JP6957132B2 - Silsesquioxane - Google Patents

Description

The present invention relates to a novel silsesquioxane. The present invention also relates to a curable composition and an adhesive composition using the above silsesquioxane.

Adhesives are used for laminating semiconductors and adhering electronic components. As such an adhesive, a thermosetting adhesive containing benzocyclobutene (BCB), a novolak epoxy resin, or polyorganosylsesquioxane is known (see Patent Document 1).

By the way, laminated semiconductors are exposed to high temperatures in the manufacturing process. Therefore, the adhesive used for laminating semiconductors is required to have high adhesiveness and heat resistance. 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.

A thermosetting adhesive containing polyorganosylsesquioxane can be cured at a lower temperature than a thermosetting adhesive containing BCB, has excellent heat resistance, and has adhesiveness and adhesion to a substrate. A cured product having excellent properties can be formed.

JP-A-2009-279840 Japanese Unexamined Patent Publication No. 2008-248236

However, when a known polyorganosylsesquioxane is used as an adhesive, cracks occur when a thermal shock such as a thermal cycle (repeating heating and cooling periodically) is applied. There was something.

Further, since the polysilsesquioxane described in Patent Document 2 is synthesized by using an acid as a raw material of a silane compound having an epoxy group, the epoxy equivalent is 2430 g / eq and the content of the epoxy group is high. The thermosetting adhesive containing a small amount of the polyorganosylsesquioxane had poor curability, and the adhesiveness was still insufficient.

Therefore, an object of the present invention is to provide a novel silsesquioxane. Another object of the present invention is to provide silsesquioxane capable of forming a cured product having excellent crack resistance (or cold thermal impact resistance), heat resistance, and adhesiveness to an adherend. It is in. Furthermore, another object of the present invention is to provide an adhesive composition capable of forming a cured product having excellent crack resistance (or cold thermal impact resistance), heat resistance, and adhesiveness to an object to be adhered. It is in.

As a result of diligent studies to solve the above problems, the present inventors have found a novel silsesquioki having a ladder skeleton containing a silicon atom to which a group containing an epoxy group is bonded, and an epoxy equivalent within a specific range. It has been found that by synthesizing sun and using it, a cured product having excellent crack resistance (or cold thermal impact resistance), heat resistance, and adhesiveness to an adherend can be formed. The present invention has been completed based on these findings.

That is, the present invention is silsesquioxane having a ladder skeleton, and the ladder skeleton has the following formula (1).
[R ¹ SiO _3/2 ] (1)
[In formula (1), R ¹ represents a group containing an epoxy group. ]
Provided is silsesquioxane, which has a structural unit represented by and has an epoxy equivalent of 200 to 1000 g / eq.

The silsesquioxane has the following formula (3) at the end of the ladder skeleton.
[R ^a R ³ SiO _2/2 ] (3)
[In formula (3), ^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. R ³ represents a hydroxy group that may be protected by a protecting group. ]
It is preferable to have a structural unit represented by. Further, it is preferable that the number average molecular weight of the silsesquioxane in terms of standard polystyrene by gel permeation chromatography is 500 to 5000.

The silsesquioxane preferably has a ratio of the structural unit represented by the formula (3) to all the ends of the ladder skeleton in an amount of 30 to 100 mol%.

［式（１ａ）中、Ｒ^1aは、直鎖又は分岐鎖状のアルキレン基を示す。］
で表される基、下記式（１ｂ）

［式（１ｂ）中、Ｒ^1bは、直鎖又は分岐鎖状のアルキレン基を示す。］
で表される基、下記式（１ｃ）

［式（１ｃ）中、Ｒ^1cは、直鎖又は分岐鎖状のアルキレン基を示す。］
で表される基、及び、下記式（１ｄ）

［式（１ｄ）中、Ｒ^1dは、直鎖又は分岐鎖状のアルキレン基を示す。］
で表される基からなる群より選択される１種以上の基であることが好ましい。 In the silsesquioxane, the R ¹ is represented by the following formula (1a).

[In formula (1a), R ^1a represents a linear or branched alkylene group. ]
The group represented by the following formula (1b)

[In formula (1b), R ^1b represents a linear or branched alkylene group. ]
The group represented by the following formula (1c)

[In formula (1c), R ^1c represents a linear or branched alkylene group. ]
The group represented by and the following formula (1d)

[In formula (1d), R ^1d represents a linear or branched alkylene group. ]
It is preferable that the group is one or more selected from the group consisting of the groups represented by.

The silsesquioxane may be used for adhesive compositions.

The present invention also provides a curable composition containing the silsesquioxane.

The present invention also provides an adhesive composition containing the silsesquioxane.

The present invention also provides a cured product of the curable composition.

The present invention also provides an adhesive sheet having an adhesive layer formed from the adhesive composition on at least one surface of the substrate.

Further, the present invention is a laminate composed of three or more layers, which has two layers to be adhered and an adhesive layer provided between the layers to be adhered, and the adhesive layer is cured. Provided is a laminate which is a layer of a cured product of the sex composition.

The present invention also provides an apparatus having the laminate.

According to the present invention, a novel silsesquioxane compound can be provided. Further, since the silsesquioxane of the present invention has the above-mentioned constitution, by curing the curable composition containing the silsesquioxane as an essential component, crack resistance, heat resistance, and adhesion to the adherend are obtained. A cured product having excellent properties can be formed.

It is a figure which shows ^{the 1} H-NMR measurement result of the ladder type silsesquioxane obtained in Example 1. FIG. It is a figure which shows ^{the 29} Si-NMR measurement result of the ladder type silsesquioxane obtained in Example 1. FIG. It is a figure which shows the FT-IR measurement result of the ladder type silsesquioxane obtained in Example 1. FIG. It is explanatory drawing (schematic diagram of the thermogravimetric analysis result) which shows the evaluation method of the heat resistance of a cured product.

[Silsesquioxane]
The silsesquioxane (polyorganosilsesquioxane) of the present invention is a silsesquioxane having a ladder skeleton, and the ladder skeleton has a structural unit represented by the following formula (1) and has an epoxy equivalent. It is 200 to 1000.
[R ¹ SiO _3/2 ] (1)

The epoxy equivalent (g / eq) of silsesquioxane of the present invention is, as described above, 200 to 1000, preferably 210 to 800, more preferably 220 to 500, and even more preferably 230 to 300. When the epoxy equivalent is within the above range, the amount of epoxy groups in silsesquioxane is moderately large, and the cured product is excellent in crack resistance while being excellent in heat resistance and adhesiveness to the adherend. The epoxy equivalent is measured according to JIS K7236: 2001.

The structural unit represented by the above formula (1) is a silsesquioxane structural unit (so-called T unit) _{generally represented by [RSiO 3/2].} In addition, R in the above formula indicates a hydrogen atom or a monovalent organic group, and the same applies to the following. The structural unit represented by the above formula (1) is formed by a hydrolysis and condensation reaction of a corresponding hydrolyzable trifunctional silane compound (specifically, for example, a compound represented by the formula (a) described later). Will be done.

^{R 1} in the formula (1) represents a group containing an epoxy group (monovalent group). That is, the silsesquioxane of the present invention is a cationically curable compound (cationically polymerizable compound) having at least an epoxy group in the molecule. 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) The group represented by the following formula (1b), the group represented by the following formula (1c), and the group represented by the following formula (1d) are preferable, and more preferably the following formula (1a). A group represented by the following formula (1c), more preferably a group represented by the following formula (1a).

In the above formula (1a), R ^1a represents a linear or branched alkylene group. Examples of the linear or branched alkylene group include methylene group, methylmethylene group, dimethylmethylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, decamethylene group and the like. Examples thereof include a linear or branched alkylene group having 1 to 10 carbon atoms. Among them, as R ^1a , a linear alkylene group having 1 to 4 carbon atoms and a branched alkylene group having 3 or 4 carbon atoms are preferable, and ethylene is more preferable, from the viewpoint of curability of the curable composition. A group, a trimethylene group, a propylene group, more preferably an ethylene group or a trimethylene group.

In the above formula (1b), R ^1b represents a linear or branched alkylene group, and a group similar to ^{R 1a is exemplified.} Among them, as R ^1b , a linear alkylene group having 1 to 4 carbon atoms and a branched alkylene group having 3 or 4 carbon atoms are preferable, and ethylene is more preferable, from the viewpoint of curability of the curable composition. A group, a trimethylene group, a propylene group, more preferably an ethylene group or a trimethylene group.

In the above formula (1c), R ^1c represents a linear or branched alkylene group, and a group similar to ^{R 1a is exemplified.} Among them, as R ^1c , a linear alkylene group having 1 to 4 carbon atoms and a branched alkylene group having 3 or 4 carbon atoms are preferable, and ethylene is more preferable, from the viewpoint of curability of the curable composition. A group, a trimethylene group, a propylene group, more preferably an ethylene group or a trimethylene group.

In the above formula (1d), R ^1d represents a linear or branched alkylene group, and a group similar to ^{R 1a is exemplified.} Among them, as 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 ethylene is more preferable, from the viewpoint of curability of the curable composition. A group, a trimethylene group, a propylene group, more preferably an ethylene group or a trimethylene group.

