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

Abstract

To provide polyorganosilsesquioxane that can form a cured matter having high surface hardness and flex property and is suitable as a material of a hard coat film, while having high heat resistance that is a feature of the polyorganosilsequioxane.SOLUTION: A polyorganosilsesquioxane of the present disclosure is a condensate in which two or more of cage type silsesquioxane containing at least one selected from the group consisting of a cage type silsesquioxane represented by the following composition formula (1), composition formula (2), composition formula (3) and composition formula (4) condenses and contains silsesquioxane having a molecular weight of 8000 or smaller. 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 of the equation is as set forth in this specification.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to polyorganosilsesquioxane, a curable composition containing said polyorganosilsesquioxane and its cured product, and a hard coat film made from said cured product. This disclosure also relates to a transfer film containing said curable composition as a hard coat layer. Furthermore, this disclosure relates to an adhesive sheet containing said curable composition as an adhesive layer. [Background technology]

[0002] Polyorganosilsesquioxanes (silsesquioxanes) are network-type polymers or polyhedral clusters obtained by hydrolyzing trifunctional silanes. Silsesquioxanes known to have random, ladder, or cage structures are common. Most high molecular weight silsesquioxanes with molecular weights of, for example, 3000 or more have had random or ladder structures. Such high molecular weight silsesquioxanes are described, for example, in Patent Document 1 below.

[0003] Furthermore, silsesquioxanes, which have a cage-like structure, are a general term for substances that have a three-dimensional ring-closed structure by siloxane bonds, with organic functional groups at each vertex of a silica cubic structure. These cubic structures mainly include octameric silsesquioxane (T8), which has a hexahedral structure, and decameric silsesquioxane (T8), which has a pyramidal pentagonal prism structure. 10 Such cage-type silsesquioxanes are known. For example, see Patent Document 2 below. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2013-35918 [Patent Document 2] Japanese Patent Publication No. 2000-334881 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, cured products obtained from conventional high molecular weight polyorganosilsesquioxanes and cage-type silsesquioxanes tended to lack sufficient hardness and had limitations in their flexibility when bent. Therefore, these cured products could not be used in applications requiring high hardness and high flexibility, and their use as hard coating materials was limited. In addition, conventional high molecular weight silsesquioxanes had the problem that as the molecular weight increased, they became less soluble in solvents such as organic solvents, making processing into hard coating materials difficult.

[0006] Accordingly, the object of the present invention is to provide a polyorganosilsesquioxane suitable as a material for hard coat films, which can be cured to have high surface hardness and flexibility while possessing the high heat resistance characteristic of polyorganosilsesquioxanes. Furthermore, the object is to provide a polyorganosilsesquioxane that, despite being a high molecular weight polyorganosilsesquioxane, has high solubility in solvents such as organic solvents.

[0007] Furthermore, an object of the present invention is to provide a curable composition containing the polyorganosilsesquioxane. Furthermore, the objective 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 this disclosure is to provide a transfer film having a hard coat layer containing the curable composition. Another object of the invention disclosed herein is to provide an adhesive sheet having an adhesive layer containing the curable composition. [Means for solving the problem]

[0008] The inventors of the present disclosure have found that a cured product of a curable composition containing a silsesquioxane having a structure in which two or more cage-type silsesquioxanes having a specific composition formula are condensed and having a molecular weight of 8000 or less 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 or an adhesive layer in an adhesive sheet. They have also found that the silsesquioxane has high solubility in a solvent such as an organic solvent 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 silsesquioxane which is a condensate in which two or more cage-type silsesquioxanes selected from the group consisting of the following composition formula (1), composition formula (2), composition formula (3) and composition formula (4) are condensed and having a molecular weight of 8000 or less. · 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 2Each of these 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 of them is a group containing a polymerizable functional group. c Each of these independently represents an alkyl group or hydrogen atom having 1 to 4 carbon atoms. ·Equation (3):[R 3 SiO 3 / 2 ]8[R 3 SiO 2 / 2 (OR c )]2 (R in equation (3)) 3 Each of these 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 of them is a group containing a polymerizable functional group. c Each of these independently represents an alkyl group or hydrogen atom having 1 to 4 carbon atoms. ·Equation (4):[R 4 SiO 3 / 2 ] 10 [R 4 SiO 2 / 2 (OR c )]2 (R in equation (4)) 4 Each of these 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 of them is a group containing a polymerizable functional group. c Each of these independently represents an alkyl group or hydrogen atom having 1 to 4 carbon atoms.

[0010] Furthermore, this disclosure relates to a group containing the polymerizable functional group as follows: [ka] [In formula (1a), R 1A This represents a linear or branched alkylene group. The base represented by the following formula (1B) [ka] [In formula (1b), R 1B This represents a linear or branched alkylene group. The base represented by the following formula (1C) [ka] [In formula (1c), R 1C This represents a linear or branched alkylene group. A base represented by the following formula (1D) [ka] [In formula (1d), R 1D This represents a linear or branched alkylene group. The present invention provides the polyorganosilsesquioxane, which is a group represented by .

[0011] Furthermore, this disclosure also relates to the R in the composition formula (1). 1 , R in composition formula (2) 2 , R in the composition formula (3) 3 , and R in composition formula (4) 4 The present invention provides a polyorganosilsesquioxane in which the proportion of groups containing polymerizable functional groups to the total is 30% or more.

[0012] Furthermore, this disclosure provides a polyorganosylsesquioxane in which the molar ratio [constituent unit represented by formula (I) / constituent unit represented by formula (II)] of the constituent unit represented by the following formula (I) is 1 or more and 500 or less. [R a SiO 3 / 2 ] (I) [In formula (I), R aThis refers to 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 R 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. c [This represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.]

[0013] Furthermore, this disclosure provides a polyorganosilsesquioxane having a number-average molecular weight of 2,000 to 50,000.

[0014] Furthermore, this disclosure provides a polyorganosilsesquioxane having a molecular weight dispersion (weight-average molecular weight / number-average molecular weight) of 1.0 to 4.0.

[0015] Furthermore, this disclosure provides a curable composition comprising the polyorganosilsesquioxane.

[0016] Furthermore, this disclosure provides the curable composition comprising a curing catalyst.

[0017] Furthermore, this disclosure provides a curable composition in which the curing catalyst is a photopolymerization initiator.

[0018] Furthermore, this disclosure provides the curable composition containing a polymerization stabilizer.

[0019] Furthermore, this disclosure provides a curable composition for forming a hard coat layer.

[0020] Furthermore, this disclosure provides a curable composition which is a curable composition for adhesives.

[0021] Furthermore, this disclosure provides a cured product of the curable composition.

[0022] Furthermore, this disclosure provides a hard coat film in which a substrate and a hard coat layer, which is a cured product, are laminated on at least one surface of the substrate.

[0023] Furthermore, this disclosure provides a transfer film comprising a substrate and a hard coat layer, which is a layer containing the curable composition, laminated on a release layer formed on at least one surface of the substrate.

[0024] Furthermore, this disclosure provides a transfer film in which an anchor coat layer and an adhesive layer are further laminated on the hard coat layer in that order.

[0025] Furthermore, this disclosure provides the transfer film comprising at least one colored layer.

[0026] Furthermore, this disclosure provides a transfer film having a hard coat layer thickness of 3 to 150 μm.

[0027] Furthermore, this disclosure provides an adhesive sheet having a substrate and an adhesive layer on at least one surface of the substrate which is a layer containing the curable composition.

[0028] Furthermore, this disclosure provides an adhesive sheet having a substrate and an adhesive layer on at least one surface of the substrate, the adhesive layer being a layer containing a silane coupling agent and the curable composition, wherein the adhesive layer is provided on the surface of the anchor coat layer. [Effects of the Invention]

[0029] The cured product (e.g., a hard coat layer) obtained from the curable composition containing the polyorganosilsesquioxane of this disclosure has high heat resistance, high surface hardness, and high flexibility. Therefore, by using a hard coat film or transfer film having this hard coat layer, it is possible to manufacture molded articles (products) with high surface hardness and high flexibility. Furthermore, the polyorganosilsesquioxane of this disclosure, despite being a high molecular weight polyorganosilsesquioxane, has high solubility in solvents such as organic solvents. Therefore, the hard coat film or transfer film containing the polyorganosilsesquioxane of this disclosure can reduce the amount of solvent used, and the uncured or semi-cured hard coat layer becomes tack-free, allowing it to be wound into a roll and handled, and the film containing the hard coat layer can be handled roll-to-roll, thus offering advantages in both quality and cost. Furthermore, the curable composition containing polyorganosilsesquioxane as an essential component of this disclosure can form a cured product (adhesive) with high heat resistance and flexibility, and is therefore preferably used as an adhesive (for example, a curable composition for multilayer semiconductors). [Brief explanation of the drawing]

[0030] [Figure 1] This is the 29Si-NMR spectrum of the epoxy group-containing condensed silsesquioxane of the present disclosure obtained in Example 1. [Figure 2] This is the GPC chart of the epoxy group-containing condensed silsesquioxane of the present disclosure obtained in Example 1. [Figure 3] This is a UPLC-MS chart of the epoxy group-containing condensed silsesquioxane of the present disclosure obtained in Example 1. [Figure 4] This is a UPLC-MS chart of the epoxy group-containing condensed silsesquioxane of the present disclosure obtained in Example 1. [Figure 5] This is an MS simulation pattern for the molecular formula C144H234O45Si18 (Z=2). [Figure 6] This is an MS simulation pattern for the molecular formula C128H210O41Si16 (Z=2). [Figure 7] This is the 29Si-NMR spectrum of the epoxy group-containing condensed silsesquioxane of the present disclosure obtained in Example 2. [Figure 8] This is the GPC chart of the epoxy group-containing condensed silsesquioxane of the present disclosure obtained in Example 2. [Figure 9] This is a schematic diagram (cross-sectional view) showing one embodiment of the hard coat film of the present disclosure. [Figure 10] This is a schematic diagram (cross-sectional view) showing one embodiment of the transfer film of the present disclosure. [Figure 11] This is a schematic diagram (cross-sectional view) showing one embodiment of the adhesive sheet of the present disclosure. [Modes for carrying out the invention]

[0031] [Polyorganosilsesquioxane] The polyorganosilsesquioxanes of this disclosure are condensates obtained by condensing two or more cage-type silsesquioxanes, each containing at least one selected from the group consisting of cage-type silsesquioxanes represented by the following compositional formulas (1), (2), (3), and (4), and include a silsesquioxane (hereinafter sometimes referred to as "condensed silsesquioxane of this disclosure") having a molecular weight of 8000 or less (preferably 1500 to 7500, more preferably 1800 to 7000, and even more preferably 2000 to 6500). ·Equation (1):[R 1 SiO 3 / 2 ]8[R 1 SiO 2 / 2 (OR c )]1 (R in equation (1)) 1 Each of these 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 of them is a group containing a polymerizable functional group. c (This represents an alkyl group or hydrogen atom having 1 to 4 carbon atoms.) ·Equation (2):[R 2 SiO 3 / 2 ]6[R 2 SiO 2 / 2 (OR c )]2 (R in equation (2)) 2 Each of these 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 of them is a group containing a polymerizable functional group. c Each of these independently represents an alkyl group or hydrogen atom having 1 to 4 carbon atoms. ·Equation (3):[R 3 SiO 3 / 2 ]8[R 3 SiO 2 / 2 (OR c )]2 (R in equation (3)) 3 Each of these 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 of them is a group containing a polymerizable functional group. c Each of these independently represents an alkyl group or hydrogen atom having 1 to 4 carbon atoms. ·Equation (4):[R 4 SiO 3 / 2 ] 10 [R 4 SiO 2 / 2 (OR c )]2 (R in equation (4)) 4 Each of these 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 of them is a group containing a polymerizable functional group. c Each of these independently represents an alkyl group or hydrogen atom having 1 to 4 carbon atoms.

[0032] The [R 1 SiO 3 / 2 structural unit in compositional formula (1), the [R 2 SiO 3 / 2 structural unit in compositional formula (2), the [R 3 SiO 3 / 2 structural unit in compositional formula (3), and the [R 4 SiO 3 / 2 structural unit in compositional 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)

[0033] Also, the [R 1 SiO 2 / 2 (OR c )] structural unit in compositional formula (1), the [R 2 SiO 2 / 2 (OR c )] structural unit in compositional formula (2), the [R 3 SiO 2 / 2 (OR c )] structural unit in compositional formula (3), and the [R 4 SiO 2 / 2 (OR c )] structural unit in compositional 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)

[0034] R a in the above formula (I), and R b in formula (II) represent 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. Also, R c in the above formula (II) represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.

[0035] The constituent unit represented by formula (I) above can be described in more detail by formula (I') below. Furthermore, the constituent unit represented by formula (II) above can be described in more detail by formula (II') below. In the structure represented by formula (I') below, the three oxygen atoms bonded to the silicon atom are each bonded to other silicon atoms (silicon atoms not shown in formula (I'). On the other hand, in the structure represented by formula (II') below, the two oxygen atoms located above and below the silicon atom are each bonded to other silicon atoms (silicon atoms not shown in formula (II')). In other words, both the T3 and T2 forms are silsesquioxane constituent units (so-called T units) formed by the hydrolysis and condensation reactions of the corresponding hydrolyzable trifunctional silane compounds. [ka] [ka]

[0036] In the above equation (I') R a , R in equation (II') b and R c R in equation (II) is the same group as described above. c The alkyl group in is generally the alkoxy group in the hydrolyzable silane compound used as a raw material for the polyorganosylsesquioxane of this disclosure (for example, the X in formulas (A) to (C) described below). 1 ~X 3 It originates from alkyl groups that form alkoxy groups, etc.

[0037] The cage-type silsesquioxane represented by the above chemical formula (1) has eight [R 1 SiO 3 / 2 A constituent unit (T3 body) represented by ] and one [R 1 SiO 2 / 2 (OR cThis is a silsesquioxane in which the constituent units (T2) represented by )] are bonded to each other via siloxane bonds (Si-O-Si) to form a cage-like structure. The specific structure of the cage-like silsesquioxane represented by the above compositional formula (1) is not particularly limited as long as it satisfies the above compositional formula (1), but examples include the cage-like silsesquioxane represented by the following formula (1').

[0038] [ka]

[0039] R in equation (1') 1a ~R 1i Each of these independently corresponds to R in empirical formula (1). 1 This is equivalent to R in equation (1'). c Also, R in the empirical formula (1) c It is synonymous with [the above].

[0040] The cage-type silsesquioxane represented by the above chemical formula (2) has six [R 2 SiO 3 / 2 The constituent unit (T3 body) represented by ] and two [R 2 SiO 2 / 2 (OR c The constituent units (T2) represented by the above compositional formula (2) are bonded to each other via siloxane bonds (Si-O-Si) to form a cage-like structure in this silsesquioxane. The specific structure of the cage-like silsesquioxane represented by the above compositional formula (2) is not particularly limited as long as it satisfies the above compositional formula (2), but examples include the cage-like silsesquioxane represented by the following formula (2') or (2"). [ka] [ka]

[0041] R in equation (2') 2a ~R 2h , R in equation (2) 2i ~R 2pThese are, independently of each other, R in empirical formula (2). 2 This is equivalent to R in equations (2') and (2") c Each of these independently corresponds to R in empirical formula (2). c It is synonymous with [the above].

[0042] The cage-type silsesquioxane represented by the above compositional formula (3) has eight [R 3 SiO 3 / 2 The constituent unit (T3 body) represented by ] and two [R 3 SiO 2 / 2 (OR c The constituent units (T2 form) represented by )] are bonded to each other via siloxane bonds (Si-O-Si) to form a cage-like structure in this silsesquioxane. The specific structure of the cage-like silsesquioxane represented by the above compositional formula (3) is not particularly limited as long as it satisfies the above compositional formula (3), but examples include the cage-like silsesquioxane represented by the following formulas (3'), (3"), or (3'''). [ka] [ka] [ka]

[0043] R in equation (3') 3a ~R 3j , R in equation (3) 3k ~R 3t , R in equation (3''') 3u ~R 3z , R 3aa ~R 3dd Each of these independently represents R in the empirical formula (3). 3 This is equivalent to R in equations (3'), (3"), and (3'''). c Each of them independently corresponds to R in composition formula (3). c It is synonymous with [the above].

