JP6785538B2 - Polyorganosylsesquioxane, curable compositions, adhesive sheets, laminates and equipment - Google Patents

Description

The present invention comprises a polyorganosylsesquioxane, a curable composition, an adhesive sheet having an adhesive layer formed using the curable composition, a cured product of the curable composition, and the curable composition. The present invention relates to a laminate and an apparatus obtained by adhering an object to be adhered using.

As an adhesive used for laminating semiconductors and adhering electronic components, a curable adhesive containing benzocyclobutene (BCB), a novolak epoxy resin, or polyorganosylsesquioxane is known (for example,). See Patent Documents 1 and 2).

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 novolac epoxy resin has a problem that the adhesive decomposes when it is applied to a high temperature process (for example, 260 to 280 ° C.) such as lead-free solder reflow, and the adhesiveness deteriorates. was there.

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

JP-A-2010-226060 Japanese Unexamined Patent Publication No. 2014-101496

Therefore, an object of the present invention is a polyorganosyl that can be cured at a low temperature to form a cured product having excellent heat resistance, crack resistance (or heat impact resistance), adhesiveness to an object to be adhered, and adhesion. To provide sesquioxane.
Another object of the present invention is a curable composition capable of curing at a low temperature to form a cured product having excellent heat resistance, crack resistance (or heat impact resistance), adhesiveness to an object to be adhered, and adhesion. It is to provide things.
Another object of the present invention is to provide a cured product of the curable composition.
Another object of the present invention is to provide an adhesive sheet having an adhesive layer formed by using the curable composition.
Another object of the present invention is to provide a laminate obtained by adhering an object to be adhered with the curable composition, and an apparatus having the laminate.

As a result of diligent studies to solve the above problems, the present inventors have conducted a silsesquioxane structural unit (unit structure) containing a polymerizable functional group and a silsesquioxane structural unit (unit structure) containing a non-polymerizable functional group. According to polyorganosylsesquioxane, which has a specific structure ratio (ratio of T3 body and T2 body) controlled to a specific range, and a number average molecular weight and a molecular weight dispersion degree controlled to a specific range. A curable composition containing polyorganosylsesquioxane can be cured at a low temperature to form a cured product having excellent heat resistance, crack resistance, adhesiveness to an adherend, and adhesion to a semiconductor. It has been found that it has excellent properties as an adhesive for lamination and electronic parts. The present invention has been completed based on these findings.

That is, the present invention has the following equation (1).

[In formula (1), R ¹ represents a group containing a polymerizable functional group. ]
The structural unit represented by and the following formula (2)

[In formula (2), R ² represents a group containing a non-polymerizable functional group. ]
It has a structural unit represented by the following formula (I).

[In the formula (I), Ra represents ^a group containing a polymerizable functional group, a group containing a non-polymerizable functional group, or a hydrogen atom. ]
The structural unit represented by and the following formula (II)

[In formula (II), R ^b represents a group containing a polymerizable functional group, a group containing a non-polymerizable functional group, or a hydrogen atom. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]
The molar ratio of the structural units represented by (I) [the structural unit represented by the formula (I) / the structural unit represented by the formula (II)] is 5 or more, the number average molecular weight is 1000 to 3000, and the molecular weight dispersion degree ( Provided are polyorganosylsesquioxane having a weight average molecular weight / number average molecular weight) of 1.0 to 3.3.

In the polyorganosylsesquioxane, the non-polymerizable functional group may contain at least a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

In the polyorganosylsesquioxane, the structural unit represented by the above formula (2) and the following formula (5) with respect to the total amount (100 mol%) of the siloxane structural unit.

[In the formula (5), R ² is the same as that in the formula (2). R ^c is the same as that in the above formula (II). ]
The ratio of the structural unit represented by is preferably 5 mol% or more.

In the polyorganosylsesquioxane, the polymerizable functional group may contain at least an epoxy group.
Further, in the polyorganosylsesquioxane, the above R ¹ is preferably represented by the following formula (1a).

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

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

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

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

The present invention also provides a curable composition containing the polyorganosylsesquioxane.
The curable composition may further contain a polymerization initiator.
The curable composition may further contain a polymerization stabilizer.
The curable composition may further contain a silane coupling agent.
The curable composition may be an adhesive composition.

The present invention also provides a cured product obtained by curing the curable composition.
Further, the present invention is an adhesive sheet having a base material and an adhesive layer on the base material.
Provided is an adhesive sheet characterized in that the adhesive layer is a layer of the curable composition.
Further, the present invention 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.
Provided is a laminate characterized in that the adhesive layer is a layer of a cured product of the curable composition.
Furthermore, the present invention provides an apparatus having the laminate.

If the adhesive layer in the laminate is cracked or peeled, the layer to be adhered may be peeled off or the wiring may be broken, resulting in a failure of the device provided with the laminate. Since the object is excellent in heat resistance, crack resistance, adhesiveness to the adherend, and adhesion, it is possible to prevent cracks and peeling from occurring in the adhesive layer, and it is possible to improve the reliability of the apparatus. When the laminate of the present invention is a three-dimensional laminate of semiconductor chips, it has higher integration and power saving than the conventional semiconductor. Therefore, if the laminate of the present invention is used, it is smaller and has higher performance. Electronic devices can be provided.

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

[Polyorganosylsesquioxane]
The polyorganosylsesquioxane has a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2); a structural unit represented by the following formula (I) (“T3 body”). ”) And the molar ratio of the structural unit represented by the following formula (II) (sometimes referred to as“ T2 body ”) [constituent unit represented by formula (I) / formula (II) The structural unit represented by; [may be described as "T3 / T2"] is 5 or more; the number average molecular weight is 1000 to 3000, and the molecular weight dispersion [weight average molecular weight / number average molecular weight] is 1. It is characterized by being 0 to 3.3.

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 (monovalent group) containing a polymerizable functional group. That is, the polyorganosylsesquioxane of the present invention is a curable compound (preferably a cationically polymerizable compound) having at least a polymerizable functional group in the molecule.

The "polymerizable functional group" in the group containing the polymerizable functional group is not particularly limited as long as it has polymerizable properties, and examples thereof include an epoxy group, an oxetane group, a vinyl ether group, and a vinyl phenyl group. ..
As the polymerizable functional group, an epoxy group, an oxetane group, a vinyl ether group, a vinylphenyl group and the like are preferable, and an epoxy group is more preferable, from the viewpoint of improving the crack resistance of the cured product.

Examples of the group containing an epoxy group include known and commonly used groups having an oxylane ring, which are not particularly limited, but from the viewpoint of curability of the curable composition and heat resistance of the cured product, the following formula (1a) The group represented by the following formula (1b), the group represented by the following formula (1c), and the group represented by the following formula (1d) are preferable, and more preferably the following formula (1a). A group represented by the following formula (1c), more preferably a group represented by the following formula (1a).

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

Examples of the group containing an epoxy group include 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.

Examples of the group containing an oxetane group include known and commonly used groups having an oxetane ring, and are not particularly limited. For example, the oxetane group itself and an alkyl group (preferably having 1 to 10 carbon atoms, more preferably carbon atoms). Examples thereof include a group formed by substituting a hydrogen atom (usually one or more, preferably one hydrogen atom) of (1 to 5 alkyl groups) with an oxetane group. From the viewpoint of curability of the curable composition and heat resistance of the cured product, a 3-oxetanyl group, an oxetane-3-ylmethyl group, a 2- (oxetane-3-yl) ethyl group and the like are preferable.

Examples of the group containing a vinyl ether group include known and commonly used groups having a vinyl ether group, and are not particularly limited. For example, the vinyl ether group itself and an alkyl group (preferably having 1 to 10 carbon atoms, more preferably carbon atoms). Examples thereof include a group formed by substituting a hydrogen atom (usually one or more, preferably one hydrogen atom) of (1 to 5 alkyl groups) with a vinyl ether group. From the viewpoint of curability of the curable composition and heat resistance of the cured product, a vinyloxymethyl group, a 2- (vinyloxy) ethyl group and the like are preferable.