^{The R 1} in the formula (1) is particularly a group represented by the above formula (1a) in which R ^1a is an ethylene group [among others, a 2- (3,4-epoxycyclohexyl) ethyl group. ] Is preferable.

The silsesquioxane of the present invention may have only one type of structural unit represented by the above formula (1), or may have two or more types of structural units represented by the above formula (1). It may be.

The ladder skeleton in the silsesquioxane of the present invention is _{represented by the following formula (2) as the silsesquioxane structural unit [RSiO 3/2} ] in addition to the structural unit represented by the above formula (1). It may have a structural unit to be used.
[R ² SiO _3/2 ] (2)

The structural unit represented by the above formula (2) is a silsesquioxane structural unit (T unit) _{generally represented by [RSiO 3/2].} That is, the structural unit represented by the above formula (2) is the hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound (specifically, for example, the compound represented by the formula (b) described later). Is formed by.

^{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 hydrogen atoms or main ribs in each of the above-mentioned aryl group, aralkyl group, cycloalkyl group, alkyl group and alkenyl group. Part or all of the ranks are alkyl groups (particularly linear or branched alkyl groups having 1 to 10 carbon atoms), ether groups, ester groups, carbonyl groups, siloxane groups, halogen atoms (fluorine atoms, etc.), Examples thereof include a group substituted with at least one selected from the group consisting of an acrylic group, a methacryl group, a mercapto group, an amino group, and a hydroxy group (hydroxyl group).

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, and more preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl. A group, more preferably a phenyl group, a 2- (3,4-cyclohexenyl) ethyl group. When a ^{substituted or unsubstituted aryl group (particularly, a phenyl group) is contained as R 2} , it is possible to prevent the degree of curing from becoming too high, and the cured product tends to have better crack resistance and adhesiveness.

The ratio of each of the above-mentioned silsesquioxane structural units (the structural unit represented by the formula (1) and the structural unit represented by the formula (2)) in the silsesquioxane of the present invention forms these structural units. It can be appropriately adjusted depending on the composition of the raw material (hydrolyzable trifunctional silane).

The rudder skeleton in the silsesquioxane of the present invention is not particularly limited, but preferably has a structural unit represented by the following formula (3) at the end.
[R ^a R ³ SiO _2/2 ] (3)

In the above formula (3), ^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. R ³ represents a hydroxy group that may be protected by a protecting group.

The ends of the ladder skeleton are the ends in the long axis direction of the ladder skeleton, and there are usually four ends in one ladder skeleton. Examples of the silicon atom at the end of the ladder skeleton include a silicon atom to which T is bonded in the formula (A) described later.

Specific examples of the R ^a include those similar to ^{R 1} in the above formula (1) ^{and R 2} in the above formula (2).

Examples of the protecting group in a protected or unprotected hydroxy group with a protecting group R ^3, a protecting group commonly used in organic synthesis [for example, an alkyl group (e.g., methyl group, of a t- butyl group and the like C _{1- 4} Alkyl group, etc.); Alkenyl group (eg, allyl group, etc.); Cycloalkyl group (eg, cyclohexyl group, etc.); Aryl group (eg, 2,4-dinitrophenyl group, etc.); Aralkyl group (eg, benzyl group, etc.) ); Substituent methyl group (eg, methoxymethyl group, methylthiomethyl group, benzyloxymethyl group, t-butoxymethyl group, 2-methoxyethoxymethyl group, etc.), substituted ethyl group (eg, 1-ethoxyethyl group, etc.), A group capable of forming an acetal or hemiacetal group with a hydroxy group such as a tetrahydropyranyl group, a tetrahydrofuranyl group, a 1-hydroxyalkyl group (for example, 1-hydroxyethyl group, etc.); an acyl group (for example, a formyl group, an acetyl group). , Propionyl group, butyryl group, isobutyryl group, pivaloyl group and the like C _1-6 aliphatic acyl group; acetoacetyl group; aromatic acyl group such as benzoyl group and the like; alkoxycarbonyl group (for example, methoxycarbonyl group and the like C _1-4 alkoxy-carbonyl group, etc.); aralkyloxycarbonyl group; substituted or unsubstituted carbamoyl group; substituted silyl group (for example, trimethylsilyl group, etc.); substituent when two or more hydroxy groups or hydroxymethyl groups are present in the molecule. Divalent hydrocarbon groups (for example, methylene group, ethylidene group, isopropylidene group, cyclopentylidene group, cyclohexylidene group, benzylidene group, etc.) which may have the above are mentioned. Above all, a substituted silyl group (particularly, a trimethylsilyl group) can be improved from the viewpoint of improving the storage stability of silsesquioxane and the curable composition while being excellent in crack resistance, heat resistance, and adhesiveness to the adherend of the cured product. ) Is preferable.

^{R 3} in the above formula (3) is preferably a hydroxy group protected by a protecting group. When the above R ³ is a hydroxy group protected by a protecting group, it is possible to suppress the condensation reaction of the terminal hydroxy group with another siloxane compound, and thus the storage stability of silsesquioxane and the curable composition. There is a tendency for sex to improve.

The proportion of the structural unit represented by the above formula (3) in all the ends (100 mol%) of the ladder skeleton is not particularly limited, but is 30 mol% or more (for example, 30 to 100 mol%). Is preferable, more preferably 50 mol% or more, still more preferably 75 mol% or more. When the proportion of the structural unit represented by the above formula (3) is 30 mol% or more, the storage stability of silsesquioxane or the curable composition tends to be further improved. In particular, it is preferable that the ratio of the structural unit represented by the above formula (3), in which R ^{3 is a hydroxy group protected by a protecting group, is within the above range.} In the present specification, the ratio of the siloxane constituent units constituting the silsesquioxane of the present invention ^{can be determined by, for example, 29} Si-NMR spectrum measurement.

The ends of the ladder skeleton may be partially or wholly the same, or may be different. Further, when two or more structural units represented by the above formula (3) are provided at the end of the ladder skeleton, the structural units represented by the two or more formulas (3) may be the same. It may be different.

The ratio of the structural unit represented by the above formula (1) to all the siloxane structural units (100 mol%) constituting the ladder skeleton is not particularly limited, but is 50 mol% or more (for example, 50 to 100 mol%). ) Is preferable, more preferably 60 to 99 mol%, further preferably 70 to 98 mol%, still more preferably 80 to 97 mol%, and particularly preferably 90 to 96 mol%. When the above ratio is 50 mol% or more, the cured product tends to be more excellent in crack resistance, heat resistance, and adhesiveness to the adherend. Further, it is preferable that the ratio of the structural unit represented by the above formula (1) to all the siloxane structural units constituting the silsesquioxane of the present invention is within the above range.

When the ladder skeleton contains the structural unit represented by the above formula (2), the ratio of the structural unit represented by the above formula (2) to all the siloxane structural units (100 mol%) constituting the ladder skeleton. Is not particularly limited, but is preferably more than 0 mol% and 50 mol% or less, more preferably 1 to 40 mol%, still more preferably 2 to 30 mol%, still more preferably 3 to 20 mol%, and particularly preferably. It is 4 to 10 mol%. When the above ratio is 50 mol% or less, the ratio of the structural unit represented by the above formula (1) is relatively increased, and the heat resistance and crack resistance of the cured product tend to be more excellent. Further, when ^{the ratio of the structural unit represented by the above formula (2) in which R 2} is a substituted or unsubstituted aryl group is within the above range, it is possible to prevent the degree of curing from becoming too high, and the resistance of the cured product It tends to have better crackability and adhesiveness. It is preferable that the ratio of the structural unit represented by the above formula (2) to all the siloxane structural units constituting the silsesquioxane of the present invention is within the above range.

The silsesquioxane of the present invention is further limited to the structural unit represented by the above formula (1), the structural unit represented by the above formula (2), and the structural unit represented by the above formula (3). , A structural unit represented by the above formula (1), a structural unit represented by the above formula (2), and a silsesquioxane structural unit other than the structural unit represented by the above formula (3) [RSiO _3/2] ], The _{structural unit represented by [R 3} SiO _1/2 ] (so-called M unit), the structural unit represented by [R ₂ SiO _2/2 ] (so-called D unit), and [SiO _4/2 ]. It may have at least one siloxane constituent unit selected from the group consisting of the represented constituent units (so-called Q units). Examples of the silsesquioxane structural unit other than the structural unit represented by the above formula (1), the structural unit represented by the above formula (2), and the structural unit represented by the above formula (3) include, for example. , The structural unit represented by the following formula (4) and the like can be mentioned.
[HSiO _3/2 ] (4)

The silsesquioxane (particularly, the ladder skeleton) of the present invention contains a structural unit (T3 body) represented by the following formula (I) as an essential structural unit. Further, a structural unit (T2 body) represented by the following formula (II) may be included.
[R ^a SiO _3/2 ] (I)
[R ^b SiO _2/2 (OR ^c )] (II)

If 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')). .. On the other hand, the two oxygen atoms located above and below the silicon atom shown in the structure represented by the following formula (II') are each other silicon atom (silicon atom not shown in the formula (II')). It is combined. That is, both the T3 body and the T2 body are structural units (T units) formed by the hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compounds.

