JP7069449B2 - Curable compositions, adhesive sheets, cured products, laminates, and equipment - Google Patents

Description

In the present invention, a curable composition, an adhesive sheet having an adhesive layer formed by using the curable composition, a cured product of the curable composition, and a layer to be adhered using the curable composition are attached. The present invention relates to a laminated product and an apparatus having the laminated product.

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

By the way, laminated semiconductors are exposed to high temperatures in the manufacturing process. Therefore, the adhesive used for laminating semiconductors is required to have high adhesion and durability. However, in order to cure the thermosetting adhesive containing BCB, it is necessary to heat it at a high temperature of about 200 to 350 ° C., and the adherend may be damaged by being exposed to the high temperature. was there. Further, the thermosetting adhesive containing a novolak epoxy resin decomposes and generates outgas when it is applied to a high temperature process (for example, 260 to 280 ° C.) such as lead-free solder reflow. There was a problem that the adhesiveness was lowered.

Japanese Unexamined Patent Publication No. 2010-226060

On the other hand, the thermosetting adhesive containing polyorganosylsesquioxane can be cured at a lower temperature than the thermosetting adhesive containing BCB, has excellent heat resistance, and has adhesiveness to the substrate. And it is possible to form a cured product having excellent adhesion. In addition, the adhesiveness can be maintained even when exposed to a high temperature process. However, the cured product of the thermosetting adhesive containing polyorganosyl sesquioxane also has a problem that cracks are likely to occur due to the application of thermal shock.

Therefore, an object of the present invention is to provide a curable composition capable of forming a cured product having excellent crack resistance (or cold thermal impact resistance). Another object of the present invention is to provide a curable composition capable of forming a cured product having excellent heat resistance, crack resistance (or cold thermal impact resistance) by curing at a low temperature. ..
Further, another object of the present invention is to provide a cured product having excellent crack resistance. Further, another object of the present invention is an adhesive sheet having an adhesive layer formed by using the curable composition, a laminate obtained by adhering an adherend using the curable composition, and a laminate. The present invention is to provide an apparatus having the laminate.

As a result of diligent studies to solve the above problems, the present inventor has found that the curable composition obtained by mixing a specific silsesquioxane with another compound having a polymerizable functional group has crack resistance (or crack resistance). It has been found that a cured product having excellent thermal impact resistance can be formed. The present invention has been completed based on these findings.

That is, the present invention is one or more selected from the group consisting of random silsesquioxane (A1) and silsesquioxane having a ladder skeleton (A2), and the following formula (1).
[R ¹ SiO _3/2 ] (1)
[In the formula (1), R ¹ represents a group containing an epoxy group. ]
A curable composition comprising a silsesquioxane (A) having a structural unit represented by (A) and a compound (B) having a polymerizable functional group other than silsesquioxane (A). offer.

The polymerizable functional group is preferably one or more selected from the group consisting of an epoxy group, an oxetanyl group, a vinyl ether group, and a vinyl phenyl group.

The curable composition preferably further contains a polymerization initiator.

The curable composition preferably further contains a polymerization stabilizer.

The curable composition preferably further contains a silane coupling agent.

The curable composition is preferably an adhesive composition.

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

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

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

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

Since the curable composition of the present invention has the above-mentioned structure, it is possible to form a cured product having excellent crack resistance. Further, by using the curable composition, an adhesive sheet and a laminate can be obtained.

The laminate obtained by using the curable composition of the present invention (for example, a three-dimensional laminate of semiconductor chips) has higher integration and power saving than conventional semiconductors, and therefore has a higher mounting density. It is possible to provide high-performance electronic devices while improving them. In particular, cracks and peeling of the adhesive layer in the laminate cause the wiring to be broken during the manufacture of the laminate and in the manufactured semiconductor chips, wafers, etc., resulting in failure of the laminate and equipment using the laminate. Causes. Therefore, an adhesive having high crack resistance after curing is very important as a material constituting the laminate. Therefore, according to the curable composition of the present invention, a highly reliable laminate can be obtained.

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

[Cursable composition]
The curable composition of the present invention is a curable composition (curable) containing silsesquioxane (A) and a compound (B) having a polymerizable functional group other than silsesquioxane (A) as essential components. (Sex resin composition). The curable composition of the present invention can form a cured product having excellent crack resistance by using such a specific silsesquioxane (A) and a specific compound (B) in combination. .. Further, the cured product is also excellent in heat resistance, adhesiveness to an object to be adhered, and adhesion. As described below, 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. ..

(Silsesquioxane (A))
The silsesquioxane (polyorganosilsesquioxane) (A) is one or more sils selected from the group consisting of random silsesquioxane (A1) and silsesquioxane having a ladder skeleton (A2). Sesquioxane. That is, as the silsesquioxane (A), only one of the random silsesquioxane (A1) and the silsesquioxane having a ladder skeleton (A2) may be used, or both may be used. .. In addition, when referring to "silsesquioxane (A)" in this specification, it refers to both random type silsesquioxane (A1) and silsesquioxane (A2) having a ladder skeleton. Further, "random type silsesquioxane (A1)" may be simply referred to as "silsesquioxane (A1)", and "silsesquioxane having a ladder skeleton (A2)" is simply referred to as "silsesquioxane". (A2) "may be referred to. One type of silsesquioxane (A) may be used alone, or two or more types may be used in combination.

The silsesquioxane (A) has a structural unit represented by the following formula (1). That is, the random type silsesquioxane (A1) is a random type silsesquioxane having a structural unit represented by the following formula (1), and the silsesquioxane having a ladder skeleton (A2) has a ladder skeleton. It is a silsesquioxane having a structural unit represented by the following formula (1).
[R ¹ SiO _3/2 ] (1)

The structural unit represented by the above formula (1) is a silsesquioxane structural unit (so-called T unit) generally represented by [RSiO _3/2 ]. In addition, R in the above formula indicates a hydrogen atom or a monovalent organic group, and the same applies to the following. The structural unit represented by the above formula (1) is formed by a hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound (specifically, for example, the compound represented by the formula (a) described later). Will be done.

R ¹ in the formula (1) represents a group containing an epoxy group (monovalent group). That is, silsesquioxane (A) is a cationically curable compound (cationically polymerizable compound) having at least an epoxy group in the molecule. Examples of the group containing an epoxy group include known and conventional groups having an oxylan ring, and the group is not particularly limited, but the following formula (1a) is used from the viewpoint of curability of the curable composition and heat resistance of the cured product. The group represented by the following formula (1b), the group represented by the following formula (1c), and the group represented by the following formula (1d) are preferable, and more preferably the following formula (1a). A group represented by the following formula (1c), more preferably a group represented by the following formula (1a).

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

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

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

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

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

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

As the silsesquioxane (A), as the silsesquioxane structural unit [RSiO _3/2 ], in addition to the structural unit represented by the above formula (1), the structural unit represented by the following formula (2) may be used. You may have.
[R ² SiO _3/2 ] (2)

The structural unit represented by the above formula (2) is a silsesquioxane structural unit (T unit) generally represented by [RSiO _3/2 ]. That is, the structural unit represented by the above formula (2) is a hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound (specifically, for example, the compound represented by the formula (b) described later). Formed by.

R ² in the above formula (2) is a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkyl group. Indicates the alkenyl group of. Examples of the aryl group include a phenyl group, a tolyl group, a naphthyl group and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the cycloalkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like. Examples of the alkyl group include a linear or branched alkyl such as a methyl group, an ethyl group, a propyl group, an n-butyl group, an isopropyl group, an isobutyl group, an s-butyl group, a t-butyl group and an isopentyl group. The group is mentioned. Examples of the alkenyl group include a linear or branched alkenyl group such as a vinyl group, an allyl group, an isopropenyl group, and a 2- (3,4-cyclohexenyl) ethyl group.

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

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

The proportion of each of the above-mentioned silsesquioxane constituent units (the constituent unit represented by the formula (1) and the constituent unit represented by the formula (2)) in the silsesquioxane (A) forms these constituent units. It is possible to appropriately adjust the composition of the raw material (hydrolyzable trifunctional silane).

The ratio of the structural unit represented by the above formula (1) to all the siloxane structural units (100 mol%) constituting the silsesquioxane (A) is not particularly limited, but is 50 mol% or more (for example, 50 mol%). ~ 100 mol%) is preferable, more preferably 60 to 99 mol%, still more preferably 70 to 98 mol%. When the above ratio is 50 mol% or more, the cured product tends to be more excellent in crack resistance. Further, it tends to be more excellent in adhesiveness and heat resistance to the object to be adhered. In the present specification, the ratio of the siloxane constituent units constituting silsesquioxane can be determined, for example, by ²⁹ Si-NMR spectrum measurement. When two or more kinds of silsesquioxane (A) are contained, in the present specification, "all siloxane constituent units constituting silsesquioxane (A)" are all silsesquioxane (A). ) Consists of all siloxane constituent units.

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

In addition to the structural unit represented by the above formula (1) and the structural unit represented by the above formula (2), the silsesquioxane (A) further includes a structural unit represented by the above formula (1) and a structural unit represented by the above formula (1). Silsesquioxane structural unit other than the structural unit represented by the above formula (2) [RSiO _3/2 ], the structural unit represented by [R ₃ SiO _1/2 ] (so-called M unit), [R ₂ SiO It has one or more siloxane structural units selected from the group consisting of the structural unit represented by [ _2/2 ] (so-called D unit) and the structural unit represented by [SiO _4/2 ] (so-called Q unit). May be. Examples of the silsesquioxane structural unit other than the structural unit represented by the above formula (1) and the structural unit represented by the above formula (2) include the structural unit represented by the following formula (3). Can be mentioned.
[HSiO _3/2 ] (3)

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

If the structural unit represented by the above formula (I) is described in more detail, it is represented by the following formula (I'). Further, if the structural unit represented by the above formula (II) is described in more detail, it is represented by the following formula (II'). Each of the three oxygen atoms bonded to the silicon atom represented in the structure represented by the following formula (I') is bonded to another silicon atom (silicon atom not represented by the formula (I')). .. On the other hand, the two oxygen atoms located above and below the silicon atom shown in the structure represented by the following formula (II') are each other silicon atom (silicon atom not shown in the formula (II')). It is combined. That is, both the T3 body and the T2 body are structural units (T units) formed by the hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound.

