JP6796582B2 - A method for producing a cured product, a cured product, and a laminate containing the cured product. - Google Patents

Description

The present invention relates to a method for producing a cured product, a cured product obtained by the above method, and a laminate having a structure in which an adherend is adhered by the cured product. The present application claims the priority of Japanese Patent Application No. 2015-122349 filed in Japan on June 17, 2015, the contents of which are incorporated herein by reference.

Thermosetting adhesives containing benzocyclobutene (BCB), novolak-based epoxy resin, or epoxy-modified polyorganosylsesquioxane are known as adhesives used for laminating semiconductors and adhering electronic components. (Patent Document 1).

However, in order to cure the thermosetting adhesive containing BCB, it is necessary to heat it at a high temperature of about 200 to 350 ° C., and the adherend may be damaged by being exposed to the high temperature. was there. Further, when a thermosetting adhesive containing a novolak epoxy resin is applied to a high temperature process such as lead-free solder reflow (for example, 260 to 280 ° C.), the adhesive decomposes to generate outgas, which causes outgassing. There was a problem that the adhesiveness was lowered.

On the other hand, a thermosetting adhesive containing an epoxy-modified polyorganosylsesquioxane can be cured at a lower temperature than a thermosetting adhesive containing BCB, and has better adhesiveness and adhesion to a substrate. An excellent cured product can be formed. In addition, the adhesiveness can be maintained even when subjected to a high temperature process. However, the cured product of the thermosetting adhesive containing the epoxy-modified polyorganosylsesquioxane has a problem that cracks are likely to occur when a cold shock is applied.

JP-A-2010-226060

Therefore, an object of the present invention is to provide a cured product having excellent heat resistance, crack resistance (or cold thermal impact resistance), adhesiveness to an object to be adhered, and adhesion.
Another object of the present invention is to provide a laminate having a structure in which an object to be adhered is adhered via the cured product.
Another object of the present invention is to provide a method for producing the cured product.

As a result of diligent studies to solve the above problems, the present inventors have applied a heat treatment for gradually changing the curing temperature to cure the curable composition, and determined the degree of curing at the end of the first stage heat treatment. It was found that a cured product having excellent heat resistance, crack resistance (or cold thermal impact resistance), adhesiveness to an object to be adhered, and adhesiveness can be obtained by setting the content to 85% or less. The present invention has been completed based on these findings.

That is, the present invention is a cured product obtained by subjecting a curable composition containing a compound having a polymerizable group to a heat treatment for gradually changing the curing temperature, and at the end of the first stage heat treatment. Provided is a cured product obtained by a heat treatment having a degree of curing of 85% or less and a degree of curing of more than 85% by the heat treatment of the second and subsequent steps.

The present invention also relates to the cured product in which the polymerizable group in the compound having a polymerizable group is one or more groups selected from the group consisting of an epoxy group, an oxetanyl group, a vinyl ether group, and a vinyl phenyl group. provide.

In the present invention, the compound having a polymerizable group is the following formula (1).
[R ¹ SiO _3/2 ] (1)
[In formula (1), R ¹ indicates a group containing an epoxy group]
Has a structural unit represented by
The following formula (I)
[R ^a SiO _3/2 ] (I)
[In formula (I), ^Ra is an epoxy group-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group. , Substituent or unsubstituted alkenyl group, or hydrogen atom]
The structural unit represented by and the following formula (II)
[R ^b SiO _2/2 (OR ^c )] (II)
[In formula (II), R ^b is an epoxy group-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group. , Substituent or unsubstituted alkenyl group, or hydrogen atom. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms]
The molar ratio of the structural unit represented by (I) [the structural unit represented by the formula (I) / the structural unit represented by the formula (II)] is 5 or more.
The structural unit represented by the above formula (1) and the following formula (4) with respect to the total amount (100 mol%) of the siloxane structural unit.
[R ¹ SiO _2/2 (OR ^c )] (4)
[In equation (4), R ¹ is the same as in equation (1). R ^c is the same as in equation (II)]
The ratio of the structural units represented by is 55 to 100 mol%, the number average molecular weight is 1000 to 3000, and the molecular weight dispersion (weight average molecular weight / number average molecular weight) is 1.0 to 3.0. The above-mentioned cured product which is an organosilsesquioxane is provided.

（式中、Ｒ^1a、Ｒ^1b、Ｒ^1c、Ｒ^1dは、同一又は異なって、直鎖又は分岐鎖状のアルキレン基を示す）The present invention also provides the cured product in which the R ¹ is one or more groups selected from the group consisting of the groups represented by the following formulas (1a) to (1d).

(In the formula, R ^1a , R ^1b , R ^1c , and R ^1d indicate the same or different, linear or branched alkylene group).

In the present invention, the epoxy-modified polyorganosylsesquioxane is further described by the following formula (2).
[R ² SiO _3/2 ] (2)
[In formula (2), R ² is a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkyl group. Indicates an alkenyl group of]
Provided is the cured product having a structural unit represented by.

The present invention also provides the cured product, wherein R ² is a substituted or unsubstituted aryl group.

The present invention also provides the cured product, wherein the curable composition further comprises a polymerization initiator.

The present invention also provides the cured product, wherein the curable composition further comprises a polymerization stabilizer.

The present invention also provides the cured product, wherein the curable composition further comprises a silane coupling agent.

The present invention is also a method for producing a cured product by subjecting a curable composition containing a compound having a polymerizable group to a heat treatment in which the curing temperature is changed stepwise, and the first stage heat treatment is performed. Provided is a method for producing a cured product, wherein the degree of curing at the end is 85% or less, and the degree of curing is increased to more than 85% by heat treatment in the second and subsequent steps.

The present invention is also a laminate composed of three or more layers.
It has two layers to be adhered and an adhesive layer between the layers to be adhered.
Provided is a laminate characterized in that the adhesive layer is a layer of the cured product.

The present invention also provides an apparatus having the above-mentioned laminate.

（式中、Ｒ^1a、Ｒ^1b、Ｒ^1c、Ｒ^1dは、同一又は異なって、直鎖又は分岐鎖状のアルキレン基を示す）
［５］エポキシ変性ポリオルガノシルセスキオキサンが、更に、下記式（２）
［Ｒ²ＳｉＯ_3/2］ （２）
［式（２）中、Ｒ²は、置換若しくは無置換のアリール基、置換若しくは無置換のアラルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアルキル基、又は、置換若しくは無置換のアルケニル基を示す］
で表される構成単位を有する［３］又は［４］に記載の硬化物。
［６］上記Ｒ²が、置換若しくは無置換のアリール基である［５］に記載の硬化物。
［７］エポキシ変性ポリオルガノシルセスキオキサンにおけるシロキサン構成単位の全量（１００モル％）に対する、上記式（１）で表される構成単位、上記式（２）で表される構成単位、上記式（４）で表される構成単位、及び下記式（５）
［Ｒ²ＳｉＯ_2/2（ＯＲ^c）］ （５）
［式（５）中、Ｒ²は、置換若しくは無置換のアリール基、置換若しくは無置換のアラルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアルキル基、又は、置換若しくは無置換のアルケニル基を示す。Ｒ^cは、水素原子又は炭素数１〜４のアルキル基を示す］
で表される構成単位の割合（総量）が６０〜１００モル％である、［５］又は［６］に記載の硬化物。
［８］硬化性組成物における上記重合性化合物の含有量（配合量）が、溶媒を除く硬化性組成物の全量（１００重量％）に対して、７０重量％以上、１００重量％未満であり、エポキシ変性ポリオルガノシルセスキオキサンの割合が、重合性化合物全量（１００重量％）の７０重量％以上である、［３］〜［７］のいずれか１つに記載の硬化物。
［９］硬化性組成物が、さらに重合開始剤を含む［１］〜［８］のいずれか１つに記載の硬化物。
［１０］硬化性組成物が、さらに重合安定剤を含む［１］〜［９］のいずれか１つに記載の硬化物。
［１１］硬化性組成物が、さらにシランカップリング剤を含む［１］〜［１０］のいずれか１つに記載の硬化物。
［１２］熱分解温度が２００℃以上である［１］〜［１１］のいずれか１つに記載の硬化物。
［１３］重合性基を有する化合物を含有する硬化性組成物に、硬化温度を段階的に変化させる加熱処理を施して硬化物を製造する方法であって、１段階目の加熱処理終了時の硬化度を８５％以下とし、２段階目以降の加熱処理によって硬化度を８５％超とすることを特徴とする硬化物の製造方法。
［１４］重合性基を有する化合物が、下記式（１）
［Ｒ¹ＳｉＯ_3/2］ （１）
［式（１）中、Ｒ¹は、エポキシ基を含有する基を示す］
で表される構成単位を有し、
下記式（Ｉ）
［Ｒ^aＳｉＯ_3/2］ （Ｉ）
［式（Ｉ）中、Ｒ^aは、エポキシ基を含有する基、置換若しくは無置換のアリール基、置換若しくは無置換のアラルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、又は水素原子を示す］
で表される構成単位と、下記式（II）
［Ｒ^bＳｉＯ_2/2（ＯＲ^c）］ （II）
［式（II）中、Ｒ^bは、エポキシ基を含有する基、置換若しくは無置換のアリール基、置換若しくは無置換のアラルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、又は水素原子を示す。Ｒ^cは、水素原子又は炭素数１〜４のアルキル基を示す］
で表される構成単位のモル比［式（Ｉ）で表される構成単位／式（II）で表される構成単位］が５以上であり、
シロキサン構成単位の全量（１００モル％）に対する上記式（１）で表される構成単位及び下記式（４）
［Ｒ¹ＳｉＯ_2/2（ＯＲ^c）］ （４）
［式（４）中、Ｒ¹は、式（１）におけるものと同じ。Ｒ^cは、式（II）におけるものと同じ］
で表される構成単位の割合が５５〜１００モル％であり、数平均分子量が１０００〜３０００、分子量分散度（重量平均分子量／数平均分子量）が１．０〜３．０であるエポキシ変性ポリオルガノシルセスキオキサンを含む、［１３］に記載の硬化物の製造方法。
［１５］１段階目の加熱処理を５分以上かけて行う［１３］又は［１４］に記載の硬化物の製造方法。
［１６］１段階目の加熱処理における加熱温度が９０℃以上、１５０℃未満である、［１５］に記載の硬化物の製造方法。
［１７］２段階目以降の加熱処理における加熱温度が１５０〜２００℃である［１３］〜［１６］のいずれか１つに記載の硬化物の製造方法。
［１８］２段階目以降の加熱処理における加熱時間が５〜１２０分である［１３］〜［１７］のいずれか１つに記載の硬化物の製造方法。
［１９］１段階目と２段階目の加熱処理にかける時間の合計（３段階目以降も行う場合は、３段階目以降の加熱処理に要する時間も合計する）が０．５〜２時間である［１３］〜［１８］のいずれか１つに記載の硬化物の製造方法。
［２０］３層以上で構成される積層物であって、２層の被接着層と、該被接着層の間の接着層とを有し、前記接着層が、［１］〜［１２］のいずれか１つに記載の硬化物の層であることを特徴とする積層物。
［２１］［２０］に記載の積層物を有する装置。That is, the present invention relates to the following.
[1] A cured product obtained by subjecting a curable composition containing a compound having a polymerizable group to a heat treatment for gradually changing the curing temperature, and the degree of curing at the end of the first stage heat treatment. A cured product obtained by heat treatment in which the degree of curing is 85% or more by heat treatment in the second and subsequent steps.
[2] The cured product according to [1], wherein the polymerizable group in the compound having a polymerizable group is one or more groups selected from the group consisting of an epoxy group, an oxetanyl group, a vinyl ether group, and a vinyl phenyl group. ..
[3] The compound having a polymerizable group has the following formula (1).
[R ¹ SiO _3/2 ] (1)
[In formula (1), R ¹ indicates a group containing an epoxy group]
Has a structural unit represented by
The following formula (I)
[R ^a SiO _3/2 ] (I)
[In formula (I), ^Ra is an epoxy group-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group. , Substituent or unsubstituted alkenyl group, or hydrogen atom]
The structural unit represented by and the following formula (II)
[R ^b SiO _2/2 (OR ^c )] (II)
[In formula (II), R ^b is an epoxy group-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group. , Substituent or unsubstituted alkenyl group, or hydrogen atom. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms]
The molar ratio of the structural unit represented by (I) [the structural unit represented by the formula (I) / the structural unit represented by the formula (II)] is 5 or more.
The structural unit represented by the above formula (1) and the following formula (4) with respect to the total amount (100 mol%) of the siloxane structural unit.
[R ¹ SiO _2/2 (OR ^c )] (4)
[In equation (4), R ¹ is the same as in equation (1). R ^c is the same as in equation (II)]
The ratio of the structural units represented by is 55 to 100 mol%, the number average molecular weight is 1000 to 3000, and the molecular weight dispersion (weight average molecular weight / number average molecular weight) is 1.0 to 3.0. The cured product according to [1], which is an organosilsesquioxane.
[4] The cured product according to [3], wherein R ¹ is one or more groups selected from the group consisting of groups represented by the following formulas (1a) to (1d).

