Polyorganosilsesquioxane, curable composition, cured product, hard coat film, transfer film, and adhesive sheet

Abstract

To provide polyorganosilsesquioxane that can form a hard coat layer that is a cured material having high surface hardness and flex resistance while having high heat resistance and is suitable as a material of a hard coat film.SOLUTION: A polyorganosilsesquioxane of the present disclosure includes a multimeric cage type silsesquioxane having three or more cage type silsesquioxanes fused, the silsesquioxanes including at least one cage type silsesquioxane selected from the group consisting of cage type silsesquioxanes represented by the following composition formula (1), composition formula (2), composition formula (3) and composition formula (4). Equation (1):[R1SiO3 / 2]8[R1SiO2 / 2(ORc)]1, equation (2):[R2SiO3 / 2]6[R2SiO2 / 2(ORc)]2, equation (3): [R3SiO3 / 2]8[R3SiO2 / 2(ORc)]2, equation (4): [R4SiO3 / 2]10[R4SiO2 / 2(ORc)]2 [description in the formula is as set forth in this specification]SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to polyorganosilsesquioxane, a curable composition containing the polyorganosilsesquioxane, a cured product thereof, and a hard coat film made of the cured product. The present disclosure relates to a transfer film containing the curable composition as a hard coat layer. The present disclosure also relates to an adhesive sheet containing the curable composition as an adhesive layer.

Background Art

[0002] Polyorganosilsesquioxane (silsesquioxane) is a network polymer or polyhedral cluster obtained by hydrolyzing trifunctional silane. As silsesquioxane, those having a random structure, a ladder structure, or a cage structure are known. Among the silsesquioxanes having a molecular weight of, for example, 3000 or more known so far, many have a random structure or a ladder structure. Such high molecular weight silsesquioxanes are described, for example, in Patent Document 1 below.

[0003] In addition, silsesquioxane having a cage structure has a three-dimensionally closed structure by siloxane bonds, and is a general term for substances having organic functional groups at each vertex around the cubic structure of silica. As the cubic structure, mainly, octamer silsesquioxane (T8) having a regular hexahedron structure and decamer silsesquioxane (T 10 ) having a side cone pentagonal prism structure are known. Such cage-type silsesquioxanes are described, for example, in Patent Document 2 below.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, the cured products obtained from conventional high molecular weight polyorganosilsesquioxanes or cage-type silsesquioxanes tend to have insufficient hardness and also have limitations in flexibility when bent. Therefore, the conventional cured products cannot be used in applications that require high hardness and high flexural resistance, and their applications as materials for hard coats have been limited. In addition, conventional polymeric silsesquioxanes have a problem that as the molecular weight increases, they become difficult to dissolve in solvents such as organic solvents, making processing into materials for hard coats and the like difficult.

[0006] Therefore, an object of the invention of the present disclosure is to provide a cured product having high surface hardness and flexural resistance while having high heat resistance, which is a characteristic of polyorganosilsesquioxane, and to provide a polyorganosilsesquioxane suitable as a material for a hard coat film. Another object is to provide a polyorganosilsesquioxane which is a high molecular weight polyorganosilsesquioxane but has high solubility in solvents such as organic solvents.

[0007] Another object of the invention of the present disclosure is to provide a curable composition containing the polyorganosilsesquioxane. Furthermore, an object is to provide a cured product of the curable composition and a hard coat film having a hard coat layer which is the cured product. Furthermore, another object of the invention of the present disclosure is to provide a transfer film having a hard coat layer containing the curable composition. Another object of the invention of the present disclosure is to provide an adhesive sheet having an adhesive layer containing the curable composition.

Means for Solving the Problems

[0008] The inventors of the present disclosure have found that a cured product of a curable composition containing a polyorganosilsesquioxane having a cage-type silsesquioxane in which three or more cage-type silsesquioxanes having a specific composition formula are condensed has high heat resistance, excellent surface hardness and flexural resistance, and is very useful as a hard coat layer in a hard coat film or a transfer film, and as an adhesive layer in an adhesive sheet. They have also found that the silsesquioxane has high solubility in solvents such as organic solvents despite having a high molecular weight. The invention of the present disclosure has been completed based on these findings.

[0009] That is, the present disclosure provides a polyorganosilsesquioxane containing a multimer cage-type silsesquioxane which is a condensate in which at least one selected from the group consisting of cage-type silsesquioxanes represented by the following composition formula (1), composition formula (2), composition formula (3) and composition formula (4) is condensed three or more times. · Formula (1): [R 1 SiO 3 / 2 8[R 1 SiO 2 / 2 (OR c )]1 (In formula (1), each R 1 is independently a group containing a polymerizable functional 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, and at least one is a group containing a polymerizable functional group. R c represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.) · Formula (2): [R 2 SiO 3 / 2 6[R 2 SiO 2 / 2 (OR c )]2 (In formula (2), R 2is, independently of each other, a group containing a polymerizable functional 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, and at least one is a group containing a polymerizable functional group. R c each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. ) · Formula (3): [R 3 SiO 3 / 2 8[R 3 SiO 2 / 2 (OR c )]2 (In formula (3), R 3 is, independently of each other, a group containing a polymerizable functional 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, and at least one is a group containing a polymerizable functional group. R c each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. ) · Formula (4): [R 4 SiO 3 / 2 10 [R 4 SiO 2 / 2 (OR c )]2 (In formula (4), R 4 is, independently of each other, a group containing a polymerizable functional 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, and at least one is a group containing a polymerizable functional group. R c each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. )

[0010] Further, the present disclosure provides a polyorganosilsesquioxane in which at least one terminal in the multimer cage-type silsesquioxane has a structure in which the cage-type silsesquioxane represented by the composition formula (1) is condensed.​

[0011] In addition, in the present disclosure, the group containing the polymerizable functional group is represented by the following formula (1A)

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0012] In addition, in the present disclosure, R in the composition formula (1) 1 , R in the composition formula (2) 2 , R in the composition formula (3) 3 , and R in the composition formula (4) 4 To provide a polyorganosilsesquioxane in which the proportion of the group containing the polymerizable functional group is 30% or more with respect to the whole.

[0013] In addition, the present disclosure provides the polyorganosilsesquioxane in which the molar ratio of the structural unit represented by the following formula (I) to the structural unit represented by the following formula (II) [structural unit represented by formula (I) / structural unit represented by formula (II)] is 1 or more and 500 or less. [R a SiO 3 / 2 (I) [In formula (I), R a represents a group containing a polymerizable functional 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.] [R b SiO 2 / 2 (OR c )] (II) [In formula (II), R b represents a group containing a polymerizable functional 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. R c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.]

[0014] Further, the present disclosure provides the polyorganosilsesquioxane having a number average molecular weight of 2000 to 50000.

[0015] Further, the present disclosure provides the polyorganosilsesquioxane having a molecular weight dispersity (weight average molecular weight / number average molecular weight) of 1.0 to 4.0.

[0016] Further, the present disclosure provides a curable composition containing the polyorganosilsesquioxane.

[0017] Further, the present disclosure provides the curable composition further containing a curing catalyst.

[0018] Further, the present disclosure provides the curable composition wherein the curing catalyst is a photo or thermal polymerization initiator.

[0019] Further, the present disclosure provides the curable composition further containing a polymerization stabilizer.

[0020] The present disclosure also provides the curable composition which is a curable composition for forming a hard coat layer.

[0021] The present disclosure also provides the curable composition which is a curable composition for an adhesive.

[0022] The present disclosure also provides a cured product of the curable composition.

[0023] The present disclosure also provides a hard coat film in which a hard coat layer, which is the cured product, is laminated on at least one surface of a base material.

[0024] The present disclosure also provides a transfer film in which a hard coat layer is laminated on a release layer formed on at least one surface of a base material, and the hard coat layer is a layer containing the curable composition.

[0025] The present disclosure also provides the transfer film in which an anchor coat layer and an adhesive layer are further laminated in this order on the hard coat layer.

[0026] The present disclosure also provides the transfer film further including at least one colored layer.

[0027] The present disclosure also provides the transfer film in which the thickness of the hard coat layer is 3 to 150 μm.

[0028] The present disclosure also provides an adhesive sheet including a base material and an adhesive layer which is a layer containing the curable composition on at least one surface of the base material.

[0029] The present disclosure also provides an adhesive sheet including a base material, an anchor coat layer containing a silane coupling agent, and an adhesive layer which is a layer containing the curable composition on at least one surface of the base material, and the adhesive layer is provided on the surface of the anchor coat layer.

Advantages of the Invention

[0030] The cured product (for example, a hard coat layer) obtained from the curable composition containing the polyorganosilsesquioxane of the present disclosure has high heat resistance, high surface hardness, and excellent flexural resistance. Therefore, by using a hard coat film or a transfer film having the hard coat layer, a molded product (product) having high surface hardness and excellent flexural resistance can be manufactured. Further, the polyorganosilsesquioxane of the present disclosure is a high molecular weight polyorganosilsesquioxane in which three or more cage structures are condensed, but has high solubility in solvents such as organic solvents. Therefore, in the hard coat film or the transfer film containing the polyorganosilsesquioxane of the present disclosure, the amount of the solvent used can be reduced, and further, the uncured or semi-cured hard coat layer becomes tack-free and can be wound up in a roll form for handling, and the film containing the hard coat layer can be handled in a roll-to-roll manner. Therefore, it is excellent in both quality and cost. Furthermore, the curable composition containing the polyorganosilsesquioxane of the present disclosure as an essential component can form a cured product (adhesive) having high heat resistance and excellent flexibility, and thus can be preferably used as a composition (adhesive) for laminated semiconductors.

Brief Description of Drawings

[0031]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Figure 10

[0032] [Polyorganosilsesquioxane] The polyorganosilsesquioxane of the present disclosure contains a multimeric cage-type silsesquioxane (hereinafter sometimes referred to as "the multimeric cage-type silsesquioxane of the present disclosure") which is a condensate in which at least one kind selected from the group consisting of cage-type silsesquioxanes represented by the following compositional formula (1), compositional formula (2), compositional formula (3) and compositional formula (4) is condensed three or more times (preferably 3 to 50, more preferably 4 to 40, still more preferably 5 to 30). Since it is a condensate in which the above cage-type silsesquioxane is condensed three or more times, the surface hardness and flexural resistance in the cured product of the curable composition containing the polyorganosilsesquioxane of the present disclosure are likely to be improved. Further, since the above multimeric cage-type silsesquioxane is contained, the solubility of the polyorganosilsesquioxane of the present disclosure in a solvent is likely to be improved.

[0033] · Formula (1): [R 1 SiO 3 / 2 8[R 1 SiO 2 / 2 (ORc )]1 (In formula (1), R 1 each independently represents a group containing a polymerizable functional 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, and at least one is a group containing a polymerizable functional group. R c represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.) · Formula (2): [R 2 SiO 3 / 2 6[R 2 SiO 2 / 2 (OR c )]2 (In formula (2), R 2 each independently represents a group containing a polymerizable functional 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, and at least one is a group containing a polymerizable functional group. R c each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.) · Formula (3): [R 3 SiO 3 / 2 8[R 3 SiO 2 / 2 (OR c )]2 (In formula (3), R 3 each independently represents a group containing a polymerizable functional 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, and at least one is a group containing a polymerizable functional group. R c each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.) · Formula (4): [R 4 SiO 3 / 2 10 [R 4 SiO 2 / 2 (OR c )]2​ (In formula (4), R 4 is independently a group containing a polymerizable functional 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, and at least one is a group containing a polymerizable functional group. R c independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.)

[0034] The structural unit represented by [R 1 SiO 3 / 2 in the composition formula (1), the structural unit represented by [R 2 SiO 3 / 2 in the composition formula (2), the structural unit represented by [R 3 SiO 3 / 2 in the composition formula (3), and the structural unit represented by [R 4 SiO 3 / 2 in the composition formula (4) are included in the structural unit represented by the following formula (I) (hereinafter, may be referred to as "T3 body" in this specification). [R a SiO 3 / 2 (I)

[0035] Also, the structural unit represented by [R 1 SiO 2 / 2 (OR c )] in the composition formula (1), the structural unit represented by [R 2 SiO 2 / 2 (OR c )] in the composition formula (2), the structural unit represented by [R 3 SiO 2 / 2 (OR c )] in the composition formula (3), and the structural unit represented by [R 4 SiO 2 / 2 (OR c )] in the composition formula (4) are included in the structural unit represented by the following formula (II) (hereinafter, may be referred to as "T2 body" in this specification). [R b SiO 2 / 2 (OR c )] (II)

[0036] R in the above formula (I) a , and R in formula (II) b represents a group containing a polymerizable functional 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. Further, R in the above formula (II) c represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.

[0037] Describing the structural unit represented by the above formula (I) in more detail, it is represented by the following formula (I'). Further, describing the structural unit represented by the above formula (II) in more detail, it is represented by the following formula (II'). Each of the three oxygen atoms bonded to the silicon atom shown in the structure represented by the following formula (I') is bonded to another silicon atom (a silicon atom not shown in formula (I')). On the other hand, each of the two oxygen atoms located above and below the silicon atom shown in the structure represented by the following formula (II') is bonded to another silicon atom (a silicon atom not shown in formula (II')). That is, both the above T3 body and T2 body are silsesquioxane structural units (so-called T units) formed by hydrolysis and condensation reactions of the corresponding hydrolyzable trifunctional silane compounds.

Chemical formula

Chemical formula

[0038] R in the above formula (I') a , R in formula (II') b and R c are the same groups as described above. The alkyl group in R in formula (II) c generally refers to the alkoxy group in the hydrolyzable silane compound used as a raw material for the polyorganosilsesquioxane of the present disclosure (for example, X in the following formulas (A) to (C) 1 ~X 3It is derived from an alkyl group that forms an alkoxy group or the like).

[0039] The cage-type silsesquioxane represented by the above compositional formula (1) has eight [R 1 SiO 3 / 2 units (T3 units) and one [R 1 SiO 2 / 2 (OR c )] units (T2 units) bonded to each other via siloxane bonds (Si-O-Si) to form a cage-type structure. The specific structure of the cage-type silsesquioxane represented by the above compositional formula (1) is not particularly limited as long as the above compositional formula (1) is satisfied. For example, a cage-type silsesquioxane represented by the following formula (1’) can be mentioned.

[0040] [Chemical formula]

[0041] R in formula (1’) 1a ~R 1i are each independently synonymous with R 1 in compositional formula (1). R c in formula (1’) is also synonymous with R c in compositional formula (1).

[0042] The cage-type silsesquioxane represented by the above compositional formula (2) has six [R 2 SiO 3 / 2 units (T3 units) and two [R 2 SiO 2 / 2 (OR c )] units (T2 units) bonded to each other via siloxane bonds (Si-O-Si) to form a cage-type structure. The specific structure of the cage-type silsesquioxane represented by the above compositional formula (2) is not particularly limited as long as the above compositional formula (2) is satisfied. For example, a cage-type silsesquioxane represented by the following formula (2’) or (2”) can be mentioned. [Chemical formula]

Chem.

[0043] R in formula (2’) 2a ~R 2h 、R in formula (2”) 2i ~R 2p are each independently synonymous with R in compositional formula (2) 2 。R in formulas (2’), (2”) c are also each independently synonymous with R in compositional formula (2) c 。

[0044] The cage-type silsesquioxane represented by the above compositional formula (3) is a silsesquioxane in which eight structural units (T3 units) represented by [R 3 SiO 3 / 2 and two structural units (T2 units) represented by [R 3 SiO 2 / 2 (OR c )] are bonded to each other via siloxane bonds (Si-O-Si) to form a cage-type structure. The specific structure of the cage-type silsesquioxane represented by the above compositional formula (3) is not particularly limited as long as the above compositional formula (3) is satisfied. For example, cage-type silsesquioxanes represented by the following formulas (3’), (3”) or (3''') can be mentioned.

Chem.

Chem.

Chem.

[0045] R in formula (3’) 3a ~R 3j 、R in formula (3”) 3k ~R 3t 、R in formula (3''') 3u ~R 3z 、R 3aa ~R 3ddis, independently of each other, R in the compositional formula (3) 3 and is synonymous. R in the formulas (3'), (3''), and (3''') c is also, independently of each other, R in the compositional formula (3) c and is synonymous.

[0046] The cage-type silsesquioxane represented by the above compositional formula (4) is a silsesquioxane in which ten structural units (T3 units) represented by [R 4 SiO 3 / 2 and two structural units (T2 units) represented by [R 4 SiO 2 / 2 (OR c )] are bonded to each other via siloxane bonds (Si-O-Si) to form a cage-type structure. The specific structure of the cage-type silsesquioxane represented by the above compositional formula (4) is not particularly limited as long as the compositional formula (4) is satisfied, and examples thereof include cage-type silsesquioxanes represented by the following formula (4') or (4"). [Chemical formula] [Chemical formula]

[0047] R in the formula (4') 4a ~R 4l , and R in the formula (4") 4m ~R 4x are, independently of each other, synonymous with R in the compositional formula (4) 4 . R in the formulas (4') and (4") c is also, independently of each other, synonymous with R in the compositional formula (4) c .

[0048] The cage-type silsesquioxane of the present disclosure may contain, within a range that does not impair the effects of the invention of the present disclosure, a cage-type silsesquioxane represented by a compositional formula other than the above compositional formula (1), compositional formula (2), compositional formula (3), and compositional formula (4). Examples of the compositional formula other than the above compositional formula (1), compositional formula (2), compositional formula (3), and compositional formula (4) include, for example, the following compositional formulas (5) to (8). · Formula (5): [R 5 SiO 3 / 2 6[R 5 SiO 2 / 2 (OR c )]3 (In formula (5), each R 5 is independently a group containing a polymerizable functional 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, and at least one is a group containing a polymerizable functional group. Each R c independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.) · Formula (6): [R 6 SiO 3 / 2 8[R 6 SiO 2 / 2 (OR c )]3 (In formula (6), each R 6 is independently a group containing a polymerizable functional 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, and at least one is a group containing a polymerizable functional group. Each R c independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.) · Formula (7): [R 7 SiO 3 / 2 10 [R 7 SiO 2 / 2 (OR c )]1 (In formula (7), each R 7 ​is, independently of one another, a group containing a polymerizable functional 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, and at least one is a group containing a polymerizable functional group. R c represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.) · Formula (8): [R 8 SiO 3 / 2 12 [R 8 SiO 2 / 2 (OR c )]1 (In Formula (8), R 8 is, independently of one another, a group containing a polymerizable functional 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, and at least one is a group containing a polymerizable functional group. R c represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.)

[0049] The multimeric cage-type silsesquioxane of the present disclosure includes those in which the cage-type silsesquioxanes represented by the above compositional formulas (1) to (8) are mixed. That is, the multimeric cage-type silsesquioxane of the present disclosure may be a condensate in which at least one selected from the group consisting of the cage-type silsesquioxanes represented by the above compositional formulas (1), (2), (3), (4), (5), (6), (7), and (8) is condensed three or more times.

[0050] In addition, even when a cage-type silsesquioxane having three hydroxyl groups represented by -OR c as in the above compositional formulas (5) and (6) is included, when two of them are condensed, it is included in the multimeric cage-type silsesquioxane of the present disclosure. Also, the three -ORs in the above compositional formulas (5) and (6) c ​Even when all of the hydroxyl groups represented by the formula are condensed, as long as the effects of the invention of the present disclosure are not impaired, they are included in the multimer cage-type silsesquioxane of the present disclosure.

