JP6557521B2 - Polyorganosilsesquioxane, hard coat film, adhesive sheet, laminate and apparatus - Google Patents

Description

  The present invention relates to a polyorganosilsesquioxane, a curable composition containing the polyorganosilsesquioxane, and a cured product thereof. The present invention also relates to a hard coat film having a hard coat layer formed from a hard coat liquid (hard coat agent) containing the polyorganosilsesquioxane. The present invention also relates to a composition (adhesive composition) containing the polyorganosilsesquioxane, and an adhesive sheet, laminate and apparatus using the composition.

  Conventionally, a hard coat film having a hard coat layer on one side or both sides of a substrate and having a hard hardness of about 3H on the surface of the hard coat layer has been distributed. As a material for forming a hard coat layer in such a hard coat film, a UV acrylic monomer is mainly used (for example, see Patent Document 1). There is also an example in which nanoparticles are added to the hard coat layer in order to further improve the pencil hardness of the hard coat layer surface.

  On the other hand, glass is known as a material having a very high surface hardness. In particular, glass whose surface pencil hardness is increased to 9H by an alkali ion exchange treatment is known. However, flexibility and workability are known. Therefore, it is impossible to manufacture and process by roll-to-roll method, and it is necessary to manufacture and process by a single wafer, which requires high production cost.

  On the other hand, curable adhesives containing benzocyclobutene (BCB), novolac epoxy resins, or polyorganosilsesquioxanes are known as adhesives used for semiconductor lamination and electronic component adhesion ( For example, refer to Patent Document 2 or 3).

JP 2009-279840 A JP 2010-2226060 A JP 2014-101396 A

  However, it has not been said that the hard coat film using the above-mentioned UV acrylic monomer has sufficient surface hardness. Generally, in order to increase the hardness, it is conceivable to use a polyfunctional UV acryl monomer or to increase the thickness of the hard coat layer. However, if such a method is adopted, the curing shrinkage of the hard coat layer may be reduced. As a result, there is a problem that curls and cracks occur in the hard coat film. Further, when nanoparticles are added to the hard coat layer, if the compatibility between the nanoparticles and the UV acrylic monomer is poor, there is a problem that the nanoparticles aggregate and the hard coat layer is whitened.

  On the other hand, in the alkali ion exchange treatment of glass, since a large amount of alkali waste liquid is generated, there is a problem that the environmental load is large. Further, the glass has a drawback that it is heavy and easily broken, and a cost is high. For this reason, an organic material excellent in flexibility and workability and having a high surface hardness is required.

  On the other hand, in order to cure the thermosetting adhesive containing BCB, it is necessary to heat at a high temperature of about 200 to 350 ° C., and the adherend may be damaged by being exposed to the high temperature. was there. In addition, a thermosetting adhesive containing a novolac epoxy resin is likely to degrade its adhesiveness due to decomposition of the adhesive when subjected to a high-temperature process (for example, 260 to 280 ° C.) such as lead-free solder reflow. That was the problem.

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

Accordingly, an object of the present invention is to provide a polyorganosilsesquioxane that can be cured to form a cured product having high surface hardness and excellent flexibility and workability.
Another object of the present invention is to provide a hard coat film which has flexibility and can be manufactured and processed by a roll-to-roll method while maintaining high surface hardness.
Furthermore, the other object of this invention is to provide the said hard coat film which can be further stamped.
On the other hand, another object of the present invention is to cure at a low temperature to form a cured product (adhesive) excellent in heat resistance, crack resistance (or thermal shock resistance), adhesion to an adherend and adhesion. It is providing a curable composition (adhesive composition) and an adhesive sheet, a laminate, and an apparatus using the same.

The present inventors have a silsesquioxane structural unit (T unit structure) containing an epoxy group and an organosiloxane unit (D unit structure), and the ratio of a specific structure (ratio of T3 body / D2 body). According to the polyorganosilsesquioxane controlled in a specific range and the number average molecular weight and molecular weight dispersity controlled in a specific range, it is high by curing the curable composition containing the polyorganosilsesquioxane. It has been found that a cured product having surface hardness and excellent flexibility and workability can be formed. In addition, the inventors of the present invention have a hard coat film having a hard coat layer formed from a hard coat solution containing the polyorganosilsesquioxane having flexibility while maintaining high surface hardness. It was found that it is a hard coat film that can be manufactured and processed by the to-roll method.
In addition, the present inventors have found that the curable composition containing the polyorganosilsesquioxane is cured at a low temperature, resulting in heat resistance, crack resistance (or thermal shock resistance), adhesion to an adherend and adhesion. It has been found that it can be preferably used as a composition for an adhesive (adhesive) capable of forming a cured product (adhesive) having excellent properties. The present invention has been completed based on these findings.

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

[In Formula (1), R < ¹ > shows group containing an epoxy group. ]
And a structural unit represented by the following formula (2)

[In the formula (2), R ² and R ³ are the same or different and each represents a group containing an epoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cyclohexane. An alkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom is shown. ]
Having a structural unit represented by
Formula (I)

[In the formula (I), R ^a is a group containing an epoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group. Represents a substituted or unsubstituted alkenyl group or a hydrogen atom. ]
The molar ratio of the structural unit represented by the formula (2) and the structural unit represented by the formula (2) [the structural unit represented by the formula (I) / the structural unit represented by the formula (2)] is 0.1 to 0.1. 20
A polyorganosilsesquioxane having a number average molecular weight of 1000 to 3000 and a molecular weight dispersity (weight average molecular weight / number average molecular weight) of 1.0 to 3.0 is provided.

  In the polyorganosilsesquioxane, the structural unit represented by the formula (1) with respect to the total amount (100 mol%) of the siloxane structural unit, and the following formula (5)

[In formula (5), R ¹ is the same as that in formula (1). R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]
And the following formula (2 ′)

[In the formula (2 ′), R ^2a and R ^3a are the same or different and are each an epoxy group-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted group. A cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom; However, at least one of R ^2a and R ^3a is a group containing an epoxy group. ]
The ratio of the structural unit represented by may be 5 to 95 mol%.

  The polyorganosilsesquioxane further has the following formula (3)

[In the formula (3), R ⁴ represents a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted group. An alkenyl group of ]
You may have the structural unit represented by these.

In the polyorganosilsesquioxane, the R ¹ is represented by the following formula (1a)

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

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

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

[In formula (1d), R ^1d represents a linear or branched alkylene group. ]
The group represented by these may be sufficient.

In the polyorganosilsesquioxane, R ⁴ may be a substituted or unsubstituted aryl group.

Moreover, this invention provides the curable composition containing the said polyorgano silsesquioxane.
The curable composition may further contain a polymerization initiator.
The polymerization initiator may be a cationic photopolymerization initiator.
The polymerization initiator may be a thermal cationic 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 further contain a vinyl ether compound.
The curable composition may further contain a vinyl ether compound having a hydroxyl group in the molecule.
The curable composition may be a curable composition for forming a hard coat layer.
The curable composition may be an adhesive composition.

Moreover, this invention provides the hardened | cured material obtained by hardening the said curable composition.
The present invention also provides a hard coat film having a base material and a hard coat layer formed on at least one surface of the base material, wherein the hard coat layer is the curable composition for forming the hard coat layer. A hard coat film characterized by being a cured product layer of a product.
In the hard coat film, the hard coat layer may have a thickness of 1 to 200 μm.
The hard coat film can be manufactured by a roll-to-roll method.
The hard coat film may further have a surface protective film on the surface of the hard coat layer.

  The present invention also includes a step A for feeding a substrate wound in a roll shape, and applying the curable composition for forming a hard coat layer to at least one surface of the fed substrate, and then the curable composition. Including a step B in which a hard coat layer is formed by curing and a step C in which the obtained hard coat film is wound around a roll again, and the steps A to C are continuously performed. A method for producing a hard coat film is provided.

Further, the present invention is an adhesive sheet having a substrate and an adhesive layer on the substrate,
An adhesive sheet is provided in which the adhesive layer is a layer of the adhesive composition.
The present invention is a laminate composed of three or more layers,
Having two layers to be adhered and an adhesion layer between the layers to be adhered;
The adhesive layer is a layer of a cured product of the curable composition for adhesives.
Moreover, this invention provides the apparatus which has the said laminated body.

Since the polyorganosilsesquioxane of the present invention has the above-described configuration, it has a high surface hardness, flexibility and processing by curing a curable composition containing the polyorganosilsesquioxane as an essential component. A cured product having excellent properties can be formed. Moreover, since the hard coat film of this invention has the said structure, it has a flexibility, maintaining high surface hardness, and manufacture and a process by roll to roll are possible. For this reason, the hard coat film of the present invention is excellent in both quality and cost.
Furthermore, the curable composition containing the polyorganosilsesquioxane as an essential component is cured at a low temperature to form a cured product excellent in heat resistance, crack resistance, adhesion to an adherend and adhesion. be able to. Therefore, the curable composition of the present invention can be preferably used as an adhesive composition (adhesive). Moreover, an adhesive sheet, a laminate, and a device can be obtained by using the adhesive composition. Moreover, since the adhesive sheet of this invention has the said structure, it is excellent in heat resistance, crack resistance, the adhesiveness with respect to a to-be-adhered body, and adhesiveness.
If cracks or peeling occurs in the adhesive layer in the laminate, the adherend layer may peel off or the wiring may be destroyed, resulting in a failure of the device provided with the laminate. Since the object is excellent in heat resistance, crack resistance, adhesion to an adherend and adhesion, it is possible to prevent the adhesion layer from being cracked or peeled off, and to improve the reliability of the apparatus. And, when the laminate of the present invention is a three-dimensional laminate of semiconductor chips, it is more integrated and power-saving than the conventional semiconductor, so if the laminate of the present invention is used, it is smaller and has higher performance. An electronic device can be provided.

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

[Polyorganosilsesquioxane]
The polyorganosilsesquioxane (silsesquioxane) of the present invention has a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2);
Molar ratio of the structural unit represented by the following formula (I) (sometimes referred to as “T3 body”) and the structural unit represented by the following formula (2) (sometimes referred to as “D2 body”) [formula The structural unit represented by (I) / the structural unit represented by formula (2); “may be described as“ T3 body / D2 body ”] is 0.1-20;
The number average molecular weight is 1000 to 3000, and the molecular weight dispersity [weight average molecular weight / number average molecular weight] is 1.0 to 3.0.

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

R ¹ in the formula (1) represents a group (monovalent group) containing an epoxy group. That is, the polyorganosilsesquioxane of the present invention is a cationic curable compound (cationic polymerizable compound) having at least an epoxy group in the molecule. Examples of the group containing an epoxy group include known or conventional groups having an oxirane ring, and are not particularly limited. However, from the viewpoints of curability of the curable composition, surface hardness and heat resistance of the cured product, The group represented by (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 preferred, and more preferably the following formula ( The group represented by 1a), the group represented by the following formula (1c), and more preferably the group represented by the following formula (1a).

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

In the above formula (1b), R ^1b represents a linear or branched alkylene group, and examples thereof include the same groups as R ^1a . Among 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, more preferably, from the viewpoint of the surface hardness or curability of the cured product. An ethylene group, a trimethylene group, and a propylene group, and more preferably an ethylene group and a trimethylene group.

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

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

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

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

In addition to the silsesquioxane structural unit represented by the above formula (1), the polyorganosilsesquioxane of the present invention is represented by the following formula (2) as an organosiloxane structural unit [R ₂ SiO _2/2 ]. It is characterized by having a structural unit.