(In the formula, R ^1a , R ^1b , R ^1c , and R ^1d indicate the same or different, linear or branched alkylene group).
[5] Epoxy-modified polyorganosylsesquioxane is further added to the following formula (2).
[R ² SiO _3/2 ] (2)
[In formula (2), R ² is a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkyl group. Indicates an alkenyl group of]
The cured product according to [3] or [4], which has a structural unit represented by.
[6] The cured product according to [5], wherein R ² is a substituted or unsubstituted aryl group.
[7] The structural unit represented by the above formula (1), the structural unit represented by the above formula (2), and the above formula with respect to the total amount (100 mol%) of the siloxane structural unit in the epoxy-modified polyorganosylsesquioxane. The structural unit represented by (4) and the following formula (5)
[R ² SiO _2/2 (OR ^c )] (5)
[In formula (5), R ² is a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkyl group. Indicates the alkenyl group of. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms]
The cured product according to [5] or [6], wherein the ratio (total amount) of the structural units represented by is 60 to 100 mol%.
[8] The content (blending amount) of the polymerizable compound in the curable composition is 70% by weight or more and less than 100% by weight with respect to the total amount (100% by weight) of the curable composition excluding the solvent. The cured product according to any one of [3] to [7], wherein the ratio of the epoxy-modified polyorganosylsesquioxane is 70% by weight or more of the total amount of the polymerizable compound (100% by weight).
[9] The cured product according to any one of [1] to [8], wherein the curable composition further contains a polymerization initiator.
[10] The cured product according to any one of [1] to [9], wherein the curable composition further contains a polymerization stabilizer.
[11] The cured product according to any one of [1] to [10], wherein the curable composition further contains a silane coupling agent.
[12] The cured product according to any one of [1] to [11], which has a thermal decomposition temperature of 200 ° C. or higher.
[13] A method for producing a cured product by subjecting a curable composition containing a compound having a polymerizable group to a heat treatment for gradually changing the curing temperature, at the end of the first stage heat treatment. A method for producing a cured product, wherein the degree of curing is 85% or less, and the degree of curing is increased to more than 85% by heat treatment in the second and subsequent stages.
[14] The compound having a polymerizable group has the following formula (1).
[R ¹ SiO _3/2 ] (1)
[In formula (1), R ¹ indicates a group containing an epoxy group]
Has a structural unit represented by
The following formula (I)
[R ^a SiO _3/2 ] (I)
[In formula (I), ^Ra is an epoxy group-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group. , Substituent or unsubstituted alkenyl group, or hydrogen atom]
The structural unit represented by and the following formula (II)
[R ^b SiO _2/2 (OR ^c )] (II)
[In formula (II), R ^b is an epoxy group-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group. , Substituent or unsubstituted alkenyl group, or hydrogen atom. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms]
The molar ratio of the structural unit represented by (I) [the structural unit represented by the formula (I) / the structural unit represented by the formula (II)] is 5 or more.
The structural unit represented by the above formula (1) and the following formula (4) with respect to the total amount (100 mol%) of the siloxane structural unit.
[R ¹ SiO _2/2 (OR ^c )] (4)
[In equation (4), R ¹ is the same as in equation (1). R ^c is the same as in equation (II)]
The ratio of the structural units represented by is 55 to 100 mol%, the number average molecular weight is 1000 to 3000, and the molecular weight dispersion (weight average molecular weight / number average molecular weight) is 1.0 to 3.0. The method for producing a cured product according to [13], which comprises an organosilsesquioxane.
[15] The method for producing a cured product according to [13] or [14], wherein the first-step heat treatment is carried out over 5 minutes or more.
[16] The method for producing a cured product according to [15], wherein the heating temperature in the first-stage heat treatment is 90 ° C. or higher and lower than 150 ° C.
[17] The method for producing a cured product according to any one of [13] to [16], wherein the heating temperature in the second and subsequent heat treatments is 150 to 200 ° C.
[18] The method for producing a cured product according to any one of [13] to [17], wherein the heating time in the second and subsequent heat treatments is 5 to 120 minutes.
[19] The total time required for the first and second stages of heat treatment (if the third and subsequent stages are also performed, the total time required for the third and subsequent stages of heat treatment) is 0.5 to 2 hours. The method for producing a cured product according to any one of [13] to [18].
[20] A laminate composed of three or more layers, which has two layers to be adhered and an adhesive layer between the layers to be adhered, and the adhesive layers are [1] to [12]. A laminate characterized by being a layer of the cured product according to any one of the above.
[21] An apparatus having the laminate according to [20].

If the adhesive layer in the laminate is cracked or peeled, the layer to be adhered may be peeled off or the wiring may be destroyed, and as a result, the device provided with the laminate may be damaged. Since the material has excellent heat resistance, crack resistance, adhesiveness to the adherend, and adhesion, the adhesive layer does not crack or peel even when a cold impact is applied, and a reliable device should be formed. Can be done. When the laminate of the present invention is a three-dimensional laminate of semiconductor chips, it has higher integration and power saving than the conventional semiconductor. Therefore, if the laminate of the present invention is used, it is smaller and has higher performance. Electronic devices can be provided.

It is explanatory drawing (schematic diagram of the thermogravimetric analysis result) which shows the evaluation method of the heat resistance of a cured product.

[Curable composition]
The curable composition in the present invention contains at least a compound having a polymerizable group (hereinafter, may be referred to as a "polymerizable compound"). The curable composition in the present invention may further contain other components such as a polymerization initiator, a polymerization stabilizer, a surface conditioner or a surface modifier.

(Compound having a polymerizable group)
The polymerizable group in the compound having a polymerizable group may be any group that can be polymerized to form a cured product by subjecting it to a heat treatment, and includes, for example, a cationically polymerizable group and a radically polymerizable group. .. In the present invention, one or more groups selected from the group consisting of an epoxy group, an oxetanyl group, a vinyl ether group, and a vinyl phenyl group are preferable.

That is, as the polymerizable compound in the present invention, a compound having an epoxy group (hereinafter, may be referred to as "epoxy compound"), a compound having an oxetanyl group (hereinafter, may be referred to as "oxetan compound"), vinyl ether. One or more selected from the group consisting of a compound having a group (hereinafter sometimes referred to as "vinyl ether compound") and a compound having a vinyl phenyl group (hereinafter sometimes referred to as "vinyl phenyl compound"). Compounds are preferred.

(Epoxy compound)
As the epoxy compound, a known or commonly used compound having one or more epoxy groups (oxylan rings) in the molecule can be used, and is not particularly limited, but for example, an epoxy-modified siloxane compound and an alicyclic epoxy compound (fat). (Cyclic epoxy resin), aromatic epoxy compound (aromatic epoxy resin), aliphatic epoxy compound (aliphatic epoxy resin) and the like can be mentioned.

<Epoxy-modified siloxane compound>
Examples of the epoxy-modified siloxane compound include epoxy-modified silicone and epoxy-modified polyorganosylsesquioxane. These can be used alone or in combination of two or more.

The epoxy-modified silicone is a compound in which an epoxy group (for example, a glycidyl group, an alicyclic epoxy group, etc.) is introduced into at least one of the terminal and side chains of the dimethyl silicone skeleton.

The epoxy-modified polyorganosilsesquioxane is a polysiloxane compound having a silsesquioxane structure and an epoxy group bonded thereto, and the silsesquioxane structure includes a random type structure, a basket type structure, and a ladder. Includes type structure.

A preferable epoxy-modified polyorganosylsesquioxane is, for example, the following formula (1).
[R ¹ SiO _3/2 ] (1)
[In formula (1), R ¹ indicates a group containing an epoxy group]
Has a structural unit represented by
The following formula (I)
[R ^a SiO _3/2 ] (I)
[In formula (I), ^Ra is an epoxy group-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group. , Substituent or unsubstituted alkenyl group, or hydrogen atom]
The structural unit represented by (sometimes referred to as "T3 body") and the following formula (II)
[R ^b SiO _2/2 (OR ^c )] (II)
[In formula (II), R ^b is an epoxy group-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group. , Substituent or unsubstituted alkenyl group, or hydrogen atom. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms]
The molar ratio of the structural unit represented by (sometimes referred to as "T2 body") [the structural unit represented by the formula (I) / the structural unit represented by the formula (II); "T3 body / T2 body" May be described as] is 5 or more,
The structural unit represented by the above formula (1) and the following formula (4) with respect to the total amount (100 mol%) of the siloxane structural unit.
[R ¹ SiO _2/2 (OR ^c )] (4)
[In equation (4), R ¹ is the same as in equation (1). R ^c is the same as in equation (II)]
The ratio (total weight) of the constituent units represented by is 55 to 100 mol%, the number average molecular weight is 1000 to 3000, and the molecular weight dispersion (weight average molecular weight / number average molecular weight) is 1.0 to 3.0. Compounds can be mentioned.

