein, αb: mol% of component (B), αc: mol% of component (C)).

  In the present embodiment, it is important that the mixing index α is in the range of 0.001 to 19. When the mixing index α is less than 0.001, the fluidity and storage stability of the resin composition are lowered, and when it exceeds 19, the fluidity of the resin composition and the crack resistance of the cured product are deteriorated. In particular, when considering use in a sealing material application, since high crack resistance is required, the mixing index α is preferably 0.2 to 5, and more preferably 0.3 to 2.

((D) component)
In addition to the components (A) to (C) described above, the composition according to the present embodiment has n = 0 indicating the number of R ¹ in the general formula (1) as a component (D), that is, (OR ² ) May be further cohydrolyzed and condensed.

  Examples of the component (D) include tetramethoxysilane and tetraethoxysilane. These may be used alone or in combination.

(Other alkoxysilane compounds)
The composition in this embodiment may further cohydrolyze and condense the alkoxysilane compound represented by the general formula (1) other than the components (B) to (D) described above. Examples of such compounds include dimethyldimethoxysilane, dimethylethoxysilane, hydroxymethyltrimethylsilane, methoxytrimethylsilane, methyltrimethoxysilane, mercaptomethyltrimethoxysilane, methoxydimethylvinylsilane, trimethoxyvinylsilane, bis (2-chloro Ethoxy) methylsilane, ethoxytrimethylsilane, diethoxymethylsilane, ethyltriethoxysilane, dimethoxymethyl-3,3,3-trifluoropropylsilane, ethoxydimethylvinylsilane, 3-chloropropyldimethoxymethylsilane, chloromethyldiethoxymethylsilane , Methyltris (ethylmethylketoxime) silane, trimethylpropoxysilane, trimethoxyisopropoxysilane, diethoxydi Tilsilane, 3- [dimethoxy (methyl) silyl] propane-1-thiol, trimethoxy (propyl) silane, (3-mercaptopropyl) trimethoxysilane, 3-aminopropyltrimethoxysilane, diethoxymethylvinylsilane, butoxytrimethylsilane, Butyltrimethoxysilane, methyltriethoxysilane, methoxyltriethoxysilane, triethoxyvinylsilane, diethoxydiethylsilane, dimethoxyldipropoxysilane, ethyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane Allyltriethoxysilane, 3-bromopropyltriethoxysilane, 3-allylaminopropyltrimethoxysilane, hexyloxytrimethylsilane, propyltriethoxysilane, Xyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- (triethoxysilyl) propyl isocyanate, 3-ureidopropyltriethoxysilane, Methoxytripropylsilane, dibutoxydimethylsilane, methyltripropoxysilane, methyltriisopropoxysilane, octyloxytrimethylsilane, pentyltriethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, hexyltriethoxysilane, Examples include 3-methacryloxypropyltriethoxysilane, octyltriethoxysilane, dodecyloxytrimethylsilane, and diethoxydodecylmethylsilane.

In this embodiment, the mixing ratio of the “alkoxysilane compound where n = 2”, “alkoxysilane compound where n = 1” and “alkoxysilane compound where n = 0” of the alkoxysilane compound is expressed by the following formula ( It is represented by the mixture index β calculated in 3).
Mixing index β = {(β ⁿ² ) / (β ⁿ⁰ + β ⁿ¹ )} (3)
In the above formula (3),
β ⁿ² : content (mol%) of the alkoxysilane compound in which n = 2 in the general formula (1),
β ⁿ⁰ : the content (mol%) of the alkoxysilane compound in which n = 0 in the general formula (1),
β ⁿ¹ : content (mol%) of an alkoxysilane compound in which n = 1 in the general formula (1),
And 0 ≦ {(β ⁿ⁰ ) / (β ⁿ⁰ + β ⁿ¹ + β ⁿ² )} ≦ 0.1.

  In the composition of the present embodiment, the mixing index β is preferably 0.01 to 1.4, more preferably 0.03 to 1.2, and still more preferably 0.05 to 1.0. Depending on the composition, if the mixing index β is less than 0.01, the fluidity of the resin composition may deteriorate, and if it exceeds 1.4, the crack resistance may deteriorate.

The mixing ratio of the (A) epoxy resin and the alkoxysilane compound “alkoxysilane compound where n = 0 to 2” in the present embodiment is represented by a mixing index γ calculated by the following formula (4).
Mixing index γ = (γa) / (γs) (4)
In the above formula (4),
γa: mass of epoxy resin (g),
γs: mass (g) of alkoxysilane compound in which n = 0 to 2 in the general formula (1)
The mixing index γ is preferably 0.02 to 15, more preferably 0.04 to 7, and still more preferably 0.08 to 5. Depending on the composition, when the mixing index γ is less than 0.02, when the composition is a cured product, there may be a problem in crack resistance as the cured product. There is a possibility that light resistance may deteriorate.

(Cohydrolysis condensation process)
In the present embodiment, first, the resin composition can be obtained by cohydrolyzing and condensing the above-described (A) epoxy resin and the above-described alkoxysilane compound represented by the formula (1).
The “cohydrolytic condensation” in the present embodiment means a hydrolysis condensation reaction performed in the presence of an epoxy resin, and is clearly distinguished from a reaction in the absence of an epoxy resin.

The “cohydrolytic condensation” in the present embodiment is composed of at least two steps of a reflux step without dehydration and a subsequent dehydration condensation step.
The above-mentioned “refluxing process without dehydration” means that the reaction is carried out while returning the water and solvent blended for cohydrolysis and the water and solvent derived from the alkoxysilane compound generated during the reaction to the reaction solution. It is a process. Although the method is not particularly limited, the reaction is usually carried out while attaching a cooling pipe to the upper part of the reaction vessel and refluxing the generated water or solvent.
The above-mentioned “dehydration condensation step” is a step in which the condensation reaction is performed while removing the blended water and solvent and the water and solvent generated in the above “refluxing step without dehydration”. The method is not particularly limited, but usually the reaction is carried out by distillation under reduced pressure using a rotary evaporator or the like.

The heating temperature during the cohydrolysis condensation reaction is preferably 130 ° C. or lower, more preferably 0 to 120 ° C., and still more preferably 0 to 100 ° C.
If it exceeds 130 ° C., the resin composition may be altered depending on the composition. The reaction time for cohydrolytic condensation is preferably 0.5 to 24 hours, more preferably 1 to 12 hours. If it is less than 0.5 hour, the remaining amount of unreacted substances may increase depending on the composition.

