JP2017008145A - Curable composition, adhesive sheet, laminate and device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition capable of forming a cured article cured at low temperature and excellent in heat resistance, crack resistance, adhesiveness and adhesion to an adherend.SOLUTION: There is provided a curable composition containing polyorganosilsesquioxane (A) having an epoxy group in a side chain, a specific siloxy group as a constitutional unit, number average molecular weight of 1000 to 3000 and molecular weight dispersion degree (weight average molecular weight/number average molecular weight) of 1.0 to 3.0 and a compound (B) having a polymerizable functional group other than the polyorganosilsesquioxane (A).SELECTED DRAWING: None

Description

  The present invention relates to a curable composition, an adhesive sheet having an adhesive layer formed using the curable composition, a cured product of the curable composition, and an adherend using the curable composition. The present invention relates to a laminate and an apparatus obtained by bonding.

  Thermosetting adhesives containing benzocyclobutene (BCB), novolac epoxy resin, or polyorganosilsesquioxane are known as adhesives used for semiconductor lamination and electronic component bonding (for example, Patent Documents 1 and 2).

  However, in order to cure the thermosetting adhesive containing BCB, it is necessary to heat 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. In addition, a thermosetting adhesive containing a novolac epoxy resin is likely to degrade its adhesiveness due to decomposition of the adhesive when subjected to a high-temperature process (for example, 260 to 280 ° C.) such as lead-free solder reflow. That was the problem.

  On the other hand, the thermosetting adhesive containing polyorganosilsesquioxane can be cured at a lower temperature than the thermosetting adhesive containing BCB, and has excellent adhesion and adhesion to the substrate. A cured product can be formed. In addition, adhesion can be maintained even when subjected to a high temperature process. However, a cured product of a curable adhesive containing polyorganosilsesquioxane has a problem that cracks are likely to occur due to thermal shock.

JP 2010-2226060 A JP 2014-101396 A

Accordingly, an object of the present invention is to provide a curable composition that can be cured at a low temperature to form a cured product having excellent heat resistance, crack resistance (or thermal shock resistance), adhesion to an adherend, and adhesion. To provide things.
Another object of the present invention is to provide a cured product of the curable composition.
Another object of the present invention is to provide an adhesive sheet having an adhesive layer formed using the curable composition.
Another object of the present invention is to provide a laminate obtained by adhering an adherend with the curable composition, and an apparatus having the laminate.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have a silsesquioxane structural unit (unit structure) containing an epoxy group, and a ratio of a specific structure (a ratio of a T3 body and a T2 body, an epoxy group). Of the silsesquioxane-containing unit containing the polyorganosilsesquioxane whose number average molecular weight and molecular weight dispersity are controlled within the specific range, and other compounds having a polymerizable functional group Can be cured at a low temperature to form a cured product having excellent heat resistance, crack resistance, adhesion to the adherend and adhesion, and semiconductor lamination and electronic components. It has been found that it has excellent properties as an adhesive. The present invention has been completed based on these findings.

  That is, the present invention provides the following formula (1):

[In Formula (1), R < ¹ > shows group containing an epoxy group. ]
Having a structural unit represented by the following formula (I)

[In the formula (I), R ^a is a group containing an epoxy 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. Represents a substituted or unsubstituted alkenyl group or a hydrogen atom. ]
A structural unit represented by the following formula (II):

[In the formula (II), R ^b represents 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. Represents a substituted or unsubstituted alkenyl group or a hydrogen atom. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]
The molar ratio of the structural unit represented by [the structural unit represented by the formula (I) / the structural unit represented by the formula (II)] is 5 or more, and is based on the total amount (100 mol%) of the siloxane structural unit. The structural unit represented by the formula (1) and the following formula (4)

[In formula (4), R ¹ is the same as that in formula (1). R ^c is the same as in formula (II). ]
A polyorganosyl having a proportion of structural units represented by the formula: 55 to 100 mol%, a number average molecular weight of 1000 to 3000, and a molecular weight dispersity (weight average molecular weight / number average molecular weight) of 1.0 to 3.0. Sesquioxane (A),
A curable composition containing a compound (B) other than polyorganosilsesquioxane (A) having a polymerizable functional group is provided.

  In the curable composition, the polymerizable functional group may be at least one selected from the group consisting of an epoxy ring, an oxetane ring, a vinyl ether group, and a vinylphenyl group.

  In the curable composition, the polyorganosilsesquioxane (A) is further represented by the following formula (2):

[In the formula (2), R ² represents 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 group. An alkenyl group of ]
You may have the structural unit represented by these.
In the above curable composition, R ¹ is the following formula (1a)

[In Formula (1a), R ^1a represents a linear or branched alkylene group. ]
A group represented by formula (1b):

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

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

[In formula (1d), R ^1d represents a linear or branched alkylene group. ]
It may be at least one selected from the group consisting of groups represented by:

In the curable composition, R ² may be a substituted or unsubstituted aryl group.
The curable composition may further contain a polymerization initiator.
The curable composition may further contain a polymerization stabilizer.
The curable composition may further contain a silane coupling agent.
The curable composition may be an adhesive composition.

Moreover, this invention provides the hardened | cured material obtained by hardening the said curable composition.
The present invention also provides an adhesive sheet having a base material and an adhesive layer on the base material, wherein the adhesive layer is a layer of the curable composition. provide.
Furthermore, the present invention is a laminate composed of three or more layers, which has two adherend layers and an adhesive layer between the adherend layers, and the adhesive layer has the curable composition described above. Provided is a laminate characterized by being a layer of a cured product.
Furthermore, this invention provides the apparatus which has the said laminated body.

  If cracks or peeling occurs in the adhesive layer in the laminate, the adherend layer may peel off or the wiring may be destroyed, resulting in a failure of the device provided with the laminate. Since the object is excellent in heat resistance, crack resistance, adhesion to an adherend and adhesion, it is possible to prevent the adhesion layer from being cracked or peeled off, and to improve the reliability of the apparatus. And, when the laminate of the present invention is a three-dimensional laminate of semiconductor chips, it is more integrated and power-saving than the conventional semiconductor, so if the laminate of the present invention is used, it is smaller and has higher performance. An electronic device can be provided.

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

[Curable composition]
The curable composition of the present invention has a silsesquioxane structural unit (unit structure) containing an epoxy group, and a ratio of a specific structure (a ratio of T3 and T2 forms, a silsesquioxane structure containing an epoxy group). A polyorganosilsesquioxane (A) in which the ratio of units) is controlled to a specific range, and the number average molecular weight and molecular weight dispersity are controlled to a specific range, and a polyorganosilsesquioxane having a polymerizable functional group It is a curable composition (curable resin composition) containing a compound (B) other than (A) 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, a polymerization stabilizer, a silane coupling agent, a solvent, a surface conditioner, or a surface modifier. .

[Polyorganosilsesquioxane (A)]
The polyorganosilsesquioxane (A) has a structural unit represented by the following formula (1); a structural unit represented by the following formula (I) (sometimes referred to as “T3 body”); The molar ratio of the structural unit represented by the following formula (II) (sometimes referred to as “T2 body”) [the structural unit represented by the formula (I) / the structural unit represented by the formula (II); May be described as “body / T2 body”] is 5 or more; the structural unit represented by the following formula (1) and the following formula (4) with respect to the total amount (100 mol%) of the siloxane structural unit. The ratio (total amount) of structural units is 55 to 100 mol%; the number average molecular weight is 1000 to 3000, and the molecular weight dispersity [weight average molecular weight / number average molecular weight] is 1.0 to 3.0. And

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 the above formula, R represents 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 hydrolysis and condensation reaction of a corresponding hydrolyzable trifunctional silane compound (specifically, for example, a compound represented by the following formula (a)). Is done.

R ¹ in the formula (1) represents a group (monovalent group) containing an epoxy group. That is, the polyorganosilsesquioxane (A) of the present invention is a cationic curable compound (cationic polymerizable compound) having at least an epoxy group in the molecule. Examples of the group containing an epoxy group include known or commonly used groups having an oxirane ring, and are not particularly limited. However, from the viewpoint of curability of the curable composition and heat resistance of the cured product, the following formula (1a) Group represented by the following formula (1b), a group represented by the following formula (1c), and a 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 a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and a decamethylene group. Examples thereof include a linear or branched alkylene group having 1 to 10 carbon atoms. Among these, R ^1a is preferably a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms, more preferably an ethylene group, from the viewpoint of curability of the cured product. A trimethylene group and a propylene group, more preferably an ethylene group and a trimethylene group.

In the above formula (1b), R ^1b represents a linear or branched alkylene group, and examples thereof include the same groups as R ^1a . Among these, R ^1b is preferably a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms, more preferably an ethylene group, from the viewpoint of curability of the cured product. A trimethylene group and a propylene group, more preferably an ethylene group and a trimethylene group.

In said formula (1c), R ^<1c> shows a linear or branched alkylene group, and the group similar to R ^<1a> is illustrated. Among these, R ^1c is preferably a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms, more preferably an ethylene group, from the viewpoint of curability of the cured product. A trimethylene group and a propylene group, more preferably an ethylene group and a trimethylene group.

In the above formula (1d), R ^1d represents a linear or branched alkylene group, and examples thereof include the same groups as R ^1a . Among these, R ^1d is preferably a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms, more preferably an ethylene group, from the viewpoint of curability of the cured product. A trimethylene group and a propylene group, more preferably an ethylene group and a trimethylene group.

R ¹ in formula (1) is particularly a group represented by the above formula (1a), wherein R ^1a is an ethylene group [in particular, 2- (3 ′, 4′-epoxycyclohexyl) Ethyl group] is preferable.

  The polyorganosilsesquioxane (A) of the present invention may have only one type of structural unit represented by the above formula (1), or the structural unit represented by the above formula (1). You may have 2 or more types.

The polyorganosilsesquioxane (A) of the present invention is represented by the following formula (2) in addition to the structural unit represented by the above formula (1) as the silsesquioxane structural unit [RSiO _3/2 ]. May have a structural unit.