R ^a in the above formula (I) (same as R ^a in the formula (I')) and R ^b in the formula (II) (same as R ^b in the formula (II')) are epoxy groups, respectively. A group containing, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom. show. Specific examples of R ^a and R ^b include those similar to R ¹ in the above formula (1) and R ² in the above formula (2). In addition, R a in the formula (I) and R ^b in the formula (II ⁾ are groups bonded to a silicon atom in the hydrolyzable trifunctional silane compound used as a raw material of silsesquioxane (A), respectively. A group other than an alkoxy group and a halogen atom; for example, a group derived from ^R1 , ^R2 , a hydrogen atom, etc. in the formulas (a) to (c) described later, or a group of silsesquioxane (A). It is a group obtained by epoxidizing a group bonded to a silicon atom (a group other than an alkoxy group and a halogen atom; for example, R ² in the formula (b) described later) in the hydrolyzable trifunctional silane compound used as a raw material. ..

R c in the above formula (II) (the same ^{applies to R c in} the formula (II')) indicates 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 a linear or branched alkyl group 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 in R ^c in the formula (II) is generally an alkoxy group in the hydrolyzable silane compound used as a raw material for silsesquioxane (A) (for example, as X ¹ to X ³ described later). It is derived from an alkyl group that forms an alkoxy group, etc.).

Examples of the 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 ¹ in the following formula (4) and R ² in the following formula (5) are the same as R ¹ in the above formula (1) and R ² in the above formula (2), respectively. R ^{c in the following formulas (4) to (6) represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, like R c in} the formula (II).
[R ¹ SiO _2/2 (OR ^c )] (4)
[R ² SiO _2/2 (OR ^c )] (5)
[HSiO _2/2 (OR ^c )] (6)

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

The 5% weight loss temperature (T _d5 ) of silsesquioxane (A) under an air atmosphere is not particularly limited, but is preferably 330 ° C. or higher (for example, 330 to 450 ° C.), more preferably 340 ° C. or higher, and further. It is preferably 350 ° C. or higher. When the 5% weight loss temperature is 330 ° C. or higher, the heat resistance of the cured product tends to be further improved. The 5% weight loss temperature is the temperature at which 5% of the weight before heating is reduced when heated at a constant temperature rise rate, and is an index of heat resistance. The 5% weight loss temperature can be measured by TGA (thermogravimetric analysis) under an air atmosphere and a heating rate of 5 ° C./min.

Hereinafter, preferred embodiments of silsesquioxane (A1) and silsesquioxane (A2) will be described.

1. 1. Random silsesquioxane (A1)
The ratio of the structural unit represented by the above formula (1) to all the siloxane structural units (100 mol%) constituting the silsesquioxane (A1) is not particularly limited, but is 50 mol% or more (for example, 50 mol%). ~ 100 mol%) is preferable, more preferably 60 to 95 mol%, still more preferably 70 to 90 mol%. When the above ratio is 50 mol% or more, the cured product tends to be more excellent in crack resistance. Further, it tends to be more excellent in adhesiveness and heat resistance to the object to be adhered.

When the silsesquioxane (A1) contains the structural unit represented by the above formula (2), the above formula (2) in all the siloxane constituent units (100 mol%) constituting the silsesquioxane (A1). The ratio of the structural unit represented by is not particularly limited, but is preferably more than 0 mol% and 50 mol% or less, more preferably 5 to 40 mol%, and particularly preferably 10 to 30 mol%. When the above ratio is 50 mol% or less, the ratio of the structural unit represented by the above formula (1) is relatively increased, and the heat resistance and crack resistance of the cured product tend to be more excellent. Further, when the ratio of the structural unit represented by the above formula (2) in which R ² is a substituted or unsubstituted aryl group is within the above range, it is possible to prevent the degree of curing from becoming too high, and the resistance of the cured product. It tends to have better crackability and adhesiveness.

The silsesquioxane (A1) is a random type silsesquioxane, but there is no problem even if a ladder structure, a cage structure (complete cage structure, incomplete cage structure) and the like are mixed. However, the ratio of the total number of siloxane constituent units constituting the ladder skeleton and cage structure in silsesquioxane (A1) is relative to all the siloxane constituent units (100 mol%) constituting silsesquioxane (A1). It is preferably less than 50 mol%.

The structural unit represented by the above formula (1) in silsesquioxane (A1) may be a siloxane structural unit constituting a random structure, or a siloxane structural unit excluding the siloxane structural unit constituting the random structure. May be.

The fact that silsesquioxane is a random type and has a ladder structure is due to the FT-IR spectrum measurement and the constitution represented by the above formula (I) (T3 body) and the above formula (II). It can be confirmed from the molar ratio [T3 body / T2 body] of the unit (T2 body). The fact that silsesquioxane has an incomplete cage type silsesquioxane structure has no intrinsic absorption peaks near 1050 cm ^-1 and 1150 cm ^{-1 in the FT-IR spectrum, respectively, and one near 1100 cm -1 .} Confirmed by having an intrinsic absorption peak [Reference: R. H. Laney, M. Itoh, A. Sakakibara and T.M. Suzuki, Chem. Rev. 95, 1409 (1995)]. On the other hand, in general, when the FT-IR spectrum has an intrinsic absorption peak near 1050 cm ^-1 and around 1150 cm ^-1 , it is identified as having a ladder-type silsesquioxane structure. Further, the complete cage type silsesquioxane is a polyorganosilsesquioxane composed of only T3 bodies, and T2 bodies are not present in the molecule. Then, when the silsesquioxane does not correspond to any of the ladder type, the complete cage type, and the incomplete cage type, it can be identified as a random type silsesquioxane. However, if it is difficult to identify the type from the intrinsic absorption peak in the FT-IR spectrum, [T3 / T2] is the ladder in consideration of the molecular weight (number average molecular weight, etc.) in addition to the intrinsic absorption peak in the FT-IR spectrum. It can be identified by comprehensively judging whether or not it corresponds to a type or a basket type. The FT-IR spectrum of silsesquioxane can be measured, for example, by the following devices and conditions.
Measuring device: Product name "FT-720" (manufactured by HORIBA, Ltd.)
Measurement method: Transmission method Resolution: 4 cm ^-1
Wavenumber range: 400-4000 cm ^-1
Accumulation number: 16 times

[T3 / T2] in silsesquioxane can be determined, for example, by ²⁹ Si-NMR spectrum measurement. ²⁹ In the Si-NMR spectrum, the silicon atom in the structural unit (T3 body) represented by the above formula (I) and the silicon atom in the structural unit (T2 body) represented by the above formula (II) are at different positions. Since a signal (peak) is shown in (chemical shift), [T3 / T2] can be obtained by calculating the integration ratio of each of these peaks. Specifically, for example, when silsesquioxane has a structural unit represented by the above formula (1) and R ¹ is a 2- (3,4-epoxycyclohexyl) ethyl group, the above formula (1). The signal of the silicon atom in the structure (T3 body) represented by I) appears at -64 to -70 ppm, and the signal of the silicon atom in the structure (T2 body) represented by the above formula (II) is -54 to -60 ppm. Appears in. Therefore, in this case, [T3 body / T2 body] can be obtained by calculating the integral ratio of the signal (T3 body) of −64 to −70 ppm and the signal (T2 body) of −54 to −60 ppm. Even when R ¹ is not a 2- (3,4-epoxycyclohexyl) ethyl group, the signal of the silicon atom in the T3 body and the signal of the silicon atom in the T2 body may fluctuate, respectively, but T3 Since the signal of the silicon atom in the body and the signal of the silicon atom in the T2 body appear in different ranges, [T3 body / T2 body] can be obtained in the same manner as described above.

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

The [T3 / T2] in silsesquioxane (A1) is not particularly limited, but is preferably 0.5 to 5, more preferably 1 to 4, and even more preferably 1.2 to 3. When [T3 body / T2 body] is 0.5 or more, the crack resistance tends to be further improved.

The epoxy equivalent (g / eq) of silsesquioxane (A1) is not particularly limited, but is preferably 150 to 1000, more preferably 160 to 800, still more preferably 170 to 600, and particularly preferably 180 to 400. .. When the epoxy equivalent is within the above range, the amount of epoxy groups in silsesquioxane (A1) becomes appropriate, and the crack resistance of the cured product tends to be more excellent. Further, it tends to be more excellent in adhesiveness and heat resistance to the object to be adhered. In this specification, the epoxy equivalent is measured according to JIS K7236: 2001.

The standard polystyrene-equivalent number average molecular weight (Mn) of silsesquioxane (A1) in terms of standard polystyrene is not particularly limited, but is preferably 500 to 5000, more preferably 700 to 3000, and even more preferably 800 to 2000. Is. When the number average molecular weight is 500 or more, cissing is less likely to occur when the curable composition containing silsesquioxane (A1) is applied to a substrate or the like, and dents or dents are less likely to occur on the coating film surface. Membrane properties tend to improve. In addition, the heat resistance and adhesiveness of the cured product of the curable composition tend to be further improved. On the other hand, when the number average molecular weight is 5000 or less, the compatibility with other components in the curable composition is improved, and the heat resistance of the cured product tends to be further improved.