[0044] The cage-type silsesquioxane represented by the above compositional formula (4) consists of 10 [R4 SiO 3 / 2 The constituent unit (T3 body) represented by ] and two [R 4 SiO 2 / 2 (OR c The constituent units (T2) represented by the above compositional formula (4) are bonded to each other via siloxane bonds (Si-O-Si) to form a cage-like structure in this silsesquioxane. The specific structure of the cage-like silsesquioxane represented by the above compositional formula (4) is not particularly limited as long as it satisfies compositional formula (4), but examples include the cage-like silsesquioxane represented by the following formula (4') or (4”). [ka] [ka]

[0045] R in equation (4') 4a ~R 4l , R in equation (4) 4m ~R 4x Each of these independently represents R in the empirical formula (4). 4 This is equivalent to R in equations (4') and (4") c Each of them independently corresponds to R in empirical formula (4). c It is synonymous with [the above].

[0046] The condensed silsesquioxanes of this disclosure may contain cage-type silsesquioxanes represented by compositional formulas other than compositional formulas (1), (2), (3), and (4) above, to the extent that they do not impair the effects of the invention of this disclosure. Examples of compositional formulas other than compositional formulas (1), (2), (3), and (4) above include the following compositional formulas (5) to (8). ·Equation (5):[R 5 SiO 3 / 2 ]6[R 5 SiO 2 / 2 (OR c )3 (R in equation (5)) 5Each of these 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 of them is a group containing a polymerizable functional group. c Each of these independently represents an alkyl group or hydrogen atom having 1 to 4 carbon atoms. ·Equation (6):[R 6 SiO 3 / 2 ]8[R 6 SiO 2 / 2 (OR c )3 (R in equation (6)) 6 Each of these 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 of them is a group containing a polymerizable functional group. c Each of these independently represents an alkyl group or hydrogen atom having 1 to 4 carbon atoms. ·Equation (7):[R 7 SiO 3 / 2 ] 10 [R 7 SiO 2 / 2 (OR c )]1 (R in equation (7)) 7 Each of these 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 of them is a group containing a polymerizable functional group. c (This represents an alkyl group or hydrogen atom having 1 to 4 carbon atoms.) ·Equation (8):[R 8 SiO 3 / 2 ] 12 [R 8 SiO 2 / 2 (OR c )]1 (R in equation (8)) 8Each of these 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 of them is a group containing a polymerizable functional group. c (This represents an alkyl group or hydrogen atom having 1 to 4 carbon atoms.)

[0047] The condensed silsesquioxanes of this disclosure also include those containing a mixture of cage-type silsesquioxanes represented by the above compositional formulas (1) to (8). That is, the condensed silsesquioxanes of this disclosure may be condensates obtained by the condensation of two or more cage-type silsesquioxanes, each containing at least one selected from the group consisting of cage-type silsesquioxanes represented by the above compositional formulas (1), (2), (3), (4), (5), (6), (7), and (8).

[0048] Note that, as in the above composition formulas (5) and (6), -OR c Even if a cage-type silsesquioxane having three hydroxyl groups represented by is included, if condensation occurs at two of them, it is included in the condensed silsesquioxane of this disclosure. Also, the three -ORs of the above composition formulas (5) and (6) c Even if all the hydroxyl groups represented by are condensed, they shall be included in the condensed silsesquioxane of this disclosure as long as the effects of the invention of this disclosure are not impaired.

[0049] The "cationically polymerizable functional group" in the above-mentioned polymerizable functional group is not particularly limited as long as it has cationic polymerizability, and examples include epoxy groups, oxetane groups, vinyl ether groups, vinylphenyl groups, etc. The "radical polymerizable functional group" in the group containing the above polymerizable functional group is not particularly limited as long as it has radical polymerizability, and examples include (meth)acryloxy group, (meth)acrylamide group, vinyl group, vinylthio group, etc. From the viewpoint of the surface hardness of the cured product (e.g., 4H or higher), epoxy groups and (meth)acrylooxy groups are preferred as polymerizable functional groups, with epoxy groups being more preferred.

[0050] R in the above composition formula (1) 1 , R in equation (1') 1a ~R 1i , R in composition formula (2) 2 , R in equation (2') 2a ~R 2h , R in equation (2) 2i ~R 2p , R in the composition formula (3) 3 , R in equation (3') 3a ~R 3j , R in equation (3) 3k ~R 3t , R in equation (3''') 3u ~R 3z , R 3aa ~R 3dd , R in the composition formula (4) 4 , R in equation (4') 4a ~R 4l , R in equation (4) 4m ~R 4x , R in the composition formula (5) 5 , R in the composition formula (6) 6 , R in the composition formula (7) 7 , R in the composition formula (8) 8 , R in equation (I) a , and R in equation (II) b The polymerizable functional group in is not particularly limited, but groups containing epoxy groups are preferred, and from the viewpoint of curability of the curable composition, surface hardness and heat resistance of the cured product, the group represented by formula (1A), the group represented by formula (1B), the group represented by formula (1C), and the group represented by formula (1D) below are preferred, more preferably the group represented by formula (1A), the group represented by formula (1C), and even more preferably the group represented by formula (1A) below. [ka] [ka] [ka] [ka]

[0051] In the above formula (1A), R 1A R represents a linear or branched alkylene group. Examples of linear or branched alkylene groups 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 these, R 1A From the viewpoint of surface hardness and curability of the cured product, linear alkylene groups having 1 to 4 carbon atoms and branched alkylene groups having 3 or 4 carbon atoms are preferred, more preferably ethylene groups, trimethylene groups, propylene groups, and even more preferably ethylene groups and trimethylene groups.

[0052] In the above formula (1B), R 1B R represents a linear or branched alkylene group. 1A Similar groups are given as examples. Among them, R 1B From the viewpoint of surface hardness and curability of the cured product, linear alkylene groups having 1 to 4 carbon atoms and branched alkylene groups having 3 or 4 carbon atoms are preferred, more preferably ethylene groups, trimethylene groups, propylene groups, and even more preferably ethylene groups and trimethylene groups.

[0053] In the above equation (1C), R 1C R represents a linear or branched alkylene group. 1A Similar groups are given as examples. Among them, R 1C From the viewpoint of surface hardness and curability of the cured product, linear alkylene groups having 1 to 4 carbon atoms and branched alkylene groups having 3 or 4 carbon atoms are preferred, more preferably ethylene groups, trimethylene groups, propylene groups, and even more preferably ethylene groups and trimethylene groups.

[0054] In the above formula (1D), R 1DR represents a linear or branched alkylene group. 1A Similar groups are given as examples. Among them, R 1D From the viewpoint of surface hardness and curability of the cured product, linear alkylene groups having 1 to 4 carbon atoms and branched alkylene groups having 3 or 4 carbon atoms are preferred, more preferably ethylene groups, trimethylene groups, propylene groups, and even more preferably ethylene groups and trimethylene groups.

[0055] R in the above composition formula (1) 1 , R in equation (1') 1a ~R 1i , R in composition formula (2) 2 , R in equation (2') 2a ~R 2h , R in equation (2) 2i ~R 2p , R in the composition formula (3) 3 , R in equation (3') 3a ~R 3j , R in equation (3) 3k ~R 3t , R in equation (3''') 3u ~R 3z , R 3aa ~R 3dd , R in the composition formula (4) 4 , R in equation (4') 4a ~R 4l , R in equation (4) 4m ~R 4x , R in the composition formula (5) 5 , R in the composition formula (6) 6 , R in the composition formula (7) 7 , R in the composition formula (8) 8 , R in equation (I) a , and R in equation (II) b The groups containing polymerizable functional groups in the above formula are preferably groups containing epoxy groups, and are groups represented by the above formula (1A), R 1A A group in which the group is an ethylene group [of which a 2-(3',4'-epoxycyclohexyl)ethyl group] is more preferred.

[0056] R in the above composition formula (1) 1 , R in equation (1') 1a ~R 1i, R in composition formula (2) 2 , R in equation (2') 2a ~R 2h , R in equation (2) 2i ~R 2p , R in the composition formula (3) 3 , R in equation (3') 3a ~R 3j , R in equation (3) 3k ~R 3t , R in equation (3''') 3u ~R 3z , R 3aa ~R 3dd , R in the composition formula (4) 4 , R in equation (4') 4a ~R 4l , R in equation (4) 4m ~R 4x , R in the composition formula (5) 5 , R in the composition formula (6) 6 , R in the composition formula (7) 7 , R in the composition formula (8) 8 , R in equation (I) a , and R in equation (II) b Examples of aryl groups in the substituted or unsubstituted aryl groups include phenyl, tolyl, and naphthyl groups.

[0057] R in the above composition formula (1) 1 , R in equation (1') 1a ~R 1i , R in composition formula (2) 2 , R in equation (2') 2a ~R 2h , R in equation (2) 2i ~R 2p , R in the composition formula (3) 3 , R in equation (3') 3a ~R 3j , R in equation (3) 3k ~R 3t , R in equation (3''') 3u ~R 3z , R 3aa ~R 3dd , R in the composition formula (4) 4 , R in equation (4') 4a ~R 4l , R in equation (4) 4m~R 4x , R in the composition formula (5) 5 , R in the composition formula (6) 6 , R in the composition formula (7) 7 , R in the composition formula (8) 8 , R in equation (I) a , and R in equation (II) b Examples of the substituted or unsubstituted aralkyl groups include benzyl groups, phenethyl groups, and the like.

[0058] R in the above composition formula (1) 1 , R in equation (1') 1a ~R 1i , R in composition formula (2) 2 , R in equation (2') 2a ~R 2h , R in equation (2) 2i ~R 2p , R in the composition formula (3) 3 , R in equation (3') 3a ~R 3j , R in equation (3) 3k ~R 3t , R in equation (3''') 3u ~R 3z , R 3aa ~R 3dd , R in the composition formula (4) 4 , R in equation (4') 4a ~R 4l , R in equation (4) 4m ~R 4x , R in the composition formula (5) 5 , R in the composition formula (6) 6 , R in the composition formula (7) 7 , R in the composition formula (8) 8 , R in equation (I) a , and R in equation (II) b Examples of substituted or unsubstituted cycloalkyl groups include cyclobutyl, cyclopentyl, and cyclohexyl groups.

[0059] R in the above composition formula (1) 1 , R in equation (1') 1a ~R 1i , R in composition formula (2) 2, R in equation (2') 2a ~R 2h , R in equation (2) 2i ~R 2p , R in the composition formula (3) 3 , R in equation (3') 3a ~R 3j , R in equation (3) 3k ~R 3t , R in equation (3''') 3u ~R 3z , R 3aa ~R 3dd , R in the composition formula (4) 4 , R in equation (4') 4a ~R 4l , R in equation (4) 4m ~R 4x , R in the composition formula (5) 5 , R in the composition formula (6) 6 , R in the composition formula (7) 7 , R in the composition formula (8) 8 , R in equation (I) a , and R in equation (II) b Examples of alkyl groups in the substituted or unsubstituted alkyl groups include linear or branched alkyl groups such as methyl, ethyl, propyl, n-butyl, isopropyl, isobutyl, s-butyl, t-butyl, and isopentyl groups.

[0060] R in the above composition formula (1) 1 , R in equation (1') 1a ~R 1i , R in composition formula (2) 2 , R in equation (2') 2a ~R 2h , R in equation (2) 2i ~R 2p , R in the composition formula (3) 3 , R in equation (3') 3a ~R 3j , R in equation (3) 3k ~R 3t , R in equation (3''') 3u ~R 3z , R 3aa ~R 3dd , R in the composition formula (4) 4 , R in equation (4') 4a ~R4l , R in equation (4) 4m ~R 4x , and R in equation (I) a , R in the composition formula (5) 5 , R in the composition formula (6) 6 , R in the composition formula (7) 7 , R in the composition formula (8) 8 , R in equation (II) b Examples of substituted or unsubstituted alkenyl groups include linear or branched alkenyl groups such as vinyl groups, allyl groups, and isopropenyl groups.

[0061] R in the above composition formula (1) 1 The number of groups containing polymerizable functional groups in is preferably 3 to 9, more preferably 5 to 9, even more preferably 7 to 9, and even more preferably 9 (all groups containing polymerizable functional groups). R in the above composition formula (2) 2 The groups containing polymerizable functional groups in are preferably 3 to 8, more preferably 5 to 8, even more preferably 7 to 8, and even more preferably 8 (all groups containing polymerizable functional groups). R in the above composition formula (3) 3 The number of groups containing polymerizable functional groups in is preferably 3 to 10, more preferably 5 to 10, even more preferably 7 to 10, and even more preferably 10 (all groups containing polymerizable functional groups). R in the above composition formula (4) 4 The number of groups containing polymerizable functional groups is preferably 3 to 12, more preferably 5 to 12, even more preferably 7 to 12, and even more preferably 12 (all groups containing polymerizable functional groups). A larger number of these groups containing polymerizable functional groups is preferable from the viewpoint of curability when used as a curable composition and surface hardness of the cured product.

[0062] Furthermore, in the polyorganosilsesquioxane of this disclosure, R in the above composition formula (1) 1 , R in composition formula (2) 2 , R in the composition formula (3) 3 , and R in composition formula (4) 4The ratio of groups containing polymerizable functional groups (e.g., groups containing epoxy groups) to the total (number of groups containing polymerizable functional groups / R) 1 ~R 4 The total number of polymerizable functional groups is, for example, 30% or more, preferably 50% or more, and more preferably 80% or more. The proportion of groups containing the polymerizable functional groups is preferable to be high from the viewpoint of curability when used as a curable composition and surface hardness of the cured product, and is preferably equal to or greater than the above value.

[0063] The polyorganosilsesquioxane of this disclosure has a molar ratio [constituent unit represented by formula (I) / constituent unit represented by formula (II); T3 / T2] of the constituent unit represented by formula (I) (T3 isomer) to the constituent unit represented by formula (II) (T2 isomer) of, for example, 1 or more and 500 or less. The constituent unit represented by formula (I) and the constituent unit represented by formula (II) include the T3 and T2 isomers that constitute the cage-type silsesquioxanes represented by the above compositional formulas (1), (2), (3), and (4), and further include the T3 and T2 isomers of all other silsesquioxanes (perfect cage-type silsesquioxane, ladder-type silsesquioxane, random-type silsesquioxane, etc.).

[0064] The lower limit of the above ratio [T3 / T2] 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 20, and still more preferably 40. By setting the above ratio [T3 / T2] to 1 or more, the surface of the uncured or semi-cured hard coat layer is more likely to become tack-free, blocking resistance is improved, winding onto a roll becomes easier, and it can be preferably used as a component of a hard coat layer that has flexibility resistance, and the surface hardness and adhesion of the cured product and hard coat layer are significantly improved. On the other hand, the upper limit of the above ratio [T3 / T2] is preferably 500, more preferably 400, 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 compound / T2 compound] to 500 or less, compatibility with other components in the curable composition is improved, and viscosity is also suppressed, making it easier to handle and easier to apply as a hard coat layer.

[0065] The polyorganosilsesquioxane disclosed herein is the silsesquioxane constituent unit [RSiO 3 / 2 In addition to ](T units), there is also [(R)3SiO 1 / 2 The constituent unit represented by ] (so-called M unit), [(R)2SiO 2 / 2 The constituent units represented by ] (so-called D units), and [SiO 4 / 2 It may have at least one siloxane structural unit selected from the group consisting of structural units represented by ] (so-called Q units). In addition to the structural units represented by the above formula (I), other silsesquioxane structural units include [HSiO 3 / 2 Examples of constituent units are shown in the formula. In the above formula, R represents a hydrogen atom or a monovalent organic group.