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 a hydrolysis and condensation reaction of a corresponding hydrolyzable trifunctional silane compound (specifically, for example, a compound represented by the following formula (b)). It 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 group An alkenyl group of As said aryl group, a phenyl group, a tolyl group, a naphthyl group etc. are mentioned, for example. 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 linear or branched alkyl groups such as methyl group, ethyl group, propyl group, n-butyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, and isopentyl group. Groups. As said alkenyl group, linear or branched alkenyl groups, such as a vinyl group, an allyl group, and an isopropenyl group, are mentioned, for example.

  As the above-mentioned substituted aryl group, substituted aralkyl group, substituted cycloalkyl group, substituted alkyl group, and substituted alkenyl group, the above-mentioned aryl group, aralkyl group, cycloalkyl group, alkyl group, and alkenyl group are each a hydrogen atom or main chain. Part or all of the case is an ether group, ester group, carbonyl group, siloxane group, halogen atom (fluorine atom, etc.), acrylic group, methacryl group, mercapto group, amino group, and hydroxy group (hydroxyl group). And a group substituted with at least one selected.

Among them, R ² is preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, more preferably a substituted or unsubstituted aryl group, more preferably a phenyl group. is there.

  In the polyorganosilsesquioxane (A) of the present invention, the ratio of each of the above silsesquioxane structural units (the structural unit represented by the formula (1) and the structural unit represented by the formula (2)) is as follows. It is possible to adjust appropriately according to the composition of the raw material (hydrolyzable trifunctional silane) for forming the structural unit.

The polyorganosilsesquioxane (A) of the present invention is represented by the above formula (1) in addition to the structural unit represented by the above formula (1) and the structural unit represented by the formula (2). Structural units other than the structural units represented by formula (2) and silsesquioxane structural units [RSiO _3/2 ], [R ₃ SiO _1/2 ] (so-called M units), [ R ₂ SiO _2/2 ] at least one siloxane selected from the group consisting of a structural unit (so-called D unit) and a structural unit represented by [SiO _4/2 ] (so-called Q unit) You may have a unit. In addition, as a silsesquioxane structural unit other than the structural unit represented by the said Formula (1) and the structural unit represented by Formula (2), the structural unit etc. which are represented by following formula (3) etc. are mentioned, for example. Can be mentioned.

  In the polyorganosilsesquioxane (A) of the present invention, the proportion of the structural unit (T3 form) represented by the above formula (I) and the structural unit (T2 form) represented by the above formula (II) [T3 form] / T2 body] is 5 or more as described above, preferably 5 to 18, more preferably 6 to 16, and still more preferably 7 to 14. By setting the ratio [T3 body / T2 body] to 5 or more, the cured product and the adhesiveness are remarkably improved.

  When the structural unit represented by the above formula (I) is described in more detail, it is represented by the following formula (I ′). Further, when 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 shown in the structure represented by the following formula (I ′) is bonded to another silicon atom (a silicon atom not shown in the formula (I ′)). . On the other hand, two oxygen atoms located above and below the silicon atom shown in the structure represented by the following formula (II ′) are each replaced with another silicon atom (a silicon atom not shown in the formula (II ′)). Are connected. That is, the T3 body and the T2 body are structural units (T units) formed by hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound.

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, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, or hydrogen atom Show. Specific examples of R ^a and R ^b are the same as R ¹ in the above formula (1) and R ² in the above formula (2). In addition, R ^a in the formula (I) and R ^b in the formula (II) are respectively silicon atoms in the hydrolyzable trifunctional silane compound used as a raw material of the polyorganosilsesquioxane (A) of the present invention. Derived from a group bonded to (group other than an alkoxy group and a halogen atom; for example, R ¹ , R ² and a hydrogen atom in formulas (a) to (c) described below).

R ^c in the formula (II) (Formula (II ') in the R ^c versa) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include linear or branched alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. . The alkyl group represented by R ^c in the formula (II) is generally an alkoxy group (for example, X ¹ described later) in the hydrolyzable silane compound used as a raw material for the polyorganosilsesquioxane (A) of the present invention. Derived from an alkyl group forming an alkoxy group or the like as X ³ .

The said ratio [T3 body / T2 body] in the polyorgano silsesquioxane (A) of this invention can be calculated | required by ²⁹ Si-NMR spectrum measurement, for example. ^{29 In the} Si-NMR spectrum, the silicon atom in the structural unit (T3 form) represented by the above formula (I) is different from the silicon atom in the structural unit (T2 form) represented by the above formula (II). In order to show a signal (peak) in (chemical shift), the ratio [T3 body / T2 body] can be obtained by calculating the integration ratio of these respective peaks. Specifically, for example, the polyorganosilsesquioxane (A) of the present invention is represented by the above formula (1), and R ¹ is a 2- (3 ′, 4′-epoxycyclohexyl) ethyl group. In the case of having a unit, the signal of the silicon atom in the structure (T3 form) represented by the above formula (I) appears at −64 to −70 ppm, and in the structure (T2 form) represented by the above formula (II). The silicon atom signal appears at -54 to -60 ppm. Therefore, in this case, the ratio [T3 body / T2 body] can be obtained by calculating the integral ratio of the signal (T3 body) of −64 to −70 ppm and the signal (T2 body) of −54 to −60 ppm. it can.

The ²⁹ Si-NMR spectrum of the polyorganosilsesquioxane (A) of the present invention can be measured by, for example, the following apparatus and conditions.
Measuring apparatus: Trade name “JNM-ECA500NMR” (manufactured by JEOL Ltd.)
Solvent: Deuterated chloroform Accumulated times: 1800 times Measurement temperature: 25 ° C

That the ratio [T3 / T2] of the polyorganosilsesquioxane (A) of the present invention is 5 or more is a certain amount or more with respect to T3 in the polyorganosilsesquioxane (A) of the present invention. It means that T2 body exists. Examples of such a T2 body include a structural unit represented by the following formula (4), a structural unit represented by the following formula (5), a structural unit represented by the following formula (6), and the like. R ² in R ¹ and the following formula (5) in the following equation (4) is the same as R ² in R ¹ and the formula in the formula (1) (2). R ^c in the formula (4) to (6), like the R ^c in Formula (II), a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In general, a complete cage silsesquioxane is a polyorganosilsesquioxane composed only of a T3 form, and no T2 form exists in the molecule. That is, the ratio [T3 body / T2 body] is 5 or more, the number average molecular weight is 1000 to 3000, the molecular weight dispersity is 1.0 to 3.0, and in the FT-IR spectrum as described later. It is suggested that the polyorganosilsesquioxane (A) of the present invention having one intrinsic absorption peak in the vicinity of 1100 cm ⁻¹ has an incomplete cage silsesquioxane structure.

The polyorganosilsesquioxane (A) of the present invention has a cage-type (incomplete cage-type) silsesquioxane structure. The polyorganosilsesquioxane (A) of the present invention has an FT-IR spectrum. 1050 cm ^-1 and around 1150cm respectively in the vicinity of ^-1 does not have a specific absorption peak is confirmed by the fact that with a single specific absorption peak in the vicinity of 1100 cm ^-1 [ref: R. H. Raney, M.M. Itoh, A.D. Sakakibara and T. Suzuki, Chem. Rev. 95, 1409 (1995)]. On the other hand, in general, when the FT-IR spectrum has intrinsic absorption peaks near 1050 cm ⁻¹ and 1150 cm ⁻¹ , it is identified as having a ladder-type silsesquioxane structure. In addition, the FT-IR spectrum of the polyorganosilsesquioxane (A) of this invention can be measured with the following apparatus and conditions, for example.
Measuring device: Trade name “FT-720” (manufactured by Horiba, Ltd.)
Measurement method: Transmission method Resolution: 4 cm ^-1
Measurement wavenumber range: 400 to 4000 cm ⁻¹
Integration count: 16 times

  The total amount of siloxane structural units in the polyorganosilsesquioxane (A) of the present invention [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%), the above formula (1 ) And the ratio (total amount) of the structural unit represented by the above formula (4) is 55 to 100 mol%, preferably 65 to 100 mol%, more preferably, as described above. 80 to 99 mol%. By making the said ratio 55 mol% or more, the sclerosis | hardenability of a curable composition improves and the adhesiveness of hardened | cured material becomes remarkably high. In addition, the ratio of each siloxane structural unit in the polyorganosilsesquioxane (A) of the present invention can be calculated by, for example, the composition of raw materials or NMR spectrum measurement.

  The total amount of siloxane structural units in the polyorganosilsesquioxane (A) of the present invention [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%), the above formula (2 The ratio (total amount) of the structural unit represented by formula (5) and the structural unit represented by the above formula (5) is not particularly limited, but is preferably 0 to 70 mol%, more preferably 0 to 60 mol%, still more preferably. Is 0 to 40 mol%, particularly preferably 1 to 15 mol%. Since the ratio of the structural unit represented by the formula (1) and the structural unit represented by the formula (4) can be relatively increased by setting the ratio to 70 mol% or less, the curable composition There is a tendency that the curability of the cured product is improved and the adhesiveness of the cured product becomes higher.

  The total amount of siloxane structural units in the polyorganosilsesquioxane (A) of the present invention [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%), the above formula (1 ), The structural unit represented by the above formula (2), the structural unit represented by the above formula (4), and the ratio (total amount) of the structural unit represented by the above formula (5) are as follows: Although not specifically limited, 60-100 mol% is preferable, More preferably, it is 70-100 mol%, More preferably, it is 80-100 mol%. There exists a tendency for the adhesiveness of hardened | cured material to become higher by making the said ratio 60 mol% or more.

  The number average molecular weight (Mn) in terms of standard polystyrene by gel permeation chromatography of the polyorganosilsesquioxane (A) of the present invention is 1000 to 3000, preferably 1000 to 2800, more preferably as described above. Is 1100-2600. By setting the number average molecular weight to 1000 or more, the heat resistance and adhesiveness of the cured product are further improved. On the other hand, by setting the number average molecular weight to 3000 or less, compatibility with other components in the curable composition is improved, and the heat resistance of the cured product is further improved.

  The molecular weight dispersity (Mw / Mn) in terms of standard polystyrene by gel permeation chromatography of the polyorganosilsesquioxane (A) of the present invention is 1.0 to 3.0 as described above, preferably It is 1.1 to 2.0, more preferably 1.2 to 1.9, and particularly preferably 1.45 to 1.8. By setting the molecular weight dispersity to 3.0 or less, the adhesiveness of the cured product becomes higher. On the other hand, when the molecular weight dispersity is 1.0 or more, it tends to be liquid and the handleability tends to be improved.