The molecular weight dispersion (Mw / Mn) in terms of standard polystyrene by gel permeation chromatography of silsesquioxane (A1) is not particularly limited, but is preferably 3.0 or less (for example, 1.0 to 3.0). , More preferably 1.1 to 2.0, still more preferably 1.1 to 1.5. When the molecular weight dispersion is 3.0 or less, the adhesiveness of the cured product tends to be higher. On the other hand, when the molecular weight dispersion degree is 1.1 or more, it tends to be liquid and the handleability tends to be improved.

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

2. 2. Silsesquioxane with a ladder skeleton (A2)
The ladder skeleton in silsesquioxane (A2) is not particularly limited, but preferably has a structural unit represented by the following formula (7) at the terminal.
[R ^a R ³ SiO _2/2 ] (7)

In the above formula (7), Ra 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. , Substituent or unsubstituted alkenyl group, or hydrogen atom. R ³ represents a hydroxy group that may be protected with a protecting group.

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

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

The protective group in the hydroxy group which may be protected by the protective group of R ³ is a protective group commonly used in the field of organic synthesis [for example, C1- of an alkyl group (for example, a methyl group, a t _- butyl group, etc.). ₄ Alkyl group, etc.); Alkenyl group (eg, allyl group, etc.); Cycloalkyl group (eg, cyclohexyl group, etc.); Aryl group (eg, 2,4-dinitrophenyl group, etc.); Aralkyl group (eg, benzyl group, etc.) ); Substituent methyl group (eg, methoxymethyl group, methylthiomethyl group, benzyloxymethyl group, t-butoxymethyl group, 2-methoxyethoxymethyl group, etc.), substituted ethyl group (eg, 1-ethoxyethyl group, etc.), A group capable of forming an acetal or hemiacetal group with a hydroxy group such as a tetrahydropyranyl group, a tetrahydrofuranyl group, a 1-hydroxyalkyl group (for example, 1-hydroxyethyl group, etc.); an acyl group (for example, a formyl group, an acetyl group). , C _1-6 aliphatic acyl group such as propionyl group, butyryl group, isobutyryl group, pivaloyl group; acetacetyl group; aromatic acyl group such as benzoyl group, etc.); alkoxycarbonyl group (for example, C such as methoxycarbonyl group). _1-4 alkoxy-carbonyl group, etc.); aralkyloxycarbonyl group; substituted or unsubstituted carbamoyl group; substituted silyl group (eg, trimethylsilyl group, etc.); substituent when two or more hydroxy groups or hydroxymethyl groups are present in the molecule. Divalent hydrocarbon groups (eg, methylene group, ethylidene group, isopropylidene group, cyclopentylidene group, cyclohexylidene group, benzylidene group, etc.) which may have the above are mentioned. Above all, a substituted silyl group (particularly, from the viewpoint of improving the storage stability of silsesquioxane (A2) and the curable composition while being excellent in crack resistance, heat resistance, and adhesiveness to the adherend of the cured product. , Trimethylsilyl group) is preferable.

R ³ in the above formula (7) is preferably a hydroxy group protected by a protecting group. When the above R ³ is a hydroxy group protected by a protecting group, it is possible to suppress the condensation reaction of the terminal hydroxy group with another siloxane compound, and thus the storage stability of silsesquioxane and the curable composition. There is a tendency for sex to improve.

The proportion of the structural unit represented by the above formula (7) in all the ends (100 mol%) of the ladder skeleton is not particularly limited, but is 30 mol% or more (for example, 30 to 100 mol%). Is preferable, more preferably 50 mol% or more, still more preferably 75 mol% or more. When the ratio of the structural unit represented by the above formula (7) is 30 mol% or more, the storage stability of silsesquioxane (A2) or the curable composition tends to be further improved. In particular, it is preferable that the ratio of the structural unit represented by the above formula (7), in which R ³ is a hydroxy group protected by a protecting group, is within the above range.

The ends of the ladder skeleton may be partially or wholly the same, or may be different. Further, when two or more structural units represented by the above formula (7) are provided at the end of the ladder skeleton, even if the two or more structural units represented by the above formula (7) are the same. It may or may not be different.

The silsesquioxane (A2) is a ladder-type silsesquioxane and may have a ladder skeleton. However, the silsesquioxane (A2) may have a mixture of cage structures (complete cage structure, incomplete cage structure), random structures, and the like. For example, the ratio of the siloxane constituent unit constituting the ladder skeleton to all the siloxane constituent units (100 mol%) constituting the silsesquioxane (A2) is preferably 50 mol% or more. On the other hand, the ratio of the siloxane constituent units in the silsesquioxane (A2) excluding the siloxane constituent units constituting the ladder skeleton is the ratio of all the siloxane constituent units (100 mol%) constituting the silsesquioxane (A2). It is preferably 50 mol% or less.

The structural unit represented by the above formula (1) in silsesquioxane (A2) may be a siloxane structural unit constituting a ladder skeleton, or a siloxane structural unit excluding the siloxane structural unit constituting the ladder skeleton. May be.

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

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

The ratio of the structural unit represented by the above formula (1) to all the siloxane structural units (100 mol%) constituting the silsesquioxane (A2) is not particularly limited, but is 50 mol% or more (for example, 50 mol%). ~ 100 mol%) is preferable, more preferably 60 to 99 mol%, still more preferably 70 to 98 mol%, still more preferably 80 to 97 mol%, and particularly preferably 90 to 96 mol%. When the above ratio is 50 mol% or more, the cured product tends to be more excellent in crack resistance, heat resistance, and adhesiveness to the adherend. The ratio of the structural unit represented by the above formula (1) to all the siloxane structural units (100 mol%) constituting the ladder skeleton is preferably within the above range.

When the silsesquioxane (A2) contains the structural unit represented by the above formula (2), the above formula (2) in all the siloxane constituent units (100 mol%) constituting the silsesquioxane (A2). The ratio of the structural unit represented by is not particularly limited, but is preferably more than 0 mol% and 50 mol% or less, more preferably 1 to 40 mol%, still more preferably 2 to 30 mol%, still more preferably 3. It is -20 mol%, particularly preferably 4-10 mol%. When the above ratio is 50 mol% or less, the ratio of the structural unit represented by the above formula (1) is relatively increased, and the heat resistance and crack resistance of the cured product tend to be more excellent. Further, when the ratio of the structural unit represented by the above formula (2) in which R ² is a substituted or unsubstituted aryl group is within the above range, it is possible to prevent the degree of curing from becoming too high, and the resistance of the cured product. It tends to have better crackability and adhesiveness. It is preferable that the ratio of the structural unit represented by the above formula (2) to all the siloxane structural units constituting the ladder skeleton is within the above range.

The [T3 / T2] in silsesquioxane (A2) (particularly the ladder skeleton) is not particularly limited, but is preferably 0.2 to 5, more preferably 0.3 to 4, and even more preferably 0. 33 to 3. When [T3 body / T2 body] is 0.2 or more, the crack resistance and the adhesiveness of the cured product tend to be further improved.

The epoxy equivalent (g / eq) of silsesquioxane (A2) is not particularly limited, but is preferably 200 to 1000, more preferably 210 to 800, still more preferably 220 to 500, and particularly preferably 230 to 300. .. When the epoxy equivalent is within the above range, the amount of epoxy groups in silsesquioxane (A2) is moderately large, and the cured product tends to be more excellent in crack resistance. Further, it tends to be more excellent in heat resistance and adhesiveness to an object to be adhered.

The standard polystyrene-equivalent number average molecular weight (Mn) of silsesquioxane (A2) in terms of standard polystyrene is not particularly limited, but is preferably 500 to 5000, more preferably 700 to 3000, and even more preferably 800 to 2000. Is. When the number average molecular weight is 500 or more, cissing is less likely to occur when the curable composition containing silsesquioxane (A2) is applied to a substrate or the like, and dents or dents are less likely to occur on the coating film surface. Membrane properties tend to improve. In addition, the heat resistance and adhesiveness of the cured product of the curable composition tend to be further improved. On the other hand, when the number average molecular weight is 5000 or less, the compatibility with other components in the curable composition is improved, and the heat resistance of the cured product tends to be further improved.

The molecular weight dispersion (Mw / Mn) in terms of standard polystyrene by gel permeation chromatography of silsesquioxane (A2) is not particularly limited, but is preferably 3.0 or less (for example, 1.0 to 3.0). , More preferably 1.1 to 2.0, still more preferably 1.1 to 1.5. When the molecular weight dispersion is 3.0 or less, the adhesiveness of the cured product tends to be higher. On the other hand, when the molecular weight dispersion degree is 1.1 or more, it tends to be liquid and the handleability tends to be improved.

Among them, silsesquioxane (A2) preferably has a structural unit represented by the above formula (7) at the end of the ladder skeleton and has the above number average molecular weight of 500 to 5000. In this case, the cured product is more excellent in terms of heat resistance and adhesiveness.

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

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

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

X ¹ in the above formula (a) represents an alkoxy group or a halogen atom. Examples of the alkoxy group in X ¹ include an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group and an isobutyloxy group. Further, examples of the halogen atom in X ¹ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. Among them, as X ¹ , an alkoxy group is preferable, and a methoxy group and an ethoxy group are more preferable. The three X ^1s may be the same or different.

The compound represented by the above formula (b) is a compound forming a structural unit represented by the formula (2) in the silsesquioxane (A). R ² in the formula (b) is a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted, as in the case of R ² in the above formula (2). An alkyl group of, or a substituted or unsubstituted alkenyl group is shown. However, at least the compound represented by the above formula (b) in which R ² is a substituted or unsubstituted alkenyl group is used. As R ² in the formula (b) other than the substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group is preferable, and a substituted or unsubstituted aryl group is more preferable. It is preferably a phenyl group.

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

The compound represented by the above formula (c) is a compound forming a structural unit represented by the formula (3) in the silsesquioxane (A). 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, as X3 ^, an alkoxy group is preferable, and a methoxy group and an ethoxy group are more preferable. The ^three X3s may be the same or different.