[0066] The above ratio [T3 / T2] in the polyorganosylsesquioxane of this disclosure is, for example, 29This can be determined by Si-NMR spectroscopy. 29 In the Si-NMR spectrum, the silicon atoms in the constituent unit represented by formula (I) (T3 form) and the silicon atoms in the constituent unit represented by formula (II) (T2 form) show signals (peaks) at different positions (chemical shifts). Therefore, the ratio [T3 form / T2 form] can be determined by calculating the integral ratio of these respective peaks. The signal for the silicon atoms in the structure represented by formula (I) (T3 form) appears at -64 to -70 ppm, and the signal for the silicon atoms in the structure represented by formula (II) (T2 form) appears at -54 to -60 ppm. Thus, in this case, the ratio [T3 form / T2 form] can be determined by calculating the integral ratio of the signal at -64 to -70 ppm (T3 form) and the signal at -54 to -60 ppm (T2 form).

[0067] Polyorganosilsesquioxane 29 Si-NMR spectra can be measured, for example, using the following apparatus and conditions. Measurement device: "Brucker AVANCE (600MHz)" (manufactured by Brucker) Solvent: Deuterated chloroform Total number of times: 8000 Measurement temperature: 25℃ Sample: Polyorganosilsesquioxane / Acetylacetone chromium(III) / Deuterated chloroform (1% tetramethylsilane) = 2.0:0.10:4.0 (weight ratio)

[0068] The fact that the above ratio [T3 / T2] of the polyorganosilsesquioxanes disclosed herein is between 1 and 500 means that in the polyorganosilsesquioxanes disclosed herein, the amount of T2 isomer is equal to or relatively less than that of T3 isomer, and the hydrolysis and condensation reaction of silanol is more advanced.

[0069] The proportion of each silsesquioxane constituent unit in the polyorganosilsesquioxane of this disclosure can be appropriately adjusted by the composition of the raw materials (hydrolyzable trifunctional silanes) used to form these constituent units.

[0070] The condensed 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 by two or more, means that among the cage-type silsesquioxanes represented by the above compositional formula (1), compositional formula (2), compositional formula (3) and compositional formula (4), two or more (for example, 2 to 5, preferably 2 to 3, more preferably 2) in one kind, or two or more (for example, 2 to 5, preferably 2 to 3, more preferably 2) in two or more kinds 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 is an alkoxy group, the hydrolyzed hydroxyl group) are dehydrated to form a siloxane bond (Si-O-Si).

[0071] Since the cage-type silsesquioxanes represented by the above compositional formula (2), compositional formula (3) and compositional formula (4) have two -OR c groups represented by in the molecule, the polyorganosilsesquioxane of the present disclosure in which these are condensed has a structure in which these cage-type structures are linearly connected.

[0072] Since the cage-type silsesquioxane represented by the above compositional formula (1) has only one -OR c group represented by in the molecule, it condenses at the end of the structure in which the above cage-type structures are linearly connected.

[0073] Further, the condensed silsesquioxane of the present disclosure may not have a cage-type structure derived from the cage-type silsesquioxanes represented by the above compositional formula (2), compositional formula (3) and compositional formula (4), and may be a condensate of two cage-type silsesquioxanes represented by the above compositional formula (1).

[0074] The cage-type structural units derived from the cage-type silsesquioxanes represented by the above compositional formula (1), compositional formula (2), compositional formula (3) and compositional formula (4) of the condensed silsesquioxane of the present disclosure are not particularly limited in their condensation forms, and may be of a random type or a block type.

[0075] For example, when the cage-type silsesquioxane of the present disclosure contains a cage-type structure derived from the cage-type silsesquioxane represented by the above formula (2’), it has a repeating structure of a cage-type silsesquioxane structure represented by the following formula (2a) in the molecule.

Chemical formula

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

Chemical formula

[0077] Each symbol in the above formula (2b) has the same meaning as the above formula (2”). For example, when the cage-type silsesquioxane of the present disclosure contains a cage-type structure derived from the cage-type silsesquioxane represented by the above formula (3’), it has a repeating structure of a cage-type silsesquioxane structure represented by the following formula (3a) in the molecule.

Chemical formula

[0078] Each symbol in the above formula (3a) has the same meaning as the above formula (3’). Furthermore, if the condensed silsesquioxane of this disclosure contains a cage-type structure derived from the cage-type silsesquioxane represented by formula (3") above, it has a repeating structure of the cage-type silsesquioxane structure represented by formula (3b) below within the molecule. [ka]

[0079] Each symbol in equation (3b) above has the same meaning as in equation (3) above. Furthermore, if the condensed silsesquioxane of this disclosure contains a cage-type 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) within the molecule. [ka]

[0080] Each symbol in equation (3c) above is equivalent to that in equation (3'''). For example, if the condensed silsesquioxane of this disclosure contains a cage-type structure derived from the cage-type silsesquioxane represented by formula (4') above, it has a repeating structure of the cage-type silsesquioxane structure represented by formula (4a) below within the molecule. [ka]

[0081] Each symbol in equation (4a) above has the same meaning as in equation (4') above. Furthermore, if the condensed silsesquioxane of this disclosure contains a cage-type structure derived from the cage-type silsesquioxane represented by formula (4") above, it has a repeating structure of the cage-type silsesquioxane structure represented by formula (4b) below within the molecule. [ka]

[0082] Each symbol in equation (4b) above has the same meaning as in (4) above. For example, when the condensed silsesquioxane of the present disclosure contains a cage structure derived from the cage-type silsesquioxane represented by the above formula (1’), it has a cage-type silsesquioxane structure represented by the following formula (1a) and / or a cage-type silsesquioxane structure represented by the following formula (1b) at both ends or one end thereof.

Chemical formula

Chemical formula

[0083] Each symbol in the above formula (1a) has the same meaning as in the above formula (1’). R in the above formula (1b) 1j ~R 1r has the same meaning as R in the above (1’). 1a ~R 1i [[ID=二十六]] 1i

[0084] The condensed silsesquioxane of the present disclosure includes, for example, two or more condensates in one kind such as a condensate of the cage-type silsesquioxane represented by two compositional formulas (1), and two or more different condensates such as a condensate of the cage-type silsesquioxane represented by the compositional formula (1) and the cage-type silsesquioxane represented by the compositional formula (2). Among them, the condensed silsesquioxane of the present disclosure is preferably a condensate of a cage-type silsesquioxane represented by one of the above compositional formulas (1) and a cage-type silsesquioxane represented by another of the above compositional formulas (1), or a condensate of a cage-type silsesquioxane represented by one of the above compositional formulas (1) and any one of the cage-type silsesquioxanes represented by the compositional formula (2), the compositional formula (3), and the compositional formula (4).

[0085] Among the condensed silsesquioxanes of the present disclosure, the silsesquioxane that is a condensate of a cage-type silsesquioxane represented by one of the above compositional formulas (1) and a cage-type silsesquioxane represented by one of the above compositional formulas (2) is, for example, a group represented by -OR in the above formula (1’) c and two -ORs in the above formula (2’) cExamples include condensed silsesquioxanes represented by the following formulas (1a-2a) formed by the condensation of one of the groups represented by . Note that the substituent (R) in formula (1a-2b) 1a ~R 1i and R 2a ~R 2h ) is the same as in equations (1a) and (2b). [ka]

[0086] Among the condensed silsesquioxanes of this disclosure, a silsesquioxane that is a condensate of one cage-type silsesquioxane represented by one of the compositional formulas (1) and another cage-type silsesquioxane represented by the other compositional formula (1) is, for example, a silsesquioxane that is a condensate of two of the -OR in the two formulas (1'). c Examples include condensed silsesquioxanes represented by the following formula (1a-1b), which are formed by the condensation of groups represented by the following formulas. Note that the substituent (R) in formula (1a-1b) 1a ~R 1r ) is the same as in equations (1a) and (1b). [ka]

[0087] Among the condensed silsesquioxanes of this disclosure, a silsesquioxane that is a condensate of one cage-type silsesquioxane represented by one composition formula (2) and another cage-type silsesquioxane represented by another composition formula (2) is, for example, a condensed silsesquioxane represented by the following formula (2a-2a) formed by the condensation of the groups represented by -ORc in two of the aforementioned formulas (2'). Note that the substituent (R) in formula (2a-2a) 2a ~R 2h ) is the same as in equation (2a). [ka]

[0088] The polyorganosilsesquioxanes disclosed herein may include, in addition to the condensed silsesquioxanes disclosed herein, monomeric cage-type silsesquioxanes such as cage-type (structural) silsesquioxanes (i.e., perfect cage-type silsesquioxanes) in which there is no cleavage in the silica stereostructure, such as a hexahedral structure, and monomeric cage-type silsesquioxanes that are not condensed, such as those represented by the above compositional formulas (1), (2), (3), and (4) (i.e., incomplete cage-type silsesquioxanes). In this specification, both the above-mentioned perfect cage-type silsesquioxanes and incomplete cage-type silsesquioxanes will be collectively referred to as monomeric cage-type silsesquioxanes. The monomer cage-type silsesquioxane content in the polyorganosilsesquioxane of this 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 polyorganosilsesquioxane of this disclosure. When the monomer cage-type silsesquioxane content is within the above range, the surface hardness of the cured product can be further improved.

[0089] The polyorganosilsesquioxanes of this disclosure may have cage-type silsesquioxanes other than the condensed silsesquioxanes of this disclosure. Furthermore, the polyorganosilsesquioxanes of this disclosure may have silsesquioxane structures other than cage-type silsesquioxanes, such as ladder-type or random-type silsesquioxanes. Furthermore, they may have a combination of two or more of these silsesquioxane structures.

[0090] The polyorganosilsesquioxane of the present disclosure contains 20% by weight or more (preferably 25-90% by weight, more preferably 30-80% by weight, and even more preferably 40-70% by weight) of the total amount of the polyorganosilsesquioxane of the present disclosure. The cage-type silsesquioxane content is, for example, 40-99.5% by weight, preferably 45-98% by weight, and more preferably 50-96% by weight, of the total amount of the polyorganosilsesquioxane of the present disclosure.

[0091] The number-average molecular weight (Mn) of the polyorganosilsesquioxane disclosed herein, measured by gel permeation chromatography on a standard polystyrene basis, is, for example, 2,000 to 50,000, preferably 2,500 to 40,000, and more preferably 3,000 to 30,000. By setting the number-average molecular weight to 2,000 or higher, the surface of the uncured or semi-cured hard coat layer is more likely to become tack-free, improving blocking resistance and making it easier to wind onto a roll. Therefore, by setting the number-average molecular weight to 2,000 or higher, it can be preferably used as a component of the hard coat layer of a transfer film for in-mold injection molding, and the heat resistance, scratch resistance, and adhesion of the cured product are further improved. On the other hand, by setting the number-average molecular weight to 50,000 or lower, the compatibility with other components in the curable composition is improved, and the heat resistance of the cured product is further improved.

[0092] The molecular weight dispersibility (Mw / Mn) of the polyorganosilsesquioxanes disclosed herein, measured by gel permeation chromatography on a standard polystyrene basis, is, for example, 1.0 to 4.0, preferably 1.1 to 3.0, and more preferably 1.2 to 2.5. A molecular weight dispersibility of 4.0 or less improves solubility in solvents, resulting in higher surface hardness and adhesion of the cured product. On the other hand, a molecular weight dispersibility of 1.1 or higher tends to make the product more liquid and improves handling.

[0093] The number-average molecular weight and molecular weight dispersion of the polyorganosilsesquioxanes disclosed herein can be determined by GPC measurement. Furthermore, the content of the monomeric cage-type silsesquioxanes and condensed silsesquioxanes in the polyorganosilsesquioxanes disclosed herein can be determined from the area ratio of the corresponding peak area values ​​in the GPC measurement. The GPC measurement can be performed using the following apparatus and conditions. Measuring device: Product 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: 0.6mL / min Measurement temperature: 40℃ Measurement time: 13 min Injection volume: 20μL Eluent: THF, sample concentration 0.1~0.2% by weight Molecular weight: Equivalent to standard polystyrene

[0094] The temperature at which the polyorganosilsesquioxanes of this disclosure lose 5% of their weight in an air atmosphere (T d5 The 5% weight loss temperature 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. A 5% weight loss temperature of 330°C or higher tends to improve the heat resistance of the cured product. The polyorganosilsesquioxane of this disclosure has a ratio [T3 / T2] of 1 to 500, a number-average molecular weight of 2000-50000, and a molecular weight dispersion of 1.0-4.0, so that the 5% weight loss temperature of its cured product is 330°C or higher. The 5% weight loss temperature is the temperature at which 5% of the weight before heating is lost when heated at a constant heating rate, and serves as an indicator of heat resistance. The above 5% weight loss temperature can be measured by TGA (thermogravimetric analysis) under an air atmosphere and a heating rate of 5°C / min.

[0095] The polyorganosilsesquioxanes of this disclosure can be produced by known or conventional methods for producing polysiloxanes, and are not particularly limited, but for example, they can be produced by hydrolyzing and condensing one or more hydrolyzable silane compounds. However, as the hydrolyzable silane compound, it is necessary to use a hydrolyzable trifunctional silane compound (a compound represented by the following formula (a)) as the essential hydrolyzable silane compound.

[0096] More specifically, for example, a polyorganosilsesquioxane of this disclosure can be produced by hydrolyzing and condensing a compound represented by the following formula (a), which is a hydrolyzable silane compound for forming silsesquioxane constituent units (T units) in the polyorganosilsesquioxane of this disclosure, and optionally further, a compound represented by the following formula (b) and a compound represented by the following formula (c), to produce cage-type silsesquioxanes represented by the above compositional formulas (1), (2), (3), and / or (4). Further hydrolysis and condensation reactions can then produce the polyorganosilsesquioxane of this disclosure, which includes a condensed silsesquioxane of this disclosure in which two or more of one of the cage-type silsesquioxanes represented by the above compositional formulas (1), (2), (3), and (4) are condensed. [ka] [ka] [ka]

[0097] The compound represented by formula (A) above is [R] in the condensed silsesquioxane of this disclosure. A SiO 3 / 2 ] or [R A SiO 2 / 2 (OR c It is a compound that forms a constituent unit represented by )]. R in formula (A) A This is R in the above composition formula (1). 1 , R in composition formula (2) 2 , R in the composition formula (3) 3 , R in the composition formula (4) 4 (i.e., substituents in cage-type silsesquioxane) indicate a group containing a polymerizable functional group. R in formula (A) AAs for the polymerizable functional group, the group represented by formula (1A), the group represented by formula (1B), the group represented by formula (1C), and the group represented by formula (1D) are preferred, more preferably the group represented by formula (1A), the group represented by formula (1C), even more preferably the group represented by formula (1A), and even more preferably the group represented by formula (1A), R 1A The group is an ethylene group [particularly the 2-(3',4'-epoxycyclohexyl)ethyl group].

[0098] X in equation (A) above 1 X represents an alkoxy group or a halogen atom. 1 Examples of alkoxy groups in include alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropyloxy, butoxy, and isobutyloxy groups. 1 Examples of halogen atoms in this include fluorine, chlorine, bromine, and iodine atoms. Among them, X 1 As such, an alkoxy group is preferred, and more preferably a methoxy group or an ethoxy group. Note that the three X 1 These may be the same or they may be different.

[0099] The compound represented by formula (B) above is [R] in the condensed silsesquioxane of this disclosure. B SiO 3 / 2 ] or [R B SiO 2 / 2 (OR c It is a compound that forms a constituent unit represented by )]. R in formula (B) B R 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. B The preferred members are substituted or unsubstituted aryl groups, substituted or unsubstituted alkyl groups, and substituted or unsubstituted alkenyl groups; more preferably, substituted or unsubstituted aryl groups; and even more preferably, phenyl groups.

[0100] X in equation (B) above 2 X represents an alkoxy group or a halogen atom. 2 A concrete example of this is X 1 Examples include the following. Among them, X 2 As such, an alkoxy group is preferred, and more preferably a methoxy group or an ethoxy group. Note that the three X 2 These may be the same or they may be different.