When the structural unit represented by the above formula (I) is described in more detail, it is represented by the following formula (I'). Further, if the structural unit represented by the above formula (II) is described in more detail, it is represented by the following formula (II'). Each of the three oxygen atoms bonded to the silicon atom represented in the structure represented by the following formula (I') is bonded to another silicon atom (silicon atom not represented by the formula (I')). .. In addition, the two oxygen atoms located above and below the silicon atom shown in the structure represented by the following formula (II') are also other silicon atoms (silicon atoms not shown in the formula (II')). It is combined. That is, both the T3 body and the T2 body are structural units (so-called T units) generally represented by [RSiO _3/2 ], and are subjected to the hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound. It is formed. In addition, R in the above formula indicates a hydrogen atom or a monovalent organic group, and the same applies to the following.

R ^a in the above formula (I) (formula (I ') in the R ^a same) and formula (II) in the R ^b (wherein (II') in the R ^b versa), respectively, an epoxy group A group containing, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom. Shown. Specific examples of R ^a and R ^b include those similar to R ¹ in the formula (1) and R ² in the formula (2) described later. R ^a in the formula (I) and R ^b in the formula (II) are groups bonded to a silicon atom in the hydrolyzable trifunctional silane compound used as a raw material for the epoxy-modified polyorganosylsesquioxane, respectively. It is derived from (groups other than alkoxy groups and halogen atoms; for example, R ¹ , R ² , hydrogen atoms, etc. in the formulas (a) to (c) described later).

The formula (II) in the (OR ^c) group (the formula (II ') in the (OR ^c) group versa) indicates a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms. Examples of the alkoxy group having 1 to 4 carbon atoms include an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group and an isobutyloxy group. The (OR ^c ) group in the formula (II) is generally an alkoxy group (for example, X ^{1 to} X ³ described later) in the hydrolyzable silane compound used as a raw material for the epoxy-modified polyorganosylsesquioxane. It is derived from the alkoxy group of.

The structural unit represented by the above formula (1) is a T unit (particularly T3 body), and the hydrolysis of the corresponding hydrolyzable trifunctional silane compound (for example, the compound represented by the formula (a) described later) and It is formed by a condensation reaction.

R ¹ in the formula (1) represents a group containing an epoxy group (monovalent group). Examples of the group containing an epoxy group include known and commonly used groups having an oxylane ring, and are not particularly limited, but from the viewpoint of curability of the curable composition and heat resistance of the cured product, the following formula (1a) One or more groups selected from the group consisting of the groups represented by (1d) are preferable, and the group represented by the following formula (1a) or (1c) is preferable, and the following formula (1a) is particularly preferable. ) Is the group represented by.

In the formula, R ^1a , R ^1b , R ^1c , and R ^1d represent the same or different linear or branched alkylene groups, for example, methylene group, methylmethylene group, dimethylmethylene group, ethylene group, propylene. Examples thereof include a linear or branched alkylene group having 1 to 10 carbon atoms such as a group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group and a decamethylene group.

As R ^1a , R ^1b , R ^1c , and R ^1d , a linear alkylene group having 1 to 4 carbon atoms and a branched alkylene group having 3 or 4 carbon atoms are preferable, and more preferably an ethylene group. , Trimethylene group, propylene group, more preferably ethylene group, trimethylene group.

R ^{1 in the} formula (1) is a group represented by the above formula (1a) in which R ^1a is an ethylene group [for example, 2- (3', 4'-epoxycyclohexyl)). Ethyl group] is preferable.

The epoxy-modified polyorganosylsesquioxane may have only one structural unit represented by the above formula (1), or may have two or more structural units represented by the above formula (1). It may be a thing.

Epoxy-modified polyorganosylsesquioxane has the following formula (2) as a T unit (particularly T3 body) in addition to the structural unit represented by the above formula (1).
[R ² SiO _3/2 ] (2)
It may have a structural unit represented by. The structural unit represented by the above formula (2) is formed by a hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound (for example, the compound represented by the formula (b) described later).

R ² in the above formula (2) is a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkyl group. Indicates the alkenyl group of. Examples of the aryl group include a phenyl group, a tolyl group, a naphthyl group and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the cycloalkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like. Examples of the alkyl group include a linear or branched alkyl such as a methyl group, an ethyl group, a propyl group, an n-butyl group, an isopropyl group, an isobutyl group, an s-butyl group, a t-butyl group and an isopentyl group. Group is mentioned. Examples of the alkenyl group include a linear or branched alkenyl group such as a vinyl group, an allyl group, and an isopropenyl group.

Examples of the above-mentioned substituted aryl group, substituted aralkyl group, substituted cycloalkyl group, substituted alkyl group, and substituted alkenyl group include the hydrogen atom or main chain skeleton of the above-mentioned aryl group, aralkyl group, cycloalkyl group, alkyl group and alkenyl group. Part or all selected from the group consisting of ether group, ester group, carbonyl group, siloxane group, halogen atom (fluorine atom, etc.), acrylic group, methacryl group, mercapto group, amino group, and hydroxy group (hydroxyl group). Included are groups substituted with at least one species.

Among them, as R ² , a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group is preferable, a substituted or unsubstituted aryl group is more preferable, and a phenyl group is further preferable. Is.

The proportion of the structural unit represented by the formula (1) and the structural unit represented by the formula (2) in the epoxy-modified polyorganosylsesquioxane is the raw material for forming these structural units (hydrolyzable three). It can be appropriately adjusted depending on the composition of the functional silane).

The epoxy-modified polyorganosylsesquioxane has a T unit (particularly T3 body) other than the structural unit represented by the above formula (1) and the structural unit represented by the formula (2), for example, the following formula ( 3)
[HSiO _3/2 ] (3)
It may have a structural unit represented by.

When the above ratio [T3 body / T2 body] of the epoxy-modified polyorganosylsesquioxane is 5 or more, it means that a certain amount or more of T2 body is present with respect to the T3 body. As such a T2 body, for example, the following equation (4)
[R ¹ SiO _2/2 (OR ^c )] (4)
The structural unit represented by the following formula (5)
[R ² SiO _2/2 (OR ^c )] (5)
The structural unit represented by the following formula (6)
[HSiO _2/2 (OR ^c )] (6)
Examples include the structural units represented by. The above R ¹ , R ² , and (OR ^c ) are the same as described above.

Ratio of the structural unit (T3 body) represented by the above formula (I) to the structural unit (T2 body) represented by the above formula (II) in the epoxy-modified polyorganosylsesquioxane [T3 body / T2 body] Is 5 or more as described above, preferably 5 to 18, more preferably 6 to 16, and even more preferably 7-14. By setting the above ratio [T3 body / T2 body] to 5 or more, the adhesiveness of the cured product is remarkably improved.

The above ratio [T3 / T2] in the epoxy-modified polyorganosylsesquioxane can be determined by, for example, ²⁹ Si-NMR spectrum measurement. ^{29 In the} Si-NMR spectrum, the silicon atom in the structural unit (T3 body) represented by the above formula (I) and the silicon atom in the structural unit (T2 body) represented by the above formula (II) are at different positions. Since the signal (peak) is shown in (chemical shift), the above ratio [T3 / T2] can be obtained by calculating the integration ratio of each peak. For example, when the epoxy-modified polyorganosylsesquioxane has a structural unit represented by the above formula (1) and R ¹ is a 2- (3', 4'-epoxycyclohexyl) ethyl group, the above formula is used. The signal of the silicon atom in the structure (T3 body) represented by (I) appears at -64 to -70 ppm, and the signal of the silicon atom in the structure (T2 body) represented by the above formula (II) is -54 to-. Appears at 60 ppm. Therefore, in this case, the above ratio [T3 body / T2 body] can be obtained by calculating the integral ratio of the signal (T3 body) of -64 to -70 ppm and the signal (T2 body) of -54 to -60 ppm. it can.

The ²⁹ Si-NMR spectrum of the epoxy-modified polyorganosylsesquioxane can be measured by, for example, the following equipment and conditions.
Measuring device: Product name "JNM-ECA500NMR" (manufactured by JEOL Ltd.)
Solvent: Deuterated chloroform Number of integrations: 1800 Measurement temperature: 25 ° C

In general, the complete cage type silsesquioxane is a polyorganosylsesquioxane composed of only T3 bodies, and the T2 body is not present in the molecule. That is, it is suggested that the epoxy-modified polyorganosylsesquioxane having the above ratio [T3 / T2] of 5 or more has an incomplete cage-type silsesquioxane structure.

Epoxy-modified polyorganosilsesquioxane cage to have (especially incomplete cage) silsesquioxane structures, respectively have an intrinsic absorption peak near 1050 cm ^-1 and near 1150 cm ^-1 in the FT-IR spectrum However, it can be confirmed from the fact that it has one intrinsic absorption peak near 1100 cm ^-1 [References: RHRaney, M. Itoh, A. Sakakibara and T. Suzuki, Chem. Rev. 95, 1409 (1995)]. On the other hand, in general, when the FT-IR spectrum has an intrinsic absorption peak near 1050 cm ^-1 and 1150 cm ^-1 , respectively, it is identified as having a ladder-type silsesquioxane structure. The FT-IR spectrum of the epoxy-modified polyorganosylsesquioxane can be measured by, for example, the following equipment and conditions.
Measuring device: Product name "FT-720" (manufactured by HORIBA, Ltd.)
Measurement method: Transmission method Resolution: 4 cm ^-1
Wavenumber range: 400-4000 cm ^-1
Accumulation number: 16 times

In addition to the above-mentioned T unit, the epoxy-modified polyorganosylsesquioxane is, for example, a structural unit represented by [R ₃ SiO _1/2 ] (so-called M unit) and a structural unit represented by [R ₂ SiO]. It may have at least one siloxane structural unit selected from the group consisting of (so-called D unit) and the structural unit represented by [SiO ₂ ] (so-called Q unit).

It is represented by the above formula (1) with respect to the total amount of siloxane structural units in the epoxy-modified polyorganosylsesquioxane [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%). The ratio (total amount) of the structural unit and the structural unit represented by the above formula (4) is 55 to 100 mol%, preferably 65 to 100 mol%, and more preferably 80 to 99 mol, as described above. %. By setting the above ratio to 55 mol% or more, the curability of the curable composition is improved, and the adhesiveness of the cured product is remarkably increased. The ratio of each siloxane structural unit in the epoxy-modified polyorganosylsesquioxane can be calculated by, for example, the composition of the raw material, the NMR spectrum measurement, or the like.

It is expressed by the above formula (2) with respect to the total amount of siloxane structural units in the epoxy-modified polyorganosylsesquioxane [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%). The ratio (total amount) of the structural unit and the structural unit represented by the above formula (5) is not particularly limited, but is preferably 0 to 70 mol%, more preferably 0 to 60 mol%, and further preferably 0 to 40. It is in mol%, particularly preferably 1 to 15 mol%. By setting the above ratio to 70 mol% or less, the ratio of the structural unit represented by the formula (1) and the structural unit represented by the formula (4) can be relatively increased, so that the curable composition The curability of the cured product tends to be improved, and the adhesiveness of the cured product tends to be higher.