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

The amount and composition of the hydrolyzable silane compound used can be appropriately adjusted according to the desired structure of silsesquioxane (A). For example, the amount of the compound represented by the above formula (b) is not particularly limited, but is preferably 10 to 100 mol%, more preferably 10 to 100 mol%, based on the total amount (100 mol%) of the hydrolyzable silane compound used. Is 65 to 100 mol%, more preferably 80 to 99 mol%.

The amount of the compound represented by the above formula (b) in which R ² is a group other than the substituted or unsubstituted alkenyl group is not particularly limited, but the total amount (100 mol%) of the hydrolyzable silane compound used. ), It is preferably 0 to 70 mol%, more preferably 0 to 60 mol%, still more preferably 0 to 40 mol%, and particularly preferably 1 to 15 mol%.

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

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

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

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

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

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

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

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

When preparing silsesquioxane (A1), the reaction temperature of the hydrolysis and condensation reactions is not particularly limited, but is preferably 15 to 100 ° C, more preferably 20 to 80 ° C. By controlling the reaction temperature within the above range, the degree of polymerization tends to be improved. The reaction time of the hydrolysis and condensation reactions is not particularly limited, but is preferably 0.1 to 10 hours, more preferably 1 to 8 hours.

When preparing silsesquioxane (A2), the reaction conditions for hydrolyzing and condensing the hydrolyzable silane compound are particularly such that silsesquioxane has a ladder skeleton. It is important to choose the conditions. The reaction temperature of the hydrolysis and condensation reaction is not particularly limited, but is preferably −20 to 100 ° C., more preferably 0 to 80 ° C. By controlling the reaction temperature within the above range, it tends to be possible to efficiently have a ladder skeleton. The reaction time of the hydrolysis and condensation reactions is not particularly limited, but is preferably 0.1 to 10 hours, more preferably 1.5 to 8 hours.

Further, in the preparation of silsesquioxane (A1) and the preparation of silsesquioxane (A2), the hydrolysis and condensation reactions can be carried out under normal pressure, under pressure or under reduced pressure. .. The atmosphere for carrying out the hydrolysis and condensation reactions is not particularly limited, and may be, for example, any of an inert gas atmosphere such as a nitrogen atmosphere and an argon atmosphere, and an oxygen presence such as under air. However, it is preferable to use an inert gas atmosphere. Further, in the above hydrolysis and condensation reaction, the reaction temperature may be constant or may be changed in the middle.

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

In the above-mentioned alkenyl group-containing silsesquioxane, the carbon-carbon double bond portion in the alkenyl group is subsequently epoxidized by an epoxidation reaction by a known or conventional method to form an epoxy group, and the silsesquioxane (A1). ) Or silsesquioxane (A2) is obtained. The epoxidation reaction is not particularly limited, but can be carried out by using, for example, an oxidizing agent such as peracid.

Further, as the above-mentioned oxidizing agent, known or commonly used oxidizing agents such as hydrogen peroxide and organic peracid can be used, and the present invention is not particularly limited. Examples thereof include benzoic acid, trifluoroperacetic acid, and metachloroperbenzoic acid. It should be noted that one type of oxidizing agent may be used alone, or two or more types may be used in combination.

More specifically, the above-mentioned epoxidation reaction can be carried out according to, for example, a well-known and commonly used method described in Japanese Patent Application Laid-Open No. 60-161973.

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

Further, in the case of silsesquioxane (A2) having a protecting group protected by a protecting group at the end of the rudder skeleton, the hydroxy group at the end of the rudder skeleton is protected by the protecting group before or after the epoxidation reaction. A reaction (end cap reaction) may be carried out. The end cap reaction can be carried out by a known or conventional method. For example, when the protecting group is a trimethylsilyl group, the endcap reaction can be carried out by adding hexamethyldisiloxane and stirring after the hydrolysis and condensation reactions.

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

In particular, in order to make it easier to obtain a random type silsesquioxane, a compound represented by the formula (b) in which R ² is a substituted or unsubstituted alkenyl group is hydrolyzed using an acid catalyst (particularly, a carboxylic acid). A method of decomposing and condensing the reaction and then epoxidizing is preferable.

Further, in order to make it easier to obtain silsesquioxane having a ladder skeleton (particularly, silsesquioxane having an epoxy equivalent within a specific range), the formula (b) in which R ² is a substituted or unsubstituted alkenyl group is used. A method in which the compound represented by (1) is hydrolyzed and condensed using an acid catalyst (particularly, mineral acid) and then epoxidized is preferable. Further, in the above hydrolysis and condensation reaction, it is preferable to react at a relatively low temperature for a long time under acidic conditions and then raise the temperature, whereby a one-membered ring cyclotetrasiloxane is first efficiently obtained, and then the said. It is presumed that the one-membered ring is polycyclized, and silsesquioxane (A2) can be obtained more efficiently. The temperature range and the total reaction time at this time can be appropriately selected from the above ranges.

The content (blending amount) of silsesquioxane (A) in the curable composition of the present invention is not particularly limited, but is 30 to 85 with respect to the total amount (100% by weight) of the curable composition excluding the solvent. The weight is preferably%, more preferably 35 to 80% by weight, still more preferably 40 to 75% by weight, and particularly preferably 45 to 58% by weight. When the content is 30% by weight or more, the heat resistance of the cured product tends to be further improved. When the content is 85% by weight or less (particularly, 58% by weight or less), the crack resistance tends to be further improved.

The content (blending amount) of silsesquioxane (A) with respect to the total amount (100% by weight) of the curable compound contained in the curable composition of the present invention is not particularly limited, but is preferably 30 to 90% by weight. It is more preferably 35 to 85% by weight, still more preferably 40 to 75% by weight. When the content is 30% by weight or more, the heat resistance of the cured product tends to be further improved.

[Compound (B)]
The curable composition of the present invention contains a compound (B) having a polymerizable functional group (hereinafter, may be simply referred to as “compound (B)”) in addition to the above-mentioned silsesquioxane (A). do. The compound (B) is a compound other than silsesquioxane (A).

The "polymerizable functional group" of the compound (B) is not particularly limited as long as it is a polymerizable functional group. As the polymerizable functional group, an epoxy group, an oxetanyl group, a vinyl ether group, and a vinylphenyl group are preferable, and an epoxy group is more preferable, from the viewpoint of improving the crack resistance of the cured product. The compound (B) may contain only one kind of the above-mentioned polymerizable functional group, or may contain two or more kinds of the above-mentioned polymerizable functional group.

The number of the polymerizable functional groups contained in one molecule of compound (B) is not particularly limited, but is preferably 1 to 50, more preferably 1 to 30, and even more preferably 2 to 20.

The compound (B) may be a low molecular weight compound such as a monomer or an oligomer, or may be a high molecular weight compound obtained by polymerizing the monomer or the oligomer. The molecular weight of the compound (B) (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 300 to 100,000 from the viewpoint of improving the crack resistance of the cured product. ..

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

The polymerizable functional group equivalent of the compound (B) is not particularly limited, but is preferably 100 to 100,000, more preferably 150 to 50,000, from the viewpoint of improving the crack resistance of the cured product. The polymerizable functional group equivalent means the molecular weight of the compound per polymerizable functional group (in the case of a polymer compound, the weight average molecular weight), and can be measured by a known method. For example, when the polymerizable functional group is an epoxy group, it can be measured by a method according to JIS K 7236: 2001 (method for determining the epoxy equivalent of an epoxy resin).

As the compound (B) having an epoxy group, a known or commonly used compound having one or more epoxy groups (oxylan rings) in the molecule other than silsesquioxane (A) can be used and is not particularly limited. However, for example, an alicyclic epoxy compound (alicyclic epoxy resin), an aromatic epoxy compound (aromatic epoxy resin), an aliphatic epoxy compound (aliphatic epoxy resin), and the like can be mentioned.

Examples of the alicyclic epoxy compound include known and commonly used compounds having one or more alicyclics and one or more epoxy groups in the molecule, and are not particularly limited, but for example, (1) in the molecule. A compound having an epoxy group (referred to as "alicyclic epoxy group") composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic; (2) The epoxy group is directly bonded to the alicyclic by a single bond. (3) Compounds having an alicyclic and a glycidyl ether group in the molecule (glycidyl ether type epoxy compound) and the like can be mentioned.

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

In the above formula (i), Y represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include a divalent hydrocarbon group, an alkenylene group in which a part or all of a carbon-carbon double bond is epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and the like. Examples thereof include a group in which a plurality of groups are linked. A substituent such as an alkyl group may be bonded to one or more of the carbon atoms constituting the cyclohexane ring (cyclohexene oxide group) in the formula (i).

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

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

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

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

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

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

Examples of the aromatic epoxy compound include bisphenols (for example, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, etc.) and an epibis-type glycidyl ether type epoxy resin obtained by a condensation reaction with epihalohydrin; these epis. High molecular weight epibistype glycidyl ether type epoxy resin obtained by further addition reaction of bistype glycidyl ether type epoxy resin with the above bisphenols; phenols (eg, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol) F, bisphenol S, etc.) and aldehydes (eg, formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, salicylaldehyde, etc.) and polyhydric alcohols obtained by condensing reaction with epihalohydrin are further subjected to condensation reaction. Alkyl-type glycidyl ether-type epoxy resin (for example, a substituted or unsubstituted glycidyl etherified modified product of a polycondensate of substituted or unsubstituted phenol and formaldehyde); two phenol skeletons at the 9-position of the fluorene ring. Examples thereof include epoxy compounds in which a glycidyl group is bonded directly or via an alkyleneoxy group to an oxygen atom obtained by removing a hydrogen atom from the hydroxy group of the phenol skeleton. The epoxy resin having a bisphenol skeleton may be referred to as a bisphenol type epoxy resin (for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, etc.).