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. show. Specific examples of R ^a and R ^b include those similar to ^{R 1} in the above formula (1) ^{and R 2} in the above formula (2). ^{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 silsesquioxane of the present invention, respectively. A group other than an alkoxy group and a halogen atom; for example, ^{a group derived from (R 1} , R ² , hydrogen atom, etc. in the formulas (a) to (c) described later), or the silsesquioxane of the present invention. It is a group obtained by epoxidizing a group bonded to a silicon atom (a group other than an alkoxy group and a halogen atom; for example, R ^{2 in the formula (b) described later) in the hydrolyzable trifunctional silane compound used as a raw material.} ..

R ^c in the formula (II) (Formula (II ') in the R ^c versa) is a hydrogen atom or a monovalent organic group (excluding a siloxane structural unit monovalent). Examples of the monovalent organic group include a group exemplified as a protecting group in a hydroxy group which may be protected by a protecting group ^{of R 3 in the above formula (3) (excluding a substituted silyl group).} Be done. ^{The monovalent organic group in R c} in the formula (II) is generally an alkoxy group in the hydrolyzable silane compound used as a raw material for the silsesquioxane of the present invention (for example, X ^{1 to} X described later). ^It is derived from an alkyl group that forms an alkoxy group as 3) and a protective group that protects the terminal hydroxy group in the end cap reaction.

Examples of the T2 body include a structural unit represented by the following formula (5), a structural unit represented by the following formula (6), a structural unit represented by the following formula (7), and the like. R ² in R ¹ and the following formula (6) in the following equation (5) is the same as R ² in R ¹ and the formula in the formula (1) (2). ^{R c} in the following formulas (5) to (7) represents a hydrogen atom or a monovalent organic group, like ^{R c} in the formula (II).
[R ¹ SiO _2/2 (OR ^c )] (5)
[R ² SiO _2/2 (OR ^c )] (6)
[HSiO _2/2 (OR ^c )] (7)

As the T2 body, ^{a structural unit represented by the above formula (5) in which R 1} is a group represented by the above formula (1a) (particularly, a 2- (3,4-epoxycyclohexyl) ethyl group) is preferable. ..

Examples of the ladder skeleton having the structural unit represented by the above formula (1) include a structure represented by the following formula (A).

In the above formula (A), p is an integer of 0 or more (preferably an integer of 1 to 5000, more preferably an integer of 1 to 2000, still more preferably an integer of 1 to 1000). R ^a in the above formula (A) (hereinafter sometimes referred to as "side chain") shows the same as R ^a in the formula (I). However, ^a part of Ra is R ¹ , and the ratio thereof is controlled in the range where the epoxy equivalent is 200 to 1000. The R ^a may each be the same or may be different. T indicates a terminal group of the ladder skeleton. Examples of T located at the end of the rudder skeleton include a hydrogen atom, a halogen atom, a monovalent organic group (including a group containing a monovalent siloxane structural unit), and a monovalent oxygen atom-containing group (for example, the above-mentioned protective group). (Hydroxy group which may be protected, etc.), monovalent nitrogen atom-containing group, or monovalent sulfur atom-containing group. Of these, a hydroxy group, which may be protected by a protecting group, is preferable. The Ts may be the same or different.

The silsesquioxane of the present invention is a ladder-type silsesquioxane and may have a ladder skeleton. However, the silsesquioxane of the present invention may have a mixture of cage structures (complete cage structure, incomplete cage structure), random structures, and the like. For example, the ratio of the siloxane constituent unit constituting the ladder skeleton to all the siloxane constituent units (100 mol%) constituting the silsesquioxane of the present invention is preferably 50 mol% or more. On the other hand, the ratio of the siloxane constituent units excluding the siloxane constituent units constituting the ladder skeleton in the silsesquioxane of the present invention is the ratio of all the siloxane constituent units (100 mol%) constituting the silsesquioxane of the present invention. It is preferably 50 mol% or less.

The silsesquioxane of the present invention has a ladder skeleton, silsesquioxane of the present invention, that each around 1050 cm ^-1 and near 1150 cm ^-1 in the FT-IR spectrum having specific absorption peaks, and, T3 It is confirmed from the measurement result of the molar ratio of the body to the T2 body (sometimes referred to as "[T3 body / T2 body]"). The FT-IR spectrum of silsesquioxane of the present invention can be measured by, for example, the following devices 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

The [T3 / T2] in silsesquioxane of the present invention ^{can be determined, for example, by 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 a signal (peak) is shown in (chemical shift), [T3 / T2] can be obtained by calculating the integration ratio of each of these peaks. Specifically, for example, when silsesquioxane has a structural unit represented by the above formula (1) and R ¹ is a 2- (3,4-epoxycyclohexyl) ethyl group, the above formula (1). 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 -60 ppm. Appears in. Therefore, in this case, [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. Even when R ¹ is not a 2- (3,4-epoxycyclohexyl) ethyl group, the signal of the silicon atom in the T3 body and the signal of the silicon atom in the T2 body may fluctuate, respectively, but T3 Since the signal of the silicon atom in the body and the signal of the silicon atom in the T2 body appear in different ranges, [T3 body / T2 body] can be obtained in the same manner as described above.

^{The 29} Si-NMR spectrum of silsesquioxane of the present invention can be measured by, for example, the following devices and conditions.
Measuring device: Product name "JNM-ECA500NMR" (manufactured by JEOL Ltd.)
Solvent: Deuterated chloroform Number of integrations: 1800 Measurement temperature: 25 ° C

The [T3 / T2] in the silsesquioxane (particularly the ladder skeleton) of the present invention is not particularly limited, but is preferably 0.2 to 5, more preferably 0.3 to 4, and even more preferably 0. It is 33 to 3. When [T3 body / T2 body] is 0.2 or more, the adhesiveness of the cured product tends to be further improved, and the crack resistance tends to be further improved.

The standard polystyrene-equivalent number average molecular weight (Mn) of the silsesquioxane of the present invention in terms of standard polystyrene is not particularly limited, but is preferably 500 to 5000, more preferably 700 to 3000, and even more preferably 800 to 2000. Is. When the number average molecular weight is 500 or more, repelling is less likely to occur when the curable composition containing silsesquioxane of the present invention is applied to a substrate or the like, and dents or dents are less likely to occur on the coating film surface. Membrane properties tend to improve. Further, the heat resistance and adhesiveness of the cured product of the curable composition tend to be improved. On the other hand, when the number average molecular weight is 5000 or less, the compatibility with other components in the adhesive composition is improved, and the heat resistance of the cured product tends to be further improved.

The molecular weight dispersion (Mw / Mn) of the silsesquioxane of the present invention in terms of standard polystyrene by gel permeation chromatography is not particularly limited, but is preferably 3.0 or less (for example, 1.0 to 3.0). , More preferably 1.1 to 2.0, still more preferably 1.1 to 1.5. When the molecular weight dispersion is 3.0 or less, the adhesiveness of the cured product tends to be higher. On the other hand, when the molecular weight dispersity is 1.1 or more, it tends to be liquid and the handleability tends to be improved.

The number average molecular weight and molecular weight dispersion of silsesquioxane of the present invention can be measured by the following devices and conditions.
Measuring device: Product name "LC-20AD" (manufactured by Shimadzu Corporation)
Columns: Shodex KF-801 x 2, KF-802, and KF-803 (manufactured by Showa Denko KK)
Measurement temperature: 40 ° C
Eluent: THF, sample concentration 0.1-0.2 wt%
Flow rate: 1 mL / min Detector: UV-VIS detector (trade name "SPD-20A", manufactured by Shimadzu Corporation)
Molecular weight: Standard polystyrene conversion

The silsesquioxane of the present invention preferably has a structural unit represented by the above formula (3) at the end of the ladder skeleton and has the above number average molecular weight of 500 to 5000. In this case, the cured product is more excellent in terms of heat resistance and adhesiveness.

The silsesquioxane of the present invention can be produced in the same manner as a general method for producing a polysiloxane, and is not particularly limited, but for example, one or more hydrolyzable silane compounds are hydrolyzed and used. It can be produced by a method of condensing.

More specifically, for example, a compound represented by the following formula (b), which is a hydrolyzable silane compound for forming a silsesquioxane structural unit (T unit) in the silsesquioxane of the present invention, is required. Further, the compound represented by the following formula (a) and the compound represented by the following formula (c) are further hydrolyzed and condensed, and then epoxidized to produce the silsesquioxane of the present invention. can. However, as the compound represented by the following formula (b), it is necessary to use the compound represented by the formula (b) in which ^{R 2 is a substituted or unsubstituted alkenyl group as an essential hydrolyzable silane compound.}
R ¹ Si (X ¹ ) ₃ (a)
R ² Si (X ² ) ₃ (b)
HSi (X ³ ) ₃ (c)

The compound represented by the above formula (a) is a compound forming a structural unit represented by the formula (1) in silsesquioxane of the present invention. R ¹ in the formula (a), like that of R ¹ in the formula (1), a group containing an epoxy group. ^{That is, R 1} in the formula (a) includes a group represented by the above formula (1a), a group represented by the above formula (1b), a group represented by the above formula (1c), and the above formula (1d). ) Is preferable, a group represented by the above formula (1a) is preferable, a group represented by the above formula (1c) is more preferable, and a group represented by the above formula (1a) is particularly preferable. Is a group represented by the above formula (1a), and is a group in which R ^1a is an ethylene group [among others, a 2- (3,4-epoxycyclohexyl) ethyl group].