The structural unit represented by the above formula (2) is an organosiloxane structural unit (D unit) generally represented by [R ₂ SiO _2/2 ]. That is, the structural unit represented by the above formula (2) is a hydrolysis and condensation reaction of a corresponding hydrolyzable bifunctional silane compound (specifically, for example, a compound represented by the following formula (b)). It is formed by.

R ² and R ³ in the above formula (2) are the same or different and each represents a group containing an epoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cyclohexane. An alkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom is shown. Examples of the group containing the epoxy group include the same groups as those described above for R ¹ . As said aryl group, a phenyl group, a tolyl group, a naphthyl group etc. are mentioned, for example. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the cycloalkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like. Examples of the alkyl group include linear or branched alkyl groups such as methyl group, ethyl group, propyl group, n-butyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, and isopentyl group. Groups. As said alkenyl group, linear or branched alkenyl groups, such as a vinyl group, an allyl group, and an isopropenyl group, are mentioned, for example.

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

Among them, R ² and R ³ are preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, more preferably a substituted or unsubstituted alkyl group, and still more preferably A methyl group and an ethyl group.

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

  In the polyorganosilsesquioxane of the present invention, the proportion of the structural unit represented by the above formula (1) and the structural unit represented by the above formula (2) [the structural unit / formula represented by the formula (1) ( The structural unit represented by 2)] is not particularly limited, but is preferably 0.05 to 20, more preferably 0.1 to 5, and still more preferably 0.3 to 5. By making the said ratio 0.05 or more, there exists a tendency for the surface hardness and adhesiveness of hardened | cured material or a hard-coat layer to improve remarkably. On the other hand, when the ratio is 20 or less, crack resistance tends to be improved, and it becomes easy to apply without diluting in a solvent, and a process of removing the solvent by drying tends to be unnecessary. .

  In the polyorganosilsesquioxane of the present invention, the ratio of each siloxane structural unit (silsesquioxane structural unit represented by formula (1), polyorganosiloxane structural unit represented by formula (2)) is as follows: It is possible to adjust appropriately according to the composition of the raw materials (hydrolyzable trifunctional silane, hydrolyzable bifunctional silane) for forming these structural units.

The polyorganosilsesquioxane of the present invention has a constitution represented by the following formula (3) in addition to the constitutional unit represented by the above formula (1) as a silsesquioxane constitution unit [RSiO _3/2 ]. You may have a unit.

The structural unit represented by the above formula (3) is a silsesquioxane structural unit (T unit) generally represented by [RSiO _3/2 ]. That is, the structural unit represented by the above formula (3) is a hydrolysis and condensation reaction of a corresponding hydrolyzable trifunctional silane compound (specifically, for example, a compound represented by the following formula (c)). It is formed by.

R ⁴ in the above formula (3) is a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted group An alkenyl group of Specific examples of R ⁴ include a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group in the above R ² and R ³ , and Examples are the same as the substituted or unsubstituted alkenyl group.

Among them, R ⁴ is preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, more preferably a substituted or unsubstituted aryl group, more preferably a phenyl group. is there.

  The polyorganosilsesquioxane of the present invention may have only one type of structural unit represented by the above formula (3), or two or more types of structural units represented by the above formula (3). You may have.

  Each of the above-mentioned siloxane structural units (the structural unit represented by the formula (1), the structural unit represented by the formula (2), the structural unit represented by the formula (3)) in the polyorganosilsesquioxane of the present invention. This ratio can be appropriately adjusted depending on the composition of the raw materials (hydrolyzable trifunctional silane, hydrolyzable bifunctional silane) for forming these structural units.

In addition to the structural unit represented by the above formula (1), the structural unit represented by the formula (2), and the structural unit represented by the formula (3), the polyorganosilsesquioxane of the present invention further includes These are represented by the structural units represented by the above formula (1) and silsesquioxane structural units other than the structural unit represented by the formula (3) [RSiO _3/2 ], [R ₃ SiO _1/2 ]. A structural unit (so-called M unit), a structural unit represented by [R ₂ SiO _2/2 ] other than the structural unit represented by formula (2) (so-called D unit), and [SiO _4/2 ] It may have at least one siloxane structural unit selected from the group consisting of structural units (so-called Q units).

  In the polyorganosilsesquioxane of the present invention, the ratio of the structural unit (T3 body) represented by the above formula (I) and the structural unit (D2 body) represented by the above formula (2) [T3 body / D2 body] ] Is 0.1-20 as mentioned above, Preferably it is 0.1-5, More preferably, it is 0.3-5. When the ratio [T3 body / D2 body] is 0.1 or more, the surface hardness and adhesiveness of the cured product and the hard coat layer tend to be improved. On the other hand, when the ratio is 20 or less, the crack resistance tends to be improved, and it becomes easy to apply without diluting in a solvent, and the process of removing the solvent by drying tends to be unnecessary.

  When the structural unit represented by the above formula (I) is described in more detail, it is represented by the following formula (I ′). Moreover, when the structural unit represented by the above formula (2) is described in more detail, it is represented by the following formula (2a). Each of the three oxygen atoms bonded to the silicon atom shown in the structure represented by the following formula (I ′) is bonded to another silicon atom (a silicon atom not shown in the formula (I ′)). . On the other hand, two oxygen atoms located above and below the silicon atom shown in the structure represented by the following formula (2a) are bonded to other silicon atoms (silicon atoms not shown in the formula (2a)), respectively. ing. That is, the T3 body is a structural unit (T unit) formed by hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound, and the D2 body is the corresponding hydrolyzable bifunctional silane compound. It is a structural unit (D unit) formed by hydrolysis and condensation reaction.

R ^2, R ³ in the formula (I) in the R ^a (R ^a same in formula (I ')) and the formula (2a) (R ² in the formula (2), R ³⁾ is a virtual , Respectively, a group containing an epoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group Or a hydrogen atom. Specific examples of R ^a are the same as R ² and R ³ in the above formula (2). In the formula (I), ^Ra represents a group bonded to a silicon atom in the hydrolyzable trifunctional silane compound used as a raw material for the polyorganosilsesquioxane of the present invention (a group other than an alkoxy group and a halogen atom; For example, it is derived from the formulas (a), (c), and (d) described later, R ¹ , R ⁴ , hydrogen atoms, etc. In the formula (2), R ² and R ³ are groups bonded to silicon atoms (other than alkoxy groups and halogen atoms) in the hydrolyzable bifunctional silane compound used as a raw material for the polyorganosilsesquioxane of the present invention. Derived from, for example, R ² and R ³ in formula (b) described later).

  Moreover, the polyorganosilsesquioxane of this invention can also contain the structural unit (T2 body) represented by following formula (II) in addition to the said T3 body and D2 body.

  When the structural unit represented by the above formula (II) is described in more detail, it is represented by the following formula (II ′).

  Two oxygen atoms located above and below the silicon atom shown in the structure represented by the formula (II ′) are bonded to other silicon atoms (silicon atoms not shown in the formula (II ′)), respectively. ing. That is, the T2 isomer is a structural unit (T unit) formed by hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound.

R ^b in the formula (II) (Formula (II ') in the R ^b) is a virtual, group containing an epoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted A substituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom is shown. Specific examples of R ^b are the same as R ² and R ³ in the above formula (2). In the formula (II), R ^b represents a group (group other than an alkoxy group and a halogen atom) bonded to a silicon atom in the hydrolyzable trifunctional silane compound used as a raw material of the polyorganosilsesquioxane of the present invention; For example, it is derived from the formulas (a), (c), and (d) described later, R ¹ , R ⁴ , hydrogen atoms, etc.

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

Presence ratio of each of the structural units (T3 body, D2 body, T2 body, etc.) in the polyorganosilsesquioxane of the present invention (for example, the above-mentioned [T3 body / D2 body], [T3 body / T2 body], etc.) Can be determined by, for example, ²⁹ Si-NMR spectrum measurement. ^{In the 29} Si-NMR spectrum, the silicon atom in the structural unit (T3 form) represented by the formula (I), the structural unit (D2 form) represented by the formula (2), and the formula (II) Since a signal (peak) is shown at a different position (chemical shift) from the silicon atom in the structural unit (T2 body), the abundance ratio of each structural unit is obtained by calculating the integration ratio of each of these peaks. It is done. Specifically, for example, the polyorganosilsesquioxane 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 form) represented by the above formula (I) appears at −64 to −70 ppm, and the silicon atom in the structure (T2 form) represented by the above formula (II) The signal appears at -54 to -60 ppm. Moreover, the signal of the silicon atom in the structure (D2 form) represented by Formula (2) having a structural unit in which R ² and R ³ are methyl groups appears at −10 to −25 ppm. Therefore, in this case, by calculating an integration ratio of a signal (T3 body) of −64 to −70 ppm, a signal (D2 body) of −10 to −25 ppm, and a signal (T2 body) of −54 to −60 ppm. , The abundance ratio of each structural unit (for example, the above-mentioned [T3 body / D2 body] and the like) can be obtained.

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

In the polyorganosilsesquioxane of the present invention, in addition to the D2 form relative to the T3 form, when a certain amount or more of the T2 form exists, the T2 form may be represented by, for example, the following formula (5) Examples thereof include a unit, a structural unit represented by the following formula (6), and a structural unit represented by the following formula (7). R ⁴ R ¹ and the following formula in the formula (5) in (6) are respectively the same as R ⁴ in R ¹ and the formula (3) in the formula (1). R ^c in the formula (5) to (7), like the R ^c in above-mentioned formula (II), a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In general, the complete cage silsesquioxane is a polyorganosilsesquioxane composed only of T3 form, and D2 form and T2 form do not exist in the molecule. In contrast, in the polyorganosilsesquioxane of the present invention, the ratio [T3 body / D2 body] is 0.1 to 20, the number average molecular weight is 1000 to 3000, and the molecular weight dispersity is 1.0. To 3.0, and the polyorganosilsesquioxane of the present invention having one intrinsic absorption peak in the vicinity of 1100 cm ⁻¹ in the FT-IR spectrum as described later has a cage-cleavable silsesquioxane structure. It is suggested to have

  In addition, when not including the structural unit (D2 body) represented by Formula (2) as a structural unit of polyorganosilsesquioxane, for example, the ratio of [T3 body / T2 body] is in the range of 3 to 15 In this case, it is suggested that it has an incomplete cage silsesquioxane structure located between the complete cage silsesquioxane structure and the cage cleavage silsesquioxane structure.

  In contrast, the polyorganosilsesquioxane of the present invention contains a structural unit (D2 form) represented by the formula (2), so that a structure in which the cage is reliably cleaved at the D2 form part is formed. There is no transition to a complete cage silsesquioxane structure, or the cage-cleavable silsesquioxane structure is stabilized by the D2 form forming a partial linear structure and linking the cage structures. It is thought that it forms. Since the polyorganosilsesquioxane of the present invention has such a cage cleavage type silsesquioxane structure, there are effects unique to the present invention such as improved crack resistance and being able to be applied without being diluted in a solvent. It is inferred that In addition, the said description is guess and does not limit this invention at all.