[0051] The "cationic polymerizable functional group" in the group containing the polymerizable functional group is not particularly limited as long as it has cationic polymerizability, and examples thereof include an epoxy group, an oxetane group, a vinyl ether group, and a vinylphenyl group. The "radical polymerizable functional group" in the group containing the polymerizable functional group is not particularly limited as long as it has radical polymerizability, and examples thereof include a (meth)acryloxy group, a (meth)acrylamide group, a vinyl group, and a vinylthio group. From the viewpoint of the surface hardness of the cured product (for example, 4H or more), as the polymerizable functional group, an epoxy group, a (meth)acryloxy group, etc. are preferable, and an epoxy group is more preferable.

[0052] The substituent of the multimer cage-type silsesquioxane of the present disclosure (R in the above compositional formula (1) 1 , R in the formula (1') 1a ~R 1i , R in the compositional formula (2) 2 , R in the formula (2') 2a ~R 2h , R in the formula (2”) 2i ~R 2p , R in the compositional formula (3) 3 , R in the formula (3') 3a ~R 3j , R in the formula (3”) 3k ~R 3t , R in the formula (3''') 3u ~R 3z , R 3aa ~R 3dd , R in the compositional formula (4) 4 , R in the formula (4') 4a ~R 4l , R in the formula (4”) 4m ~R 4x , R in the compositional formula (5) 5 , R in the compositional formula (6) 6 , R in the compositional formula (7) 7 , R in the compositional formula (8) 8, R in formula (I) a , and R in formula (II) b As the group containing a polymerizable functional group in (), a group containing an epoxy group is preferable, and from the viewpoints of the curability of the curable composition, the surface hardness and heat resistance of the cured product, the group represented by the following formula (1A), the group represented by the formula (1B), the group represented by the formula (1C), and the group represented by the formula (1D) are preferable, and more preferably the group represented by the following formula (1A) and the group represented by the formula (1C), and even more preferably the group represented by the following formula (1A). [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula]

[0053] In the above formula (1A), R 1A represents a linear or branched alkylene group. Examples of the linear or branched alkylene group include linear or branched alkylene groups having 1 to 10 carbon atoms such as methylene group, methylmethylene group, dimethylmethylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, and decamethylene group. Among them, as R 1A , from the viewpoints of the surface hardness and curability of the cured product, a linear alkylene group having 1 to 4 carbon atoms and a branched alkylene group having 3 or 4 carbon atoms are preferable, and more preferably an ethylene group, a trimethylene group, a propylene group, and even more preferably an ethylene group and a trimethylene group.

[0054] In the above formula (1B), R 1B represents a linear or branched alkylene group, and groups similar to R 1A are exemplified. Among them, R 1BFrom the viewpoints of the surface hardness and curability of the cured product, a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms is preferable, more preferably an ethylene group, a trimethylene group, a propylene group, and even more preferably an ethylene group or a trimethylene group.

[0055] In the above formula (1C), R 1C represents a linear or branched alkylene group, and groups similar to R 1A are exemplified. Among them, as R 1C From the viewpoints of the surface hardness and curability of the cured product, a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms is preferable, more preferably an ethylene group, a trimethylene group, a propylene group, and even more preferably an ethylene group or a trimethylene group.

[0056] In the above formula (1D), R 1D represents a linear or branched alkylene group, and groups similar to R 1A are exemplified. Among them, as R 1D From the viewpoints of the surface hardness and curability of the cured product, a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms is preferable, more preferably an ethylene group, a trimethylene group, a propylene group, and even more preferably an ethylene group or a trimethylene group.

[0057] As the group containing a polymerizable functional group, it is a group represented by the above formula (1A) in which R 1a is an ethylene group [among them, 2-(3’,4’-epoxycyclohexyl)ethyl group] is preferable.

[0058] R in the above composition formula (1) 1 , R in the formula (1') 1a ~R 1i , R in the composition formula (2) 2 , R in the formula (2') 2a ~R 2h , R in the formula (2”) 2i ~R 2p , R in the composition formula (3) 3 , R in the formula (3') 3a ~R 3j, R in formula (3'') 3k ~R 3t , R in formula (3''') 3u ~R 3z , R 3aa ~R 3dd , R in compositional formula (4) 4 , R in formula (4') 4a ~R 4l , R in formula (4'') 4m ~R 4x , R in compositional formula (5) 5 , R in compositional formula (6) 6 , R in compositional formula (7) 7 , R in compositional formula (8) 8 , R in formula (I) a , and R in formula (II) b Examples of the aryl group in the substituted or unsubstituted aryl group include a phenyl group, a tolyl group, a naphthyl group, and the like.

[0059] , R in the above compositional formula (1) 1 , R in formula (1') 1a ~R 1i , R in compositional formula (2) 2 , R in formula (2') 2a ~R 2h , R in formula (2'') 2i ~R 2p , R in compositional formula (3) 3 , R in formula (3') 3a ~R 3j , R in formula (3'') 3k ~R 3t , R in formula (3''') 3u ~R 3z , R 3aa ~R 3dd , R in compositional formula (4) 4 , R in formula (4') 4a ~R 4l , R in formula (4'') 4m ~R 4x , and R in formula (I) a , R in compositional formula (5) 5 , R in compositional formula (6) 6 , R in compositional formula (7) 7 , R in compositional formula (8) 8 , R in formula (II) bExamples of the aralkyl group in the substituted or unsubstituted aralkyl group include a benzyl group, a phenethyl group, and the like.

[0060] R in the above compositional formula (1) 1 and R in formula (1') 1a ~R 1i and R in compositional formula (2) 2 and R in formula (2') 2a ~R 2h and R in formula (2”) 2i ~R 2p and R in compositional formula (3) 3 and R in formula (3') 3a ~R 3j and R in formula (3”) 3k ~R 3t and R in formula (3''') 3u ~R 3z and R 3aa ~R 3dd and R in compositional formula (4) 4 and R in formula (4') 4a ~R 4l and R in formula (4”) 4m ~R 4x and R in compositional formula (5) 5 and R in compositional formula (6) 6 and R in compositional formula (7) 7 and R in compositional formula (8) 8 and R in formula (I) a and R in formula (II) b Examples of the cycloalkyl group in the substituted or unsubstituted cycloalkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like.

[0061] R in the above compositional formula (1) 1 and R in formula (1') 1a ~R 1i and R in compositional formula (2) 2 and R in formula (2') 2a ~R 2h and R in formula (2”) 2i ~R 2p and R in compositional formula (3) 3 and R in formula (3') 3a ~R 3j and R in formula (3”)3k ~R 3t 、R in formula (3''')[ 3u ~R 3z 、R 3aa ~R 3dd 、R in compositional formula (4)[ 4 、R in formula (4')[ 4a ~R 4l 、R in formula (4'')[ 4m ~R 4x 、R in compositional formula (5)[ 5 、R in compositional formula (6)[ 6 、R in compositional formula (7)[ 7 、R in compositional formula (8)[ 8 、R in formula (I)[ a 、and R in formula (II)[ b As the alkyl group in the substituted or unsubstituted alkyl group, for example, 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, isopentyl group, etc. can be mentioned.

[0062] R in the above compositional formula (1)[ 1 、R in formula (1')[ 1a ~R 1i 、R in compositional formula (2)[ 2 、R in formula (2')[ 2a ~R 2h 、R in formula (2'')[ 2i ~R 2p 、R in compositional formula (3)[ 3 、R in formula (3')[ 3a ~R 3j 、R in formula (3'')[ 3k ~R 3t 、R in formula (3''')[ 3u ~R 3z 、R 3aa ~R 3dd 、R in compositional formula (4)[ 4 、R in formula (4')[ 4a ~R 4l 、R in formula (4'')[ 4m ~R 4x 、R in compositional formula (5)[ 5 、R in compositional formula (6)[ 6 、R in compositional formula (7)[ 7 、R in compositional formula (8)[ 8, R in formula (I) a , and R in formula (II) b Examples of the alkenyl group in the substituted or unsubstituted alkenyl group include linear or branched alkenyl groups such as vinyl group, allyl group, isopropenyl group, etc.

[0063] The number of groups containing a polymerizable functional group in R in the above compositional formula (1) is preferably 3 to 9, more preferably 5 to 9, still more preferably 7 to 9, and even more preferably 9 (all are groups containing a polymerizable functional group). R in the above compositional formula (2) 1 The group containing a polymerizable functional group in is preferably 3 to 8, more preferably 5 to 8, still more preferably 7 to 8, and even more preferably 8 (all are groups containing a polymerizable functional group). R in the above compositional formula (3) 2 The number of groups containing a polymerizable functional group in is preferably 3 to 10, more preferably 5 to 10, still more preferably 7 to 10, and even more preferably 10 (all are groups containing a polymerizable functional group). R in the above compositional formula (4) 3 The number of groups containing a polymerizable functional group in is preferably 3 to 12, more preferably 5 to 12, still more preferably 7 to 12, and even more preferably 12 (all are groups containing a polymerizable functional group). From the viewpoints of the curability of the curable composition and the surface hardness of the cured product, the larger the number of these groups containing a polymerizable functional group, the better. 4 The number of groups containing a polymerizable functional group in is preferably 3 to 12, more preferably 5 to 12, still more preferably 7 to 12, and even more preferably 12 (all are groups containing a polymerizable functional group). From the viewpoints of the curability of the curable composition and the surface hardness of the cured product, the larger the number of these groups containing a polymerizable functional group, the better.

[0064] In addition, in the substituent of the multimer cage-type silsesquioxane of the present disclosure, the substituent (R in the above compositional formula (1) 1 , R in compositional formula (2) 2 , R in compositional formula (3) 3 , and R in compositional formula (4) 4 ) The ratio of the group containing a polymerizable functional group (for example, a group containing an epoxy group) to the whole (the number of groups containing a polymerizable functional group / the total number of substituents) is, for example, 30% or more, preferably 50% or more, and more preferably 80% or more. The number of the groups containing a polymerizable functional group is preferably higher from the viewpoints of the curability of the curable composition and the surface hardness of the cured product, and is preferably not less than the above value.

[0065] The polyorganosilsesquioxane of the present disclosure has a molar ratio of the structural unit (T3 form) represented by the above formula (I) to the structural unit (T2 form) represented by the above formula (II) [structural unit represented by formula (I) / structural unit represented by formula (II); T3 form / T2 form] of, for example, 1 or more and 500 or less. The structural unit represented by the formula (I) and the structural unit represented by the formula (II) include the T3 form and the T2 form that constitute the cage-type silsesquioxane represented by the above compositional formula (1), compositional formula (2), compositional formula (3), and compositional formula (4), and further include the T3 form and the T2 form of all silsesquioxanes other than these (perfect cage-type silsesquioxane, ladder-type silsesquioxane, random-type silsesquioxane, etc.).

[0066] The lower limit value of the above ratio [T3 form / T2 form] is 1 as described above, preferably 2, more preferably 3, more preferably 4, more preferably 6, more preferably 7, more preferably 8, more preferably 8, more preferably 10, more preferably 15, and still more preferably 20. By setting the above ratio [T3 form / T2 form] to 1 or more, the surface of the uncured or semi-cured hard coat layer is likely to be tack-free, the blocking resistance is improved, it is easy to wind around a roll, and it can be preferably used as a component of a hard coat layer having flexural resistance. Also, the surface hardness and adhesiveness of the cured product and the hard coat layer are significantly improved. On the other hand, the upper limit value of the above ratio [T3 form / T2 form] is preferably 500, more preferably 400, still more preferably 300, more preferably 100, more preferably 50, more preferably 40, more preferably 30, more preferably 25, more preferably 20, more preferably 18, and still more preferably 18. By setting the above ratio [T3 form / T2 form] to 500 or less, the compatibility with other components in the curable composition is improved, and the viscosity is also suppressed, so that it is easy to handle and easy to coat as a hard coat layer.

[0067] The above ratio [T3 form / T2 form] in the polyorganosilsesquioxane of the present disclosure is, for example, 29It can be determined by Si-NMR spectrum measurement. 29 In the Si-NMR spectrum, the silicon atom in the structural unit (T3 form) represented by the above formula (I) and the silicon atom in the structural unit (T2 form) represented by the above formula (II) show signals (peaks) at different positions (chemical shifts). Therefore, the ratio [T3 form / T2 form] can be determined by calculating the integration ratio of these respective peaks. 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 signal of the silicon atom in the structure (T2 form) represented by the above formula (II) appears at -54 to -60 ppm. Therefore, in this case, the ratio [T3 form / T2 form] can be determined by calculating the integration ratio of the signal (T3 form) at -64 to -70 ppm and the signal (T2 form) at -54 to -60 ppm.

[0068] The polyorganosilsesquioxane of the present disclosure 29 The Si-NMR spectrum can be measured, for example, by the following apparatus and conditions. Measuring apparatus: "Brucker AVANCE (600 MHz)" (manufactured by Brucker) Solvent: deuterated chloroform Number of integrations: 8000 times Measurement temperature: 25 °C Sample: polyorganosilsesquioxane / acetylacetone chromium(III) / deuterated chloroform (1% tetramethylsilane) = 2.0:0.10:4.0 (weight ratio)

[0069] The fact that the ratio [T3 form / T2 form] of the polyorganosilsesquioxane of the present disclosure is 1 or more and 500 or less means that the abundance of the T2 form relative to the T3 form in the polyorganosilsesquioxane of the present disclosure is equivalent or relatively small, and the hydrolysis and condensation reaction of silanol has proceeded more.

[0070] The multimeric cage-type silsesquioxane of the present disclosure, which is a condensate in which at least one selected from the group consisting of the cage-type silsesquioxanes represented by the above compositional formula (1), compositional formula (2), compositional formula (3), and compositional formula (4) is condensed three or more times, means that among the cage-type silsesquioxanes represented by the above compositional formula (1), compositional formula (2), compositional formula (3), and compositional formula (4), in one kind, three or more (for example, 3 to 50, preferably 4 to 40, more preferably 5 to 30, still more preferably 6 to 20), or in two or more kinds (for example, 3 to 50, preferably 4 to 40, more preferably 5 to 30, still more preferably 6 to 20) are condensed. Here, "condensation" means that the hydroxyl groups (-OR c represented by -OR c in the above compositional formula (1), compositional formula (2), compositional formula (3), and compositional formula (4) (when -OR

[0071] is an alkoxy group, it is the hydrolyzed hydroxyl group) are dehydrated to form a siloxane bond (Si-O-Si). c Since the cage-type silsesquioxanes represented by the above compositional formula (2), compositional formula (3), and compositional formula (4) have two -OR

[0072] groups represented by in the molecule, it is considered that the multimeric cage-type silsesquioxane of the present disclosure in which these are condensed has a structure in which these cage-type structures are connected linearly. c Since the cage-type silsesquioxane represented by the above compositional formula (1) has only one -OR

[0073] group represented by in the molecule, it is considered that it condenses at the terminal of the structure in which the above cage-type structures are connected linearly.

[0074] The condensation form of each cage-type structural unit derived from the cage-type silsesquioxanes represented by the above compositional formula (1), compositional formula (2), compositional formula (3), and compositional formula (4) in the multimeric cage-type silsesquioxane of the present disclosure is not particularly limited, and it may be a random type or a block type.For example, when the linear silsesquioxane of the present disclosure contains a cage structure derived from the cage-type silsesquioxane represented by the above formula (2’), it has a repeating structure of the cage-type silsesquioxane structure represented by the following formula (2a) in the molecule.

Chemical formula

[0075] Each symbol in the above formula (2a) has the same meaning as the above formula (2’). In addition, when the linear silsesquioxane of the present disclosure contains a cage structure derived from the cage-type silsesquioxane represented by the above formula (2”), it has a repeating structure of the cage-type silsesquioxane structure represented by the following formula (2b) in the molecule.

Chemical formula

[0076] Each symbol in the above formula (2b) has the same meaning as the above formula (2”). For example, when the linear silsesquioxane of the present disclosure contains a cage structure derived from the cage-type silsesquioxane represented by the above formula (3’), it has a repeating structure of the cage-type silsesquioxane structure represented by the following formula (3a) in the molecule.

Chemical formula

[0077] Each symbol in the above formula (3a) has the same meaning as the above formula (3’). In addition, when the linear silsesquioxane of the present disclosure contains a cage structure derived from the cage-type silsesquioxane represented by the above formula (3”), it has a repeating structure of the cage-type silsesquioxane structure represented by the following formula (3b) in the molecule.

Chemical formula

[0078] Each symbol in the above formula (3b) has the same meaning as the above formula (3”). In addition, when the multimeric cage-type silsesquioxane of the present disclosure contains a cage structure derived from the cage-type silsesquioxane represented by the above formula (3'''), it has a repeating structure of the cage-type silsesquioxane structure represented by the following formula (3c) in the molecule.

Chemical formula

[0079] Each symbol in the above formula (3c) has the same meaning as in the above formula (3'''). For example, when the linear silsesquioxane of the present disclosure contains a cage structure derived from the cage-type silsesquioxane represented by the above formula (4’), it has a repeating structure of the cage-type silsesquioxane structure represented by the following formula (4a) in the molecule.

Chemical formula

[0080] Each symbol in the above formula (4a) has the same meaning as in the above (4’). In addition, when the linear silsesquioxane of the present disclosure contains a cage structure derived from the cage-type silsesquioxane represented by the above formula (4”), it has a repeating structure of the cage-type silsesquioxane structure represented by the following formula (4b) in the molecule.

Chemical formula

[0081] Each symbol in the above formula (4b) has the same meaning as in the above (4”). For example, when the linear silsesquioxane of the present disclosure contains a cage structure derived from the cage-type silsesquioxane represented by the above formula (1’), it has the cage-type silsesquioxane structure represented by the following formula (1a) and / or the cage-type silsesquioxane structure represented by the following formula (1b) at both ends or one end thereof.

Chemical formula

Chemical formula

[0082] Each symbol in the above formula (1a) has the same meaning as in the above (1’). R in the above formula (1b) 1j ~R 1r is the same as R 1a ~R 1i in the above (1’) and has the same meaning.

[0083] The multimeric cage-type silsesquioxane of the present disclosure includes, for example, one or more condensates selected from the group consisting of the cage-type silsesquioxanes represented by the above compositional formula (2), compositional formula (3), and compositional formula (4), and two or more condensates selected from the group consisting of the cage-type silsesquioxanes represented by the above compositional formula (1), the above compositional formula (2), compositional formula (3), and compositional formula (4).