In addition, the number average molecular weight and molecular weight dispersity of the polyorganosilsesquioxane (A) of the present invention can be measured by the following apparatus and conditions.
Measuring apparatus: Trade name “Alliance HPLC system 2695” (manufactured by Waters), “Refractive Index Detector 2414” (manufactured by Waters)
Column: Tskel GMH _HR- M × 2 (manufactured by Tosoh Corporation)
Guard column: Tskel guard column H _HR L (manufactured by Tosoh Corporation)
Column oven: COLUMN HEATER U-620 (manufactured by Sugai)
Solvent: THF
Measurement conditions: 40 ° C
Molecular weight: Standard polystyrene conversion

The 5% weight loss temperature (T _d5 ) in the air atmosphere of the polyorganosilsesquioxane (A) of the present invention is not particularly limited, but is preferably 330 ° C. or higher (for example, 330 to 450 ° C.), more preferably It is 340 ° C or higher, more preferably 350 ° C or higher. When the 5% weight reduction temperature is 330 ° C. or higher, the heat resistance of the cured product tends to be further improved. Particularly, in the polyorganosilsesquioxane (A) of the present invention, the ratio [T3 / T2] is 5 or more, the number average molecular weight is 1000 to 3000, and the molecular weight dispersity is 1.0 to 3. By being one and having one intrinsic peak in the vicinity of 1100 cm ⁻¹ in the FT-IR spectrum, the 5% weight loss temperature is controlled to 330 ° C. or higher. The 5% weight reduction temperature is a temperature at the time when 5% of the weight before heating is reduced when heated at a constant rate of temperature increase, and serves as an index of heat resistance. The 5% weight loss temperature can be measured by TGA (thermogravimetric analysis) under an air atmosphere at a temperature rising rate of 5 ° C./min.

  The polyorganosilsesquioxane (A) of the present invention can be produced by a known or conventional polysiloxane production method, and is not particularly limited. For example, one or two or more hydrolyzable silane compounds may be used. It can be produced by a method of hydrolysis and condensation. However, as the hydrolyzable silane compound, a hydrolyzable trifunctional silane compound (compound represented by the following formula (a)) for forming the structural unit represented by the above formula (1) is essential. It is necessary to use it as a hydrolyzable silane compound.

  More specifically, for example, it is represented by the following formula (a) which is a hydrolyzable silane compound for forming a silsesquioxane structural unit (T unit) in the polyorganosilsesquioxane (A) of the present invention. The polyorganosilsesquioxane of the present invention by a method of hydrolyzing and condensing a compound represented by the following formula (b) and a compound represented by the following formula (c) as necessary. (A) can be manufactured.

The compound represented by the above formula (a) is a compound that forms the structural unit represented by the formula (1) in the polyorganosilsesquioxane (A) 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) is a group represented by the above formula (1a), a group represented by the above formula (1b), a group represented by the above formula (1c), or the above formula (1d). The group represented by the above formula (1a), the group represented by the above formula (1c), more preferably the group represented by the above formula (1a), particularly preferably Is a group represented by the above formula (1a), wherein R ^1a is an ethylene group [in particular, a 2- (3 ′, 4′-epoxycyclohexyl) ethyl group].

X ¹ in the above formula (a) represents an alkoxy group or a halogen atom. The alkoxy group in X ^1, for example, a methoxy group, an ethoxy group, a propoxy group, isopropyloxy group, a butoxy group, an alkoxy group having 1 to 4 carbon atoms such as isobutyl group and the like. As the halogen atom in X ^1, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, X ¹ is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. The three X ¹ may be the same or different.

The compound represented by the above formula (b) is a compound that forms the structural unit represented by the formula (2) in the polyorganosilsesquioxane (A) 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 An alkyl group, or a substituted or unsubstituted alkenyl group. That is, R ² in formula (b) is preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, more preferably a substituted or unsubstituted aryl group, More preferred is 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, X ² is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. The three X ² may be the same or different.

The compound represented by the above formula (c) is a compound that forms the structural unit represented by the formula (3) in the polyorganosilsesquioxane (A) 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, X ³ is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. The three X ³ may be the same or different.

  As said hydrolysable silane compound, you may use together hydrolysable silane compounds other than the compound represented by said formula (a)-(c). For example, hydrolyzable trifunctional silane compounds other than the compounds represented by the above formulas (a) to (c), hydrolyzable monofunctional silane compounds that form M units, and hydrolyzable bifunctional silanes that form D units Examples thereof include hydrolyzable tetrafunctional silane compounds that form compounds and Q units.

  The amount and composition of the hydrolyzable silane compound can be appropriately adjusted according to the desired structure of the polyorganosilsesquioxane (A) of the present invention. For example, although the usage-amount of the compound represented by the said formula (a) is not specifically limited, 55-100 mol% is preferable with respect to the whole quantity (100 mol%) of the hydrolysable silane compound to be used, More preferably Is 65 to 100 mol%, more preferably 80 to 99 mol%.

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

  Furthermore, the ratio of the compound represented by the formula (a) and the compound represented by the formula (b) (the ratio of the total amount) to the total amount (100 mol%) of the hydrolyzable silane compound to be used is not particularly limited. 60-100 mol% is preferable, More preferably, it is 70-100 mol%, More preferably, it is 80-100 mol%.

  Moreover, when using together 2 or more types as said hydrolysable silane compound, the hydrolysis and condensation reaction of these hydrolysable silane compounds can also be performed simultaneously, and can also be performed sequentially. When performing the said reaction sequentially, the order which performs reaction is not specifically limited.

  The hydrolysis and condensation reaction of the hydrolyzable silane compound can be performed in the presence of a solvent or in the absence. Among these, 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 Etc. Among them, ketone and ether are preferable. In addition, a solvent can also be used individually by 1 type and can also be used in combination of 2 or more type.

  The usage-amount of a solvent is not specifically limited, It can adjust suitably according to desired reaction time etc. within the range of 0-2000 weight part with respect to 100 weight part of whole quantity of a hydrolysable silane compound. .

  The hydrolysis and condensation reaction of the hydrolyzable silane compound is preferably allowed to proceed 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, nitric acid, phosphoric acid and boric acid; phosphoric acid esters; carboxylic acids such as acetic acid, formic acid and trifluoroacetic acid; methanesulfonic acid, trifluoromethanesulfonic acid, p -Sulfonic acids such as toluenesulfonic acid; solid acids such as activated clay; Lewis acids such as iron chloride. Examples of the alkali catalyst include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkaline earth metals such as magnesium hydroxide, calcium hydroxide, and barium hydroxide. Hydroxides; carbonates of alkali metals such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate; carbonates of alkaline earth metals such as magnesium carbonate; lithium hydrogen carbonate, sodium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate Alkali metal hydrogen carbonates such as cesium hydrogen carbonate; organic acid salts of alkali metals such as lithium acetate, sodium acetate, potassium acetate and cesium acetate (for example, acetate); organic acids of alkaline earth metals such as magnesium acetate Salt (eg acetate); lithium methoxide, sodium methoxy Alkali metal alkoxides such as sodium ethoxide, sodium isopropoxide, potassium ethoxide and potassium t-butoxide; alkali metal phenoxides such as sodium phenoxide; triethylamine, N-methylpiperidine, 1,8-diazabicyclo [5.4 0.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene and the like amines (tertiary amine, etc.); pyridine, 2,2′-bipyridyl, 1,10 -Nitrogen-containing aromatic heterocyclic compounds such as phenanthroline. In addition, a catalyst can also be used individually by 1 type and can also be used in combination of 2 or more type. Further, the catalyst can be used in a state dissolved or dispersed in water, a solvent or the like.

  The usage-amount of the said catalyst is not specifically limited, It can adjust suitably in the range of 0.002-0.200 mol with respect to 1 mol of whole quantity of a hydrolysable silane compound.

  The amount of water used in the hydrolysis and condensation reaction is not particularly limited, and can be appropriately adjusted within a 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 to be used (total amount used) may be added all at once or sequentially. When adding sequentially, you may add continuously and may add intermittently.

  As the reaction conditions for performing the hydrolysis and condensation reaction of the hydrolyzable silane compound, the ratio [T3 body / T2 body] in the polyorganosilsesquioxane (A) of the present invention is 5 or more. It is important to select such reaction conditions. Although the reaction temperature of the said hydrolysis and condensation reaction is not specifically limited, 40-100 degreeC is preferable, More preferably, it is 45-80 degreeC. By controlling the reaction temperature within the above range, the ratio [T3 / T2] tends to be more efficiently controlled to 5 or more. Moreover, the reaction time of the said hydrolysis and condensation reaction is although it does not specifically limit, 0.1 to 10 hours are preferable, More preferably, it is 1.5 to 8 hours. The hydrolysis and condensation reaction can be performed under normal pressure, or can be performed under pressure or under reduced pressure. In addition, the atmosphere at the time of performing the hydrolysis and condensation reaction is not particularly limited, and may be any of, for example, in an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere, or in the presence of oxygen such as in the air. However, an inert gas atmosphere is preferred.

  The polyorganosilsesquioxane (A) of the present invention is obtained by hydrolysis and condensation reaction of the hydrolyzable silane compound. After completion of the hydrolysis and condensation reaction, it is preferable to neutralize the catalyst in order to suppress the ring opening of the epoxy group. Further, the polyorganosilsesquioxane (A) of the present invention can be separated from, for example, separation means such as water washing, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc. Separation and purification may be performed by a separation means combining the above.

  Since the polyorganosilsesquioxane (A) of the present invention has the above-described configuration, it has high heat resistance by curing a curable composition containing the polyorganosilsesquioxane (A) as an essential component. In addition, a cured product having excellent adhesiveness can be formed.

  In the curable composition of the present invention, the polyorganosilsesquioxane (A) of the present invention can be used singly or in combination of two or more.

  The content (blending amount) of the polyorganosilsesquioxane (A) of the present invention in the curable composition of the present invention is not particularly limited, but is based on the total amount (100% by weight) of the curable composition excluding the solvent. The content is preferably 35% by weight or more and less than 85% by weight, more preferably 40 to 80% by weight, and still more preferably 45 to 70% by weight. By setting the content of the polyorganosilsesquioxane (A) of the present invention to 35% by weight or more, the heat resistance of the cured product tends to be further improved. On the other hand, when the content of the polyorganosilsesquioxane (A) of the present invention is less than 85% by weight, the crack resistance tends to be improved.