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

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

As the compound (B) having a vinyl ether group, a known or commonly used compound having one or more vinyl ether groups in the molecule can be used, and is not particularly limited, but for example, 2-hydroxyethyl vinyl ether (ethylene glycol monovinyl ether). ), 3-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-hydroxymethylpropyl vinyl ether, 4-hydroxycyclohexylvinyl ether, 1,6-hexanediol monovinyl ether, 1,6-hexanediol divinyl ether , 1,8-octanediol divinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, 1,4-cyclohexanedimethanol divinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanol divinyl ether, 1,2-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, penta. Ethylene 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, zip Lopyrene 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, oligopropylene glycol Divinyl ether, polypropylene glycol monovinyl ether, polypropylene glycol divinyl ether, isosorbide divinyl ether, oxanorborne divinyl ether, phenylvinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octyl vinyl ether, cyclohexyl vinyl ether, hydroquinone divinyl ether, 1,4-butane Divinyl divinyl ether, cyclohexanedimethanol divinyl ether, trimethylolpropane divinyl ether, trimethylolpropanetrivinyl ether, bisphenol A divinyl ether, bisphenol F divinyl ether, hydroxyoxanorbornane methanol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol Examples thereof include trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, and dipentaerythritol hexavinyl ether.

Further, as the 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 yellowing is less likely to occur due to heating). There is an advantage that a substance (adhesive layer) can be 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, and more preferably 1 or 2.

As the compound (B) having a vinyl phenyl group, a known or commonly used compound having one or more vinyl phenyl groups in the molecule can be used, and is not particularly limited, but for example, styrene, divinylbenzene, methoxystyrene, and the like. Ethoxystyrene, hydroxystyrene, vinylnaphthalene, vinylanthracene, 4-vinylphenyl acetate, 4-vinylphenylboronic acid, boronic acid (4-vinylphenyl), 4-ethenylphenylboronic acid, N- (p-vinylphenyl) Maleimide and the like can be mentioned.

In the curable composition of the present invention, it is preferable to use a compound having an epoxy group as the compound (B) in combination with the silsesquioxane (A). As the compound (B) having an epoxy group, an alicyclic epoxy compound and an aromatic epoxy compound are more preferable, and more preferably, a compound in which an epoxy group is directly bonded to the aliquot by a single bond, Epibis type. Glysidyl ether type epoxy resin, novolak alkyl type glycidyl ether type epoxy resin, particularly preferably the compound represented by the above formula (ii), bisphenol A type epoxy resin, bisphenol F type epoxy resin, substituted or unsubstituted phenol and formaldehyde. It is a glycidyl etherified modified product with a substituted or unsubstituted epichlorohydrin of the polycondensate of. When these compounds (B) are used, the crack resistance of the cured product tends to be higher.

In the curable composition of the present invention, the compound (B) may be used alone or in combination of two or more. The compound (B) can also be produced by a known or conventional method, and for example, the product names "EHPE3150", "Selokiside 2021P" (all manufactured by Daicel Corporation), the product names "jER4004P", " Commercial products such as "jER4005P", "jER4007P", "jER4010P" (all manufactured by Mitsubishi Chemical Corporation), and the trade name "RE-303S-L" (manufactured by Nippon Kayaku Co., Ltd.) can also be used.

The content (blending amount) of the compound (B) with respect to the total amount (100% by weight) of the curable compound contained in the curable composition of the present invention is not particularly limited, but is preferably 15 to 70% by weight, more preferably. It is 20 to 65% by weight, more preferably 25 to 60% by weight, and particularly preferably 42 to 55% by weight. When the content is 15% by weight or more (particularly 42% by weight or more), the crack resistance tends to be further improved. By setting the content to 70% by weight or less (particularly 55% by weight or less), the desired performance for the curable composition or the cured product (for example, quick curing or viscosity adjustment for the curable composition) can be achieved. The heat resistance of the cured product tends to be improved. The content of the compound (B) having an epoxy group is preferably within the above range, and in this case, 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, the crack resistance of the cured product is particularly high, and the heat resistance tends to be further improved.

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

In the present invention, the adhesive layer can be quickly formed by heating and drying without advancing the curing reaction, and the adhesive is not adhered at a temperature lower than 50 ° C., and damage to the semiconductor chip can be suppressed. It is preferable to use a polymerization initiator having the following curing properties in that an adhesive layer having the property of developing adhesiveness by heating at a high temperature and then rapidly curing until it becomes tack-free can be obtained. ..

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

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

The thermosetting time in the present invention is defined as a method according to JIS K5909 (1994) until the curable composition is heated on a hot plate to become rubbery (more specifically, cured). It is the time until the thread does not rise to the tip of the needle. When a polymerization initiator having a thermal curing time of 3.5 minutes or more is used, cation species are less likely to be generated when a cationic polymerization initiator is used during heat drying, and anionic species are less likely to be generated when an anionic polymerization initiator is used. After that, the polymerization does not easily proceed at room temperature, so that an adhesive layer having better storage stability tends to be obtained.

In the present invention, it is particularly preferable to use a cationic polymerization initiator because the curing time until it becomes tack-free can be further shortened. Cationic polymerization initiators include photocationic polymerization initiators and thermal cationic polymerization initiators.

As the photocationic polymerization initiator, a known or conventional photocationic polymerization initiator can be used, for example, a sulfonium salt (salt of sulfonium ion and anion), iodonium salt (salt of iodonium ion and anion). , Selenium salt (salt of selenium ion and anion), ammonium salt (salt of ammonium ion and anion), phosphonium salt (salt of phosphonium ion and anion), salt of transition metal complex ion and anion, etc. .. These can be used alone or in combination of two or more.

Examples of the sulfonium salt include triphenyl sulfonium salt, tri-p-tolyl sulfonium salt, tri-o-tolyl sulfonium salt, tris (4-methoxyphenyl) sulfonium salt, 1-naphthyldiphenyl sulfonium salt and 2-naphthyl diphenyl. 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 , 4- (P-trilthio) phenyldi- (p-phenyl) sulfonium salt and other triarylsulfonium salts; Diarylsulfonium salt; monoarylsulfonium salt such as phenylmethylbenzylsulfonium salt, 4-hydroxyphenylmethylbenzylsulfonium salt, 4-methoxyphenylmethylbenzylsulfonium salt; dimethylphenacylsulfonium salt, phenacyltetrahydrothiophenium salt, dimethylbenzyl Examples thereof include trialkylsulfonium salts such as sulfonium salts.

Examples of the diphenyl [4- (phenylthio) phenyl] sulfonium salt include the trade name "CPI-101A" (manufactured by San-Apro Co., Ltd., diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate 50% propylene carbonate solution. ), Commercial products such as trade name "CPI-100P" (manufactured by San-Apro Co., Ltd., diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphart 50% propylene carbonate solution) can be used.

Examples of the iodonium salt include the trade name "UV9380C" (manufactured by Momentive Performance Materials Japan GK, bis (4-dodecylphenyl) iodonium hexafluoroantimonate 45% alkyl glycidyl ether solution), and the trade name " RHODORSIL PHOTOINITIOTOR 2074 "(manufactured by Rhodia Japan Co., Ltd., tetrakis (pentafluorophenyl) borate [(1-methylethyl) phenyl] (methylphenyl) iodonium), trade name" WPI-124 "(Wako Pure Chemical Industries, Ltd.) Co., Ltd.), 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 salts, tri-p-tolyl selenium salts, tri-o-tolyl selenium salts, tris (4-methoxyphenyl) selenium salts, 1-naphthyldiphenyl selenium salts and the like. Salts; diallyl selenium salts such as diphenylphenacyl selenium salt, diphenylbenzyl selenium salt, diphenylmethyl selenium salt; monoaryl selenium salts such as phenylmethyl benzyl selenium salt; trialkyl selenium salts such as dimethyl phenacyl selenium salt and the like. ..

Examples of the ammonium salt include tetra (tetramethylammonium salt, ethyltrimethylammonium salt, diethyldimethylammonium salt, triethylmethylammonium salt, tetraethylammonium salt, trimethyl-n-propylammonium salt, trimethyl-n-butylammonium salt and the like). Alkylammonium salt; Pyrrolidium salt such as N, N-dimethylpyrrolidium salt, N-ethyl-N-methylpyrrolidium salt; N, N'-dimethylimidazolinium salt, N, N'-diethylimidazolinium salt, etc. Imidazolinium salt; tetrahydropyrimidium salt such as N, N'-dimethyltetrahydropyrimidium salt, N, N'-diethyltetrahydropyrimidium salt; N, N-dimethylmorpholinium salt, N, N -Morholinium salt such as diethylmorpholinium salt; piperidinium salt such as N, N-dimethylpiperidinium salt, N, N-diethylpiperidinium salt; pyridinium salt such as N-methylpyridinium salt and N-ethylpyridinium salt. Imidazolium salts such as N, N'-dimethylimidazolium salt; quinolium salts such as N-methylquinolium salt; isoquinolium salts such as N-methylisoquinolium salt; thiazonium salts such as benzylbenzothiazonium salt; Examples thereof include acridium salts such as benzyl acridium salts.

Examples of the phosphonium salt include tetraarylphosphonium salts such as tetraphenylphosphonium salt, tetra-p-tolylphosphonium salt and tetrakis (2-methoxyphenyl) phosphonium salt; triarylphosphonium salt such as triphenylbenzylphosphonium salt; triethyl. 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 chromium (η ⁵ -cyclopentadienyl) (η ⁶ -toluene) Cr ⁺ , (η ⁵ -cyclopentadienyl) (η ⁶ -xylene) Cr ⁺ and the like. Salts of complex cations; salts of iron complex cations such as (η ⁵ -cyclopentadienyl) (η ⁶ -toluene) Fe ⁺ , (η ⁵ -cyclopentadienyl) (η ⁶ -xylene) Fe ⁺ , etc. Be done.