[0084] The multimeric cage-type silsesquioxane of the present disclosure includes, for example, the following. · A condensate of the cage-type silsesquioxane represented by 3 or more compositional formulas (2) · A condensate of the cage-type silsesquioxane represented by 3 or more compositional formulas (3) · A condensate of the cage-type silsesquioxane represented by 3 or more compositional formulas (4) · A condensate of 2 or more cage-type silsesquioxanes represented by compositional formula (2) and 1 cage-type silsesquioxane represented by compositional formula (1) · A condensate of 2 or more cage-type silsesquioxanes represented by compositional formula (3) and 1 cage-type silsesquioxane represented by compositional formula (1) · A condensate of 2 or more cage-type silsesquioxanes represented by compositional formula (4) and 1 cage-type silsesquioxane represented by compositional formula (1) · A condensate of 1 or more cage-type silsesquioxanes represented by compositional formula (2) and 2 cage-type silsesquioxanes represented by compositional formula (1) · A condensate of 1 or more cage-type silsesquioxanes represented by compositional formula (3) and 2 cage-type silsesquioxanes represented by compositional formula (1) · A condensate of a cage-type silsesquioxane represented by the compositional formula (4) above and two cage-type silsesquioxanes represented by the compositional formula (1) · Two or more condensates selected from the group consisting of cage-type silsesquioxanes represented by the compositional formula (2), compositional formula (3), and compositional formula (4) · A condensate of two or more cage-type silsesquioxanes selected from the group consisting of cage-type silsesquioxanes represented by the compositional formula (2), compositional formula (3), and compositional formula (4) and one cage-type silsesquioxane represented by the compositional formula (1) · A condensate of two or more cage-type silsesquioxanes selected from the group consisting of cage-type silsesquioxanes represented by the compositional formula (2), compositional formula (3), and compositional formula (4) and two cage-type silsesquioxanes represented by the compositional formula (1)

[0085] When the multimeric cage-type silsesquioxane of the present disclosure has, for example, one or more selected from the group consisting of the repeating structures of the cage-type silsesquioxanes represented by the above formulas (2a), (3a), and (4a) and may have the cage-type silsesquioxane structure represented by the above formula (1a) and / or formula (1b), it may have the structure represented by the following formula (X).

Chemical formula

[0086] R in the above formula (X) 1a ~R 1r 、R 2a ~R 2h 、R 3a ~R 3j 、R 4a ~R 4l are the same as in the above formulas (1a), (1b), (2a), (3a), and (4a). p1 and p2 are each independently 0 or 1. q1, q2, and q3 are each independently 0 or a natural number. p1 + p2 + q1 + q2 + q3 is a natural number of 3 or more. q1 + q2 + q3 is a natural number of 1 or more. When q1 + q2 + q3 is 1, p1 and p2 are 1. When q1 + q2 + q3 is 2, p1 + p2 is 1 or 2. When q1 + q2 + q3 is 3 or more, p1 + p2 is 0, 1, or 2.

[0087] In the above formula, the multimer cage-type silsesquioxane of the present disclosure may have, instead of or in addition to formula (1a), formula (1b), formula (2a), formula (3a), formula (4a), for example, a repeating structure represented by formula (2b), formula (3b), formula (3c), and / or formula (4b), and a repeating structure derived from the cage-type silsesquioxane represented by the above composition formulas (5) to (8).

[0088] In the above formula (X), the condensed form of the repeating structures represented by the above formula (2a), formula (3b), and formula (4a) is not particularly limited and may be of a random type or a block type.

[0089] In the polyorganosilsesquioxane of the present disclosure, the proportion of the silsesquioxane having at least one hydroxyl group as a substituent is, for example, 5% by weight or more, preferably 10 to 50% by weight, more preferably 15 to 40% by weight, based on the polyorganosilsesquioxane of the present disclosure. When the proportion of the cage-type silsesquioxane represented by formula (1) having a hydroxyl group is 5% by weight or more, the flexural resistance in the cured product (for example, the hard coat layer) can be further improved. The proportion of the silsesquioxane having at least one hydroxyl group as a substituent can be estimated from the above molar ratio [T3 body / T2 body].

[0090] The polyorganosilsesquioxane of the present disclosure may include, in addition to the multimeric cage-type silsesquioxane of the present disclosure, cage-type silsesquioxanes without any cleavage in the three-dimensional structure of silica such as a regular hexahedron structure (i.e., a complete cage-type silsesquioxane), and monomeric cage-type silsesquioxanes such as those represented by the above compositional formula (1), compositional formula (2), compositional formula (3), compositional formula (4), etc., which are not condensed (i.e., incomplete cage-type silsesquioxanes). In this specification, both the above complete cage-type silsesquioxane and incomplete cage-type silsesquioxane are collectively referred to as monomeric cage-type silsesquioxanes. The proportion of the monomeric cage-type silsesquioxane in the polyorganosilsesquioxane of the present disclosure is, for example, 5% by weight or more, preferably 10% by weight or more, more preferably 20% by weight or more, and, for example, 50% by weight or less, preferably 40% by weight or less, more preferably 20% by weight or less, based on the total amount of the polyorganosilsesquioxane of the present disclosure. When the total proportion of the above monomeric cage-type silsesquioxane is within the range of 40% by weight or more, the surface hardness of the cured product in a hard coat layer or the like can be further improved.

[0091] The polyorganosilsesquioxane of the present disclosure may have a cage-type (structure) silsesquioxane other than the multimeric cage-type silsesquioxane of the present disclosure. Further, the polyorganosilsesquioxane of the present disclosure may have a silsesquioxane structure such as a ladder type or a random type in addition to the cage-type silsesquioxane. Further, the polyorganosilsesquioxane of the present disclosure may have a combination of two or more of these silsesquioxane structures.

[0092] The content of the multimeric cage-type silsesquioxane of the present disclosure in the polyorganosilsesquioxane of the present disclosure is, for example, 20% by weight or more (preferably 25 to 90% by weight, more preferably 30 to 80% by weight, still more preferably 40 to 70% by weight) based on the total amount of the polyorganosilsesquioxane of the present disclosure.

[0093] The multimeric cage-type silsesquioxane of the present disclosure has a structure in which at least three selected from the group consisting of the cage-type silsesquioxanes represented by the above compositional formula (1), compositional formula (2), compositional formula (3), and compositional formula (4) are condensed. The multimeric cage-type silsesquioxane of the present disclosure having such a structure can be estimated from spectrum analysis using mass spectrometry (MS). For example, when the polyorganosilsesquioxane of the present disclosure contains a mixture of a plurality of multimeric cage-type silsesquioxanes having one or more arbitrary repeating structures selected from the repeating structures represented by the formulas (2a), (3a), and (4a) in the above formula (X), the difference in molecular weight between each multimeric cage-type silsesquioxane is the same as the molecular weight of two T3 units. Therefore, when spectrum analysis is performed on a polyorganosilsesquioxane containing such a mixture of multimeric cage-type silsesquioxanes using mass spectrometry, a characteristic spectrum in which a plurality of molecular ion peaks (m / z) having a molecular weight difference corresponding to two T3 units appears is obtained. For example, when 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane in which all substituents are 3,4-epoxycyclohexylethyl groups is used as a raw material of polyorganosilsesquioxane, a characteristic spectrum having a plurality of molecular ion peaks having a molecular weight difference of about 354.1319, which is the molecular weight of two corresponding T3 units, is obtained. This is based on the difference in molecular weight of each repeating structure derived from the compositional formulas (2), (3), and (4). Specifically, when the linear silsesquioxane of the present disclosure is a mixture containing the repeating structure (3a) and the repeating structure (2a), the above molecular weight difference is [repeating structure (3)] - [repeating structure (2)] = C 16 H 26 becomes O5Si2 (molecular weight: about 354.1319).

[0094] The polyorganosilsesquioxane of the present disclosure may have only one type of the multimeric cage-type silsesquioxane of the present disclosure, or may have two or more types of the multimeric cage-type silsesquioxane of the present disclosure.

[0095] The polyorganosilsesquioxane of the present disclosure has, in addition to the above silisesquioxane structural unit [RSiO 3 / 2 (T unit), further at least one siloxane structural unit selected from the group consisting of a structural unit represented by [(R)3SiO 1 / 2 (so-called M unit), a structural unit represented by [(R)2SiO 2 / 2 (so-called D unit), and a structural unit represented by [SiO 4 / 2 (so-called Q unit). In addition, other silisesquioxane structural units other than the structural unit represented by the above formula (I) include a structural unit represented by [HSiO 3 / 2 and the like. R in the above formula represents a hydrogen atom or a monovalent organic group.

[0096] The ratio of each silisesquioxane structural unit in the polyorganosilsesquioxane of the present disclosure can be appropriately adjusted according to the composition of the raw material (hydrolyzable trifunctional silane) for forming these structural units.

[0097] The number average molecular weight (Mn) in terms of standard polystyrene of the multimer cage-type silisesquioxane of the present disclosure by gel permeation chromatography is, for example, 2000 to 50000, preferably 2500 to 40000, more preferably 3000 to 30000.

[0098] The number average molecular weight (Mn) in terms of standard polystyrene of the polyorganosilsesquioxane of the present disclosure by gel permeation chromatography is, for example, 2000 to 50000, preferably 2500 to 40000, more preferably 3000 to 30000. By setting the number average molecular weight to a certain value or more, the surface of the uncured or semi-cured hard coat layer tends to be tack-free, the blocking resistance is improved, it becomes easier to wind around a roll, and it can be preferably used as a component of the hard coat layer of the transfer film for in-mold injection molding. Also, 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 a certain value or less, the compatibility with other components in the curable composition is improved, and the heat resistance of the cured product is further improved.

[0099] The molecular weight distribution (Mw / Mn) in terms of standard polystyrene of the polyorganosilsesquioxane of the present disclosure by gel permeation chromatography is, for example, from 1.0 to 4.0, preferably from 1.1 to 3.0, more preferably from 1.2 to 2.5. By setting the molecular weight distribution to 4.0 or less, the solubility in a solvent becomes good, and the surface hardness and adhesiveness of the cured product become higher. On the other hand, by setting the molecular weight distribution to 1.1 or more, it tends to become liquid and the handleability tends to be improved.

[0100] Incidentally, the number average molecular weight and molecular weight distribution of the polyorganosilsesquioxane of the present disclosure can be determined by GPC measurement. Further, the contents of the above monomer cage-type silsesquioxane and multimer cage-type silsesquioxane in the polyorganosilsesquioxane of the present disclosure can be determined from the area ratio of the corresponding peak area values in GPC measurement. GPC measurement can be performed using the following apparatus and conditions. Measuring apparatus: Trade name "GPC semi-micro system" (manufactured by Shimadzu Corporation) Detector: RI detector (manufactured by Shoko Science Co., Ltd.) Columns: KF-G4A (guard column), KF-602, and KF-603 (manufactured by Shoko Science Co., Ltd.) Flow rate: 0.6 mL / min Measurement temperature: 40 °C Measurement time: 13 min Injection volume: 20 μL Eluent: THF, sample concentration 0.1 to 0.2% by weight Molecular weight: In terms of standard polystyrene

[0101] The 5% weight loss temperature (T) of the polyorganosilsesquioxane of the present disclosure in an air atmosphere d5) is not particularly limited, but is preferably 330°C or higher (for example, 330 - 450°C), more preferably 340°C or higher, and even more preferably 350°C or higher. When the 5% weight loss temperature is 330°C or higher, the heat resistance of the cured product tends to be further improved. When the polyorganosilsesquioxane of the present disclosure has the above ratio [T3 body / T2 body] of 1 or more and 500 or less, a number average molecular weight of 2000 - 50000, and a molecular weight dispersity of 1.0 - 4.0, the 5% weight loss temperature of the cured product thereof becomes 330°C or higher. The 5% weight loss temperature is the temperature at which the weight before heating decreases by 5% when heated at a constant heating rate, and serves as an index of heat resistance. The above 5% weight loss temperature can be measured by TGA (thermogravimetric analysis) under an air atmosphere at a heating rate of 5°C / min.

[0102] The polyorganosilsesquioxane of the present disclosure can be produced by a known or conventional method for producing polysiloxane, and is not particularly limited. For example, it can be produced by a method of hydrolyzing and condensing one or more hydrolyzable silane compounds. However, as the above hydrolyzable silane compound, it is necessary to use a hydrolyzable trifunctional silane compound (compound represented by the following formula (a)) as an essential hydrolyzable silane compound.

[0103] 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 disclosure, and, if necessary, further a compound represented by the following formula (B) and a compound represented by the following formula (C) are hydrolyzed and condensed to produce a cage-type silsesquioxane represented by the above composition formula (1), composition formula (2), composition formula (3) and / or composition formula (4), and by further hydrolysis and condensation reaction, the polyorganosilsesquioxane of the present disclosure containing a multimer cage-type silsesquioxane in which 3 or more of the cage-type silsesquioxanes represented by the above composition formula (1), composition formula (2), composition formula (3) and composition formula (4) are condensed can be produced. [Chemical formula] [Chemical formula] [Chemical formula]

[0104] The compound represented by the above formula (A) is [R in the multimer cage-type silsesquioxane of the present disclosure A SiO 3 / 2 or [R A SiO 2 / 2 (OR c )] is a compound that forms a structural unit. R A in the formula (A) represents a group containing a polymerizable functional group. That is, as R A in the formula (A), the group represented by the above formula (1A), the group represented by the above formula (1B), the group represented by the above formula (1C), and the group represented by the above formula (1D) are preferable, more preferably the group represented by the above formula (1A), the group represented by the above formula (1C), still more preferably the group represented by the above formula (1A), and even more preferably the group represented by the above formula (1A), and R 1A is a group in which the ethylene group is an ethylene group [among them, a 2-(3’,4’-epoxycyclohexyl)ethyl group].

[0105] X 1 in the above formula (A) represents an alkoxy group or a halogen atom. Examples of the alkoxy group in X 1 include alkoxy groups having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, and an isobutyloxy group. Examples of the halogen atom in X 1 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, as X 1 , an alkoxy group is preferable, and more preferably a methoxy group or an ethoxy group. It should be noted that the three X 1 may be the same or different from each other.

[0106] The compound represented by the above formula (B) is [R in the multimeric cage-type silsesquioxane of the present disclosure B SiO 3 / 2 or [R B SiO 2 / 2 (OR c )] is a compound that forms a structural unit. R B in formula (B) 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. As R B in formula (B), a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group is preferable, a substituted or unsubstituted aryl group is more preferable, and a phenyl group is even more preferable.

[0107] X 2 in the above formula (B) represents an alkoxy group or a halogen atom. Specific examples of X 2 include those exemplified as X 1 . Among them, as X 2 , an alkoxy group is preferable, and a methoxy group or an ethoxy group is more preferable. Note that the three X 2 may be the same as each other or different from each other.

[0108] The compound represented by the above formula (C) is [HSiO 3 / 2 or [HSiO 2 / 2 (OR c )] is a compound that forms a structural unit in the multimeric cage-type silsesquioxane of the present disclosure. X 3 in the above formula (C) represents an alkoxy group or a halogen atom. Specific examples of X 3 include those exemplified as X 1 . Among them, as X 3 , an alkoxy group is preferable, and a methoxy group or an ethoxy group is more preferable. Note that the three X 3 may be the same as each other or different from each other.

[0109] As the hydrolyzable silane compound, hydrolyzable silane compounds other than the compounds represented by the above formulas (A) to (C) may be used in combination. For example, hydrolyzable trifunctional silane compounds other than the compounds represented by the above formulas (A) to (C), hydrolyzable monofunctional silane compounds that form M units, hydrolyzable bifunctional silane compounds that form D units, hydrolyzable tetrafunctional silane compounds that form Q units, and the like can be mentioned.

[0110] The amount of use and composition of the hydrolyzable silane compound can be appropriately adjusted according to the structure of the desired polyorganosilsesquioxane of the present disclosure. For example, the amount of use of the compound represented by the above formula (A) is not particularly limited, but is preferably 30 to 100 mol%, more preferably 55 to 100 mol%, still more preferably 65 to 100 mol%, and even more preferably 80 to 99 mol% with respect to the total amount (100 mol%) of the hydrolyzable silane compound used.

[0111] Also, the amount of use of the compound represented by the above formula (B) is not particularly limited, but is preferably 0 to 70 mol%, more preferably 0 to 60 mol%, still more preferably 0 to 40 mol%, and even more preferably 1 to 15 mol% with respect to the total amount (100 mol%) of the hydrolyzable silane compound used.

[0112] Furthermore, the ratio (total amount ratio) of the compound represented by formula (a) to the compound represented by formula (b) with respect to the total amount (100 mol%) of the hydrolyzable silane compound 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%.

[0113] When two or more of the above hydrolyzable silane compounds are used in combination, the hydrolysis and condensation reactions of these hydrolyzable silane compounds can be carried out simultaneously or sequentially. When the above reactions are carried out sequentially, the order of the reactions is not particularly limited.

[0114] The hydrolysis and condensation reactions of the above hydrolyzable silane compound may be carried out in one step or may be carried out in two or more steps. However, in order to efficiently produce the polyorganosilsesquioxane of the present disclosure, it is preferable to carry out the hydrolysis and condensation reactions in two or more steps (preferably two steps). Hereinafter, a mode of carrying out the hydrolysis and condensation reactions of the hydrolyzable silane compound in two steps will be described, but the method for producing the polyorganosilsesquioxane of the present disclosure is not limited thereto.

[0115] When the hydrolysis and condensation reactions of the present disclosure are carried out in two steps, preferably, in the first-stage hydrolysis and condensation reaction, a polyorganosilsesquioxane (hereinafter referred to as "intermediate polyorganosilsesquioxane") in which the ratio [T3 body / T2 body] is 1 or more and less than 20 and the number average molecular weight is 1000 to 3000 is obtained, and in the second stage, the intermediate polyorganosilsesquioxane is further subjected to hydrolysis and condensation reactions to obtain the polyorganosilsesquioxane of the present disclosure.

[0116] The first-stage hydrolysis and condensation reaction can be carried out in the presence or absence of a solvent. Among them, it is preferably carried 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; esters such as methyl acetate, ethyl acetate, isopropyl acetate, and butyl acetate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; nitriles such as acetonitrile, propionitrile, and benzonitrile; and alcohols such as methanol, ethanol, isopropyl alcohol, and butanol. Among the above solvents, ketones and ethers are preferable. The solvent can be used alone or in combination of two or more.

[0117] The amount of the solvent used in the hydrolysis and condensation reactions in the first stage is not particularly limited, and can be appropriately adjusted within the range of 0 to 2000 parts by weight with respect to 100 parts by weight of the total amount of the hydrolyzable silane compound, according to the desired reaction time and the like.

[0118] The hydrolysis and condensation reactions in the first stage are preferably carried out in the presence of a catalyst and water. The above catalyst may be an acid catalyst or an alkali catalyst, but an alkali catalyst is preferred in order to suppress the decomposition of polymerizable functional groups such as epoxy groups. Examples of the above acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid; phosphate esters; carboxylic acids such as acetic acid, formic acid, and trifluoroacetic acid; sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid; solid acids such as activated clay; and Lewis acids such as iron chloride. Examples of the above alkali catalyst include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; hydroxides of alkaline earth metals such as magnesium hydroxide, calcium hydroxide, and barium hydroxide; carbonates of alkali metals such as lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate; carbonates of alkaline earth metals such as magnesium carbonate; hydrogen carbonates of alkali metals such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and cesium hydrogen carbonate; organic acid salts of alkali metals (e.g., acetates) such as lithium acetate, sodium acetate, potassium acetate, and cesium acetate; organic acid salts of alkaline earth metals (e.g., acetates) such as magnesium acetate; alkoxides of alkali metals such as lithium methoxide, sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium ethoxide, and potassium t-butoxide; phenoxides of alkali metals such as sodium phenoxide; amines (e.g., tertiary amines) such as triethylamine, N-methylpiperidine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and 1,5-diazabicyclo[4.3.0]nona-5-ene; and nitrogen-containing aromatic heterocyclic compounds such as pyridine, 2,2'-bipyridyl, and 1,10-phenanthroline. The catalyst can be used alone or in combination of two or more. In addition, the catalyst can be used in a state dissolved or dispersed in water, a solvent, or the like.

[0119] The amount of the catalyst used in the hydrolysis and condensation reaction in the first stage is not particularly limited and can be appropriately adjusted within the range of 0.002 to 0.200 mol with respect to 1 mol of the total amount of the hydrolyzable silane compound.