  The polyorganosilsesquioxane of this invention with respect to the whole quantity (100 weight%) of the curable compound (Polyorganosilsesquioxane (A) and below-mentioned polymerizable compound (B)) contained in the curable composition of this invention. The proportion of (A) is not particularly limited, but is preferably 30 to 90% by weight, more preferably 35 to 85% by weight, and still more preferably 40 to 75% by weight. By setting the content of the polyorganosilsesquioxane (A) of the present invention to 30% by weight or more, the heat resistance of the cured product tends to be further improved.

[Compounds other than polyorganosilsesquioxane (A) having a polymerizable functional group (B)]
The curable composition of the present invention comprises a compound (B) other than the polyorganosilsesquioxane (A) having a polymerizable functional group (hereinafter simply referred to as “polyorganosilsesquioxane (A)”). , Sometimes referred to as “polymerizable compound (B)”.

The “polymerizable functional group” of the polymerizable compound (B) of the present invention is not particularly limited as long as it has polymerizability, and examples thereof include an epoxy ring, an oxetane ring, a vinyl ether group, and a vinylphenyl group. .
As the polymerizable functional group, an epoxy ring, an oxetane ring, a vinyl ether group, a vinylphenyl group, and the like are preferable, and an epoxy ring is more preferable from the viewpoint of improving crack resistance of the cured product.

  The polymerizable compound (B) of the present invention may contain one of the above polymerizable functional groups or may contain two or more kinds in combination.

  Although the number of the said polymerizable functional group which the polymeric compound (B) of this invention has in 1 molecule is not specifically limited, 1-50 pieces are preferable, More preferably, it is 1-30 pieces, More preferably, it is 2-20. It is a piece.

The polymerizable compound (B) of the present invention may be a low molecular compound or a polymer compound in which monomer components are polymerized.
The molecular weight of the polymerizable compound (B) of the present invention (in the case of a polymer compound, the weight average molecular weight) is not particularly limited, but is preferably 200 to 500,000, more preferably from the viewpoint of improving crack resistance of the cured product. 300 to 100,000.
The weight average molecular weight of the polymerizable compound (B) of the present invention can be measured by the same method as that for the polyorganosilsesquioxane (A) described above.

Although the polymeric functional group equivalent of the polymeric compound (B) of this invention is not specifically limited, From a viewpoint of the crack-proof improvement of hardened | cured material, 100-100000 are preferable, More preferably, it is 150-50000.
The polymerizable functional group equivalent of the polymerizable compound (B) of the present invention means the molecular weight of the compound per functional group (in the case of a polymer compound, the weight average molecular weight) and can be measured by a known method. it can. For example, when the polymerizable functional group is an epoxy ring, it can be measured by a method based on JIS K 7236: 2001 (how to obtain an epoxy equivalent of an epoxy resin).

  As the polymerizable compound (B) having an epoxy ring, a known or commonly used compound other than the polyorganosilsesquioxane (A) having at least one epoxy group (oxirane ring) in the molecule may be used. Although it is not specifically limited, For example, an alicyclic epoxy compound (alicyclic epoxy resin), an aromatic epoxy compound (aromatic epoxy resin), an aliphatic epoxy compound (aliphatic epoxy resin) etc. are mentioned.

  Examples of the alicyclic epoxy compound include known or conventional compounds having one or more alicyclic rings and one or more epoxy groups in the molecule, and are not particularly limited. For example, (1) A compound having an epoxy group (referred to as “alicyclic epoxy group”) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring; (2) the epoxy group is directly bonded to the alicyclic ring by a single bond. (3) compounds having an alicyclic ring and a glycidyl ether group in the molecule (glycidyl ether type epoxy compound) and the like.

  As said (1) compound which has an alicyclic epoxy group in a molecule | numerator, the compound represented by following formula (i) is mentioned.

  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 divalent hydrocarbon groups, alkenylene groups in which part or all of carbon-carbon double bonds are epoxidized, carbonyl groups, ether bonds, ester bonds, carbonate groups, amide groups, and the like. And a group in which a plurality of are connected.

  As said bivalent hydrocarbon group, a C1-C18 linear or branched alkylene group, a bivalent alicyclic hydrocarbon group, etc. are mentioned. 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, 1,3-cyclopentylene group, And divalent cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group, and cyclohexylidene group.

  Examples of the alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond is epoxidized (sometimes referred to as “epoxidized alkenylene group”) include, for example, a vinylene group, a propenylene group, and a 1-butenylene group. , A 2-butenylene group, a butadienylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group, etc., and a linear or branched alkenylene group having 2 to 8 carbon atoms. In particular, the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, more preferably 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized. Alkenylene group.

  Representative examples of the alicyclic epoxy compound represented by the above formula (i) include 3,4,3 ′, 4′-diepoxybicyclohexane, and the following formulas (i-1) to (i-10): The compound etc. which are represented by these are mentioned. In the following formulas (i-5) and (i-7), l and m each represent an integer of 1 to 30. 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. -Like alkylene groups are preferred. N1-n6 in following formula (i-9) and (i-10) show the integer of 1-30, respectively. Other 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) oxirane, bis (3,4-epoxycyclohexylmethyl) ether and the like.

  Examples of the compound (2) in which the epoxy group is directly bonded to the alicyclic ring with a single bond include compounds 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 alcohols having 1 to 15 carbon atoms) such as 2,2-bis (hydroxymethyl) -1-butanol. p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or more, n in each group in () (inside the outer parenthesis) may be the same or different. Specific examples of the compound represented by the above formula (ii) include 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol [for example, , Trade name “EHPE3150” (manufactured by Daicel Corporation), etc.].

  Examples of the compound (3) having an alicyclic ring and a glycidyl ether group in the molecule include glycidyl ethers of alicyclic alcohols (particularly alicyclic polyhydric alcohols). More specifically, for example, 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, 2,2-bis [3,5-dimethyl-4- (2,3-epoxypropoxy) Compound obtained by hydrogenating bisphenol A type epoxy compound such as cyclohexyl] propane (hydrogenated bisphenol A type epoxy compound); bis [o, o- (2,3-epoxypropoxy) cyclohexyl] methane, bis [o , P- (2,3-epoxypropoxy) cyclohexyl] methane, bis [p, p- (2,3-epoxypropoxy) cyclohexyl] methane, bis [3,5-dimethyl-4- (2, 3-epoxypropoxy) cyclohexyl] Compound obtained by hydrogenating bisphenol F-type epoxy compound such as methane (hydrogenated bisphenol F-type epoxy compound) Hydrogenated biphenol type epoxy compound; hydrogenated phenol novolak type epoxy compound; hydrogenated cresol novolak type epoxy compound; hydrogenated cresol novolak type epoxy compound of bisphenol A; hydrogenated naphthalene type epoxy compound; epoxy compound obtained from trisphenolmethane And hydrogenated epoxy compounds of the following aromatic epoxy compounds.

Examples of the aromatic epoxy compound include epibis type glycidyl ether type epoxy resins obtained by condensation reaction of bisphenols [for example, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol and the like] and epihalohydrin; High molecular weight epibis type glycidyl ether type epoxy resin obtained by further addition reaction of bis type glycidyl ether type epoxy resin with the above bisphenols; phenols [for example, phenol, C _1-9 alkylphenol, xylenol, resorcin, catechol, Bisphenol A, bisphenol F, bisphenol S, etc.] and an aldehyde [eg, formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzalde A novolac alkyl type glycidyl ether type epoxy resin obtained by condensation reaction of polyhydric alcohols obtained by condensation reaction with hydride, salicylaldehyde, etc.] with epihalohydrin; two phenol skeletons at the 9-position of the fluorene ring And an epoxy compound in which a glycidyl group is bonded to an oxygen atom obtained by removing a hydrogen atom from a hydroxy group of these phenol skeletons directly or via an alkyleneoxy group.

  Examples of the aliphatic epoxy compound include a glycidyl ether of an alcohol having no q-valent cyclic structure (q is a natural number); a monovalent or polyvalent carboxylic acid [for example, acetic acid, propionic acid, butyric acid, stearic acid, Adipic acid, sebacic acid, maleic acid, itaconic acid, etc.] glycidyl ester; epoxidized oils and fats having double bonds such as epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil; polyolefins such as epoxidized polybutadiene (poly Epoxidized product of alkadiene). Examples of the alcohol having no q-valent cyclic structure include monohydric alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, and 1-butanol; ethylene glycol, 1,2-propanediol, 1 , 3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and other dihydric alcohols; Examples include trihydric or higher polyhydric alcohols such as glycerin, diglycerin, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol. That. The q-valent alcohol may be polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, or the like.

  Examples of the polymerizable compound (B) having an oxetane ring include known or 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- (hydroxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyl) Oxymethyl) oxetane, 3-ethyl-3- (chloromethyl) oxetane, 3,3-bis (chloromethyl) oxetane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis { [1-Ethyl (3-oxetanyl)] methyl} ether, 4,4′-bis [(3-ethyl-3-oxetanyl) Toximethyl] 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, xylylenebisoxetane, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane, oxetanylsil Examples thereof include sesquioxane and phenol novolac oxetane.

  The polymerizable compound (B) having a vinyl ether group may be a known or conventional compound having one or more vinyl ether groups in the molecule, and is not particularly limited. For example, 2-hydroxyethyl vinyl ether (ethylene glycol) Monovinyl ether), 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl Vinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1-hydroxymethyl ester Pyrvinyl ether, 4-hydroxycyclohexyl vinyl 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-cyclohexanedimethanol 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 glycol 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, oligo Propylene glycol divinyl ether, polypropylene glycol monovinyl ether, polypropylene glycol divinyl ether, isosorbide divinyl ether, oxanorbornene divinyl ether, phenyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octyl vinyl ether, cyclohexyl Nyl ether, hydroquinone divinyl ether, 1,4-butanediol divinyl ether, cyclohexane dimethanol divinyl ether, trimethylolpropane divinyl ether, trimethylolpropane trivinyl ether, bisphenol A divinyl ether, bisphenol F divinyl ether, hydroxyoxanorbornane methanol divinyl ether, Examples include 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, and the like.