Examples of the group containing a vinylphenyl group include known and commonly used groups having a vinylphenyl group, and are not particularly limited. For example, the vinylphenyl group itself and an alkyl group (preferably having 1 to 10 carbon atoms, more preferably). Is a group formed by substituting a hydrogen atom (usually one or more, preferably one hydrogen atom) of an alkyl group having 1 to 5 carbon atoms with a vinylphenyl group. From the viewpoint of curability of the curable composition and heat resistance of the cured product, a 4-vinylphenyl group, a 3-vinylphenyl group, a 2-vinylphenyl group and the like are preferable.

As R ¹ in the formula (1), a group containing an epoxy group is preferable, and in particular, a group represented by the above formula (1a) in which R ^1a is an ethylene group [among others, 2- ( 3', 4'-epoxycyclohexyl) ethyl group] is preferable.

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

The polyorganosilsesquioxane of the present invention has a structural unit represented by the following formula (2) in addition to the structural unit represented by the above formula (1) as a structural unit [RSiO _3/2 ]. It is characterized by having.

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

R ² in the above formula (2) represents a group (monovalent group) containing a non-polymerizable functional group.
The group containing the non-polymerizable functional group is not particularly limited as long as it does not exhibit polymerizable properties, and is, for example, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted group. Cycloalkyl groups, substituted or unsubstituted alkyl groups, or substituted or unsubstituted alkenyl groups can be mentioned. 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 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, an isopentyl group, a hexyl group, a heptyl group and an octyl group. A linear or branched chain such as a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecil group, an icosanyl group, a henicosanyl group, or a docosanyl group. An alkyl group is mentioned, and a linear or branched alkyl group having 1 to 20 carbon atoms is preferable. Examples of the alkenyl group include a linear or branched alkenyl group such as a vinyl group, an allyl group, and an isopropenyl group.

Examples of the above-mentioned substituted aryl group, substituted aralkyl group, substituted cycloalkyl group, substituted alkyl group, and substituted alkenyl group include hydrogen atoms or main ribs in each of the above-mentioned aryl group, aralkyl group, cycloalkyl group, alkyl group and alkenyl group. Part or all of the case consists of a group consisting of an ether group, an ester group, a carbonyl group, a siloxane group, a halogen atom (fluorine atom, etc.), an acrylic group, a methacryl group, a mercapto group, an amino group, and a hydroxy group (hydroxyl group). Examples include groups substituted with at least one selected.

The polyorganosylsesquioxane of the present invention may have only one structural unit represented by the above formula (2), or may have two or more structural units represented by the above formula (2). It may have.

The ratio of each of the above-mentioned silsesquioxane structural units (the structural unit represented by the formula (1) and the structural unit represented by the formula (2)) in the polyorganosilsesquioxane of the present invention is these structural units. It is possible to appropriately adjust the composition of the raw material (hydrolyzable trifunctional silane) for forming the above.

The polyorganosylsesquioxane of the present invention is a structural unit represented by the above formula (1) and a structural unit represented by the above formula (1) in addition to the structural unit represented by the above formula (2). And the silsesquioxane structural unit [RSiO _3/2 ] other than the structural unit represented by the formula (2), the structural unit represented by [R ₃ SiO _1/2 ] (so-called M unit), [R ₂ SiO It has at least one siloxane structural unit 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). You may be doing it. As the silsesquioxane structural unit other than the structural unit represented by the above formula (1) and the structural unit represented by the formula (2), for example, the structural unit represented by the following formula (3) and the like are used. Can be mentioned.

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

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') become other silicon atoms (silicon atoms not shown in the formula (II')). It is combined. That is, both the T3 body and the T2 body are structural units (T units) formed by the hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compounds.

R ^a in the above formula (I) (formula (I ') in the R ^a same) and formula (II) in the R ^b (wherein (II') in the R ^b versa), respectively, polymerizable Indicates a group containing a functional group, a group containing a non-polymerizable functional group, or a hydrogen atom. Specific examples of R ^a and R ^b include those similar to R ¹ in the above formula (1) and R ² in the above formula (2). R ^a in the formula (I) and R ^b in the formula (II) were each bonded to a silicon atom in the hydrolyzable trifunctional silane compound used as a raw material for the polyorganosylsesquioxane of the present invention. It is derived from a group (a group other than an alkoxy group and a halogen atom; for example, R ¹ , R ² , hydrogen atom in the formulas (a) to (c) described later).

R ^c in the formula (II) (Formula (II ') in the R ^c versa) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include 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 ^Rc in formula (II) is generally an alkoxy group in the hydrolyzable silane compound used as a raw material for the polyorganosylsesquioxane of the present invention (for example, X ^{1 to} X ³ described later). It is derived from an alkyl group that forms (such as an alkoxy group).

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

The ²⁹ Si-NMR spectrum of the polyorganosylsesquioxane of the present invention 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 fact that the above ratio [T3 body / T2 body] of the polyorganosylsesquioxane of the present invention is 5 or more means that in the polyorganosylsesquioxane of the present invention, there are T2 bodies above a certain level with respect to the T3 body. Means to be. Examples of such a T2 body include a structural unit represented by the following formula (4), a structural unit represented by the following formula (5), a structural unit represented by the following formula (6), and the like. R ² in R ¹ and the following formula (5) in the following equation (4) is the same as R ² in R ¹ and the formula in the formula (1) (2). R ^c in the 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).

In general, the complete cage type silsesquioxane is a polyorganosylsesquioxane composed of only T3 bodies, and the T2 body is not present in the molecule. That is, the above ratio [T3 body / T2 body] is 5 or more, the number average molecular weight is 1000 to 3000, the molecular weight dispersion is 1.0 to 3.3, and further, in the FT-IR spectrum as described later. It is suggested that the polyorganosilsesquioxane of the present invention having one intrinsic absorption peak near 1100 cm ^-1 has an incomplete cage type silsesquioxane structure.

The fact that the polyorganosilsesquioxane of the present invention has a cage-type (incomplete cage-type) silsesquioxane structure means that the polyorganosilsesquioxane of the present invention has a 1050 cm ^-1 vicinity and 1150 cm in the FT-IR spectrum. respectively in the vicinity of ^-1 it does not have a specific absorption peak is confirmed by the fact that with a single specific absorption peak in the vicinity of 1100 cm ^-1 [ref: R. H. Laney, M.R. 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 1150 cm ^-1 , respectively, it is identified as having a ladder-type silsesquioxane structure. The FT-IR spectrum of the polyorganosylsesquioxane of the present invention can be measured by, for example, the following devices and conditions.
Measuring device: Product name "FT-720" (manufactured by HORIBA, Ltd.)
Measurement method: Transmission method Resolution: 4 cm ^-1
Wavenumber range: 400-4000 cm ^-1
Accumulation number: 16 times

The first preferred embodiment of the polyorganosylsesquioxane of the present invention [hereinafter referred to as "polyorganosylsesquioxane (A)". ], R ² is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. Since R ² is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, the crack resistance of the cured product obtained by curing the curable composition tends to be improved.
In the polyorganosylsesquioxane (A), the number of carbon atoms of the "alkyl group" is preferably 4 to 20, more preferably 10 to 20, and 14 to 20 from the viewpoint of improving the crack resistance of the cured product. Is even more preferable.
In the polyorganosylsesquioxane (A), the "alkyl group" may be a straight chain or a branched chain, but a straight chain is preferable from the viewpoint of improving the crack resistance of the cured product.

The above formula (2) with respect to the total amount of siloxane structural units in the polyorganosylsesquioxane (A) of the present invention [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%). The ratio (total amount) of the structural unit represented by) and the structural unit represented by the above formula (5) is not particularly limited, but is preferably 1 to 40 mol%, more preferably 3 to 30 mol%, still more preferably. Is 5 to 25 mol%. By setting the above ratio to 1 mol% or more, the crack resistance of the cured product obtained by curing the curable composition tends to be improved. On the other hand, by setting the above ratio to 40 mol% or less, the ratio of the structural unit represented by the formula (1) and the structural unit represented by the formula (4) can be relatively increased, so that the curability is curable. The curability of the composition is improved, and the adhesiveness of the cured product tends to be higher. The ratio of each siloxane structural unit in the polyorganosylsesquioxane of the present invention can be calculated, for example, by measuring the composition of raw materials or NMR spectrum.