The polyorganosilsesquioxane of the present invention has a cage-cleavable silsesquioxane structure, polyorganosilsesquioxane of the present invention, the FT-IR spectra 1050 cm ^-1 and near 1150 cm ^-1, respectively in the vicinity of This is confirmed by having one intrinsic absorption peak in the vicinity of 1100 cm ⁻¹ without having an intrinsic absorption peak. On the other hand, in general, when the FT-IR spectrum has intrinsic absorption peaks near 1050 cm ⁻¹ and 1150 cm ⁻¹ , it is identified as having a ladder-type silsesquioxane structure. In addition, the FT-IR spectrum of the polyorganosilsesquioxane of this invention can be measured with the following apparatus and conditions, for example.
Measuring device: Trade name “FT-720” (manufactured by Horiba, Ltd.)
Measurement method: Transmission method Resolution: 4 cm ^-1
Measurement wavenumber range: 400 to 4000 cm ⁻¹
Integration count: 16 times

  The total amount of siloxane structural units in the polyorganosilsesquioxane of the present invention [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%). The proportion (total amount) of the structural unit, the structural unit represented by the above formula (5), and the structural unit represented by the following formula (2 ′) is not particularly limited, but is preferably 5 to 95 mol%. More preferably, it is 15-90 mol%, More preferably, it is 20-85 mol%, Most preferably, it is 25-80 mol%. By making the said ratio 5 mol% or more, the sclerosis | hardenability of a curable composition improves and the surface hardness and adhesiveness of hardened | cured material become remarkably high. On the other hand, when the ratio is 95 mol% or less, the gas barrier property of the cured product tends to be improved. In addition, the ratio of each siloxane structural unit in the polyorganosilsesquioxane of this invention is computable by the composition of a raw material, NMR spectrum measurement, etc., for example.

R ^2a and R ^3a in the above formula (2 ′) are the same or different and are each an epoxy group-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted group. A cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom; However, at least one of R ^2a and R ^3a is a group containing an epoxy group. Specific examples of R ^2a and R ^3a are the same as those described above for R ² and R ³ .

  The total amount of siloxane structural units in the polyorganosilsesquioxane of the present invention [all siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%). The proportion (total amount) of the structural unit, the structural unit represented by the above formula (6) and the structural unit represented by the above formula (2 ″) is not particularly limited, but is preferably 5 to 95 mol%. Preferably it is 10-85 mol%, More preferably, it is 15-80 mol%, Most preferably, it is 20-75 mol% By making the said ratio into 95 mol% or less, it is relatively represented by Formula (1). The proportion of the structural unit represented by formula (5) and the structural unit represented by formula (2 ′) can be increased, so that the curability of the curable composition is improved and the cured product is obtained. Higher surface hardness and adhesion I tend. Contrast, by setting the ratio 5 mol% or more, there is a tendency to increase the gas barrier properties of the cured product.

R ^2b and R ^3b in the above formula (2 ″) are the same or different and each represents a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, substituted or unsubstituted A substituted alkyl group, or a substituted or unsubstituted alkenyl group, and specific examples of R ^2b and R ^3b are the same as those described above for R ⁴ .
R ^2b and R ^3b are preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, more preferably a substituted or unsubstituted alkyl group, and still more preferably a methyl group. , An ethyl group.

  The total amount of siloxane structural units in the polyorganosilsesquioxane of the present invention [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%). Although the ratio of the structural unit to be formed is not particularly limited, it is preferably 5 to 95 mol%, more preferably 10 to 85 mol%, still more preferably 15 to 80 mol%, and particularly preferably 20 to 75 mol%. By making the said ratio 95 mol% or less, the sclerosis | hardenability of a curable composition improves and there exists a tendency for the surface hardness and adhesiveness of hardened | cured material to become higher. On the other hand, when the ratio is 5 mol% or more, crack resistance tends to be improved, and it becomes easy to apply without diluting in a solvent, and a step of removing the solvent from the drying ability becomes unnecessary. Tend.

  The total amount of siloxane structural units in the polyorganosilsesquioxane of the present invention [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%). The structural unit represented by the above formula (3), the structural unit represented by the above formula (5), the structural unit represented by the above formula (6), and the above formula (2 ′). The proportion (total amount) of the structural units is not particularly limited, but is preferably 60 to 100 mol%, more preferably 70 to 100 mol%, still more preferably 80 to 100 mol%. By setting the above ratio to 60 mol% or more, the surface hardness and adhesiveness of the cured product tend to be higher.

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

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

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

The 5% weight loss temperature (T _d5 ) in the air atmosphere of the polyorganosilsesquioxane of the present invention is not particularly limited, but is preferably 330 ° C. or higher (for example, 330 to 450 ° C.), more preferably 340 ° C. or higher. More preferably, it is 350 ° C. or higher. When the 5% weight reduction temperature is 330 ° C. or higher, the heat resistance of the cured product tends to be further improved. In particular, in the polyorganosilsesquioxane of the present invention, the ratio [T3 / D2] is 0.1 to 20, the number average molecular weight is 1000 to 3000, and the molecular weight dispersity is 1.0 to 3. By being one and having one intrinsic peak in the vicinity of 1100 cm ⁻¹ in the FT-IR spectrum, the 5% weight loss temperature is controlled to 330 ° C. or higher. The 5% weight reduction temperature is a temperature at the time when 5% of the weight before heating is reduced when heated at a constant rate of temperature increase, and serves as an index of heat resistance. The 5% weight loss temperature can be measured by TGA (thermogravimetric analysis) under an air atmosphere at a temperature rising rate of 5 ° C./min.

  The polyorganosilsesquioxane of the present invention can be produced by a known or conventional polysiloxane production method, and is not particularly limited. For example, one or two or more hydrolyzable silane compounds are hydrolyzed and It can be produced by a method of condensation. However, as the hydrolyzable silane compound, a hydrolyzable trifunctional silane compound (compound represented by the following formula (a)) for forming the structural unit represented by the above formula (1) and the above described It is necessary to use a hydrolyzable bifunctional silane compound (compound represented by the following formula (b)) for forming the structural unit represented by the formula (2) 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. And a compound represented by the following formula (b) which is a hydrolyzable silane compound for forming an organosiloxane structural unit (D2 unit), and if necessary, a compound represented by the following formula (c), The polyorganosilsesquioxane of this invention can be manufactured by the method of hydrolyzing and condensing the compound represented by Formula (d).

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

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

The compound represented by the above formula (b) is a compound that forms the structural unit represented by the formula (2) in the polyorganosilsesquioxane of the present invention. R ² and R ³ in the formula (b), like the R ^2, R ³ in the formula (2), identical or different, each group containing an epoxy group, a substituted or unsubstituted aryl group, a substituted Or an unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom; That is, R ² and R ³ in formula (b) are preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, more preferably a substituted or unsubstituted group. An alkyl group, more preferably a methyl group or an ethyl group.

X ² in the above formula (b) represents an alkoxy group or a halogen atom. Specific examples of X ² include those exemplified as X ¹ . Among them, X ² is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. Note that the two X ^{2 s} may be the same or different.

The compound represented by the above formula (c) is a compound that forms the structural unit represented by the formula (3) in the polyorganosilsesquioxane of the present invention. R ⁴ in formula (c) is a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted group An alkenyl group is shown. That is, R ⁴ in the formula (c) is preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, more preferably a substituted or unsubstituted aryl group, More preferred is a phenyl group.

X ³ in the above formula (c) represents an alkoxy group or a halogen atom. Specific examples of X ³ include those exemplified as X ¹ . Among them, X ³ is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. The three X ³ may be the same or different.

The compound represented by the above formula (d) is a compound that forms a structural unit containing a hydrosilyl group (SiH group) in the polyorganosilsesquioxane of the present invention. X ⁴ in the above formula (d) represents an alkoxy group or a halogen atom. Specific examples of X ⁴ include those exemplified as X ¹ . Among them, X ⁴ is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. The three X ⁴ may be the same or different.

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

  The amount and composition of the hydrolyzable silane compound can be appropriately adjusted according to the desired structure of the polyorganosilsesquioxane of the present invention. For example, the amount of the compound represented by the above formula (a) and the compound represented by the following formula (b ′) is not particularly limited, but is based on the total amount (100 mol%) of the hydrolyzable silane compound to be used. 5 to 95 mol% is preferable, more preferably 15 to 90 mol%, still more preferably 20 to 85 mol%, and particularly preferably 25 to 80 mol%.

Formula (b ') R ^2a and R ^3a in the above formula (2' R ^2a in) the same as R ^3a, X ² in formula (b ') is X in the above formula (b) Same as ² .

  The amount of the compound represented by the formula (b) is not particularly limited, but is preferably 5 to 95 mol%, more preferably based on the total amount (100 mol%) of the hydrolyzable silane compound to be used. Is 10 to 85 mol%, more preferably 15 to 80 mol%, particularly preferably 20 to 75 mol%.

  The amount of the compound represented by the above formula (c) and the compound represented by the following formula (b ″) is not particularly limited, but is based on the total amount (100 mol%) of the hydrolyzable silane compound to be used. The content is preferably 5 to 95 mol%, more preferably 10 to 85 mol%, still more preferably 15 to 80 mol%, and particularly preferably 20 to 75 mol%.

Formula (b ") R ^2b and R ^3b in the above formula (2" R ^2b in) is the same as R ^3b, X ² in formula (b "), the X in the above formula (b) Same as ² .

  Furthermore, the ratio (total amount) of the compound represented by the formula (a), the compound represented by the formula (b) and the compound represented by the formula (c) with respect to the total amount (100 mol%) of the hydrolyzable silane compound to be used. Is not particularly limited, but is preferably 60 to 100 mol%, more preferably 70 to 100 mol%, and still more preferably 80 to 100 mol%.

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

  The hydrolysis and condensation reaction of the hydrolyzable silane compound can be performed in the presence of a solvent or in the absence. Among these, it is preferable to carry out in the presence of a solvent. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methyl acetate and ethyl acetate. , Esters such as isopropyl acetate and butyl acetate; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; nitriles such as acetonitrile, propionitrile and benzonitrile; alcohols such as methanol, ethanol, isopropyl alcohol and butanol Etc. Among them, ketone and ether are preferable. In addition, a solvent can also be used individually by 1 type and can also be used in combination of 2 or more type.

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

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

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

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

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

  As reaction conditions for performing the hydrolysis and condensation reaction of the hydrolyzable silane compound, the ratio [T3 body / D2 body] in the polyorganosilsesquioxane of the present invention is 0.1 to 20, in particular. It is important to select such reaction conditions. Although the reaction temperature of the said hydrolysis and condensation reaction is not specifically limited, 40-100 degreeC is preferable, More preferably, it is 45-80 degreeC. By controlling the reaction temperature within the above range, the ratio [T3 body / D2 body] tends to be more efficiently controlled to 0.1-20. Moreover, the reaction time of the said hydrolysis and condensation reaction is although it does not specifically limit, 0.1 to 10 hours are preferable, More preferably, it is 1.5 to 8 hours. The hydrolysis and condensation reaction can be performed under normal pressure, or can be performed under pressure or under reduced pressure. In addition, the atmosphere at the time of performing the hydrolysis and condensation reaction is not particularly limited, and may be any of, for example, in an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere, or in the presence of oxygen such as in the air. However, an inert gas atmosphere is preferred.

  The polyorganosilsesquioxane of the present invention is obtained by hydrolysis and condensation reaction of the hydrolyzable silane compound. After completion of the hydrolysis and condensation reaction, it is preferable to neutralize the catalyst in order to suppress the ring opening of the epoxy group. In addition, the polyorganosilsesquioxane of the present invention can be combined with, for example, separation means such as water washing, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, and the like. Separation and purification may be performed by separation means or the like.

  Since the polyorganosilsesquioxane of the present invention has the above-described configuration, it can have high surface hardness and heat resistance by curing a curable composition containing the polyorganosilsesquioxane as an essential component. A cured product excellent in flexibility and workability can be formed. Moreover, the hardened | cured material excellent in adhesiveness can be formed.