  In addition, as a polymerizable compound (B) having a vinyl ether group, particularly when a vinyl ether compound having one or more hydroxyl groups in the molecule is used, it is excellent in heat-resistant yellowing (characteristic that hardly causes yellowing by heating). There is an advantage that a cured product can be obtained. For this reason, the hardened | cured material of higher quality and durability is obtained. The number of hydroxyl groups 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.

  As the polymerizable compound (B) having a vinylphenyl group, a known or conventional compound having one or more vinylphenyl groups in the molecule can be used, and is not particularly limited. For example, styrene, divinylbenzene, methoxy Styrene, ethoxystyrene, hydroxystyrene, vinylnaphthalene, vinylanthracene, 4-vinylphenyl acetate, (4-vinylphenyl) dihydroxyborane, (4-vinylphenyl) boranoic acid, (4-vinylphenyl) boronic acid, 4-ester Tenenylphenylboronic acid, 4-vinylphenylboranoic acid, 4-vinylphenylboronic acid, p-vinylphenylboronic acid, p-vinylphenylboronic acid, N- (4-vinylphenyl) maleimide, N- (p-vinyl Phenyl) maleimide, N- (p-vinylphenyl) male Imide and the like.

In the curable composition of the present invention, it is preferable to use a compound having an epoxy ring as the polymerizable compound (B) together with the polyorganosilsesquioxane (A) of the present invention, and an alicyclic epoxy compound or aromatic An epoxy compound is more preferable, a compound in which an epoxy group is directly bonded to the alicyclic ring by a single bond, an epibis type glycidyl ether type epoxy resin, or a novolak alkyl type glycidyl ether type epoxy resin is more preferable, and the above formula is particularly preferable. Glycididine by epichlorohydrin or 2-methylepichlorohydrin of a compound represented by (ii), bisphenol A type epoxy resin, bisphenol F type epoxy resin, or phenol / formaldehyde polycondensate or C _1-9 alkylphenol / formaldehyde polycondensate This is a modified etherified product. Thereby, there exists a tendency for the crack resistance of hardened | cured material to become higher.

  In the curable composition of this invention, a polymeric compound (B) can also be used individually by 1 type, and can also be used in combination of 2 or more type. The polymerizable compound (B) can also be produced by a known or conventional method. For example, trade names “EHPE3150”, “Celoxide 2021P” (above, manufactured by Daicel Corporation), trade names “jER4004P” , “JER4005P”, “jER4007P”, “jER4010P” (manufactured by Mitsubishi Chemical Corporation), and trade name “RE-303S-L” (manufactured by Nippon Kayaku Co., Ltd.) may be used. it can.

  The content (blending amount) of the polymerizable compound (B) in the curable composition of the present invention is not particularly limited, but the total amount of the polyorganosilsesquioxane (A) and the polymerizable compound (B) of the present invention ( 100% by weight; the total amount of the curable compound) is preferably 15 to 65% by weight, more preferably 20 to 60% by weight, still more preferably 30 to 55% by weight. By setting the content of the polymerizable compound (B) to 65% by weight or less (particularly 55% by weight or less), desired performance (for example, fast curability to the curable composition) for the curable composition or the cured product. And viscosity adjustment) and the heat resistance of the cured product tends to be further improved. On the other hand, crack resistance may be imparted by setting the content of the polymerizable compound (B) to 15% by weight or more.

  The content (blending amount) of the polymerizable compound (B) having an epoxy ring in the curable composition of the present invention is not particularly limited, but the polyorganosilsesquioxane (A) of the present invention and the polymerizable compound (B) ) To 100% by weight (100% by weight; the total amount of polymerizable compounds), preferably 10 to 70% by weight, more preferably 15 to 65% by weight, and still more preferably 25 to 60% by weight. By controlling the content of the polymerizable compound (B) having an epoxy ring within the above range, a cured product having very high crack resistance tends to be obtained. In particular, by controlling the content of the alicyclic epoxy compound within the above range, in addition to the particularly high crack resistance of the cured product, the heat resistance tends to be further improved.

[Polymerization initiator]
The curable composition of the present invention preferably further contains a polymerization initiator. A polymerization initiator is a compound which can start thru | or accelerate | stimulate the polymerization reaction of curable compounds, such as the polyorgano silsesquioxane (A) of this invention, and a polymeric compound (B). The polymerization initiator includes a cationic polymerization initiator and an anionic polymerization initiator. The cationic polymerization initiator is a compound that generates cationic species by heating to initiate a curing reaction of the polymerizable compound, and the anionic polymerization initiator generates anionic species by heating to generate a polymerizable compound. It is a compound that initiates the curing reaction. When the curable composition of the present invention contains a polymerization initiator, the curing time until tack-free can be shortened. In addition, a polymerization initiator can be used individually by 1 type or in combination of 2 or more types.

  As the curable composition of the present invention, an adhesive layer can be rapidly formed by heating and drying without causing a curing reaction to proceed, and the obtained adhesive layer has adhesiveness at less than 50 ° C. Therefore, it is possible to perform cutting without attaching glue to the cutting blade, and it develops adhesiveness by heating at a temperature that can suppress damage to the adherend such as a semiconductor chip, and then promptly From the viewpoint of curing properties, it is preferable to use a polymerization initiator having the curing properties described below.

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

  In the case of an anionic polymerization initiator, the composition obtained by adding 1 part by weight of an anionic polymerization initiator to 100 parts by weight of bisphenol A diglycidyl ether has a heat curing time at 130 ° C. (conforming to JIS K5909 1994). It is preferable to use a polymerization initiator that is 3.5 minutes or longer.

  The heat curing 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 needle tip no longer rises about the thread shape. When a polymerization initiator having a heat curing time below the above range is used, a cationic species is generated when a cationic polymerization initiator is used during drying by heating, and an anionic species is generated when an anionic polymerization initiator is used. However, since the polymerization proceeds gradually, it becomes difficult to form an adhesive layer having storage stability.

  In the present invention, it is particularly preferable to use a cationic polymerization initiator from the viewpoint that the curing time until tack-free can be further shortened. The cationic polymerization initiator includes a photocationic polymerization initiator and a thermal cationic polymerization initiator.

  As the photocationic polymerization initiator, known or commonly used photocationic polymerization initiators can be used. For example, sulfonium salts (salts of sulfonium ions and anions), iodonium salts (salts of iodonium ions and anions). Selenium salt (selenium ion and anion salt), ammonium salt (ammonium ion and anion salt), phosphonium salt (phosphonium ion and anion salt), transition metal complex ion and anion salt, etc. . These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the sulfonium salt include triphenylsulfonium salt, tri-p-tolylsulfonium salt, tri-o-tolylsulfonium salt, tris (4-methoxyphenyl) sulfonium salt, 1-naphthyldiphenylsulfonium salt, and 2-naphthyldiphenyl. Sulfonium salt, tris (4-fluorophenyl) sulfonium salt, tri-1-naphthylsulfonium salt, tri-2-naphthylsulfonium salt, tris (4-hydroxyphenyl) sulfonium salt, diphenyl [4- (phenylthio) phenyl] sulfonium salt , Triarylsulfonium salts such as 4- (p-tolylthio) phenyldi- (p-phenyl) sulfonium salt; diphenylphenacylsulfonium salt, diphenyl-4-nitrophenacylsulfonium salt, diphenylbenzyl Diarylsulfonium salts such as ruphonium salt and diphenylmethylsulfonium salt; monoarylsulfonium salts such as phenylmethylbenzylsulfonium salt, 4-hydroxyphenylmethylbenzylsulfonium salt and 4-methoxyphenylmethylbenzylsulfonium salt; dimethylphenacylsulfonium salt, phena And trialkylsulfonium salts such as siltetrahydrothiophenium salt and dimethylbenzylsulfonium salt.

  Examples of the diphenyl [4- (phenylthio) phenyl] sulfonium salt include a trade name “CPI-101A” (manufactured by San Apro Co., Ltd., diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate 50% propylene carbonate solution). ), Trade name “CPI-100P” (manufactured by San Apro Co., Ltd., diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate 50% propylene carbonate solution) and the like can be used.

  Examples of the iodonium salt include trade name “UV9380C” (Momentive Performance Materials Japan GK, bis (4-dodecylphenyl) iodonium hexafluoroantimonate 45% alkyl glycidyl ether solution), trade name “RHODORSIL”. “PHOTOINITIATOR 2074” (Rhodia Japan K.K., tetrakis (pentafluorophenyl) borate [(1-methylethyl) phenyl] (methylphenyl) iodonium), trade name “WPI-124” (Wako Pure Chemical Industries, Ltd.) Manufactured), diphenyliodonium salt, di-p-tolyliodonium salt, bis (4-dodecylphenyl) iodonium salt, bis (4-methoxyphenyl) iodonium salt, and the like.

  Examples of the selenium salt include triaryl selenium such as triphenyl selenium salt, tri-p-tolyl selenium salt, tri-o-tolyl selenium salt, tris (4-methoxyphenyl) selenium salt, and 1-naphthyldiphenyl selenium salt. Salts: Diaryl phenacyl selenium salts, diphenyl benzyl selenium salts, diaryl selenium salts such as diphenyl methyl selenium salts; monoaryl selenium salts such as phenyl methyl benzyl selenium salts; trialkyl selenium salts such as dimethyl phenacyl selenium salts, etc. .

  Examples of the ammonium salt include tetramethylammonium salt, ethyltrimethylammonium salt, diethyldimethylammonium salt, triethylmethylammonium salt, tetraethylammonium salt, trimethyl-n-propylammonium salt, and trimethyl-n-butylammonium salt. Pyrrolium salts such as alkyl ammonium salts; N, N-dimethylpyrrolidinium salts, N-ethyl-N-methylpyrrolidinium salts; N, N′-dimethylimidazolinium salts, N, N′-diethylimidazolinium salts, etc. Imidazolinium salts; tetrahydropyrimidinium salts such as N, N′-dimethyltetrahydropyrimidinium salt, N, N′-diethyltetrahydropyrimidinium salt; N, N-dimethylmorpholinium salt, N, N -Diethylmorpholini Morpholinium salts such as N salt, piperidinium salts such as N, N-dimethylpiperidinium salt and N, N-diethylpiperidinium salt; pyridinium salts such as N-methylpyridinium salt and N-ethylpyridinium salt; N, N '-Imidazolium salt such as dimethylimidazolium salt; Quinolium salt such as N-methylquinolium salt; Isoquinolium salt such as N-methylisoquinolium salt; Thiazonium salt such as benzylbenzothiazonium salt; And the like.