[0120] The amount of water used in the hydrolysis and condensation reaction in the first stage is not particularly limited and can be appropriately adjusted within the range of 0.5 to 20 mol with respect to 1 mol of the total amount of the hydrolyzable silane compound.

[0121] The method of adding the water in the hydrolysis and condensation reaction in the first stage is not particularly limited. The total amount of water used (total usage amount) may be added all at once, or may be added sequentially. When adding sequentially, it may be added continuously or intermittently.

[0122] As the reaction conditions for the hydrolysis and condensation reaction in the first stage, it is important to select reaction conditions such that the ratio [T3 body / T2 body] in the intermediate polyorganosilsesquioxane is 1 or more and less than 20. The reaction temperature of the hydrolysis and condensation reaction in the first stage is not particularly limited, but is preferably 40 to 100 °C, more preferably 45 to 80 °C. By controlling the reaction temperature within the above range, there is a tendency to be able to more efficiently control the ratio [T3 body / T2 body] to 1 or more and less than 20. Also, the reaction time of the hydrolysis and condensation reaction in the first stage is not particularly limited, but is preferably 0.1 to 10 hours, more preferably 1.5 to 8 hours. Further, the hydrolysis and condensation reaction in the first stage can be carried out under normal pressure, or can be carried out under pressure or reduced pressure. Incidentally, the atmosphere when carrying out the hydrolysis and condensation reaction in the first stage is not particularly limited, and may be any of, for example, an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere, or an oxygen presence such as under air, etc., but an inert gas atmosphere is preferred.

[0123] Through the hydrolysis and condensation reactions in the first stage, an intermediate polyorganosilsesquioxane is obtained. After completion of the hydrolysis and condensation reactions in the first stage, it is preferable to neutralize the catalyst in order to suppress decomposition of polymerizable functional groups such as ring-opening of epoxy groups. Further, the intermediate polyorganosilsesquioxane may be separated and purified by separation means such as, for example, washing with water, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or separation means combining these. Further, a reaction solution containing the intermediate polyorganosilsesquioxane may be subjected to the hydrolysis and condensation reactions in the first stage.

[0124] The polyorganosilsesquioxane of the present disclosure can be produced by subjecting the intermediate polyorganosilsesquioxane obtained by the hydrolysis and condensation reactions in the first stage to the hydrolysis and condensation reactions in the second stage. The hydrolysis and condensation reactions in the second stage can be carried out in the presence or absence of a solvent. When the hydrolysis and condensation reactions in the second stage are carried out in the presence of a solvent, the solvents exemplified in the hydrolysis and condensation reactions in the first stage can be used. As the solvent for the hydrolysis and condensation reactions in the second stage, the intermediate polyorganosilsesquioxane containing the reaction solvent, extraction solvent, etc. of the hydrolysis and condensation reactions in the first stage can be used as it is, or after partially or completely distilling off. Further, a solvent having a boiling point higher than that of the solvent used in the hydrolysis and condensation reactions in the first stage can be added to the reaction solution containing the intermediate polyorganosilsesquioxane, and then heated and distilled off to replace the solvent. The solvent can be used alone or in combination of two or more.

[0125] When a solvent is used in the hydrolysis and condensation reactions in the second stage, the amount used is not particularly limited, and can be appropriately adjusted according to the desired reaction time, etc. within the range of 0 to 2000 parts by weight with respect to 100 parts by weight of the intermediate polyorganosilsesquioxane.

[0126] The hydrolysis and condensation reaction in the second stage is preferably carried out in the presence of a catalyst and water. As the above catalyst, the catalysts mentioned in the hydrolysis and condensation reaction in the first stage can be used. In order to suppress the decomposition of polymerizable functional groups such as epoxy groups, it is preferably an alkali catalyst, more preferably hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide, cesium hydroxide; carbonates of alkali metals such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate. Note that the catalyst can be used alone or in combination of two or more. In addition, the catalyst can also be used in a state dissolved or dispersed in water, a solvent, etc. Also, the catalyst used in the hydrolysis and condensation reaction in the first stage can be directly used in the hydrolysis and condensation reaction in the second stage.

[0127] The amount of the above catalyst used in the hydrolysis and condensation reaction in the second stage is not particularly limited, and can be appropriately adjusted preferably in the range of 0.01 to 10000 ppm, more preferably 0.1 to 1000 ppm, based on the intermediate polyorganosilsesquioxane (1000000 ppm).

[0128] The amount of water used in the hydrolysis and condensation reaction in the second stage is not particularly limited, and can be appropriately adjusted preferably in the range of 10 to 100000 ppm, more preferably 100 to 20000 ppm, based on the intermediate polyorganosilsesquioxane (1000000 ppm). When the amount of water used is greater than 100000 ppm, the ratio [T3 body / T2 body] and number average molecular weight of polyorganosilsesquioxane tend to be difficult to control within a predetermined range.

[0129] The method of adding the above water in the hydrolysis and condensation reaction in the second stage is not particularly limited, and the total amount of water used (total usage amount) can be added all at once or sequentially. When adding sequentially, it can be added continuously or intermittently. Also, the water used in the hydrolysis and condensation reaction in the first stage can be directly used, or the remaining water after partially distilling off can be used.

[0130] As reaction conditions for the hydrolysis and condensation reactions in the second stage, it is important to select reaction conditions such that the above ratio [T3 form / T2 form] in the polyorganosilsesquioxane of the present disclosure is 10 or more and 500 or less, and the number average molecular weight is 2,500 to 50,000. The reaction temperature for the hydrolysis and condensation reactions in the second stage varies depending on the catalyst used and is not particularly limited, but is preferably 5 to 200°C, more preferably 30 to 150°C, and even more preferably 80 to 120°C. By controlling the reaction temperature within the above range, there is a tendency that the above ratio [T3 form / T2 form] and the number average molecular weight can be more efficiently controlled within a desired range. Further, the reaction time for the hydrolysis and condensation reactions in the second stage is not particularly limited, but is preferably 0.5 to 1,000 hours, more preferably 1 to 500 hours, and even more preferably 5 to 200 hours. Further, by performing timely sampling while carrying out the hydrolysis and condensation reactions within the above reaction temperature range and monitoring the above ratio [T3 form / T2 form] and the number average molecular weight during the reaction, it is also possible to obtain the polyorganosilsesquioxane of the present disclosure having a desired ratio [T3 form / T2 form] and number average molecular weight.

[0131] The hydrolysis and condensation reactions in the second stage can be carried out under normal pressure, or can also be carried out under pressure or reduced pressure. Note that the atmosphere when carrying out the hydrolysis and condensation reactions in the second stage is not particularly limited, and may be any of, for example, an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere, or an oxygen presence such as under air, etc., but an inert gas atmosphere is preferred.

[0132] The polyorganosilsesquioxane of the present disclosure is obtained by the above hydrolysis and condensation reactions in the second stage. After completion of the above hydrolysis and condensation reactions in the second stage, it is preferable to neutralize the catalyst in order to suppress decomposition of polymerizable functional groups such as ring-opening of epoxy groups. Further, the polyorganosilsesquioxane of the present disclosure may be separated and purified by separation means such as, for example, washing with water, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or separation means combining these.

[0133] The polyorganosilsesquioxane of the present disclosure contains a multimeric cage-type silsesquioxane having a structure in which three or more cage-type silsesquioxanes are bonded. Therefore, compared with conventional polyorganosilsesquioxanes, it is considered to have a tendency to have a highly flexible structure while maintaining high curability. Thus, the cured product of the curable composition containing the polyorganosilsesquioxane of the present disclosure has high surface hardness and heat resistance, and is excellent in flexural resistance and processability. In general, silsesquioxanes of polymers having a ladder structure are known to be difficult to dissolve in organic solvents (for example, Y. Kaneko, N. Iyi, Z. Kristallogr., 2007, 222, 656). However, the multimeric cage-type silsesquioxane of the present disclosure is considered to have a linear structure and is considered to be excellent in solubility in solvents such as organic solvents despite having a high molecular weight. The "linear structure" means that three or more of the cage-type silsesquioxanes represented by the above compositional formula (1), compositional formula (2), compositional formula (3), and / or compositional formula (4) are not three-dimensional but are condensed in series, resulting in the formation of a linear condensate. It should be noted that the above mechanism is only a presumption, and the present invention should not be construed as being limited to these mechanisms.

[0134] [Curable Composition] The curable composition of the present disclosure is a curable composition (curable resin composition) containing the above-described polyorganosilsesquioxane of the present disclosure as an essential component. As will be described later, the curable composition of the present disclosure may further contain other components such as a curing catalyst (for example, a photo cationic polymerization initiator, a radical polymerization initiator), a surface conditioner or a surface modifier, a polymerization stabilizer, and a silane coupling agent. The curable composition of the present disclosure can be used as a curable composition for forming a hard coat layer or a curable composition for an adhesive (for example, a curable composition for a laminated semiconductor) according to its use.

[0135] In the curable composition of the present disclosure, the polyorganosilsesquioxane of the present disclosure can be used alone or in combination of two or more.

[0136] The content (blending amount) of the polyorganosilsesquioxane of the present disclosure in the curable composition of the present disclosure is not particularly limited, but is preferably 70% by weight or more and less than 100% by weight, more preferably 80 to 99.8% by weight, and still more preferably 90 to 99.5% by weight, based on the total amount (100% by weight) of the curable composition excluding the solvent. By setting the content of the polyorganosilsesquioxane of the present disclosure to 70% by weight or more, the surface hardness and adhesiveness of the cured product tend to be further improved. On the other hand, by setting the content of the polyorganosilsesquioxane of the present disclosure to less than 100% by weight, a curing catalyst can be contained, and thus the curing of the curable composition tends to proceed more efficiently.

[0137] The content of the polyorganosilsesquioxane of the present disclosure with respect to the total amount (100% by weight) of the cation-curable compound or radical-curable compound contained in the curable composition of the present disclosure is not particularly limited, but is preferably 70 to 100% by weight, more preferably 75 to 98% by weight, and still more preferably 80 to 95% by weight. By setting the above content to 70% by weight or more, the surface hardness and adhesiveness of the cured product tend to be further improved.

[0138] The curable composition of the present disclosure preferably further contains a curing catalyst. Among them, in terms of shortening the curing time until it becomes more tack-free, it is preferable to contain a photo or thermal polymerization initiator as the curing catalyst, and more preferably to contain a cationic polymerization initiator or a radical polymerization initiator.

[0139] The above cationic polymerization initiator is a compound capable of initiating or promoting the cationic polymerization reaction of a cation-curable compound such as the polyorganosilsesquioxane of the present disclosure. The above cationic polymerization initiator is not particularly limited, and examples thereof include photo cationic polymerization initiators (photoacid generators), thermal cationic polymerization initiators (thermal acid generators), and the like.

[0140] As the above-mentioned photo cationic polymerization initiator, known or commonly used photo cationic polymerization initiators can be used. For example, sulfonium salts (salts of sulfonium ions and anions), iodonium salts (salts of iodonium ions and anions), selenium salts (salts of selenium ions and anions), ammonium salts (salts of ammonium ions and anions), phosphonium salts (salts of phosphonium ions and anions), salts of transition metal complex ions and anions, etc. can be mentioned. These can be used alone or in combination of two or more.

[0141] Examples of the above-mentioned sulfonium salts include [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium tris(pentafluoroethyl) trifluorophosphate, triphenylsulfonium salt, tri-p-tolylsulfonium salt, tri-o-tolylsulfonium salt, tris(4-methoxyphenyl) sulfonium salt, 1-naphthyldiphenylsulfonium salt, 2-naphthyldiphenylsulfonium salt, tris(4-fluorophenyl) sulfonium salt, tri-1-naphthylsulfonium salt, tri-2-naphthylsulfonium salt, tris(4-hydroxyphenyl) sulfonium salt, diphenyl[4-(phenylthio)phenyl]sulfonium salt, 4-(p-tolylthio)phenyl di-(p-phenyl)sulfonium salt and other triaryl sulfonium salts; diaryl sulfonium salts such as diphenylphenacylsulfonium salt, diphenyl 4-nitrophenacylsulfonium salt, diphenylbenzylsulfonium salt, diphenylmethylsulfonium salt; monoaryl sulfonium salts such as phenylmethylbenzylsulfonium salt, 4-hydroxyphenylmethylbenzylsulfonium salt, 4-methoxyphenylmethylbenzylsulfonium salt; trialkyl sulfonium salts such as dimethylphenacylsulfonium salt, phenacyltetrahydrothiophenium salt, dimethylbenzylsulfonium salt, etc.

[0142] Examples of the diphenyl[4-(phenylthio)phenyl]sulfonium salt include diphenyl[4-(phenylthio)phenyl]sulfonium hexafluoroantimonate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, and the like.

[0143] Examples of the iodonium salt include the product named "UV9380C" (manufactured by Momentive Performance Materials Japan G.K., bis(4-dodecylphenyl)iodonium hexafluoroantimonate 45% alkyl glycidyl ether solution), the product named "RHODORSIL PHOTOINITIATOR 2074" (manufactured by Rhodia Japan Ltd., tetrakis(pentafluorophenyl)borate=[(1-methylethyl)phenyl](methylphenyl)iodonium), the product named "WPI-124" (manufactured by Wako Pure Chemical Industries, Ltd.), diphenyl iodonium salt, di-p-tolyl iodonium salt, bis(4-dodecylphenyl)iodonium salt, bis(4-methoxyphenyl)iodonium salt, and the like.

[0144] Examples of the selenium salt include triarylselenium salts such as triphenylselenium salt, tri-p-tolylselenium salt, tri-o-tolylselenium salt, tris(4-methoxyphenyl)selenium salt, 1-naphthyldiphenylselenium salt; diarylselenium salts such as diphenylphenacylselenium salt, diphenylbenzylselenium salt, diphenylmethylselenium salt; monoarylselenium salts such as phenylmethylbenzylselenium salt; trialkylselenium salts such as dimethylphenacylselenium salt, and the like.

[0145] Examples of the ammonium salt include tetraalkylammonium salts such as tetramethylammonium salt, ethyltrimethylammonium salt, diethyldimethylammonium salt, triethylmethylammonium salt, tetraethylammonium salt, trimethyl-n-propylammonium salt, trimethyl-n-butylammonium salt; pyrrolidinium salts such as N,N-dimethylpyrrolidinium salt, N-ethyl-N-methylpyrrolidinium salt; imidazolinium salts such as N,N'-dimethylimidazolinium salt, N,N'-diethylimidazolinium salt; tetrahydropyrimidinium salts such as N,N'-dimethyltetrahydropyrimidinium salt, N,N'-diethyltetrahydropyrimidinium salt; morpholinium salts such as N,N-dimethylmorpholinium salt, N,N-diethylmorpholinium salt; piperidinium salts such as N,N-dimethylpiperidinium salt, N,N-diethylpiperidinium salt; pyridinium salts such as N-methylpyridinium salt, N-ethylpyridinium salt; imidazolium salts such as N,N'-dimethylimidazolium salt; quinolinium salts such as N-methylquinolinium salt; isoquinolinium salts such as N-methylisoquinolinium salt; thiazonium salts such as benzylbenzothiazonium salt; acridinium salts such as benzylacridinium salt, etc.

[0146] Examples of the phosphonium salt include tetraarylphosphonium salts such as tetraphenylphosphonium salt, tetra-p-tolylphosphonium salt, tetrakis(2-methoxyphenyl)phosphonium salt; triarylphosphonium salts such as triphenylbenzylphosphonium salt; tetraalkylphosphonium salts such as triethylbenzylphosphonium salt, tributylbenzylphosphonium salt, tetraethylphosphonium salt, tetrabutylphosphonium salt, triethylphenacylphosphonium salt, etc.

[0147] Examples of the salt of the transition metal complex ion include salts of chromium complex cations such as (η5-cyclopentadienyl)(η6-toluene)Cr + , (η5-cyclopentadienyl)(η6-xylene)Cr + ; salts of iron complex cations such as (η5-cyclopentadienyl)(η6-toluene)Fe+ 、(η5-Cyclopentadienyl)(η6-xylene)Fe + Salts of iron complex cations such as etc. can be mentioned.

[0148] Examples of the anions constituting the above salts include, for example, SbF6 - 、PF6 - 、BF4 - 、(CF3CF2)3PF3 - 、(CF3CF2CF2)3PF3 - 、(C6F5)4B - 、(C6F5)4Ga - 、Sulfonic acid anions (trifluoromethanesulfonic acid anion, pentafluoroethanesulfonic acid anion, nonafluorobutanesulfonic acid anion, methanesulfonic acid anion, benzenesulfonic acid anion, p-toluenesulfonic acid anion, etc.), (CF3SO2)3C - 、(CF3SO2)2N - 、Perhalogenate ions, halogenated sulfonate ions, sulfate ions, carbonate ions, aluminate ions, hexafluorobismuthate ions, carboxylate ions, arylborate ions, thiocyanate ions, nitrate ions, etc. can be mentioned.

[0149] Examples of the above thermal cationic polymerization initiators include, for example, arylsulfonium salts, aryliodonium salts, allene-ion complexes, quaternary ammonium salts, aluminum chelates, boron trifluoride amine complexes, etc.

[0150] Examples of the arylsulfonium salt include hexafluoroantimonate salts and the like. In the curable composition of the present disclosure, for example, commercially available products such as the trade names "SP-66", "SP-77" (both manufactured by ADEKA Corporation); the trade names "Sun-Aid SI-60L", "Sun-Aid SI-80L", "Sun-Aid SI-100L", "Sun-Aid SI-150L" (all manufactured by Sanshin Chemical Industry Co., Ltd.) can be used. Examples of the aluminum chelate include aluminum diisopropyl ethylacetoacetate, aluminum tris(ethylacetoacetate), and the like. Examples of the boron trifluoride amine complex include boron trifluoride monoethylamine complex, boron trifluoride imidazole complex, boron trifluoride piperidine complex, and the like.

[0151] The radical polymerization initiator is a compound that can initiate or accelerate the radical polymerization reaction of radical curable compounds such as the polyorganosilsesquioxane of the present disclosure. Examples of the radical polymerization initiator include photo radical polymerization initiators, thermal radical polymerization initiators, and the like.

[0152] Examples of the above photo radical polymerization initiator include benzophenone, acetophenone benzyl, benzyldimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyldisulfite, methyl orthobenzoylbenzoate, ethyl 4-dimethylaminobenzoate (manufactured by Nippon Kayaku Co., Ltd., trade name "Kayacure EPA", etc.), 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., trade name "Kayacure DETX", etc.), 2-methyl-1-[4-(methyl)phenyl]-2-morpholinopropanone-1 (manufactured by Ciba Geigy AG, trade name "Irgacure 907", etc.), 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Geigy AG, trade name "Irgacure 184", etc.), 2-amino-2-benzoyl-1-phenylalkane compounds such as 2-dimethylamino-2-(4-morpholino)benzoyl-1-phenylpropane, aminobenzene derivatives such as tetra(t-butylperoxycarbonyl)benzophenone, benzyl, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 4,4-bisdiethylaminobenzophenone, imidazole compounds such as 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole (manufactured by Hodogaya Chemical Co., Ltd., trade name "B-CIM", etc.), halomethylated triazine compounds such as 2,6-bis(trichloromethyl)-4-(4-methoxynaphthalen-1-yl)-1,3,5-triazine, and halomethyloxadiazole compounds such as 2-trichloromethyl-5-(2-benzofuran-2-yl-ethenyl)-1,3,4-oxadiazole. Further, a photosensitizer can be added as necessary.