The resin composition of this embodiment may be performed by adding a hydrolysis-condensation catalyst during the co-hydrolysis condensation of the above-described (A) epoxy resin and alkoxysilane compound.
The hydrolysis condensation catalyst is not particularly limited as long as it promotes a conventionally known hydrolysis condensation reaction. For example, a metal (lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, Strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, bismuth, etc., organic metals (lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium) Strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, bismuth and other organic oxides, organic acid salts, organic halides, alkoxides, etc.), inorganic bases Magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc.), organic base (Ammonia, tetramethylammonium hydroxide, etc.).

Among the above organic metals, organic tin is preferable.
Organotin refers to those in which at least one organic group is bonded to a tin atom, and examples of the structure include monoorganotin, diorganotin, triorganotin, tetraorganotin, etc. Among them, Diorganotin is preferred.

  Examples of the organic tin include tin tetrachloride, monobutyltin trichloride, monobutyltin oxide, monooctyltin trichloride, tetra n-octyltin, tetra n-butyltin, dibutyltin oxide, dibutyltin diacetate, dibutyltin dioctate, dibutyl Tin diversate, dibutyltin dilaurate, dibutyltin oxylaurate, dibutyltin stearate, dibutyltin dioleate, dibutyltin / silicon ethyl reactant, dibutyltin salt and silicate compound, dioctyltin salt and silicate compound, dibutyltin bis ( Acetylacetonate), dibutyltin bis (ethyl malate), dibutyltin bis (butylmalate), dibutyltin bis (2-ethylhexylmalate), dibutyltin bis (benzylmalate), dibutyltin bis Allyl malate), dibutyltin bis (oleylmalate), dibutyltin malate, dibutyltin bis (O-phenylphenoxide), dibutyltin bis (2-ethylhexylmercaptoacetate), dibutyltin bis (2-ethylhexylmercaptopropionate) Dibutyltin bis (isononyl 3-mercaptopropionate), dibutyltin bis (isooctylthioglycolate), dibutyltin bis (3-mercaptopropionate), dioctyltin oxide, dioctyltin dilaurate, dioctyltin diacetate, Dioctyltin dioctate, dioctyltin didodecyl mercapto, dioctyltin versatate, dioctyltin distearate, dioctyltin bis (ethyl malate), dioctyltin bis (octylmalate), dioctyl Rutin malate, dioctyltin bis (isooctylthioglycolate), dioctyltin bis (2-ethylhexyl mercaptoacetate), dibutyltin dimethoxide, dibutyltin diethoxide, dibutyltin dibutoxide, dioctyltin dimethoxide, dioctyltin diethoxide, dioctyltin dibutoxide, Examples include tin octylate and tin stearate. Among these, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, and dioctyltin diacetate are preferable.

  These hydrolytic condensation catalysts may be used alone or in combination. For example, organic acid tin and alkaline organic tin can be used in combination, or after reacting with an organic acid salt such as tin, treatment with an inorganic base is also possible. In this case, the inorganic base is preferably a hydroxide of a polyvalent cation such as magnesium hydroxide, calcium hydroxide, strontium hydroxide or barium hydroxide.

The addition amount of the hydrolysis-condensation catalyst is not particularly limited, but the preferable addition amount can be obtained from the mixing index δ which is a ratio to (OR ² ) in the above general formula (1). Here, the mixing index δ is expressed by the following formula (5).
Mixing index δ = (δe) / (δs) (5)
In formula (5),
δe: addition amount of hydrolytic condensation catalyst (mol number),
δs: Indicates the amount (mol number) of (OR ² ) in the general formula (1).

  The mixing index δ is preferably 0.0005 to 5, more preferably 0.001 to 1, and still more preferably 0.005 to 0.5. Depending on the composition of the resin composition, if the mixing index δ is less than 0.0005, the effect of promoting hydrolysis condensation may be difficult to obtain. If it exceeds 5, the ring opening of the cyclic ether group may be promoted. This is not preferable because it may lead to deterioration of storage stability.

In the step of obtaining the resin composition of the present embodiment by cohydrolysis condensation, the amount of water added is not particularly limited, but the preferred amount added is the ratio to (OR ² ) in the above general formula (1). Can be obtained from the mixing index ε. Here, the mixing index ε is expressed by the following formula (6).
Mixing index ε = (εw) / (εs) (6)
In formula (6),
εw: amount of water added (in mol),
εs: Indicates the amount (mol number) of (OR ² ) in the general formula (1).

  The mixing index ε is preferably 0.1 to 5, more preferably 0.2 to 3, and still more preferably 0.3 to 1.5. Depending on the composition of the resin composition, if the mixing index ε is less than 0.1, the hydrolysis reaction may not proceed. If it exceeds 5, the storage stability of the resin composition may be reduced.

  The addition of water in the co-hydrolysis condensation described above is mainly performed by hydrolysis of the alkoxysilane compound, and therefore needs to be performed in the “refluxing process without dehydration”. The timing of the addition is not particularly limited, and may be added first or gradually during the reaction using a feed pump or the like.

  The cohydrolysis condensation reaction of the present embodiment can be performed without a solvent or in a solvent. The solvent is not particularly limited as long as it is an organic solvent that can dissolve an epoxy resin and an alkoxysilane compound and is inactive to these, and for example, an aprotic polar solvent such as tetrahydrofuran or dioxane is preferably used. Can be used. Moreover, since it is easy to obtain, alcohol solvents such as methanol, ethanol, butanol, isopropanol, and n-butanol can be used. However, these promote the ring opening of the epoxy group. May not be suitable for use.

  The amount of the solvent added is preferably 0.01 to 20 times, more preferably 0.02 to 15 times, and more preferably 0.02 to 15 times the total mass of the epoxy resin and alkoxysilane compound subjected to the cohydrolysis condensation reaction. The amount is preferably 0.03 to 10 times. Since the molecular weight of the resin composition of the present embodiment can be controlled by the addition amount of the solvent, a resin composition having an appropriate molecular weight and thus an appropriate viscosity can be obtained by setting the addition amount in the above range. Can do.

(Oxetane compound)
The oxetane compound of the present embodiment is not particularly limited as long as it is a compound containing an oxetane ring. Specific examples of the compound having one oxetane ring include 3-ethyl-3-hydroxymethyloxetane and 3- (meth). Allyloxymethyl-3-ethyloxetane, 3-ethyl-3- (cyclohexyloxy) methyloxetane, 3-ethyl-3- (2-ethylcyclohexyloxymethyl) oxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene 3-ethyl-3- (phenoxymethyl) oxetane, 4-fluoro- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) ) Methyl] benzene, [1- (3-ethyl-3-oxetanylmethoxy) ethyl] fur Nyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl) -3-oxetanylmethyl) ether, dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl) -3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3- Ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3- Oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, and the like. .