^{X 1} in the above formula (a) represents an alkoxy group or a halogen atom. Examples of the alkoxy group in X ¹ 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. 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. Among them, as X ¹ , an alkoxy group is preferable, 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) in the silsesquioxane of the present invention. R ² in formula (b), like the R ² in the formula (2), a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted Indicates an alkyl group of, or a substituted or unsubstituted alkenyl group. However, at least the compound represented by the above formula (b) in which ^{R 2 is a substituted or unsubstituted alkenyl group is used. As R 2} in the formula (b) other than the substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group is preferable, and a substituted or unsubstituted aryl group is more preferable. It is preferably a phenyl group.

^{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 (4) in silsesquioxane of the present invention. ^{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 them, the 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, a hydrolyzable trifunctional silane compound other than the compounds represented by the above formulas (a) to (c), a hydrolyzable monofunctional silane compound forming an M unit, and a hydrolyzable bifunctional silane forming a D unit. 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 silsesquioxane of the present invention. For example, the amount of the compound represented by the above formula (b) is not particularly limited, but is preferably 10 to 100 mol%, more preferably 10 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) in which R 2} is a group other than the substituted or unsubstituted alkenyl group is not particularly limited, but the total amount (100 mol%) of the hydrolyzable silane compound used. ), More preferably 0 to 60 mol%, further 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 or absence of a 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. It should be noted that one type of solvent 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. -Sulfonic 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 alkaline 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. Hydroxide; Alkaline metal carbonate such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate; Alkaline earth metal carbonate 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 acetate); alkaline earth metal organic acid salts such as magnesium acetate (eg) Acetate); Alkali metal alkoxides such as lithium methoxyd, sodium methoxydo, sodium ethoxydo, sodium isopropoxide, potassium ethoxydo, potassium t-butoxide; alkali metal phenoxide 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. 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.

As the reaction conditions for hydrolyzing and condensing the hydrolyzable silane compound, it is particularly important to select reaction conditions such that the silsesquioxane of the present invention has a ladder skeleton. .. The reaction temperature of the hydrolysis and condensation reactions is not particularly limited, but is preferably -20 to 100 ° C, more preferably 0 to 80 ° C. By controlling the reaction temperature within the above range, it tends to be possible to efficiently have a ladder skeleton. 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 for performing the hydrolysis and condensation reactions 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. Further, in the above hydrolysis and condensation reaction, the reaction temperature may be constant or may be changed in the middle.

By the hydrolysis and condensation reaction of the hydrolyzable silane compound, a ladder-type silsesquioxane in which an alkenyl group is bonded to a silicon atom (sometimes referred to as "alkenyl group-containing ladder-type silsesquioxane") can be obtained.

The alkenyl group-containing ladder-type silsesquioxane is then subjected to an epoxidation reaction by a known or conventional method to epoxidize the carbon-carbon double bond portion in the alkenyl group to form an epoxy group, and the silsesquioxane of the present invention is obtained. Oxane is obtained. The epoxidation reaction is not particularly limited, but can be carried out by using, for example, an oxidizing agent such as peracid.

Further, as the above-mentioned oxidizing agent, known or commonly used oxidizing agents such as hydrogen peroxide and organic peracid can be used and are not particularly limited. For example, examples of the organic peracid include performic acid, peracetic acid and excess. Examples thereof include benzoic acid, trifluoroperacetic acid, and metachloroperbenzoic acid. One type of oxidizing agent may be used alone, or two or more types may be used in combination.

More specifically, the above-mentioned epoxidation reaction can be carried out according to, for example, a well-known and commonly used method described in JP-A-60-161973.

After completion of the epoxidation reaction, it is preferable to neutralize the catalyst in order to suppress ring opening of the epoxy group. Further, the silsesquioxane of the present invention can be separated by, for example, water washing, acid washing, alkaline washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography and the like, or a separation means combining these. It may be separated and purified by the above.

Further, in the case of the silsesquioxane of the present invention having a protecting group protected by a protecting group at the end of the rudder skeleton, the hydroxy group at the end of the rudder skeleton is protected by the protecting group before or after the epoxidation reaction. The reaction (end cap reaction) may be carried out. The end cap reaction can be carried out by a known or conventional method. For example, when the protecting group is a trimethylsilyl group, the endcap reaction can be carried out by adding hexamethyldisiloxane and stirring after the hydrolysis and condensation reactions.

Although the ^{method of hydrolyzing and condensing the compound represented by the formula (b) in which R 2} is a substituted or unsubstituted alkenyl group and then epoxidizing the compound is described, the production of silsesquioxane of the present invention has been described. The method is not limited to this method, and in addition, for example, a structural unit represented by the above formula (1) in which ^{R 1 is a group represented by the above formula (1a) as a hydrolyzable silane compound is used.} It may be produced by a method of hydrolysis and condensation.

Among them, from the viewpoint of making it easier to obtain silsesquioxane having a ladder skeleton in which the epoxy equivalent is within a specific range, a compound represented by the formula (b) in which ^{R 2 is a substituted or unsubstituted alkenyl group is used.} A method of hydrolyzing and condensing with an acid catalyst (particularly mineral acid) and then epoxidizing is preferable. Further, in the above hydrolysis and condensation reaction, it is preferable to react at a relatively low temperature for a long time under acidic conditions and then raise the temperature, whereby a one-membered ring cyclotetrasiloxane is first efficiently obtained, and then the above-mentioned It is presumed that the one-membered ring is polycyclic, and the silsesquioxane of the present invention can be obtained more efficiently. The temperature range and the total reaction time at this time can be appropriately selected from the above ranges.

Since the silsesquioxane of the present invention has the above-mentioned constitution, by curing the curable composition containing the silsesquioxane as an essential component, crack resistance, heat resistance, and adhesiveness to the adherend can be obtained. An excellent cured product can be formed. Further, since the silsesquioxane of the present invention has these properties after curing, it can be preferably used for curable composition applications (particularly, adhesive composition applications).

[Curable composition]
The curable composition of the present invention is a curable composition (curable resin composition) containing the above-mentioned silsesquioxane of the present invention as an essential component. As will be described later, the curable composition of the present invention may further contain other components such as a polymerization initiator (particularly a photocationic polymerization initiator), a surface conditioner or a surface modifier.

In the curable composition of the present invention, the silsesquioxane of the present invention may be used alone or in combination of two or more.

The content (blending amount) of silsesquioxane of the present invention in the curable composition of the present invention is not particularly limited, but is 70% by weight with respect to the total amount (100% by weight) of the curable composition excluding the solvent. The above (for example, 70 to 100% by weight) is preferable, more preferably 80% by weight or more (for example, 80 to 99.8% by weight), still more preferably 90% by weight or more (for example, 90 to 99.5% by weight). , Particularly preferably 95% by weight or more. By setting the content of silsesquioxane of the present invention to 70% by weight or more, the heat resistance and crack resistance of the cured product tend to be further improved.

The ratio of silsesquioxane of the present invention to the total amount (100% by weight) of the cationically curable compound contained in the curable composition of the present invention is not particularly limited, but is preferably 70 to 100% by weight, more preferably 75. ~ 100% by weight, more preferably 80-100% by weight. By setting the content of silsesquioxane of the present invention to 70% by weight or more, the heat resistance and crack resistance of the cured product tend to be further improved.

(Polymerization 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 of 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 semiconductor chip 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 suitable temperature and then rapidly curing until it becomes tack-free can be obtained. ..

That is, in the case of a cationic polymerization initiator, 100 parts by weight of 3,4-epoxycyclohexylmethyl (3', 4'-epoxy) cyclohexanecarboxylate [for example, trade name "Ceroxide 2021P" (manufactured by Daicel Co., Ltd.)] On the other hand, 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 (min).

In the case of an anionic polymerization initiator, the thermosetting time (JIS K5909 1994 compliant) 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. It is preferable to use a polymerization initiator that lasts 3.5 minutes or longer.

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 having a thermosetting time of 3.5 minutes or more is used, cation species are less likely to be generated when a cationic polymerization initiator is used during heat drying, and anionic species are less likely to be generated when an anionic polymerization initiator is used. After that, the polymerization does not easily proceed at room temperature, so that an adhesive layer having better storage stability tends to be obtained.

The cationic polymerization initiator comprises a cationic portion that absorbs heat and an anionic 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. Of these, the aryl sulfonium salt is preferable.

Examples of the cation part 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 , Hexafluorobismasate ion, carboxylic acid ion, arylborate ion, thiocyanate ion, nitrate ion and the like.