[0153] Examples of the thermal radical polymerization initiator include hydroperoxides, dialkyl peroxides, peroxy esters, diacyl peroxides, peroxy dicarbonates, peroxy ketals, ketone peroxides, etc. (specifically, benzoyl peroxide, t-butyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di(2-ethylhexanoyl)peroxyhexane, t-butyl peroxybenzoate, t-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-dibutylperoxyhexane, 2,4-dichlorobenzoyl peroxide, 1,4-di(2-t-butylperoxyisopropyl)benzene, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, methyl ethyl ketone peroxide, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, etc.). Organic peroxides such as these can be mentioned.

[0154] In the curable composition of the present disclosure, the curing catalyst can be used alone or in combination of two or more.

[0155] The content (blending amount) of the above curing catalyst in the curable composition of the present disclosure is preferably 0.01 to 3.0 parts by weight, more preferably 0.05 to 3.0 parts by weight, and still more preferably 0.1 to 1.0 parts by weight (for example, 0.3 to 1.0 parts by weight) with respect to 100 parts by weight of the total amount of the polyorganosilsesquioxane of the present disclosure and other cation-curable compounds and / or other radical-curable compounds described later. By setting the content of the curing catalyst to 0.01 part by weight or more, the curing reaction can proceed efficiently and sufficiently, and the surface hardness and adhesiveness of the cured product tend to be further improved. On the other hand, by setting the content of the curing catalyst to 3.0 parts by weight or less, the storage stability of the curable composition tends to be further improved, and the coloring of the cured product tends to be suppressed.

[0156] The curable composition of the present disclosure may further contain a cationically curable compound other than the polyorganosilsesquioxane of the present disclosure (which may be referred to as "other cationically curable compound") and / or a radically curable compound other than the polyorganosilsesquioxane of the present disclosure (which may be referred to as "other radically curable compound"). As the other cationically curable compound, known or commonly used cationically curable compounds can be used, and examples include epoxy compounds, oxetane compounds, vinyl ether compounds, etc. other than the polyorganosilsesquioxane of the present disclosure. In the curable composition of the present disclosure, the other cationically curable compound can be used alone or in combination of two or more.

[0157] As the above epoxy compound, known or commonly used compounds having one or more epoxy groups (oxirane rings) in the molecule can be used, and there is no particular limitation. For example, alicyclic epoxy compounds (alicyclic epoxy resins), aromatic epoxy compounds (aromatic epoxy resins), aliphatic epoxy compounds (aliphatic epoxy resins), etc. can be mentioned.

[0158] Examples of the above alicyclic epoxy compounds include known or commonly used compounds having one or more alicyclic rings and one or more epoxy groups in the molecule, and there is no particular limitation. For example, (1) compounds having an epoxy group (referred to as "alicyclic epoxy group") composed of two adjacent carbon atoms and an oxygen atom constituting an alicyclic ring in the molecule; (2) compounds in which an epoxy group is directly bonded to an alicyclic ring by a single bond; (3) compounds having an alicyclic ring and a glycidyl ether group in the molecule (glycidyl ether type epoxy compounds), etc. can be mentioned.

[0159] Examples of the above compound (1) having an alicyclic epoxy group in the molecule include compounds represented by the following formula (i).

Chemical formula

[0160] 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 above linking group include a divalent hydrocarbon group, an alkenylene group in which part or all of the carbon-carbon double bond is epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and a group formed by linking a plurality of these groups.

[0161] Examples of the above divalent hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms and a divalent alicyclic hydrocarbon group. 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 above divalent alicyclic hydrocarbon group include divalent cycloalkylene groups (including cycloalkylidene groups) such as a 1,2-cyclopentylene group, a 1,3-cyclopentylene group, a cyclopentylidene group, a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group, and a cyclohexylidene group.

[0162] Examples of the alkenylene group in the above alkenylene group in which part or all of the carbon-carbon double bond is epoxidized (sometimes referred to as an "epoxidized alkenylene group") include linear or branched alkenylene groups having 2 to 8 carbon atoms such as a vinylene group, a propenylene group, a 1-butenylene group, a 2-butenylene group, a butadienylene group, a pentenylene group, a hexenylene group, a heptenylene group, and an octenylene group. As the above epoxidized alkenylene group, an alkenylene group in which all of the carbon-carbon double bonds are epoxidized is preferable, and more preferably an alkenylene group having 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized.

[0163] Typical examples of the alicyclic epoxy compound represented by the above formula (i) include (3,4,3’,4’-diepoxy)bicyclohexyl, compounds represented by the following formulas (i-1) to (i-10), etc. 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 alkylene group having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group, and an isopropyl group is preferable. In the following formulas (i-9) and (i-10), n1 to n6 each represent an integer of 1 to 30. Further, other examples of the alicyclic epoxy compound represented by the above formula (i) include, for example, 2,2-bis(3,4-epoxycyclohexyl)propane, 1,2-bis(3,4-epoxycyclohexyl)ethane, 2,3-bis(3,4-epoxycyclohexyl)oxirane, bis(3,4-epoxycyclohexylmethyl)ether, etc. [Chemical formula] [Chemical formula]

[0164] Examples of the compound in which an epoxy group is directly bonded to the above-mentioned (2) alicyclic ring by a single bond include, for example, compounds represented by the following formula (ii). [Chemical formula]

[0165] In formula (ii), R" is a group obtained by removing p hydroxyl groups (-OH) from the structural formula of a p-valent alcohol (a p-valent organic group), and p and n each represent a natural number. The p-valent alcohol [R"(OH) pExamples thereof include polyhydric alcohols such as 2,2-bis(hydroxymethyl)-1-butanol (alcohols having 1 to 15 carbon atoms, etc.). p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or more, n in the groups within each () (inside the outer parentheses) may be the same or different. Specific examples of the compound represented by the above formula (ii) include 1,2-epoxy-4-(2-oxiranyl)cyclohexane adducts of 2,2-bis(hydroxymethyl)-1-butanol [e.g., product name "EHPE3150" (manufactured by Daicel Corporation), etc.].

[0166] Examples of the compound having an alicyclic ring and a glycidyl ether group in the molecule in the above (3) include glycidyl ethers of alicyclic alcohols (e.g., alicyclic polyhydric alcohols). More specifically, for example, compounds obtained by hydrogenating bisphenol A type epoxy compounds such as 2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propane and 2,2-bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]propane (hydrogenated bisphenol A type epoxy compounds); compounds obtained by hydrogenating bisphenol F type epoxy compounds such as bis[o,o-(2,3-epoxypropoxy)cyclohexyl]methane, bis[o,p-(2,3-epoxypropoxy)cyclohexyl]methane, bis[p,p-(2,3-epoxypropoxy)cyclohexyl]methane, and bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]methane (hydrogenated bisphenol F type epoxy compounds); hydrogenated biphenol type epoxy compounds; hydrogenated phenol novolak type epoxy compounds; hydrogenated cresol novolak type epoxy compounds; hydrogenated cresol novolak type epoxy compounds of bisphenol A; hydrogenated naphthalene type epoxy compounds; hydrogenated epoxy compounds of epoxy compounds obtained from trisphenol methane; hydrogenated epoxy compounds of the following aromatic epoxy compounds, etc.

[0167] Examples of the aromatic epoxy compound include an epibis type glycidyl ether type epoxy resin obtained by a condensation reaction between bisphenols and epihalohydrin; a high molecular weight epibis type glycidyl ether type epoxy resin obtained by further addition reaction of these epibis type glycidyl ether type epoxy resins with the bisphenols; a novolak alkyl type glycidyl ether type epoxy resin obtained by subjecting polyhydric alcohols obtained by a condensation reaction between phenols and aldehydes to a further condensation reaction with epihalohydrin; an epoxy compound in which two phenol skeletons are bonded to the 9-position of a fluorene ring, and glycidyl groups are bonded to the oxygen atoms obtained by removing hydrogen atoms from the hydroxy groups of these phenol skeletons, directly or via an alkyleneoxy group, and the like.

[0168] Examples of the aliphatic epoxy compound include glycidyl ethers of alcohols having no q-valent cyclic structure (q is a natural number); glycidyl esters of monovalent or polyvalent carboxylic acids; epoxidized products of oils and fats having double bonds such as epoxidized linseed oil, epoxidized soybean oil, and epoxidized castor oil; epoxidized products of polyolefins (including polyalkadienes) such as epoxidized polybutadiene, and the like.

[0169] Examples of the oxetane compound include known or commonly used compounds having one or more oxetane rings in the molecule. As the vinyl ether compound, known or commonly used compounds having one or more vinyl ether groups in the molecule can be used.

[0170] As other radical curable compounds, known or commonly used radical curable compounds can be used and are not particularly limited. For example, (meth)acrylic compounds other than the polyorganosilsesquioxane of the present disclosure can be mentioned. In the curable composition of the present disclosure, other radical curable compounds can be used alone or in combination of two or more.

[0171] As the above (meth)acrylic compound, a known or commonly used compound having one or more (meth)acrylic groups in the molecule can be used, and it is not particularly limited. For example, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaglycerol tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerin tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tris((meth)acryloyloxyethyl)isocyanurate and other polyfunctional acrylate esters can be mentioned.

[0172] The content (blending amount) of other cation-curable compounds and / or other radical-curable compounds in the curable composition of the present disclosure is not particularly limited. However, with respect to the total amount (100% by weight; the total amount of the cation-curable compound and the radical-curable compound) of the polyorganosilsesquioxane, other cation-curable compounds and other radical-curable compounds of the present disclosure, 50% by weight or less (for example, 0 to 50% by weight) is preferable, more preferably 30% by weight or less (for example, 0 to 30% by weight), and even more preferably 10% by weight or less. By setting the content of other cation-curable compounds and / or other radical-curable compounds to 50% by weight or less (for example, 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 cation-curable compounds and / or other radical-curable compounds to 10% by weight or more, desired properties (for example, fast curability and viscosity adjustment for the curable composition) may be imparted to the curable composition and the cured product.

[0173] The curable composition of the present disclosure may further contain a polymerization stabilizer. The polymerization stabilizer is a compound that suppresses the progress of cationic polymerization by trapping cations and has the effect of allowing the polymerization to proceed when the ability of the polymerization stabilizer to trap cations is saturated and deactivated. By containing a polymerization stabilizer in the curable composition of the present disclosure, after coating and drying to form an adhesive layer, the progress of polymerization can be suppressed over a long period of time, and excellent adhesiveness can be exhibited by heating at the timing when adhesiveness is required, thereby forming an adhesive layer having excellent storage stability. When the curable composition of the present disclosure is a curable composition for an adhesive, it is preferably contained a polymerization stabilizer.

[0174] Examples of the above-mentioned 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-piperidinyl benzoate, (mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl)-1,2,3,4-butanetetracarboxylate, 3,9-bis(2,3-di-t-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, mixed(2,2,6,6-tetramethyl-4-piperidyl / β,β,β’,β’-tetramethyl-3-9-[2,4,8,10-tetraoxaspiro[5.5]undecane]diethyl)-1,2,3,4-butanetetracarboxylate, poly([6-N-morpholyl-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]), [N-(2,2,6,6-tetramethyl-4-piperidyl)-2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)imino]propionamide, trade names "LA-77", "LA-67", "LA-57" (above, manufactured by ADEKA CORPORATION), trade names "TINUVIN123", "TINUVIN152" (above, manufactured by Ciba Japan Co., Ltd.) and other hindered amine compounds, (4-hydroxyphenyl)dimethylsulfonium methyl sulfite (for example, trade name "Sun Aid SI Agent", manufactured by Sanshin Chemical Industry Co., Ltd.) and other sulfonium sulfate compounds, trade name "Adekastab PEP-36" (manufactured by ADEKA CORPORATION) and other phosphite compounds. Among them, from the viewpoint of making it less likely to cause partial curing during drying of the adhesive and having better adhesiveness of the cured product to the adherend, sulfonium sulfate compounds and phosphite compounds are preferred.

[0175] The above polymerization stabilizer may be used alone or in combination of two or more. In the curable composition for an adhesive of the present disclosure, it is particularly preferable to contain two or more polymerization stabilizers. As a result, the storage stability of the curable composition for an adhesive is remarkably excellent, it is more difficult for partial curing to occur during drying of the adhesive, and the adhesiveness of the cured product to the adherend tends to be even more excellent. As the above two or more polymerization stabilizers, it is preferable to contain at least a sulfonium sulfate compound and a phosphite compound.

[0176] When the curable composition of the present disclosure contains the above polymerization stabilizer, its content (blending amount) is not particularly limited, but based on 100 parts by weight of the polyorganosilsesquioxane of the present disclosure (when other cation-curable compounds are included, the total amount of polyorganosilsesquioxane and other cation-curable compounds), 0.005 parts by weight or more is preferable, preferably 0.01 to 10 parts by weight, and more preferably 0.02 to 1 part by weight. When the above content is 0.005 parts by weight or more, it is more difficult for partial curing to occur during drying of the adhesive, and the adhesiveness of the cured product to the adherend tends to be more excellent. When two or more polymerization stabilizers are used, the total amount of the polymerization stabilizer (C) is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 1 part by weight, based on 100 parts by weight of the polyorganosilsesquioxane of the present disclosure (when other cation-curable compounds are included, the total amount of polyorganosilsesquioxane and other cation-curable compounds).

[0177] When the curable composition of the present disclosure contains the above polymerization stabilizer and a curing catalyst, the content (blending amount) of the polymerization stabilizer is not particularly limited, but based on 100 parts by weight of the curing catalyst, 1 part by weight or more is preferable, more preferably 3 to 200 parts by weight, and even more preferably 5 to 150 parts by weight. When the above content is 1 part by weight or more, it is more difficult for partial curing to occur during drying of the adhesive, and the adhesiveness of the cured product to the adherend tends to be more excellent. When two or more polymerization stabilizers are used, the total amount of the polymerization stabilizer is preferably 100 to 200 parts by weight, more preferably 110 to 150 parts by weight, based on 100 parts by weight of the curing catalyst.

[0178] The curable composition of the present disclosure may preferably further contain a solvent. Examples of the solvent include water, organic solvents, etc., and any solvent that can dissolve the polyorganosilsesquioxane of the present disclosure and additives used as necessary and does not inhibit polymerization is not particularly limited.

[0179] As the solvent, it is preferable to use one or more solvents having a boiling point (at 1 atm) of 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.).

[0180] The solvent may be used in an appropriate amount according to the application of the curable composition. The amount of the solvent used is, for example, about 30 to 80% by weight, preferably 40 to 70% by weight, more preferably 50 to 60% by weight, as the concentration of the non-volatile content contained in the curable composition of the present disclosure. If 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 with an appropriate film thickness. On the other hand, if the amount of the solvent used is too small, the viscosity of the curable composition tends to be too high and it becomes difficult to apply it uniformly.

[0181] The curable composition of the present disclosure may further contain, as optional other components, inorganic fillers such as precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate, carbon black, silicon carbide, silicon nitride, boron nitride, etc., inorganic fillers treated with organosilicon compounds such as organohalosilanes, organoalkoxysilanes, and organosilazanes; organic resin fine powders such as silicone resins, epoxy resins, and fluororesins; fillers such as conductive metal powders of silver, copper, etc., curing aids, stabilizers, flame retardants, flame retardant aids, reinforcing materials, nucleating agents, coupling agents, lubricants, waxes, plasticizers, mold release agents, impact resistance improvers, hue improvers, clarifying agents, rheology modifiers (such as fluidity improvers), processability improvers, colorants (dyes, pigments, etc.), antistatic agents, dispersants, surface modifiers (such as defoamers, leveling agents, anti-crawling agents, etc.), surface treatment agents (such as slip agents, etc.), matting agents, defoamers, foam suppressants, degassing agents, antibacterial agents, preservatives, viscosity adjusters, thickeners, photosensitizers, foaming agents, and other conventional additives. These additives can be used alone or in combination of two or more kinds.

[0182] The curable composition of the present disclosure is not particularly limited, but can be prepared by stirring and mixing the above components at room temperature or while heating as necessary. In addition, the curable composition of the present disclosure can be used as a one-component composition in which each component is used as it is after being pre-mixed, or, for example, as a multi-component (for example, two-component) composition in which two or more components stored separately are mixed at a predetermined ratio before use.

[0183] The curable composition of the present disclosure is preferably liquid at room temperature (about 25°C), although not particularly limited. More specifically, the curable composition of the present disclosure preferably has a viscosity at 25°C of 300 to 20,000 mPa·s, more preferably 500 to 10,000 mPa·s, and even more preferably 1,000 to 8,000 mPa·s, as the viscosity of a solution [for example, a curable composition (solution) in which the proportion of methyl isobutyl ketone is 20% by weight] diluted with 20% of a solvent. By setting the above viscosity to 300 mPa·s or more, the heat resistance of the cured product tends to be further improved. On the other hand, by setting the above viscosity to 20,000 mPa·s or less, the preparation and handling of the curable composition become easy, and bubbles are less likely to remain in the cured product. The viscosity of the curable composition of the present disclosure is measured using a viscometer (trade name "MCR301", manufactured by Anton Paar) under the conditions of a swing angle of 5%, a frequency of 0.1 to 100 (1 / s), and a temperature of 25°C.

[0184] [Cured product] By advancing the polymerization reaction of the cationically curable compound or the radically curable compound in the curable composition of the present disclosure, the curable composition can be cured, and a cured product (sometimes referred to as "the cured product of the present disclosure") can be obtained. The curing method can be appropriately selected from well-known methods and is not particularly limited. For example, methods such as irradiation with active energy rays and / or heating can be mentioned. As the above active energy rays, for example, any of infrared rays, visible light, ultraviolet rays, X-rays, electron beams, α-rays, β-rays, γ-rays, etc. can be used. Among them, ultraviolet rays are preferred in terms of excellent handleability.

[0185] The conditions (such as the irradiation conditions of the active energy rays) when curing the curable composition of the present disclosure by irradiation with active energy rays can be appropriately adjusted according to the type and energy of the active energy rays to be irradiated, the shape and size of the cured product, etc., and are not particularly limited. However, when irradiating with ultraviolet rays, for example, 1 to 1,000 mJ / cm 2It is preferably at such a level. For the irradiation of active energy rays, for example, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, sunlight, an LED lamp, a laser, etc. can be used. After the irradiation of active energy rays, further heat treatment (annealing, aging) can be performed to further advance the curing reaction.

[0186] On the other hand, the conditions for curing the curable composition of the present disclosure by heating are not particularly limited. For example, 30 to 200 °C is preferable, and more preferably 50 to 190 °C. The curing time can be set as appropriate.

[0187] As described above, the curable composition of the present disclosure can form a cured product having high surface hardness, heat resistance, excellent flexural resistance and processability by curing. Therefore, the curable composition of the present disclosure is preferably used as a "curable composition for forming a hard coat layer" (sometimes referred to as a "hard coat liquid" or a "hard coat agent", etc.) for forming a hard coat layer in a hard coat film or an adhesive for a laminated semiconductor. When the curable composition of the present disclosure is used as a curable composition for forming a hard coat layer, a hard coat film having a hard coat layer formed from the composition has flexibility while maintaining high hardness and high heat resistance, and is suitable for roll-to-roll production and processing. In addition, when the curable composition of the present disclosure is used as a curable composition for adhesiveness, it cures at a low temperature and can form a cured product excellent in crack resistance, heat resistance, adhesiveness and adhesion to an adherend. Therefore, even when a thermal shock is applied, cracks and peeling do not occur in the adhesive layer, and a reliable device can be formed.