  Specific examples of the compound having two or more oxetane rings include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 ′-(1,3- (2-methylenyl) propanedii. Rubis (oxymethylene)) bis- (3-ethyloxetane), bis [1-ethyl (3-oxetanyl)] methyl ether, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 3 -Ethyl-3-{[(3-ethyloxetanyl) methoxy] methyl} oxetane, 1,3-bis [(3-ethyloxetane-3-yl) methoxy] benzene, 1,2-bis [(3-ethyl- 3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl 3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethyleneglycolbis (3-ethyl-3-oxetanylmethyl) ether, tetraethyleneglycolbis (3-ethyl-3- Oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3) -Oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetani Methyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ) Ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-) 3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetani) Rumethyl) ether, PO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3- Ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F bis (3-ethyl-3-oxetanylmethyl) ether, oxetanylsilsesquioxane, oxetanyl silicate, phenol novolac oxetane and the like. Typical examples of oxetane compounds are shown below.

  In general, an epoxy compound is said to start polymerization quickly, but the subsequent polymerization reaction is not fast. On the other hand, the oxetane compound is said to have high nucleophilicity of ether oxygen compared to the epoxy compound, but the subsequent polymerization rate is high, although the polymerization start is slow. In other words, by blending the oxetane compound with the resin composition of the present invention having an epoxy group, acceleration of the polymerization rate due to the interaction can be expected. Depending on the selection of the oxetane compound, the viscosity of the resin composition can be lowered.

  The oxetane compound is blended at a mass ratio of resin composition: oxetane compound = 5: 95 to 95: 5 (100 in total). Within this range, the ratio is not particularly limited, but is preferably 20:80 to 80:20, and particularly preferably 30:70 to 70:30. When the blending ratio of the resin composition is less than 5, the curing reaction may not proceed normally, and when it exceeds 95, the light resistance of the cured product may be inferior.

  The viscosity of the composition of the present embodiment needs to be 100 Pa · s or less in terms of fluidity. If it is in the said range, the viscosity will not be specifically limited, However, Preferably it is 0.05-50 Pa.s, Most preferably, it is 0.2-30 Pa.s. If it exceeds 100 Pa · s, the fluidity is impaired, and if it is less than 0.05 Pa · s, a problem due to liquid dripping may occur in the production of products such as LEDs, which is not preferable.

  The composition of this embodiment may further contain a cationic polymerization initiator described later. The cationic polymerization initiator is not particularly limited as long as it generates a cationic species and cures epoxy, oxetane, vinyl ether or the like, but the use of a thermal cationic polymerization initiator described later is preferable.

  The thermal cationic polymerization initiator is not particularly limited as long as it is a compound that generates a cationic species by heat and initiates polymerization. For example, a quaternary ammonium salt, a sulfonium salt, a phosphonium salt, an aromatic And various onium salts such as group onium salts.

  Examples of the quaternary ammonium salt include tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogen sulfate, tetraethylammonium tetrafluoroborate, tetraethylammonium-p-toluenesulfonate, N, N-dimethyl. -N-benzylanilinium hexafluoroantimonate, N, N-dimethyl-N-benzylanilinium tetrafluoroborate, N, N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N, N-diethyl-N-benzyl Trifluoromethanesulfonate, N, N-dimethyl-N- (4-methoxybenzyl) pyridinium hexafluoroantimonate, N, N-diethyl N-(4-methoxybenzyl) preparative Luigi hexafluoroantimonate and the like.

  Examples of the sulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsinate, tris (4-methoxyphenyl) sulfonium hexafluoroarsinate, diphenyl (4-phenylthiophenyl). ) Sulfonium hexafluoroarsinate and the like.

  Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.

  As specific examples of the aromatic onium salt, compounds exemplified in Japanese Patent Publication No. 52-14277, Japanese Patent Publication No. 52-14278, Japanese Patent Publication No. 52-14279, and the like can be used.

Among them, PF6 @ ^- or SbF6 @ ^- use of the onium salt is particularly preferred that the counter ion. These may be used alone or in combination. Typical examples of the cationic polymerization initiator are shown below.

(Cured product)
Here, the cured product is obtained by curing the composition of the present embodiment described above by irradiating with heat or energy rays.
Although it does not specifically limit as a preparation method of the hardened | cured material in this embodiment, Thermal curing or energy beam curing is preferable, Especially preferably, thermal curing is used.

First, thermosetting will be described.
Thermal curing is a method of obtaining a cured product by causing a chemical reaction by heat and generating three-dimensional cross-linking between molecules.
Examples of the thermosetting method include a method in which a curing agent and a curing accelerator are contained in the composition and heat-treated, and a method in which the composition is thermally cured using the above-described thermal cationic polymerization initiator. In particular, a method of heat-treating a curing agent or a curing accelerator in advance is preferable.
The method of using the thermal cationic polymerization initiator is not particularly limited, but a general method is to include a thermal cationic polymerization initiator in the composition and heat-treat this.

Next, energy beam curing will be described.
The energy ray curing means that the cured product is irradiated by irradiating the composition of the present embodiment with a predetermined energy ray (ultraviolet rays, near ultraviolet rays, visible light, near infrared rays, infrared rays, electron beams, etc.). How to get.
As the energy ray, light is preferable, and ultraviolet light is more preferable.
Sources of energy rays include, for example, low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, UV lamp, xenon lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, argon ion laser, helium cadmium laser. And various light sources such as a helium neon laser, a krypton ion laser, various semiconductor lasers, a YAG laser, an excimer laser, a light emitting diode, a CRT light source, a plasma light source, and an electron beam irradiator.
In the energy ray curing step, the polymerization initiator added to the composition is decomposed by energy ray stimulation to generate a polymerization initiating species, the polymerizable functional group of the target substance is polymerized, and curing proceeds.

Among the polymerization initiators, those that are decomposed by energy ray stimulation and generate polymerization active species are called photopolymerization initiators, and can be roughly classified into the following three (1) to (3) depending on the generated active species. .
These photopolymerization initiators may be used alone or in combination of two or more.
(1) Those that generate radicals upon irradiation with energy rays.
(2) Those that generate cations by irradiation with energy rays (when the energy rays are light, they are called photoacid generators).
(3) Those that generate anions upon irradiation with energy rays (referred to as photobase generators when the energy rays are light).