Examples of the cationic polymerization initiator include the trade names "Sun Aid SI-110L", "Sun Aid SI-145L", "Sun Aid SI-150L", "Sun Aid SI-160L", and "Sun Aid SI-180L". Commercially available products such as those manufactured by Shin Kagaku Kogyo 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. Further, 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).

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, more preferably 0.05, based on 100 parts by weight of silsesquioxane of the present invention. It is ~ 3.0 parts by weight, more 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 sufficiently, and the adhesiveness of the cured product tends 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 improved and the coloring of the cured product tends to be suppressed.

(Polymerization stabilizer)
The curable composition of the present invention preferably further contains a polymerization stabilizer. The above-mentioned polymerization stabilizer is a compound having an action of suppressing the progress of cation polymerization by trapping cations, and proceeding with polymerization at the stage where the ability of the polymerization stabilizer to trap cations is saturated and deactivated. When the curable composition of the present invention contains a polymerization stabilizer together with a cationic polymerization initiator, it is coated and dried to form a layer of the curable composition (for example, an adhesive layer), and then polymerized over a long period of time. Forming a layer (for example, an adhesive layer) of a curable composition having excellent storage stability, which can suppress the progress and exhibits excellent adhesiveness by heating at a timing when adhesiveness is required. Can be done.

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- [2,4,8,10-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" (all manufactured by ADEKA Co., Ltd.), trade names "TINUVIN123", "TINUVIN152" (Above, manufactured by Ciba Japan Co., Ltd.) and (4-hydroxyphenyl) dimethylsulfonium methylsulfite (for example, trade name "Sun Aid SI Auxiliary Agent", manufactured by Sanshin Chemical Industry Co., Ltd.) ) And other sulfonium sulfate compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol -Diphosfite (trade name "Adecastab PEP-36", manufactured by ADEKA Co., Ltd.), bis (2,4-di-t-butylphenyl) pentaerythritol-diphosfite, tris (2,4-di-) Sub-types such as t-butylphenyl) phosphite, tris (mono, dinonylphenyl) phosphite, tris (2-ethylhexyl) phosphite, trisphenylphosphite, tris (monononylphenyl) phosphite, trisisodecylphosphite, etc. Phosphite ester compounds and the like can be mentioned. Of these, sulfonium sulfate compounds and phosphite ester compounds are preferable from the viewpoint of making the curable composition (adhesive) less likely to be partially cured during drying and having better adhesion of the cured product to the adherend. .. These can be used alone or in combination of two or more.

When the curable composition of the present invention contains a cationic polymerization initiator, the amount of the polymerization stabilizer used is, for example, 0.1 parts by weight or more, preferably 0.3 to 3 parts by weight, based on 100 parts by weight of the cationic polymerization initiator. It is 20 parts by weight, particularly preferably 0.5 to 15 parts by weight.

(Silane coupling agent)
The curable composition of the present invention may further contain a silane coupling agent. By containing the silane coupling agent, it is possible to impart more excellent properties such as adhesion, weather resistance and heat resistance to the obtained cured product.

Examples of the silane coupling agent include 3-trimethoxysilylpropyl (meth) acrylate, 3-triethoxysilylpropyl (meth) acrylate, 3-dimethoxymethylsilylpropyl (meth) acrylate, and 3-diethoxymethylsilylpropyl. (Meta) acrylate, 2- (3,4-epylcyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane , 3-Glycydoxypropyltriethoxysilane and the like. These can be used alone or in combination of two or more. When a silane coupling agent whose functional group is a (meth) acryloyloxy group is used, a small amount of a radical polymerization initiator may be added.

Examples of the silane coupling agent include the trade name "KBE-403" (3-glycidoxypropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) and the trade name "Z-6040" (3-glycidoxy). Commercially available products such as propyltrimethoxysilane and Toray Dow Corning Co., Ltd. can be used.

When the curable composition of the present invention contains a silane coupling agent, the amount used thereof is, for example, more than 0% by weight and 10% by weight with respect to 100 parts by weight of the polymerizable compound contained in the curable composition of the present invention. It is about parts or less, and the upper limit thereof is preferably 5 parts by weight, more preferably 3 parts by weight, and further preferably 1 part by weight. The lower limit is preferably 0.005 parts by weight, more preferably 0.01 parts by weight.

The curable composition of the present invention may further contain a cationic curable compound other than the silsesquioxane of the present invention (sometimes referred to as "other cationic curable compounds"). As the other cation-curable compound, a known or commonly used cation-curable compound can be used, and is not particularly limited. For example, an epoxy compound other than silsesquioxane of the present invention (“other epoxy compound”) (Sometimes referred to as), oxetane compounds, vinyl ether compounds, etc. may be mentioned. In the curable composition of the present invention, one type of other cationic curable compound may be used alone, or two or more types may be used in combination.

As the above-mentioned other 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 alicyclic epoxy compound (alicyclic ring type). (Epoxy resin), aromatic epoxy compound (aromatic epoxy resin), aliphatic epoxy compound (aliphatic epoxy resin) and the like can be mentioned.

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. For example, (1) in the molecule. A compound having an epoxy group (referred to as "alicyclic epoxy group") composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic; (2) The epoxy group is directly bonded to the alicyclic by a single bond. Compounds; (3) Compounds having an alicyclic ring and a glycidyl ether group in the molecule (glycidyl ether type epoxy compound) and the like can be mentioned.

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 groups are linked. A substituent such as an alkyl group may be bonded to one or more carbon atoms constituting the cyclohexane ring (cyclohexene oxide group) in the formula (i).

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

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) are 3,4,3', 4'-diepoxybicyclohexane, and the following formulas (i-1) to (i-10). Examples thereof include compounds represented by. In addition, l and m in the following formulas (i-5) and (i-7) represent integers of 1 to 30, respectively. R'in the following formula (i-5) is an alkylene group having 1 to 8 carbon atoms, and among them, a linear or branched chain having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group and an isopropylene group. The shape of the alkylene group is preferable. N1 to n6 in the following formulas (i-9) and (i-10) represent integers of 1 to 30, respectively. Examples of the alicyclic epoxy compound represented by the above formula (i) include 2,2-bis (3,4-epoxycyclohexyl) propane and 1,2-bis (3,4-epoxycyclohexyl). ) Ethane, 2,3-bis (3,4-epoxycyclohexyl) oxylane, bis (3,4-epoxycyclohexylmethyl) ether and the like can be mentioned.

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 parentheses (in parentheses on the outside) 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 glycidyl ether group in the molecule (3) described above 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- (2,5-dimethylpropoxy) 3-Epoxypropoxy) 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; hydride naphthalene type epoxy compound; hydride epoxy compound of epoxy compound obtained from trisphenol methane; hydride epoxy compound of the following aromatic epoxy compound and the like. Be done.

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; these epis. 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.

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 [for example, 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 (poly) such as epoxidized polybutadiene (Including alkaziene) epoxides and the like can be mentioned. 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.

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. For example, 3,3-bis (vinyloxymethyl) oxetane, 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.

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, trimethylolpropane divinyl ether, trimethylolpropanetrivinyl 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.

As other cationic curable compounds, in particular, when a vinyl ether compound having one or more hydroxyl groups in the molecule is used among the above-mentioned vinyl ether compounds, heat-resistant yellowing (characteristic that yellowing due to heating is unlikely to occur) occurs. There is an advantage that an excellent cured product (adhesive layer) can be obtained. The number of hydroxyl groups contained in the molecule of the vinyl ether compound having one or more hydroxyl groups in the molecule is not particularly limited, but is preferably 1 to 4, more preferably 1 or 2.

The content (blending amount) of the other cationic curable compound in the curable composition of the present invention is not particularly limited, but the total amount (100% by weight; cation) of the silsesquioxane of the present invention and the other cationic curable compound. 50% by weight or less (for example, 0 to 50% by weight) is preferable, more preferably 30% by weight or less, still more preferably 10% by weight or less, and particularly preferably 5% by weight or less, based on the total amount of the curable compound. be. When the curable composition of the present invention contains other cationic curable compounds, the lower limit of the content is not particularly limited, but may be 0.1% by weight. By blending other cationically curable compounds in the above range, desired performance (for example, quick curing and viscosity adjustment for the curable composition) can be imparted to the curable composition and the cured product. In some cases.

(solvent)
The curable composition of the present invention may further contain a solvent. Examples of the solvent include water, organic solvents and the like, and particularly as long as it can dissolve the silsesquioxane of the present invention and additives used as needed and does not inhibit polymerization. There are no restrictions.

As the solvent, it is preferable to use a solvent that can impart fluidity suitable for coating by spin coating and can be easily removed by heating at a temperature at which the progress of polymerization can be suppressed, and has a boiling point (1). One or more solvents (for example, toluene, butyl acetate, methyl isobutyl ketone, xylene, mesitylene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, etc.) with a temperature of 170 ° C. or lower (at atmospheric pressure) may be used. preferable.