The above formula (1) with respect to the total amount of siloxane structural units in the polyorganosylsesquioxane (A) of the present invention [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%). The ratio (total amount) of the structural unit represented by) and the structural unit represented by the above formula (4) is not particularly limited, but is preferably 50 to 99 mol%, more preferably 65 to 97 mol%, still more preferably. Is 75-95 mol%. By setting the above ratio to 50 mol% or more, the curability of the curable composition tends to be improved, and the adhesiveness of the cured product tends to be remarkably increased. On the other hand, when the above ratio is 99 mol% or less, the crack resistance of the cured product obtained by curing the curable composition tends to be improved.

A second preferred embodiment of the polyorganosylsesquioxane of the present invention [hereinafter referred to as "polyorganosylsesquioxane (B)". ], The structural unit represented by the above formula (2) and the above formula with respect to the total amount of the siloxane structural unit [total siloxane structural unit; total amount of M unit, D unit, T unit, and Q unit] (100 mol%). The ratio (total amount) of the constituent units represented by (5) is 5 mol% or more. By setting the above ratio to 5 mol% or more, the crack resistance of the cured product obtained by curing the curable composition tends to be improved.
In polyorganosylsesquioxane (B), the lower limit of the above ratio is preferably 10 mol% or more, more preferably 25% or more. The upper limit of the above ratio is not particularly limited, but is preferably 60 mol% or less, more preferably 55 mol% or less, still more preferably 50 mol% or less. By setting the upper limit of the above ratio to 60 mol% or less, the ratio of the structural unit represented by the formula (1) and the structural unit represented by the formula (4) can be relatively increased, so that the curability can be increased. The curability of the composition is improved, and the adhesiveness of the cured product tends to be higher.

The above formula (1) with respect to the total amount of siloxane structural units in the polyorganosylsesquioxane (B) of the present invention [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%). The ratio (total amount) of the structural unit represented by) and the structural unit represented by the above formula (4) is not particularly limited, but is preferably 40 to 95 mol%, more preferably 45 to 90 mol%, still more preferably. Is 50-75 mol%. By setting the above ratio to 40 mol% or more, the curability of the curable composition tends to be improved, and the adhesiveness of the cured product tends to be significantly increased. On the other hand, when the above ratio is 95 mol% or less, the crack resistance of the cured product obtained by curing the curable composition tends to be improved.

In the polyorganosylsesquioxane (B) of the present invention, the group containing the non-polymerizable functional group represented by R ² is a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted group. Substituted cycloalkyl groups, substituted or unsubstituted alkyl groups, or substituted or unsubstituted alkenyl groups are preferable, and substituted or unsubstituted aryl groups, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups are preferable. More preferably, it is a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, particularly preferably a phenyl group, an alkyl group having 1 to 4 carbon atoms (eg, a methyl group).

Total amount of siloxane constituent units in the polyorganosylsesquioxane of the present invention (including polyorganosylsesquioxane (A) and (B); the same applies hereinafter) [total siloxane constituent units; M units, D units, T units , And the total amount of Q units] (100 mol%), the structural unit represented by the above formula (1), the structural unit represented by the above formula (2), the structural unit represented by the above formula (4), The ratio (total amount) of the structural units represented by the above formula (5) is not particularly limited, but is preferably 60 to 100 mol%, more preferably 70 to 100 mol%, and further preferably 80 to 100 mol%. is there. By setting the above ratio to 60 mol% or more, the adhesiveness of the cured product tends to be higher.

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

The molecular weight dispersion (Mw / Mn) of the polyorganosylsesquioxane of the present invention in terms of standard polystyrene by gel permeation chromatography is 1.0 to 3.3, preferably 1.1, as described above. It is ~ 2.0, more preferably 1.2 to 1.9, and particularly preferably 1.45 to 1.8. By setting the molecular weight dispersion to 3.3 or less, the adhesiveness of the cured product becomes higher. On the other hand, when the molecular weight dispersity is 1.0 or more (particularly 1.1 or more), it tends to be liquid and the handleability tends to be improved.

The number average molecular weight and molecular weight dispersion of the polyorganosylsesquioxane of the present invention can be measured by the following devices and conditions.
Measuring device: Product name "Alliance HPLC System 2695" (manufactured by Waters), "Refractive Index Detector 2414" (manufactured by Waters)
Column: Tskgel GMH _HR- M x 2 (manufactured by Tosoh Corporation)
Guard column: Tskgel guard column H _HR L (Tosoh Co., Ltd.)
Column oven: COLUMN HEATER U-620 (manufactured by Sugai)
Solvent: THF
Measurement conditions: 40 ° C
Molecular weight: Standard polystyrene conversion

The 5% weight loss temperature (T _d5 ) of the polyorganosylsesquioxane of the present invention in an air atmosphere is not particularly limited, but is preferably 330 ° C. or higher (for example, 330 to 450 ° C.), and more preferably 340 ° C. or higher. , More 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. In particular, the polyorganosylsesquioxane of the present invention has the above ratio [T3 / T2] of 5 or more, a number average molecular weight of 1000 to 3000, and a molecular weight dispersion of 1.0 to 3.3. The 5% weight loss temperature is controlled to 330 ° C. or higher by having one intrinsic peak near 1100 cm ^-1 in the FT-IR spectrum. The 5% weight loss temperature is the temperature at which 5% of the weight before heating is reduced when heated at a constant heating 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.

The polyorganosylsesquioxane of the present invention can be produced by a known or conventional 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. However, the hydrolyzable silane compound includes a hydrolyzable trifunctional silane compound (a compound represented by the following formula (a)) for forming a structural unit represented by the above formula (1) and the above-mentioned above-mentioned hydrolyzable silane compound. It is necessary to use a hydrolyzable trifunctional silane compound (compound represented by the following formula (b)) for forming the structural unit represented by the formula (1) as an essential hydrolyzable silane compound.

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

The compound represented by the above formula (a) is a compound forming a structural unit represented by the formula (1) in the polyorganosylsesquioxane of the present invention. R ¹ in the formula (a), like that of R ¹ in the formula (1), a group containing a polymerizable functional group. That is, as R ¹ in the formula (a), a group containing an epoxy group is preferable, and the group represented by the above formula (1a), the group represented by the above formula (1b), and the above formula (1c). The group represented, the group represented by the above formula (1d) is more preferable, the group represented by the above formula (1a), the group represented by the above formula (1c), and even more preferably the above formula. A group represented by (1a), particularly preferably a group represented by the above formula (1a), wherein R ^1a is an ethylene group [among others, 2- (3', 4'-epoxycyclohexyl) ethyl. Group].

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

The compound represented by the above formula (b) is a compound forming a structural unit represented by the formula (2) in the polyorganosylsesquioxane of the present invention. R ² in formula (b), like the R ² in the formula (2) shows a non-polymerizable functional groups.
R ² in the polyorganosylsesquioxane (A) is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 4 to 20 carbon atoms, and more preferably 10 carbon atoms. It is an alkyl group of ~ 20, more preferably an alkyl group having 14 to 20 carbon atoms.
R ² in polyorganosylsesquioxane (B) is not particularly limited, but is preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, and more preferably a substituted or unsubstituted alkenyl group. It is an unsubstituted aryl group, a substituted or unsubstituted alkyl group, particularly preferably a phenyl group, or an alkyl group having 1 to 4 carbon atoms (eg, a methyl group).

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

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

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

The amount and composition of the hydrolyzable silane compound used can be appropriately adjusted according to the desired structure of the polyorganosylsesquioxane of the present invention.
For example, the amount of the compound represented by the above formula (b) in the polyorganosylsesquioxane (A) is not particularly limited, but is based on the total amount (100 mol%) of the hydrolyzable silane compound used. It is preferably 1 to 40 mol%, more preferably 3 to 30 mol%, still more preferably 5 to 25 mol%.
The lower limit of the amount of the compound represented by the above formula (b) in the polyorganosylsesquioxane (B) is 5 mol% with respect to the total amount (100 mol%) of the hydrolyzable silane compound used. The above is preferably 10 mol% or more, more preferably 25% or more, and the upper limit of the amount of the compound represented by the above formula (b) used is not particularly limited, but is preferably 60 mol% or less. It is preferably 55 mol% or less, more preferably 50 mol% or less.