  Examples of photopolymerization initiators used for energy ray curing include benzoins and benzoin alkyl ethers (benzoin, benzyl, benzoin methyl ether, benzoin isopropyl ether, etc.), acetophenones (acetophenone, 2,2-dimethoxy-2- Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-monoforino-propane-1 -One, N, N-dimethylaminoacetophenone, etc.), anthraquinones (2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amyla Traquinone, 2-aminoanthraquinone, etc.), thioxanthones (2,4-dimethylthiosantone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc.), ketals (acetophenone dimethyl ketal, benzyldimethyl) Ketones), benzophenones (benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, etc.), xanthones, benzoates (ethyl-4-dimethylaminobenzoate, 2- ( Dimethylamino) ethyl benzoate, etc.), amines (triethylamine, triethanolamine, etc.), iodonium salt compounds, sulfonium salt compounds, ammonium salt compounds, phosphonium salt compounds, Rusoniumu salt compound, a stibonium salt compound, an oxonium salt compound, a selenonium salt compound, a stannonium salt compound and the like.

(Composition and cured product additive)
In the composition of the present embodiment and the cured product thereof, various organic resins, inorganic fillers, colorants, leveling agents, lubricants, surfactants, silicone-based resins are used as long as the effects of the present invention are not impaired. A compound, a reactive diluent, a non-reactive diluent, an antioxidant, a light stabilizer and the like can be appropriately added. In addition, other additives for resin in general (plasticizers, flame retardants, stabilizers, antistatic agents, impact resistance enhancers, foaming agents, antibacterial / antifungal agents, conductive fillers, antifogging agents, crosslinking agents, etc.) The material provided as may be blended.

  Here, the organic resin is not particularly limited, and examples thereof include an epoxy resin, an acrylic resin, a polyester resin, and a polyimide resin. Among these, those having a highly reactive organic group such as an epoxy resin are preferable.

  Examples of inorganic fillers include silicas (melted crushed silica, crystal crushed silica, spherical silica, fumed silica, colloidal silica, precipitated silica, etc.) silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, sulfuric acid Barium, calcium sulfate, mica, talc, clay, aluminum oxide, magnesium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber And molybdenum disulfide, and the like, preferably silicas, calcium carbonate, aluminum oxide, aluminum hydroxide, calcium silicate, and the like. Further, considering the physical properties of the cured product, silicas are more preferable. These inorganic fillers may be used alone or in combination.

  The colorant is not particularly limited as long as it is a substance used for the purpose of coloring. For example, phthalocyanine, azo, disazo, quinacridone, anthraquinone, flavantron, perinone, perylene, dioxazine, condensed azo, azomethine-based various organic materials Inorganic pigments such as system dyes, titanium oxide, lead sulfate, chrome yellow, zinc yellow, chrome vermilion, valve shell, cobalt violet, bitumen, ultramarine, carbon black, chrome green, chrome oxide, cobalt green and the like. These colorants may be used alone or in combination.

  The leveling agent is not particularly limited. For example, oligomers having a molecular weight of 4000 to 12000 made of acrylates such as ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate, epoxidized soybean fatty acid, epoxidized abiethyl alcohol, hydrogenated castor oil And titanium-based coupling agents. These leveling agents may be used alone or in combination.

  The lubricant is not particularly limited, and hydrocarbon lubricants such as paraffin wax, microwax and polyethylene wax, higher fatty acid lubricants such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and behenic acid, stearylamide Higher fatty acid amide lubricants such as palmitylamide, oleylamide, methylenebisstearamide, ethylenebisstearamide, hydrogenated castor oil, butyl stearate, ethylene glycol monostearate, pentaerythritol (mono-, di-, tri -, Or tetra-) higher fatty acid ester lubricants such as stearate, alcohol lubricants such as cetyl alcohol, stearyl alcohol, polyethylene glycol, polyglycerol, lauric acid, myristic acid, palmitic acid, stearic acid, Examples include metal soaps that are metal salts such as magnesium, calcium, cadmium, barium, zinc, and lead such as rachidic acid, behenic acid, ricinoleic acid, and naphthenic acid, and natural waxes such as carnauba wax, candelilla wax, beeswax, and montan wax. . These lubricants may be used alone or in combination.

  The surfactant refers to an amphiphilic substance having a hydrophobic group having no affinity for the solvent in the molecule and an amphiphilic group (usually a hydrophilic group) having an affinity for the solvent. Moreover, the kind is not specifically limited, For example, a silicon-type surfactant, a fluorine-type surfactant, etc. are mentioned. Surfactants may be used alone or in combination.

  Examples of the silicone compound include, but are not limited to, silicone resin, silicone condensate, silicone partial condensate, silicone oil, silane coupling agent, silicone oil, polysiloxane, and the like. Or what modified | denatured by introduce | transducing an organic group into a side chain is also contained. The modification method is not particularly limited. For example, amino modification, epoxy modification, alicyclic epoxy modification, carbinol modification, methacryl modification, polyether modification, mercapto modification, carboxyl modification, phenol modification, silanol modification, polyether modification. , Polyether / methoxy modification, diol modification and the like.

  The reactive diluent is not particularly limited. For example, alkyl glycidyl ether, alkylphenol monoglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, alkanoic acid glycidyl ester, ethylene glycol diglycidyl Examples include ether and propylene glycol diglycidyl ether.

  The non-reactive diluent is not particularly limited, and examples thereof include high-boiling solvents such as benzyl alcohol, butyl diglycol, and propylene glycol monomethyl ether.

The antioxidant is not particularly limited, and examples thereof include organic phosphorus antioxidants such as triphenyl phosphate and phenylisodecyl phosphite, and organic sulfur antioxidants such as distearyl-3,3′-thiodipropinate. And phenolic antioxidants such as 2,6-di-tert-butyl-p-cresol.
The light stabilizer is not particularly limited, and examples thereof include benzotriazole-based, benzophenone-based, salicylate-based, cyanoacrylate-based, nickel-based, and triazine-based ultraviolet absorbers, hindered amine-based light stabilizers, and the like.