It is represented by the above formula (1) with respect to the total amount of siloxane structural units in the epoxy-modified polyorganosylsesquioxane [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%). The ratio (total amount) of the structural unit represented by the above formula (2), the structural unit represented by the above formula (4), and the structural unit represented by the above formula (5) is not particularly limited. However, it is preferably 60 to 100 mol%, more preferably 70 to 100 mol%, still more preferably 80 to 100 mol%. By setting the above ratio to 60 mol% or more, the adhesiveness of the cured product tends to be higher.

The standard polystyrene-equivalent molecular weight dispersion (Mw / Mn) of the epoxy-modified polyorganosylsesquioxane by GPC is 1.0 to 3.0, preferably 1.1 to 2.0, as described above. It is more preferably 1.2 to 1.9, and particularly preferably 1.45 to 1.80. By setting the molecular weight dispersion to 3.0 or less, the adhesiveness of the cured product becomes higher. On the other hand, when the molecular weight dispersity is 1.0 or more (preferably 1.1 or more), it tends to be liquid and the handleability tends to be improved.

The standard polystyrene-equivalent number average molecular weight (Mn) of the epoxy-modified polyorganosylsesquioxane by GPC is 1000 to 3000 as described above, preferably 1000 to 2800, and more preferably 1000 to 2600. By setting the number average molecular weight to 1000 or more, the heat resistance and adhesiveness of the cured product are further improved. On the other hand, when the number average molecular weight is 3000 or less, the compatibility with other components in the curable composition is improved, and the heat resistance of the cured product is further improved.

The number average molecular weight and the molecular weight dispersion of the epoxy-modified polyorganosylsesquioxane can be measured by the methods described in Examples.

The epoxy-modified polyorganosylsesquioxane can be produced, for example, by a method of hydrolyzing and condensing one or more hydrolyzable silane compounds. However, as the hydrolyzable silane compound, a hydrolyzable trifunctional silane compound (a compound represented by the following formula (a)) for forming a structural unit represented by the above formula (1) is indispensable. Must be used as a hydrolyzable silane compound.

More specifically, the epoxy-modified polyorganosylsesquioxane is, for example, a hydrolyzable silane compound for forming T units, according to the following formula (a).
R ¹ Si (X ¹ ) ₃ (a)
The compound represented by the following formula (b), if necessary.
R ² Si (X ² ) ₃ (b)
The compound represented by the following formula (c)
HSi (X ³ ) ₃ (c)
It can be produced by a method of hydrolyzing and condensing the compound represented by.

The compound represented by the above formula (a) is a compound forming the structural unit represented by the formula (1) and the structural unit represented by the formula (4) in the epoxy-modified polyorganosylsesquioxane. R ¹ in the formula (a), the above formula (1), corresponding to R ¹ in (4).

X ¹ in the above formula (a) represents an alkoxy group or a halogen atom. Examples of the alkoxy group in X ¹ include the same examples as the alkoxy group having 1 to 4 carbon atoms in the (OR ^c ) group. Further, examples of the halogen atom in X ¹ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. Of these, an alkoxy group is preferable as X ¹ , and a methoxy group and an ethoxy group are more preferable. Incidentally, three of X ¹ may each be the same or may be different.

The compound represented by the above formula (b) is a compound forming a structural unit represented by the formula (2) and a structural unit represented by the formula (5) in the epoxy-modified polyorganosylsesquioxane. R ² in formula (b), the above formula (2), corresponding to R ² in (5).

X ² in the above formula (b) represents an alkoxy group or a halogen atom. Specific examples of X ² include those exemplified as X ¹ . Among them, as X ² , an alkoxy group is preferable, and a methoxy group and an ethoxy group are more preferable. Note that three X ² may each be the same or may be different.

The compound represented by the above formula (c) is a compound forming a structural unit represented by the formula (3) and a structural unit represented by the formula (6) in the epoxy-modified polyorganosylsesquioxane. X ³ in the above formula (c) represents an alkoxy group or a halogen atom. Specific examples of X ³ include those exemplified as X ¹ . Among these, as X ^3, alkoxy groups are preferred, more preferably a methoxy group, an ethoxy group. Incidentally, the three X ³ may each be the same or may be different.

As the hydrolyzable silane compound, a hydrolyzable silane compound other than the compounds represented by the above formulas (a) to (c) may be used in combination. For example, hydrolyzable trifunctional silane compounds other than the compounds represented by the above formulas (a) to (c), hydrolyzable monofunctional silane compounds forming M units, and hydrolyzable bifunctional silanes forming D units. Examples thereof include compounds, hydrolyzable tetrafunctional silane compounds forming Q units, and the like.

The amount and composition of the hydrolyzable silane compound used can be appropriately adjusted according to the desired structure of the epoxy-modified polyorganosylsesquioxane. For example, the amount of the compound represented by the above formula (a) is not particularly limited, but is preferably 55 to 100 mol%, more preferably 55 to 100 mol%, based on the total amount (100 mol%) of the hydrolyzable silane compound used. Is 65 to 100 mol%, more preferably 80 to 99 mol%.

The amount of the compound represented by the above formula (b) is not particularly limited, but is preferably 0 to 70 mol%, more preferably 0 to 70 mol%, based on the total amount (100 mol%) of the hydrolyzable silane compound used. Is 0 to 60 mol%, more preferably 0 to 40 mol%, and particularly preferably 1 to 15 mol%.

Further, the ratio (ratio of the total amount) of the compound represented by the formula (a) and the compound represented by the formula (b) to the total amount (100 mol%) of the hydrolyzable silane compound used is not particularly limited. It is preferably 60 to 100 mol%, more preferably 70 to 100 mol%, still more preferably 80 to 100 mol%.

When two or more kinds of the hydrolyzable silane compounds are used in combination, the hydrolysis and condensation reactions of these hydrolyzable silane compounds can be carried out simultaneously or sequentially. When the above reactions are carried out sequentially, the order in which the reactions are carried out is not particularly limited.

The hydrolysis and condensation reaction of the hydrolyzable silane compound can be carried out in the presence of a solvent or in the absence of the solvent. Above all, it is preferable to carry out in the presence of a solvent. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methyl acetate and ethyl acetate. , Esters such as isopropyl acetate and butyl acetate; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; nitriles such as acetonitrile, propionitrile and benzonitrile; alcohols such as methanol, ethanol, isopropyl alcohol and butanol. And so on. Of these, ketones and ethers are preferable as the solvent. As the solvent, one type may be used alone, or two or more types may be used in combination.

The amount of the solvent used is not particularly limited, and can be appropriately adjusted in the range of 0 to 2000 parts by weight with respect to 100 parts by weight of the total amount of the hydrolyzable silane compound, depending on the desired reaction time and the like. ..

The hydrolysis and condensation reaction of the hydrolyzable silane compound is preferably carried out in the presence of a catalyst and water. The catalyst may be an acid catalyst or an alkali catalyst. Examples of the acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid, nitrate, phosphoric acid and boric acid; phosphoric acid esters; carboxylic acids such as acetic acid, formic acid and trifluoroacetic acid; methanesulfonic acid, trifluoromethanesulfonic acid and p. − Sulphonic acids such as toluene sulfonic acid; solid acids such as active white clay; Lewis acids such as iron chloride can be mentioned. Examples of the alkali catalyst include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide; and alkaline earth metals such as magnesium hydroxide, calcium hydroxide and barium hydroxide. Hydroxides; Alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate; Alkali earth metal carbonates such as magnesium carbonate; Lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate Alkali metal hydrogen carbonates such as: Lithium acetate, sodium acetate, potassium acetate, cesium acetate and other alkali metal organic acid salts (eg acetates); alkaline earth metal organic acid salts such as magnesium acetate (eg) Acetate); Alkoxides of alkali metals such as lithium methoxydo, sodium methoxydo, sodium ethoxide, sodium isopropoxide, potassium ethoxide, potassium t-butoxide; Alkali metal phenoxides such as sodium phenoxide; triethylamine, N-methyl Amines such as piperidine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] nona-5-ene (tertiary amines, etc.); pyridine , 2,2'-bipyridyl, 1,10-phenanthroline and other nitrogen-containing aromatic heterocyclic compounds and the like. It should be noted that one type of catalyst may be used alone, or two or more types may be used in combination. The catalyst can also be used in a state of being dissolved or dispersed in water, a solvent or the like.

The amount of the catalyst used is not particularly limited, and can be appropriately adjusted within the range of 0.002 to 0.200 mol with respect to 1 mol of the total amount of the hydrolyzable silane compound.

The amount of water used in the hydrolysis and condensation reactions is not particularly limited, and can be appropriately adjusted within the range of 0.5 to 20 mol with respect to 1 mol of the total amount of the hydrolyzable silane compound.

The method for adding water is not particularly limited, and the total amount of water used (total amount used) may be added all at once, or may be added sequentially. When added sequentially, it may be added continuously or intermittently.

The reaction conditions for hydrolyzing and condensing the hydrolyzable silane compound are particularly such that the ratio [T3 / T2] in the epoxy-modified polyorganosylsesquioxane is 5 or more. It is important to choose. The reaction temperature of the hydrolysis and condensation reactions is not particularly limited, but is preferably 40 to 100 ° C, more preferably 45 to 80 ° C. By controlling the reaction temperature within the above range, the ratio [T3 / T2] tends to be controlled to 5 or more more efficiently. The reaction time of the hydrolysis and condensation reactions is not particularly limited, but is preferably 0.1 to 10 hours, more preferably 1.5 to 8 hours. Further, the hydrolysis and condensation reactions can be carried out under normal pressure, under pressure or under reduced pressure. The atmosphere at which the hydrolysis and condensation reactions are carried out is not particularly limited, and may be, for example, any of an inert gas atmosphere such as a nitrogen atmosphere and an argon atmosphere, and an oxygen presence such as air. However, it is preferable to use an inert gas atmosphere.

Epoxy-modified polyorganosylsesquioxane is obtained by the hydrolysis and condensation reaction of the hydrolyzable silane compound. After completion of the hydrolysis and condensation reactions, it is preferable to neutralize the catalyst in order to suppress ring opening of the epoxy group. Further, the obtained epoxy-modified polyorganosylsesquioxane may be used for separation means such as water washing, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc. Separation and purification may be performed by a separation means or the like in combination with.

<Alicyclic epoxy compound>
Examples of the alicyclic epoxy compound include known and commonly used compounds having one or more alicyclics and one or more epoxy groups in the molecule, and are not particularly limited, and examples thereof include the following compounds. Be done.
(1) An epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting an alicyclic in the molecule (in the present specification, it may be referred to as an "alicyclic epoxy group". An alicyclic epoxy group. (Contains, for example, a cyclohexene oxide group, etc.) (2) A compound in which an epoxy group is directly bonded to an alicyclic with a single bond (3) A compound having an alicyclic and a glycidyl ether group in the molecule ( Glycidyl ether type epoxy compound)

Examples of the compound (1) having an alicyclic epoxy group in the molecule include a compound represented by the following formula (i).