Examples of the anions constituting the above-mentioned 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- ^, Sulfonic acid anion (trifluoromethane sulfonic acid anion, pentafluoroethane sulfonic acid anion, nonafluorobutane sulfonic acid anion, methane sulfonic acid anion, benzene sulfonic acid Anion, p-toluene sulfonic acid anion, etc.), (CF ₃ SO ₂ ) ₃ C- ^, (CF ₃ SO ₂ ) ₂ N- ^, perhalogenate ion, halide sulfonic acid ion, sulfate ion, carbonate ion, aluminic acid Examples thereof include an ion, a hexafluorobismasic acid ion, a carboxylate ion, an arylborate ion, a thiocyanate ion, and a nitrate ion.

Examples of the thermal cationic polymerization initiator include aryl sulfonium salts, aryl iodonium salts, allen-ion complexes, quaternary ammonium salts, aluminum chelates, boron trifluoride amine complexes and the like. These can be used alone or in combination of two or more. Moreover, as an anion constituting the above-mentioned salt, the same thing as an anion in a photocationic polymerization initiator can be mentioned.

Examples of the aryl sulfonium salt include hexafluoroantimonate salt and the like. In the curable composition of the present invention, for example, trade names "SP-66" and "SP-77" (all manufactured by ADEKA Corporation); trade names "Sun Aid SI-60L" and "Sun Aid SI-60S". , "Sun Aid SI-80L", "Sun Aid SI-100L", "Sun Aid SI-150L" (all manufactured by Sanshin Chemical Industry Co., Ltd.) and the like can be used. Examples of the aluminum chelate include ethyl acetoacetate aluminum diisopropyrate, aluminum tris (ethyl acetoacetate) and the like. Examples of the boron trifluoride amine complex include a boron trifluoride monoethylamine complex, a boron trifluoride imidazole complex, and a boron trifluoride piperidine complex.

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

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

When the curable composition of the present invention contains a polymerization initiator, the content (blending amount) of the polymerization initiator is not particularly limited, but the total amount of silsesquioxane (A) and compound (B) is 100. With respect to parts by weight, 0.005 to 5 parts by weight is preferable, more preferably 0.01 to 3 parts by weight, still more preferably 0.03 to 1 part by weight, and particularly preferably 0.07 to 0.8 parts by weight. Is. By setting the content of the polymerization initiator to 0.005 part by weight or more, the curing reaction can be efficiently and sufficiently proceeded, and the adhesiveness of the cured product tends to be further improved. On the other hand, when the content of the polymerization initiator is 5 parts by weight or less, the storage stability of the curable composition tends to be improved and the coloring of the cured product tends to be suppressed.

(Polymerization stabilizer)
The above-mentioned polymerization stabilizer is a compound having an action of suppressing the progress of cation polymerization by trapping cations, saturate the ability of the polymerization stabilizer to trap cations, and proceed with polymerization at the stage of deactivation. When the curable composition of the present invention contains a polymerization stabilizer together with a cationic polymerization initiator, it is coated and dried to form a layer of the curable composition (for example, an adhesive layer), and then polymerized over a long period of time. Forming a layer (for example, an adhesive layer) of a curable composition having excellent storage stability, which can suppress the progress and exhibits excellent adhesiveness by heating at a timing when adhesiveness is required. Can be done. In addition, the cured product tends to be more excellent in adhesiveness and adhesion to the adherend.

Examples of the polymerization stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and poly ([6- (1,1,3,3-tetramethylbutyl) imino-1, 3,5-Triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] Hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) Imino]), Tetrakiss (2,2,6,6-tetramethyl-4-piperidyl) Butane-1,2,3,4-tetracarboxylate, 2,2,6,6-tetramethyl-4-piperidi Nylbenzoate, (mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, 3,9-bis (2,3-di-t) -Butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, mixed (2,2,6,6-tetramethyl-4-piperidyl / β , Β, β', β'-tetramethyl-3-9- [2,4,8,10-tetraoxaspiro [5.5] undecane] diethyl) -1,2,3,4-butanetetracarboxylate , Poly ([6-N-morphoryl-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2) , 6,6-Tetramethyl-4-piperidyl) imino]), [N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl-2- (2,2,6,6) -Tetramethyl-4-piperidyl) imino] Propionamide, trade names "LA-77", "LA-67", "LA-57" (all manufactured by ADEKA Co., Ltd.), trade names "TINUVIN123", "TINUVIN152" (Above, manufactured by Ciba Japan Co., Ltd.) and (4-hydroxyphenyl) dimethylsulfonium methylsulfite (for example, trade name "Sun Aid SI Auxiliary Agent", manufactured by Sanshin Chemical Industry Co., Ltd.) ) And other sulfonium sulfate compounds, such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, bis (2,6-di-t-butyl-4-methylphenyl). Pentaerythritol-diphosphite (trade name "Adecastab PEP-36", manufactured by ADEKA Co., Ltd.), bis (2,4-di-t-butylphenyl) pentaerythritol-diphosphite, Tris (2, 4-Di-t-butylphenyl) phosphite, tris (mono, dinonylphenyl) phosphite, tris (2-ethylhexyl) phosphite, trisphenylphosphite, tris (monononylphenyl) phosphite, trisisodecylphos Examples thereof include phosphite ester compounds such as phyto. Of these, sulfonium sulfate compounds and phosphite ester compounds are preferable from the viewpoint of making it more difficult for the curable composition (adhesive) to partially cure during drying and having better adhesion of the cured product to the adherend. .. These can be used alone or in combination of two or more.

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

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

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

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

When the curable composition of the present invention contains a silane coupling agent, the amount of the silane coupling agent used is, for example, 0 with respect to 100 parts by weight of the total amount of silsesquioxane (A) and compound (B). It is about 10 parts by weight, and the upper limit thereof 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. Examples of the solvent include water, organic solvents and the like, which can dissolve silsesquioxane (A), compound (B) and, if necessary, additives used, and do not inhibit polymerization. There is no particular limitation as long as it is a thing.

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

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

Further, the curable composition of the present invention has, as other optional components, precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate. , Carbon black, silicon carbide, silicon nitride, boron nitride and other inorganic fillers, inorganic fillers obtained by treating these fillers with organic silicon compounds such as organohalosilane, organoalkoxysilane and organosilazane; silicone resin, epoxy resin. , Fluorine resin and other organic resin fine powders; Fillers such as silver, copper and other conductive metal powders, curing agents (amine-based curing agents, polyaminoamide-based curing agents, acid anhydride-based curing agents, phenol-based curing agents, etc. ), Curing aid, Curing accelerator (imidazole, alkali metal or alkaline earth metal alkoxide, phosphin, amide compound, Lewis acid complex compound, sulfur compound, boron compound, condensing organic metal compound, etc.), stabilizer (Antioxidant, UV absorber, light resistance stabilizer, heat stabilizer, heavy metal inactivating agent, etc.), flame retardant (phosphorus flame retardant, halogen flame retardant, inorganic flame retardant, etc.), flame retardant aid , Reinforcing material (other fillers, etc.), nucleating agent, lubricant, wax, plasticizing agent, mold release agent, impact resistance improving agent, hue improving agent, clearing agent, rheology adjusting agent (fluidity improving agent, etc.), processing Sex improver, colorant (dye, pigment, etc.), antistatic agent, dispersant, surface conditioner (leveling agent, armpit inhibitor, etc.), surface modifier (slip agent, etc.), matting agent, defoaming agent , Antifoaming agents, defoaming agents, antibacterial agents, preservatives, viscosity modifiers, thickeners, photosensitizers, foaming agents and the like. These additives may be used alone or in combination of two or more. The content (blending amount) of the additive is not particularly limited, but is preferably 100 parts by weight or less, more preferably 30 parts by weight, based on 100 parts by weight of the total amount of silsesquioxane (A) and compound (B). It is not less than a part by weight (for example, 0.01 to 30 parts by weight), more preferably 10 parts by weight or less (for example, 0.1 to 10 parts by weight).

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

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

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

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

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

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

The cured product obtained by curing the curable composition of the present invention has excellent crack resistance. Therefore, the curable composition of the present invention can be preferably used as an adhesive (sometimes referred to as an "adhesive composition"), particularly a thermosetting adhesive, and by curing it, it has excellent crack resistance. It can be converted into an adhesive (furthermore, an adhesive having excellent crack resistance, heat resistance, adhesiveness to an object to be adhered, and adhesiveness).

[Adhesive sheet]
By using the curable composition (adhesive composition) of the present invention, an adhesive layer formed from the curable composition of the present invention ("adhesive layer of the present invention") is formed on at least one surface of the base material. An adhesive sheet (sometimes referred to as "the adhesive sheet of the present invention") having an adhesive sheet (which may be referred to as "adhesive sheet of the present invention") can be obtained. The adhesive sheet of the present invention is not particularly limited, but can be obtained, for example, by applying the curable composition of the present invention to a substrate and further drying it if necessary. The method of application is not particularly limited, and well-known and conventional means can be used. Further, the drying means and conditions are not particularly limited, and conditions that can remove volatile substances such as a solvent as much as possible can be set, and well-known and commonly used means can be used. In particular, the curable composition of the present invention is obtained by adding 1 part by weight to 100 parts by weight of celloxide 2021P (manufactured by Daicel Corporation) at 130 ° C. for a thermosetting time of 3.5 minutes or more. When a certain polymerization initiator is contained, the adhesive layer can be formed by quickly removing volatile substances such as a solvent while suppressing the progress of the curing reaction by heating and drying. The adhesive layer thus obtained does not have adhesiveness below 50 ° C., and develops adhesiveness by heating at a temperature at which damage to electronic components such as semiconductor chips can be suppressed, and then rapidly. Has the property of hardening to.

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

The adhesive sheet of the present invention includes not only sheet-like forms but also sheet-like forms such as film-like, tape-like, and plate-like forms.