[0188] In addition, in the curable composition of the present disclosure, the surface of the uncured or semi-cured hard coat layer coated and dried on the release layer provided on the substrate becomes tack-free, improving the blocking resistance. Therefore, it can be wound into a roll for handling. Further, by transferring and curing the hard coat layer onto the surface of the molded article, a hard coat layer having high surface hardness can be formed. Accordingly, the curable composition of the present disclosure can be preferably used as a curable composition for forming a hard coat layer for forming a hard coat layer excellent in flexural resistance.

[0189] [Hard coat film] The hard coat film of the present disclosure is a hard coat film in which a substrate and a hard coat layer formed on at least one surface of the substrate are laminated, and the hard coat layer is a hard coat layer (a cured product layer of the curable composition of the present disclosure) formed by the curable composition of the present disclosure (curable composition for forming a hard coat layer). FIG. 8 is a schematic diagram (cross-sectional view) showing an embodiment of the hard coat film of the present disclosure. 1 represents the hard coat film, 11 represents the hard coat layer, and 12 represents the substrate.

[0190] Note that the hard coat layer in the hard coat film of the present disclosure may be formed only on one surface (one side) of the substrate or may be formed on both surfaces (both sides).

[0191] Further, the hard coat layer in the hard coat film of the present disclosure may be formed only on a part or on the entire surface of each surface of the substrate.

[0192] The substrate in the hard coat film of the present disclosure is the substrate of the hard coat film and refers to the part constituting other than the hard coat layer. As the above substrate, known or conventional substrates such as plastic substrates, metal substrates, ceramic substrates, semiconductor substrates, glass substrates, paper substrates, wood substrates (wooden substrates), and substrates having a painted surface can be used, and there is no particular limitation. Among them, a plastic substrate (a substrate composed of a plastic material) is preferable.

[0193] The plastic material constituting the plastic substrate is not particularly limited. For example, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyimide; polycarbonate; polyamide; polyacetal; polyphenylene oxide; polyphenylene sulfide; polyethersulfone; polyetheretherketone; homopolymers of norbornene-based monomers (such as addition polymers and ring-opening polymers), copolymers of norbornene-based monomers and olefin-based monomers such as copolymers of norbornene and ethylene (such as cyclic olefin copolymers such as addition polymers and ring-opening polymers), cyclic polyolefins such as derivatives thereof; vinyl-based polymers (for example, acrylic resins such as polymethyl methacrylate (PMMA), polystyrene, polyvinyl chloride, acrylonitrile-styrene-butadiene resin (ABS resin), etc.); vinylidene-based polymers (for example, polyvinylidene chloride, etc.); cellulose-based resins such as triacetyl cellulose (TAC); epoxy resins; phenolic resins; melamine resins; urea resins; maleimide resins; various plastic materials such as silicone. Note that 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.

[0194] Among them, when the purpose is to obtain a hard coat film with excellent transparency as the hard coat film of the present disclosure, it is preferable to use a substrate with excellent transparency (transparent substrate) as the plastic substrate, and more preferably a polyester film (for example, PET, PEN), a cyclic polyolefin film, a polycarbonate film, a TAC film, or a PMMA film.

[0195] The above-mentioned plastic substrate may, if necessary, contain other additives such as antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, crystal nucleating agents, flame retardants, flame retardant aids, fillers, plasticizers, impact resistance improvers, reinforcing agents, dispersants, antistatic agents, foaming agents, antibacterial agents, etc. In addition, the additives can be used alone or in combination of two or more kinds.

[0196] The above-mentioned plastic substrate may have a single-layer structure or a multi-layer (laminated) structure, and its structure is not particularly limited. For example, the above-mentioned plastic substrate may be a plastic substrate having a laminated structure such as "plastic film / other layer" or "other layer / plastic film / other layer" in which a layer other than the hard coat layer of the present disclosure (sometimes referred to as "other layer") is formed on at least one surface of the plastic film. Examples of the above-mentioned other layer include hard coat layers other than the hard coat layer of the present disclosure. In addition, examples of the material constituting the above-mentioned other layer include the above-mentioned plastic materials.

[0197] Known or conventional surface treatments such as roughening treatment, easy adhesion treatment, antistatic treatment, sandblasting treatment (sand mat treatment), corona discharge treatment, plasma treatment, chemical etching treatment, water mat treatment, flame treatment, acid treatment, alkali treatment, oxidation treatment, ultraviolet irradiation treatment, silane coupling agent treatment, etc. may be performed on part or all of the surface of the above-mentioned plastic substrate. The above-mentioned plastic substrate may be an unstretched film or a stretched film.

[0198] The above-mentioned plastic substrate can be manufactured by known or conventional methods such as, for example, a method of forming the above-mentioned plastic material into a film to obtain a plastic substrate (plastic film), and, if necessary, further forming an appropriate layer (for example, the above-mentioned other layer, etc.) on the above-mentioned plastic film or performing an appropriate surface treatment. In addition, commercially available products can also be used as the above-mentioned plastic substrate.

[0199] The thickness of the above-mentioned base material is not particularly limited, and for example, it can be appropriately selected from the range of 0.01 to 10,000 μm.

[0200] The hard coat layer in the hard coat film of the present disclosure is a layer that constitutes at least one surface layer in the hard coat film of the present disclosure, and is a layer (cured product layer) formed by a cured product (resin cured product) obtained by curing the curable composition (curable composition for forming a hard coat layer) of the present disclosure.

[0201] The thickness of the hard coat layer of the present disclosure (when the hard coat layer is provided on both surfaces of the base material, the thickness of each hard coat layer) is not particularly limited, but is preferably 1 to 200 μm, more preferably 3 to 150 μm. Even when the hard coat layer of the present disclosure is thin (for example, when the thickness is 5 μm or less), it is possible to maintain a high hardness on the surface (for example, the pencil hardness is 3H or more). Also, even when it is thick (for example, when the thickness is 50 μm or more), problems such as crack generation due to curing shrinkage are less likely to occur, so it is possible to significantly increase the pencil hardness by thickening the film (for example, the pencil hardness is 9H or more).

[0202] The haze of the hard coat layer is not particularly limited, but in the case of a thickness of 50 μm, it is preferably 1.5% or less, more preferably 1.0% or less. The lower limit of the haze is not particularly limited, but is, for example, 0.1%. By setting the haze to 1.0% or less, for example, it tends to be suitable for use in applications that require very high transparency (such as surface protection sheets for displays such as touch panels). The haze of the hard coat layer of the present disclosure can be measured in accordance with JIS K7136.

[0203] The total light transmittance of the hard coat layer is not particularly limited, but when the thickness is 50 μm, it is preferably 85% or more, more preferably 90% or more. The upper limit of the total light transmittance is not particularly limited, but for example, it is 99%. By setting the total light transmittance to 85% or more, it 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 total light transmittance of the hard coat layer of the present disclosure can be measured in accordance with JIS K7361-1.

[0204] The hard coat film of the present disclosure may further have a surface protection film on the surface of the hard coat layer of the present disclosure. By having the surface protection film, the punching processability of the hard coat film tends to be further improved. When having such a surface protection film, 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 during punching, punching using a Thomson blade can be performed without causing such problems. As the above surface protection film, a known or commonly used surface protection film can be used.

[0205] The hard coat film of the present disclosure can be manufactured according to a known or commonly used method for manufacturing a hard coat film, and the manufacturing method is not particularly limited. For example, the curable composition of the present disclosure (curable composition for forming a hard coat layer) is applied to at least one surface of the above base material, and after removing the solvent by drying as necessary, the curable composition (curable composition layer) can be manufactured by curing it. The conditions for curing the curable composition are not particularly limited, and can be appropriately selected from, for example, the conditions for forming the above-mentioned cured product.

[0206] The hard coat layer of the hard coat film of the present disclosure is a hard coat layer formed from a curable composition (curable composition for forming a hard coat layer) of the present disclosure that can form a cured product excellent in bending resistance and processability. Therefore, the hard coat film of the present disclosure can be manufactured by a roll-to-roll method. By manufacturing the hard coat film of the present disclosure by a roll-to-roll method, its productivity can be significantly increased. As a method for manufacturing the hard coat film of the present disclosure by a roll-to-roll method, a known or conventional roll-to-roll manufacturing method can be adopted, and it is not particularly limited. For example, a step of feeding out a substrate wound in a roll shape (step A), applying the curable composition (curable composition for forming a hard coat layer) of the present disclosure to at least one surface of the fed-out substrate, and then, if necessary, removing the solvent by drying, and then curing the curable composition (curable composition layer) to form the hard coat layer of the present disclosure (step B), and then, a step of winding the obtained hard coat film around a roll again (step C) are included as essential steps, and methods of continuously performing these steps (steps A to C) and the like can be mentioned. Note that the method may include steps other than steps A to C.

[0207] The thickness of the hard coat film of the present disclosure is not particularly limited, and can be appropriately selected from the range of 1 to 10,000 μm.

[0208] The pencil hardness of the surface of the hard coat layer of the hard coat film of the present disclosure is preferably 4H or more, more preferably 5H or more, and even more preferably 6H or more. The pencil hardness can be evaluated according to the method described in JIS K5600-5-4.

[0209] The haze of the hard coat film of the present disclosure is not particularly limited, but is preferably 1.5% or less, more preferably 1.0% or less. The lower limit of the haze is not particularly limited, but is, for example, 0.1%. By setting the haze to 1.0% or less, for example, it tends to be suitable for use in applications that require very high transparency (such as surface protection sheets for displays such as touch panels). The haze of the hard coat film of the present disclosure can be easily controlled within the above range, for example, by using the above-mentioned transparent substrate as the base material. The haze can be measured in accordance with JIS K7136.

[0210] The total light transmittance of the hard coat film of the present disclosure is not particularly limited, but is preferably 85% or more, more preferably 90% or more. The upper limit of the total light transmittance is not particularly limited, but is, for example, 99%. By setting the total light transmittance to 90% or more, for example, it tends to be suitable for use in applications that require very high transparency (such as surface protection sheets for displays such as touch panels). The total light transmittance of the hard coat film of the present disclosure can be easily controlled within the above range, for example, by using the above-mentioned transparent substrate as the base material. The total light transmittance can be measured in accordance with JIS K7361-1.

[0211] The hard coat film of the present disclosure has flexibility while maintaining high hardness and high heat resistance, and can be manufactured and processed by a roll-to-roll method. Therefore, it has high quality and excellent productivity. When the surface protection film is provided on the surface of the hard coat layer of the present disclosure, it also has excellent punching processability. For this reason, it can be preferably used in any application that requires such characteristics. The hard coat film of the present disclosure can be used, for example, as a surface protection film for various products, a surface protection film for members or parts of various products, etc., or as a constituent material for various products and their members or parts. Examples of the above products include display devices such as liquid crystal displays and organic EL displays; input devices such as touch panels; solar cells; various household appliances; various electric and electronic products; various electric and electronic products of portable electronic terminals (for example, game devices, personal computers, tablets, smartphones, mobile phones, etc.); various optical devices, etc. Further, examples of the mode in which the hard coat film of the present disclosure is used as a constituent material for various products and their members or parts include a mode in which it is used in a laminate of a hard coat film and a transparent conductive film in a touch panel, etc.

[0212] [Film for transfer] The transfer film (transfer hard coat film) of the present disclosure is a film having a base material and an uncured or semi-cured hard coat layer on a release layer formed on at least one surface of the base material, wherein the uncured or semi-cured hard coat layer is a layer containing the curable composition of the present disclosure (curable composition for forming a hard coat layer, which may be hereinafter referred to as "the hard coat agent of the present disclosure"). Here, "uncured" means a state in which the polymerizable functional groups of the polyorganosilsesquioxane of the present disclosure contained in the curable composition for forming the hard coat layer (hard coat agent) of the present disclosure have not undergone a polymerization reaction. Also, "semi-cured" means a state in which a part of the polymerizable functional groups has undergone a polymerization reaction and unreacted polymerizable functional groups remain. In the present specification, the uncured or semi-cured hard coat layer formed by the curable composition (hard coat agent) of the present disclosure may be simply referred to as "hard coat layer", and the hard coat layer transferred and cured on a molded article may be referred to as "cured hard coat layer". FIG. 9 is a schematic diagram (cross-sectional view) showing an embodiment of the transfer film of the present disclosure. 2 is the transfer film, 21 is the base material, 22 is the release layer, 23 is the hard coat layer (uncured or semi-cured hard coat layer), 24 is the anchor coat layer, 25 is the coloring layer, and 26 is the adhesive layer.

[0213] The base material in the transfer film of the present disclosure refers to the base material of the transfer film and constitutes the part other than the transfer layer containing the hard coat layer of the present disclosure. Here, the transfer layer refers to the layer in the transfer film of the present disclosure excluding the base material on which the release layer is formed, and is the part transferred to the surface of the molded article.

[0214] As the above base material, the base materials mentioned for the hard coat film can be used. Among them, a plastic base material (plastic film) is preferable as the base material. The thickness of the above base material can be appropriately selected from the range of, for example, 0.01 to 10000 μm. From the viewpoints of moldability, shape followability, handleability, etc., 2 to 250 μm is preferable, 5 to 100 μm is more preferable, and 20 to 100 μm is even more preferable.

[0215] The release layer in the transfer film of the present disclosure is a layer that constitutes at least one surface layer of the base material in the transfer film of the present disclosure, and is a layer provided to facilitate the peeling of the transfer layer from the base material. By providing the release layer, the transfer layer can be surely and easily transferred from the transfer film to the object to be transferred (molded product), and the base material can be surely peeled off.

[0216] In the transfer film of the present disclosure, the peel strength between the release layer and the hard coat layer is not particularly limited, but is preferably 30 to 500 mN / 24 mm, more preferably 40 to 300 mN / 24 mm, and still more preferably 50 to 200 mN / 24 mm. When the peel strength is within this range, the hard coat layer does not peel off during normal handling, and the hard coat can be easily peeled off simultaneously with the transfer to the molded product. The peel strength between the hard coat layer and the release layer of the present disclosure can be measured in accordance with JIS Z0237.

[0217] Note that the release layer in the transfer film of the present disclosure may be formed only on one surface (one side) of the base material, or may be formed on both surfaces (both sides). Further, the release layer in the transfer film of the present disclosure may be formed only on a part or on the entire surface of each surface of the base material.

[0218] As a component for forming the release layer, publicly known and commonly used release agents can be used without particular limitation. For example, at least one selected from unsaturated ester resins, epoxy resins, epoxy-melamine resins, amino alkyd resins, acrylic resins, melamine resins, silicone resins, fluorine resins, cellulose resins, urea resin resins, polyolefin resins, paraffin resins, and cycloolefin resins can be used. From the viewpoint of the peelability between the release layer and the hard coat layer of the present disclosure that is in contact with the release layer in the transfer layer, the release layer is preferably a melamine resin or a cycloolefin resin, and a cycloolefin copolymer resin (COC resin) such as a 2-norbornene-ethylene copolymer is more preferable.

[0219] As for the method of forming the release layer on the substrate surface, a publicly known and commonly used release treatment method can be used without particular limitation. For example, the above resin is dispersed or dissolved in a solvent (such as alcohols like methanol and butanol, aromatic hydrocarbons like toluene and xylene, tetrahydrofuran, etc.), and then coated by a known coating method such as bar coating, Mayer bar coating, gravure coating, roll coating, etc., dried, and heated at 80 to 200 °C to form a release layer. The thickness of the release layer is not particularly limited either, and it can usually be selected from the range of 0.01 to 5 μm, preferably 0.1 to 3.0 μm.

[0220] The hard coat layer in the transfer film of the present disclosure is a layer that constitutes at least one surface layer in the above release layer, and is an uncured layer obtained by drying the curable composition (hard coat agent) of the present disclosure, or a semi-cured layer that is partially cured. The semi-cured hard coat layer can be formed by partially advancing the curing of the uncured hard coat layer by the above-mentioned active energy ray irradiation or heating. The uncured or semi-cured hard coat layer of the present disclosure has low tackiness such that resin does not adhere when a finger touches the surface and excellent blocking resistance, and can be wound and handled in a roll shape.

[0221] Note that the hard coat layer in the transfer film of the present disclosure may be formed only on one release layer (one side) of the above substrate, or may be formed on both release layers (both sides). Also, the hard coat layer of the present disclosure in the transfer film of the present disclosure may be formed only on a part or on the entire surface of each surface of the above release layer.

[0222] As a method of laminating a hard coat layer on the release layer of the transfer film of the present disclosure, although not particularly limited, a curable composition (hard coat agent) of the present disclosure is applied and dried on the release layer by a known method to form an uncured hard coat layer, or further, the uncured hard coat layer is irradiated with active energy rays or heated to form a semi-cured hard coat layer. As a coating method of the curable composition (hard coat agent) of the present disclosure, known coating methods can be used without limitation. For example, bar coater coating, Mayer bar coating, air knife coating, gravure coating, offset printing, flexographic printing, screen printing, etc. can be mentioned. The heating temperature when forming the hard coat layer is not particularly limited, but can be appropriately selected preferably from 50 to 200°C. The heating time is also not particularly limited, but can be appropriately selected preferably from 1 to 60 minutes. The conditions for irradiating the hard coat layer with active energy rays are not particularly limited, and can be appropriately selected, for example, from the conditions for forming the cured product described above.

[0223] The thickness of the hard coat layer in the transfer film of the present disclosure (when having hard coat layers on both sides of the substrate, the thickness of each hard coat layer) is not particularly limited, but is preferably 1 to 200 μm, more preferably 3 to 150 μm. Even when the hard coat layer is thin (for example, when the thickness is 5 μm or less), it is possible to maintain a high hardness on the surface (for example, the pencil hardness is 5H or more). Also, even when it is thick (for example, when the thickness is 50 μm or more), problems such as crack generation due to curing shrinkage etc. are less likely to occur, so it is possible to significantly increase the pencil hardness by thickening the film (for example, the pencil hardness is 9H or more).

[0224] The haze of the hard coat layer in the transfer film of the present disclosure is not particularly limited, but when the thickness is 50 μm, it is preferably 1.5% or less, more preferably 1.0% or less. The lower limit of the haze is not particularly limited, but is, for example, 0.1%. By setting the haze to 1.0% or less, for example, when the transfer film of the present disclosure is used as a decorative film, patterns, designs, etc. can be clearly transferred, which is preferable. The haze of the hard coat layer of the present disclosure can be measured in accordance with JIS K7136.

[0225] The total light transmittance of the hard coat layer in the transfer film of the present disclosure is not particularly limited, but when the thickness is 50 μm, it is preferably 85% or more, more preferably 90% or more. The upper limit of the total light transmittance is not particularly limited, but is, for example, 99%. By setting the total light transmittance to 85% or more, for example, when the transfer film of the present disclosure is used as a decorative film, patterns, designs, etc. can be clearly transferred, which is preferable. The total light transmittance of the hard coat layer of the present disclosure can be measured in accordance with JIS K7361-1.

[0226] The transfer film of the present disclosure preferably further has an anchor coat layer and an adhesive layer laminated in this order on the hard coat layer. Further, when the transfer film of the present disclosure is used as a decorative film, at least one coloring layer is laminated. The lamination position of the coloring layer is not particularly limited, but a mode in which one layer or two or more layers are laminated between the anchor coat layer and the adhesive layer is preferable.