[Curable composition]
The curable composition of the present invention is a curable composition (curable resin composition) containing the polyorganosilsesquioxane of the present invention as an essential component. As will be described later, the curable composition of the present invention further includes other initiators such as a polymerization initiator, a polymerization stabilizer, a silane coupling agent, other cationic curable compounds, a solvent, a surface conditioner, or a surface modifier. Ingredients may be included.

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

  The content (blending amount) of the polyorganosilsesquioxane 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 not less than 100% by weight and more preferably less than 100% by weight, more preferably 80 to 99.8% by weight, and still more preferably 90 to 99.5% by weight. By setting the content of the polyorganosilsesquioxane of the present invention to 70% by weight or more, the surface hardness and heat resistance of the cured product tend to be further improved. On the other hand, by setting the content of the polyorganosilsesquioxane of the present invention to less than 100% by weight, it is possible to contain a curing catalyst, thereby allowing the curing of the curable composition to proceed more efficiently. There is a tendency to be able to.

  The ratio of the polyorganosilsesquioxane of the present invention to the total amount (100% by weight) of the cationic 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. Is 75 to 98% by weight, more preferably 80 to 95% by weight. By setting the content of the polyorganosilsesquioxane of the present invention to 70% by weight or more, the surface hardness 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 that can initiate or accelerate a polymerization reaction of a curable compound such as the polyorganosilsesquioxane 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 cationic species by heating to initiate a curing reaction of the polymerizable compound, and the anionic polymerization initiator generates anionic species by heating to generate a polymerizable compound. It is a compound that initiates the curing reaction. When the curable composition of the present invention contains a polymerization initiator, the curing time until tack-free can be shortened. In addition, a polymerization initiator can be used individually by 1 type or in combination of 2 or more types.

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

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

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

  The heat curing time in the present invention is determined by a method based on JIS K5909 (1994) until the composition is heated on a hot plate to become rubbery (more specifically, curing proceeds). , Until the needle tip no longer rises about the thread shape. When a polymerization initiator having a heat curing time below the above range is used, a cationic species is generated when a cationic polymerization initiator is used during drying by heating, and an anionic species is generated when an anionic polymerization initiator is used. However, since the polymerization proceeds gradually, it becomes difficult to form an adhesive layer having storage stability.

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

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

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

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

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

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

  Examples of the ammonium salt include tetramethylammonium salt, ethyltrimethylammonium salt, diethyldimethylammonium salt, triethylmethylammonium salt, tetraethylammonium salt, trimethyl-n-propylammonium salt, and trimethyl-n-butylammonium salt. Pyrrolium salts such as alkyl ammonium salts; N, N-dimethylpyrrolidinium salts, N-ethyl-N-methylpyrrolidinium salts; N, N′-dimethylimidazolinium salts, N, N′-diethylimidazolinium salts, etc. Imidazolinium salts; tetrahydropyrimidinium salts such as N, N′-dimethyltetrahydropyrimidinium salt, N, N′-diethyltetrahydropyrimidinium salt; N, N-dimethylmorpholinium salt, N, N -Diethylmorpholinium salt Morpholinium salts such as N, N-dimethylpiperidinium salt, piperidinium salts such as N, N-diethylpiperidinium salt; pyridinium salts such as N-methylpyridinium salt and N-ethylpyridinium salt; N, N′- Imidazolium salts such as dimethylimidazolium salt; quinolinium salts such as N-methylquinolium salt; isoquinolium salts such as N-methylisoquinolium salt; thiazonium salts such as benzylbenzothiazonium salt; Examples include an acridium salt.

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

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

Examples of the anion constituting the above-described salt include SbF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , (CF ₃ CF ₂ ) ₃ PF ₃ ⁻ , (CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ Ga ⁻ , sulfonate anion (trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, nonafluorobutanesulfonate anion, methanesulfonate anion, benzenesulfonate Anion, p-toluenesulfonic acid anion, etc.), (CF ₃ SO ₂ ) ₃ C ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , perhalogenate ion, halogenated sulfonate ion, sulfate ion, carbonate ion, aluminate Ion, hexafluorobismuth acid ion, carboxylate ion, arylborate ion, thiocyanate ion, nitrate ion and the like.

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

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

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

  The content (blending amount) of the polymerization initiator in the curable composition of the present invention is not particularly limited, but is 0.01 to 3.0 weights with respect to 100 parts by weight of the polyorganosilsesquioxane of the present invention. Parts, preferably 0.05 to 3.0 parts by weight, 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 be efficiently and sufficiently advanced, and the surface hardness and adhesiveness of the cured product tend to be further improved. On the other hand, when the content of the polymerization initiator is 3.0 parts by weight or less, the storability of the curable composition tends to be further improved, and 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 polymerization stabilizer is a compound having an action of suppressing the progress of cationic polymerization by trapping cations, saturating the ability of trapping cations by the polymerization stabilizer, and allowing the polymerization to proceed at the stage of deactivation. When the curable composition of the present invention contains a polymerization stabilizer together with a cationic polymerization initiator, after the coating and drying to form an adhesive layer, the progress of polymerization can be suppressed over a long period of time. It is possible to form an adhesive layer that exhibits excellent adhesiveness and is excellent in storage stability by heating at the timing required.

  Examples of the polymerization stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, poly ([6- (1,1,3,3-tetramethylbutyl) imino-1, 3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) Imino]), tetrakis (2,2,6,6-tetramethyl-4-piperidyl) butane-1,2,3,4-tetracarboxylate, 2,2,6,6-tetramethyl-4-piperidi Nylbenzoate, (mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, mixed (2,2,6,6-tetramethyl) -4-piperidic /Β,β,β′,β′-tetramethyl-3-9-[2,4,8,10-tetraoxaspiro(5.5)undecane]diethyl)-1,2,3,4-butanetetra Carboxylate, poly ([6-N-morpholyl-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2 , 2,6,6-tetramethyl-4-piperidyl) imino]), [N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl-2- (2,2,6 , 6-tetramethyl-4-piperidyl) imino] propionamide, trade names “LA-77”, “LA-67”, “LA-57” (manufactured by ADEKA), trade names “TINUVIN123”, “TINUVIN152” (Ciba Japan Co., Ltd. )) Hindered amine compounds, (4-hydroxyphenyl) dimethylsulfonium methylsulfite (Sun aid SI auxiliary, manufactured by Sanshin Chemical Industry Co., Ltd.) and the like, for example, 9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (trade name “ADK STAB PEP-36”, ADEKA), bis (2,4-di-t-butylphenyl) pentaerythritol-diphosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (mono, dinonylphenyl) phosphite, Tris (2-ethylhexyl) phosphite, Trisphenyl phosphite, Tris Nonylphenyl) phosphite, may be mentioned phosphorous acid ester compounds such as tris isodecyl phosphite, sulfonium sulfate compounds, phosphorous acid ester compounds are preferred. These can be used alone or in combination of two or more.

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

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

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

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

  When the curable composition of the present invention contains a silane coupling agent, the amount used is a polymerizable compound (polyorganosilsesquioxane (A) and polymerizable compound contained in the curable composition of the present invention. The total amount of (B)) is, for example, about 0 to 10 parts by weight with respect to 100 parts by weight, and the upper limit is preferably 5 parts by weight, particularly preferably 3 parts by weight, and most preferably 1 part by weight. The lower limit is preferably 0.005 parts by weight, particularly preferably 0.01 parts by weight.

[solvent]
The curable composition of the present invention may further contain a solvent. In particular, when a hard coat is formed with the curable composition of the present invention, the polyorganosilsesquioxane has the above-described configuration ( In particular, since it has a structural unit represented by the formula (2), it can be applied to a substrate without being diluted with a solvent. Thereby, since the process of removing the solvent by drying after coating can be omitted, the hard coat can be formed economically, efficiently and safely.
When the curable composition of the present invention contains a solvent, the solvent can dissolve the polyorganosilsesquioxane and additives used as necessary and does not inhibit polymerization. There is no particular limitation.

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

  When the curable composition of the present invention contains a solvent, 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%. It is preferable to use it in the range of% by weight from the viewpoint of excellent coating properties when spin coating. When the amount of the solvent used is excessive, the viscosity of the curable composition tends to be low, and it becomes difficult to form a layer having an appropriate film thickness (for example, about 0.5 to 30 μm). On the other hand, when the amount of the solvent used is too small, the viscosity of the curable composition becomes too high and it tends to be difficult to uniformly apply it to the support or the adherend.

[Leveling agent]
The curable composition of the present invention may preferably contain a leveling agent. By containing a leveling agent, the surface smoothness of the resulting cured product can be improved, transparency, gloss (appearance), slipperiness, etc. can be improved, and the cured product of the curable composition of the present invention can be applied to a hard coat. It is suitable when doing.

As the leveling agent, a silicone leveling agent and a fluorine leveling agent are preferable from the viewpoint of excellent surface tension reducing ability.
As the silicone leveling agent, a known or conventional silicone leveling agent can be used, and is not particularly limited. For example, trade names “BYK-300”, “BYK-301 / 302”, “BYK-306”, “BYK” -307 "," BYK-310 "," BYK-315 "," BYK-313 "," BYK-320 "," BYK-322 "," BYK-323 "," BYK-325 "," BYK-330 " ”,“ BYK-331 ”,“ BYK-333 ”,“ BYK-337 ”,“ BYK-341 ”,“ BYK-344 ”,“ BYK-345 / 346 ”,“ BYK-347 ”,“ BYK-348 ” ”,“ BYK-349 ”,“ BYK-370 ”,“ BYK-375 ”,“ BYK-377 ”,“ BYK-378 ”,“ BYK-UV3500 ”,“ BY ” -UV3510 "," BYK-UV3570 "," BYK-3550 "," BYK-SILCLEAN3700 "," BYK-SILCLEAN3720 "(manufactured by Big Chemie Japan Co., Ltd.), trade names" ACFS180 "," ACFS360 "," ACS20 "(manufactured by Algin Chemie), trade names" Polyflow KL-400X "," Polyflow KL-400HF "," Polyflow KL-401 "," Polyflow KL-402 "," Polyflow KL-403 "," Polyflow KL " -404 "(manufactured by Kyoeisha Chemical Co., Ltd.), trade names" KP-323 "," KP-326 "," KP-341 "," KP-104 "," KP-110 "," KP-112 ""(Shin-Etsu Chemical Co., Ltd.), trade names" LP-7001 "," LP- 002, 8032ADDITIVE, 57ADDITIVE, L-7604, FZ-2110, FZ-2105, 67ADDITIVE, 8618ADDITIVE, 3ADDITIVE, 56ADDITIVE (above, Toray Dow) Commercial products such as Corning Corporation) can be used.