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

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

The adhesive sheet of the present invention may have other layers (for example, an intermediate layer, an undercoat layer, etc.) in addition to the base material, the adhesive layer, and the anchor coat layer.

[Laminate]
By using the curable composition (adhesive composition) of the present invention, it is a laminate (laminated body) composed of three or more layers (at least three layers), and two layers to be adhered and these. A laminate having at least an adhesive layer (a layer for adhering the adhered layers to each other) located between the adhered layers, and the adhesive layer is a layer of a cured product of the curable composition of the present invention (“book”. It may be referred to as "laminate of the invention"). The laminate of the present invention is not particularly limited, but for example, the adhesive layer of the present invention is formed on one of the adherend layers (for example, it can be formed in the same manner as the adhesive layer in the adhesive sheet of the present invention), and further. It can be obtained by adhering the other adhesive layer to the adhesive layer and then curing the adhesive layer of the present invention by light irradiation, heating, or the like. Further, in the laminate of the present invention, for example, when the adhesive sheet of the present invention is a single-sided adhesive sheet, the adhesive sheet of the present invention is attached to the adhesive layer, and then the adhesive sheet is subjected to light irradiation, heating or the like. It can be obtained by curing the adhesive layer of the present invention inside. In this case, in the obtained laminate, the base material in the adhesive sheet of the present invention corresponds to the layer to be adhered. Further, the laminate of the present invention is, for example, when the adhesive sheet of the present invention is a double-sided adhesive sheet and a release liner as a base material is attached to both sides of the adhesive layer. One of the release liners of the present invention is peeled off and attached to the adhered layer to the exposed adhesive layer, and then the other release liner is peeled off and exposed to the other. It can be obtained by laminating the adhesive layer of the present invention and then curing the adhesive layer of the present invention by light irradiation, heating or the like. However, the method for producing the laminate of the present invention is not limited to these methods.

The layer to be adhered in the laminate of the present invention is not particularly limited, and examples thereof include the same as the base material in the adhesive sheet. The laminate of the present invention may have only two layers to be adhered, or may have three or more layers. The thickness of the layer to be adhered is not particularly limited, and can be appropriately selected in the range of, for example, 1 to 100,000 μm. The layer to be adhered does not have to have a strict layered form.

Even if the laminate of the present invention has only one layer of a cured product (sometimes referred to as "adhesive layer of the present invention") of the adhesive layer formed from the adhesive composition of the present invention. It may have two or more kinds. Further, the thickness of the adhesive layer of the present invention is not particularly limited and can be appropriately selected in the range of, for example, 0.1 to 10000 μm.

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

Specific examples of the laminate of the present invention include semiconductor chips and wafers.

In the laminate of the present invention, the cured product of the adhesive layer has excellent crack resistance, and further, has excellent adhesiveness, adhesion, and heat resistance to the object to be adhered. Therefore, when the laminate of the present invention is, for example, a three-dimensional laminate of semiconductor chips, it has higher integration and power saving than conventional semiconductors, and thus provides high-performance electronic devices while improving the mounting density. be able to. In particular, cracks and peeling of the adhesive layer in the laminate cause the wiring to be broken during the manufacture of the laminate and in the manufactured semiconductor chips, wafers, etc., resulting in failure of the laminate and equipment using the laminate. Causes. Therefore, an adhesive having high crack resistance, adhesiveness to an adherend, adhesiveness, and heat resistance is very important as a material constituting the laminate. Therefore, the laminate of the present invention has high reliability.

Further, by using the laminate of the present invention (for example, semiconductor chip, wafer, etc.), a highly integrated microprocessor, semiconductor memory, power supply IC, communication IC, semiconductor sensor, MEMS, etc., or these can be used. A combined semiconductor can be obtained. These semiconductors are used in devices such as high-performance servers, workstations, in-vehicle computers, personal computers, communication devices, photographing devices, and image display devices. Therefore, examples of the apparatus of the present invention having (or having) the laminate of the present invention include a server, a workstation, an in-vehicle computer, a personal computer, a communication device, a photographing device, an image display device, and the like. Can be mentioned.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The molecular weight of the product was measured by Alliance HPLC System 2695 (manufactured by Waters), Reflective Index Detector 2414 (manufactured by Waters), column: Tskgel GMH _HR -M × 2 (manufactured by Tosoh Corporation), guard column: Tskgel guard. Volume H HRL (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 ratio of T2 to T3 [T3 / T2] in the product was measured by ²⁹ Si-NMR spectrum measurement by JEOL ECA500 (500 MHz). The FT-IR spectrum was measured under the above-mentioned conditions.

Preparation Example 1
(Preparation of polyorganosylsesquioxane containing cyclohexenylethyl group)
In a 200 ml flask (reaction vessel) equipped with a thermometer, stirrer, reflux condenser, Dean Stark, and nitrogen introduction tube, 2- (3,4-cyclohexenyl) ethyltrimethoxysilane (hereinafter referred to as "3,4-cyclohexenyl) ethyltrimethoxysilane" under a nitrogen stream. , 219 mmol (50.34 g) (referred to as "CHMS"), 11.5 mmol (2.28 g) of phenyltrimethoxysilane (hereinafter referred to as "PMS"), and 17.35 g of toluene, and heated to 35 ° C. bottom. To the mixture thus obtained, 3.5 mmol of formic acid (0.88 g of 18.23% aqueous solution of formic acid ) was added, and then 759 mmol (13.66 g) of water was added dropwise over 60 minutes. By dropping water during the dropping, heat generation was confirmed and condensation started. Then, the polycondensation reaction was carried out under a nitrogen stream for 30 minutes at 35 ° C.
When the product in the reaction solution after the polycondensation reaction at this time was analyzed, the number average molecular weight was 390 and the molecular weight dispersion was 1.13. The reaction temperature was raised to 70 ° C. over 30 minutes. Distillation of methanol as a by-product was confirmed at 70 ° C. The polycondensation reaction was continued at 70 ° C. for 1 hour, and about 30 g of methanol was distilled off from Dean Stark. When the product in the reaction solution at this time was analyzed, the number average molecular weight was 673 and the molecular weight dispersion was 1.15. To this, 105.24 g of toluene and 21.13 g of a 5% aqueous sodium carbonate solution ( 9.97 mmol of sodium carbonate) were added, and the mixture was cooled to room temperature. The underlayer liquid was washed with water until it became neutral, the organic layer was concentrated under the conditions of 1 mmHg and 50 ° C., and the solvent was distilled off to obtain a fluid and transparent liquid cyclohexenylethyl group-containing silsesquioxane. 41.1 g was obtained. The number average molecular weight is 1500, the molecular weight dispersion is 1.50, and the molar ratio of T2 to T3 [T3 / T2] calculated from the ²⁹ Si-NMR spectrum of the above product is 1.78. Met.

(Epoxidation process)
In a 1000 ml flask (reaction vessel) equipped with a thermometer, agitator, a reflux condenser, and a nitrogen introduction tube, 36.0 g of the above transparent liquid and 200 g of ethyl acetate are placed under a nitrogen stream and stirred and mixed at 20 ° C. Was done. Separately, in an Erlenmeyer flask, 328 mmol (56.56 g) of metachloroperbenzoic acid (mCPBA) and 165 g of ethyl acetate were added, and the mixture was stirred and mixed. At a reaction temperature of 20 ° C., a mCPBA ethyl acetate solution was added dropwise over 45 minutes. At this time, a slight fever was confirmed.
After the dropping, aging was carried out at 20 ° C. for 3 hours. At this time, it was confirmed that mCPBA had disappeared by the peroxide checker.
20.0 g of normal heptane and 157.8 g of a 10% sodium thiosulfate aqueous solution were added to the reaction mixture, and the mixture was stirred for 10 minutes and quenched. After that, it was transferred to a separating funnel, the lower layer water was discharged, and the mixture was extracted and washed twice with 156.8 g of 5% NaOH aqueous solution and twice with 156.8 g of water to confirm that it was neutral.
An ethyl acetate solution containing an epoxycyclohexylethyl group-containing random silsesquioxane was concentrated and distilled off at 1 mmHg and 50 ° C. to obtain 30.4 g of an epoxycyclohexylethyl group-containing random silsesquioxane. The obtained epoxy equivalent of the epoxy cyclohexylethyl group-containing random silsesquioxane had an epoxy equivalent of 195 g / eq, a number average molecular weight of 1213, and a dispersity of 1.28. From ¹ H-NMR, the conversion rate from the cyclohexenylethyl group before epoxidation to the epoxycyclohexylethyl group was 94%. In addition, from the FT-IR analysis results, it was confirmed that the peak shape was neither a ladder type nor a basket type, and the molar ratio [T3 body / T2 body] of ²⁹ Si-NMR results was about 1.8. From this, it was confirmed that the obtained silsesquioxane was a random type silsesquioxane because it was different from both the ladder type and the cage type structures.

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

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

Preparation Example 3
(Preparation of polyorganosyl sesquioxane containing epoxycyclohexylethyl group)
2- (3,4-Epoxycyclohexyl) ethyltrimethoxysilane (hereinafter, "EMS") in a 300 ml flask (reaction vessel) equipped with a thermometer, agitator, a reflux condenser, and a nitrogen introduction tube under a nitrogen stream. 161.5 mmol (39.79 g), 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 (1.7 mmol as potassium carbonate) of a 5% potassium carbonate aqueous solution was added dropwise in 5 minutes, and then 1700 mmol (30.60 g) of water was added dropwise over 20 minutes. .. No significant temperature increase occurred during the dropping. Then, the polycondensation reaction was carried out under a nitrogen stream for 4 hours at 50 ° C.
When the product in the reaction solution after the polycondensation reaction was analyzed, the epoxy equivalent was 195 g / eq, the number average molecular weight was 1900, and the molecular weight dispersion was 1.5. The molar ratio of T2 to T3 [T3 / T2] calculated from the ²⁹ Si-NMR spectrum of the above product was 10.3.
Then, the reaction solution is cooled, washed with water until the lower layer liquid becomes neutral, the upper layer liquid is separated, and then the solvent is retained from the upper layer liquid under the conditions of 1 mmHg and 40 ° C. until the solvent amount becomes 25% by weight. The mixture was removed to obtain a colorless and transparent liquid product (polyorganosyl sesquioxane containing an epoxycyclohexylethyl group).
When the FT-IR spectrum of the obtained polyorganosyl sesquioxane was measured by the above method, it was confirmed that it had one intrinsic absorption peak near 1100 cm ^-1 .