[0101] The compound represented by formula (C) above is [HSiO] in the condensed silsesquioxane of this disclosure. 3 / 2 ] or [HSiO 2 / 2 (OR c It is a compound that forms a constituent unit represented by ) in formula (C) above. 3 X represents an alkoxy group or a halogen atom. 3 A concrete example of this is X 1 Examples include the following. Among them, X 3 As such, an alkoxy group is preferred, and more preferably a methoxy group or an ethoxy group. Note that the three X 3 These may be the same or they may be different.

[0102] Other hydrolyzable silane compounds besides those represented by formulas (A) to (C) may be used in combination with the above hydrolyzable silane compounds. For example, other hydrolyzable trifunctional silane compounds besides those represented by formulas (A) to (C), hydrolyzable monofunctional silane compounds that form M units, hydrolyzable difunctional silane compounds that form D units, hydrolyzable tetrafunctional silane compounds that form Q units, and so on.

[0103] The amount and composition of the above hydrolyzable silane compound can be appropriately adjusted according to the desired structure of the polyorganosilsesquioxane of this disclosure. For example, the amount of the compound represented by formula (A) is not particularly limited, but is preferably 30 to 100 mol%, more preferably 55 to 100 mol%, more preferably 65 to 100 mol%, and even more preferably 80 to 99 mol%, relative to the total amount (100 mol%) of the hydrolyzable silane compound used.

[0104] Furthermore, the amount of compound represented by formula (B) above is not particularly limited, but is preferably 0 to 70 mol%, more preferably 0 to 60 mol%, even more preferably 0 to 40 mol%, and even more preferably 1 to 15 mol%, relative to the total amount (100 mol%) of the hydrolyzable silane compound used.

[0105] Furthermore, the ratio (total amount) of the compound represented by formula (A) and the compound represented by formula (B) relative 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 even more preferably 80 to 100 mol%.

[0106] Furthermore, when two or more hydrolyzable silane compounds are used in combination, the hydrolysis and condensation reactions of these hydrolyzable silane compounds can be carried out simultaneously or sequentially. When the above reactions are carried out sequentially, the order in which the reactions are carried out is not particularly limited.

[0107] The hydrolysis and condensation reactions of the hydrolyzable silane compound may be carried out in one step or in two or more steps. However, in order to efficiently produce the polyorganosilsesquioxane of this disclosure, it is preferable to carry out the hydrolysis and condensation reactions in two or more steps (preferably two steps). The following describes an embodiment in which the hydrolysis and condensation reactions of the hydrolyzable silane compound are carried out in two steps, but the method for producing the polyorganosilsesquioxane of this disclosure is not limited thereto.

[0108] When the hydrolysis and condensation reaction of the present disclosure is carried out in two steps, preferably, in the first hydrolysis and condensation reaction, a polyorganosylsesquioxane (hereinafter referred to as "intermediate polyorganosylsesquioxane") is obtained in which the above ratio [T3 isomer / T2 isomer] is 1 or more and less than 20, and the number average molecular weight is, for example, 1000 to 3000. In the second step, the intermediate polyorganosylsesquioxane is subjected to further hydrolysis and condensation reactions to obtain the polyorganosylsesquioxane of the present disclosure.

[0109] The first stage of hydrolysis and condensation reaction can be carried out in the presence or absence of a solvent. It is preferable to carry out the reaction in the presence of a solvent. Examples of solvents 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. Ketones and ethers are particularly preferred among these solvents. Note that a single solvent may be used, or two or more solvents may be used in combination.

[0110] The amount of solvent used in the first hydrolysis and condensation reaction is not particularly limited and can be appropriately adjusted within the range of 0 to 2000 parts by weight per 100 parts by weight of the total amount of hydrolyzable silane compound, depending on the desired reaction time, etc.

[0111] The first stage of hydrolysis and condensation reaction is preferably carried out in the presence of a catalyst and water. The catalyst may be an acid catalyst or an alkaline catalyst, but an alkaline catalyst is preferred in order to suppress the decomposition of polymerizable functional groups such as epoxy groups. Examples of the 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-mentioned alkaline catalysts include: alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide, and barium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate; alkaline earth metal carbonates such as magnesium carbonate; alkali metal bicarbonates such as lithium bicarbonate, sodium bicarbonate, sodium bicarbonate, potassium bicarbonate, and cesium bicarbonate; alkali metal organic acid salts (e.g., acetates) such as lithium acetate, sodium acetate, potassium acetate, and cesium acetate; and vinegar. Examples of catalysts include organic acid salts of alkaline earth metals such as magnesium acid (e.g., acetate); alkali metal alkoxides such as lithium methoxide, sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium ethoxide, and potassium t-butoxide; alkali metal phenoxides such as sodium phenoxide; amines such as triethylamine, N-methylpiperidine, 1,8-diazabicyclo[5.4.0]undeca-7-ene, and 1,5-diazabicyclo[4.3.0]nona-5-ene (tertiary amines, etc.); and nitrogen-containing aromatic heterocyclic compounds such as pyridine, 2,2'-bipyridyl, and 1,10-phenanthroline. The catalyst can be used individually or in combination of two or more. Furthermore, the catalyst can be used dissolved or dispersed in water or a solvent.

[0112] The amount of the catalyst used in the first stage of hydrolysis and condensation reaction is not particularly limited and can be appropriately adjusted within the range of 0.002 to 0.200 moles per mole of the total amount of hydrolyzable silane compound.

[0113] The amount of water used in the first stage of hydrolysis and condensation reaction is not particularly limited and can be appropriately adjusted within the range of 0.5 to 20 moles per mole of the total amount of hydrolyzable silane compound.

[0114] The method of adding water in the first stage of hydrolysis and condensation reaction is not particularly limited; the entire amount of water used may be added at once, or it may be added sequentially. When adding sequentially, it may be added continuously or intermittently.

[0115] For the first stage of hydrolysis and condensation, it is important to select reaction conditions such that the ratio [T3 / T2] of the intermediate polyorganosylsesquioxane is between 1 and 20. The reaction temperature for the first stage of hydrolysis and condensation is not particularly limited, but is preferably 40 to 100°C, and more preferably 45 to 80°C. By controlling the reaction temperature within the above range, the ratio [T3 / T2] tends to be controlled more efficiently to between 1 and 20. The reaction time for the first stage of hydrolysis and condensation is not particularly limited, but is preferably 0.1 to 10 hours, and more preferably 1.5 to 8 hours. The first stage of hydrolysis and condensation can be carried out under normal pressure, or under pressure or reduced pressure. The atmosphere during the first stage of hydrolysis and condensation is not particularly limited, and may be any of the following: an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere, or in the presence of oxygen such as air, but an inert gas atmosphere is preferred.

[0116] The first stage hydrolysis and condensation reaction described above yields the intermediate polyorganosylsesquioxane. After the completion of the first stage hydrolysis and condensation reaction, it is preferable to neutralize the catalyst to suppress the decomposition of polymerizable functional groups, such as ring-opening of epoxy groups. The intermediate polyorganosylsesquioxane may also be separated and purified by separation methods such as washing with water, acid washing, alkaline washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination thereof. Alternatively, the reaction solution containing the intermediate polyorganosylsesquioxane may be subjected to the first stage hydrolysis and condensation reaction.

[0117] The polyorganosylsesquioxane of this disclosure can be produced by subjecting the intermediate polyorganosylsesquioxane obtained by the first stage hydrolysis and condensation reaction to a second stage hydrolysis and condensation reaction. The second stage of hydrolysis and condensation can be carried out in the presence or absence of a solvent. When the second stage of hydrolysis and condensation is carried out in the presence of a solvent, the solvents listed for the first stage of hydrolysis and condensation can be used. As the solvent for the second stage of hydrolysis and condensation, the intermediate polyorganosylsesquioxane, which includes the reaction solvent and extraction solvent from the first stage of hydrolysis and condensation, may be used as is, or partially or completely removed by distillation. Alternatively, the solvent can be changed by adding a solvent with a higher boiling point than the solvent used in the first stage of hydrolysis and condensation to the reaction solution containing the intermediate polyorganosylsesquioxane, and then heating and distilling it off. Note that one solvent may be used alone, or two or more solvents may be used in combination.

[0118] When a solvent is used in the second stage of hydrolysis and condensation reaction, the amount used is not particularly limited and can be appropriately adjusted within the range of 0 to 2000 parts by weight per 100 parts by weight of the intermediate polyorganosylsesquioxane, depending on the desired reaction time, etc.

[0119] The second stage of hydrolysis and condensation reaction is preferably carried out in the presence of a catalyst and water. The catalyst can be one of the catalysts mentioned in the first stage of hydrolysis and condensation reaction. To suppress the decomposition of polymerizable functional groups such as epoxy groups, an alkaline catalyst is preferred, and more preferably, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, or cesium hydroxide; or an alkali metal carbonate such as lithium carbonate, sodium carbonate, potassium carbonate, or cesium carbonate. The catalyst can be used alone or in combination of two or more. The catalyst can also be used dissolved or dispersed in water or a solvent. Furthermore, the catalyst used in the first stage of hydrolysis and condensation reaction can be used directly in the second stage of hydrolysis and condensation reaction.

[0120] The amount of the catalyst used in the second hydrolysis and condensation reaction is not particularly limited and can be appropriately adjusted within the range of preferably 0.01 to 10,000 ppm, more preferably 0.1 to 1,000 ppm, relative to the intermediate polyorganosylsesquioxane (1,000,000 ppm).

[0121] The amount of water used in the second hydrolysis and condensation reaction is not particularly limited and can be appropriately adjusted within the range of preferably 10 to 100,000 ppm, more preferably 100 to 20,000 ppm, relative to the intermediate polyorganosylsesquioxane (1,000,000 ppm). If the amount of water used is greater than 100,000 ppm, it tends to become difficult to control the ratio of polyorganosylsesquioxane [T3 / T2] and the number-average molecular weight within the predetermined range.

[0122] The method of adding water in the second stage of hydrolysis and condensation reaction is not particularly limited; the entire amount of water to be used may be added at once, or it may be added sequentially. When adding sequentially, it may be added continuously or intermittently. In addition, the water used in the first stage of hydrolysis and condensation reaction may be used as is, or the remaining water after a portion has been distilled off may be used.

[0123] For the second stage hydrolysis and condensation reaction, it is important to select reaction conditions such that the ratio [T3 / T2] of the polyorganosylsesquioxane of this disclosure is between 20 and 500, and the number average molecular weight is between 2000 and 50000. The reaction temperature for the second stage hydrolysis and condensation reaction 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, the ratio [T3 / T2] and the number average molecular weight tend to be controlled more efficiently to the desired range. The reaction time for the second stage hydrolysis and condensation reaction is not particularly limited, but is preferably 0.5 to 1000 hours, more preferably 1 to 500 hours, and even more preferably 5 to 200 hours. Furthermore, by performing hydrolysis and condensation reactions within the above reaction temperature range and sampling at appropriate intervals, while monitoring the above ratio [T3 isomer / T2 isomer] and number-average molecular weight, it is possible to obtain the polyorganosylsesquioxane of this disclosure having a desired ratio [T3 isomer / T2 isomer] and number-average molecular weight.

[0124] The second stage of hydrolysis and condensation reaction can be carried out under normal pressure, or under pressure or reduced pressure. The atmosphere during the second stage of hydrolysis and condensation reaction is not particularly limited and may be any of the following: an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere, or in the presence of oxygen such as air, but an inert gas atmosphere is preferred.

[0125] The polyorganosilsesquioxane of this disclosure is obtained by the second stage hydrolysis and condensation reaction described above. After the completion of the second stage hydrolysis and condensation reaction, it is preferable to neutralize the catalyst in order to suppress the decomposition of polymerizable functional groups, such as ring-opening of epoxy groups. The polyorganosilsesquioxane of this disclosure may also be separated and purified by separation means such as washing with water, acid washing, alkaline washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or separation means combining these.

[0126] The polyorganosilsesquioxanes of this disclosure contain condensed silsesquioxanes in which two or more cage-type silsesquioxanes are condensed in a linear manner, and are therefore considered to have superior curability compared to conventional polyorganosilsesquioxanes. Accordingly, the cured products of curable compositions containing the polyorganosilsesquioxanes of this disclosure have high surface hardness and excellent heat resistance. Furthermore, the polyorganosilsesquioxanes of this disclosure have excellent solubility in solvents such as organic solvents. "Condensation of two or more cage-type silsesquioxanes in a linear manner" means that two or more cage-type silsesquioxanes represented by the above compositional formulas (1), (2), (3), and / or (4) are condensed in series rather than three-dimensionally, resulting in the formation of a linear condensate. Furthermore, the polyorganosilsesquioxanes of this disclosure, as shown in the above compositional formulas (5) and (6), have an -OR structure. c Even if the compound contains a cage-type silsesquioxane having three hydroxyl groups, if condensation occurs at two of these groups, it may still fall under the category of "two or more cage-type silsesquioxanes condensing in a linear chain." However, the above mechanism is merely a presumption, and the present invention should not be interpreted as being limited to these mechanisms.

[0127] [Curable composition] The curable composition of this disclosure is a curable composition (curable resin composition) containing the polyorganosilsesquioxane of this disclosure as an essential component. As described below, the curable composition of this disclosure may further contain other components such as curing catalysts (e.g., photocationic polymerization initiators, radical polymerization initiators), surface modifiers or surface modifiers, polymerization stabilizers, and silane coupling agents. Depending on its application, the curable composition of this disclosure can be used as a curable composition for hard coat layer formation or as a curable composition for adhesives (e.g., a curable composition for multilayer semiconductors). In the curable composition of this disclosure, one type of polyorganosilsesquioxane of this disclosure may be used alone, or two or more types may be used in combination.

[0128] The content (amount) of the polyorganosilsesquioxane of this disclosure in the curable composition of this 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 even 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 this disclosure to 70% by weight or more, the surface hardness and adhesion of the cured product tend to be further improved. On the other hand, by setting the content of the polyorganosilsesquioxane of this disclosure to less than 100% by weight, a curing catalyst can be included, which tends to allow the curing of the curable composition to proceed more efficiently.

[0129] The proportion of the polyorganosilsesquioxane of this disclosure to the total amount (100% by weight) of the cationic curable compound or radical curable compound contained in the curable composition of this disclosure is not particularly limited, but is preferably 70 to 100% by weight, more preferably 75 to 98% by weight, and even more preferably 80 to 95% by weight. By increasing the content of the polyorganosilsesquioxane of this disclosure to 70% by weight or more, the surface hardness and adhesion of the cured product tend to be further improved.

[0130] The curable composition of this disclosure preferably further comprises a curing catalyst. In particular, the curing catalyst preferably comprises a photopolymerization initiator or a thermal polymerization initiator, and more preferably a cationic polymerization initiator or a radical polymerization initiator, as this shortens the curing time until tack-free formation. In the curable composition of this disclosure, one type of curing catalyst may be used alone, or two or more types may be used in combination.

[0131] The cationic polymerization initiator described above is a compound that can initiate or accelerate the cationic polymerization reaction of cationic curable compounds such as polyorganosylsesquioxanes of this disclosure. The cationic polymerization initiator is not particularly limited, but examples include photocatalytic cationic polymerization initiators (photoacid generators) and thermal cationic polymerization initiators (thermal acid generators).

[0132] As the above-mentioned photocationic polymerization initiator, known or conventional photocationic polymerization initiators can be used, for example, sulfonium salts (salts of sulfonium ions and anions), iodonium salts (salts of iodonium ions and anions), selenium salts (salts of selenium ions and anions), ammonium salts (salts of ammonium ions and anions), phosphonium salts (salts of phosphonium ions and anions), and salts of transition metal complex ions and anions. These can be used individually or in combination of two or more.

[0133] Examples of the above 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, and diphenyl[4-(phenylthio)phenyl]sulfonium Examples include triarylsulfonium salts such as 4-(p-tolylthio)phenyldi-(p-phenyl)sulfonium salt; diarylsulfonium salts such as diphenylphenacylsulfonium salt, diphenyl4-nitrophenacylsulfonium salt, diphenylbenzylsulfonium salt, and diphenylmethylsulfonium salt; monoarylsulfonium salts such as phenylmethylbenzylsulfonium salt, 4-hydroxyphenylmethylbenzylsulfonium salt, and 4-methoxyphenylmethylbenzylsulfonium salt; and trialkylsulfonium salts such as dimethylphenacylsulfonium salt, phenacyltetrahydrothiophenium salt, and dimethylbenzylsulfonium salt.