  As the fluorine leveling agent, for example, a known or conventional fluorine leveling agent can be used, and is not particularly limited. For example, trade names “DSX” and “DAC-HP” (manufactured by Daikin Industries, Ltd.); Product names “S-242”, “S-243”, “S-420”, “S-611”, “S-651”, “S-386” (above, manufactured by AGC Seimi Chemical Co., Ltd.); Name “BYK-340” (manufactured by Big Chemie Japan Co., Ltd.); trade names “AC110a”, “AC100a” (above, made by Algin Chemie); trade names “Megafuck F-114”, “Megafuck F-410” , “Megafuck F-444”, “Megafuck EXPTP-2066”, “Megafuck F-430”, “Megafuck F-472SF”, “Megafuck F-47” ”,“ Megafuck F-552 ”,“ Megafuck F-553 ”,“ Megafuck F-554 ”,“ Megafuck F-555 ”,“ Megafuck R-94 ”,“ Megafuck RS-72-K ” ”,“ Megafuck RS-75 ”,“ Megafuck F-556 ”,“ Megafuck EXPTF-1367 ”,“ Megafuck EXPTF-1437 ”,“ Megafuck F-558 ”,“ Megafuck EXPTF-1537 ”( Product name “FC-4430”, “FC-4432” (manufactured by Sumitomo 3M Co., Ltd.); product names “Furgent 100”, “Furgent 100C”, “Furgent” 110 "," Factent 150 "," Factent 150CH "," Factent AK "," Factent 501 " "Factent 250", "Factent 251", "Factent 222F", "Factent 208G", "Factent 300", "Factent 310", "Factent 400SW" (above, manufactured by Neos Co., Ltd.) ); Trade names “PF-136A”, “PF-156A”, “PF-151N”, “PF-636”, “PF-6320”, “PF-656”, “PF-6520”, “PF-651” "," PF-652 "," PF-3320 "(above, manufactured by Kitamura Chemical Sangyo Co., Ltd.), and other commercial products can also be used.

These leveling agents can be used alone or in combination of two or more.
When the curable composition of the present invention contains a leveling agent, the amount used thereof is, for example, 0 to 10 parts by weight with respect to 100 parts by weight of the polyorganosilsesquioxane contained in the curable composition of the present invention. The upper limit is preferably 5 parts by weight, particularly preferably 3 parts by weight, and most preferably 1 part by weight. The lower limit is preferably 0.005 parts by weight, particularly preferably 0.01 parts by weight.

[Other cationic curable compounds]
The curable composition of the present invention may further contain a cationic curable compound other than the polyorganosilsesquioxane of the present invention (sometimes referred to as “other cationic curable compounds”). As other cationic curable compounds, known or conventional cationic curable compounds can be used, and are not particularly limited. For example, epoxy compounds other than the polyorganosilsesquioxane of the present invention (“other epoxy compounds”). And oxetane compounds, vinyl ether compounds, and the like. In addition, in the curable composition of this invention, another cationic curable compound can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  As said other epoxy compound, the well-known thru | or usual compound which has one or more epoxy groups (oxirane ring) in a molecule | numerator can be used, Although it does not specifically limit, For example, an alicyclic epoxy compound (alicyclic) Epoxy resin), aromatic epoxy compounds (aromatic epoxy resins), aliphatic epoxy compounds (aliphatic epoxy resins), and the like.

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

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

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

  As said bivalent hydrocarbon group, a C1-C18 linear or branched alkylene group, a bivalent alicyclic hydrocarbon group, etc. are mentioned. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclopentylene group, And divalent cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group, and cyclohexylidene group.

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

Representative examples of the alicyclic epoxy compound represented by the above formula (i) include 3,4,3 ′, 4′-diepoxybicyclohexane, and the following formulas (i-1) to (i-10): The compound etc. which are represented by these are mentioned. In the following formulas (i-5) and (i-7), l and m each represent an integer of 1 to 30. R ′ in the following formula (i-5) is an alkylene group having 1 to 8 carbon atoms, and among them, a linear or branched chain having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group, and an isopropylene group. -Like alkylene groups are preferred. N1-n6 in following formula (i-9) and (i-10) show the integer of 1-30, respectively. Other examples of the alicyclic epoxy compound represented by the above formula (i) include 2,2-bis (3,4-epoxycyclohexyl) propane and 1,2-bis (3,4-epoxycyclohexyl). ) Ethane, 2,3-bis (3,4-epoxycyclohexyl) oxirane, bis (3,4-epoxycyclohexylmethyl) ether and the like.

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

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

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

  Examples of the aromatic epoxy compound include epibis type glycidyl ether type epoxy resins obtained by condensation reaction of bisphenols [for example, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol and the like] and epihalohydrin; High molecular weight epibis type glycidyl ether type epoxy resin obtained by addition reaction of bis type glycidyl ether type epoxy resin with the above bisphenols; phenols [eg, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, bisphenol S, etc.] and aldehyde [eg, formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, salicy A novolak alkyl type glycidyl ether type epoxy resin obtained by further condensing a polyhydric alcohol obtained by a condensation reaction with an aldehyde etc. with an epihalohydrin; two phenol skeletons are bonded to the 9-position of the fluorene ring. In addition, an epoxy compound in which a glycidyl group is bonded to an oxygen atom obtained by removing a hydrogen atom from the hydroxy group of the phenol skeleton, either directly or via an alkyleneoxy group.

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

  Examples of the oxetane compound include known or commonly used compounds having one or more oxetane rings in the molecule, and are not particularly limited. For example, 3,3-bis (vinyloxymethyl) oxetane, 3-ethyl-3- (Hydroxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3- Ethyl-3- (chloromethyl) oxetane, 3,3-bis (chloromethyl) oxetane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis {[1-ethyl (3- Oxetanyl)] methyl} ether, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] bisi Chlohexyl, 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 And phenol novolac oxetane.

  The vinyl ether compound may be a known or conventional compound having one or more vinyl ether groups in the molecule, and is not particularly limited. For example, 2-hydroxyethyl vinyl ether (ethylene glycol monovinyl ether), 3-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-hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl vinyl ether, 1-methyl-3 -Hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1-hydroxymethylpropyl vinyl ether 4-hydroxycyclohexyl vinyl ether, 1,6-hexanediol monovinyl ether, 1,6-hexanediol divinyl ether, 1,8-octanediol divinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, 1,4-cyclohexanedi Methanol divinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanol divinyl ether, 1,2-cyclohexanedimethanol monovinyl ether, 1,2-cyclohexanedimethanol divinyl ether, p-xylene glycol monovinyl ether P-xylene glycol divinyl ether, m-xylene glycol monovinyl ether, m-xylene glycol divinyl ether, o-xy Glycol monovinyl ether, o-xylene glycol divinyl ether, ethylene glycol divinyl ether, diethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, tetraethylene glycol monovinyl ether, tetraethylene glycol divinyl ether, penta Ethylene glycol monovinyl ether, pentaethylene glycol divinyl ether, oligoethylene glycol monovinyl ether, oligoethylene glycol divinyl ether, polyethylene glycol monovinyl ether, polyethylene glycol divinyl ether, dipropylene glycol monovinyl ether, dipropylene glycol Coal 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, oxanorbornene divinyl ether, phenyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octyl vinyl ether, cyclohexyl vinyl ether, ha Droquinone divinyl ether, 1,4-butanediol divinyl ether, cyclohexane dimethanol divinyl ether, trimethylolpropane divinyl ether, trimethylolpropane trivinyl ether, bisphenol A divinyl ether, bisphenol F divinyl ether, hydroxyoxanorbornane methanol divinyl ether, 1, Examples include 4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, and dipentaerythritol hexavinyl ether.

  In the curable composition of the present invention, it is preferable to use a vinyl ether compound in combination with the polyorganosilsesquioxane of the present invention as another cationic curable compound. Thereby, there exists a tendency for the surface hardness of hardened | cured material to become higher. In particular, when the curable composition of the present invention is cured by irradiation with active energy rays (particularly ultraviolet rays), a cured product having a very high surface hardness is excellent even when the irradiation amount of active energy rays is reduced. For example, there is an advantage that it can be obtained with high productivity (for example, it is not necessary to perform heat treatment for aging). For this reason, it becomes possible to make the manufacturing line speed of hardened | cured material and a hard coat film higher, and these productivity improves further.

  In addition, as the other cationic curable compound, particularly when a vinyl ether compound having one or more hydroxyl groups in the molecule is used, the surface hardness is higher, and further, heat-resistant yellowing (yellowing due to heating hardly occurs). There is an advantage that a cured product having excellent properties can be obtained. For this reason, the hardened | cured material and hard coat film of higher quality and durability are obtained. The number of hydroxyl groups in the molecule of the vinyl ether compound having one or more hydroxyl groups in the molecule is not particularly limited, but is preferably 1 to 4, more preferably 1 or 2. Specifically, examples of the vinyl ether compound having one or more hydroxyl groups in the molecule include 2-hydroxyethyl vinyl ether (ethylene glycol monovinyl ether), 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl. Vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl vinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl Vinyl ether, 1-hydroxymethylpropyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 1,6-hexa Diol monovinyl ether, 1,8-octanediol divinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,2-cyclohexanedimethanol monovinyl ether, p-xylene glycol monovinyl ether, m-xylene glycol monovinyl ether, o-xylene glycol monovinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, pentaethylene glycol monovinyl ether, oligoethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, tripropylene glycol Monovinyl ether, tetra B propylene glycol monomethyl ether, pentaethylene glycol monomethyl ether, oligo propylene glycol monomethyl ether, polypropylene glycol monovinyl ether, pentaerythritol trivinyl ether, dipentaerythritol penta vinyl ether.

  The content (blending amount) of the other cationic curable compound in the curable composition of the present invention is not particularly limited, but the total amount of the polyorganosilsesquioxane of the present invention and the other cationic curable compound (100% by weight). Preferably 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), and further preferably 10% by weight, based on the total amount of the cationic curable compound. % Or less. By setting the content of other cationic curable compounds to 50% by weight or less (particularly 10% by weight or less), the scratch resistance of the cured product tends to be further improved. On the other hand, by setting the content of other cationic curable compounds to 10% by weight or more, desired performance for the curable composition or the cured product (for example, quick curability or viscosity adjustment for the curable composition). May be granted.

  The content (blending amount) of the vinyl ether compound (particularly, the vinyl ether compound having one or more hydroxyl groups in the molecule) in the curable composition of the present invention is not particularly limited, but the polyorganosilsesquioxane of the present invention and The amount is preferably 0.01 to 10% by weight, more preferably 0.05 to 9% by weight, still more preferably 1 to 1%, based on the total amount of other cationic curable compounds (100% by weight; the total amount of the cationic curable compound). 8% by weight. By controlling the content of the vinyl ether compound within the above range, the surface hardness of the cured product becomes higher, and the surface hardness is extremely high even when the irradiation amount of active energy rays (for example, ultraviolet rays) is lowered. There is a tendency to get things. In particular, by controlling the content of the vinyl ether compound having one or more hydroxyl groups in the molecule within the above range, in addition to particularly high surface hardness of the cured product, there is a tendency to further improve its heat-resistant yellowing. is there.

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

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

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

[Cured product]
By proceeding the polymerization reaction of the cationic curable compound (such as the polyorganosilsesquioxane of the present invention) in the curable composition of the present invention, the curable composition can be cured, and the cured product ("present" May be referred to as “the cured product of the invention”). The curing method can be appropriately selected from well-known methods and is not particularly limited, and examples thereof include a method of irradiation with active energy rays and / or heating. As the active energy ray, for example, any of infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α rays, β rays, γ rays and the like can be used. Among these, ultraviolet rays are preferable in terms of excellent handleability.

Conditions for curing the curable composition of the present invention by irradiation with active energy rays (irradiation conditions for active energy rays, etc.) depend on the type and energy of the active energy rays to be irradiated, the shape and size of the cured product, etc. Although it can adjust suitably and it is not specifically limited, When irradiating an ultraviolet-ray, it is preferable to set it as about 1-1000 mJ / cm < ² >, for example. For irradiation with active energy rays, for example, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, sunlight, an LED lamp, a laser, or the like can be used. After the irradiation with the active energy ray, a heating treatment (annealing and aging) can be further performed to further advance the curing reaction.