In the above formula (i), Y represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include a divalent hydrocarbon group, an alkenylene group in which part or all of the carbon-carbon double bond is epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and the like. Examples thereof include a group in which a plurality of these are linked.

Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms and a divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, a trimethylene group and the like. Examples of the divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms include a 1,2-cyclopentylene group, a 1,3-cyclopentylene group, a cyclopentylidene group and a 1,2-cyclohexylene group. , 1,3-Cyclohexylene group, 1,4-cyclohexylene group, cycloalkylene group such as cyclohexylidene group (including cycloalkylidene group) and the like.

Examples of the alkenylene group in the alkenylene group in which a part or all of the carbon-carbon double bond is epoxidized (sometimes referred to as “epoxidized alkenylene group”) include a vinylene group, a propenylene group, and a 1-butenylene group. , 2-Butenylene group, butazienylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group and the like, such as a linear or branched alkenylene group having 2 to 8 carbon atoms. In particular, as the epoxidized alkenylene group, an alkenylene group in which the entire carbon-carbon double bond is epoxidized is preferable, and more preferably, the entire carbon-carbon double bond is epoxidized and has 2 to 4 carbon atoms. It is an alkenylene group.

Typical examples of the alicyclic epoxy compound represented by the above formula (i) include (3,4,3', 4'-diepoxy) bicyclohexyl and bis (3,4-epoxycyclohexylmethyl) ether. 1,2-Epoxy-1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, 2,2-bis (3,4-epoxycyclohexane-1-yl) propane, 1,2-bis (3,4-epoxycyclohexane-1-yl) Examples thereof include 3,4-epoxycyclohexane-1-yl) ethane and compounds represented by the following formulas (i-1) to (i-10). In addition, R'in the following formula (i-5) is an alkylene group having 1 to 8 carbon atoms, and among them, a linear chain having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group and an isopropylene group. Alternatively, a branched alkylene group is preferable. Further, n ^{1 to} n ⁸ in the following formulas (i-5), (i-7), (i-9), and (i-10) represent integers of 1 to 30, respectively.

Examples of the compound in which the epoxy group is directly bonded to the alicyclic (2) by a single bond include a compound represented by the following formula (ii).

In formula (ii), R "is a group (p-valent organic group) obtained by removing p hydroxyl groups (-OH) from the structural formula of a p-valent alcohol, and p and n each represent a natural number. Examples of the valent alcohol [R "(OH) _p ] include polyhydric alcohols such as 2,2-bis (hydroxymethyl) -1-butanol (alcohols having 1 to 15 carbon atoms) and the like. p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or more, n in each group in [] (inside the outer square brackets) may be the same or different. Specific examples of the compound represented by the above formula (ii) include 1,2-epoxy-4- (2-oxylanyl) cyclohexane adducts of 2,2-bis (hydroxymethyl) -1-butanol [for example. , Product name "EHPE3150" (manufactured by Daicel Corporation), etc.] and the like.

Examples of the compound having an alicyclic and a glycidyl ether group in the above-mentioned (3) molecule include glycidyl ether of an alicyclic alcohol (particularly, an alicyclic polyhydric alcohol). More specifically, for example, 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, 2,2-bis [3,5-dimethyl-4- (2,3-epoxypropoxy)). Cyclohexyl] A compound obtained by hydrogenating a bisphenol A type epoxy compound such as propane (hydrogenated bisphenol A type epoxy compound); bis [o, o- (2,3-epoxypropoxy) cyclohexyl] methane, bis [o , P- (2,3-epoxypropoxy) cyclohexyl] methane, bis [p, p- (2,3-epoxypropoxy) cyclohexyl] methane, bis [3,5-dimethyl-4- (2,3-epoxypropoxy) 3-Epoxy propoxy) Cyclohexyl] A compound obtained by hydrogenating a bisphenol F type epoxy compound such as methane (hydrogenated bisphenol F type epoxy compound); hydrided biphenol type epoxy compound; hydride hydrogenated phenol novolac type epoxy compound; hydride cresol Novolak type epoxy compound; bisphenol A hydride cresol novolak type epoxy compound; hydrogenated naphthalene type epoxy compound; compound obtained by hydrogenating epoxy compound obtained from trisphenol methane; compound obtained by hydrogenating the following aromatic epoxy compound, etc. Be done.

<Aromatic epoxy compound>
Examples of the aromatic epoxy compound include epibis-type glycidyl ether-type epoxy resins obtained by a condensation reaction between bisphenols [for example, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, etc.] and epihalohydrin; High molecular weight epibistype glycidyl ether type epoxy resin obtained by further addition reaction of bistype glycidyl ether type epoxy resin with the above bisphenols; phenols [for example, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, bisphenol S, etc.] and aldehydes [for example, formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, salicylaldehyde, etc.] and polyhydric alcohols obtained by condensing reaction with epihalohydrin. Alkyl type glycidyl ether type epoxy resin; two phenol skeletons are bonded to the 9-position of the fluorene ring, and glycidyl is attached to the oxygen atom obtained by removing the hydrogen atom from the hydroxy group of these phenol skeletons, either directly or via an alkyleneoxy group. Examples thereof include an epoxy compound to which a group is bonded.

<Aliphatic epoxy compound>
Examples of the aliphatic epoxy compound include glycidyl ethers of alcohols having no q-valent cyclic structure (q is a natural number); monovalent or polyvalent carboxylic acids [eg, acetic acid, propionic acid, butyric acid, stearic acid, etc. Glycidyl ester of adipic acid, sebacic acid, maleic acid, itaconic acid, etc.; epoxidized fats and oils having double bonds such as epoxidized flaxseed oil, epoxidized soybean oil, epoxidized castor oil; polyolefin such as epoxidized polybutadiene Examples thereof include epoxidized compounds (including alkadiene). Examples of the alcohol having no q-valent cyclic structure include monohydric alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol and 1-butanol; ethylene glycol, 1,2-propanediol, 1 , 3-Propanediol, 1,4-Butanediol, Neopentyl glycol, 1,6-hexanediol, Diethylene glycol, Triethylene glycol, Tetraethylene glycol, Dipropylene glycol, Polyethylene glycol, Polypropylene glycol and other dihydric alcohols; Examples thereof include trihydric or higher polyhydric alcohols such as glycerin, diglycerin, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol. Further, the q-valent alcohol may be a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyolefin polyol or the like.

(Oxetane compound)
Examples of the oxetane compound include known and commonly used compounds having one or more oxetane rings in the molecule, and are not particularly limited, but for example, 3,3-bis (vinyloxymethyl) oxetane and 3-ethyl-3-3. (Hydroxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3- Ethyl-3- (chloromethyl) oxetane, 3,3-bis (chloromethyl) oxetane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis {[1-ethyl (3-ethyl (3-ethyl) Oxetane)] methyl} ether, 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] bicyclohexyl, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] cyclohexane, 1 , 4-Bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 3-ethyl-3-{[(3-ethyloxetane-3-yl) methoxy] methyl)} oxetane, xylylene bisoxetane , 3-Ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane, oxetanylsilsesquioxane, phenol novolac oxetane and the like.

(Vinyl ether compound)
As the vinyl ether compound, a known or commonly used compound having one or more vinyl ether groups in the molecule can be used, and is not particularly limited, but for example, 2-hydroxyethyl vinyl ether (ethylene glycol monovinyl ether), 3-hydroxy. Propyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxyisobutylvinyl ether, 2-hydroxyisobutylvinyl ether, 1-methyl-3 -Hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1-hydroxymethylpropyl vinyl ether, 4-hydroxycyclohexylvinyl ether, 1,6-hexanediol monovinyl ether, 1,6-hexanediol divinyl ether, 1,8- Octanediol divinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, 1,4-cyclohexanedimethanol divinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanol divinyl ether, 1,2-cyclohexane Dimethanol monovinyl ether, 1,2-cyclohexanedimethanol divinyl ether, p-xylene glycol monovinyl ether, p-xylene glycol divinyl ether, m-xylene glycol monovinyl ether, m-xylene glycol divinyl ether, o-xylene glycol monovinyl ether, o-xylene glycol divinyl ether, ethylene glycol divinyl ether, diethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, tetraethylene glycol monovinyl ether, tetraethylene glycol divinyl ether, pentaethylene glycol monovinyl ether, Pentaethylene glycol divinyl ether, oligoethylene glycol monovinyl ether, oligoethylene glycol divinyl ether, polyethylene glycol monovinyl ether, polyethylene glycol divinyl ether, dipropylene glycol monovinyl ether, dipropylene grease Cole divinyl ether, tripropylene glycol monovinyl ether, tripropylene glycol divinyl ether, tetrapropylene glycol monovinyl ether, tetrapropylene glycol divinyl ether, pentapropylene glycol monovinyl ether, pentapropylene glycol divinyl ether, oligopropylene glycol monovinyl ether, oligopropylene glycol di Vinyl ether, polypropylene glycol monovinyl ether, polypropylene glycol divinyl ether, isosorbide divinyl ether, oxanolborne divinyl ether, phenylvinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octyl vinyl ether, cyclohexyl vinyl ether, hydroquinone divinyl ether, 1,4-butanediol Divinyl Ether, Cyclohexanedimethanol Divinyl Ether, Trimethylol Propane Divinyl Ether, Trimethylol Propane Trivinyl Ether, Bisphenol A Divinyl Ether, Bisphenol F Divinyl Ether, Hydroxyoxanorbornane Methanol Divinyl Ether, 1,4-Cyclohexanediol Divinyl Ether, Pentaerythritol Tri Examples thereof include vinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether and the like.

(Vinyl phenyl compound)
Examples of the vinylphenyl compound include styrene, divinylbenzene, methoxystyrene, ethoxystyrene, hydroxystyrene, vinylnaphthalene, vinylanthracene, 4-vinylphenyl acetate, (4-vinylphenyl) dihydroxyborane, and 4-ethenylphenylborone. Acids, 4-vinylphenylboranoic acid, 4-vinylphenylboronic acid, p-vinylphenylboric acid, N- (4-vinylphenyl) maleinimide and the like, and derivatives thereof and the like can be mentioned.

The content (blending amount) of the polymerizable compound in the curable composition in the present invention is not particularly limited, but is 70% by weight or more, 100% by weight, based on the total amount (100% by weight) of the curable composition excluding the solvent. It is preferably less than% by weight, more preferably 80 to 99.8% by weight, still more preferably 90 to 99.5% by weight. By setting the content of the polymerizable compound to 70% by weight or more, the heat resistance of the cured product tends to be further improved.

Further, it is preferable that the curable composition in the present invention contains an epoxy-modified polyorganosylsesquioxane as a polymerizable compound in that a cured product having excellent heat resistance and crack resistance can be formed. The proportion of the epoxy-modified polyorganosylsesquioxane is preferably 70% by weight or more (for example, 70 to 100% by weight), more preferably 75% by weight, based on the total amount (100% by weight) of the polymerizable compound contained in the curable composition. % Or more, more preferably 80% by weight or more.