[0134] Examples of the above-mentioned diphenyl[4-(phenylthio)phenyl]sulfonium salts include diphenyl[4-(phenylthio)phenyl]sulfonium hexafluoroantimonate and diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate.

[0135] Examples of the iodonium salts mentioned above include the product name "UV9380C" (manufactured by Momentive Performance Materials Japan LLC, bis(4-dodecylphenyl)iodonium = hexafluoroantimonate 45% alkylglycidyl ether solution), the product name "RHODORSIL PHOTOINITIATOR 2074" (manufactured by Rhodia Japan Co., Ltd., tetrakis(pentafluorophenyl)borate = [(1-methylethyl)phenyl](methylphenyl)iodonium), the product name "WPI-124" (manufactured by Wako Pure Chemical Industries, Ltd.), diphenyliodonium salt, di-p-tolyliodonium salt, bis(4-dodecylphenyl)iodonium salt, bis(4-methoxyphenyl)iodonium salt, etc.

[0136] Examples of the selenium salts mentioned above include triarylselenium salts such as triphenylselenium salt, tri-p-tolylselenium salt, tri-o-tolylselenium salt, tris(4-methoxyphenyl)selenium salt, and 1-naphthyldiphenylselenium salt; diarylselenium salts such as diphenylphenacylselenium salt, diphenylbenzylselenium salt, and diphenylmethylselenium salt; monoarylselenium salts such as phenylmethylbenzylselenium salt; and trialkylselenium salts such as dimethylphenacylselenium salt.

[0137] Examples of the above ammonium salts include tetraalkylammonium salts such as tetramethylammonium salt, ethyltrimethylammonium salt, diethyldimethylammonium salt, triethylmethylammonium salt, tetraethylammonium salt, trimethyl-n-propylammonium salt, and trimethyl-n-butylammonium salt; pyrrolidium salts such as N,N-dimethylpyrrolidium salt and N-ethyl-N-methylpyrrolidium salt; imidazolinium salts such as N,N'-dimethylimidazolinium salt and N,N'-diethylimidazolinium salt; and N,N'-dimethyltetrahydropyrimidium salt and N,N'-diethyl Examples include tetrahydropyrimidium salts such as trahydropyrimidium salt; morpholinium salts such as N,N-dimethylmorpholinium salt and N,N-diethylmorpholinium salt; piperidinium salts such as N,N-dimethylpiperidinium salt and N,N-diethylpiperidinium salt; pyridinium salts such as N-methylpyridinium salt and N-ethylpyridinium salt; imidazolium salts such as N,N'-dimethylimidazolium salt; quinolium salts such as N-methylquinolium salt; isoquinolium salts such as N-methylisoquinolium salt; thiazonium salts such as benzylbenzothiazonium salt; and acridium salts such as benzylacridium salt.

[0138] Examples of the phosphonium salts mentioned above include tetraarylphosphonium salts such as tetraphenylphosphonium salt, tetra-p-tolylphosphonium salt, and tetrakis(2-methoxyphenyl)phosphonium salt; triarylphosphonium salts such as triphenylbenzylphosphonium salt; and tetraalkylphosphonium salts such as triethylbenzylphosphonium salt, tributylbenzylphosphonium salt, tetraethylphosphonium salt, tetrabutylphosphonium salt, and triethylphenacylphosphonium salt.

[0139] Examples of salts of the above transition metal complex ions include (η5-cyclopentadienyl)(η6-toluene)Cr + (η5-cyclopentadienyl)(η6-xylene)Cr + Salts of chromium complex cations such as (η5-cyclopentadienyl)(η6-toluene)Fe+ (η5-cyclopentadienyl)(η6-xylene)Fe + Examples include salts of iron complex cations.

[0140] An example of anion that makes up the aforementioned salt is SbF6. - PF6 - BF4 - (CF3CF2)3PF3 - (CF3CF2CF2)3PF3 - (C6F5)4B - , (C6F5)4Ga - , sulfonate anions (trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, nonafluorobutanesulfonate anion, methanesulfonate anion, benzenesulfonate anion, p-toluenesulfonate anion, etc.), (CF3SO2)3C - (CF3SO2)2N - Examples include perhalate ions, halogenated sulfonate ions, sulfate ions, carbonate ions, aluminate ions, hexafluorobismuth ions, carboxylate ions, arylborate ions, thiocyanate ions, and nitrate ions.

[0141] Examples of the above-mentioned thermal cationic polymerization initiators include aryl sulfonium salts, aryl iodonium salts, allene ion complexes, quaternary ammonium salts, aluminum chelates, and boron trifluoride amine complexes.

[0142] Examples of the above aryl sulfonium salts include hexafluoroantimonate salts. In the curable composition of this disclosure, commercially available products such as "SP-66" and "SP-77" (both manufactured by ADEKA Corporation); and "San-Aid SI-60L", "San-Aid SI-80L", "San-Aid SI-100L", and "San-Aid SI-150L" (all manufactured by Sanshin Chemical Industry Co., Ltd.) can be used. Examples of the above aluminum chelates include ethyl acetacetate aluminum diisopropylate and aluminum tris(ethyl acetate). Examples of the above boron trifluoride amine complexes include boron trifluoride monoethylamine complex, boron trifluoride imidazole complex, and boron trifluoride piperidine complex.

[0143] The radical polymerization initiator described above is a compound that can initiate or accelerate the radical polymerization reaction of a radical-curable compound such as polyorganosylsesquioxane according to this disclosure. Examples of the radical polymerization initiator include photoradical polymerization initiators and thermal radical polymerization initiators.

[0144] Examples of the above-mentioned photoradical polymerization initiators include benzophenone, acetophenone benzyl, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyl disulfite, orthobenzoyl methyl benzoate, 4-dimethylaminobenzoate ethyl (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-Gaigi Co., Ltd., trade name "Irgacure 907", etc.), 1-hydroxycyclohexylphenyl ketone (manufactured by Ciba-Gaigi Co., Ltd., trade name "Irgacure 184", etc.), and 2-dimethylamino Examples include 2-amino-2-benzoyl-1-phenylalkane compounds such as -2-(4-morpholino)benzoyl-1-phenylpropane, aminobenzene derivatives such as tetra(t-butylperoxycarbonyl)benzophenone, benzyl, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 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-ylethenyl)-1,3,4-oxadiazole. Additionally, a photosensitizer can be added as needed.

[0145] Examples of thermal radical polymerization initiators include hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides, peroxydicarbonates, peroxyketals, ketone peroxides, etc. (specifically, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di(2-ethylhexanoyl)peroxyhexane, t-butylperoxybenzoate, t-butyl peroxide, cumenehydroperoxide) Examples of organic peroxides include phosphates, dicumyl peroxides, di-t-butyl peroxides, 2,5-dimethyl-2,5-dibutylperoxyhexane, 2,4-dichlorobenzoyl peroxides, 1,4-di(2-t-butylperoxyisopropyl)benzene, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, methyl ethyl ketone peroxides, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, etc.

[0146] The content (amount blended) of the curing catalyst in the curable composition of this disclosure is preferably 0.01 to 3.0 parts by weight, more preferably 0.05 to 3.0 parts by weight, and even more preferably 0.1 to 1.0 parts by weight (for example, 0.3 to 1.0 parts by weight) per 100 parts by weight of the total amount of the polyorganosylsesquioxane of this disclosure and other cationic curable compounds described later. By setting the content of the curing catalyst to 0.01 parts by weight or more, the curing reaction can be carried out efficiently and sufficiently, and the surface hardness and adhesion 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 shelf life of the curable composition tends to be further improved and discoloration of the cured product tends to be suppressed.

[0147] The curable compositions of this disclosure may further contain cationic curable compounds other than the polyorganosylsesquioxanes of this disclosure (sometimes referred to as "other cationic curable compounds") and / or radical curable compounds other than the polyorganosylsesquioxanes of this disclosure (sometimes referred to as "other radical curable compounds"). Other cationic curable compounds may include known or conventional cationic curable compounds, such as epoxy compounds other than the polyorganosylsesquioxanes of this disclosure, oxetane compounds, vinyl ether compounds, etc. In the curable compositions of this disclosure, the other cationic curable compounds may be used individually or in combination of two or more.

[0148] The epoxy compounds mentioned above can be known or conventional compounds having one or more epoxy groups (oxirane rings) in their molecules, and are not particularly limited. Examples include alicyclic epoxy compounds (alicyclic epoxy resins), aromatic epoxy compounds (aromatic epoxy resins), and aliphatic epoxy compounds (aliphatic epoxy resins).

[0149] Examples of the above-mentioned alicyclic epoxy compounds include, but are not limited to, known or conventional compounds having one or more alicyclic rings and one or more epoxy groups in their molecule. Examples include: (1) compounds having an epoxy group composed of two adjacent carbon atoms and an oxygen atom constituting an alicyclic ring (referred to as an "alicyclic epoxy group") in their molecule; (2) compounds in which an epoxy group is directly bonded to an alicyclic ring by a single bond; and (3) compounds having an alicyclic ring and a glycidyl ether group in their molecule (glycidyl ether type epoxy compounds).

[0150] Examples of compounds having an alicyclic epoxy group in the molecule mentioned above (1) include compounds represented by the following formula (i). [ka]

[0151] In formula (i) above, Y represents a single bond or a linking group (a divalent group having one or more atoms). Examples of such linking groups include divalent hydrocarbon groups, alkenylene groups in which part or all of the carbon-carbon double bonds are epoxidized, carbonyl groups, ether bonds, ester bonds, carbonate groups, amide groups, and groups formed by linking multiple such groups.

[0152] Examples of the above-mentioned divalent hydrocarbon groups include linear or branched alkylene groups having 1 to 18 carbon atoms, and divalent alicyclic hydrocarbon groups. Examples of linear or branched alkylene groups having 1 to 18 carbon atoms include methylene groups, methylmethylene groups, dimethylmethylene groups, ethylene groups, propylene groups, and trimethylene groups. Examples of the above-mentioned divalent alicyclic hydrocarbon groups include divalent cycloalkylene groups (including cycloalkylidene groups) such as 1,2-cyclopentylene groups, 1,3-cyclopentylene groups, cyclopentylidene groups, 1,2-cyclohexylene groups, 1,3-cyclohexylene groups, 1,4-cyclohexylene groups, and cyclohexylidene groups.

[0153] Examples of alkenylene groups in which part or all of the carbon-carbon double bonds are epoxidized (sometimes referred to as "epoxidized alkenylene groups") include linear or branched alkenylene groups having 2 to 8 carbon atoms, such as vinylene groups, propenylene groups, 1-butenylene groups, 2-butenylene groups, butadienylene groups, pentenylene groups, hexenylene groups, heptenylene groups, and octenylene groups. Preferably, the epoxidized alkenylene group is an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, and more preferably, an alkenylene group having 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized.

[0154] Typical examples of alicyclic epoxy compounds represented by formula (i) above include (3,4,3',4'-diepoxy)bicyclohexyl and compounds represented by the following formulas (i-1) to (i-10). In formulas (i-5) and (i-7) below, l and m represent integers from 1 to 30, respectively. In formula (i-5) below, R' is an alkylene group having 1 to 8 carbon atoms, and among these, linear or branched alkylene groups having 1 to 3 carbon atoms, such as methylene, ethylene, propylene, and isopropylene groups, are preferred. In formulas (i-9) and (i-10) below, n1 to n6 represent integers from 1 to 30, respectively. Other examples of alicyclic epoxy compounds represented by formula (i) above include 2,2-bis(3,4-epoxycyclohexyl)propane, 1,2-bis(3,4-epoxycyclohexyl)ethane, 2,3-bis(3,4-epoxycyclohexyl)oxirane, and bis(3,4-epoxycyclohexylmethyl)ether. [ka] [ka]

[0155] Examples of compounds in which an epoxy group is directly bonded to the alicyclic ring by a single bond include, for example, the compound represented by the following formula (ii). [ka]

[0156] In formula (ii), R'' is the 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 are natural numbers. p-valent alcohol [R''(OH) pExamples of polyhydric alcohols (alcohols with 1 to 15 carbon atoms, etc.) such as 2,2-bis(hydroxymethyl)-1-butanol are used. p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or greater, the n in each group in parentheses (in the outer brackets) may be the same or different. Specific examples of compounds represented by the above formula (ii) include the 1,2-epoxy-4-(2-oxyranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol [for example, trade name "EHPE3150" (manufactured by Daicel Corporation)].

[0157] As mentioned above, (3) compounds having alicyclic and glycidyl ether groups in the molecule include, for example, glycidyl ethers of alicyclic alcohols (e.g., alicyclic polyhydric alcohols). More specifically, for example, hydrogenated compounds of 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); bis[o,o-(2,3-epoxypropoxy)cyclohexyl]methane, bis[o,p-(2,3-epoxypropoxy)cyclohexyl]methane, bis[p,p-(2,3-epoxypropoxy)cyclohexyl]methane, bis[3,5-dimethyl Examples include hydrogenated compounds of bisphenol F type epoxy compounds such as -4-(2,3-epoxypropoxy)cyclohexyl]methane (hydrogenated bisphenol F type epoxy compounds); hydrogenated biphenol type epoxy compounds; hydrogenated phenol novolac type epoxy compounds; hydrogenated cresol novolac type epoxy compounds; hydrogenated cresol novolac type epoxy compounds of bisphenol A; hydrogenated naphthalene type epoxy compounds; hydrogenated epoxy compounds of epoxy compounds obtained from trisphenolmethane; and hydrogenated epoxy compounds of the following aromatic epoxy compounds.

[0158] Examples of the above aromatic epoxy compounds include epibis-type glycidyl ether epoxy resins obtained by the condensation reaction of bisphenols with epihalohydrins; high molecular weight epibis-type glycidyl ether epoxy resins obtained by further addition reactions of these epibis-type glycidyl ether epoxy resins with the above bisphenols; novolac alkyl-type glycidyl ether epoxy resins obtained by further condensation reactions of polyhydric alcohols obtained by the condensation reaction of phenols and aldehydes with epihalohydrins; and epoxy compounds in which two phenol skeletons are bonded to the 9th position of a fluorene ring, and glycidyl groups are bonded directly or via alkylene oxy groups to the oxygen atoms obtained by removing hydrogen atoms from the hydroxyl groups of these phenol skeletons.

[0159] Examples of the above-mentioned aliphatic epoxy compounds include glycidyl ethers of alcohols (where q is a natural number) that do not have a cyclic structure with a q-valence; glycidyl esters of monovalent or polyvalent carboxylic acids; epoxides of oils and fats having double bonds, such as epoxides of linseed oil, epoxides of soybean oil, and epoxides of castor oil; and epoxides of polyolefins (including polyalkadienes), such as epoxides of polybutadiene.

[0160] Examples of the oxetane compounds include known and conventional compounds having one or more oxetane rings in their molecules. Examples of the vinyl ether compounds include known and conventional compounds having one or more vinyl ether groups in their molecules.

[0161] Other radical-curable compounds can be known or conventional radical-curable compounds, and are not particularly limited, but examples include (meth)acrylic compounds other than the polyorganosylsesquioxanes of this disclosure. Examples of the above (meth)acrylic compounds include known or conventional compounds having one or more (meth)acrylic groups in the molecule.

[0162] The content (amount) of other cationic curable compounds and / or other radical curable compounds in the curable composition of this disclosure is not particularly limited, but is preferably 50% by weight or less (e.g., 0 to 50% by weight), more preferably 30% by weight or less (e.g., 0 to 30% by weight), and even more preferably 10% by weight or less, based on the total amount (100% by weight; total amount of cationic curable compounds and radical curable compounds) of the polyorganosylsesquioxane, other cationic curable compounds and other radical curable compounds of this disclosure.