The solvent can be used in a spin coating range in which the concentration of the non-volatile component contained in the curable composition is, for example, about 30 to 80% by weight, preferably 40 to 70% by weight, and particularly preferably 50 to 60% by weight. It is preferable because it is excellent in coatability. If the amount of the solvent used is excessive, the viscosity of the curable composition tends to be low, and it tends to be difficult to form a layer having an appropriate film thickness (for example, about 0.5 to 30 μm). On the other hand, if the amount of the solvent used is too small, the viscosity of the curable composition becomes too high, and it tends to be difficult to uniformly apply the curable composition to the support or the adherend.

The curable composition of the present invention further includes precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, and calcium carbonate as any other components. , Carbon black, silicon carbide, silicon nitride, boron nitride and other inorganic fillers, and these fillers treated with organic silicon compounds such as organohalosilane, organoalkoxysilane and organosilazane; silicone resin, epoxy resin , Organic resin fine powder such as fluororesin; filler such as conductive metal powder such as silver and copper, curing agent (amine-based curing agent, polyaminoamide-based curing agent, acid anhydride-based curing agent, phenol-based curing agent, etc. ), Hardening aids, Hardening accelerators (imidazoles, alkali metals or alkaline earth metal alkoxides, phosphines, amide compounds, Lewis acid complex compounds, sulfur compounds, boron compounds, condensing organic metal compounds, etc.), stabilizers (Antioxidants, UV absorbers, light resistance stabilizers, 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.), nucleating agents, coupling agents other than silane coupling agents, lubricants, waxes, plasticizers, mold release agents, impact resistance improvers, hue improvers, clearing agents, rheology adjustment Agent (fluidity improver, etc.), processability improver, colorant (dye, pigment, etc.), antistatic agent, dispersant, surface conditioner (leveling agent, armpit inhibitor, etc.), surface modifier (slip agent) Etc.), including conventional additives such as matting agents, defoaming agents, defoaming agents, defoaming agents, antibacterial agents, preservatives, viscosity modifiers, thickeners, photosensitizers, foaming agents, etc. May be good. These additives may be used alone or in combination of two or more. The content (blending amount) of the additive is not particularly limited, but is preferably 100 parts by weight or less, more preferably 30 parts by weight or less (for example, 0. 01 to 30 parts by weight), more preferably 10 parts by weight or less (for example, 0.1 to 10 parts by weight).

The curable composition of 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 of the present invention can be used as a one-component composition in which each component is mixed in advance and used as it is, or for example, two or more components stored separately. 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 of the present invention is not particularly limited, but is preferably liquid at room temperature (about 25 ° C.). The viscosity of the curable composition of the present invention is not particularly limited, but it is preferably adjusted according to the film thickness when coating by spin coating, for example, when coating with a film thickness of 0.1 to 50 μm. It is preferably 1 to 5000 mPa · s. When the viscosity of the curable composition of the present invention is within the above range, it becomes easy to form a coating film having a uniform film thickness on a substrate such as a silicon wafer. The viscosity of the curable composition of the present invention was determined by using a viscometer (trade name "MCR301", manufactured by Anton Pearl Co., Ltd.), a swing angle of 5%, a frequency of 0.1 to 100 (1 / s), and a temperature: Measured at 25 ° C.

[Cured product]
By advancing the polymerization reaction of the cationically curable compound (silsesquioxane of the present invention, etc.) in the curable composition of the present invention, the curable composition can be cured, and the cured product (“the present invention” (Sometimes referred to as a "cured product") can be obtained. The curing method can be appropriately selected from well-known methods, and is not particularly limited, and examples thereof include a method of irradiating with active energy rays and / or heating. As the active energy ray, for example, any of infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α rays, β rays, γ rays and the like can be used. Of these, ultraviolet rays are preferable because they are easy to handle.

The conditions for curing the curable composition of the present invention by irradiation with active energy rays (irradiation conditions for active energy rays, etc.) depend on the type and energy of the active energy rays to be irradiated, the shape and size of the cured product, and the like. It can be adjusted as appropriate, and is not particularly limited, but when irradiating with ultraviolet rays, it is preferably about 1 to ^{1000 mJ / cm 2 for example.} For irradiation of the active energy rays, for example, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, sunlight, an LED lamp, a laser, or the like can be used. After irradiation with the active energy rays, further heat treatment (annealing, aging) can be performed to further proceed the curing reaction.

On the other hand, the conditions for curing the curable composition of the present invention by heating are not particularly limited, but are preferably, for example, 30 to 200 ° C, more preferably 50 to 190 ° C. The curing time can be set as appropriate.

The cured product of the present invention has excellent heat resistance. Therefore, the thermal decomposition temperature of the cured product of the present invention is not particularly limited, but is preferably 200 ° C. or higher (for example, 200 to 500 ° C.), more preferably 260 ° C. or higher, still more preferably 300 ° C. or higher. The thermal decomposition temperature is determined by the method described in Examples.

The cured product obtained by curing the curable composition of the present invention has excellent adhesiveness and adhesion to an object to be adhered. Therefore, the curable composition of the present invention can be preferably used as an adhesive (sometimes referred to as an "adhesive composition"), particularly a heat-curable adhesive, and by curing it, the adhesiveness to the adherend is adhered to. And it can be converted into an adhesive material with excellent adhesion.

[Adhesive sheet]
By using the curable composition of the present invention (composition for adhesive), an adhesive layer formed from the curable composition of the present invention is formed on at least one surface of the base material (“adhesive layer of the present invention”). An adhesive sheet having (sometimes referred to as "the adhesive sheet of the present invention") can be obtained. The adhesive sheet of the present invention includes not only sheet-like forms but also sheet-like forms such as film-like, tape-like, and plate-like forms. The adhesive sheet of the present invention is not particularly limited, but can be obtained, for example, by applying the curable composition of the present invention to a substrate and further drying it if necessary. The method of application 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 set, and well-known and commonly used means can be used. In particular, the thermosetting composition of the present invention is obtained by adding 1 part by weight to 100 parts by weight of celloxide 2021P (manufactured by Daicel Co., Ltd.) at 130 ° C. for a thermosetting time of 3.5 minutes or more. When a certain polymerization initiator is contained, it is possible to form an adhesive layer by quickly removing volatile components such as a solvent while suppressing the progress of the curing reaction by heating and drying. When the adhesive layer thus obtained is used for laminating semiconductors or adhering electronic components, it exhibits adhesiveness by heating at a temperature at which damage to electronic components such as semiconductor chips can be suppressed, and then exhibits adhesiveness. Has the property of curing quickly.

The adhesive sheet of the present invention may be a single-sided adhesive sheet having an adhesive layer only on one side of the base material, or a double-sided adhesive sheet having an adhesive layer on both sides of the base material. When the adhesive sheet of the present invention is a double-sided adhesive sheet, at least one adhesive layer may be the adhesive layer of the present invention, the other may be the adhesive layer of the present invention, or the other adhesive layer. It may be an agent layer.

As the base material in the adhesive sheet of the present invention, a well-known and commonly used base material (base material used for the adhesive sheet) can be used, and is not particularly limited, but for example, a plastic base material, a metal base material, or a ceramic base material. Examples thereof include materials, semiconductor base materials, glass base materials, paper base materials, wood base materials, and base materials whose surface is a painted surface. Further, the base material in the adhesive sheet of the present invention may be a so-called release liner. The adhesive sheet of the present invention may have only one layer of the base material, or may have two or more layers. The thickness of the base material is not particularly limited, and can be appropriately selected in the range of 1 to 10000 μm, for example.

The adhesive sheet of the present invention may have only one adhesive layer of the present invention, or may have two or more kinds of the adhesive layer. The thickness of the adhesive layer of the present invention is not particularly limited, and can be appropriately selected in the range of 0.1 to 10000 μm, for example. The same applies to other adhesive layers (adhesive layers other than the adhesive layer of the present invention).

The adhesive sheet of the present invention may have other layers (for example, an intermediate layer, an undercoat layer, etc.) in addition to the base material and the adhesive layer. Examples of the undercoat layer include an anchor coat layer containing a silane coupling agent. When having the anchor coat layer, examples of the adhesive sheet of the present invention include a base material, the anchor coat layer, and an adhesive sheet having the adhesive layer of the present invention in this order.