You may add the following substance further to the composition of this embodiment, and its hardened | cured material.
For example, solvents, oils and fats, processed oils, natural resins, synthetic resins, pigments, dyes, pigments, release agents, preservatives, adhesives, deodorants, flocculants, cleaning agents, deodorants, pH adjusters, photosensitive materials, Ink, electrode, plating solution, catalyst, resin modifier, plasticizer, softener, agrochemical, insecticide, fungicide, pharmaceutical raw material, emulsifier / surfactant, rust inhibitor, metal compound, filler, cosmetic / pharmaceutical raw material , Dehydrating agent, drying agent, antifreeze, adsorbent, colorant, rubber, foaming agent, colorant, abrasive, mold release agent, flocculant, antifoaming agent, curing agent, reducing agent, flux agent, film treatment agent, Casting raw materials, minerals, acids / alkalis, shot agents, antioxidants, surface coating agents, additives, oxidants, explosives, fuels, bleaches, light emitting elements, fragrances, concrete, fibers (carbon fibers, aramid fibers, glass) Fiber), glass, metal, excipient, disintegrant, Mixture, fluidizing agents, gelling agents, stabilizers, preservatives, buffering agents, suspending agents, thickeners, and the like.

(Use of composition and cured product of this embodiment)
Applications of the composition and the cured product of the present embodiment are not particularly limited. For example, electronic materials (such as castings and circuit units such as insulators, AC transformers, switchgears, packages of various parts, IC / LED / semiconductor sealing materials, generators, motors and other rotating machinery coils, winding impregnation, printed wiring boards, glass substitute transparent substrates, insulation boards, medium-sized insulators, coils, connectors, terminals, various cases, Electrical parts, etc.), paint (corrosion-resistant paint, maintenance, marine paint, corrosion-resistant lining, primer for automobiles and home appliances, beverage / beer can, exterior lacquer, extruded tube paint, general corrosion-resistant paint, maintenance process, lacquer for woodworking products , Automotive electrodeposition primer, other industrial electrodeposition coating, beverage / beer can inner surface lacquer, coil coating, drum / can inner surface coating, acid resistance Inning, wire enamel, insulation paint, automotive primer, exterior and anticorrosion coating of various metal products, pipe interior and exterior coating, electrical component insulation coating, etc.), composite materials (chemical plant pipes and tanks, aircraft materials, automotive parts, etc.) , Various sporting goods, carbon fiber composite materials, aramid fiber composite materials, etc.), civil engineering and building materials (floor materials, paving materials, membranes, anti-slip / thin layer pavement, concrete jointing / uplifting, anchor embedded adhesion, precast concrete joining , Tile adhesion, crack repair of concrete structures, grouting and leveling of pedestals, anticorrosion and waterproofing of water and sewage facilities, corrosion resistant laminated lining of tanks, anticorrosion coating of iron structures, mastic coating of exterior walls of buildings, etc.), adhesion Agent (same or different of metal, glass, ceramics, cement concrete, wood, plastic, etc.) Adhesives of materials, adhesives for assembling automobiles, railway vehicles, aircraft, etc., adhesives for manufacturing prefabricated composite panels, etc .: including one-part, two-part, and sheet types), aircraft, automobile, plastic molding Jigs (resin molds such as press dies, stretched dies, matched dies, vacuum molding / blow molding molds, master models, casting patterns, laminated jigs, various inspection jigs, etc.), modifiers / stabilizers (fiber Resin processing, stabilizers for polyvinyl chloride, additives to synthetic rubber, etc.).

(Encapsulant)
The sealing material is a member having a function of protecting a predetermined target from factors (foreign substances) such as temperature, humidity, and dust mainly in an airtight and liquidtight state. Foreign materials include sound, vibration, and erosion by chemical materials.

  The sealing material in the present embodiment may be used in combination with other sealing materials made of epoxy resin, silicone resin, epoxy silicone resin, acrylic resin, urethane resin, urea resin, imide resin, glass or the like.

The sealing material is not particularly limited as long as it satisfies the above-described requirements, but is mainly used for semiconductors, light-emitting diode (LED) applications, and liquid crystal applications. That is, in these applications, a semiconductor encapsulant for protecting the semiconductor from temperature, moisture, dust, etc., an LED encapsulant for protecting the LED and extending its durability life, and a liquid crystal for protecting the liquid crystal It is used as a sealing material, and among these, the use as an LED sealing material is preferable.
An LED is a semiconductor element that emits light when a voltage is applied in the forward direction. As a light emission principle, an electroluminescence (EL) effect is used.
Applications of LED sealing materials include, for example, displays, light-emitting display boards, traffic lights, display backlights (organic EL displays, mobile phones, mobile PCs, etc.), automobile interior / exterior certification, illumination, lighting equipment, flashlights, etc. Can be expanded to a wide range of fields.

As a usage site of the LED sealing material, for example, it is often used for protecting an LED chip body, a joint between the LED chip and a wire or a lead wire, and the like. It can also be used in a lead-free reflow mounting process corresponding to the RoHS directive, which is becoming the mainstream instead of the conventional lead solder process.
Furthermore, you may mix | blend a fluorescent substance with the LED sealing material mentioned above. Thus, by absorbing light emitted from the light emitting element and performing wavelength conversion, it is possible to provide an LED having a color tone different from the color tone of the light emitting element at the site of the sealing material. The shape of the LED is not particularly limited and can be appropriately selected according to the application. For example, a shell type, a surface mount type (SMD type), a chip on board type (COB type), a power LED type, a plate And thin film.

Moreover, the composition of this embodiment and its hardened | cured material can be utilized besides the said sealing material.
For example, semiconductor / LED peripheral materials (lens materials, substrate materials, die bond materials, chip coating materials, laminated plates, optical fibers, optical waveguides, optical filters, adhesives for electronic components, coating materials, sealing materials, insulating materials, photoresists) , Encap materials, potting materials, light transmission layers and interlayer insulation layers of optical disks, printed wiring boards, laminates, light guide plates, antireflection films, etc.).
Examples of the lens material include a lens for an optical device, a lens for an automobile lamp, a spectacle lens, a pickup lens such as a CD / DVD, and a lens for a projector.

  Although the Example which demonstrated this embodiment concretely is illustrated below, this embodiment is not limited to a following example, unless the summary is exceeded.

  The physical properties in Examples and Comparative Examples were evaluated as follows.

<Epoxy equivalent (WPE)>
It was measured according to “JIS K 7236: 2001 (How to determine epoxy equivalent of epoxy resin)”.
<Viscosity>
Measurement was performed under the following conditions.
Rotating E-type viscometer: “TV-22” manufactured by Toki Sangyo Co., Ltd.
Rotor: 3 ° × R14 (Other rotors may be selected as necessary.)
Measurement temperature: 25 ° C
Sample volume: 0.4mL

<Calculation of mixing index α>
The mixing index α was calculated from the following formula (2).
Mixing index α = (αc) / (αb) (2)
here,
αb: (B) In the general formula (1), n = 1 to 2, and R ¹ is an alkoxysilane compound content (mol%) having at least one cyclic ether group,
αc: (C) Content (mol%) of an alkoxysilane compound having n = 1 to 2 and having at least one aryl group as R ¹ in the general formula (1).