[0163] The curable composition of this disclosure may further contain a polymerization stabilizer. The polymerization stabilizer is a compound that inhibits the progress of cationic polymerization by trapping cations, and allows polymerization to proceed when the cation-trapping ability of the polymerization stabilizer is saturated and deactivated. By containing a polymerization stabilizer, the curable composition of this disclosure can suppress the progress of polymerization over a long period of time after coating and drying to form an adhesive layer, and can form an adhesive layer with excellent storage stability that exhibits excellent adhesion when heated at the timing when adhesion is required. When the curable composition of this disclosure is a curable composition for adhesives, it is preferable that it contains a polymerization stabilizer.

[0164] Examples of the polymerization stabilizers mentioned above 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]), and tetrakis(2,2,6,6-tetramethyl-4-piperidyl)butane-1,2,3,4-tetracarbocyanide. Silate, 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 Examples include hindered amine compounds such as ru-4-piperidyl)imino]propionamide, trade names "LA-77", "LA-67", "LA-57" (all manufactured by ADEKA Corporation), trade names "TINUVIN123", "TINUVIN152" (both manufactured by Ciba Japan Co., Ltd.), sulfonium sulfate compounds such as (4-hydroxyphenyl)dimethylsulfonium methyl sulfite (for example, trade name "San-Aid SI Auxiliary Agent", manufactured by Sanshin Chemical Industry Co., Ltd.), and phosphite compounds such as trade name "ADEKA Stab PEP-36" (manufactured by ADEKA Corporation). Among these, sulfonium sulfate compounds and phosphite compounds are preferred from the viewpoint of making partial hardening during the drying of the adhesive less likely and providing superior adhesion of the cured product to the adherend.

[0165] The polymerization stabilizers described above may be used individually or in combination of two or more. In the curable adhesive composition of this disclosure, it is preferable to contain two or more polymerization stabilizers. This significantly improves the storage stability of the curable adhesive composition, further reduces the likelihood of partial curing during the drying of the adhesive, and tends to improve the adhesion of the cured product to the adherend. It is preferable that the two or more polymerization stabilizers include at least a sulfonium sulfate compound and a phosphite compound.

[0166] When the curable composition of this disclosure contains the above-mentioned polymerization stabilizer, the content (amount blended) is not particularly limited, but is preferably 0.005 parts by weight or more, more preferably 0.01 to 10 parts by weight, and more preferably 0.02 to 1 part by weight, per 100 parts by weight of the polyorganosilsesquioxane of this disclosure (or, if other cationic curable compounds are included, the total amount of polyorganosilsesquioxane and other cationic curable compounds). When the above content is 0.005 parts by weight or more, partial curing during drying of the adhesive is less likely to occur, and the adhesion of the cured product to the adherend tends to be better. When two or more polymerization stabilizers are used, the total amount of polymerization stabilizers is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 1 part by weight, per 100 parts by weight of the polyorganosilsesquioxane of this disclosure (or, if other cationic curable compounds are included, the total amount of polyorganosilsesquioxane and other cationic curable compounds).

[0167] When the curable composition of this disclosure contains the above-mentioned polymerization stabilizer and curing catalyst, the content (amount blended) of the polymerization stabilizer is not particularly limited, but is preferably 1 part by weight or more, more preferably 3 to 200 parts by weight, and even more preferably 5 to 150 parts by weight, per 100 parts by weight of the curing catalyst. When the above content is 1 part by weight or more, partial curing during the drying of the adhesive is less likely to occur, and the adhesion of the cured product to the adherend tends to be better. When two or more polymerization stabilizers are used, the total amount of polymerization stabilizers is preferably 100 to 200 parts by weight, and more preferably 110 to 150 parts by weight, per 100 parts by weight of the curing catalyst.

[0168] The curable composition of this disclosure may preferably further contain a solvent. Examples of solvents include water, organic solvents, etc., and are not particularly limited as long as they can dissolve the polyorganosilsesquioxane of this disclosure and any additives used as needed, and do not inhibit polymerization.

[0169] It is preferable to use one or more solvents with a boiling point (at 1 atmosphere) 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.).

[0170] The solvent should be used in an appropriate amount depending on the application of the curable composition. The amount of solvent used is, for example, about 30 to 80% by weight, preferably 40 to 70% by weight, and more preferably 50 to 60% by weight, as a concentration of nonvolatile matter contained in the curable composition of this disclosure. If the amount of solvent used is excessive, the viscosity of the curable composition tends to become low, making it difficult to form a layer of an appropriate thickness. On the other hand, if the amount of solvent used is too little, the viscosity of the curable composition tends to become too high, making it difficult to apply uniformly.

[0171] The curable composition of this disclosure further includes, as any other optional component, 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, and boron nitride; inorganic fillers obtained by treating these fillers with organosilicon compounds such as organohalosilane, organoalkoxysilane, and organosilazane; and silicone resin. The product may contain conventional additives such as fine organic resin powders like epoxy resins and fluororesins; fillers such as silver and copper powders; curing aids; stabilizers; flame retardants; flame retardant aids; reinforcing agents; nucleating agents; lubricants; waxes; plasticizers; mold release agents; impact resistance modifiers; color modifiers; transparency agents; rheology modifiers; processability modifiers; colorants; antistatic agents; dispersants; surface modifiers; surface modifiers; matting agents; defoaming agents; antifoaming agents; antifungal agents; preservatives; viscosity modifiers; thickeners; photosensitizers; and foaming agents. These additives may be used individually or in combination of two or more.

[0172] The curable compositions of this disclosure are not particularly limited, but can be prepared by stirring and mixing each of the above components at room temperature or, if necessary, while heating. The curable compositions of this disclosure can be used as a one-component composition in which the components are pre-mixed and used as is, or they can be used as a multi-component (e.g., two-component) composition in which two or more components that have been stored separately are mixed in a predetermined ratio before use.

[0173] The curable composition of this disclosure is not particularly limited, but is preferably a liquid at room temperature (about 25°C). More specifically, the curable composition of this disclosure, when diluted in 20% solvent [for example, a curable composition (solution) in which the proportion of methyl isobutyl ketone is 20% by weight], preferably has a viscosity of 300 to 20,000 mPa·s at 25°C, more preferably 500 to 10,000 mPa·s, and even more preferably 1,000 to 8,000 mPa·s. Setting the viscosity to 300 mPa·s or higher tends to further improve the heat resistance of the cured product. On the other hand, setting the viscosity to 20,000 mPa·s or lower makes the preparation and handling of the curable composition easier, and tends to reduce the likelihood of air bubbles remaining in the cured product. The viscosity of the curable composition disclosed herein is measured using a viscometer (product name "MCR301," manufactured by Anton Paar) under the following conditions: amplitude 5%, frequency 0.1-100 (1 / s), and temperature 25°C.

[0174] [Cured product] The curable composition can be cured by allowing a polymerization reaction of a cationic curable compound or a radical curable compound in the curable composition of this disclosure to proceed, thereby obtaining a cured product (sometimes referred to as "the cured product of this disclosure"). The curing method can be appropriately selected from well-known methods and is not particularly limited, but examples include irradiation with active energy rays and / or heating. As the active energy rays, for example, infrared rays, visible light, ultraviolet rays, X-rays, electron beams, alpha rays, beta rays, gamma rays, etc., can be used. Among these, ultraviolet rays are preferred in terms of their ease of handling.

[0175] The conditions for curing the curable composition of this disclosure by irradiation with active energy rays (irradiation conditions for active energy rays, etc.) 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, but when irradiating with ultraviolet light, for example, 1 to 1000 mJ / cm² 2It is preferable to maintain a certain degree of intensity. For irradiation with active energy rays, for example, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, carbon arcs, metal halide lamps, sunlight, LED lamps, lasers, etc., can be used. After irradiation with active energy rays, further heat treatment (annealing, aging) can be applied to further advance the hardening reaction.

[0176] On the other hand, the conditions for curing the curable composition of this disclosure by heating are not particularly limited, but are preferably 30 to 200°C, and more preferably 50 to 190°C. The curing time can be set as appropriate.

[0177] As described above, the curable composition of this disclosure, when cured, can form a cured product with high surface hardness and heat resistance, as well as excellent flexibility and processability. Therefore, the curable composition of this disclosure can be preferably used as a "curable composition for forming a hard coat layer" (sometimes referred to as "hard coat liquid" or "hard coat agent") for forming a hard coat layer in a hard coat film, or as an adhesive for multilayer semiconductors. When the curable composition of this 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 maintains high hardness and high heat resistance while being flexible, making it suitable for roll-to-roll manufacturing and processing. Furthermore, when the curable composition of this disclosure is used as an adhesive curable composition, it can cure at low temperatures and form a cured product with excellent crack resistance, heat resistance, adhesion to the adherend, and bonding properties. Therefore, even when subjected to thermal shock, cracks or peeling will not occur in the adhesive layer, making it possible to form a reliable device.

[0178] Furthermore, the curable composition of this disclosure has a tack-free surface on the uncured or semi-cured hard coat layer applied and dried on a release layer provided on a substrate, improving blocking resistance, making it possible to handle it by winding it into a roll. Moreover, by transferring and curing the hard coat layer on the surface of a molded product, a hard coat layer with high surface hardness can be formed. Therefore, the curable composition of this disclosure can also be preferably used as a hard coat layer forming composition for forming a hard coat layer with excellent flexibility.

[0179] [Hard coat film] The hard coat film of this disclosure is a hard coat film comprising a substrate and a hard coat layer formed on at least one surface of the substrate, wherein the hard coat layer is a hard coat layer (cured layer of the curable composition of this disclosure) formed by the curable composition of this disclosure (curable composition for forming a hard coat layer). Figure 9 is a schematic diagram (cross-sectional view) showing one embodiment of the hard coat film of this disclosure. 1 represents the hard coat film, 11 represents the hard coat layer, and 12 represents the substrate.

[0180] Furthermore, the hard coat layer in the hard coat film of this disclosure may be formed on only one surface (one side) of the substrate, or on both surfaces (both sides).

[0181] Furthermore, the hard coat layer in the hard coat film of this disclosure may be formed only on a portion of each surface of the substrate, or it may be formed on the entire surface.

[0182] In the hard coat film of this disclosure, the substrate refers to the substrate of the hard coat film, specifically the portion other than the hard coat layer. The substrate can be a known or conventional substrate such as a plastic substrate, a metal substrate, a ceramic substrate, a semiconductor substrate, a glass substrate, a paper substrate, a wood substrate (wooden substrate), or a substrate whose surface is a painted surface, and is not particularly limited. Among these, a plastic substrate (a substrate made of plastic material) is preferred.

[0183] The plastic materials constituting the above-mentioned plastic substrate are not particularly limited, but examples include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyimides; polycarbonates; polyamides; polyacetals; polyphenylene oxides; polyphenylene sulfides; polyethersulfones; polyetheretherketones; homopolymers of norbornene monomers (addition polymers, ring-opening polymers, etc.); copolymers of norbornene monomers and olefin monomers (cyclic olefin copolymers such as addition polymers, ring-opening polymers, etc.), and derivatives thereof; cyclic polyolefins; vinyl polymers (e.g., acrylic resins such as polymethyl methacrylate (PMMA), polystyrene, polyvinyl chloride, acrylonitrile-styrene-butadiene resin (ABS resin), etc.); vinylidene polymers (e.g., polyvinylidene chloride, etc.); cellulose resins such as triacetylcellulose (TAC); epoxy resins; phenolic resins; melamine resins; urea resins; maleimide resins; and various other plastic materials such as silicones. The above-mentioned plastic substrate may be composed of only one type of plastic material, or it may be composed of two or more types of plastic materials.

[0184] In particular, when the objective is to obtain a hard coat film with excellent transparency as the hard coat film of this disclosure, it is preferable to use a transparent substrate as the plastic substrate, and more preferably a polyester film (e.g., PET, PEN), a cyclic polyolefin film, a polycarbonate film, a TAC film, or a PMMA film.

[0185] The above-mentioned plastic substrate may contain other additives as needed, such as antioxidants, UV absorbers, light stabilizers, heat stabilizers, crystal nucleating agents, flame retardants, flame retardant aids, fillers, plasticizers, impact modifiers, reinforcing agents, dispersants, antistatic agents, foaming agents, and antibacterial agents. Note that one additive may be used alone, or two or more may be used in combination.

[0186] The above-mentioned plastic substrate may have a single-layer structure or a multi-layer (laminate) 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 this 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 this disclosure. Examples of materials constituting the above-mentioned other layer include the plastic materials mentioned above.

[0187] The surface of the above-mentioned plastic substrate may be partially or entirely subjected to known or conventional surface treatments such as roughening, easy adhesion treatment, antistatic treatment, sandblasting (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, or silane coupling agent treatment. The above-mentioned plastic substrate may be an unstretched film or a stretched film.

[0188] The above-mentioned plastic substrate can be manufactured by known or conventional methods, such as, for example, forming the above-mentioned plastic material into a film to form a plastic substrate (plastic film), or, if necessary, forming an appropriate layer (for example, the other layers mentioned above) on the plastic film or applying an appropriate surface treatment. Commercially available products can also be used as the above-mentioned plastic substrate.

[0189] The thickness of the above-mentioned substrate is not particularly limited, but can be appropriately selected from, for example, a range of 0.01 to 10000 μm.

[0190] The hard coat layer in the hard coat film of the present disclosure is a layer constituting at least one surface layer of the hard coat film of the present disclosure, and is a layer (cured product layer) formed by curing a curable product (resin cured product) obtained by curing the curable composition (curable composition for forming a hard coat layer) of the present disclosure.

[0191] The thickness of the hard coat layer in this disclosure (or the thickness of each hard coat layer if the substrate has hard coat layers on both sides) is not particularly limited, but is preferably 1 to 200 μm, and more preferably 3 to 150 μm. Even when the hard coat layer in this disclosure is thin (for example, with a thickness of 5 μm or less), it is possible to maintain high surface hardness (for example, a pencil hardness of 3H or higher). Furthermore, even when it is thick (for example, with a thickness of 50 μm or more), problems such as crack formation due to hardening shrinkage are less likely to occur, making it possible to significantly increase the pencil hardness by increasing the film thickness (for example, a pencil hardness of 9H or higher).

[0192] The haze of the hard coat layer is not particularly limited, but is preferably 1.5% or less, and more preferably 1.0% or less, for a thickness of 50 μm. 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, it tends to be suitable for use in applications where very high transparency is required (for example, surface protective sheets for displays such as touch panels). The haze of the hard coat layer of this disclosure can be measured in accordance with JIS K7136.

[0193] The total light transmittance of the hard coat layer is not particularly limited, but is preferably 85% or higher, and more preferably 90% or higher, for a thickness of 50 μm. The upper limit of the total light transmittance is not particularly limited, but is, for example, 99%. A total light transmittance of 85% or higher tends to make it suitable for applications requiring very high transparency (e.g., surface protective sheets for displays such as touch panels). The total light transmittance of the hard coat layer of this disclosure can be measured in accordance with JIS K7361-1.

[0194] The hard coat film of this disclosure may further have a surface protective film on the surface of the hard coat layer of this disclosure. The presence of a surface protective film in the hard coat film of this disclosure tends to further improve the die-cutting processability of the hard coat film. When such a surface protective film is present, for example, even if the hard coat layer has very high hardness and is prone to peeling or cracking from the substrate during die-cutting, die-cutting using a Thomson blade can be performed without causing such problems. As the surface protective film, known or conventional surface protective films can be used.

[0195] The hard coat film of this disclosure can be manufactured in accordance with known or conventional methods for manufacturing hard coat films, and the manufacturing method is not particularly limited. For example, it can be manufactured by applying the curable composition of this disclosure (curable composition for forming a hard coat layer) to at least one surface of the substrate, removing the solvent by drying as necessary, and then curing the curable composition (curable composition layer). The conditions for curing the curable composition are not particularly limited and can be appropriately selected from, for example, the conditions for forming the cured product described above.