(Polymer initiator)
The polymerization initiator includes a cationic polymerization initiator and an anionic polymerization initiator. The cationic polymerization initiator is a compound that generates a cationic species by heating to initiate a curing reaction of a polymerizable compound, and the anionic polymerization initiator generates an anionic species by heating to initiate a polymerizable compound. It is a compound that initiates the curing reaction of. When the curable composition in the present invention contains a polymerization initiator, the curing time until it becomes tack-free can be shortened. The polymerization initiator may be used alone or in combination of two or more.

In the present invention, the adhesive layer can be formed quickly without advancing the curing reaction by heating and drying, and the adhesive layer does not have adhesiveness below 50 ° C., and damage to the adherend can be suppressed. It is preferable to use a polymerization initiator having the following curing characteristics in that an adhesive layer having the property of exhibiting adhesiveness by heating at a temperature and then rapidly curing until it becomes tack-free can be obtained.

That is, in the case of a cationic polymerization initiator, with respect to 100 parts by weight of 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate [for example, trade name "Ceroxide 2021P" (manufactured by Daicel Co., Ltd.)]. The thermosetting time of the composition obtained by adding 1 part by weight of the cationic polymerization initiator at 130 ° C. is 3.5 minutes or more (for example, 3.5 to 7.0 minutes, preferably 4.5 to 6.0 minutes). It is preferable to use a polymerization initiator which is.

In the case of an anionic polymerization initiator, the thermosetting time of the composition obtained by adding 1 part by weight of the anionic polymerization initiator to 100 parts by weight of bisphenol A diglycidyl ether at 130 ° C. is 3.5 minutes or more. It is preferable to use a certain polymerization initiator.

The thermosetting time in the present invention is determined by a method based on JIS K5909 (1994) until the composition is heated on a hot plate to become rubbery (more specifically, curing proceeds). , Until the thread does not rise to the needle tip). When a polymerization initiator whose thermosetting time is less than the above range is used, cation seeds are generated when a cationic polymerization initiator is used during heating and drying, and anionic species are generated when an anionic polymerization initiator is used, and thereafter at room temperature. However, since the polymerization gradually proceeds, it becomes difficult to form an adhesive layer having storage stability.

The cationic polymerization initiator comprises a cation portion that absorbs heat and an anion portion that is a source of acid. Examples of the cationic polymerization initiator include aryl sulfonium salts, aryl iodonium salts, allen-ion complexes, quaternary ammonium salts, aluminum chelates, boron trifluoride amine complexes and the like. In the present invention, the aryl sulfonium salt is particularly preferable in terms of curing rate.

Examples of the cation portion in the aryl sulfonium salt include (4-hydroxyphenyl) methylbenzyl sulfonium ion, triphenyl sulfonium ion, diphenyl [4- (phenylthio) phenyl] sulfonium ion, 4- (4-biphenylylthio) phenyl-. Examples thereof include aryl sulfonium ions such as 4-biphenylyl phenyl sulfonium ion and tri-p-tolyl sulfonium ion (particularly, triaryl sulfonium ion).

The anionic portion of the arylsulfonium salts, for _{^{example, SbF 6 -, PF 6 -}} , BF 4 -, (CF 3 CF 2) 3 PF 3 -, (CF 3 CF 2 CF 2) 3 PF 3 -, (C 6 ^{_{F 5) 4 B -, (}} C 6 F 5) 4 Ga -, a sulfonate anion (trifluoromethanesulfonic acid anion, pentafluoroethanesulfonate anion, nonafluorobutanesulfonic acid anion, methanesulfonic acid anion, benzenesulfonic acid anion , p- toluenesulfonate anion, _{etc.), (CF 3 SO 2)} 3 C -, (CF 3 SO 2) 2 N -, perhalogenated acid ion, halide sulfonate ion, sulfate ion, carbonate ion, aluminate ion , Hexafluorobismasic acid ion, carboxylic acid ion, arylborate ion, thiocyanate ion, nitrate ion and the like.

Examples of the cationic polymerization initiator include trade names "SP-66" and "SP-77" (all manufactured by ADEKA Corporation); trade names "Sun Aid SI-60L", "Sun Aid SI-80L", and "Sun Aid SI-80L". Commercially available products such as "Sun Aid SI-100L" and "Sun Aid SI-150L" (all manufactured by Sanshin Chemical Industry Co., Ltd.) can be used.

Examples of the anionic polymerization initiator include primary amines, secondary amines, tertiary amines, imidazoles, boron trifluoride-amine complexes and the like. Examples of the imidazoles include 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, and 2,4-diamino-6- [2-]. Methylimidazolyl- (1)] ethyl-s-triazine, 2-phenylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl- 2-Undecylimidazole and the like are included. In addition, the tertiary amine includes, for example, tris (dimethylaminomethyl) phenol, benzyldimethylamine, DBU (1,8-diazabicyclo [5.4.0] undecene-7) and the like.

In the present invention, it is preferable to use a cationic polymerization initiator (particularly preferably a thermal cationic polymerization initiator, most preferably an aryl sulfonium salt) in terms of curing rate.

The content (blending amount) of the above-mentioned polymerization initiator is not particularly limited, but is preferably 0.01 to 3.0 parts by weight with respect to 100 parts by weight of the polymerizable compound contained in the curable composition in the present invention. It is more preferably 0.05 to 2.0 parts by weight, further preferably 0.1 to 1.0 parts by weight, and particularly preferably 0.3 to 0.8 parts by weight. By setting the content of the polymerization initiator to 0.01 parts by weight or more, the curing reaction can proceed efficiently, and the heat resistance and adhesiveness of the cured product tend to be further improved. On the other hand, when the content of the polymerization initiator is 3.0 parts by weight or less, the storage stability of the curable composition tends to be further improved, and the coloring of the cured product tends to be suppressed.

(Polymerization stabilizer)
The polymerization stabilizer is a compound that suppresses the progress of cation polymerization by trapping cations. The ability of the polymerization stabilizer to trap cations is saturated and lost by heating. When the curable composition in the present invention contains a cationic polymerization initiator, it is possible to contain a polymerization stabilizer together with the cationic polymerization initiator for long-term polymerization after coating and drying to form an adhesive layer. It is preferable in that it is possible to form an adhesive layer having excellent storage stability, which can suppress the progress and can exhibit excellent adhesiveness by heating at a timing when adhesiveness is required.

Examples of the polymerization stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and poly ([6- (1,1,3,3-tetramethylbutyl) imino-1, 3,5-Triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] Hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) Imino]), tetrakis (2,2,6,6-tetramethyl-4-piperidyl) butane-1,2,3,4-tetracarboxylate, 2,2,6,6-tetramethyl-4-piperidi Nylbenzoate, (mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, 3,9-bis (2,3-di-t) -Butyl-4-methylphenoxy) -2,4,8,10-Tetraoxa-3,9-diphosphaspiro [5.5] undecane, mixed (2,2,6,6-tetramethyl-4-piperidyl / β , Β, β', β'-tetramethyl-3-9- [2,4,5,10-tetraoxaspiro [5.5] undecane] diethyl) -1,2,3,4-butanetetracarboxylate , Poly ([6-N-morpholyl-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2) , 6,6-Tetramethyl-4-piperidyl) imino]), [N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl-2- (2,2,6,6) -Tetramethyl-4-piperidyl) imino] Propionamide, trade names "LA-77", "LA-67", "LA-57" (above, manufactured by ADEKA), trade names "TINUVIN123", "TINUVIN152" (above) , Hindered amine compounds such as Ciba Japan Co., Ltd., and sulfonium sulfate compounds such as (4-hydroxyphenyl) dimethylsulfonium methylsulfite (Sun Aid SI aid, manufactured by Sanshin Chemical Industry Co., Ltd.), Examples thereof include phosphite compounds such as the trade name "PEP-36" (manufactured by ADEKA Co., Ltd.). These can be used alone or in combination of two or more.

The amount of the polymerization stabilizer used is, for example, 1 part by weight or more, preferably 3 to 20 parts by weight, particularly preferably 5 to 15 parts by weight, based on 100 parts by weight of the cationic polymerization initiator.

Further, the curable composition in the present invention further comprises precipitated silica, wet silica, fumed silica, fired silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate, as required. Inorganic fillers such as carbon black, silicon carbide, silicon nitride, boron nitride, etc., inorganic fillers obtained by treating these fillers with organic silicon compounds such as organohalosilane, organoalkoxysilane, and organosilazane; silicone resin, epoxy resin, Fine powder of organic resin such as fluororesin; filler such as conductive metal powder such as silver and copper, curing aid, solvent (organic solvent, etc.), stabilizer (antioxidant, ultraviolet absorber, light resistance stabilizer, Heat stabilizers, heavy metal defoamers, etc.), flame retardants (phosphorus flame retardants, halogen flame retardants, inorganic flame retardants, etc.), flame retardants, reinforcing materials (other fillers, etc.), nuclear agents , Coupling agent (silane coupling agent, etc.), Lubricants, wax, plasticizer, mold release agent, impact resistance improver, hue improver, clearing agent, rheology adjuster (fluidity improver, etc.), processability improvement Agents, colorants (dye, pigment, etc.), antistatic agents, dispersants, surface conditioners (leveling agents, armpit inhibitors, etc.), surface modifiers (slip agents, etc.), matting agents, defoamers, suppressors It may contain one or more conventional additives such as foaming agents, defoaming agents, foaming agents, antibacterial agents, preservatives, viscosity modifiers and thickeners.

The curable composition in the present invention is not particularly limited, but can be prepared by stirring and mixing each of the above components at room temperature or, if necessary, while heating. The curable composition in the present invention can be used as a one-component composition in which each component is mixed in advance and used as it is. For example, two or more components stored separately can be used. Can also be used as a multi-component (for example, two-component) composition which is used by mixing in a predetermined ratio before use.

The curable composition in the present invention is not particularly limited, but is preferably a liquid at room temperature (about 25 ° C.). When coating by spin coating, the viscosity of the curable composition is preferably adjusted according to the coating film thickness, and when coating with a film thickness of 0.1 to 50 μm, it is 1 to 5000 mPa · s. Is preferable. At this viscosity, a coating film having a uniform film thickness can be formed on a substrate such as a silicon wafer. The viscosity of the curable composition was determined by using a viscometer (trade name "MCR301", manufactured by Anton Pearl Co., Ltd.) at a swing angle of 5%, a frequency of 0.1 to 100 (1 / s), and a temperature of 25 ° C. Measured under conditions.