Examples 1 to 16, Comparative Example 1
(Preparation of adhesive composition)
An adhesive composition was prepared by mixing and dissolving according to the compositions and amounts shown in Tables 1 and 2. The numbers in the table are parts by weight. The blending amount of the trade name "SI-150L" is shown in terms of solid content. Further, "-" in the blending amount in the table indicates that the component is not blended.

(Preparation of adhesive layer)
Spin-coat a silane coupling agent (trade name "KBE403", manufactured by Shin-Etsu Chemical Co., Ltd.) on a silicon plate (size: 2 cm x 5 cm, manufactured by SUMCO Corporation, obtained by dicing a silicon wafer with a diameter of 100 mm). And heated at 120 ° C. for 5 minutes to obtain a silicon plate with a silane coupling agent layer. The adhesive composition is applied to a silicon plate with a silane coupling agent layer by spin coating, and heated at 80 ° C. for 4 minutes and then at 100 ° C. for 2 minutes to remove residual solvent to obtain a silicon plate with an adhesive layer. Obtained. The film thickness of the adhesive layer was 5 to 6 μm.

(Preparation of laminate)
Apply a silane coupling agent (trade name "KBE403", manufactured by Shin-Etsu Chemical Co., Ltd.) to a glass plate (4 inches, manufactured by SCHOTT Japan Co., Ltd.) by spin coating, heat at 120 ° C. for 5 minutes, and silane. A glass plate with a coupling agent layer was obtained. Under reduced pressure, the silane coupling agent layer surface of the prepared glass plate with a silane coupling agent layer is combined with the adhesive layer surface of the silicon plate with an adhesive layer, and a pressure of 200 g / cm ² is applied while heating at 60 ° C. After bonding, the mixture was heated at 150 ° C. for 30 minutes and then at 170 ° C. for 30 minutes to obtain a laminate.

The adhesive compositions, adhesive layers, and laminates obtained in Examples 1 to 16 and Comparative Example 1 were evaluated as follows. The results are shown in Tables 1 and 2. In addition, "-" in the evaluation in the table indicates that the evaluation has not been performed.

(1) Heat-resistant adhesive The cured product obtained by heating the adhesive composition is heated in a nitrogen atmosphere using a thermogravimetric analyzer (trade name "TG-DTA6300", manufactured by Seiko Denshi Kogyo Co., Ltd.). Thermogravimetric analysis was performed under the condition of a speed of 10 ° C./min, and the heat resistance was evaluated according to the following criteria. As shown in FIG. 1, the thermal decomposition temperature (T) is a tangent line where there is no initial weight loss or where the weight is gradually reduced (range indicated by A in the figure), and the weight is rapidly reduced. It is the temperature at which the tangents of the inflections where they are occurring (the range indicated by B in the figure) intersect. The results are shown in the "heat resistance" columns of Tables 1 and 2.
Evaluation Criteria: Pass (◯) when the thermal decomposition temperature (T) is 260 ° C. or higher.

(2) Adhesiveness A grid tape test (JIS K5400-8.5 compliant) was conducted on the cured product of the adhesive layer obtained by heating the adhesive layer in the silicon plate with the adhesive layer, and silicon was siliconized according to the following criteria. The adhesion to the board was evaluated. The results are shown in the "Adhesion" column of Tables 1 and 2.
Evaluation criteria: Pass (○) when no peeling of the adhesive layer is observed.

(3) Crack resistance A
The silicon plate with the adhesive layer is heated at 150 ° C. for 30 minutes, then heated at 170 ° C. for 30 minutes to cure and cool the adhesive layer, and then subjected to thermal impact (heating at 250 ° C. for 30 minutes, followed by room temperature). Quenching) was given. In order to evaluate the number of cracks generated at that time, the range of 20 mm square with the center of the silicon plate as the apex was divided into 2 mm squares of 100 squares in total, and the number of 2 mm squares without cracks was counted. The results are shown in the "Crack resistance A" column of Tables 1 and 2.
◎ (Very good): The number of 2 mm square cells without cracks is 65 or more 〇 (Good): The number of 2 mm square cells without cracks is 50 or more and less than 65 △ (No): Cracks occur The number of non-existing 2 mm square cells is 1 or more and less than 50 × (defective): Cracks occur in all 2 mm square cells

(4) Crack resistance B
The cured product of the adhesive layer obtained by heating the adhesive layer in the silicon plate with the adhesive layer is subjected to a cold impact (heated at 250 ° C. for 30 minutes and then rapidly cooled to room temperature) and cracked according to the following criteria. The degree of was evaluated. The results are shown in the "Crack resistance B" column of Table 2.
◎ (Extremely good): The area of the cured product in the crack-free part is 80% or more ○ (Good): The area of the cured product in the crack-free part is 60% or more × (Defective): The cured product in the crack-free part Area is less than 60%

(5) Adhesiveness A razor blade (trade name "Razor for single-edged trimming", manufactured by Nissin EM Co., Ltd.) was inserted into the adhesive interface of the laminate, and the adhesiveness was evaluated according to the following criteria. The results are shown in the "Adhesiveness" column of Tables 1 and 2.
Evaluation criteria: Pass (○) when no peeling is seen on the adhesive surface.

The symbols in the table indicate the following compounds.
Preparation Example 1: Polyorganosylsesquioxane obtained in Preparation Example 1: Polyorganosylsesquioxane obtained in Preparation Example 2: Polyorganosylsesquioxane obtained in Preparation Example2 Preparation Example 3: Polyorganosylsesquioki obtained in Preparation Example3 Sun 4004P: Phenolic / formaldehyde polycondensate or alkyl (C = 1-9) phenol / formaldehyde polycondensate with epichlorohydrin or 2-methylepicrolhydrin-based glycidyl etherified modified product (trade name "jER4004P", manufactured by Mitsubishi Chemical Corporation) ), Weight average molecular weight: 5000, Epoxy equivalent: 840-975
4005P: Glycidyl etherified modified product of phenol / formaldehyde polycondensate or alkyl (C = 1-9) phenol / formaldehyde polycondensate with epichlorohydrin or 2-methylepichlorohydrin (trade name "jER4005P", manufactured by Mitsubishi Chemical Corporation). , Weight average molecular weight: 6200, Epoxy equivalent: 950-1200
4007P: Glycidyl etherified modified product of phenol / formaldehyde polycondensate or alkyl (C = 1-9) 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: Glycidyl etherified modified product of phenol / formaldehyde polycondensate or alkyl (C = 1-9) phenol / formaldehyde polycondensate with epichlorohydrin or 2-methylepichlorohydrin (trade name "jER4010P", manufactured by Mitsubishi Chemical Corporation). , Weight average molecular weight: 45000, Epoxy equivalent: 3800-4600
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
EHPE: 1,2-Epoxy-4- (2-oxylanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol (trade name "EHPE3150", manufactured by Daicel Corporation), weight average molecular weight: 2400, epoxy equivalent: 177
PGMEA: Propylene glycol monomethyl ether acetate SI-150L: Antimony sulfonium salt (trade name "SI-150L", manufactured by Sanshin Chemical Industry Co., Ltd.), seroxide 2021P (manufactured by Daicel Co., Ltd.) 1 per 100 parts by weight Thermal curing time of the composition obtained by adding parts by weight at 130 ° C.: 5.4 minutes)
SI Auxiliary: (4-Hydroxyphenyl) DimethylSulfonium Methylsulfite (trade name "Sun Aid SI Auxiliary", manufactured by Sanshin Chemical Industry Co., Ltd.)

Claims (9)

It is one or more selected from the group consisting of random type silsesquioxane (A1) and silsesquioxane having a ladder skeleton (A2), and is the following formula (1).
[R ¹ SiO _3/2 ] (1)
[In the formula (1), R ¹ is a group having the same structure as R ² except that the carbon-carbon double bond portion in the alkenyl group in R ² in the following formula (2) is epoxidized. There is the following formula (1a)

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

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

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

[In formula (1d), R ^1d represents a linear or branched alkylene group. ]
Indicates one or more groups selected from the group consisting of the groups represented by. ]
The structural unit represented by and the following formula (2)
[R ² SiO _3/2 ] (2)
[In formula (2), R ² represents a substituted or unsubstituted alkenyl group. ]
It contains silsesquioxane (A) having a structural unit represented by (A) and a compound (B) having a polymerizable functional group other than silsesquioxane (A), and the polymerizable functional group is an epoxy group. , One or more selected from the group consisting of an oxetanyl group, a vinyl ether group, and a vinyl phenyl group. The curable composition according to claim 1, further comprising a polymerization initiator. The curable composition according to claim 1 or 2, further comprising a polymerization stabilizer. The curable composition according to any one of claims 1 to 3, further comprising a silane coupling agent. The curable composition according to any one of claims 1 to 4, which is an adhesive composition. An adhesive sheet having an adhesive layer formed from the curable composition according to claim 5 on at least one surface of a substrate. The cured product of the curable composition according to any one of claims 1 to 4 . It is a laminate composed of three or more layers.
It has two layers to be adhered and an adhesive layer between the layers to be adhered.
A laminate characterized in that the adhesive layer is a layer of a cured product of the curable composition according to claim 5. The apparatus having the laminate according to claim 8.

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