[0196] The hard coat layer in the hard coat film of this disclosure is formed from a curable composition of this disclosure (curable composition for hard coat layer formation) that can form a cured product with excellent flexibility and processability. Therefore, the hard coat film of this disclosure can be manufactured using a roll-to-roll method. By manufacturing the hard coat film of this disclosure using a roll-to-roll method, its productivity can be significantly increased. A known or conventional roll-to-roll manufacturing method can be used to produce the hard coat film of this disclosure, and is not particularly limited. For example, a method can be used that includes, as essential steps, a step of unwinding a substrate wound on a roll (step A), a step of applying the curable composition of this disclosure (curable composition for forming a hard coat layer) to at least one surface of the unwinding substrate, then, if necessary, removing the solvent by drying, and then curing the curable composition (curable composition layer) to form the hard coat layer of this disclosure (step B), and then winding the obtained hard coat film back onto a roll (step C), and these steps (steps A to C) are carried out in a continuous manner. Note that this method may also include steps other than steps A to C.

[0197] The thickness of the hard coat film of this disclosure is not particularly limited and can be appropriately selected from the range of 1 to 10,000 μm.

[0198] The pencil hardness of the hard coat layer surface of the hard coat film disclosed herein is preferably 4H or higher, more preferably 5H or higher, and even more preferably 6H or higher. The pencil hardness can be evaluated in accordance with the method described in JIS K5600-5-4.

[0199] The haze of the hard coat film disclosed herein is not particularly limited, but is preferably 1.5% or less, and 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, the film tends to be suitable for use in applications requiring very high transparency (for example, surface protective sheets for displays such as touch panels). The haze of the hard coat film disclosed herein can be easily controlled to the above range, for example, by using the transparent substrate described above as the base material. The haze can be measured in accordance with JIS K7136.

[0200] The total light transmittance of the hard coat film disclosed herein is not particularly limited, but is preferably 85% or higher, and more preferably 90% or higher. The upper limit of the total light transmittance is not particularly limited, but is, for example, 99%. A total light transmittance of 90% or higher tends to make the film suitable for applications requiring very high transparency (e.g., surface protective sheets for displays such as touch panels). The total light transmittance of the hard coat film disclosed herein can be easily controlled to the above range, for example, by using the transparent substrate described above as the base material. The total light transmittance can be measured in accordance with JIS K7361-1.

[0201] The hard coat film of this disclosure is flexible while maintaining high hardness and high heat resistance, and can be manufactured and processed using a roll-to-roll method, thus possessing high quality and excellent productivity. When a surface protective film is present on the surface of the hard coat layer of this disclosure, it also exhibits excellent die-cutting properties. For this reason, it can be preferably used in any application where such properties are required. The hard coat film of this disclosure can be used, for example, as a surface protective film on various products, a surface protective film on components or parts of various products, or as a component of various products or their components or parts. Examples of such products include display devices such as liquid crystal displays and organic EL displays; input devices such as touch panels; solar cells; various home appliances; various electrical and electronic products; various electrical and electronic products such as portable electronic terminals (e.g., game consoles, personal computers, tablets, smartphones, mobile phones, etc.); and various optical instruments. Furthermore, an example of how the hard coat film of this disclosure can be used as a component of various products or their components or parts is its use in a laminate of a hard coat film and a transparent conductive film in a touch panel.

[0202] [Transfer film] The transfer film (transfer hard coat film) of this disclosure is a film having a substrate and an uncured or semi-cured hard coat layer on a release layer formed on at least one surface of the substrate, wherein the uncured or semi-cured hard coat layer is a layer containing the curable composition of this disclosure (curable composition for hard coat layer formation (hereinafter sometimes referred to as "hard coat agent of this disclosure"). Here, "uncured" means a state in which the polymerizable functional groups of the polyorganosilsesquioxane of this disclosure contained in the hard coat layer formation curable composition (hard coat agent) of this disclosure have not undergone polymerization. Furthermore, "semi-cured" means a state in which the polymerizable functional groups of the polyorganosilsesquioxane contained in the hard coat layer formation curable composition (hard coat agent) of this disclosure have not undergone polymerization. This means that some polymerizable functional groups have undergone polymerization, while unreacted polymerizable functional groups remain. In this specification, an uncured or semi-cured hard coat layer formed by the curable composition (hard coat agent) of this disclosure may be simply referred to as the "hard coat layer," and a hard coat layer transferred and cured onto a molded product may be referred to as the "cured hard coat layer." Figure 10 is a schematic diagram (cross-sectional view) showing one embodiment of the transfer film of this disclosure. 2 is the transfer film, 21 is the substrate, 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.

[0203] In the transfer film of this disclosure, the substrate refers to the substrate of the transfer film, excluding the transfer layer which includes the hard coat layer of this disclosure. Here, the transfer layer refers to the layer in the transfer film of this disclosure excluding the substrate on which the release layer is formed, and which is transferred to the surface of the molded product.

[0204] As the substrate mentioned above, any of the substrates listed for the hard coat film can be used, but a plastic substrate (plastic film) is particularly preferred. The thickness of the substrate can be appropriately selected from, for example, a range of 0.01 to 10000 μm, but from the viewpoint of moldability, shape conformability, and handling, 2 to 250 μm is preferred, 5 to 100 μm is more preferred, and 20 to 100 μm is even more preferred.

[0205] The release layer in the transfer film of this disclosure is a layer that constitutes at least one surface layer of the substrate in the transfer film of this disclosure, and is provided to facilitate the peeling of the transfer layer from the substrate. By providing a release layer, the transfer layer can be reliably and easily transferred from the transfer film to the object to be transferred (molded product), and the substrate can be reliably peeled off.

[0206] In the transfer film of this 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 even more preferably 50 to 200 mN / 24 mm. Having a peel strength within this range allows the hard coat layer to be easily peeled off simultaneously with the transfer to the molded product without peeling during normal handling. The peel strength between the hard coat layer and the release layer of this disclosure can be measured in accordance with JIS Z0237.

[0207] Furthermore, the release layer in the transfer film of this disclosure may be formed on only one surface (one side) of the substrate, or on both surfaces (both sides). Also, the release layer in the transfer film of this disclosure may be formed on only a portion of each surface of the substrate, or on the entire surface.

[0208] As components for forming the release layer, any known and publicly available 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, fluororesins, cellulose resins, urea resins, polyolefin resins, paraffin resins, and cycloolefin resins can be used. From the viewpoint of releaseability between the release layer and the hard coat layer of this disclosure that is in contact with the release layer in the transfer layer, melamine resins and cycloolefin resins are preferred as the release layer, and cycloolefin copolymer resins (COC resins) such as 2-norbornene-ethylene copolymers are more preferred.

[0209] The method for forming the release layer on the substrate surface can also be any known and publicly used release treatment method without particular limitation. For example, the resin can be dispersed or dissolved in a solvent (e.g., alcohols such as methanol and butanol, aromatic hydrocarbons such as toluene and xylene, tetrahydrofuran, etc.), coated and dried using a known coating method such as bar coating, Meyer bar coating, gravure coating, or roll coating, and then heated at 80 to 200°C to form the release layer. The thickness of the release layer is also not particularly limited and can usually be selected from a range of 0.01 to 5 μm, preferably 0.1 to 3.0 μm.

[0210] The hard coat layer in the transfer film of this disclosure is a layer constituting at least one surface layer of the release layer, and is either an uncured layer obtained by drying the curable composition (hard coat agent) of this disclosure, or a partially cured layer. The partially cured hard coat layer can be formed by partially curing the uncured hard coat layer by the above-mentioned active energy ray irradiation or heating. The uncured or partially cured hard coat layer of this disclosure has low tackiness and excellent blocking resistance, preventing resin from adhering when a finger is brought into contact with the surface, and can be handled by winding it into a roll.

[0211] Furthermore, the hard coat layer in the transfer film of this disclosure may be formed on only one release layer (one side) of the substrate, or on both release layers (both sides). Also, the hard coat layer in the transfer film of this disclosure may be formed on only a portion of each surface of the release layer, or on the entire surface.

[0212] The method for laminating a hard coat layer on the release layer of the transfer film of this disclosure is not particularly limited, but includes methods such as coating and drying the curable composition (hard coat agent) of this disclosure on the release layer using a known method to form an uncured hard coat layer, or further irradiating the uncured hard coat layer with activation energy rays or heating it to form a semi-cured hard coat layer. The coating method for the curable composition (hard coat agent) of this disclosure can be any known coating method without limitation, such as bar coater coating, Meyer bar coating, air knife coating, gravure coating, offset printing, flexographic printing, screen printing, etc. The heating temperature when forming the hard coat layer is not particularly limited, but can preferably be appropriately selected from 50 to 200°C. The heating time is also not particularly limited, but can preferably be appropriately selected from 1 to 60 minutes. The conditions for irradiating the hard coat layer with activation energy rays are not particularly limited and can be appropriately selected from, for example, the conditions for forming the cured product described above.

[0213] The thickness of the hard coat layer in the transfer film of this disclosure (or the thickness of each hard coat layer if the substrate has hard coat layers on both sides) is not particularly limited, but is preferably 1 to 200 μm, and 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 high surface hardness (for example, to achieve a pencil hardness of 5H or higher). Furthermore, even when the hard coat layer is thick (for example, when the thickness is 50 μm or more), problems such as crack formation due to hardening shrinkage are less likely to occur, making it possible to significantly increase the pencil hardness by increasing the film thickness (for example, to achieve a pencil hardness of 9H or higher).

[0214] The haze of the hard coat layer in the transfer film of this disclosure is not particularly limited, but is preferably 1.5% or less, and more preferably 1.0% or less, for a thickness of 50 μm. The lower limit of the haze is not particularly limited, but is, for example, 0.1%. A haze of 1.0% or less is preferable because, for example, when the transfer film of this disclosure is used as a decorative film, patterns, designs, etc., can be transferred clearly. The haze of the hard coat layer of this disclosure can be measured in accordance with JIS K7136.

[0215] The total light transmittance of the hard coat layer in the transfer film of this disclosure is not particularly limited, but is preferably 85% or more, and more preferably 90% or more, for a thickness of 50 μm. The upper limit of the total light transmittance is not particularly limited, but is, for example, 99%. A total light transmittance of 85% or more is preferable because, for example, when the transfer film of this disclosure is used as a decorative film, patterns, designs, etc., can be transferred clearly. The total light transmittance of the hard coat layer of this disclosure can be measured in accordance with JIS K7361-1.

[0216] The transfer film of this disclosure preferably has an anchor coat layer and an adhesive layer further laminated on a hard coat layer in that order. Furthermore, when the transfer film of this disclosure is used as a decorative film, at least one colored layer is laminated. The position of the laminated colored layer is not particularly limited, but preferably it is laminated between the anchor coat layer and the adhesive layer, with one or more layers.

[0217] The anchor coat layer in the transfer film of this disclosure is provided to improve the adhesion between the hard coat layer and the adhesive layer or colored layer, etc. The anchor coat layer is preferably transparent or translucent in order to clearly transfer the patterns, designs, etc. of the colored layer, and is made of phenolic resin, alkyd resin, melamine resin (e.g., methylated melamine resin, butylated melamine resin, methyl etherified melamine resin, butyl etherified melamine resin, methyl butyl mixed etherified melamine resin, etc.), epoxy resin (e.g., bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyfunctional epoxy resin, flexible epoxy resin, brominated epoxy resin, glycidyl ester type epoxy resin, polymer type epoxy resin, biphenyl type epoxy resin, etc.), urea resin, unsaturated polyester resin, urethane resin [e.g., One or more of the following can be used as a thermosetting resin, such as a urethane resin obtained by reacting a polyisocyanate compound (O=C=NRN=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, thermosetting resins such as thermosetting polyimides and silicone resins, or thermoplastic resins such as vinyl chloride-vinyl acetate copolymer resins, acrylic resins (e.g., acrylic polyol resins), chlorinated rubber, polyamide resins, nitrated cotton resins, and cyclic polyolefin resins, but epoxy resins are preferred.

[0218] The above-mentioned anchor coating resin may further contain, as an optional component, conventional additives such as waxes, silica, plasticizers, leveling agents, surfactants, dispersants, defoamers, UV absorbers, UV stabilizers, and antioxidants, to the extent that they do not impair the effects of the disclosure. These additives can be used individually or in combination of two or more.

[0219] The anchor coat layer can be formed by applying a coating solution, obtained by dissolving the above-mentioned resin in a solvent, onto the hard coat layer of this disclosure using a known coating method such as bar coating, Meyer bar coating, gravure coating, or roll coating, drying it, and heating it as necessary. The temperature at which the anchor coat layer is formed is not particularly limited, but can be appropriately selected from 50 to 200°C. The heating time is also not particularly limited, but can be appropriately selected from 10 seconds to 60 minutes.

[0220] The thickness of the anchor coat layer is typically around 0.1 to 20 μm, preferably in the range of 0.5 to 5 μm.

[0221] The anchor coat layer of this disclosure may be formed using a commercially available anchor coat agent. Examples of commercially available anchor coat agents include K468HP Anchor (an epoxy resin-based anchor coat agent manufactured by Toyo Ink Co., Ltd.) and TM-VMAC (an acrylic polyol resin-based anchor coat agent manufactured by Dainichi Seika Kogyo Co., Ltd.).

[0222] The adhesive layer in the transfer film of this disclosure is provided to transfer the transfer layer (including a hard coat layer, an optionally laminated anchor coat layer, and a colored layer) to a molded product with good adhesion. Examples of adhesive layers include heat-sensitive adhesives and pressure adhesives, but in this disclosure, it is preferable that the adhesive layer is a heat-seal layer that exhibits adhesion to the molded product by heating and pressurizing as needed. Examples of resins used in the adhesive layer include acrylic resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, styrene-acrylic copolymer resins, polyester resins, and polyamide resins, either alone or in mixtures of two or more, but acrylic resins and vinyl chloride-vinyl acetate copolymer resins are preferred.

[0223] Examples of acrylic resins used in the adhesive layer of this 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, as well as acrylic resins modified with fluorine, etc., and these can be used individually or as a mixture of two or more. In addition, acrylic polyols obtained by copolymerizing alkyl (meth)acrylate esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and octyl (meth)acrylate with (meth)acrylate 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 used. Furthermore, as vinyl chloride-vinyl acetate copolymer resins, those typically used have a vinyl acetate content of about 5 to 20% by mass and an average degree of polymerization of about 350 to 900. If necessary, carboxylic acids such as maleic acid and fumaric acid may be further copolymerized into the vinyl chloride-vinyl acetate copolymer resin. In addition, as a secondary component resin, other resins may be mixed as appropriate, such as thermoplastic polyester resins, thermoplastic urethane resins, chlorinated polyethylene, chlorinated polyolefin resins such as chlorinated polypropylene, etc.

[0224] The adhesive layer can be formed by applying and drying, and optionally heating, a solution or emulsion of one or more of the above-mentioned resins in an applicable form using a known coating method such as bar coating, Meyer bar coating, gravure coating, or roll coating. The temperature used when heating to form the adhesive layer can be appropriately selected from 50 to 200°C, and the heating time can be appropriately selected from 10 seconds to 60 minutes.

[0225] The thickness of the adhesive layer is preferably about 0.1 to 10 μm, and more preferably 0.5 to 5 μm, from the standpoint of being able to transfer the transfer film to the molded product with good adhesion and efficiency.

[0226] The adhesive layer may contain organic UV absorbers such as benzophenone compounds, benzotriazole compounds, oxalic acid anilide compounds, cyanoacrylate compounds, and salicylate compounds, as well as additives of inorganic UV-absorbing fine particles such as oxides of zinc, titanium, cerium, tin, and iron. In addition, coloring pigments, whitening pigments, extender pigments, fillers, antistatic agents, antioxidants, and fluorescent whitening agents may be used as additives as appropriate and as needed.

[0227] Commercially available adhesives may be used as the above-mentioned adhesive. Examples of commercially available adhesives include K588HP Adhesive Gloss A Varnish (vinyl chloride-vinyl acetate copolymer resin adhesive manufactured by Toyo Ink Co., Ltd.) and PSHP780 (acrylic resin adhesive manufactured by Toyo Ink Co., Ltd.).