  On the other hand, the conditions for curing the curable composition of the present invention by heating are such that the curable composition of the present invention contains polyorganosilsesquioxane, so that it can be quickly heated by heating at a low temperature of less than 200 ° C. A cured product can be formed. That is, it has low temperature curability. As heating temperature, it is 50-190 degreeC, for example. The curing time can be appropriately set.

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

[Curable composition for forming hard coat layer]
As described above, the curable composition of the present invention can be cured to form a cured product having high surface hardness and heat resistance and excellent flexibility and workability. Accordingly, the curable composition of the present invention particularly includes a “curable composition for forming a hard coat layer” (“hard coat liquid”, “hard coat agent” and the like for forming a hard coat layer in a hard coat film. And may be particularly preferably used. The curable composition of the present invention is used as a curable composition for forming a hard coat layer, and a hard coat film having a hard coat layer formed from the composition is flexible while maintaining high hardness and high heat resistance. It can be manufactured and processed by roll-to-roll.

[Hard coat film]
The hard coat film of the present invention is a film having a substrate and a hard coat layer formed on at least one surface of the substrate, wherein the hard coat layer is a curable composition (hard It is a hard coat layer (cured product layer of the curable composition of the present invention) formed by a curable composition for forming a coat layer). In the present specification, the hard coat layer formed of the curable composition of the present invention may be referred to as “the hard coat layer of the present invention”.

  In addition, the hard coat layer of the present invention in the hard coat film of the present invention may be formed only on one surface (one surface) of the substrate, or may be formed on both surfaces (both surfaces). .

  In addition, the hard coat layer of the present invention in the hard coat film of the present invention may be formed on only a part or on the entire surface of each surface of the substrate.

  The base material in the hard coat film of the present invention is a base material of the hard coat film and refers to a part constituting other than the hard coat layer of the present invention. As said base material, well-known, such as a plastic base material, a metal base material, a ceramic base material, a semiconductor base material, a glass base material, a paper base material, a wood base material (wood base material), and the base material whose surface is a coating surface Thru | or a usual base material can be used and it does not specifically limit. Among these, a plastic substrate (a substrate made of a plastic material) is preferable.

  Although the plastic material which comprises the said plastic base material is not specifically limited, For example, Polyesters, such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); Polyimide; Polycarbonate; Polyamide; Polyacetal; Polyphenylene oxide; Polyphenylene sulfide; Polyether Sulfone; Polyetheretherketone; Norbornene monomer homopolymer (addition polymer, ring-opening polymer, etc.), Norbornene monomer and olefin monomer copolymer (addition polymer, such as norbornene and ethylene copolymer) And cyclic olefin copolymers such as ring-opening polymers), cyclic polyolefins such as derivatives thereof; vinyl polymers (for example, acrylic resins such as polymethyl methacrylate (PMMA), polystyrene , Polyvinyl chloride, acrylonitrile-styrene-butadiene resin (ABS resin, etc.); vinylidene polymers (eg, polyvinylidene chloride, etc.); cellulose resins such as triacetyl cellulose (TAC); epoxy resins; phenol resins; Various plastic materials such as melamine resin; urea resin; maleimide resin; The plastic substrate may be composed of only one kind of plastic material or may be composed of two or more kinds of plastic materials.

  Above all, as the plastic substrate, when the purpose is to obtain a hard coat film excellent in transparency as the hard coat film of the present invention, a substrate excellent in transparency (transparent substrate) is used. And more preferably a polyester film (particularly PET, PEN), a cyclic polyolefin film, a polycarbonate film, a TAC film, and a PMMA film.

  If necessary, the plastic substrate is made of an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a crystal nucleating agent, a flame retardant, a flame retardant aid, a filler, a plasticizer, and an impact modifier. , Other additives such as reinforcing agents, dispersants, antistatic agents, foaming agents, antibacterial agents and the like may be included. In addition, an additive can also be used individually by 1 type and can also be used in combination of 2 or more type.

  The plastic substrate may have a single-layer configuration or a multilayer (lamination) configuration, and the configuration (structure) is not particularly limited. For example, the above-mentioned plastic substrate is “plastic film / other layer” in which a layer other than the hard coat layer of the present invention (sometimes referred to as “other layer”) is formed on at least one surface of the plastic film. Alternatively, it may be a plastic substrate having a laminated structure such as “other layer / plastic film / other layer”. Examples of the other layers include hard coat layers other than the hard coat layer of the present invention. In addition, as a material which comprises the said other layer, the above-mentioned plastic material etc. are mentioned, for example.

  Roughening treatment, easy adhesion treatment, antistatic treatment, sandblast treatment (sand mat treatment), corona discharge treatment, plasma treatment, chemical etching treatment, water mat treatment, flame are applied to part or all of the surface of the plastic substrate. Known or conventional surface treatments such as treatment, acid treatment, alkali treatment, oxidation treatment, ultraviolet irradiation treatment, silane coupling agent treatment, etc. may be applied. The plastic substrate may be an unstretched film or a stretched film (uniaxially stretched film, biaxially stretched film, etc.).

  The plastic base material is, for example, a method of forming the plastic material described above into a film shape to form a plastic base material (plastic film), and if necessary, an appropriate layer (for example, the above-mentioned other layers) on the plastic film. For example, a layer or the like, or an appropriate surface treatment. In addition, a commercial item can also be used as said plastic base material.

  Although the thickness of the said base material is not specifically limited, For example, it can select suitably from the range of 0.01-10000 micrometers.

  The hard coat layer of the present invention in the hard coat film of the present invention is a layer constituting at least one surface layer in the hard coat film of the present invention, and the curable composition of the present invention (curable composition for forming a hard coat layer). It is a layer (cured product layer) formed by a cured product (resin cured product) obtained by curing the product.

  The thickness of the hard coat layer of the present invention (in the case where the hard coat layer of the present invention is provided on both surfaces of the substrate) is not particularly limited, but is preferably 1 to 200 μm, more preferably 3 ~ 150 μm. In particular, even when the hard coat layer of the present invention is thin (for example, when the thickness is 5 μm or less), it is possible to maintain a high surface hardness (for example, the pencil hardness is set to H or more). . In addition, even when the thickness is thick (for example, when the thickness is 50 μm or more), it is difficult to cause defects such as cracks due to curing shrinkage, etc. 9H or higher).

  The haze of the hard coat layer of the present invention is not particularly limited, but is preferably 1.5% or less, more preferably 1.0% or less in the case of a thickness of 50 μm. The lower limit of haze is not particularly limited, but is 0.1%, for example. By setting the haze to 1.0% or less, for example, the haze tends to be suitable for use in applications that require very high transparency (for example, surface protection sheets for displays such as touch panels). The haze of the hard coat layer of the present invention can be measured according to JIS K7136.

  The total light transmittance of the hard coat layer of the present invention is not particularly limited, but is preferably 85% or more, more preferably 90% or more in the case of a thickness of 50 μm. The upper limit of the total light transmittance is not particularly limited, but is 99%, for example. By setting the total light transmittance to 85% or more, for example, it tends to be suitable for use in applications that require extremely high transparency (for example, surface protection sheets for displays such as touch panels). The total light transmittance of the hard coat layer of the present invention can be measured according to JIS K7361-1.

  The hard coat film of the present invention may further have a surface protective film on the surface of the hard coat layer of the present invention. When the hard coat film of the present invention has a surface protective film, the punchability of the hard coat film tends to be further improved. In the case of having a surface protective film in this way, for example, even if the hardness of the hard coat layer is very high and peeling or cracking from the base material is likely to occur at the time of punching, such a problem occurs. It is possible to perform punching using a Thomson blade without causing it to occur.

  As the surface protective film, a known or conventional surface protective film can be used, and is not particularly limited. For example, a film having a pressure-sensitive adhesive layer on the surface of a plastic film can be used. Examples of the plastic film include polyester (polyethylene terephthalate, polyethylene naphthalate, etc.), polyolefin (polyethylene, polypropylene, cyclic polyolefin, etc.), polystyrene, acrylic resin, polycarbonate, epoxy resin, fluorine resin, silicone resin, diacetate resin, Examples thereof include plastic films formed from plastic materials such as triacetate resin, polyarylate, polyvinyl chloride, polysulfone, polyethersulfone, polyetheretherimide, polyimide, and polyamide. Examples of the adhesive layer include an acrylic adhesive, a natural rubber adhesive, a synthetic rubber adhesive, an ethylene-vinyl acetate copolymer adhesive, an ethylene- (meth) acrylate copolymer adhesive, Examples thereof include a pressure-sensitive adhesive layer formed from one or more known or common pressure-sensitive adhesives such as a styrene-isoprene block copolymer pressure-sensitive adhesive and a styrene-butadiene block copolymer pressure-sensitive adhesive. In the pressure-sensitive adhesive layer, various additives (for example, an antistatic agent, a slip agent, etc.) may be contained. In addition, the plastic film and the pressure-sensitive adhesive layer may each have a single layer configuration, or may have a multilayer (multi-layer) configuration. Moreover, the thickness of a surface protection film is not specifically limited, It can select suitably.

  Examples of the surface protective film include the product name “Sanitek” series (manufactured by Sanei Kaken Co., Ltd.), the product name “E-MASK” series (manufactured by Nitto Denko Corporation), and the product name “Mastak” series (Fujimori Industry ( Commercially available products such as the product name “Hitarex” series (manufactured by Hitachi Chemical Co., Ltd.) and the product name “Alphan” series (manufactured by Oji F-Tex Co., Ltd.) are available from the market.

  The hard coat film of the present invention can be produced in accordance with a known or commonly used method for producing a hard coat film, and the production method is not particularly limited. For example, the hard coat film of the present invention is applied to at least one surface of the substrate. It can be produced by applying a curable composition (a curable composition for forming a hard coat layer), removing the solvent by drying as necessary, and then curing the curable composition (curable composition layer). . The conditions for curing the curable composition are not particularly limited, and can be appropriately selected from, for example, the conditions for forming the cured product described above.

  Since the polyorganosilsesquioxane contained in the curable composition of the present invention has the above-described configuration, it is considered to have a cage cleavage silsesquioxane structure, and has high fluidity. Even if it is not diluted with a solvent, it can be easily applied to a substrate. Therefore, since it can be applied directly to a substrate without being diluted in a solvent and cured immediately without drying the solvent, a hard coat film can be produced economically, efficiently and safely.

  In particular, the hard coat layer of the present invention in the hard coat film of the present invention is more than the curable composition of the present invention (a curable composition for forming a hard coat layer) capable of forming a cured product having excellent flexibility and processability. Since it is the formed hard coat layer, the hard coat film of the present invention can be produced by a roll-to-roll method. By producing the hard coat film of the present invention by a roll-to-roll method, the productivity can be remarkably increased. As a method for producing the hard coat film of the present invention by a roll-to-roll method, a known or conventional roll-to-roll method can be adopted, and is not particularly limited. For example, a base material wound in a roll shape And applying the curable composition of the present invention (a curable composition for forming a hard coat layer) to at least one surface of the fed substrate, and then drying the solvent as necessary. After removing by step, the step of forming the hard coat layer of the present invention by curing the curable composition (curable composition layer) (step B), and then the obtained hard coat film again in a roll The method of including the process (process C) to wind up as an essential process, and implementing these processes (process AC) continuously is mentioned. In addition, the said method may include processes other than process AC.

  The thickness of the hard coat film of this invention is not specifically limited, It can select suitably from the range of 1-10000 micrometers.