<Calculation of mixing index β>
The mixing index β was calculated from the following formula (3).
Mixing index β = {(β ⁿ² ) / (β ⁿ⁰ + β ⁿ¹ )} (3)
here,
β ⁿ² : content (mol%) of the alkoxysilane compound in which n = 2 in the general formula (1),
β ⁿ⁰ : the content (mol%) of the alkoxysilane compound in which n = 0 in the general formula (1),
β ⁿ¹ : content (mol%) of an alkoxysilane compound in which n = 1 in the general formula (1),
At this time, 0 ≦ {(β ⁿ⁰ ) / (β ⁿ⁰ + β ⁿ¹ + β ⁿ² )} ≦ 0.1.

<Calculation of mixing index γ>
The mixing index γ was calculated from the following equation (4).
Mixing index γ = (γa) / (γs) (4)
here,
γa: mass of epoxy resin (g),
γs: Mass (g) of the alkoxysilane compound in which n = 0 to 2 in the general formula (1).

<Calculation of mixing index δ>
The mixing index δ was calculated from the following equation (5).
Mixing index δ = (δe) / (δs) (5)
here,
δe: addition amount of hydrolytic condensation catalyst (mol number),
δs: The amount (mol number) of (OR ² ) in the general formula (1).

<Calculation of mixing index ε>
The mixing index ε was calculated from the following equation (6).
Mixing index ε = (εw) / (εs) (6)
here,
εw: amount of water added (in mol),
[epsilon] s: the amount (mol number) of (OR2) in the general formula (1).

<Calculation of mixing index ζ>
The mixing index ζ was calculated from the following equation (7).
Mixing index ζ = (ζf) / (ζk) (7)
here,
ζf: addition amount (number of moles) of curing agent,
ζk: The amount (mol number) of cyclic ether groups contained in the epoxy resin and the alkoxysilane compound.

<Calculation of mixing index η>
The mixing index η was calculated from the following formula (8).
Mixing index η = (ηg) / (ηk) (8)
here,
ηg: mass (g) of curing accelerator,
ηk: mass (g) of epoxy resin and alkoxysilane compound.

<Measurement of viscosity of composition>
The container containing the composition immediately after production was sealed and the temperature was adjusted at 25 ° C. for 1 hour, and then the viscosity at 25 ° C. was measured.
When the viscosity was 1000 Pa · s or less, it was judged that there was fluidity.

<Light resistance test of cured product>
The light resistance of the cured product was evaluated by the following method.
(1) The cured product solution prepared by the method described later was cured to produce a cured product of 20 mm × 10 mm × thickness 3 mm.
(2) The cured product was covered with a black mask of 25 mm × 15 mm × thickness 1.2 mm with a hole having a diameter of 5.5 mm to obtain a sample for light resistance test.
(3) A UV irradiation device (USHIO INC., “Spot Cure SP7-250DB”) is connected to the sample in a constant temperature incubator at 50 ° C. via an optical fiber so that the sample can be irradiated with UV light. Got ready.
(4) The sample was set in a constant temperature incubator at 50 ° C. with the black mask on top.
(5) UV light of 2 W / cm 2 was irradiated from the upper part of the black mask for 96 hours so that UV light could be irradiated to a hole having a diameter of 5.5 mm.
(6) The UV-irradiated sample was measured with a spectrocolorimeter (Nippon Denshoku Industries Co., Ltd., “SD5000”) with an integrating sphere opening modified to a diameter of 10 mm.
(7) Yellowness (YI) was determined according to “ASTM D1925-70 (1988): Test Method for Yellowness Index of Plastics”. When this YI was 11 or less, it was judged to have light resistance.

<Crack test of cured product>
The presence or absence of cracks in the cured product was evaluated by the following method.
(1) The board | substrate shown below was prepared.
・ Substrate: “Amodel A-4122NL WH 905” manufactured by Solvay Advanced Polymers Co., Ltd. (having a depression of 10 mm in diameter and 1.2 mm in depth in the center of a flat plate of 15 mm × 15 mm × thickness 2 mm)
(2) Five of the cured product solutions prepared by the method described below were poured into the substrate, and the cured products were used as crack test samples.
(3) The sample was sprayed with a penetrating liquid (manufactured by Kosai Co., Ltd., “Microcheck”), and visually observed under a magnifying glass for cracks, and the number of the samples was recorded.
(4) When no crack was found in 4/5 samples, it was judged to have crack resistance.

<Surface tackiness test of cured product>
The surface tackiness of the cured product was evaluated by the following method.
(1) The cured product solution prepared by the method described later was cured to produce a cured product of 20 mm × 10 mm × thickness 3 mm.
(2) The surface of the obtained cured product was lightly pressed with a thumb wearing latex gloves, and when no stickiness was observed, it was judged that the surface tackiness was good.

About the raw material used by the Example and the comparative example, it shows to the following (1)-(circle).
(1) Epoxy resin (1-1) Epoxy resin A: Poly (bisphenol A-2-hydroxypropyl ether) (hereinafter referred to as Bis-A epoxy resin)
・ Product name: “AER”, manufactured by Asahi Kasei Epoxy Corporation
Moreover, the epoxy equivalent (WPE) and viscosity measured by the above-mentioned method were as follows.
Epoxy equivalent (WPE): 187 g / eq
Viscosity (25 ° C.): 14.3 Pa · s
(1-2) Epoxy resin B: 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate (hereinafter referred to as alicyclic epoxy resin)
・ Product name: “Celoxide 2021P” manufactured by Daicel Chemical Industries, Ltd.
Moreover, the epoxy equivalent (WPE) and viscosity measured by the above-mentioned method were as follows.
Epoxy equivalent (WPE): 131 g / eq
Viscosity (25 ° C.): 227 mPa · s

(2) Alkoxysilane compound H: 3-glycidoxypropyltrimethoxysilane (hereinafter referred to as GPTMS)
・ Product name: “KBM-403”, manufactured by Shin-Etsu Chemical Co., Ltd.
(3) Alkoxysilane compound I: phenyltrimethoxysilane (hereinafter referred to as PTMS)
・ Product name: “KBM-103” manufactured by Shin-Etsu Chemical Co., Ltd.
(4) Alkoxysilane compound J: Dimethyldimethoxysilane (hereinafter referred to as DMDMS)
・ Product name: “KBM-22” manufactured by Shin-Etsu Chemical Co., Ltd.
(5) Alkoxysilane compound K: tetraethoxysilane (hereinafter referred to as TEOS)
・ Product name: “KBE-04”, manufactured by Shin-Etsu Chemical Co., Ltd.