[0227] The anchor coat layer in the transfer film of the present disclosure is provided to improve the adhesion between the hard coat layer and the adhesive layer, the colored layer, or the like. The anchor coat layer is preferably a transparent or translucent layer in order to clearly transfer the pattern, design, etc. of the colored layer, and is a phenolic resin, an alkyd resin, a melamine resin (for example, methylated melamine resin, butylated melamine resin, methyl etherified melamine resin, butyl etherified melamine resin, methyl butyl mixed etherified melamine resin, etc.), an epoxy resin (for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyfunctional epoxy resin, flexible epoxy resin, brominated epoxy resin, glycidyl ester type epoxy resin, high molecular type epoxy resin, biphenyl type epoxy resin, etc.), a urea resin, an unsaturated polyester resin, a urethane resin [for example, a urethane resin obtainable by reacting a polyisocyanate compound (O=C=N-R-N=C=O) having two or more isocyanate groups with a polyol compound (HO-R’-OH) having two or more hydroxyl groups, a polyamine (H2N-R”-NH2), or a compound having active hydrogen (-NH2, -NH, -CONH-, etc.) such as water], a thermosetting resin such as a thermosetting polyimide or a silicone resin, or a thermoplastic resin such as a vinyl chloride-vinyl acetate copolymer resin, an acrylic resin (for example, an acrylic polyol resin, etc.), a chlorinated rubber, a polyamide resin, a nitrocellulose resin, a cyclic polyolefin resin, etc. A single kind or a mixture of two or more kinds is used, but an epoxy resin is preferred.

[0228] The resin for the anchor coat may further contain, as other optional components, conventional additives such as wax, silica, a plasticizer, a leveling agent, a surfactant, a dispersant, an antifoaming agent, an ultraviolet absorber, an ultraviolet stabilizer, and an antioxidant, as long as the effects of the present disclosure are not impaired. These additives can be used alone or in combination of two or more.

[0229] The anchor coat layer can be formed by applying a coating solution obtained by dissolving the above resin in a solvent onto the hard coat layer of the present disclosure by a known coating method such as bar coating, Mayer bar coating, gravure coating, roll coating, etc., drying, and, if necessary, heating. The temperature when heating during the formation of the anchor coat layer is not particularly limited, but can be appropriately selected preferably from 50 to 200 °C. The heating time is also not particularly limited, but can be appropriately selected preferably from 10 seconds to 60 minutes.

[0230] The thickness of the anchor coat layer is usually about 0.1 to 20 μm, preferably in the range of 0.5 to 5 μm.

[0231] The anchor coat layer of the present disclosure may be formed using a commercially available anchor coat agent. Examples of commercially available anchor coat agents include K468HP Anchor (epoxy resin-based anchor coat agent manufactured by Toyo Ink Co., Ltd.), TM-VMAC (acrylic polyol resin-based anchor coat agent manufactured by Dainichi Seika Kogyo Co., Ltd.), and the like.

[0232] The adhesive layer in the transfer film of the present disclosure is provided for transferring the transfer layer (including the hard coat layer, the anchor coat layer laminated as desired, and the colored layer) to the molded product with good adhesiveness. Examples of the adhesive layer include those composed of a heat-sensitive adhesive, a pressure-sensitive adhesive, etc. In the present disclosure, it is preferably a heat-seal layer that exhibits adhesiveness to the molded product by heating and pressure as necessary. Examples of the resin used for the adhesive layer include one kind alone or a mixture of two or more kinds of resins such as acrylic resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, styrene-acrylic copolymer resins, polyester resins, polyamide resins, etc., but acrylic resins and vinyl chloride-vinyl acetate copolymer resins are preferred.

[0233] Examples of the acrylic resin used in the adhesive layer of the present disclosure include acrylic resins such as polymethyl (meth)acrylate, polyethyl (meth)acrylate, polybutyl (meth)acrylate, methyl (meth)acrylate-butyl (meth)acrylate copolymer, and methyl (meth)acrylate-styrene copolymer, and modified acrylic resins modified with fluorine or the like. These can be used as one kind or a mixture of two or more kinds. In addition, (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and octyl (meth)acrylate, and (meth)acrylic acid esters having a hydroxyl group in the molecule such as 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate can also be copolymerized to obtain an acrylic polyol which can be used. As for the vinyl chloride-vinyl acetate copolymer resin, usually, those having a vinyl acetate content of about 5 to 20% by mass and an average degree of polymerization of about 350 to 900 are used. If necessary, carboxylic acids such as maleic acid and fumaric acid may be further copolymerized with the vinyl chloride-vinyl acetate copolymer resin. In addition, as the resin of the auxiliary component, if necessary, other resins may be appropriately mixed, for example, resins such as thermoplastic polyester resins, thermoplastic urethane resins, and chlorinated polyolefin resins such as chlorinated polyethylene and chlorinated polypropylene.

[0234] The adhesive layer can be formed by applying a solution or emulsion or other coatable form of one kind or two or more kinds of the above resins by a known coating method such as bar coating, Mayer bar coating, gravure coating, or roll coating, drying, and, if necessary, heating. When heating is performed when forming the adhesive layer, the temperature can be appropriately selected preferably from 50 to 200°C. The heating time can be appropriately selected preferably from 10 seconds to 60 minutes.

[0235] As the thickness of the adhesive layer, from the viewpoint of enabling the transfer film to be adhesively and efficiently transferred to the molded article, about 0.1 to 10 μm is preferable, and 0.5 to 5 μm is more preferable.

[0236] The adhesive layer may be blended with organic ultraviolet absorbers such as benzophenone-based compounds, benzotriazole-based compounds, oxalic acid anilide-based compounds, cyanoacrylate-based compounds, and salicylate-based compounds, and also with additives of fine particles having inorganic ultraviolet absorption ability such as oxides of zinc, titanium, cerium, tin, iron, etc. Further, as additives, coloring pigments, white pigments, extender pigments, fillers, antistatic agents, antioxidants, fluorescent brighteners, etc. can also be appropriately used as necessary.

[0237] As the above adhesive, commercially available products may be used. Examples of commercially available adhesives include K588HP Adhesive Gloss A Varnish (vinyl chloride-vinyl acetate copolymer resin-based adhesive manufactured by Toyo Ink Co., Ltd.), PSHP780 (acrylic resin-based adhesive manufactured by Toyo Ink Co., Ltd.), etc.

[0238] The coloring layer in the transfer film of the present disclosure is provided when the decorative film for transferring the pattern layer and / or the concealing layer to the molded article. Here, the pattern layer is a layer provided for expressing a pattern-like pattern such as a pattern, characters, etc., and the concealing layer is usually a solid layer provided for concealing the coloring of an injection resin, etc. The concealing layer may form a decorative layer alone, in addition to being provided inside the pattern layer to enhance the pattern of the pattern layer.

[0239] The pattern layer according to the present disclosure is a layer provided for expressing a pattern-like pattern such as a pattern, characters, etc. The pattern of the pattern layer is arbitrary, and examples thereof include patterns composed of wood grain, stone grain, cloth grain, sand grain, geometric patterns, characters, etc.

[0240] The colored layer is usually formed by printing ink on the above hard coat layer or anchor coat layer by a known printing method such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, sublimation transfer printing, inkjet printing, etc., and can be formed between the hard coat layer and the adhesive layer or between the anchor coat layer and the adhesive layer. From the viewpoint of design, the thickness of the colored layer is preferably 3 to 40 μm, more preferably 10 to 30 μm.

[0241] Examples of the binder resin of the printing ink used for forming the colored layer include polyester resins, polyurethane resins, acrylic resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, cellulose resins, etc. Among them, it is preferable to use an acrylic resin alone or a mixture of an acrylic resin and a vinyl chloride-vinyl acetate copolymer resin as the main component. Among these, it is preferable to mix an acrylic resin, a vinyl chloride-vinyl acetate copolymer resin, or another acrylic resin because the printability and moldability become better. Here, examples of the acrylic resin include acrylic resins such as polymethyl (meth)acrylate, polyethyl (meth)acrylate, polybutyl (meth)acrylate, methyl (meth)acrylate-butyl (meth)acrylate copolymer, methyl (meth)acrylate-styrene copolymer, and modified acrylic resins with fluorine, etc. These can be used as one kind or a mixture of two or more kinds. In addition, an acrylic polyol obtained by copolymerizing an alkyl (meth)acrylate such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, etc. and a (meth)acrylate ester having a hydroxyl group in the molecule such as 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, etc. can also be used. Further, as the vinyl chloride-vinyl acetate copolymer resin, those having a vinyl acetate content of about 5 to 20% by mass and an average degree of polymerization of about 350 to 900 are usually used. If necessary, a carboxylic acid such as maleic acid or fumaric acid may be further copolymerized with the vinyl chloride-vinyl acetate copolymer resin. The mixing ratio of the acrylic resin and the vinyl chloride-vinyl acetate copolymer resin is about acrylic resin / vinyl chloride-vinyl acetate copolymer resin = 1 / 9 to 9 / 1 (mass ratio). In addition, as the resin of the auxiliary component, if necessary, other resins may be appropriately mixed, for example, resins such as thermoplastic polyester resins, thermoplastic urethane resins, chlorinated polyolefin resins such as chlorinated polyethylene and chlorinated polypropylene.

[0242] Examples of the colorant used for the colored layer include metallic pigments composed of flaky foil powder of metals, alloys, or metal compounds such as aluminum, chromium, nickel, tin, titanium, iron phosphide, copper, gold, silver, and brass; pearlescent (pearl) pigments composed of mica-like iron oxide, titanium dioxide-coated mica, titanium dioxide-coated bismuth oxychloride, bismuth oxychloride, titanium dioxide-coated talc, fish scale foil, colored titanium dioxide-coated mica, and basic lead carbonate; fluorescent pigments such as strontium aluminate, calcium aluminate, barium aluminate, zinc sulfide, and calcium sulfide; white inorganic pigments such as titanium dioxide, zinc white, and antimony trioxide; inorganic pigments such as zinc white, red lead, vermilion, ultramarine, cobalt blue, titanium yellow, yellow lead, and carbon black; and organic pigments (including dyes) such as isoindolinone yellow, Hansa yellow A, quinacridone red, permanent red 4R, phthalocyanine blue, indanthrene blue RS, and aniline black. One or more of these can be mixed and used.

[0243] Such a colored layer is a layer provided to impart design characteristics to the transfer film of the present disclosure. However, for the purpose of improving design characteristics, a metal thin film layer or the like may be further formed. The metal thin film layer can be formed by a method such as vacuum deposition or sputtering using a metal such as aluminum, chromium, gold, silver, or copper. This metal thin film layer may be provided over the entire surface or partially in a pattern.

[0244] In addition to the above components, a printing ink used for forming the colored layer may be appropriately added with an anti-settling agent, a curing catalyst, an ultraviolet absorber, an antioxidant, a leveling agent, a thickening agent, an antifoaming agent, a lubricant, and the like. The printing ink is usually provided in a form in which the above components are dissolved or dispersed in a solvent. Any solvent can be used as long as it can dissolve or disperse the binder resin, and an organic solvent and / or water can be used. Examples of the organic solvent include hydrocarbons such as toluene and xylene; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate, cellosolve acetate, and butyl cellosolve acetate; and alcohols.

[0245] In addition to the above-mentioned base material, release layer, hard coat layer, anchor coat layer, adhesive layer, and coloring layer, the transfer film of the present disclosure may further include, if desired, a low reflection layer, an antistatic layer, an ultraviolet absorption layer, a near infrared blocking layer, an electromagnetic wave absorption layer, etc., laminated in any order.

[0246] The thickness of the transfer film of the present disclosure is not particularly limited and can be appropriately selected from the range of 1 to 10,000 μm. However, from the viewpoints of moldability, shape followability, handleability, etc., 2 to 250 μm is preferable, 5 to 150 μm is more preferable, and 25 to 150 μm is even more preferable.

[0247] The hard coat layer of the transfer film of the present disclosure is tack-free and excellent in antiblocking properties, and can be wound into a roll for handling. Therefore, it can be suitably used as a transfer film for in-mold injection molding. For example, the transfer film of the present disclosure is continuously conveyed by a conveying roll or the like in a mold composed of a fixed mold and a movable mold. The base film side is in contact with the fixed mold surface. After appropriate position adjustment, the movable mold moves to close the mold. Then, a thermoplastic resin previously melted by heat is injection-filled into the mold from the transfer layer side of the transfer film at high temperature and high pressure, and after rapid cooling, the mold is opened, and a molded product (in-mold molded product) with the hard coat layer of the present disclosure transferred to the outermost surface can be taken out.

[0248] When the hard coat layer of the above-mentioned molded product of the present disclosure is uncured or semi-cured, the hard coat layer may be cured by irradiating with active energy rays and / or heating. The conditions for irradiating with active energy rays and / or heating the hard coat layer are not particularly limited, and can be appropriately selected, for example, from the conditions for forming the above-mentioned cured product.

[0249] After the transfer layer of the transfer film of the present disclosure is transferred to a molded article, the cured hard coat layer of the present disclosure is formed on the outermost surface of the molded article, so that the pencil hardness of the surface of the molded article can be made very high, preferably 5H or more, more preferably 6H or more. The pencil hardness can be evaluated according to the method described in JIS K5600-5-4.

[0250] The molded article (in-mold molded article) produced by the in-mold injection molding method using the transfer film of the present disclosure has a very high surface hardness, and the pattern and design are transferred clearly. Therefore, it can be preferably used for any molded article that requires such characteristics. The transfer film of the present disclosure can be preferably used for various exterior molded articles that require high surface hardness, scratch resistance, design, and durability, such as automotive interior and exterior parts such as dashboards and housings of home appliances.

[0251] [Adhesive sheet] By using the curable composition (curable composition for adhesives, curable composition for laminated semiconductors) of the present disclosure, an adhesive sheet having an adhesive layer formed from the curable composition of the present disclosure on at least one surface of a substrate can be obtained. FIG. 10 is a schematic diagram (cross-sectional view) showing an embodiment of the adhesive sheet of the present disclosure. 3 represents the adhesive sheet, 31 represents the adhesive layer, 32 represents the substrate, and 33 represents the anchor coat layer.

[0252] The above-mentioned adhesive sheet can be obtained, for example, by applying the curable composition of the present disclosure (curable composition for adhesives, curable composition for laminated semiconductors) to a substrate and further drying it as necessary. The method of application is not particularly limited, and well-known and commonly used means can be utilized. Also, the means and conditions for drying are not particularly limited, and conditions can be set to remove as much volatile matter such as solvents as possible, and well-known and commonly used means can be used. When the curable composition of the present disclosure contains a polymerization initiator such that the thermosetting time at 130°C of the composition obtained by adding 1 part by weight to 100 parts by weight of Celloxide 2021P (manufactured by Daicel Corporation) is 3.5 minutes or more, by heat drying, while suppressing the progress of the curing reaction, volatile matter such as solvents can be quickly removed to form an adhesive layer. The adhesive layer thus obtained has no adhesiveness at temperatures below 50°C, exhibits adhesiveness by heating at a temperature capable of suppressing damage to electronic components such as semiconductor chips, and then quickly cures. The above-mentioned adhesive sheet includes not only sheet-like forms but also forms similar to sheet-like forms such as film-like, tape-like, and plate-like forms.

[0253] The above-mentioned adhesive sheet 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 adhesive layers on both sides of the substrate. When the above-mentioned adhesive sheet is a double-sided adhesive sheet, at least one of the adhesive layers may be an adhesive layer formed from the curable composition of the present disclosure, and the other may be the said adhesive layer or an adhesive layer other than the said adhesive layer (other adhesive layer).

[0254] As the base material in the adhesive sheet of the present disclosure, well-known and commonly used base materials (base materials used in adhesive sheets) can be used, and there is no particular limitation. For example, plastic base materials, metal base materials, ceramic base materials, semiconductor base materials, glass base materials, paper base materials, wood base materials, base materials whose surfaces are painted surfaces, etc. can be mentioned. Further, the base material in the adhesive sheet of the present disclosure may be a so-called release liner. Note that the adhesive sheet of the present disclosure may have only one layer of the base material, or may have two or more layers. Further, the thickness of the above base material is not particularly limited, and can be appropriately selected, for example, in the range of 1 to 10,000 μm.

[0255] The above adhesive sheet may have only one layer of the adhesive layer formed from the curable composition of the present disclosure, or may have two or more types of the adhesive layer. Further, the thickness of the adhesive layer in the above adhesive sheet is not particularly limited, and can be appropriately selected, for example, in the range of 0.1 to 10,000 μm.

[0256] Further, as another aspect of the above adhesive sheet, by using a silane coupling agent and the polyorganosilsesquioxane of the present disclosure, an adhesive sheet excellent in crack resistance, heat resistance, adhesiveness to an adherend, and adhesion can be obtained. Specifically, on at least one surface of the base material, there is an anchor coat layer containing a silane coupling agent, and an adhesive layer formed from a curable composition containing the polyorganosilsesquioxane of the present disclosure, and the adhesive sheet in which the adhesive layer is provided on the surface of the anchor coat layer is excellent in crack resistance, heat resistance, adhesiveness to an adherend, and adhesion.

[0257] Further, in another aspect of the above adhesive sheet, it may have only one layer of the anchor coat layer, or may have two or more types of the anchor coat layer. Further, the thickness of the anchor coat layer can be appropriately selected, for example, in the range of 0.001 to 10,000 μm.

[0258] In addition to the base material, the adhesive layer, and the anchor coat layer, the above-mentioned adhesive sheet may also have other layers (for example, an intermediate layer, an undercoat layer, etc.).

[0259] By using the above-mentioned adhesive sheet, a laminate in which an adherend layer (adherend) is attached to the adhesive layer of the adhesive sheet can be obtained. And when the laminate obtained by using the above-mentioned adhesive sheet is a three-dimensional laminate of semiconductor chips, it is more highly integrated and power-saving than conventional semiconductors. Therefore, by using the laminate, it is possible to provide a smaller and higher-performance electronic device while improving the mounting density.

[0260] Each aspect disclosed in this specification can be combined with any other features disclosed in this specification. Each configuration and their combinations in each embodiment are examples, and within the scope not departing from the gist of the present invention, additions, omissions, substitutions, and other changes of the configuration can be made as appropriate. The present disclosure is not limited by the embodiments, but is limited only by the claims.

Examples

[0261] Hereinafter, the present disclosure will be described in more detail based on examples, but the present disclosure is not limited by these examples. Note that Example 2 shall be read as Reference Example 1.

[0262] The number average molecular weight and molecular weight dispersity of the product were measured under the following GPC condition 1. Also, the contents of monomeric cage-type silsesquioxane and polymeric cage-type silsesquioxane in the product were determined from the area ratio of the areas of the corresponding peaks in the GPC measurement. GPC fractionation is shown in GPC condition 2. As shown in Figure 3, it was fractionated into four fractions. The measurement of the ratio [T3 body / T2 body] of the T2 body and the T3 body in the product was carried out by Brucker AVANCE (600 MHz). 29It was performed by Si-NMR spectrum measurement. In addition, mass spectrometry of the above-mentioned fraction was performed using the following quadrupole-time-of-flight mass spectrometer (manufactured by Waters, product name "Xevo G2-XS QTof").