[Laminate]
By using the curable composition (composition for adhesive) of the present invention, it is a laminate (laminate) composed of three or more layers (at least three layers), and two layers to be adhered (adhesive). A body) and an adhesive layer (a layer for adhering the adhered layers to each other) located between these adhered layers, and the adhesive layer is a layer of a cured product of the curable composition of the present invention (the body). It is possible to obtain a laminate (sometimes referred to as "the laminate of the present invention") which is (sometimes referred to as "the adhesive layer of the present invention"). The laminate of the present invention is not particularly limited, but for example, the adhesive layer of the present invention is formed on one layer to be adhered (for example, it can be formed in the same manner as the adhesive layer in the adhesive sheet of the present invention), and further. It can be obtained by adhering the other layer to be adhered to the adhesive layer and then curing the adhesive layer of the present invention by subjecting it to heat treatment. Further, in the laminate of the present invention, for example, when the adhesive sheet of the present invention is a single-sided adhesive sheet, the adhesive sheet of the present invention is attached to a layer to be adhered, and then heat treatment is performed to obtain the above-mentioned adhesive sheet. It can be obtained by curing the adhesive layer of the present invention inside. In this case, a laminate in which the base material in the adhesive sheet of the present invention hits the layer to be adhered is obtained. Further, in the laminate of the present invention, for example, when the adhesive sheet of the present invention is a double-sided adhesive sheet and release liners as a base material are attached to both sides of the adhesive layer, the present invention One of the release liners of the adhesive sheet of the present invention is attached to the adhesive layer exposed by peeling off the adhesive layer, and then the other release liner is peeled off and exposed to the adhesive layer. It can be obtained by curing the adhesive layer of the present invention by adhering the layers to be adhered to the above and then applying a heat treatment. However, the method for producing the laminate of the present invention is not limited to these methods.

The layer to be adhered in the laminate of the present invention is not particularly limited, and examples thereof include those similar to the base material in the adhesive sheet. 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 of the present invention, or may have two or more kinds of the adhesive layer. The thickness of the adhesive layer of the present invention 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 adhesive layer and the adhesive layer of the present invention.

The laminate of the present invention has a structure in which the adherend is adhered by an adhesive layer having excellent adhesiveness and adhesion to the adherend, as well as heat resistance and crack resistance. 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 provided with 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.

Further, by using the laminate of the present invention (for example, semiconductor chip, wafer, etc.), a microprocessor, a semiconductor memory, a power supply IC, a communication IC, a semiconductor sensor, a MEMS, etc., which are highly integrated, or these can be used. A combined semiconductor can be obtained. These semiconductors are used in devices such as high-performance servers, workstations, in-vehicle computers, personal computers, communication devices, photographing devices, and image display devices. That is, the device has the laminate of the present invention.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples. The molecular weight of the product was measured by Alliance HPLC System 2695 (manufactured by Waters), Refractometer Index 2414 (manufactured by Waters), column: Tskgel GMH _HR- M × 2 (manufactured by Tosoh Corporation), guard column: Tskgel guard. column (manufactured by Tosoh (Ltd.)) H _HR L, column oven: cOLUMN HEATER U-620 (manufactured by Sugai), solvent: THF, measuring conditions: 40 ° C., the molecular weight was performed by standard polystyrene. The molar ratio of T2 to T3 [T3 / T2] in the product was measured by ²⁹ Si-NMR spectrum measurement by JEOL ECA500 (500 MHz). The FT-IR spectrum was measured under the above-mentioned conditions.

Example 1
(Preparation of polyorganosylsesquioxane containing cyclohexenylethyl group)
2- (3,4-Cyclohexenyl) ethyltrimethoxysilane (hereinafter, "CHMS") in a 1000 ml flask (reaction vessel) equipped with a thermometer, agitator, a reflux condenser, and a nitrogen introduction tube under a nitrogen stream. 950 mmol (218.91 g), 50 mmol (9.92 g) of phenyltrimethoxysilane (hereinafter referred to as “PMS”), and 114.39 g of methyl isobutyl ketone were charged and cooled to 10 ° C. To the mixture thus obtained, 2.0 g (10 mmol as hydrochloric acid) of a 5N-HCL aqueous solution was added, and then 3000 mmol (54.0 g) of water was added dropwise over 60 minutes. By dropping water during the dropping, heat generation was confirmed and condensation was started. Then, the polycondensation reaction was carried out at 10 ° C. for 1 hour under a nitrogen stream.
When the product in the reaction solution after the polycondensation reaction at this time was analyzed, the number average molecular weight was 613 and the molecular weight dispersion was 1.12. Then, 343.2 g of methyl isobutyl ketone was added, and the reaction temperature was raised to 70 ° C. over 30 minutes. 100 mmol (20.02 g) of 5N-HCL was added at 70 ° C., and the polycondensation reaction was carried out as it was for 3 hours. When the product in the reaction solution after the polycondensation reaction at this time was analyzed, the number average molecular weight was 942 and the molecular weight dispersion was 1.14. The molar ratio of T2 to T3 [T3 / T2] calculated from the ^{29 Si-NMR spectrum of the product was 1.0.} Next, 500 mmol (81.2 g) of hexamethyldisiloxane was added to the polycondensation reaction solution at 70 ° C., and a terminal end cap reaction was carried out at 70 ° C. for 3 hours. ^{By 1} H-NMR analysis of the above product, the conversion rate (TMS conversion rate) from the terminal hydroxy group to the trimethylsilyloxy group was 75%.
Then, the reaction solution is cooled, washed with water until the lower layer liquid becomes neutral, the upper layer liquid is separated, and then the solvent is distilled off from the upper layer liquid under the conditions of 1 mmHg and 50 ° C. to obtain a slightly yellow transparent liquid. The product (cyclohexenyl group-containing polyorganosylsesquioxane) was obtained in an amount of 169.5 g.
The number average molecular weight of this concentrate was 1033.

(Epoxidation process)
Put 60.5 g of the above concentrate and 240 g of ethyl acetate in a 1000 ml flask (reaction vessel) equipped with a thermometer, agitator, a reflux condenser, and a nitrogen introduction tube under a nitrogen stream, and stir and mix at 20 ° C. went. Separately, 465 mmol of mCPBA and 240 g of ethyl acetate were placed in an Erlenmeyer flask, and the mixture was stirred and mixed. At a reaction temperature of 20 ° C., a solution of mCPBA in ethyl acetate was added dropwise over 45 minutes. At this time, a slight fever was confirmed.
After the dropping, aging was carried out at 20 ° C. for 3 hours. At this time, it was confirmed by the peroxide checker that mCPBA had disappeared.
57.8 g of normal heptane and 231.8 g of a 10% aqueous sodium thiosulfate solution were added to the reaction mixture, and the mixture was stirred for 10 minutes and quenched. After that, the mixture was transferred to a separating funnel, the lower layer water was discharged, and the mixture was extracted and washed twice with 231.8 g of 5% NaOH aqueous solution and twice with 231.8 g of water to confirm that it was neutral.
An ethyl acetate solution containing an epoxycyclohexylethyl group-containing ladder-type silsesquioxane was concentrated and distilled off at 1 mmHg and 50 ° C. to obtain 61.3 g of an epoxycyclohexylethyl group-containing ladder-type silsesquioxane. The obtained epoxy equivalent of the rudder-type silsesquioxane containing a cyclohexylethyl group had an epoxy equivalent of 260 g / eq, a number average molecular weight of 1062, and a dispersity of 1.12. ^{From 1} H-NMR, the conversion rate from the cyclohexenylethyl group before epoxidation to the epoxycyclohexylethyl group was 95%. Further, from the results of FT-IR analysis, 1100 cm ^-1, and that the rudder specific peak there are two in the vicinity of 1200 cm ^-1, than the molar ratio of ²⁹ Si-NMR results [T3 body / T2 body], this compound ladder It was confirmed that the skeleton was included as the main. ^{The measurement results of the 1} H-NMR spectrum of the obtained ladder-type silsesquioxane, ^{the measurement results of the 29} Si-NMR spectrum, and the measurement results of the FT-IR spectrum are shown in FIGS. 1 to 3, respectively.

Comparative Example 1
(Preparation of polyorganosylsesquioxane containing epoxycyclohexylethyl group)
2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (hereinafter, "EMS") in a 300 ml flask (reaction vessel) equipped with a thermometer, agitator, a reflux condenser, and a nitrogen introduction tube under a nitrogen stream. 161.5 mmol (39.79 g), 9 mmol (1.69 g) of phenyltrimethoxysilane (hereinafter referred to as “PMS”), and 165.9 g of acetone were charged and the temperature was raised to 50 ° C. To the mixture thus obtained, 4.70 g (1.7 mmol as potassium carbonate) of a 5% aqueous potassium carbonate solution was added dropwise over 5 minutes, and then 1700 mmol (30.60 g) of water was added dropwise over 20 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 epoxy equivalent was 195 g / eq, the number average molecular weight was 1900, and the molecular weight dispersion was 1.5. The molar ratio of T2 to T3 [T3 / T2] calculated from ^{the 29 Si-NMR spectrum of the product was 10.3.}
Then, the reaction solution is cooled, washed with water until the lower layer liquid becomes neutral, the upper layer liquid is separated, and then the solvent is retained from the upper layer liquid under the conditions of 1 mmHg and 40 ° C. until the solvent amount becomes 25% by weight. The mixture was removed to obtain a colorless and transparent liquid product (polyorganosylsesquioxane containing an epoxycyclohexylethyl group).
When the FT-IR spectrum of the obtained polyorganosylsesquioxane was measured by the above method, it was confirmed that it had one intrinsic absorption peak near ^{1100 cm -1.}

The adhesive compositions and adhesive layers obtained in Example 2 and Comparative Example 2 below were evaluated as follows.