(6) Solvent (6-1) Tetrahydrofuran: Wako Pure Chemical Industries, Ltd., stabilizer-free type (hereinafter referred to as THF)

(7) Hydrolysis condensation catalyst: dibutyltin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter referred to as DBTDL)
(8) Oxetane compound: 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane (manufactured by Toagosei Co., Ltd., “Aron Oxetane OXT-221”)
(9) Cationic polymerization initiator-Brand name: "San-Aid SI-100L" manufactured by Sanshin Chemical Industry Co., Ltd.
(10) Curing agent: “4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30”
-Product name: “Rikacid MH-700G” manufactured by Shin Nippon Rika Co., Ltd.
(11) Curing accelerator: Amine-based compound-Product name: "U-CAT 18X" manufactured by Sun Apro Co., Ltd.
(12) Silicone resin ・ Product name: “EG6301 (liquid A / liquid B)” manufactured by Toray Dow Corning Co., Ltd.

(Synthesis Example 1)
Resin composition A: Resin composition A was produced and evaluated by the following procedure.
(1) Preparation: A circulating water bath was set at 5 ° C. and refluxed to the cooling pipe. Further, an oil bath at 80 ° C. was placed on the magnetic stirrer.
(2) According to the composition ratio in Table 1, in an atmosphere of 25 ° C., the alicyclic epoxy resin, the alkoxysilane compound and THF are placed in a flask containing a stirrer, mixed and stirred, and further hydrolyzed with water. A condensation catalyst was added and mixed and stirred.
(3) Subsequently, a cooling tube was set on the flask, and it was immediately immersed in an oil bath at 80 ° C. to start stirring, and reacted for 8 hours while refluxing.
(4) After completion of the reaction, after cooling to 25 ° C., the cooling tube was removed from the flask, and a sample solution was collected after completion of the refluxing process.
(5) The solution after completion of the refluxing process was distilled off at 400 Pa and 50 ° C. for 1 hour using an evaporator, and then further dehydrated and condensed while being distilled off at 80 ° C. for 5 hours.
(6) After completion of the reaction, the mixture was cooled to 25 ° C. to obtain a resin composition A.
(7) Table 3 shows the mixing indices α1 to ε1 in this resin composition.
(8) Further, according to the above method, the epoxy equivalent (WPE) of the resin composition A obtained in the above (6) was measured.
The said resin composition was epoxy equivalent (WPE) = 158g / eq, and showed the appropriate value.

(Synthesis Example 2)
Resin composition B: According to the composition ratio in Table 1, resin composition B was synthesized and evaluated in the same manner as in Synthesis Example 1. Table 3 shows the mixing indices α2 to ε2.
The epoxy equivalent (WPE) of the resin composition B was 163 g / eq, which was an appropriate value.

(Synthesis Example 3)
Resin composition C: Resin composition C was synthesized and evaluated in the same manner as in Synthesis Example 1 in accordance with the composition ratio in Table 1. Table 3 shows the mixing indices α3 to ε3.
The epoxy equivalent (WPE) of the resin composition C was 160 g / eq, which was an appropriate value.

Example 1
Composition 1 was prepared and evaluated according to the following procedure.
(1) Composition 1 was obtained by mixing and stirring 75% by mass of resin composition A of Synthesis Example 1 and 25% by mass of an oxetane compound, and further degassing under vacuum. The viscosity of composition 1 was 1.82 Pa · s, and it was a liquid excellent in fluidity.
(2) 0.8% by mass of a cationic polymerization initiator was added to and mixed with 99.2% by mass of Composition 1, and degassing treatment was performed under the same conditions as in (1) to prepare a cured product solution. .
(3) A 3 mm thick, U-shaped silicon rubber is sandwiched between two stainless steel plates coated with a release agent, and the cured product produced with this molding jig is about 50 mm × about 20 mm × thickness 30 mm. Thus, a molding jig was produced.
(4) The molding jig and the above-described crack test substrate were prepared by pouring the above-described cured product solution into the five.
(5) The molding jig and the crack test substrate were placed in an oven and cured at 85 ° C. for 1 hour, and further at 150 ° C. for 3 hours to produce a cured product.
(6) Table 3 shows the results of the light resistance test, the crack resistance test, and the surface tack test performed by the above-described method using the above sample. It was judged that YI = 6.8 ≦ 11, which is an index of the light resistance test of the cured product, and had light resistance. Further, no cracks were generated in all of the 5/5 samples, and it was judged that the samples had crack resistance. Furthermore, no stickiness was observed and the surface tackiness was good.
From the above results, the composition 1 of Example 1 has fluidity, and the cured product of the composition has light resistance and crack resistance, and also has good surface tackiness. It was judged that the test was acceptable.

(Example 2)
Composition 2 was produced and evaluated by the following procedure.
(1) 70% by mass of resin composition B of Synthesis Example 2 and 30% by mass of an oxetane compound were mixed and stirred, and degassed in the same manner as in Example 1 to obtain Composition 2. The viscosity of the composition 2 was 2.78 Pa · s, and it was a liquid excellent in fluidity.
(2) 0.6% by weight of cationic polymerization initiator was added to and mixed with 99.4% by weight of Composition 1, and deaeration treatment was performed under the same conditions as in (1) to prepare a cured product solution. .
(3) Using the solution for cured product, a curing treatment was performed in the same manner as in Example 1 to prepare a cured product.
YI = 7.9 ≦ 11, which is an index of the light resistance test of this cured product, and it was judged that it had light resistance. Further, no cracks were generated in all of the 5/5 samples, and it was judged that the samples had crack resistance. Furthermore, no stickiness was observed and the surface tackiness was good.
From the above results, the composition 2 of Example 2 has fluidity, and the cured product of the composition has light resistance and crack resistance, and also has good surface tackiness. It was judged that the test was acceptable.