[Cured product]
The cured product of the present invention is a cured product obtained by subjecting the curable composition to a heat treatment in which the curing temperature is changed stepwise, and the degree of curing at the end of the first stage heat treatment is 85% or less ( For example, it is set to 50 to 85%, particularly preferably 55 to 85%, further preferably 60 to 80%), and the degree of curing is increased to more than 85% (preferably 90% or more, particularly preferably 95%) by the second and subsequent heat treatments. It should be noted that the upper limit of the degree of curing is 100%), which is a cured product obtained by the heat treatment. The degree of curing at the end of the first stage heat treatment is determined by measuring the calorific value of the sample at the end of the first stage heat treatment and the calorific value of the sample before the heat treatment by DSC, and using the following formula. Can be calculated.
Curing degree (%) = [1- (calorific value at the end of the first stage heat treatment / calorific value before heat treatment)] x 100

That is, the method for producing a cured product of the present invention is a method for producing a cured product by subjecting a curable composition containing a compound having a polymerizable group to a heat treatment for gradually changing the curing temperature. The degree of curing at the end of the first stage heat treatment is set to 85% or less (for example, 50 to 85%, particularly preferably 55 to 85%, more preferably 60 to 80%), and the degree of curing is achieved by the second and subsequent stages of heat treatment. Is more than 85% (preferably 90% or more, particularly preferably 95% or more, and the upper limit of the degree of curing is 100%). By controlling the degree of curing at the end of the first stage heat treatment to 85% or less, it is possible to form a structure that facilitates stress relaxation, and it is considered that the crack resistance of the finally obtained cured product is improved. ..

The degree of curing can be controlled by adjusting the heating temperature and the heating time. In the present invention, it is further excellent to cure slowly over a certain period of time until the degree of curing reaches 50 to 85% (preferably 55 to 85%, more preferably 60 to 80%). It is preferable in that a cured product having cracking property can be obtained, and the first step heat treatment is carried out for, for example, 5 minutes or more (preferably 5 to 120 minutes, particularly preferably 10 to 60 minutes, most preferably 30 to 60 minutes. ) Is preferable.

The heating temperature in the first-stage heat treatment may be such that the degree of curing at the end of the first-stage heat treatment does not exceed 85% even if the heat treatment is performed for 5 minutes or more, and the curable composition is polymerized. When the epoxy-modified polyorganosylsesquioxane is contained as the sex compound, it is, for example, 90 ° C. or higher and lower than 150 ° C., preferably 100 to 140 ° C., particularly preferably 110 to 140 ° C. When the first-stage heat treatment is performed at a temperature in the above range, a cured product having excellent crack resistance can be produced with good workability. On the other hand, if the first-stage heat treatment is performed at a temperature exceeding 150 ° C., it cannot be cured slowly, and the crack resistance of the obtained cured product tends to decrease. Further, since the curing proceeds too quickly, it tends to be difficult to complete the first stage heat treatment when the degree of curing is 85% or less. If the first-stage heat treatment is performed at a temperature of less than 90 ° C., it takes too much time to cure and the workability tends to decrease.

The heating temperature in the second and subsequent heat treatments is, for example, 150 to 200 ° C., preferably 160 to 190 ° C., particularly preferably 160 to 180 ° C. The heating time is, for example, 5 to 120 minutes, preferably 10 to 60 minutes. When the heat treatment temperature of the second and subsequent steps is lower than 150 ° C., it becomes difficult to increase the degree of curing of the obtained cured product to 100%, and heat resistance, crack resistance, adhesiveness to the adherend and adhesion to the adherend are deteriorated. Tends to decline. Further, even if the degree of curing can be increased to nearly 100%, it takes too much time to cure and the workability is lowered, which is not preferable. On the other hand, if the heat treatment temperature in the second and subsequent stages exceeds 200 ° C., the adherend may be deteriorated by heat.

The heat treatment at each stage may be performed while changing the temperature stepwise within the above range, or may be fixed at a specific temperature within the above range and the heat treatment may be performed. Further, the heat treatment of the present invention may be performed in two or more stages, and may be in two stages or in multiple stages of three or more stages.

In addition, the total time required for the first and second stages of heat treatment (if the third and subsequent stages are also performed, the time required for the third and subsequent stages of heat treatment is also totaled) is, for example, 0.5 to 2 hours. The degree, preferably 0.75 to 1.5 hours.

The cured product of the present invention obtained by the above production method has excellent crack resistance, and crack generation is suppressed even when a cold shock is applied.

The cured product of the present invention obtained by the above production method has excellent heat resistance, and the thermal decomposition temperature is, for example, 200 ° C. or higher (for example, 200 to 500 ° C.), preferably 260 ° C. or higher. The thermal decomposition temperature is determined by the method described in Examples.

The shape of the cured product of the present invention can be appropriately adjusted according to the intended use and is not particularly limited, and examples thereof include a sheet shape, a film shape, a tape shape, and a plate shape. The thickness of the cured product is not particularly limited.

The cured product of the present invention has heat resistance, crack resistance, and excellent adhesiveness and adhesion to an adherend. Therefore, when the curable composition of the present invention is used as an adhesive, particularly a thermosetting adhesive, the cured product of the present invention obtained by curing the adhesive has heat resistance, crack resistance, and adherence. It becomes an adhesive material having excellent adhesiveness and adhesiveness, and can be used for bonding desired objects to be adhered to each other.

[Laminate]
The laminate of the present invention is a laminate composed of three or more layers, and has two layers to be adhered and an adhesive layer between the layers to be adhered, and the adhesive layer is the cured product. It is characterized by being a layer of.

The laminate of the present invention is not particularly limited, but for example, one of the layers to be adhered is coated with the curable composition of the present invention and, if necessary, dried to form an adhesive layer, or one of them. The curable composition of the present invention is applied to the surface of a release paper or the like in advance, and an adhesive layer obtained by drying the adhesive layer is attached to the layer to be adhered. It can be obtained by adhering the other layer to be adhered to the layer and then performing the heat treatment as described above to cure the adhesive layer. However, the method for producing a laminate of the present invention is not limited to the above method.

The method of applying the curable composition is not particularly limited, and well-known and commonly used means can be used. Further, the drying means and conditions are not particularly limited, and conditions that can remove volatile substances such as a solvent as much as possible can be appropriately set, and well-known and commonly used means can be used. In particular, the polymerization initiation of the composition obtained by adding 1 part by weight of the curable composition to 100 parts by weight of Celoxide 2021P (manufactured by Daicel Co., Ltd.) at 130 ° C. for a thermosetting time of 3.5 minutes or more. When the agent is contained, volatile components such as a solvent can be quickly removed by heating and drying while suppressing the progress of the curing reaction, and the workability is excellent. Further, the obtained adhesive layer does not have adhesiveness below 50 ° C., and exhibits adhesiveness by heating at a temperature at which damage to the adherend can be suppressed.

The adherend forming the adhered layer in the laminate of the present invention is not particularly limited, and for example, a plastic substrate, a metal substrate, a ceramic substrate, a semiconductor substrate (including a semiconductor chip, a semiconductor wafer, etc.), and glass. Examples thereof include a base material, a paper base material, a wood base material, and a base material whose surface is a painted surface. The laminate of the present invention may have only two layers to be adhered, or may have three or more layers. The thickness of the layer to be adhered is not particularly limited, and can be appropriately selected in the range of, for example, 1 to 100,000 μm. The layer to be adhered does not have to have a strict layered form.

The laminate of the present invention may have only one adhesive layer, or may have two or more layers. The thickness of the adhesive layer is not particularly limited and can be appropriately selected in the range of 0.1 to 10000 μm, for example.

The laminate of the present invention may have other layers (for example, an intermediate layer, an undercoat layer, another adhesive layer, etc.) in addition to the above-mentioned layer to be adhered and the adhesive layer.

The laminate of the present invention has a structure in which the adherend is adhered by an adhesive layer having excellent heat resistance, crack resistance, adhesiveness to the adherend, and adhesion. Therefore, the laminate of the present invention can prevent the adherend from peeling or the wiring from being broken due to cracks or peeling in the adhesive layer, and the reliability of the device including the laminate can be prevented. Can be improved. When the laminate of the present invention is a three-dimensional laminate of semiconductor chips, it has higher integration and power saving than the conventional semiconductor. Therefore, if the laminate of the present invention is used, it is smaller and has higher performance. Electronic devices can be provided.

Examples of the laminate of the present invention include a microprocessor, a semiconductor memory, a power supply IC, a communication IC, a semiconductor sensor, a MEMS, and a semiconductor combining these. These are used in high-performance servers, workstations, in-vehicle computers, personal computers, communication devices, photographing devices, image display devices, and the like.

Therefore, examples of the apparatus of the present invention having (or having the laminate) the laminate include a server, a workstation, an in-vehicle computer, a personal computer, a communication device, a photographing device, an image display device, and the like. Can be done.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.
The number average molecular weight and the molecular weight dispersion of the product were determined by GPC analysis under the following conditions.
Alliance HPLC System 2695 (manufactured by Waters)
Refractometer Index Director 2414 (manufactured by Waters)
Column: Tskgel GMH _HR- M x 2 (manufactured by Tosoh Corporation)
Guard column: Tskgel guard column H _HR L (Tosoh Co., Ltd.)
Column oven: COLUMN HEATER U-620 (manufactured by Sugai)
Solvent: THF
Measurement conditions: 40 ° C
Molecular weight: Standard polystyrene conversion The ratio of T2 to T3 [T3 / T2] in the product was measured by ²⁹ Si-NMR spectrum measurement by JEOL ECA500 (500 MHz).

Preparation Example 1
(Preparation of epoxy-modified polyorganosylsesquioxane)
2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 161.5 mmol (39.) in a 300 mL flask (reaction vessel) equipped with a thermometer, stirrer, reflux condenser, and nitrogen introduction tube under a nitrogen stream. 79 g), 9 mmol (1.69 g) of phenyltrimethoxysilane, and 165.9 g of acetone were charged and the temperature was raised to 50 ° C. To the mixture thus obtained, 1700 mmol (30.60 g) of water was added dropwise over 20 minutes, and then 4.70 g (1.7 mmol as potassium carbonate) of a 5% potassium carbonate aqueous solution was added dropwise over 5 minutes. No significant temperature rise occurred during the dropping. Then, the polycondensation reaction was carried out under a nitrogen stream for 4 hours at 50 ° C.
When the product in the reaction solution after the polycondensation reaction was analyzed, the number average molecular weight was 1900 and the molecular weight dispersion was 1.5. The ratio of T2 to T3 [T3 / T2] calculated from the ²⁹ Si-NMR spectrum of the product was 10.3.
Then, methyl isobutyl ketone and saline solution are added, and after heating and stirring, the reaction solution is cooled, washed with water until the lower layer liquid becomes neutral, the upper layer liquid is separated, and then 1 mmHg, 40 ° C. Under the conditions, the solvent was distilled off from the upper layer solution until the amount of the solvent became 25% by weight to obtain a colorless and transparent liquid product (epoxy-modified polyorganosylsesquioxane).

(Preparation of curable composition)
100 parts by weight of the obtained epoxy-modified polyorganosylsesquioxane, 50 parts by weight of propylene glycol monomethyl ether acetate, antimony sulfonium salt (trade name "SI-150L", manufactured by Sanshin Chemical Industry Co., Ltd., seroxide 2021P ((( (Manufactured by Daicel Co., Ltd.) 1 part by weight added to 100 parts by weight, thermosetting time at 130 ° C.: 0.45 parts by weight (solid content equivalent), (4-hydroxyphenyl) ) Dimethylsulfonium methylsulfite (trade name "Sun Aid SI Auxiliary", manufactured by Sanshin Chemical Industry Co., Ltd.) was mixed by 0.05 parts by weight to obtain a curable composition.