The amount of the compound represented by the above formula (a) in the polyorganosylsesquioxane (A) is not particularly limited, but is based on the total amount (100 mol%) of the hydrolyzable silane compound used. It is preferably 50 to 99 mol%, more preferably 65 to 97 mol%, still more preferably 75 to 95 mol%.
The amount of the compound represented by the above formula (a) in the polyorganosylsesquioxane (B) is not particularly limited, but is based on the total amount (100 mol%) of the hydrolyzable silane compound used. It is preferably 40 to 95 mol%, more preferably 45 to 90 mol%, still more preferably 50 to 75 mol%.

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

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

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

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

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

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

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

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

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

The polyorganosylsesquioxane of the present invention can be obtained by the hydrolysis and condensation reaction of the hydrolyzable silane compound. After completion of the hydrolysis and condensation reactions, it is preferable to neutralize the catalyst in order to suppress ring opening of the epoxy group. Further, the polyorganosylsesquioxane of the present invention can be separated by, for example, water washing, acid washing, alkaline washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography and the like, or a combination thereof. It may be separated and purified by a separation means or the like.

Since the polyorganosylsesquioxane of the present invention has the above-mentioned structure, it has high heat resistance and crack resistance by curing a curable composition containing the polyorganosylsesquioxane as an essential component. In addition, a cured product having excellent adhesiveness can be formed.

[Curable composition]
The curable composition of the present invention is a curable composition (curable resin composition) containing the above-mentioned polyorganosylsesquioxane of the present invention as an essential component. As will be described later, the curable composition of the present invention further comprises other polymerization initiators, polymerization stabilizers, silane coupling agents, other cationic curable compounds, solvents, surface conditioners, surface modifiers and the like. It may contain an ingredient.

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

The content (blending amount) of the polyorganosylsesquioxane of the present invention in the curable composition of the present invention is not particularly limited, but is 70 with respect to the total amount (100% by weight) of the curable composition excluding the solvent. It is preferably 80% by weight or more and less than 100% by weight, more preferably 80 to 99.8% by weight, and further preferably 90 to 99.5% by weight. By setting the content of the polyorganosylsesquioxane of the present invention to 70% by weight or more, the adhesiveness of the cured product tends to be further improved. On the other hand, by setting the content of the polyorganosylsesquioxane of the present invention to less than 100% by weight, a curing catalyst can be contained, whereby the curing of the curable composition can proceed more efficiently. There is a tendency to be able to do it.

The ratio of the polyorganosylsesquioxane of the present invention to the total amount (100% by weight) of the cationically curable compound contained in the curable composition of the present invention is not particularly limited, but is preferably 70 to 100% by weight, more preferably 70% by weight. Is 75 to 98% by weight, more preferably 80 to 95% by weight. By setting the content of the polyorganosylsesquioxane of the present invention to 70% by weight or more, the crack resistance and adhesiveness of the cured product tend to be further improved.

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

As the curable composition of the present invention, an adhesive layer can be rapidly formed by heating and drying without advancing the curing reaction, and the obtained adhesive layer has adhesiveness at less than 50 ° C. Since it does not, the cutting process can be performed without adhesive adhering to the cutting blade, and the adhesiveness is developed by heating at a temperature at which damage to the object to be adhered such as semiconductor chips can be suppressed, and then promptly thereafter. From the viewpoint of having a curing property, it is preferable to use a polymerization initiator having the following curing property.

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

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

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

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 commonly used photocationic polymerization initiator can be used. For example, a sulfonium salt (a salt of a sulfonium ion and an anion) and an iodonium salt (a salt of an iodonium ion and an anion) can be used. , 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 triphenylsulfonium salt, tri-p-tolylsulfonium salt, tri-o-tolylsulfonium salt, tris (4-methoxyphenyl) sulfonium salt, 1-naphthyldiphenylsulfonium salt, and 2-naphthyldiphenyl. Sulfonium salt, tris (4-fluorophenyl) sulfonium salt, tri-1-naphthylsulfonium salt, tri-2-naphthylsulfonium salt, tris (4-hydroxyphenyl) sulfonium salt, diphenyl [4- (phenylthio) phenyl] sulfonium salt , 4- (P-trilthio) phenyldi- (p-phenyl) sulfonium salt and other triarylsulfonium salts; diphenylphenacil sulfonium salt, diphenyl4-nitrophenacil sulfonium salt, diphenylbenzylsulfonium salt, diphenylmethylsulfonium salt and the like Diarylsulfonium salt; monoarylsulfonium salt such as phenylmethylbenzylsulfonium salt, 4-hydroxyphenylmethylbenzylsulfonium salt, 4-methoxyphenylmethylbenzylsulfonium salt; dimethylphenacil sulfonium salt, phenacyltetrahydrothiophenium salt, dimethylbenzyl Examples thereof include trialkyl sulfonium 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 name such as "CPI-100P" (manufactured by San-Apro Co., Ltd., diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate 50% propylene carbonate solution) and the like can be used.

Examples of the iodonium salt include the trade name "UV9380C" (manufactured by Momentive Performance Materials Japan GK, bis (4-dodecylphenyl) iodonium = hexafluoroantimonate 45% alkylglycidyl ether solution), and the trade name " RHODORSIL PHOTOINITIATOR 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.), diphenyl iodonium salt, di-p-tolyl iodonium salt, bis (4-dodecylphenyl) iodonium salt, bis (4-methoxyphenyl) iodonium salt and the like.

Examples of the selenium salt include triaryl selenium salts such as triphenyl selenium salt, tri-p-tolyl selenium salt, tri-o-tolyl selenium salt, tris (4-methoxyphenyl) selenium salt, and 1-naphthyldiphenyl selenium salt. Salts; Diarylselenium salts such as diphenylphenacyl selenium salt, diphenylbenzyl selenium salt, diphenylmethyl selenium salt; Monoaryl selenium salts such as phenyl methyl benzyl selenium salt; Trialkyl selenium salts such as dimethyl phenacyl selenium salt and the like. ..

Examples of the ammonium salt include 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 Morphorinium salts such as −diethylmorpholinium salt; piperidinium salts such as N, N-dimethylpiperidinium salt, N, N-diethylpiperidinium salt; pyridinium salts 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 benzylacrydium 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 salts of chromium complex cations such as (η5-cyclopentadienyl) (η6-toluene) Cr ⁺ and (η5-cyclopentadienyl) (η6-xylene) Cr ^+. Examples thereof include salts of iron complex cations such as (η5-cyclopentadienyl) (η6-toluene) Fe ⁺ and (η5-cyclopentadienyl) (η6-xylene) Fe ⁺ .

The anion constituting the salt described above, for _{^{example, SbF 6 -, PF 6 -}} , BF 4 -, (CF 3 CF 2) 3 PF 3 -, (CF 3 CF 2 CF 2) 3 PF 3 -, (C ^{_{6 F 5) 4 B -,}} (C 6 F 5) 4 Ga -, a sulfonate anion (trifluoromethanesulfonic acid anion, pentafluoroethanesulfonate anion, nonafluorobutanesulfonic acid anion, methanesulfonic acid anion, benzenesulfonic acid anion, p- toluenesulfonate anion, _{etc.), (CF 3 SO 2)} 3 C -, (CF 3 SO 2) 2 N -, perhalogenated acid ion, a halogenated sulfonic acid ion, carbonate ion, aluminate Examples thereof include an ion, a hexafluorobismasic acid ion, a carboxylic acid 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.

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-80L". , "Sun Aid SI-100L", "Sun Aid SI-150L" (all manufactured by Sanshin Chemical Industry Co., Ltd.) and other commercially available products can be used. Examples of the aluminum chelate include ethyl acetoacetate aluminum diisopropyrate and aluminum tris (ethyl acetoacetate). 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 imidazoles include 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, and 2,4-diamino-6- [2-]. Methylimidazolyl- (1)] ethyl-s-triazine, 2-phenylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl- 2-Undecylimidazole and the like can be mentioned. In addition, examples of the tertiary amine include tris (dimethylaminomethyl) phenol, benzyldimethylamine, DBU (1,8-diazabicyclo (5,4,0) undecene-7) and the like.