(Example 3)
Composition 3 was produced and evaluated by the following procedure.
(1) 80% by mass of resin composition C of Synthesis Example 2 and 20% by mass of an oxetane compound were mixed and stirred, and degassed by the same method as in Example 1 to obtain Composition 3. The viscosity of the composition 3 was 2.27 Pa · s, and it was a liquid excellent in fluidity.
(2) 0.7% by mass of a cationic polymerization initiator was added to and mixed with 99.3% by mass of Composition 3, and deaeration treatment was performed under the same conditions as in (1) to prepare a cured product solution. .
(3) Using the solution for cured product, a curing treatment was performed in the same manner as in Example 1 to prepare a cured product.
YI = 8.8 ≦ 11, which is an index of the light resistance test of the cured product, and it was determined that the cured product has light resistance. Further, no cracks were generated in 4/5 samples, and it was judged to have crack resistance. Furthermore, no stickiness was observed and the surface tackiness was good.
From the above results, the composition 3 of Example 3 has fluidity, and the cured product of the composition has light resistance and crack resistance, and also has good surface tackiness. It was judged that the test was acceptable.

(Comparative Example 1)
In place of the cationic polymerization initiator, the curing agent and the curing accelerator were added to the Bis-A epoxy resin and the alicyclic epoxy resin, mixed and stirred, and degassed under vacuum. This was used as a cured product solution. Next, in the same manner as in Example 1, the above-mentioned cured product solution was poured into the molding jig and the above-described five crack test substrates, and subjected to a curing treatment at 110 ° C. for 4 hours. Produced.
Table 3 shows the results of evaluation performed in the same manner as in Example 1.
It was found that YI = 13.9> 11, which is an index of the light resistance test of the cured product, and no light resistance. Further, no cracks were observed in 4/5 samples, and the samples had crack resistance. Further, no stickiness was observed and the surface tackiness was good.
From the above results, the cured product of Comparative Example 1 was judged to be unacceptable as a comprehensive judgment because it had no light resistance.

(Comparative Example 2)
The above-mentioned silicone resin prepared by mixing A liquid and B liquid in a mass ratio of 1: 1 was mixed and stirred and degassed under vacuum to obtain a cured product solution.
Next, in the same manner as in Example 1, the above-described cured product solution was poured into the molding jig and the above-described five crack test substrates, and subjected to a curing treatment at 150 ° C. for 1 hour. Produced.
Table 3 shows the results of evaluation performed in the same manner as in Example 1.
It was judged that YI = 2.3 ≦ 11, which is an index of the light resistance test of the cured product, and had light resistance. Further, no cracks were observed in 5/5 samples, and the samples had crack resistance. However, stickiness was observed and surface tackiness was poor. From the above results, although the cured product of Comparative Example 2 had light resistance and crack resistance, it was judged that the surface tackiness was poor and it was rejected as a comprehensive judgment.

As shown in Tables 1 to 3, a resin composition obtained by mixing an epoxy resin and a specific alkoxysilane compound at a specific ratio in this embodiment and cohydrolyzing and condensing, and an oxirane compound The composition containing was excellent in fluidity.
Moreover, the hardened | cured material which used the composition of this embodiment was excellent in light resistance, crack resistance, and surface tackiness.

  The composition and the cured product of this embodiment are, for example, electronic materials (insulators, AC transformers, switchgear and other castings and circuit units, various parts packages, IC / LED / semiconductor sealing materials, power generation, etc. Industrial applicability as rotating machines such as motors and motors, winding impregnations, printed wiring boards, insulation boards, medium-sized insulators, coils, connectors, terminals, various cases, electrical components, etc.) .

Claims (8)

(A) an epoxy resin;
An alkoxysilane compound represented by the following general formula (1):
A resin composition obtained by cohydrolyzing and condensing

(In the formula (1), n = 0 to 3, and R ¹ represents a hydrogen atom or an organic group. The plurality of R ² may be the same or different, and may be a hydrogen atom or a carbon number of 1 to 8. Represents an alkyl group of
The alkoxysilane compound is
(B) n = 1-2, and as R ¹ , at least one alkoxysilane compound having at least one cyclic ether group;
(C) n = 1-2, and as R ¹ , at least one alkoxysilane compound having at least one aryl group;
And a resin composition in which the mixing index α of (B) and (C) represented by the following formula (2) is 0.001 to 19 and an oxetane compound , the resin composition: The oxetane compound = a composition containing at a mass ratio of 5:95 to 95: 5 ;
Mixing index α = (αc) / (αb) (2)
(In formula (2), αb: content (mol%) of the component (B), αc: content (mol%) of the component (C)). As the alkoxysilane compound,
(D) The composition according to claim 1, further comprising at least one alkoxysilane compound in which n = 0 in the general formula (1). The composition according to claim 1 or 2, wherein a mixing index β of the alkoxysilane compound represented by the following formula (3) is 0.01 to 1.4;
Mixed index β = {(β ⁿ² ) / (β ⁿ⁰ + β ⁿ¹ )} (3)
(In formula (3),
β ⁿ² : content (mol%) of alkoxysilane compound in which n = 2 in the general formula (1),
β ⁿ⁰ : content (mol%) of an alkoxysilane compound in which n = 0 in the general formula (1),
β ⁿ¹ : content (mol%) of an alkoxysilane compound in which n = 1 in the general formula (1),
Here, 0 ≦ {(β ⁿ⁰ ) / (β ⁿ⁰ + β ⁿ¹ + β ⁿ² )} ≦ 0.1). The mixing index γ of the (A) epoxy resin and the alkoxysilane compound represented by the following general formula (4) is 0.02 to 15, according to any one of claims 1 to 3. Composition;
Mixing index γ = (γa) / (γs) (4)
(In formula (4),
γa: mass of epoxy resin (g),
γs: mass (g) of alkoxysilane compound in which n = 0 to 2 in the general formula (1)   The composition according to any one of claims 1 to 4, further comprising a cationic polymerization initiator.   Hardened | cured material obtained by hardening the composition as described in any one of Claims 1-5 with a heat | fever.   The sealing material containing the hardened | cured material of Claim 6. (A) an epoxy resin, the alkoxysilane compound, the cohydrolysis condensed with the resin composition that is obtained by represented by the following general formula (1), the oxirane compound, the resin composition: the oxetane compound = A method for producing a composition, wherein at least the addition is performed at a mass ratio of 5:95 to 95: 5 ;

(In the formula (1), n = 0 to 3, and R ¹ represents a hydrogen atom or an organic group. The plurality of R ² may be the same or different, and may be the same or different. 8 represents an alkyl group.)
The alkoxysilane compound is
(B) n = 1-2, and as R ¹ , at least one alkoxysilane compound having at least one cyclic ether group;
(C) n = 1-2, and as R ¹ , at least one alkoxysilane compound having at least one aryl group;
And the mixture index α of (B) and (C) represented by the following formula (2) is 0.001 to 19,
Mixing index α = (αc) / (αb) (2)
(In formula (2), αb: content (mol%) of the component (B), αc: content (mol%) of the component (C)).