(1) Heat resistance The adhesive compositions obtained in Example 2 and Comparative Example 2 were heated at 130 ° C. or 150 ° C. for 30 minutes, and then heated at 170 ° C. for 30 minutes. Thermogravimetric analysis was performed using an analyzer and the thermal decomposition temperature was measured. As shown in FIG. 4, the thermal decomposition temperature is a tangent line where there is no initial weight loss or where the weight is gradually reduced (the range indicated by A in the figure), and the weight is rapidly reduced. However, it is the temperature at which the tangents of the inflection points (the range indicated by B in the figure) intersect. Then, the heat resistance was evaluated according to the following criteria. The results are shown in the "heat resistance" column of Table 1. The thermogravimetric analysis was performed using the trade name "EXSTAR6000" (manufactured by Seiko Instruments Co., Ltd.) as a thermal analyzer at a heating rate of 10 ° C./min in a nitrogen environment.
〇 (Good): Pyrolysis temperature is 260 ° C or higher × (Defective): Pyrolysis temperature is less than 260 ° C

(2) Crack resistance The glass plate with the adhesive layer obtained in Example 2 and Comparative Example 2 is heated at 130 ° C. or 150 ° C. for 30 minutes, and then heated at 170 ° C. for 30 minutes to cure the adhesive layer. After cooling, the mixture was heated at 250 ° C. for 30 minutes, and then cooled to room temperature, and then the presence or absence of cracks was confirmed. Further, after heating at 280 ° C. for 30 minutes and then cooling to room temperature, the presence or absence of cracks was confirmed. Then, the crack resistance was evaluated according to the following criteria. The results are shown in the "Crack resistance" column of Table 1.
◎ (Extremely good): No cracks were observed after heating at 280 ° C for 30 minutes and cooling to room temperature. ○ (Good): No cracks were observed after heating at 250 ° C for 30 minutes and cooling to room temperature. Although it was not seen, cracks occurred after heating at 280 ° C. for 30 minutes and cooling to room temperature. × (Defective): Cracks occurred after heating at 250 ° C. for 30 minutes and cooling to room temperature.

Example 2
(Preparation of Adhesive Composition (1))
100 parts by weight of ladder-type silsesquioxane containing an epoxycyclohexylethyl group, 100 parts by weight of propylene glycol monomethyl ether acetate, antimony sulfonium salt (trade name "SI-150L", 3) obtained as a cationically polymerizable compound in Example 1. Thermocuring time at 130 ° C. of the composition obtained by adding 1 part by weight to 100 parts by weight of Celoxide 2021P (manufactured by Daicel Co., Ltd.) manufactured by Shin Kagaku Kogyo Co., Ltd .: 5.4 minutes) 0.09 weight Parts (in terms of solid content) and 0.01 parts by weight of (4-hydroxyphenyl) dimethylsulfonium methylsulfite (trade name "Sun Aid SI Auxiliary", manufactured by Sanshin Chemical Industry Co., Ltd.) are mixed to form an adhesive composition. I got the thing (1).

(Preparation of adhesive layer (A1))
A glass plate (4 inches, manufactured by SCHOTT Japan Co., Ltd.) is coated with a silane coupling agent (trade name "KBE403", manufactured by Shin-Etsu Chemical Co., Ltd.) by spin coating, and heated at 120 ° C. for 5 minutes to form a silane cup. A glass plate with a ring agent layer was obtained. The adhesive composition (1) is applied by spin coating on the surface of the silane coupling agent layer of the glass plate with the silane coupling agent layer, and heated at 80 ° C. for 4 minutes and then at 100 ° C. for 2 minutes to remove the residual solvent. , A glass plate with an adhesive layer (A1) was obtained. The film thickness of the adhesive layer (A1) was 5 to 6 μm.

(Heat-resistant)
The thermal decomposition temperature of the cured product obtained by heating the adhesive composition (1) at 150 ° C. for 30 minutes and then at 170 ° C. for 30 minutes was 260 ° C. or higher.
The thermal decomposition temperature of the cured product obtained by heating the separately prepared adhesive layer (A1) at 130 ° C. for 30 minutes and then at 170 ° C. for 30 minutes was 260 ° C. or higher.

(Crack resistance)
The glass plate with the adhesive layer (A1) was heated at 150 ° C. for 30 minutes, and then the coating film obtained by heating at 170 ° C. for 30 minutes was cooled to room temperature, then heated at 250 ° C. for 30 minutes, and then. When it was rapidly cooled to room temperature, no cracks occurred. Then, when it was heated at 280 ° C. for 30 minutes and then rapidly cooled to room temperature , no cracks were generated.
Further, the separately prepared adhesive layer (A1) was heated at 130 ° C. for 30 minutes, and then the coating film obtained by heating at 170 ° C. for 30 minutes was cooled to room temperature and then heated at 250 ° C. for 30 minutes. Then, when it was rapidly cooled to room temperature, no cracks occurred. Then, when it was heated at 280 ° C. for 30 minutes and then rapidly cooled to room temperature , no cracks were generated.

Comparative Example 2
(Preparation of Adhesive Composition (2))
Examples except that 100 parts by weight of the epoxy cyclohexylethyl group-containing polyorganosylsesquioxane obtained in Comparative Example 1 was used instead of 100 parts by weight of the ladder-type polyorganosylsesquioxane as the cationically polymerizable compound. The adhesive composition (2) was prepared under the same procedure and conditions as in 2.

(Preparation of adhesive layer (A2))
A glass plate with an adhesive layer (A2) under the same procedure and conditions as in Example 2 except that the adhesive composition (2) was used instead of the adhesive composition (1) as the adhesive composition. Was produced. The film thickness of the adhesive layer (A2) was 5 to 6 μm.

(Heat-resistant)
The thermal decomposition temperature of the cured product obtained by heating the adhesive composition (2) at 150 ° C. for 30 minutes and then at 170 ° C. for 30 minutes was 260 ° C. or higher.
The thermal decomposition temperature of the cured product obtained by heating the separately prepared adhesive layer (A2) at 130 ° C. for 30 minutes and then at 170 ° C. for 30 minutes was 260 ° C. or higher.

(Crack resistance)
The adhesive layer (A2) was heated at 150 ° C. for 30 minutes, then the cured product obtained by heating at 170 ° C. for 30 minutes was cooled to room temperature, then heated at 250 ° C. for 30 minutes, and then to room temperature. When it was rapidly cooled, cracks occurred violently.
Further, the separately prepared adhesive layer (A2) was heated at 130 ° C. for 30 minutes, and then the coating film obtained by heating at 170 ° C. for 30 minutes was cooled to room temperature and then heated at 250 ° C. for 30 minutes. Then, when it was rapidly cooled to room temperature, no cracks occurred. Then, when it was heated at 280 ° C. for 30 minutes and then rapidly cooled to room temperature , severe cracks occurred.

Claims (9)

It is silsesquioxane having a ladder skeleton, and the ladder skeleton is the following formula (1).
[R ¹ SiO _3/2 ] (1)
[In formula (1), R ¹ is carbon in the alkenyl group in R ² in formula (2) - a group except that carbon double bond moiety is epoxidized the same structure as R ² There is the following formula (1a)

[In formula (1a), R ^1a represents a linear or branched alkylene group. ]
The group represented by the following formula (1b)

[In formula (1b), R ^1b represents a linear or branched alkylene group. ]
The group represented by the following formula (1c)

[In formula (1c), R ^1c represents a linear or branched alkylene group. ]
The group represented by and the following formula (1d)

[In formula (1d), R ^1d represents a linear or branched alkylene group. ]
Indicates one or more groups selected from the group consisting of the groups represented by. ]
The structural unit represented by and the following formula (2)
[R ² SiO _3/2 ] (2)
[In formula (2), R ² represents a substituted or unsubstituted alkenyl group. ]
The ratio of the structural unit represented by the formula (1) to all the siloxane structural units (100 mol%) constituting the rudder skeleton is 60 to 99 mol%. The silsesquioxane is characterized in that the proportion of the structural unit represented by the formula (2) is 1 to 40 mol% and the epoxy equivalent is 200 to 1000 g / eq. The following formula (3) is attached to the end of the ladder skeleton.
[R ^a R ³ SiO _2/2 ] (3)
[In formula (3), ^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. R ³ represents a hydroxy group that may be protected by a protecting group. ]
The silsesquioxane according to claim 1, wherein the silsesquioxane has a structural unit represented by the above, and the number average molecular weight of the silsesquioxane in terms of standard polystyrene by gel permeation chromatography is 500 to 5000. The silsesquioxane according to claim 2, wherein the ratio of the structural unit represented by the formula (3) to all the ends of the ladder skeleton is 30 to 100 mol%. A curable composition containing silsesquioxane according to any one of claims 1 to 3. An adhesive composition containing silsesquioxane according to any one of claims 1 to 3. A cured product of the curable composition according to claim 4. An adhesive sheet having an adhesive layer formed from the adhesive composition according to claim 5 on at least one surface of a base material. It is a laminate composed of three or more layers.
It has two layers to be adhered and an adhesive layer provided between the layers to be adhered.
A laminate characterized in that the adhesive layer is a layer of a cured product of the curable composition according to claim 6. An apparatus having the laminate according to claim 8.

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