The content (blending amount) of the above-mentioned polymerization initiator in the curable composition of the present invention is not particularly limited, but is 0.01 to 3.0 weight by weight with respect to 100 parts by weight of the polyorganosylsesquioxane of the present invention. Parts are preferable, more preferably 0.05 to 3.0 parts by weight, still more preferably 0.1 to 1.0 parts by weight (for example, 0.3 to 1.0 parts by weight). By setting the content of the polymerization initiator to 0.01 parts by weight or more, the curing reaction can proceed efficiently and sufficiently, and the adhesiveness of the cured product tends to be further improved. On the other hand, when the content of the polymerization initiator is 3.0 parts by weight or less, the storage stability of the curable composition tends to be further improved, and the coloring of the cured product tends to be suppressed.

[Polymerization stabilizer]
The curable composition of the present invention preferably further contains a polymerization stabilizer. The above-mentioned polymerization stabilizer is a compound having an action of suppressing the progress of cation polymerization by trapping cations, and proceeding with polymerization at the stage where the ability of the polymerization stabilizer to trap cations is saturated and deactivated. When the curable composition of the present invention contains a polymerization stabilizer together with a cationic polymerization initiator, it is possible to suppress the progress of polymerization for a long period of time after coating and drying to form an adhesive layer, and the adhesiveness It is possible to form an adhesive layer having excellent storage stability, which exhibits excellent adhesiveness by heating at the required timing.

Examples of the polymerization stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and poly ([6- (1,1,3,3-tetramethylbutyl) imino-1, 3,5-Triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] Hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) Imino]), tetrakis (2,2,6,6-tetramethyl-4-piperidyl) butane-1,2,3,4-tetracarboxylate, 2,2,6,6-tetramethyl-4-piperidi Nylbenzoate, (mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, mixed (2,2,6,6-tetramethyl) -4-piperidyl / β, β, β', β'-tetramethyl-3-9- [2,4,8,10-tetraoxaspiro (5.5) undecane] diethyl) -1,2,3 4-Butanetetracarboxylate, poly ([6-N-morpholyl-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexa Methylene [(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 name "LA-77", "LA-67", "LA-57" (above, made by ADEKA), trade name "TINUVIN123" , "TINUVIN152" (above, Ciba Japan Co., Ltd.) and other hindered amine compounds, (4-hydroxyphenyl) dimethylsulfonium methylsulfite (San Aid SI aid, 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 (Product 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 ( Phosphite ester compounds such as monononylphenyl) phosphite and trisisodecylphosphite can be mentioned, and sulfonium sulfate compounds and phosphite ester compounds are preferable. These can be used alone or in combination of two or more.

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

[Silane coupling agent]
The curable composition of the present invention may 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-Glycydoxypropyltriethoxysilane and the like. These can be used alone or in combination of two or more. When a silane coupling agent in which the functional group is a (meth) acryloyloxy group is used, a small amount of a radical polymerization initiator may be added.

In the present invention, for example, the trade name "KBE-403" (3-glycidoxypropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) and the trade name "Z-6040" (3-glycidoxypropyltrimethoxy). Commercially available products such as silane and Toray Dow Corning Co., Ltd. can be used.

When the curable composition of the present invention contains a silane coupling agent, the amount used thereof is, for example, about 0 to 10 parts by weight with respect to 100 parts by weight of the polymerizable compound contained in the curable composition of the present invention. 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.

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

As the other epoxy compound, a known or commonly used compound having one or more epoxy groups (oxylan rings) in the molecule can be used, and the present invention is not particularly limited, but for example, an alicyclic epoxy compound (alicyclic ring type). (Epoxy resin), aromatic epoxy compound (aromatic epoxy resin), aliphatic epoxy compound (aliphatic epoxy resin) and the like can be mentioned.

Examples of the alicyclic epoxy compound include known and commonly used compounds having one or more alicyclics and one or more epoxy groups in the molecule, and are not particularly limited, 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. Compounds; (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 part or all of the carbon-carbon double bond is epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and the like. Examples thereof include a group in which a plurality of groups are linked.

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

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

Typical examples of the alicyclic epoxy compound represented by the above formula (i) are 3,4,3', 4'-diepoxybicyclohexane, and the following formulas (i-1) to (i-10). Examples thereof include compounds represented by. In addition, l and m in the following formulas (i-5) and (i-7) represent integers of 1 to 30, respectively. R'in the following formula (i-5) is an alkylene group having 1 to 8 carbon atoms, and among them, a linear or branched chain having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group and an isopropylene group. The shape of the alkylene group is preferable. N1 to n6 in the following formulas (i-9) and (i-10) represent integers of 1 to 30, respectively. In addition, 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 a p-valent alcohol, and p and n each represent a natural number. Examples of the valent alcohol [R "(OH) _p ] include polyhydric alcohols such as 2,2-bis (hydroxymethyl) -1-butanol (alcohols having 1 to 15 carbon atoms) and the like. p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or more, n in each group in () (inside the outer 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 glycidyl ether group in the molecule (3) described above include glycidyl ether of an alicyclic alcohol (particularly, an alicyclic polyhydric alcohol). More specifically, for example, 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, 2,2-bis [3,5-dimethyl-4- (2,3-epoxypropoxy)). Cyclohexyl] A compound obtained by hydrogenating a bisphenol A type epoxy compound such as propane (hydrogenated bisphenol A type epoxy compound); bis [o, o- (2,3-epoxypropoxy) cyclohexyl] methane, bis [o , P- (2,3-epoxypropoxy) cyclohexyl] methane, bis [p, p- (2,3-epoxypropoxy) cyclohexyl] methane, bis [3,5-dimethyl-4- (2,3-epoxypropoxy) 3-Epoxy propoxy) Cyclohexyl] A compound obtained by hydrogenating a bisphenol F type epoxy compound such as methane (hydrogenated bisphenol F type epoxy compound); hydrided biphenol type epoxy compound; hydride hydrogenated phenol novolac type epoxy compound; hydride cresol Novolak type epoxy compound; bisphenol A hydride cresol novolak type epoxy compound; hydride naphthalene type epoxy compound; hydride epoxy compound of epoxy compound obtained from trisphenol methane; hydride epoxy compound of the following aromatic epoxy compound, etc. Be done.

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

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

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

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

Further, as other cationic curable compounds, particularly when a vinyl ether compound having one or more hydroxyl groups in the molecule is used, a cured product having excellent heat-resistant yellowing (characteristic that yellowing due to heating is unlikely to occur) is obtained. It has the advantage of being obtained. Therefore, a cured product having higher quality and higher durability can be obtained. The number of hydroxyl groups contained in the molecule of the vinyl ether compound having one or more hydroxyl groups in the molecule is not particularly limited, but is preferably 1 to 4, and more preferably 1 or 2.

The content (blending amount) of the other cationically curable compound in the curable composition of the present invention is not particularly limited, but is the total amount (100% by weight) of the polyorganosylsesquioxane of the present invention and other cationically curable compounds. 50% by weight or less (for example, 0 to 50% by weight), more preferably 30% by weight or less (for example, 0 to 30% by weight), still more preferably 10% by weight, based on the total amount of the cationically curable compound. % Or less. By blending the content of other cationically curable compounds in the above range, desired performance (for example, quick curing and viscosity adjustment for the curable composition) is imparted to the curable composition and the cured product. You may be able to.

[solvent]
The curable composition of the present invention may preferably further contain a solvent. The solvent is not particularly limited as long as it can dissolve the above-mentioned polyorganosylsesquioxane and additives used as necessary and does not inhibit polymerization.

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.) with a temperature of 170 ° C. or lower (at atmospheric pressure) may be used. preferable.

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

The curable composition of the present invention further includes precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, and calcium carbonate as any other components. , Carbon black, silicon carbide, silicon nitride, boron nitride and other inorganic fillers, and these fillers treated with organic silicon compounds such as organohalosilane, organoalkoxysilane and organosilazane; silicone resin, epoxy resin , Organic resin fine powder such as fluororesin; filler such as conductive metal powder such as silver and copper, curing aid, stabilizer (antioxidant, ultraviolet absorber, light resistance stabilizer, heat stabilizer, heavy metal Defoamers, etc.), flame retardants (phosphorus flame retardants, halogen flame retardants, inorganic flame retardants, etc.), flame retardants, reinforcing materials (other fillers, etc.), nucleating agents, lubricants, waxes, plastics Agent, mold release agent, impact resistance improver, hue improver, clearing agent, rheology adjuster (fluidity improver, etc.), processability improver, colorant (dye, pigment, etc.), antistatic agent, dispersant , Surface conditioners (defoamers, leveling agents, anti-armpits, etc.), surface modifiers (slip agents, etc.), matting agents, defoaming agents, defoaming agents, defoaming agents, antibacterial agents, preservatives, It may contain conventional additives such as viscosity modifiers, thickeners, photosensitizers and foaming agents. These additives may be used alone or in combination of two or more.