  Examples of the phosphonium salt include tetraarylphosphonium salts such as tetraphenylphosphonium salt, tetra-p-tolylphosphonium salt and tetrakis (2-methoxyphenyl) phosphonium salt; triarylphosphonium salts such as triphenylbenzylphosphonium salt; Examples thereof include tetraalkylphosphonium salts such as benzylphosphonium salt, tributylbenzylphosphonium salt, tetraethylphosphonium salt, tetrabutylphosphonium salt, and triethylphenacylphosphonium salt.

Examples of the salt of the transition metal complex ion include salts of chromium complex cations such as (η5-cyclopentadienyl) (η6-toluene) Cr ⁺ and (η5-cyclopentadienyl) (η6-xylene) Cr ^+. And salts of iron complex cations such as (η5-cyclopentadienyl) (η6-toluene) Fe ⁺ and (η5-cyclopentadienyl) (η6-xylene) Fe ⁺ .

Examples of the anion constituting the above-described salt include 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 ⁻ , sulfonate anion (trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, nonafluorobutanesulfonate anion, methanesulfonate anion, benzenesulfonate Anion, p-toluenesulfonic acid anion, etc.), (CF ₃ SO ₂ ) ₃ C ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , perhalogenate ion, halogenated sulfonate ion, sulfate ion, carbonate ion, aluminate Ion, hexafluorobismuth acid ion, carboxylate ion, arylborate ion, thiocyanate ion, nitrate ion and the like.

  Examples of the thermal cationic polymerization initiator include arylsulfonium salts, aryliodonium salts, allene-ion complexes, quaternary ammonium salts, aluminum chelates, and boron trifluoride amine complexes.

  Examples of the arylsulfonium salts include hexafluoroantimonate salts. In the curable composition of the present invention, for example, trade names “SP-66”, “SP-77” (manufactured by ADEKA Corporation); trade names “Sun Aid SI-60L”, “Sun Aid SI-80L”. Commercial products such as “Sun-Aid SI-100L” and “Sun-Aid SI-150L” (manufactured by Sanshin Chemical Industry Co., Ltd.) can be used. Examples of the aluminum chelate include ethyl acetoacetate aluminum diisopropylate and aluminum tris (ethyl acetoacetate). Examples of the boron trifluoride amine complex include boron trifluoride monoethylamine complex, boron trifluoride imidazole complex, and boron trifluoride piperidine complex.

  Examples of the anionic polymerization initiator include primary amines, secondary amines, tertiary amines, imidazoles, and boron trifluoride-amine complexes. Examples of the imidazoles include 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2,4-diamino-6- [2- Methylimidazolyl- (1)] ethyl-s-triazine, 2-phenylimidazoline, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl- Examples include 2-undecylimidazole. Examples of the tertiary amine include tris (dimethylaminomethyl) phenol, benzyldimethylamine, DBU (1,8-diazabicyclo (5,4,0) undecene-7), and the like.

  The content (blending amount) of the polymerization initiator in the curable composition of the present invention is not particularly limited, but the total amount of the polyorganosilsesquioxane (A) and the polymerizable compound (B) of the present invention is 100%. Is preferably 0.01 to 3.0 parts by weight, more preferably 0.05 to 3.0 parts by weight, and still more preferably 0.1 to 1.0 parts by weight (for example, 0.3 to 1 part by weight). 0.0 parts by weight). By setting the content of the polymerization initiator to 0.01 parts by weight or more, the curing reaction can be efficiently and sufficiently advanced, 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 storability of the curable composition tends to be further improved, and coloring of the cured product tends to be suppressed.

[Polymerization stabilizer]
The polymerization stabilizer is a compound having an action of suppressing the progress of cationic polymerization by trapping cations, saturating the ability of trapping cations by the polymerization stabilizer, and allowing the polymerization to proceed at the stage of deactivation. When the curable composition of the present invention contains a polymerization stabilizer together with a cationic polymerization initiator, after the coating and drying to form an adhesive layer, the progress of polymerization can be suppressed over a long period of time. It is possible to form an adhesive layer that exhibits excellent adhesiveness and is excellent in storage stability by heating at the timing required.

  Examples of the polymerization stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 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, mixed (2,2,6,6-tetramethyl) -4-piperidi /Β,β,β′,β′-tetramethyl-3-9-[2,4,8,10-tetraoxaspiro(5.5)undecane]diethyl)-1,2,3,4-butanetetra Carboxylate, 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” (manufactured by ADEKA), trade names “TINUVIN123”, “TINUVIN152” (Ciba Japan Co., Ltd. )) Hindered amine compounds, (4-hydroxyphenyl) dimethylsulfonium methylsulfite (Sun aid SI auxiliary, manufactured by Sanshin Chemical Industry Co., Ltd.) and the like, for example, 9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (trade name “ADK STAB PEP-36”, ADEKA), bis (2,4-di-t-butylphenyl) pentaerythritol-diphosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (mono, dinonylphenyl) phosphite, Tris (2-ethylhexyl) phosphite, Trisphenyl phosphite, Tris Nonylphenyl) phosphite, may be mentioned phosphorous acid ester compounds such as tris isodecyl phosphite, sulfonium sulfate compounds, phosphorous acid ester compounds are preferred. 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 100 parts by weight with respect to 100 parts by weight of the cationic polymerization initiator. 20 parts by weight, particularly preferably 0.5 to 15 parts by weight.

[Silane coupling agent]
The curable composition of the present invention may preferably contain a silane coupling agent. By containing a silane coupling agent, properties such as better adhesion, weather resistance, heat resistance and the like can be imparted to the resulting cured product.

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

  In the present invention, for example, trade name “KBE-403” (3-glycidoxypropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.), trade name “Z-6040” (3-glycidoxypropyltrimethoxy) Commercial products such as Silane 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 is a polymerizable compound (polyorganosilsesquioxane (A) and polymerizable compound contained in the curable composition of the present invention. The total amount of (B)) is, for example, about 0 to 10 parts by weight with respect to 100 parts by weight, and the upper limit is preferably 5 parts by weight, particularly preferably 3 parts by weight, and most preferably 1 part by weight. The lower limit is preferably 0.005 parts by weight, particularly preferably 0.01 parts by weight.

[solvent]
The curable composition of the present invention may preferably further contain a solvent. The solvent is not particularly limited as long as it can dissolve the polyorganosilsesquioxane (A), the polymerizable compound (B), and additives used as necessary and does not inhibit the polymerization. It will never be done.

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

  The solvent may be used in such a range that the concentration of the nonvolatile content contained in the curable composition is, for example, about 30 to 80% by weight, preferably 40 to 70% by weight, particularly preferably 50 to 60% by weight. It is preferable in that it is excellent in coatability. When the amount of the solvent used is excessive, the viscosity of the curable composition tends to be low, and it becomes difficult to form a layer having an appropriate film thickness (for example, about 0.5 to 30 μm). On the other hand, when 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 it to the support or the adherend.

  The curable composition of the present invention further includes, as other optional components, precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate. Inorganic fillers such as carbon black, silicon carbide, silicon nitride and boron nitride, inorganic fillers obtained by treating these fillers with organosilicon compounds such as organohalosilanes, organoalkoxysilanes and organosilazanes; silicone resins, epoxy resins , Organic resin fine powders such as fluororesins; fillers such as conductive metal powders such as silver and copper, curing aids, stabilizers (antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, heavy metals) Deactivators, etc.), flame retardants (phosphorous flame retardants, halogen flame retardants, inorganic flame retardants, etc.), flame retardant aids, reinforcing materials (other charge) Agents), nucleating agents, lubricants, waxes, plasticizers, mold release agents, impact modifiers, hue modifiers, clearing agents, rheology modifiers (fluidity modifiers, etc.), processability improvers, colorants ( Dyes, pigments, etc.), antistatic agents, dispersants, surface conditioners (such as antifoaming agents, leveling agents, anti-waxing agents), surface modifiers (such as slip agents), matting agents, antifoaming agents, and foam suppression Conventional additives such as an agent, a defoaming agent, an antibacterial agent, an antiseptic, a viscosity modifier, a thickener, a photosensitizer, and a foaming agent may be included. These additives can be used individually by 1 type or in combination of 2 or more types.

  Although the curable composition of this invention is not specifically limited, It can prepare by stirring and mixing each said component, heating at room temperature or as needed. In addition, the curable composition of the present invention can be used as a one-component composition in which each component is mixed in advance, for example, two or more components stored separately. Can be used as a multi-liquid composition (for example, a two-liquid system) used by mixing them at a predetermined ratio before use.

  Although the curable composition of this invention is not specifically limited, It is preferable that it is a liquid at normal temperature (about 25 degreeC). When coating by spin coating, the viscosity of the curable composition is preferably adjusted according to the coating film thickness. When coating with a film thickness of 0.1 to 50 μm, the viscosity is set to 1 to 5000 mPa · s. It is preferable. With this viscosity, for example, a coating film having a uniform film thickness can be formed on a substrate such as a silicon wafer. The viscosity of the curable composition of the present invention was measured using a viscometer (trade name “MCR301”, manufactured by Anton Paar Co., Ltd.) with a swing angle of 5%, a frequency of 0.1 to 100 (1 / s), and temperature: It is measured at 25 ° C.

[Cured product]
The curable composition is cured by advancing the polymerization reaction of the cationic curable compound (polyorganosilsesquioxane (A), polymerizable compound (B), etc. of the present invention) in the curable composition of the present invention. And a cured product (sometimes referred to as “cured product of the present invention”) 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 irradiation 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. Among these, ultraviolet rays are preferable in terms of excellent handleability.

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, etc. Although it can adjust suitably and it is not specifically limited, When irradiating an ultraviolet-ray, it is preferable to set it as about 1-1000 mJ / cm < ² >, for example. For irradiation with active energy rays, for example, a high-pressure mercury lamp, an ultrahigh-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 the irradiation with the active energy ray, a heating treatment (annealing and aging) can be further performed to further advance the curing reaction.