Example 1
Silane coupling agent (trade name "KBE403", manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter "KBE403") on a silicon plate (size: 2 cm x 5 cm, manufactured by SUMCO Corporation, obtained by dicing a silicon wafer with a diameter of 100 mm) (Sometimes referred to as)) was applied by spin coating and heated at 120 ° C. for 5 minutes to obtain a silicon plate with a silane coupling agent layer.
The curable composition obtained in Preparation Example 1 was applied to the surface of the silane coupling agent layer of a silicon plate with a silane coupling agent layer by spin coating, and then heated at 80 ° C. for 4 minutes and then at 100 ° C. for 2 minutes to remain. The solvent was removed to obtain a silicon plate with an adhesive layer [adhesive layer / silane coupling agent layer / silicon plate]. The film thickness of the adhesive layer was 5 to 6 μm.

The adhesive layer of the obtained silicon plate with an adhesive layer was used as a sample, and this was heated at 130 ° C. for 30 minutes and then at 170 ° C. for 30 minutes to obtain a cured product. The degree of curing of the adhesive layer after completion of the first-stage curing reaction (after heating at 130 ° C. for 30 minutes) was 80%. The degree of curing at the end of the first stage heat treatment is determined by measuring the calorific value of the sample at the end of the first stage heat treatment and the calorific value of the sample before the heat treatment by DSC, and using the following formula. Calculated. The degree of curing was calculated in the same manner in the following Examples and Comparative Examples.
Curing degree (%) = [1- (calorific value at the end of the first stage heat treatment / calorific value before heat treatment)] x 100

The heat resistance, crack resistance, and adhesion of the obtained cured product were evaluated by the following methods.
(Heat-resistant)
The cured product is subjected to thermogravimetric analysis under the conditions of a nitrogen atmosphere and a heating rate of 10 ° C./min using a thermal analyzer (trade name "TG-DTA6300", manufactured by Seiko Electronics Co., Ltd.) to determine the thermal decomposition temperature. When (T) was measured, it was found that the temperature was 260 ° C. or higher and the heat resistance was excellent.
As shown in FIG. 1, the thermal decomposition temperature (T) is a tangent line where there is no initial weight loss or where the weight is gradually reduced (range indicated by A in the figure), and the weight is rapidly reduced. It is the temperature at which the tangents of the inflection points where they are occurring (the range indicated by B in the figure) intersect.

(Crack resistance)
When the cured product was subjected to a cold shock of heating at 250 ° C. for 30 minutes and then rapidly cooled to room temperature, it was confirmed that the crack-free portion was 60% or more of the cured product and was excellent in crack resistance.

(Adhesion)
The adhesion of the cured product to the silicon plate was evaluated by performing a grid tape test (JIS K5400-8.5 compliant). As a result, it was confirmed that no peeling from the silicon plate was observed and the adhesion was excellent.

Example 2
The adhesive layer of the silicon plate with the adhesive layer obtained by the same method as in Example 1 was used as a sample, and this was heated at 120 ° C. for 30 minutes and then at 170 ° C. for 30 minutes to obtain a cured product. The degree of curing of the adhesive layer after the completion of the first-stage curing reaction (after heating at 120 ° C. for 30 minutes) was 60%.

The heat resistance, crack resistance, and adhesion of the obtained cured product were evaluated in the same manner as in Example 1.
(Heat-resistant)
The thermal decomposition temperature (T) was 260 ° C. or higher, and it was found that the heat resistance was excellent.

(Crack resistance)
It was confirmed that the crack-free portion was 60% or more of the cured product and was excellent in crack resistance.

(Adhesion)
No peeling from the silicon plate was observed, and it was confirmed that the adhesion was excellent.

Comparative Example 1
The adhesive layer of the silicon plate with the adhesive layer obtained by the same method as in Example 1 was used as a sample, and this was heated at 150 ° C. for 30 minutes and then at 170 ° C. for 30 minutes to obtain a cured product. .. The degree of curing of the adhesive layer after completion of the first-stage curing reaction (after heating at 150 ° C. for 30 minutes) was 95%.

When the crack resistance of the obtained cured product was evaluated by the same method as in Example 1, severe cracks were generated in the entire cured product.

Example 3
A silane coupling agent (trade name "KBE403", manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter sometimes referred to as "KBE403") is applied to a glass plate (4 inches, manufactured by SCHOTT Japan Co., Ltd.) by spin coating. The glass plate with a silane coupling agent layer was obtained by heating at 120 ° C. for 5 minutes. A silicon plate with an adhesive layer obtained in the same manner as in Example 1 under reduced pressure on the silane coupling agent layer surface of the obtained glass plate with a silane coupling agent layer [adhesive layer / silane coupling agent layer]. By aligning the adhesive layer surfaces of [/ silicon plate] and applying a pressure of 200 g / cm ² while heating at 60 ° C., heating at 130 ° C. for 30 minutes, and then heating at 170 ° C. for 30 minutes. A laminate [glass plate / silane coupling agent layer / adhesive layer / silane coupling agent layer / silicon plate] was obtained. The degree of curing of the adhesive layer after the completion of the first-stage curing reaction (after heating at 130 ° C. for 30 minutes) was 80%.

The adhesiveness of the obtained laminate was evaluated by the following method.
(Adhesiveness)
When a razor blade (trade name "single-edged trimming razor", manufactured by Nissin EM Co., Ltd.) was inserted into the adhesive interface of the laminate, it was confirmed that peeling did not occur at the interface and the adhesive layer had excellent adhesiveness. It was.

Example 4
A silicon plate with an adhesive layer obtained by the same method as in Example 3 [adhesive] on the silane coupling agent layer surface of the glass plate with the silane coupling agent layer obtained by the same method as in Example 3 under reduced pressure. The adhesive layer surfaces of the agent layer / silane coupling agent layer / silicon plate] are aligned, and they are bonded by applying a pressure of 200 g / cm ² while heating at 60 ° C., then heated at 120 ° C. for 30 minutes, and then 170. A laminate [glass plate / silane coupling agent layer / adhesive layer / silane coupling agent layer / silicon plate] was obtained by heating at ° C. for 30 minutes. The degree of curing of the adhesive layer after the completion of the first-stage curing reaction (after heating at 120 ° C. for 30 minutes) was 60%.

When the adhesiveness of the obtained laminate was evaluated by the same method as in Example 3, it was confirmed that peeling did not occur at the interface and the adhesive layer was excellent in adhesiveness.

The cured product of the present invention has heat resistance, crack resistance, and excellent adhesiveness and adhesion to an adherend. Therefore, when the curable composition of the present invention is used as an adhesive, particularly a thermosetting adhesive, the cured product of the present invention obtained by curing the adhesive has heat resistance, crack resistance, and adherence. It becomes an adhesive material having excellent adhesiveness and adhesiveness, and can be used for bonding desired objects to be adhered to each other.

Claims (14)

A method for producing a cured product by subjecting a curable composition containing an epoxy-modified polyorganosylsesquioxane to a heat treatment in which the curing temperature is changed stepwise.
The curable composition comprises a thermal cationic polymerization initiator and / or a thermal anionic polymerization initiator.
The curable composition may contain a solvent. If the curable composition contains a solvent, the solvent is removed by drying and then heat-treated in the first step.
The heat treatment at the end of the curing of the first stage was 85% or less, the curing degree of 85 percent by heat treatment of the second stage or later,
The total time required for the first and second stages of heat treatment (if the third and subsequent stages are also performed, the total time required for the third and subsequent stages of heat treatment) is 0.5 to 2 hours. How to make things. Epoxy-modified polyorganosylsesquioxane has the following formula (1).
[R ¹ SiO _3/2 ] (1)
[In formula (1), R ¹ indicates a group containing an epoxy group]
Has a structural unit represented by
The following formula (I)
[R ^a SiO _3/2 ] (I)
[In formula (I), ^Ra is an epoxy group-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group. , Substituent or unsubstituted alkenyl group, or hydrogen atom]
The structural unit represented by and the following formula (II)
[R ^b SiO _2/2 (OR ^c )] (II)
[In formula (II), R ^b is an epoxy group-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group. , Substituent or unsubstituted alkenyl group, or hydrogen atom. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms]
The molar ratio of the structural unit represented by (I) [the structural unit represented by the formula (I) / the structural unit represented by the formula (II)] is 5 or more.
The structural unit represented by the above formula (1) and the following formula (4) with respect to the total amount (100 mol%) of the siloxane structural unit.
[R ¹ SiO _2/2 (OR ^c )] (4)
[In equation (4), R ¹ is the same as in equation (1). R ^c is the same as in equation (II)]
The ratio of the structural units represented by is 55 to 100 mol%, the number average molecular weight is 1000 to 3000, and the molecular weight dispersion (weight average molecular weight / number average molecular weight) is 1.0 to 3.0. The method for producing a cured product according to claim 1, which is an organosilsesquioxane. The method for producing a cured product according to claim 2 , wherein R ¹ is one or more groups selected from the group consisting of groups represented by the following formulas (1a) to (1d).

(In the formula, R ^1a , R ^1b , R ^1c , and R ^1d indicate the same or different, linear or branched alkylene group). Epoxy-modified polyorganosylsesquioxane is further added to the following formula (2).
[R ² SiO _3/2 ] (2)
[In formula (2), R ² is a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkyl group. Indicates an alkenyl group of]
The method for producing a cured product according to claim 2 or 3 , which has a structural unit represented by. The method for producing a cured product according to claim 4 , wherein R ² is a substituted or unsubstituted aryl group. The method for producing a cured product according to any one of claims 1 to 5 , wherein the curable composition further contains a polymerization initiator. The method for producing a cured product according to any one of claims 1 to 6 , wherein the curable composition further contains a polymerization stabilizer. The method for producing a cured product according to any one of claims 1 to 7 , wherein the curable composition further contains a silane coupling agent. The method for producing a cured product according to any one of claims 1 to 8, wherein the heating temperature in the first-stage heat treatment is 100 ° C. or higher and lower than 150 ° C. The method for producing a cured product according to any one of claims 1 to 9, wherein the heating temperature in the second stage heat treatment is 150 to 200 ° C. The method for producing a cured product according to any one of claims 1 to 10, wherein the heating time in the first step is 5 to 120 minutes. The method for producing a cured product according to any one of claims 1 to 11, wherein the heating time in the second step is 5 to 120 minutes. A method for manufacturing a laminate composed of three or more layers.
It has two layers to be adhered and an adhesive layer between the layers to be adhered.
A method for producing a laminate, wherein the adhesive layer is a layer of a cured product according to any one of claims 1 to 12 . The method for manufacturing an apparatus having the laminate according to claim 13 .

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