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.). When coating by spin coating, the viscosity of the curable composition is preferably adjusted according to the coating film thickness, and when coating with a film thickness of 0.1 to 50 μm, it is 1 to 5000 mPa · s. Is preferable. At this viscosity, a coating film having a uniform film thickness can be formed on a substrate such as a silicon wafer. The viscosity of the curable composition 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 under the condition of 25 ° C.

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

The conditions for curing the curable composition of the present invention by irradiation with active energy rays (irradiation conditions for active energy rays, etc.) depend on the type and energy of the active energy rays to be irradiated, the shape and size of the cured product, and the like. It can be adjusted as appropriate and is not particularly limited, but when it is irradiated with ultraviolet rays, it is preferably about 1 to 1000 mJ / cm ² for example. For irradiation of the active energy ray, 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 the 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 condition for curing the curable composition of the present invention by heating is that since the curable composition of the present invention contains polyorganosylsesquioxane, it can be quickly heated at a low temperature of less than 200 ° C. A cured product can be formed. That is, it has low temperature curability. The heating temperature is, for example, 50 to 190 ° C. The curing time can be set as appropriate.

The cured product obtained by curing the curable composition of the present invention has excellent heat resistance, and the thermal decomposition temperature is 200 ° C. or higher (for example, 200 to 500 ° C.), preferably 260 ° C. or higher, particularly preferably 300 ° C. or higher. is there.

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

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

[Adhesive sheet]
By using the curable composition (composition for adhesive) of the present invention, it is an adhesive sheet having at least a base material and an adhesive layer on the base material, and the adhesive layer is the curing of the present invention. An adhesive sheet (sometimes referred to as "the adhesive sheet of the present invention") which is a layer of the sex composition (sometimes referred to as "the adhesive layer of the present invention") can be obtained. The adhesive sheet of the present invention includes not only sheet-like forms but also sheet-like forms such as film-like, tape-like, and plate-like forms. The adhesive sheet of the present invention is not particularly limited, but can be obtained, for example, by applying the curable composition of the present invention to a base material and further drying it if necessary. The method of application is not particularly limited, and well-known and commonly used means can be used. Further, the drying means and conditions are not particularly limited, and conditions that can remove volatile substances such as a solvent as much as possible can be set, and well-known and commonly used means can be used. In particular, when it contains a polymerization initiator having a thermosetting time of 3.5 minutes or more at 130 ° C. of a composition obtained by adding 1 part by weight to 100 parts by weight of celloxide 2021P (manufactured by Daicel Co., Ltd.). By heating and drying, an adhesive layer can be formed quickly without advancing the curing reaction, and since the obtained adhesive layer does not have adhesiveness below 50 ° C., glue is applied to the cutting blade. It can be cut without adhering, and exhibits adhesiveness by heating at a temperature at which damage to the adherend layer such as a semiconductor chip can be suppressed, and then has the property of rapidly curing.

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

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

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

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

[Laminate]
By using the curable composition (composition for adhesive) of the present invention, it is a laminate (laminate) composed of three or more layers (at least three layers), and two layers to be adhered and these. It has at least an adhesive layer (a layer that adheres the adhesive layers to each other) located between the layers to be adhered, and the adhesive layer is a layer of a cured product of the curable composition of the present invention (“Adhesion of the present invention”. A laminate (sometimes referred to as the "laminate of the present invention") that is (sometimes referred to as a "layer") can be obtained. The laminate of the present invention is not particularly limited, but for example, the adhesive layer of the present invention is formed on one layer to be adhered (for example, it can be formed in the same manner as the adhesive layer in the adhesive sheet of the present invention), and further. It can be obtained by adhering the other 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 bonded 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, a laminate in which the base material in the adhesive sheet of the present invention hits the adherend layer is obtained. Further, in the laminate of the present invention, for example, when the adhesive sheet of the present invention is a double-sided adhesive sheet and the base material is a release liner, the adhesive sheet of the present invention is attached to one layer to be adhered and peeled off. It can be obtained by peeling off the liner, then adhering the other layer to be adhered to the exposed adhesive layer, 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 adherend in the laminate of the present invention is not particularly limited, and examples thereof include those similar to the base material in the adhesive sheet. The laminate of the present invention may have only two layers of the body to be adhered, or may have three or more layers. The thickness of the adherend is not particularly limited, and can be appropriately selected in the range of 1 to 100,000 μm, for example. The adherend does not have to have a strict layered morphology.

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

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

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

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

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

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples. In addition, Examples 1 to 4 and 7 to 10 are described as reference examples.
The molecular weight of the product was measured by Alliance HPLC system 2695 (manufactured by Waters), Refractometer Index 2414 (manufactured by Waters), column: Tskgel GMH _HR- M × 2 (manufactured by Toso Co., Ltd.), guard column: Tskgel guard. column (manufactured by Tosoh (Ltd.)) H _HR L, column oven: cOLUMN HEATER U-620 (manufactured by Sugai), solvent: THF, measuring conditions: 40 ° C., the molecular weight was performed by standard polystyrene.
Measurement of FT-IR spectrum of the product, measuring apparatus: trade name "FT-720" (KK Horiba) Measurement method: transmission method, resolution: 4 cm ^-1, measured wavenumbers: 400～4000Cm ^{- 1.} Number of integrations: 16 times.

In the following, the blending amount of the product name “SI-150L” is shown in terms of solid content.

Example 1
(Preparation of polyorganosylsesquioxane (1))
2- (3,4-Epoxide cyclohexyl) 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. 101.47 mmol (25.00 g), methyltrimethoxysilane 101.47 mmol (13.82 g), and acetone 155.29 g were charged and the temperature was raised to 50 ° C. To the mixture thus obtained, 5.61 g (2.03 mmol as potassium carbonate) of a 5% aqueous potassium carbonate solution was added dropwise over 5 minutes, and then 2029 mmol (36.85 g) of water was added dropwise over 20 minutes. No significant temperature rise occurred during the dropping. Then, the polycondensation reaction was carried out under a nitrogen stream for 1 hour at 50 ° C.
Then, after adding methyl isobutyl ketone and a saline solution, the reaction solution was cooled and the upper layer solution was separated. Then, the lower layer liquid was washed with water until it became neutral, and the solvent was distilled off from the upper layer liquid under the conditions of 1 mmHg and 50 ° C. until the solvent amount became 25% by weight, and a colorless and transparent liquid resin (polyorganosilsesqui) was used. Oxane (1)) was obtained. The polystyrene-equivalent weight average molecular weight of the liquid resin (1) was 7100, and the number average molecular weight was 2200 (molecular weight dispersion: 3.23).

Example 2
(Preparation of polyorganosylsesquioxane (2))
EMS150.17 mmol (37.00 g), methyltrimethoxysilane 16.69 mmol (2.27 g) in a 300 mL flask (reaction vessel) equipped with a thermometer, agitator, reflux condenser, and nitrogen introduction tube under a nitrogen stream. ) And 157.09 g of acetone were charged and the temperature was raised to 50 ° C. To the mixture thus obtained, 4.61 g (1.67 mmol as potassium carbonate) of a 5% aqueous potassium carbonate solution was added dropwise over 5 minutes, and then 1669 mmol (30.30 g) of water was added dropwise over 20 minutes. No significant temperature rise occurred during the dropping. Then, the polycondensation reaction was carried out under a nitrogen stream for 4 hours at 50 ° C.
Then, after adding methyl isobutyl ketone and a saline solution, the reaction solution was cooled and the upper layer solution was separated. Then, the lower layer liquid was washed with water until it became neutral, and the solvent was distilled off from the upper layer liquid under the conditions of 1 mmHg and 50 ° C. until the solvent amount became 25% by weight, and a colorless and transparent liquid resin (polyorganosilsesqui) was used. Oxane (2)) was obtained. The polystyrene-equivalent weight average molecular weight of the liquid resin (2) was 2800, and the number average molecular weight was 1700 (molecular weight dispersion: 1.65).