  On the other hand, the conditions for curing the curable composition of the present invention by heating are such that the curable composition of the present invention contains a polyorganosilsesquioxane (A) and a polymerizable compound (B), and therefore 200 ° C. A cured product can be rapidly formed by heating at a low temperature below. That is, it has low temperature curability. As heating temperature, it is 50-190 degreeC, for example. The curing time can be appropriately set.

  The cured product obtained by curing the curable composition of the present invention is excellent in heat resistance, and the thermal decomposition temperature is 200 ° C. or higher (for example, 200 to 500 ° C.), preferably 260 ° C. or higher.

  The cured product obtained by curing the curable composition of the present invention has heat resistance, crack resistance, and excellent adhesion and adhesion to an adherend. Therefore, the curable composition of the present invention can be preferably used as an adhesive (sometimes referred to as an “adhesive composition”), and by curing it, heat resistance, crack resistance, and adherend It can be converted into an adhesive having excellent adhesion and adhesion. The adhesive is used, for example, as a photocurable adhesive when the curable composition of the present invention contains a cationic photopolymerization initiator, and as a thermosetting adhesive when it contains a thermal cationic polymerization initiator. be able to.

  The curable composition (adhesive composition) of the present invention is not limited to the use for obtaining an adhesive sheet or a laminate described later, and is used for various uses for bonding desired articles (parts, etc.) to each other. Can do.

[Adhesive sheet]
By using the curable composition (adhesive composition) of the present invention, an adhesive sheet having at least a substrate and an adhesive layer on the substrate, wherein the adhesive layer is cured according to the present invention. An adhesive sheet (sometimes referred to as “the adhesive sheet of the present invention”) that is a layer of the adhesive composition (sometimes referred to as “the adhesive layer of the present invention”) can be obtained. The adhesive sheet of the present invention includes not only a sheet shape but also a form similar to a sheet shape such as a film shape, a tape shape, and a plate shape. Although the adhesive sheet of this invention is not specifically limited, For example, it can obtain by apply | coating the curable composition of this invention to a base material, and also making it dry as needed. The method of application is not particularly limited, and well-known and commonly used means can be used. Also, the means and conditions for drying are not particularly limited, and conditions under which volatile components such as solvents can be removed as much as possible can be set, and well-known and commonly used means can be used. In particular, the thermosetting time at 130 ° C. of the composition obtained by adding 1 part by weight of the adhesive composition of the present invention to 100 parts by weight of Celoxide 2021P (manufactured by Daicel Corporation) is 3.5 minutes or more. In the case of containing a certain polymerization initiator, it is possible to form an adhesive layer promptly without advancing the curing reaction by heating and drying, and the obtained adhesive layer has an adhesive property at less than 50 ° C. Since there is no adhesive, cutting can be performed without sticking to the cutting blade, and adhesiveness is developed by heating at a temperature that can suppress damage to the adherend layer such as a semiconductor chip, and then promptly Has the property of curing.

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

  As a base material in the adhesive sheet of the present invention, a well-known and commonly used base material (a base material used in the adhesive sheet) can be used, and is not particularly limited. For example, plastic base material, metal base material, ceramic base material Examples include materials, semiconductor substrates, glass substrates, paper substrates, wood substrates, and substrates whose surfaces are painted surfaces. 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. Moreover, the thickness of the said base material is not specifically limited, For example, it can select suitably in the range of 1-10000 micrometers.

  The adhesive sheet of the present invention may have only one adhesive layer of the present invention, or may have two or more types. Further, the thickness of the adhesive layer of the present invention is not particularly limited, and can be appropriately selected within a range of, for example, 0.1 to 10,000 μm. The same applies to other adhesive layers (adhesive layers other than the adhesive layer of the present invention).

  In addition to the base material and the adhesive layer, the adhesive sheet of the present invention may have other layers (for example, an intermediate layer, an undercoat layer, etc.), and is surface-treated with the above-described silane coupling agent or the like. It may be.

[Laminate]
By using the curable composition (adhesive composition) of the present invention, a laminate (laminate) composed of three or more layers (at least three layers), two layers to be adhered, and these At least an adhesive layer (a layer for adhering the adherend layers), and the adhesive layer is a layer of a cured product of the curable composition of the present invention ("adhesion of the present invention"). It is possible to obtain a laminate (sometimes referred to as “a laminate of the present invention”). Although the laminate of the present invention is not particularly limited, for example, the adhesive layer of the present invention is formed on one adherend layer (for example, it can be formed in the same manner as the adhesive layer in the adhesive sheet of the present invention), and The other adhesive layer can be bonded to the adhesive layer, and then the adhesive layer of the present invention can be cured by light irradiation or heating. In addition, the laminate of the present invention is, for example, when the adhesive sheet of the present invention is a single-sided adhesive sheet, the adhesive sheet of the present invention is bonded to an adherend layer, and then the adhesive sheet is irradiated by light irradiation or heating. It can be obtained by curing the adhesive layer of the present invention inside. In this case, a laminate in which the substrate in the adhesive sheet of the present invention hits the adherend layer is obtained. Further, when the adhesive sheet of the present invention is a double-sided adhesive sheet and the base material is a release liner, the laminate of the present invention is bonded to one adhesive layer and peeled off. It can be obtained by peeling the liner, then bonding the other layer to the exposed adhesive layer, and then curing the adhesive layer of the present invention by light irradiation or heating. However, the manufacturing method of the laminate of the present invention is not limited to these methods.

  The adherend 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 of the adherend, or may have three or more layers. Moreover, the thickness of a to-be-adhered body is not specifically limited, For example, it can select suitably in the range of 1-100,000 micrometers. The adherend need not 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. Further, the thickness of the adhesive layer of the present invention is not particularly limited, and can be appropriately selected within a range of, for example, 0.1 to 10,000 μm.

  The laminate of the present invention may have other layers (for example, an intermediate layer, an undercoat layer, other adhesive layers, etc.) in addition to the adherend and the adhesive layer of the present invention. It may be surface-treated with a silane coupling agent or the like.

  The laminate of the present invention has a configuration in which an adherend is bonded by an adhesive layer having excellent heat resistance, crack resistance, adhesion to the adherend, and adhesion. Therefore, the laminate of the present invention can prevent the adherend from being peeled off 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 improved. And, when the laminate of the present invention is a three-dimensional laminate of semiconductor chips, it is more integrated and power-saving than the conventional semiconductor, so if the laminate of the present invention is used, it is smaller and has higher performance. An electronic device can be provided.

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

  Accordingly, examples of the apparatus of the present invention having (or including) the laminate include a server, a workstation, a vehicle-mounted computer, a personal computer, a communication device, a photographing device, and an image display device. Can do.

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 using Alliance HPLC system 2695 (manufactured by Waters), Refractive Index Detector 2414 (manufactured by Waters), column: Tskel GMH _HR- M × 2 (manufactured by Tosoh Corporation), guard column: Tskel guard column H _HR L (manufactured by Tosoh Corporation), column oven: COLUMN HEATER U-620 (manufactured by Sugai), solvent: THF, measurement conditions: 40 ° C., molecular weight: standard polystyrene conversion.
Moreover, the measurement of the ratio [T3 body / T2 body] of T2 body and T3 body in a product was performed by ²⁹ Si-NMR spectrum measurement by JEOL ECA500 (500 MHz).

Preparation Example 1
A 300 ml flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube was charged with 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (hereinafter, “EMS” under a nitrogen stream. 161.5 mmol (39.79 g), phenyltrimethoxysilane (hereinafter referred to as “PMS”) 9 mmol (1.69 g), and acetone 165.9 g were charged and heated to 50 ° C. To the mixture thus obtained, 4.70 g of 5% aqueous potassium carbonate solution (1.7 mmol as potassium carbonate) was added dropwise over 5 minutes, and then 1700 mmol (30.60 g) of water was added dropwise over 20 minutes. . Note that no significant temperature increase occurred during the dropping. Thereafter, the polycondensation reaction was carried out for 4 hours under a nitrogen stream while maintaining the temperature at 50 ° C.
When the product in the reaction solution after the polycondensation reaction was analyzed, the number average molecular weight was 1900 and the molecular weight dispersity was 1.5. The ratio of T2 body and T3 body [T3 body / T2 body] calculated from the ²⁹ Si-NMR spectrum of the product was 10.3.
Thereafter, the reaction solution is cooled, washed with water until the lower layer solution becomes neutral, and after separating the upper layer solution, the solvent is distilled from the upper layer solution until the amount of the solvent reaches 25% by weight under the conditions of 1 mmHg and 40 ° C. This gave a colorless and transparent liquid product (epoxy group-containing polyorganosilsesquioxane).

In addition, when the FT-IR spectrum of the polyorganosilsesquioxane obtained in Preparation Example 1 was measured by the above method, it was confirmed that the polyorganosilsesquioxane had one intrinsic absorption peak in the vicinity of 1100 cm ⁻¹ .

Examples 1-8
(Preparation of adhesive composition)
Adhesive compositions (1) to (8) were prepared by mixing and dissolving according to the compositions and amounts shown in Table 1. The numbers in the table are parts by weight. In addition, the compounding quantity of brand name "SI-150L" was shown by the quantity of solid content conversion.

(Preparation of adhesive layer)
A silane coupling agent (trade name “KBE403”, manufactured by Shin-Etsu Chemical Co., Ltd.), hereinafter referred to as “KBE403” on a silicon plate (size: 2 cm × 5 cm, obtained by dicing a silicon wafer having a diameter of 100 mm, manufactured by SUMCO Corporation) Is sometimes applied by spin coating and heated at 120 ° C. for 5 minutes to obtain a silicon plate with a silane coupling agent layer.
The adhesive composition (1) to (8) is applied to a silicon plate with a silane coupling agent layer by spin coating, and the remaining solvent is removed by heating at 80 ° C. for 4 minutes and then at 100 ° C. for 2 minutes, Silicon plates with adhesive layers (1) to (8) were obtained. The film thicknesses of the adhesive layers (1) to (8) were 5 to 6 μm.