[0263] [GPC Condition 1] Measuring device: Product name "GPC Semi-micro System" (manufactured by Shimadzu Corporation) Detector: RI detector (manufactured by Shoko Science Co., Ltd.) Column: KF-G4A (guard column), KF-602, and KF-603 (manufactured by Shoko Science Co., Ltd.) Flow rate: 0.6 mL / min Measurement temperature: 40 °C Measurement time: 13 min Injection volume: 20 μL Eluent: THF, sample concentration 0.1 - 0.2 wt% Molecular weight: Standard polystyrene conversion

[0264] [GPC Condition 2 at fractionation] Measuring device: Alliance 2695 (manufactured by Waters) Column: Shodex KF-801 × 2 pieces, KF-802, and KF-803 (manufactured by Showa Denko K.K.) Measurement temperature: 40 °C Eluent: THF, sample concentration 1.0 wt% Flow rate: 1 mL / min Detector: ShodexRI-101 (manufactured by Showa Denko K.K.) Molecular weight: Standard polystyrene conversion

[0265] In addition, UPLC-MS was performed under the following apparatus and conditions. [UPLC Condition] Measuring device: ACQUITY UPLC H-Class (manufactured by Waters) Detector, detection conditions: The following MS conditions Column: ACQUITY UPLC HSS PFP 2.1×100mm×1.8μm Mobile phase A: 5 mM ammonium formate aqueous solution Mobile phase B: Acetonitrile / THF = 6 / 4 Washing solvent: Acetonitrile / THF = 6 / 4 Flow rate: 0.35 mL / min Sample temperature: 10 °C Column temperature: 40 °C Injection volume: 2.0 μL

[0266] [MS conditions] Measuring device: Xevo-G2XS QTOFMS (manufactured by Waters) Ionization mode: ESI positive (Sensitivity Mode) Measurement method: MSE Capillary voltage: 3.2 kV Cone voltage: 30 V Source offset voltage: 80 V Desolvation gas: 1000 L / hr (200 °C) Cone gas: 50 L / hr Ion source heater: 80 °C Scan range: m / z = 100 - 3000 Scan time: 0.4 sec Collision energy: 30 - 50 eV (MSE HighEnergy) Lock mass: Leucine Enkephalin

[0267] Example 1: Production of epoxy group-containing polyorganosilsesquioxane of the present disclosure (1) Into a 1000 milliliter flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube and a Dean-Stark tube, 277.2 mmol (68.30 g) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3.0 mmol (0.56 g) of phenyltrimethoxysilane, and 275.4 g of acetone were charged under a nitrogen stream, and the temperature was raised to 50 °C. To the mixture thus obtained, 7.74 g of a 5% aqueous potassium carbonate solution (2.8 mmol as potassium carbonate) was added over 5 minutes, and then 2800.0 mmol (50.40 g) of water was added over 20 minutes. During the addition, no significant temperature rise occurred. Then, while maintaining the temperature at 50 °C, the polycondensation reaction was carried out for 5 hours under a nitrogen stream. Subsequently, 230.5 g of methyl isobutyl ketone was charged, and the temperature was raised from 50 °C to 90 °C under reduced pressure to distill off until the system contained acetone (0.0%), methyl isobutyl ketone (30.32%), and water (0.23%). Subsequently, with the temperature remaining at 90 °C, stirring was carried out for 11 hours, 273.2 g of methyl isobutyl ketone was added, and washing with water 5 times was performed with 273.2 g of water to make the electric conductivity 1.5 μS / cm or less, followed by concentration to obtain 61.1 g of a colorless transparent liquid. When the product was analyzed, the number average molecular weight was 4736, the molecular weight dispersity was 2.54, the content of monomeric cage-type silsesquioxane (retention time 7.6 - 8.3 minutes) was 6.7%, the content of polymeric cage-type silsesquioxane (retention time 4.9 - 7.6 minutes) was 93.3%, and [T3 body / T2 body] was 46.5. 29 The Si-NMR spectrum is shown in Fig. 1, and the GPC chart measured under the above GPC condition 1 is shown in Fig. 2.

[0268] The epoxy group-containing polyorganosilsesquioxane obtained in Example 1 was fractionated into 4 fractions under the above GPC condition 2. The fraction with a retention time of 22 - 25 minutes is designated as "Fr-1", the fraction with a retention time of 25 - 26 minutes is designated as "Fr-2", the fraction with a retention time of 26 - 27 minutes is designated as "Fr-3", and the fraction with a retention time of 27 - 29.5 minutes is designated as "Fr-4". The chart of preparative GPC is shown in Fig. 3.

[0269] For Fr-1, Fr-2, and Fr-3, mass spectrometry was performed under the above UPLC-MS conditions. The MS spectrum chart in the range of m / z 2321 - 2337 is shown in Fig. 4, and the MS spectrum chart in the range of m / z 1800 - 3200 is shown in Fig. 5.

[0270] From the intervals between the peaks of the stable isotopes in the MS spectrum chart shown in Fig. 4, it can be seen that the MS spectrum chart of Fr-1 (the interval between the peaks of the stable isotopes is 0.25 Da) shows peaks attributed to tetravalent ions (z = 4), the MS spectrum chart of Fr-2 (the interval between the peaks of the stable isotopes is 0.33 Da) shows peaks attributed to trivalent ions (z = 3), and the MS spectrum chart of Fr-3 (the interval between the peaks of the stable isotopes is 0.50 Da) shows peaks attributed to divalent ions (z = 2).

[0271] As shown in the MS spectrum chart of Fr-1 in Fig. 5, in the range exceeding the peak of 2149.8574 m / z (molecular weight = 2149.8574 × 4 = 8599.4296), repetitions of multiple molecular ion peaks were observed at intervals of approximately 354 in molecular weight difference (m / z × 4). This molecular weight difference a corresponds to two portions of the T3 body (molecular weight: 177.066) where R is a 2-(3’,4’-epoxycyclohexyl)ethyl group. Therefore, it is estimated that Fr-1 mainly contains the multimeric cage-type silsesquioxane of the present disclosure in which 5 or more cage-type silsesquioxanes represented by the upper composition formula (1), composition formula (2), composition formula (3), and composition formula (4) are condensed.

[0272] As shown in the MS spectrum chart of Fr-2 in Fig. 5, in the range of peaks from 1914.7667 m / z (molecular weight = 1914.7667 × 3 = 5744.3001) to 2505.6653 m / z (molecular weight = 2505.6653 × 3 = 7516.9959), repetitions of multiple molecular ion peaks were observed at intervals of approximately 354 in molecular weight difference (m / z × 3). This molecular weight difference a corresponds to two portions of the T3 body (molecular weight: 177.066) where R is a 2-(3’,4’-epoxycyclohexyl)ethyl group. Therefore, it is estimated that the polyorganosilsesquioxane contained in Fr-2 mainly contains the multimeric cage-type silsesquioxane of the present disclosure in which 3 to 4 cage-type silsesquioxanes represented by the upper composition formula (1), composition formula (2), composition formula (3), and composition formula (4) are condensed.

[0273] As shown in the MS spectrum chart of Fr-3 in Fig. 5, within the range of peaks from 2061.3303 m / z (molecular weight = 2061.3303 × 2 = 4120.6606) to 2593.0325 m / z (molecular weight = 2593.0325 × 2 = 5186.065), repetitions of multiple molecular ion peaks were observed at intervals of approximately 354 in molecular weight difference (m / z × 3). This molecular weight difference corresponds to two portions of the T3 form (molecular weight: 177.066) where R a is a 2-(3’,4’-epoxycyclohexyl)ethyl group. Therefore, it is presumed that the polyorganosilsesquioxane contained in Fr-3 mainly contains the multimeric cage-type silsesquioxane of the present disclosure in which two cage-type silsesquioxanes represented by the above compositional formula (1), compositional formula (2), compositional formula (3), and compositional formula (4) are condensed.

[0274] From the above mass spectrometry results, it can be said that the epoxy group-containing polyorganosilsesquioxane obtained in Example 1 was confirmed to contain the multimeric cage-type silsesquioxane of the present disclosure. Note that Fr-4 is considered to mainly contain monomeric cage-type silsesquioxane.

[0275] Example 2: Production of epoxy group-containing polyorganosilsesquioxane of the present disclosure (2) Into a 1000 milliliter flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube and a Dean-Stark tube, 277.2 mmol (68.30 g) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3.0 mmol (0.56 g) of phenyltrimethoxysilane, and 275.4 g of acetone were charged under a nitrogen stream, and the temperature was raised to 50°C. To the mixture thus obtained, 7.74 g of a 5% aqueous potassium carbonate solution (2.8 mmol as potassium carbonate) was added over 5 minutes, and then 2800.0 mmol (50.40 g) of water was added over 20 minutes. During the addition, no significant temperature rise occurred. Thereafter, the polycondensation reaction was carried out at 50°C for 5 hours under a nitrogen stream. After that, 230.5 g of methyl isobutyl ketone was charged, and the temperature was raised from 50 °C to 90 °C under reduced pressure to distill off until the system contained acetone (0.0%), methyl isobutyl ketone (20.58%), and water (0.35%). After that, it was stirred at 90 °C for 42 hours, 273.2 g of methyl isobutyl ketone was added, and it was washed 6 times with 273.2 g of water to make the electric conductivity 1.5 μS / cm or less, followed by concentration to obtain 50.0 g of a colorless transparent liquid. When the product was analyzed, the number average molecular weight was 9843, the molecular weight dispersity was 2.89, the content of monomeric cage-type silsesquioxane (retention time 7.6 - 8.3 minutes) was 1.9%, the content of polymeric cage-type silsesquioxane (retention time 4.7 - 7.6 minutes) was 98.1%, and [T3 body / T2 body] was 196.2. 29 The Si-NMR spectrum is shown in Fig. 6, and the GPC chart measured under the above GPC condition 1 is shown in Fig. 7.

[0276] Comparative Example 1: Production of epoxy group-containing polyorganosilsesquioxane (2) Into a 1000 milliliter flask (reaction vessel) equipped with a thermometer, a stirring device, a reflux condenser, a nitrogen inlet tube, and a Dean-Stark tube, 3.0 millimoles (0.56 g) of phenyltrimethoxysilane and 275.4 g of acetone were charged under a nitrogen stream, and the temperature was raised to 50 °C. To the mixture thus obtained, 7.74 g of a 5% aqueous potassium carbonate solution (2.8 millimoles as potassium carbonate) was added in 5 minutes, and then 2800.0 millimoles (50.40 g) of water was added over 20 minutes. At the same time as the start of dropping of potassium carbonate, 277.2 millimoles (68.30 g) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane was started to be dropped and the dropping was completed in 2 hours. During the addition, no significant temperature rise occurred. After that, the polycondensation reaction was carried out at 50 °C for 5 hours under a nitrogen stream. After that, 230.5 g of methyl isobutyl ketone was charged and washed 6 times with water (273.2 g). It was concentrated to make the electric conductivity 1.5 μS / cm or less to obtain 50.0 g of a white turbid liquid.

[0277] [Evaluation of Solvent Solubility] To 50 to 60 g of the products obtained in the above Examples and Comparative Examples, 2 L of acetone or chloroform was added to evaluate the solvent solubility. When it was completely dissolved to form a clear solution, it was evaluated as "complete dissolution", and when it was not partially dissolved and became white and turbid, it was evaluated as "cloudy". The results are shown in Table 1.

[0278] [Table 1]

[0279] Reference Example 1: Production of hard coat film A mixed solution of 100 parts by weight of the epoxy group-containing polyorganosilsesquioxane obtained in Example 1, 20 parts by weight of methyl isobutyl ketone (manufactured by Kanto Chemical Co., Inc.), and 1 part by weight of curing catalyst 1 ([diphenyl[4-(phenylthio)phenyl]sulfonium tris(pentafluoroethyl)trifluorophosphate]) was prepared and used as a hard coat liquid (curable composition). The hard coat liquid obtained above was cast-coated onto a PET film (trade name "KEB03 W", manufactured by Teijin DuPont Films Japan Limited) using a wire bar so that the thickness of the hard coat layer after curing was 5 μm, and then left in an oven at 70°C for 10 minutes (pre-baking), and then irradiated with ultraviolet rays (irradiation conditions (irradiation dose): 312 mJ / cm 2 , irradiation intensity: 80 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.

[0280] Various evaluations were performed on the hard coat film obtained above by the following methods. (1) Haze and total light transmittance The haze and total light transmittance of the hard coat film obtained above were measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., NDH-300A).

[0281] (2) Surface hardness (pencil hardness) Evaluate the pencil hardness of the surface of the hard coat layer in the hard coat film obtained above in accordance with JIS K5600-5-4.

[0282] (3) Heat resistance (5% weight loss temperature (T d5 )) Except for using a glass plate instead of a PET film, shave off approximately 5 mg of the hard coat layer in the hard coat film obtained in the same manner as above using a cutter and use this as a sample. Using a differential thermal gravimetric analyzer (manufactured by Seiko Instruments Inc., TG / DTA 6300), measure the 5% weight loss temperature of the above sample under the following conditions. Measurement temperature range: 25 to 550 °C Heating rate: 10 °C / min Gas atmosphere: Nitrogen

[0283] (4) Abrasion resistance For the surface of the hard coat layer in the hard coat film obtained above, use #0000 steel wool with a load of 1000 g / cm 2 and reciprocate 100 times to check for the presence and number of scratches on the surface of the hard coat layer, and evaluate the abrasion resistance according to the following criteria. ◎ (Extremely good abrasion resistance): Number of scratches is 0 ○ (Good abrasion resistance): Number of scratches is 1 to 10 × (Poor abrasion resistance): Number of scratches exceeds 10

[0284] (5) Flexural resistance (cylindrical mandrel method); by mandrel test Evaluate the flexural resistance of the hard coat film obtained above in accordance with JIS K5600-5-1 using a cylindrical mandrel.

Explanation of symbols

[0285] 1 Hard coat film 11 Hard coat layer 12 Substrate 2 Transfer film 21 Substrate 22 Release layer 23 Hard coat layer (uncured or semi-cured hard coat layer) 24 Anchor coat layer 25 Coloring layer 26 Adhesive layer 3 Adhesive sheet 31 Adhesive layer 32 Substrate 33 Anchor coat layer

Claims

1. A polyorganosilsesquioxane containing a multimeric cage-type silsesquioxane in which at least one cage-type silsesquioxane selected from the group consisting of the following compositional formula (1), compositional formula (2), compositional formula (3), and compositional formula (4) is condensed three or more times, The molecular weight dispersity (weight average molecular weight / number average molecular weight) is 2.54 to 4.0, A polyorganosilsesquioxane in which the proportion of silsesquioxane having at least one hydroxyl group as a substituent is 10 to 50% by weight based on the total amount of the polyorganosilsesquioxane. ・Formula (1): [R 1 SiO 3 / 2 8 8 [R 1 SiO 2 / 2 (OR c )] 1 1 (R in formula (1) 1 are each independently 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, and at least one is a group containing an epoxy group. R c represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.) ・ Formula (2): [R 2 SiO 3 / 2 6 6 [R 2 SiO 2 / 2 (OR c )] 2 2 (R in formula (2) 2 is each independently 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, and at least one is a group containing an epoxy group. R c each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.) ・Formula (3): [R 3 SiO 3 / 2 8 8 [R 3 SiO 2 / 2 (OR c )] 2 2 (R in formula (3) 3 are each independently 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, and at least one is a group containing an epoxy group. R c each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.) ・ Formula (4): [R 4 SiO 3 / 2 10 10 [R 4 SiO 2 / 2 (OR c )] 2 2 (R in formula (4) 4 is each independently 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, and at least one is a group containing an epoxy group. R c each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.)

2. The polyorganosilsesquioxane according to claim 1, wherein at least one terminal in the multimeric cage-type silsesquioxane has a structure in which the cage-type silsesquioxane represented by the compositional formula (1) is condensed.

3. The epoxy group-containing group is represented by the following formula (1A) 【Chemical 1】 [In formula (1A), R 1A represents a linear or branched alkylene group. ] A group represented by, the following formula (1B) 【Chemical 2】 [In formula (1B), R 1B represents a linear or branched alkylene group.] A group represented by, the following formula (1C) [Chemical 3] [In formula (1C), R 1C represents a linear or branched alkylene group. ] A group represented by, or a group represented by the following formula (1D) 【Chemical Formula 4】 [In formula (1D), R 1D represents a linear or branched alkylene group. ] The polyorganosilsesquioxane according to claim 1 or 2, which is a group represented by.

4. R in the above compositional formula (1) 1 R in compositional formula (2) 2 R in compositional formula (3) 3 and R in compositional formula (4) 4 The polyorganosilsesquioxane according to any one of claims 1 to 3, wherein the ratio of the group containing an epoxy group to the whole is 30% or more.

5. The molar ratio [structural unit represented by formula (I) / structural unit represented by formula (II)] of the structural unit represented by the following formula (I) [R ａ SiO ３／２ (I) [In formula (I), R a each independently represents a hydrogen atom, 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] And the structural unit represented by the following formula (II) [R ｂ SiO ２／２ (OR ｃ )](II) [In formula (II), R b represents a hydrogen atom, 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. R c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms] Is 1 or more and 500 or less, and the polyorganosilsesquioxane according to any one of claims 1 to 4.

6. The polyorganosilsesquioxane according to any one of claims 1 to 5, having a number average molecular weight of 2000 to 50000.

7. The polyorganosilsesquioxane according to any one of claims 1 to 6, and a curing catalyst, a surface conditioner, a surface modifier, other cation-curable compounds, an inorganic filler, an organic resin fine powder, a curing aid, a solvent, a stabilizer, a flame retardant, a flame retardant aid, a reinforcing material, a nucleating agent, a coupling agent, a lubricant, a wax, a plasticizer, a mold release agent, an impact resistance improver, a hue improver, a transparency agent, a rheology modifier, a processability improver, a colorant, an antistatic agent, a dispersant, a matting agent, an antifoaming agent, a defoaming agent, a deaerating agent, an antibacterial agent, a preservative, a viscosity modifier, a thickener, a photosensitizer, and a foaming agent. A curable composition containing at least one other component selected from the group consisting of.

8. The curable composition according to claim 7, wherein the curing catalyst is a photo- or thermopolymerization initiator.

9. Furthermore, the curable composition according to claim 7 or 8, which contains a polymerization stabilizer.

10. The curable composition according to any one of claims 7 to 9, which is a curable composition for forming a hard coat layer.

11. The curable composition according to any one of claims 7 to 9, which is a curable composition for an adhesive.

12. A cured product of the curable composition according to any one of claims 7 to 11.

13. A hard coat film in which a base material and a hard coat layer, which is the cured product according to claim 12, are laminated.

14. A transfer film in which a base material and a hard coat layer, which is a layer containing the curable composition according to claim 10, are laminated on a release layer formed on at least one surface of the base material.

15. The transfer film according to claim 14, wherein an anchor coat layer and an adhesive layer are further laminated on the hard coat layer in this order.

16. The transfer film according to claim 14 or 15, further comprising at least one colored layer.

17. The transfer film according to any one of claims 14 to 16, wherein the hard coat layer has a thickness of 3 to 150 μm.

18. An adhesive sheet having a base material and an adhesive layer, which is a layer containing the curable composition according to claim 11, on at least one surface of the base material.

19. An adhesive sheet having a base material and, on at least one surface of the base material, an anchor coat layer containing a silane coupling agent and an adhesive layer, which is a layer containing the curable composition according to claim 11, wherein the adhesive layer is provided on the surface of the anchor coat layer.

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