Example 3
(Preparation of polyorganosylsesquioxane (3))
EMS 207.0 mmol (51.0 g), phenyltrimethoxysilane 86.25 mmol (17.1 g) in a 1 L flask (reaction vessel) equipped with a thermometer, agitator, reflux condenser, and nitrogen introduction tube under a nitrogen stream. ), 51.75 mmol (12.23 g) of glycidyltrimethoxysilane, and 321.33 g of acetone were charged and the temperature was raised to 50 ° C. To the mixture thus obtained, 9.54 g (3.45 mmol as potassium carbonate) of a 5% aqueous potassium carbonate solution was added dropwise over 5 minutes, and then 3.45 mol (62.65 g) of water was added dropwise over 20 minutes. .. No significant temperature rise occurred during the dropping. Then, the polycondensation reaction was carried out under a nitrogen stream for 4 hours at 50 ° C.
Then, after adding methyl isobutyl ketone and a saline solution, the reaction solution was cooled and the upper layer solution was separated. Then, the lower layer liquid was washed with water until it became neutral, and the solvent was distilled off from the upper layer liquid under the conditions of 1 mmHg and 50 ° C. until the solvent amount became 25% by weight, and a colorless and transparent liquid resin (polyorganosilsesqui) was used. Oxane (3)) was obtained. The polystyrene-equivalent weight average molecular weight of the liquid resin (3) was 2700, and the number average molecular weight was 1700 (molecular weight dispersion: 1.59).

Example 4
(Preparation of polyorganosylsesquioxane (4))
EMS161.50 mmol (39.79 g), hexyltrimethoxysilane 8.50 mmol (1.75 g) in a 300 mL flask (reaction vessel) equipped with a thermometer, agitator, reflux condenser, and nitrogen introduction tube under a nitrogen stream. ) And 166.18 g of acetone were charged and the temperature was raised to 50 ° C. To the mixture thus obtained, 4.70 g (1.70 mmol as potassium carbonate) of a 5% aqueous potassium carbonate solution was added dropwise over 5 minutes, and then 1699.98 mmol (30.87 g) of water was added dropwise over 20 minutes. did. No significant temperature rise occurred during the dropping. Then, the polycondensation reaction was carried out under a nitrogen stream for 4 hours at 50 ° C.
Then, after adding methyl isobutyl ketone and a saline solution, the reaction solution was cooled and the upper layer solution was separated. Then, the lower layer liquid was washed with water until it became neutral, and the solvent was distilled off from the upper layer liquid under the conditions of 1 mmHg and 50 ° C. until the solvent amount became 25% by weight, and a colorless and transparent liquid resin (polyorganosilsesqui) was used. Oxane (4)) was obtained. The polystyrene-equivalent weight average molecular weight of the liquid resin (4) was 2800, and the number average molecular weight was 1800 (molecular weight dispersion: 1.56).

Example 5
(Preparation of polyorganosylsesquioxane (5))
EMS 161.5 mmol (39.79 g), dodecyltrimethoxysilane 8.5 mmol (2.47 g) in a 300 mL flask (reaction vessel) equipped with a thermometer, agitator, reflux condenser, and nitrogen introduction tube under a nitrogen stream. ) And 169.04 g of acetone were charged and the temperature was raised to 50 ° C. To the mixture thus obtained, 4.70 g (1.7 mmol as potassium carbonate) of a 5% aqueous potassium carbonate solution was added dropwise over 5 minutes, and then 1700 mmol (30.87 g) of water was added dropwise over 20 minutes. No significant temperature rise occurred during the dropping. Then, the polycondensation reaction was carried out under a nitrogen stream for 4 hours at 50 ° C.
Then, after adding methyl isobutyl ketone and a saline solution, the reaction solution was cooled and the upper layer solution was separated. Then, the lower layer liquid was washed with water until it became neutral, and the solvent was distilled off from the upper layer liquid under the conditions of 1 mmHg and 50 ° C. until the solvent amount became 25% by weight, and a colorless and transparent liquid resin (polyorganosilsesqui) was used. Oxane (5)) was obtained. The polystyrene-equivalent weight average molecular weight of the liquid resin (5) was 3400, and the number average molecular weight was 2100 (molecular weight dispersion: 1.62).

Example 6
(Preparation of polyorganosylsesquioxane (6))
EMS 121.76 mmol (30.00 g) and hexadecyltrimethoxysilane 30.44 mmol (10.) in a 300 mL flask (reaction vessel) equipped with a thermometer, agitator, reflux condenser, and nitrogen introduction tube under a nitrogen stream. 55 g) and 162.21 g of acetone were charged and the temperature was raised to 50 ° C. To the mixture thus obtained, 4.21 g (1.52 mmol as potassium carbonate) of a 5% aqueous potassium carbonate solution was added dropwise over 5 minutes, and then 1522 mmol (27.64 g) of water was added dropwise over 20 minutes. No significant temperature rise occurred during the dropping. Then, the polycondensation reaction was carried out under a nitrogen stream for 4 hours at 50 ° C.
Then, after adding methyl isobutyl ketone and a saline solution, the reaction solution was cooled and the upper layer solution was separated. Then, the lower layer liquid was washed with water until it became neutral, and the solvent was distilled off from the upper layer liquid under the conditions of 1 mmHg and 50 ° C. until the solvent amount became 25% by weight, and a colorless and transparent liquid resin (polyorganosilsesqui) was used. Oxane (6)) was obtained. The polystyrene-equivalent weight average molecular weight of the liquid resin (6) was 2300, and the number average molecular weight was 1800 (molecular weight dispersion: 1.28).
When the FT-IR spectrum of polyorganosilsesquioxane obtained since Example 6 was measured by the above method, it was confirmed that one of the specific absorption peaks 1089.58Cm ^-1 around 1100 cm ^-1 ..

Manufacturing example 1
(Preparation of polyorganosylsesquioxane (7))
In a 300 mL flask (reaction vessel) equipped with a thermometer, agitator, a reflux condenser, and a nitrogen introduction tube, EMS162.35 mmol (40.0 g) and acetone 40.0 g were charged under a nitrogen stream and raised to 50 ° C. It was warm. To the mixture thus obtained, 4.49 g (1.62 mmol as potassium carbonate) of a 5% aqueous potassium carbonate solution was added dropwise over 5 minutes, and then 1623.51 mmol (29.48 g) of water was added dropwise over 20 minutes. .. No significant temperature rise occurred during the dropping. Then, the polycondensation reaction was carried out under a nitrogen stream for 3 hours at 50 ° C.
Then, after adding methyl isobutyl ketone and a saline solution, the reaction solution was cooled and the upper layer solution was separated. Then, the lower layer liquid was washed with water until it became neutral, and the solvent was distilled off from the upper layer liquid under the conditions of 1 mmHg and 50 ° C. until the solvent amount became 25% by weight, and a colorless and transparent liquid resin (polyorganosilsesqui) was used. Oxane (7)) was obtained. The polystyrene-equivalent weight average molecular weight of the liquid resin (7) was 14400, and the number average molecular weight was 4000 (molecular weight dispersion: 3.60).

The ratio (molar%), weight average molecular weight, number average molecular weight, and molecular weight dispersion of the silane compounds as raw materials of the polyorganosylsesquioxane (1) to (7) obtained in Examples 1 to 6 and Production Example 1 were determined. It is shown in Table 1. Sample No. in Table 1 (1) to (7) correspond to polyorganosylsesquioxane (1) to (7).

Examples 7-12
(Preparation of adhesive composition)
Adhesive compositions (1) to (6) were prepared by mixing and dissolving according to the composition and amount shown in Table 2. Sample No. of polyorganosylsesquioxane in the table. (1) to (6) correspond to polyorganosylsesquioxane (1) to (6), respectively, and the numbers are parts by weight. The blending amount of the trade name "SI-150L" is shown in terms of solid content.

(Preparation of adhesive layer)
Silane coupling agent (trade name "KBE403", manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter "KBE403") on a silicon plate (size: 2 cm x 5 cm, manufactured by SUMCO Corporation, obtained by dicing a silicon wafer with a diameter of 100 mm) (Sometimes referred to as)) was applied by spin coating and heated at 120 ° C. for 5 minutes to obtain a silicon plate with a silane coupling agent layer.
The adhesive compositions (1) to (6) are 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. Silicon plates with adhesive layers (1) to (6) were obtained. The film thickness of the adhesive layers (1) to (6) was 5 to 6 μm.