  The pencil hardness of the hard coat layer surface of the present invention of the hard coat film of the present invention is not particularly limited, but is preferably H or more, more preferably 2H or more, and further preferably 6H or more. The pencil hardness can be evaluated according to the method described in JIS K5600-5-4.

  The haze of the hard coat film of the present invention is not particularly limited, but is preferably 1.5% or less, more preferably 1.0% or less. The lower limit of haze is not particularly limited, but is 0.1%, for example. By setting the haze to 1.0% or less, for example, the haze tends to be suitable for use in applications that require very high transparency (for example, surface protection sheets for displays such as touch panels). The haze of the hard coat film of the present invention can be easily controlled within the above range by using, for example, the above-mentioned transparent substrate as a substrate. The haze can be measured according to JIS K7136.

  Although the total light transmittance of the hard coat film of this invention is not specifically limited, 85% or more is preferable, More preferably, it is 90% or more. The upper limit of the total light transmittance is not particularly limited, but is 99%, for example. By setting the total light transmittance to 90% or more in particular, for example, there is a tendency to be suitable for use in applications that require very high transparency (for example, surface protection sheets for displays such as touch panels). The total light transmittance of the hard coat film of the present invention can be easily controlled within the above range by using, for example, the above-mentioned transparent substrate as the substrate. The total light transmittance can be measured according to JIS K7361-1.

  The hard coat film of the present invention has flexibility while maintaining high hardness and high heat resistance, and can be manufactured and processed in a roll-to-roll system, so it has high quality and high productivity. Also excellent. In particular, when the surface protective film is provided on the surface of the hard coat layer of the present invention, the punching processability is also excellent. For this reason, it can be preferably used for any application that requires such characteristics. The hard coat film of the present invention can be used as, for example, a surface protective film for various products, a surface protective film for various product members or parts, and also used as a constituent material for various products, members or parts thereof. You can also Examples of the products include display devices such as liquid crystal displays and organic EL displays; input devices such as touch panels; solar cells; various home appliances; various electric and electronic products; portable electronic terminals (for example, game machines, personal computers, tablets, Smartphones, mobile phones, etc.) and various electrical and electronic products; various optical devices. Moreover, as an aspect in which the hard coat film of the present invention is used as a constituent material of various products and its members or parts, for example, an aspect used in a laminate of a hard coat film and a transparent conductive film in a touch panel, etc. It is done.

[Adhesive composition]
The cured product obtained by curing the curable composition of the present invention is not only excellent in terms of the above-mentioned surface hardness, heat resistance, flexibility, and workability, but further, heat resistance, crack resistance, Exhibits excellent adhesion and adhesion to adherends. Therefore, the curable composition of the present invention can be preferably used as an adhesive (sometimes referred to as “adhesive composition”). The adhesive obtained by using the curable composition of the present invention as a composition for an adhesive is cured to obtain surface hardness, heat resistance, crack resistance, flexibility, workability, adhesion to an adherend, and It can be converted into an adhesive having excellent adhesion. The adhesive is, for example, a photocurable adhesive when the curable composition of the present invention contains a photocationic polymerization initiator as a curing catalyst, and a thermosetting adhesive when a thermal cationic polymerization initiator is included. Can be used as

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

[Adhesive sheet]
By using the curable composition (adhesive composition) of the present invention, an adhesive sheet having at least a substrate and an adhesive layer on the substrate, wherein the adhesive layer is cured according to the present invention. An adhesive sheet (sometimes referred to as “the adhesive sheet of the present invention”) that is a layer of the adhesive composition (sometimes referred to as “the adhesive layer of the present invention”) can be obtained. The adhesive sheet of the present invention includes not only a sheet shape but also a form similar to a sheet shape such as a film shape, a tape shape, and a plate shape. Although the adhesive sheet of this invention is not specifically limited, For example, it can obtain by apply | coating the curable composition of this invention to a base material, and also making it dry as needed. In particular, when the composition obtained by adding 1 part by weight to 100 parts by weight of Celoxide 2021P (manufactured by Daicel Corporation) contains a polymerization initiator having a heat curing time at 130 ° C. of 3.5 minutes or more. By heating and drying, an adhesive layer can be formed promptly without advancing the curing reaction, and since the obtained adhesive layer has no adhesiveness at less than 50 ° C., no adhesive is applied to the cutting blade. Cutting can be performed without adhering, and the adhesiveness is exhibited by heating at a temperature at which damage to the adherend layer such as a semiconductor chip can be suppressed.

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

  As the substrate in the adhesive sheet of the present invention, a well-known and commonly used substrate (substrate used in the adhesive sheet) can be used, and is not particularly limited. Materials, semiconductor base materials, glass base materials, paper base materials, wood base materials, base materials whose surface is a painted surface, and the like, specifically, the same as the base material in the hard coat film of the present invention. Illustrated. Moreover, what is called a release liner may be sufficient as the base material in the adhesive sheet of this invention, For example, the thing similar to the surface protection film in the hard coat film of this invention can also be used. In addition, the adhesive sheet of the present invention may have only one layer of the base material, or may have two or more layers. Moreover, the thickness of the said base material is not specifically limited, For example, it can select suitably in the range of 1-10000 micrometers.

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

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

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

  The adherend in the laminate of the present invention is not particularly limited, and examples thereof include those similar to the substrate in the hard coat film of the present invention. Note that the laminate of the present invention may have only two layers to be bonded, or may have three or more layers. Moreover, the thickness of a to-be-adhered body is not specifically limited, For example, it can select suitably in the range of 1-100,000 micrometers. The adherend need not have a strict layered form.

  The laminate of the present invention may have only one adhesive layer of the present invention, or may have two or more. Further, the thickness of the adhesive layer of the present invention is not particularly limited, and can be appropriately selected within a range of, for example, 0.1 to 10,000 μm.

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

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

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

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

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The molecular weight of the product was measured using Alliance HPLC system 2695 (manufactured by Waters), Refractive Index Detector 2414 (manufactured by Waters), column: Tskel GMH _HR- M × 2 (manufactured by Tosoh Corporation), guard column: Tskel guard column H _HR L (manufactured by Tosoh Corporation), column oven: COLUMN HEATER U-620 (manufactured by Sugai), solvent: THF, measurement conditions: 40 ° C., molecular weight: standard polystyrene conversion.

Example 1
A 1000 ml flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube was charged with 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (hereinafter, “EMS” under a nitrogen stream. And 125.0 mmol (30.80 g), 375.0 mmol (45.08 g) of dimethoxydimethylsilane, and 303.5 g of acetone, and the temperature was raised to 50 ° C. To the resulting mixture, 13.82 g of a 5% aqueous potassium carbonate solution (5.0 mmol as potassium carbonate) was added dropwise over 5 minutes, and then 5000.0 mmol (90.00 g) of water was added over 20 minutes. It was dripped. Note that no significant temperature increase occurred during the dropping. Thereafter, the polycondensation reaction was performed for 2 hours under a nitrogen stream while maintaining the temperature at 50 ° C.
Then, simultaneously with cooling the reaction solution, 151.8 g of methyl isobutyl ketone and 120.81 g of 5% saline were added. This solution was transferred to a 1 L separatory funnel, and 151.8 g of methyl isobutyl ketone was added again for washing with water. After separation, the aqueous layer is extracted, washed with water until the lower layer solution is neutral, and after the upper layer solution is separated, the solvent is completely distilled off from the upper layer solution under the conditions of 1 mmHg and 50 ° C. 45.32 g of a liquid product (epoxy group-containing polyorganosilsesquioxane) was obtained.
When the product was analyzed, the number average molecular weight was 1004 and the molecular weight dispersity was 1.60. As a result of ¹ H-NMR measurement, a peak derived from an epoxy group (3.17 ppm, broad singlet), a peak derived from a cyclohexyl group (0.9 to 2.2 ppm), and a peak derived from a methylene group adjacent to Si (0.50 ppm, broad singlet), a peak derived from a methyl group (0.1 ppm, multiplet) was confirmed. Furthermore, as a result of ²⁹ Si-NMR measurement, a peak derived from the T2 form in the vicinity of −55 to −60 ppm, a peak derived from the T3 form in the vicinity of −65 to −70 ppm, and a peak derived from the D2 form in the vicinity of −15 to −25 ppm. Were confirmed.

Examples 2 and 3
Except that the amount of raw materials (EMS and dimethoxydimethylsilane) used, the amount of solvent used, the amount of 5% aqueous potassium carbonate solution used, and the amount of water used were changed as shown in Table 1, as in Example 1, Epoxy group-containing polyorganosilsesquioxane was produced. The number average molecular weight (Mn) and molecular weight dispersity of the epoxy group-containing polyorganosilsesquioxane obtained in each example were obtained by ²⁹ Si-NMR measurement [T3 body / D2 body]. The ratio is shown in Table 1.

Example 4
In a 6 cc brown sample bottle, 1 g of the epoxy group-containing polyorganosilsesquioxane obtained in Example 1, trade name “WPI-124” (manufactured by Wako Pure Chemical Industries, Ltd., 50% solution of photoacid generator) ) 20.0 mg [20.0 mg as a 50% solution], trade name “BYK-307” (produced by BYK Chemie Co., Ltd., leveling agent) 2.0 mg, and methyl isobutyl ketone 0.67 g were added and mixed with a vibrator. Then, a curable composition (hard coat liquid) was produced.
The wire coat is used on the PET film (trade name “KEB03W”, manufactured by Teijin DuPont Films Ltd.) so that the thickness of the hard coat layer after curing is 30 μm. Then, it was allowed to stand (pre-bake) for 10 minutes in an oven at 120 ° C., and then irradiated with ultraviolet rays (irradiation conditions (irradiation amount): 434 mJ / cm ² , irradiation intensity: 120 W / cm ² ). Finally, the coating film of the hard coat liquid was cured by heat treatment (aging) at 80 ° C. for 2 hours to produce a hard coat film having a hard coat layer.

Examples 5-7
A hard coat solution was prepared in the same manner as in Example 4 except that the composition of the hard coat solution (curable composition) and the thickness of the hard coat layer were changed as shown in Table 2. A hard coat film was produced in the same manner as in Example 4 except that the hard coat solution was used and the thickness of the hard coat layer was changed as shown in Table 2. The hard coat film obtained above was evaluated by the following method. The results are shown in Table 2. In addition, the unit of the compounding quantity of the raw material of the curable composition of Table 2 is a weight part.
(1) Surface hardness (pencil hardness)
The pencil hardness of the hard coat layer surface in the hard coat film obtained above was evaluated according to JIS K5600-5-4.

The abbreviations shown in Table 2 are as follows. The sample name of polyorganosilsesquioxane corresponds to the sample name shown in Table 1.
WPI-124: Trade name “WPI-124” (manufactured by Wako Pure Chemical Industries, Ltd.), polymerization initiator (50% solution of photoacid generator)
BYK-307: Trade name “BYK-307” (manufactured by Big Chemie), leveling agent

Example 8
100 parts by weight of the epoxy group-containing polyorganosilsesquioxane (S-3) obtained in Example 3, 50 parts by weight of propylene glycol monomethyl ether acetate, antimony sulfonium salt (trade name “SI-150L”, Sanshin Chemical Industry Co., Ltd.)) 0.45 parts by weight, and (4-hydroxyphenyl) dimethylsulfonium methylsulfite (trade name “Sun-Aid SI Auxiliary Agent”, Sanshin Chemical Industry Co., Ltd.) 0.05 parts by weight Were mixed to obtain an adhesive composition (1). In addition, the compounding quantity of brand name "SI-150L" was shown by the quantity of solid content conversion.