(Production of laminate)
A silane coupling agent (trade name “KBE403”, manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter sometimes referred to as “KBE403”) is applied to a glass plate (4 inches, manufactured by SCHOTT Japan Co., Ltd.) by spin coating, The glass plate with a silane coupling agent layer was obtained by heating at 120 ° C. for 5 minutes. Under reduced pressure, the silane coupling agent layer surface of the prepared glass plate with a silane coupling agent layer is aligned with the adhesive layer (1) to (8) surface, and a pressure of 200 g / cm ² is applied while heating to 60 ° C. After bonding, the laminates (1) to (8) were obtained by heating at 150 ° C. for 30 minutes and then heating at 170 ° C. for 30 minutes.

  The adhesive compositions (1) to (8), adhesive layers (1) to (8), and laminates (1) to (8) obtained in Examples 1 to 8 were evaluated as follows.

[Evaluation]
(Heat-resistant)
The cured product obtained by heating the adhesive composition is heated at a rate of 10 ° C./min in a nitrogen atmosphere using a thermal analyzer (trade name “TG-DTA6300”, manufactured by Seiko Denshi Kogyo Co., Ltd.). The thermogravimetric analysis was performed under the following conditions, and the heat resistance was evaluated according to the following criteria. As shown in FIG. 1, the thermal decomposition temperature (T) is a tangential line where there is no initial weight loss or is gradually decreasing (range indicated by A in the figure), and a sudden weight reduction. It is the temperature at which the tangent of the inflection point where it is occurring (range indicated by B in the figure) intersects.
Evaluation criteria: A case where the thermal decomposition temperature (T) is 260 ° C. or higher is regarded as acceptable (◯).

(Adhesion)
For the cured product of the adhesive layer obtained by heating the adhesive layer in the silicon plate with the adhesive layer, a cross-cut tape test (conforms to JIS K5400-8.5) is performed, and the adhesion to the silicon plate according to the following criteria: Evaluated.
Evaluation criteria: The case where peeling of the adhesive layer is not observed is regarded as acceptable (◯).

(Crack resistance)
The cured product of the adhesive layer obtained by heating the adhesive layer in the silicon plate with the adhesive layer was given a cold shock (heated at 250 ° C. for 30 minutes and then rapidly cooled to room temperature), and cracked according to the following criteria: Was evaluated.
Evaluation criteria: A case where the crack-free portion is 60% or more of the cured product is regarded as acceptable (◯).

(Adhesiveness)
A razor blade (trade name “single-blade trimming razor”, manufactured by Nissin EM Co., Ltd.) was inserted into the adhesive interface of the laminate, and adhesion was evaluated according to the following criteria.
Evaluation criteria: A case where peeling on the adhesive surface is not observed is regarded as acceptable (◯).

[result]
(Heat-resistant)
About the hardened | cured material obtained by heating adhesive composition (1)-(8) at 150 degreeC for 30 minutes, and then heating at 170 degreeC for 30 minutes, thermal decomposition temperature was 260 degreeC or more. The results are shown in Table 1.

(Crack resistance)
The cured product obtained by heating the adhesive layers (1) to (8) at 150 ° C. for 30 minutes and then heating at 170 ° C. for 30 minutes was heated at 250 ° C. for 30 minutes and then rapidly cooled to room temperature. However, the portion without cracks was 60% or more of the cured product. The results are shown in Table 1.

(Adhesion)
The adhesive layers (1) to (8) were heated at 150 ° C. for 30 minutes and then heated at 170 ° C. for 30 minutes. As a result of the cross-cut tape test, the adhesive layers (1) to (8) Peeling of (8) was not observed, and it was confirmed that the adhesiveness was excellent. The results are shown in Table 1.

(Adhesiveness)
When a razor blade was inserted into the adhesive interfaces of the laminates (1) to (8), peeling on the adhesive surface did not occur, and it was confirmed that the adhesive layer in the laminate was excellent in adhesiveness. The results are shown in Table 1.

Comparative Example 1
(Preparation of adhesive composition (9))
An adhesive composition (9) was prepared by mixing and dissolving according to the composition and amount shown in Table 1. The numbers in the table are parts by weight.

(Preparation of adhesive layer)
A silicon plate with an adhesive layer (9) was obtained in the same manner as in Examples 1 to 8, except that the adhesive composition (9) was used in place of the adhesive compositions (1) to (8). The film thickness of the adhesive layer (9) was 5 to 6 μm.

The adhesive layer (9) obtained in Comparative Example 1 was evaluated for crack resistance.
The cured product obtained by heating the adhesive layer (2) at 150 ° C. for 30 minutes and then heating at 170 ° C. for 30 minutes was heated at 250 ° C. for 30 minutes and then rapidly cooled to room temperature. There has occurred. The results are shown in Table 1.

In addition, the symbol in Table 1 shows the following compound.
SQ: Polyorganosilsesquioxane 4004P obtained in Preparation Example 1: Phenol / formaldehyde polycondensate or alkyl (C = 1-9) phenol / formaldehyde polycondensate modified with epichlorohydrin or 2-methylepichlorohydrin Product (trade name “jER4004P”, manufactured by Mitsubishi Chemical Corporation), weight average molecular weight: 5000, epoxy equivalent: 840-975
4005P: Phenol-formaldehyde polycondensate or alkyl (C = 1 to 9) phenol-formaldehyde polycondensate glycidyl etherification modified with epichlorohydrin or 2-methylepichlorohydrin (trade name “jER4005P”, manufactured by Mitsubishi Chemical Corporation) , Weight average molecular weight: 6200, epoxy equivalent: 950-1200
4007P: Phenol / formaldehyde polycondensate or alkyl (C = 1-9) glycidyl etherification modified product of phenol / formaldehyde polycondensate with epichlorohydrin or 2-methylepichlorohydrin (trade name “jER4007P”, manufactured by Mitsubishi Chemical Corporation) , Weight average molecular weight: 20000, epoxy equivalent: 2000-2500
4010P: Phenol / formaldehyde polycondensate or alkyl (C = 1 to 9) phenol / formaldehyde polycondensate glycidyl etherification modified with epichlorohydrin or 2-methylepichlorohydrin (trade name “jER4010P”, manufactured by Mitsubishi Chemical Corporation) , Weight average molecular weight: 45000, epoxy equivalent: 3800-4600
EHPE: 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol (trade name “EHPE3150”, manufactured by Daicel Corporation), weight average molecular weight: 2400, epoxy equivalent: 177
RE-303S-L: Diglycidyl ether of bisphenol F / epichlorohydrin (trade name “RE-303S-L”, manufactured by Nippon Kayaku Co., Ltd.), molecular weight: 312, epoxy equivalent: 156
PGMEA: propylene glycol monomethyl ether acetate SI-150L: antimony-based sulfonium salt (trade name “SI-150L”, manufactured by Sanshin Chemical Industry Co., Ltd.), Celoxide 2021P (manufactured by Daicel Corporation) per 100 parts by weight (The thermosetting time at 130 ° C. of the composition obtained by adding 1 part by weight: 5.4 minutes)
SI aid: (4-Hydroxyphenyl) dimethylsulfonium methylsulfite (trade name “Sun aid SI aid”, manufactured by Sanshin Chemical Industry Co., Ltd.)

  The curable composition of the present invention can be cured at a low temperature to form a cured product excellent in heat resistance, crack resistance, adhesion to an adherend and adhesion. Therefore, it is useful as an adhesive used for bonding semiconductors and electronic parts.

A Area with almost no weight change B Area with sudden weight loss

Claims (13)

Following formula (1)

[In Formula (1), R < ¹ > shows group containing an epoxy group. ]
Having a structural unit represented by the following formula (I)

[In the formula (I), R ^a is a group containing an epoxy 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. Represents a substituted or unsubstituted alkenyl group or a hydrogen atom. ]
A structural unit represented by the following formula (II):

[In the formula (II), R ^b represents 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. Represents a substituted or unsubstituted alkenyl group or a hydrogen atom. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]
The molar ratio of the structural unit represented by [the structural unit represented by the formula (I) / the structural unit represented by the formula (II)] is 5 or more, and is based on the total amount (100 mol%) of the siloxane structural unit. The structural unit represented by the formula (1) and the following formula (4)

[In formula (4), R ¹ is the same as that in formula (1). R ^c is the same as in formula (II). ]
A polyorganosyl having a proportion of structural units represented by the formula: 55 to 100 mol%, a number average molecular weight of 1000 to 3000, and a molecular weight dispersity (weight average molecular weight / number average molecular weight) of 1.0 to 3.0. Sesquioxane (A),
A curable composition comprising a compound (B) other than polyorganosilsesquioxane (A) having a polymerizable functional group.   The curable composition according to claim 1, wherein the polymerizable functional group is at least one selected from the group consisting of an epoxy ring, an oxetane ring, a vinyl ether group, and a vinylphenyl group. Polyorganosilsesquioxane (A) is further represented by the following formula (2)

[In the formula (2), R ² represents 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 group. An alkenyl group of ]
The curable composition of Claim 1 or 2 which has a structural unit represented by these. R ¹ is represented by the following formula (1a)

[In Formula (1a), R ^1a represents a linear or branched alkylene group. ]
A group represented by formula (1b):

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

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

[In formula (1d), R ^1d represents a linear or branched alkylene group. ]
The curable composition of any one of Claims 1-3 which is at least 1 type chosen from the group which consists of group represented by these. The curable composition according to claim 3 or 4, wherein R ² is a substituted or unsubstituted aryl group.   Furthermore, the curable composition of any one of Claims 1-5 containing a polymerization initiator.   Furthermore, the curable composition of any one of Claims 1-6 containing a polymerization stabilizer.   Furthermore, the curable composition of any one of Claims 1-7 containing a silane coupling agent.   It is a composition for adhesives, The curable composition of any one of Claims 1-8.   Hardened | cured material obtained by hardening the curable composition of any one of Claims 1-8. An adhesive sheet having a substrate and an adhesive layer on the substrate,
The adhesive sheet, wherein the adhesive layer is a layer of the curable composition according to claim 9. A laminate composed of three or more layers,
Having two layers to be adhered and an adhesion layer between the layers to be adhered;
The laminate according to claim 9, wherein the adhesive layer is a layer of a cured product of the curable composition according to claim 9.   An apparatus comprising the laminate according to claim 12.

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