(Preparation of laminate)
A silane coupling agent (trade name "KBE403", manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter sometimes referred to as "KBE403") is applied to a glass plate (4 inches, manufactured by SCHOTT Japan Co., Ltd.) by spin coating. The glass plate with a silane coupling agent layer was obtained by heating at 120 ° C. for 5 minutes. Under reduced pressure, the silane coupling agent layer surface of the prepared glass plate with the silane coupling agent layer is combined with the adhesive layer (1) to (6) surfaces, and a pressure of 200 g / cm ² is applied while heating at 60 ° C. After bonding, the laminates (1) to (6) were obtained by heating at 150 ° C. for 30 minutes and then at 170 ° C. for 30 minutes.

The obtained adhesive compositions (1) to (6), adhesive layers (1) to (6), and laminates (1) to (6) were evaluated as follows.
[Evaluation]
(Heat-resistant)
The cured product obtained by heating the adhesive composition was subjected to a heating rate of 10 ° C./min under a nitrogen atmosphere using a thermogravimetric analyzer (trade name "TG-DTA6300", manufactured by Seiko Electronics Co., Ltd.). Thermogravimetric analysis was performed under the conditions of, 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 inflection points where they are occurring (the range indicated by B in the figure) intersect.
Evaluation Criteria: Pass (◯) when the thermal decomposition temperature (T) is 260 ° C. or higher.

(Adhesion)
A grid tape test (JIS K5400-8.5 compliant) was performed on the cured product of the adhesive layer obtained by heating the adhesive layer in the silicon plate with an adhesive layer, and the adhesion to the silicon plate was based on the following criteria. Was evaluated.
Evaluation Criteria: Pass (○) when no peeling of the adhesive layer is observed.

(Crack resistance)
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 thermal shock (heating at 170 ° C. for 30 minutes, heating at 200 ° C. for 30 minutes, or heating at 250 ° C. for 30 minutes. After heating for a minute and then quenching to room temperature), the degree of cracking was evaluated according to the following criteria.
Evaluation Criteria: A cold shock (heated at 170 ° C. for 30 minutes and then rapidly cooled to room temperature) is applied, and a value is defined as Δ when the crack-free portion is 80% or more of the cured product. A thermal shock (heating at 200 ° C. for 30 minutes and then quenching to room temperature) is applied, and the case where the crack-free portion is 80% or more of the cured product is marked with ◯. When a cold shock (heating at 250 ° C. for 30 minutes and then quenching to room temperature) is applied and the crack-free portion is 80% or more of the cured product, ⊚ is defined.

(Adhesiveness)
A razor blade (trade name "single-edged trimming razor", manufactured by Nissin EM) was inserted into the adhesive interface of the laminate, and the adhesion was evaluated according to the following criteria.
Evaluation Criteria: Pass (○) when no peeling is observed on the adhesive surface.

[result]
(Heat-resistant)
The pyrolysis temperature of the cured product obtained by heating the adhesive compositions (1) to (6) at 150 ° C. for 30 minutes and then at 170 ° C. for 30 minutes was 260 ° C. or higher. The results are shown in Table 2.
(Crack resistance)
The adhesive layers (1) to (6) are heated at 150 ° C. for 30 minutes, and then the cured product obtained by heating at 170 ° C. for 30 minutes is heated at 170 ° C. for 30 minutes or at 200 ° C. for 30 minutes. As a result of heating or heating at 250 ° C. for 30 minutes and then quenching to room temperature, it was confirmed that the crack resistance was excellent. The results are shown in Table 2.
(Adhesion)
The adhesive layers (1) to (6) were heated at 150 ° C. for 30 minutes, and then the cured product obtained by heating at 170 ° C. for 30 minutes was subjected to a grid tape test. As a result, the adhesive layers (1) to (1) to No peeling of (6) was observed, and it was confirmed that the adhesion was excellent. The results are shown in Table 2.
(Adhesiveness)
When the razor blade was inserted into the adhesive interface of the laminates (1) to (6), peeling did not occur on the adhesive surface, and it was confirmed that the adhesive layer in the laminate was excellent in adhesiveness. The results are shown in Table 2.

Comparative Example 1
(Preparation of Adhesive Composition (7))
The adhesive composition (7) was prepared by mixing and dissolving according to the composition and amount shown in Table 2. Sample No. of polyorganosylsesquioxane in the table. (7) corresponds to polyorganosylsesquioxane (7), and the numbers are parts by weight.
(Preparation of adhesive layer (7))
A silicon plate with an adhesive layer (7) was obtained in the same manner as in Examples 7 to 12 except that the adhesive composition (7) was used instead of the adhesive compositions (1) to (6). The film thickness of the adhesive layer (7) was 5 to 6 μm.
(Crack resistance)
The obtained adhesive layer (7) was heated at 150 ° C. for 30 minutes, then the cured product obtained by heating at 170 ° C. for 30 minutes was heated at 170 ° C. for 30 minutes, and then rapidly cooled to room temperature. , A crack occurred. The results are shown in Table 2.

The symbols in Table 2 indicate the following compounds.
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.) per 100 parts by weight Thermosetting time of the composition obtained by adding 1 part by weight at 130 ° C.: 5.4 minutes)
SI Auxiliary: (4-Hydroxyphenyl) Dimethylsulfonium Methyl Sulfite (Product Name "Sun Aid SI Auxiliary", manufactured by Sanshin Chemical Industry Co., Ltd.)

The curable composition containing silsesquioxane of the present invention can be cured at a low temperature to form a cured product having excellent heat resistance, crack resistance, adhesiveness to an adherend, and adhesion. Therefore, it is useful as an adhesive used for laminating semiconductors and adhering electronic components and the like.

A Area where there is almost no change in weight B Area where the weight decreases sharply

Claims (12)

The following formula (1)

[In formula (1), R ¹ represents a group containing an epoxy group. ]
In represented by structure Unit及beauty formula (2)

[In formula (2), R ² represents a group containing a non-polymerizable functional group. ]
It has a structural unit represented by the following formula (I).

[In formula (I), ^Ra represents an epoxy group-containing group, a non-polymerizable functional group-containing group, or a hydrogen atom. ]
The structural unit represented by and the following formula (II)

[In formula (II), R ^b represents an epoxy group-containing group, a non-polymerizable functional group-containing group, or a hydrogen atom. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]
The molar ratio of the structural units represented by (I) [constituent unit represented by formula (I) / structural unit represented by formula (II)] is 5 or more and 18 or less, the number average molecular weight is 1000 to 3000, and the molecular weight dispersion. The degree (weight average molecular weight / number average molecular weight) is 1.0 to 3.3.
A polyorganosylsesquioxane in which the non-polymerizable functional group contains at least an alkyl group having 10 to 20 carbon atoms in a substituted or unsubstituted linear or branched chain. The structural unit represented by the above formula (2) and the following formula (5) with respect to the total amount (100 mol%) of the siloxane structural unit.

[In the formula (5), R ² is the same as that in the formula (2). R ^c is the same as that in the above formula (II). ]
The polyorganosylsesquioxane according to claim 1, wherein the proportion (total amount) of the constituent units represented by is 5 mol% or more and 60% or less. The above R ¹ is the following equation (1a)

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

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

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

[In formula (1d), R ^1d represents a linear or branched alkylene group. ]
The polyorganosylsesquioxane according to claim 1 or 2, which is at least one selected from the group consisting of the groups represented by. A curable composition containing the polyorganosylsesquioxane according to any one of claims 1 to 3. The curable composition according to claim 4, further comprising a polymerization initiator. The curable composition according to claim 4 or 5, further comprising a polymerization stabilizer. The curable composition according to any one of claims 4 to 6, further comprising a silane coupling agent. The curable composition according to any one of claims 4 to 7, which is a composition for an adhesive. A cured product of the curable composition according to any one of claims 4 to 8. An adhesive sheet having a base material and an adhesive layer on the base material.
An adhesive sheet, wherein the adhesive layer is a layer of the curable composition according to claim 8. 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 8. The apparatus having the laminate according to claim 11.

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