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

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

  The adhesive composition (1), adhesive layer (1), and laminate (1) obtained in Example 8 were evaluated as follows.

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

(Adhesion)
For the cured product of the adhesive layer obtained by heating the adhesive layer in the silicon plate with the adhesive layer, a cross-cut tape test (conforms to JIS K5400-8.5) is performed, and the adhesion to the silicon plate according to the following criteria: Evaluated.
Evaluation criteria: A case where no peeling of the adhesive layer is observed is regarded as acceptable.

(Crack resistance)
The cured adhesive layer obtained by heating the adhesive layer in the silicon plate with the adhesive layer was given a thermal shock (heated at 170 ° C. for 30 minutes and then rapidly cooled to room temperature), and cracked according to the following criteria: Was evaluated.
Evaluation criteria: A case where the portion without cracks is 60% or more of the cured product is regarded as acceptable.

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

[result]
(Heat-resistant)
About the hardened | cured material obtained by heating adhesive composition (1) at 150 degreeC for 30 minutes, and then heating at 170 degreeC for 30 minutes, thermal decomposition temperature is 260 degreeC or more, and it is excellent in heat resistance. confirmed.

(Crack resistance)
The cured product obtained by heating the adhesive layer (1) at 150 ° C. for 30 minutes and then heating at 170 ° C. for 30 minutes was heated at 170 ° C. for 30 minutes and then rapidly cooled to room temperature. It was confirmed that the non-existing portion was 60% or more of the cured product and excellent in crack resistance.

(Adhesion)
As for the cured product obtained by heating the adhesive layer (1) at 150 ° C. for 30 minutes and then heating at 170 ° C. for 30 minutes, peeling of the adhesive layer (1) was observed as a result of the cross-cut tape test. It was confirmed that the adhesiveness was excellent.

(Adhesiveness)
When a razor blade was inserted into the adhesive interface of the laminate (1), peeling at the adhesive surface did not occur, and it was confirmed that the adhesive layer in the laminate was excellent in adhesiveness.

Comparative Example 1
(Preparation of epoxy group-containing polyorganosilsesquioxane)
A 300 mL flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube was charged with EMS 162.35 mmol (40.0 g) and acetone 40.0 g under a nitrogen stream and heated to 50 ° C. Warm up. To the mixture thus obtained, 4.49 g of 5% aqueous potassium carbonate solution (1.62 mmol as potassium carbonate) was added dropwise over 5 minutes, and then 163.51 mmol (29.48 g) of water was added dropwise over 20 minutes. . Note that no significant temperature increase occurred during the dropping. Thereafter, the polycondensation reaction was carried out under a nitrogen stream for 3 hours while maintaining the temperature at 50 ° C.
Subsequently, after adding methyl isobutyl ketone and brine, the reaction solution was cooled, and the upper layer solution was separated. Then, it washed with water until the lower layer liquid became neutral, the solvent was distilled off from the upper layer liquid on conditions of 1 mmHg and 50 degreeC, and the colorless and transparent liquid resin (epoxy group containing polyorgano silsesquioxane) was obtained. . The liquid resin had a polystyrene-reduced weight average molecular weight of 14400 and a number average molecular weight of 4000 (molecular weight dispersity: 3.60).
Silicone plate (2) with an adhesive composition (2) and an adhesive layer (2) in the same manner as in Example 8 except that the epoxy group-containing polyorganosilsesquioxane obtained above was used. Got. The film thickness of the adhesive layer (2) was 5 to 6 μm.
The cured product obtained by heating the adhesive layer (2) at 150 ° C. for 30 minutes and then heating at 170 ° C. for 30 minutes was heated at 170 ° C. for 30 minutes and then rapidly cooled to room temperature. There has occurred.

The curable composition containing the silsesquioxane of the present invention has high surface hardness and heat resistance, is excellent in flexibility and workability, and forms a cured product that can be manufactured and processed with roll-to-roll. it can. Therefore, it is useful as a curable composition used for hard coat films such as electronic parts.
Furthermore, the curable composition containing the silsesquioxane of the present invention can be cured at a low temperature to form a cured product having excellent heat resistance, crack resistance, adhesion to an adherend and adhesion. it can. Therefore, it is useful as an adhesive used for bonding semiconductors and electronic parts.

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

Claims (34)

Following formula (1)

[In Formula (1), R < ¹ > shows group containing an epoxy group. ]
And a structural unit represented by the following formula (2)

[In the formula (2), R ² and R ³ are the same or different and each represents a group containing an epoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cyclohexane. An alkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom is shown. ]
Having a structural unit represented by
Formula (I)

[In the formula (I), R ^a is a group containing an epoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group. Represents a substituted or unsubstituted alkenyl group or a hydrogen atom. ]
The molar ratio of the structural unit represented by the formula (2) and the structural unit represented by the formula (2) [the structural unit represented by the formula (I) / the structural unit represented by the formula (2)] is 0.1 to 0.1. 20
The number average molecular weight of 1000 to 3000, a molecular weight distribution (weight average molecular weight / number average molecular weight) for a hard coat layer formed, characterized in that it comprises a 1.0 to 3.0 der Lupo Li organosilsesquioxane Curable composition . The polyorganosilsesquioxane is a structural unit represented by the above formula (1) with respect to the total amount (100 mol%) of siloxane structural units, and the following formula (5)

[In formula (5), R ¹ is the same as that in formula (1). R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]
And the following formula (2 ′)

[In the formula (2 ′), R ^2a and R ^3a are the same or different and are each an epoxy group-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted group. A cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom; However, at least one of R ^2a and R ^3a is a group containing an epoxy group. ]
The curable composition for forming a hard coat layer according to claim 1, which is a polyorganosilsesquioxane having a proportion (total amount) of structural units represented by 5 to 95 mol%. The polyorganosilsesquioxane further comprises the following formula (3)

[In the formula (3), R ⁴ represents a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted group. An alkenyl group of ]
The curable composition for hard-coat layer formation of Claim 1 or 2 which has a structural unit represented by these . R ¹ is represented by the following formula (1a)

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

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

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

[In formula (1d), R ^1d represents a linear or branched alkylene group. ]
The curable composition for forming a hard coat layer according to claim 1, wherein the curable composition is a group represented by: The curable composition for forming a hard coat layer according to claim 3 or 4, wherein R ⁴ is a substituted or unsubstituted aryl group. Furthermore, the curable composition for hard-coat layer formation of any one of Claims 1-5 containing a polymerization initiator. The curable composition for forming a hard coat layer according to claim 6 , wherein the polymerization initiator is a cationic photopolymerization initiator. The curable composition for forming a hard coat layer according to claim 6 , wherein the polymerization initiator is a thermal cationic polymerization initiator. Further, a hard coat layer forming curable composition according to any one of claims 1 to 8 including a polymerization stabilizer. Further, a hard coat layer forming curable composition according to any one of claims 1 to 9 including a silane coupling agent. Further, a hard coat layer forming curable composition according to any one of claims 1 to 10 comprising a vinyl ether compound. Further, a hard coat layer forming curable composition according to any one of claims 1 to 11 including a vinyl ether compound having a hydroxyl group in the molecule. Cured product of a hard coat layer forming curable composition according to any one of claims 1 to 12. A hard coat film having a substrate and a hard coating layer formed on at least one surface of the substrate, the hard coat layer, a hard coat according to any one of claims 1 to 12 A hard coat film, which is a cured product layer of a layer-forming curable composition. The hard coat film according to claim 14 , wherein the hard coat layer has a thickness of 1 to 200 μm. The hard coat film according to claim 14 or 15 , which can be produced by a roll-to-roll method. Further, a hard coat film according to any one of claims 14 to 16 having a surface protective film on the hard coat layer surface. Applying the curable composition for forming a hard coat layer according to any one of claims 1 to 12 to Step A for unwinding the substrate wound in a roll, and at least one surface of the unrolled substrate; comprises a step B of forming a hard coat layer by curing the hard coat layer forming curable composition, then a step C wound into a hard coat film obtained again roll, step A~C Is carried out continuously. A method for producing a hard coat film, comprising: Following formula (1)

[In formula (1), R ¹ Represents a group containing an epoxy group. ]
And a structural unit represented by the following formula (2)

[In formula (2), R ² And R ^Three Are the same or different, respectively, a group containing an epoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted Or an unsubstituted alkenyl group or a hydrogen atom is shown. ]
Having a structural unit represented by
Formula (I)

[In formula (I), R ^a Is a group containing an epoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, Or a hydrogen atom is shown. ]
The molar ratio of the structural unit represented by the formula (2) and the structural unit represented by the formula (2) [the structural unit represented by the formula (I) / the structural unit represented by the formula (2)] is 0.1 to 0.1. 20
A curable composition for an adhesive comprising a polyorganosilsesquioxane having a number average molecular weight of 1000 to 3000 and a molecular weight dispersity (weight average molecular weight / number average molecular weight) of 1.0 to 3.0. . The polyorganosilsesquioxane is a structural unit represented by the above formula (1) with respect to the total amount (100 mol%) of siloxane structural units, and the following formula (5)

[In formula (5), R ¹ Is the same as in equation (1). R ^c Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]
And a structural unit represented by the following formula (2 ')

[In the formula (2 '), R ^2a And R ^3a Are the same or different, respectively, a group containing an epoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted Or an unsubstituted alkenyl group or a hydrogen atom is shown. However, R ^2a And R ^3a At least one of them is a group containing an epoxy group. ]
The curable composition for adhesives of Claim 19 which is a polyorganosilsesquioxane whose ratio (total amount) of the structural unit represented by 5-95 mol%. The polyorganosilsesquioxane further comprises the following formula (3)

[In formula (3), R ^Four Represents a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group. ]
The curable composition for adhesives of Claim 19 or 20 which has a structural unit represented by these. R above ¹ Is represented by the following formula (1a)

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

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

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

[In formula (1d), R ^1d Represents a linear or branched alkylene group. ]
The curable composition for adhesives according to any one of claims 19 to 21, which is a group represented by the formula: R above ^Four The curable composition for adhesives according to claim 21 or 22, wherein is a substituted or unsubstituted aryl group. Furthermore, the curable composition for adhesives of any one of Claims 19-23 containing a polymerization initiator. The curable composition for adhesives according to claim 24, wherein the polymerization initiator is a photocationic polymerization initiator. The curable composition for adhesives according to claim 24, wherein the polymerization initiator is a thermal cationic polymerization initiator. Furthermore, the curable composition for adhesives of any one of Claims 19-26 containing a polymerization stabilizer. Furthermore, the curable composition for adhesives of any one of Claims 19-27 containing a silane coupling agent. Furthermore, the curable composition for adhesives of any one of Claims 19-28 containing a vinyl ether compound. Furthermore, the curable composition for adhesives of any one of Claims 19-29 containing the vinyl ether compound which has a hydroxyl group in a molecule | numerator. Hardened | cured material of the curable composition for adhesives of any one of Claims 19-30. An adhesive sheet having a substrate and an adhesive layer on the substrate,
The said adhesive bond layer is a layer of the curable composition for adhesives of any one of Claims 19-30, The adhesive sheet characterized by the above-mentioned. A laminate composed of three or more layers,
Having two layers to be adhered and an adhesion layer between the layers to be adhered;
The said adhesive layer is a layer of the hardened | cured material of the curable composition for adhesives of any one of Claims 19-30, The laminated body characterized by the above-mentioned. 34. An apparatus comprising the laminate according to claim 33 .

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