[0228] The colored layer in the transfer film of this disclosure is provided when the film is a decorative film for transferring a pattern layer and / or an opacity layer to a molded product. Here, the pattern layer is a layer provided to express a patterned image such as a design or letters, and the opacity layer is usually a solid layer covering the entire surface and is provided to conceal the coloring of the injection-molded resin, etc. The opacity layer may be provided inside the pattern layer to enhance the image of the pattern layer, or it may form a decorative layer on its own.

[0229] The pattern layer relating to this disclosure is a layer provided to represent patterns such as designs and characters. The patterns of the pattern layer are arbitrary, but examples include patterns consisting of wood grain, stone pattern, fabric pattern, sand pattern, geometric patterns, characters, etc.

[0230] The colored layer can usually be formed between the hard coat layer and the adhesive layer, or between the anchor coat layer and the adhesive layer, by known printing methods such as gravure printing, offset printing, screen printing, transfer printing from a transfer sheet, sublimation transfer printing, or inkjet printing on the hard coat layer or anchor coat layer using printing ink. From the viewpoint of design, the thickness of the colored layer is preferably 3 to 40 μm, and more preferably 10 to 30 μm.

[0231] Preferred binder resins for printing inks used to form the colored layer include polyester resins, polyurethane resins, acrylic resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, and cellulose resins. However, it is preferable to use acrylic resin alone or a mixture of acrylic resin and vinyl chloride-vinyl acetate copolymer resin as the main component. Among these, mixing acrylic resin, vinyl chloride-vinyl acetate copolymer resin, or another acrylic resin is preferable as it improves printability and moldability. Examples of acrylic resins include 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 individually or as a mixture of two or more. In addition, acrylic polyols obtained by copolymerizing alkyl (meth)acrylate esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and octyl (meth)acrylate with (meth)acrylate 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 used. Furthermore, as vinyl chloride-vinyl acetate copolymer resins, those with 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, carboxylic acids such as maleic acid and fumaric acid may be further copolymerized into the vinyl chloride-vinyl acetate copolymer resin. The mixing ratio of the acrylic resin to the vinyl chloride-vinyl acetate copolymer resin is about 1 / 9 to 9 / 1 (by mass) for the acrylic resin / vinyl chloride-vinyl acetate copolymer resin. In addition, other resins may be mixed as auxiliary components as needed, such as thermoplastic polyester resins, thermoplastic urethane resins, chlorinated polyethylene, chlorinated polyolefin resins such as chlorinated polypropylene, etc.

[0232] The colorants used in the above-mentioned colored layer may include metallic pigments consisting of flake-like foil powders of metals, alloys, or metallic compounds such as aluminum, chromium, nickel, tin, titanium, iron phosphide, copper, gold, silver, and brass; pearlescent pigments consisting of foil powders such as 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 oxide, and antimony trioxide; inorganic pigments such as zinc oxide, red iron oxide, vermilion, ultramarine, cobalt blue, titanium yellow, lead yellow, and carbon black; and organic pigments (including dyes) such as isoindolinone yellow, Hansa yellow A, quinacridone red, permanent red 4R, phthalocyanine blue, induthlene blue RS, and aniline black, either individually or in combination of two or more.

[0233] Such a colored layer is provided to impart design appeal to the transfer film of this disclosure, but a metal thin film layer may be formed further to improve the design appeal. The metal thin film layer can be formed using a metal such as aluminum, chromium, gold, silver, or copper by methods such as vacuum deposition or sputtering. This metal thin film layer may be provided over the entire surface or partially in a patterned manner.

[0234] In addition to the above components, the printing ink used to form the colored layer may contain appropriate additives such as anti-settlement agents, curing catalysts, ultraviolet absorbers, antioxidants, leveling agents, thickeners, defoamers, and lubricants. The printing ink is provided in a form in which the above components are dissolved or dispersed in a solvent. Any solvent that dissolves or disperses the binder resin may be used, and organic solvents and / or water can be used. Examples of organic solvents 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.

[0235] In addition to the above-mentioned substrate, release layer, hard coat layer, anchor coat layer, adhesive layer, and coloring layer, the transfer film of this disclosure may optionally include a low-reflection layer, antistatic layer, ultraviolet absorption layer, near-infrared blocking layer, electromagnetic wave absorption layer, etc., laminated in any order.

[0236] The thickness of the transfer film of this disclosure is not particularly limited and can be appropriately selected from the range of 1 to 10,000 μm, but from the viewpoint of moldability, shape conformability, handling, etc., 2 to 250 μm is preferred, 5 to 150 μm is more preferred, and 25 to 150 μm is even more preferred.

[0237] The hard coat layer of the transfer film disclosed herein is tack-free, has excellent blocking resistance, and can be handled by winding it into a roll, making it suitable for use as a transfer film in in-mold injection molding. For example, the transfer film disclosed herein is continuously conveyed by a conveyor roll or the like into a mold consisting of a fixed mold and a movable mold, the base film side comes into contact with the fixed mold surface, and after appropriate positioning is performed, the movable mold moves and clamps the mold. Then, a thermoplastic resin that has been pre-melted by heat is injected 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 disclosed herein transferred to the outermost surface can be removed.

[0238] If the hard coat layer of the molded product described above is uncured or semi-cured, the hard coat layer may be cured by irradiation with active energy rays and / or heating. The conditions for irradiation with active energy rays and / or heating of the hard coat layer are not particularly limited and can be appropriately selected from, for example, the conditions for forming the cured product described above.

[0239] Since the hardened hard coat layer of the present disclosure is formed on the outermost surface of the molded product after the transfer layer of the transfer film of the present disclosure is transferred to the molded product, the pencil hardness of the surface of the molded product can be made very high, preferably 5H or higher, and more preferably 6H or higher. The pencil hardness can be evaluated in accordance with the method described in JIS K5600-5-4.

[0240] Molded articles (in-mold molded articles) manufactured by in-mold injection molding using the transfer film of this disclosure have very high surface hardness and patterns and designs are clearly transferred, making them suitable for use in any molded article requiring such properties. The transfer film of this disclosure can be suitably used, for example, in various exterior molded articles that require high surface hardness, scratch resistance, design, and durability, such as automotive dashboards and other interior and exterior parts, and casings for home appliances.

[0241] [Adhesive Sheet] By using the curable compositions of this disclosure (curable compositions for adhesion, curable compositions for multilayer semiconductors), an adhesive sheet can be obtained having an adhesive layer formed from the curable compositions of this disclosure on at least one surface of a substrate. Figure 11 is a schematic diagram (cross-sectional view) showing one embodiment of the adhesive sheet of this disclosure. 3 represents the adhesive sheet, 31 represents the adhesive layer, 32 represents the substrate, and 33 represents the anchor coat layer.

[0242] The above-mentioned adhesive sheet can be obtained, for example, by applying the curable composition of this disclosure (curable composition for adhesives, curable composition for multilayer semiconductors) to a substrate and then drying it as necessary. The application method is not particularly limited, and well-known and conventional means can be used. Similarly, the drying means and conditions are not particularly limited, and conditions can be set to remove as much volatile matter as possible, and well-known and conventional means can be used. If the curable composition of this disclosure contains a polymerization initiator whose composition obtained by adding 1 part by weight to 100 parts by weight of celloxide 2021P (manufactured by Daicel Corporation) has a heat-curing time of 3.5 minutes or more at 130°C, then by heating and drying, the progress of the curing reaction can be suppressed while rapidly removing volatile matter such as solvents to form an adhesive layer. The adhesive layer thus obtained does not have adhesive properties below 50°C, but exhibits adhesive properties when heated at a temperature that can suppress damage to electronic components such as semiconductor chips, and then rapidly hardens. The above-mentioned adhesive sheet includes not only sheet-like forms but also film-like, tape-like, plate-like, and other sheet-like forms.

[0243] The adhesive sheet described above may be a single-sided adhesive sheet having an adhesive layer on only one side of the substrate, or a double-sided adhesive sheet having adhesive layers on both sides of the substrate. If the adhesive sheet is a double-sided adhesive sheet, at least one of the adhesive layers may be formed from the curable composition of this disclosure, and the other may be said adhesive layer or an adhesive layer other than said adhesive layer (other adhesive layer).

[0244] The substrate used in the adhesive sheet of this disclosure can be a well-known and conventional substrate (a substrate used in adhesive sheets) and is not particularly limited, but examples include plastic substrates, metal substrates, ceramic substrates, semiconductor substrates, glass substrates, paper substrates, wood substrates, and substrates with painted surfaces. The substrate in the adhesive sheet of this disclosure may also be a so-called release liner. The adhesive sheet of this disclosure may have only one layer of substrate or two or more layers. Furthermore, the thickness of the substrate is not particularly limited and can be appropriately selected in the range of 1 to 10,000 μm, for example.

[0245] The adhesive sheet described above may have only one adhesive layer formed from the curable composition of this disclosure, or it may have two or more adhesive layers. Furthermore, the thickness of the adhesive layer in the adhesive sheet is not particularly limited and can be appropriately selected in the range of, for example, 0.1 to 10,000 μm.

[0246] Furthermore, in another embodiment of the adhesive sheet described above, by using a silane coupling agent and the polyorganosilsesquioxane of this disclosure, an adhesive sheet with excellent crack resistance, heat resistance, adhesion to the substrate, and bonding properties can be obtained. Specifically, an adhesive sheet having an anchor coat layer containing a silane coupling agent and an adhesive layer formed from a curable composition containing the polyorganosilsesquioxane of this disclosure on at least one surface of a substrate, wherein the adhesive layer is provided on the surface of the anchor coat layer, exhibits excellent crack resistance, heat resistance, adhesion to the substrate, and bonding properties.

[0247] Furthermore, in another embodiment of the adhesive sheet described above, the anchor coat layer may consist of only one layer, or it may consist of two or more types of anchor coat layers. The thickness of the anchor coat layer can be appropriately selected, for example, within the range of 0.001 to 10000 μm.

[0248] The above-mentioned adhesive sheet may have other layers (for example, an intermediate layer, a primer layer, etc.) in addition to the base material, adhesive layer, and anchor coat layer.

[0249] By using the above-mentioned adhesive sheet, a laminate can be obtained in which a layer to be bonded (a substrate) is attached to the adhesive layer of the adhesive sheet. Furthermore, when the laminate obtained using the above-mentioned adhesive sheet is a three-dimensional laminate of semiconductor chips, it has higher integration and lower power consumption than conventional semiconductors. Therefore, by using this laminate, it is possible to provide smaller and higher-performance electronic devices while improving mounting density.

[0250] Each aspect disclosed herein can be combined with any other features disclosed herein. Each configuration and combination thereof in each embodiment is an example, and additions, omissions, substitutions, and other modifications can be made as appropriate without departing from the spirit of the present invention. This disclosure is not limited by the embodiments, but is limited only by the claims. [Examples]

[0251] The present disclosure will be described in more detail below based on examples, but the present disclosure is not limited to these examples. Note that Example 2 shall be interpreted as Reference Example 1.

[0252] The number-average molecular weight and molecular weight dispersion of the product were measured under the following GPC conditions. The content of monomeric cage-type silsesquioxane and condensed silsesquioxane in the product was determined from the area ratio of the corresponding peak area values ​​in the GPC measurement. The ratio of T2 to T3 isomers [T3 / T2] in the product was measured using a Brucker NMR (600 MHz). 29 The measurement was performed using Si-NMR spectroscopy.

[0253] [GPC conditions] Measuring device: Product 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℃ Measurement time: 13 min Injection volume: 20 μL Eluent: THF, sample concentration 0.1~0.2% by weight Molecular weight: Equivalent to standard polystyrene

[0254] Furthermore, UPLC-MS was performed using the following equipment and conditions. [UPLC conditions] Measurement device: ACQUITY UPLC H-Class (manufactured by Waters) Detector, detection conditions: MS conditions as follows 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: 0.35mL / min Sample temperature: 10℃ Column temperature: 40℃ Injection volume: 2.0μL

[0255] [MS conditions] Measurement device: Xevo-G2XS QTOFMS (manufactured by Waters) Ionization mode: ESI positive (Sensitivity Mode) Measurement method: MSE Capillary voltage: 3.2kV Cone voltage: 30V Source offset voltage: 80V Desolvent removal gas: 1000 L / hr (200°C) Corn gas: 50L / hr Ion source heater: 80℃ Scan range: m / z = 100-3000 Scan time: 0.4 sec Collision energy: 30-50 eV (MSE High Energy) Lochmas: Leucine Enkephalin

[0256] Example 1: Preparation of epoxy group-containing polyorganosylsesquioxane according to the present disclosure (1) A 1000 ml flask (reaction vessel) equipped with a thermometer, stirrer, reflux condenser, nitrogen inlet tube, and Dean-Stark tube was charged with 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 under a nitrogen stream, and the temperature was raised to 50°C. To the mixture thus obtained, 7.74 g of 5% potassium carbonate aqueous 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. No significant temperature increase occurred during the addition. Subsequently, the polycondensation reaction was carried out at 50°C under a nitrogen stream for 5 hours. Subsequently, 230.5 g of methyl isobutyl ketone was added, and the temperature was raised from 50°C to 90°C under reduced pressure until acetone (0.0%), methyl isobutyl ketone (30.32%), and water (0.23%) were removed from the system. The mixture was then stirred at 90°C for 11 hours, 273.2 g of methyl isobutyl ketone was added, and the mixture was washed five times with 273.2 g of water until the electrical conductivity was 1.5 uS / cm or less. The mixture was then concentrated to obtain 61.1 g of a colorless, transparent liquid. Analysis of the product revealed a number-average molecular weight of 4736, a molecular weight dispersion of 2.54, a monomeric cage-type silsesquioxane content (retention time 7.6-8.3 mins) of 6.7%, a condensed silsesquioxane content (retention time 4.9-7.6 mins) of 93.3%, and a [T3 / T2] ratio of 46.5. 29 The Si-NMR spectrum is shown in Figure 1, and the GPC chart is shown in Figure 2.

[0257] The epoxy group-containing polyorganosylsesquioxane obtained in Example 1 was measured under the above UPLC-MS conditions. The MS spectra detected at retention times of 3.86 minutes and 1.81 minutes are shown in Figures 3 and 4, respectively. The molecular formula C is shown in Figure 5. 144 H 234 O 45 Si 18 MS simulation pattern (Z=2), molecular formula C shown in Figure 6. 128 H 210 O 41 Si 16 From a comparison with the MS simulation pattern (Z=2), the silsesquioxane peak at retention time 3.86 minutes is derived from the composition formula (1) (all R 1 This is a condensed silsesquioxane formed by the condensation of two cage-type silsesquioxanes represented by a 2-(3',4'-epoxycyclohexyl)ethyl group. The silsesquioxane peak with a retention time of 1.81 minutes is represented by the composition formula (1) (all R). 1 This is a cage-type silsesquioxane represented by a 2-(3',4'-epoxycyclohexyl)ethyl group and composition formula (2) (all R 2 These can be identified as condensed silsesquioxanes formed by the condensation of cage-type silsesquioxanes represented by a 2-(3',4'-epoxycyclohexyl)ethyl group. The estimated structures of the condensed silsesquioxanes at retention times of 3.86 minutes and 1.81 minutes are shown below. • Silsesquioxane peak at retention time of 3.86 minutes [ka]

[0258] All R in the above formula 1 This is a 2-(3',4'-epoxycyclohexyl)ethyl group. • Silsesquioxane peak at retention time of 1.81 minutes [ka] All R in the above formula 1 and R 2 This is a 2-(3',4'-epoxycyclohexyl)ethyl group.

[0259] Example 2: Preparation of epoxy group-containing polyorganosylsesquioxane according to the present disclosure (2) A 1000 ml flask (reaction vessel) equipped with a thermometer, stirrer, reflux condenser, nitrogen inlet tube, and Dean-Stark tube was charged with 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 under a nitrogen stream, and the temperature was raised to 50°C. To the mixture thus obtained, 7.74 g of 5% potassium carbonate aqueous 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. No significant temperature increase occurred during the addition. Subsequently, the polycondensation reaction was carried out at 50°C under a nitrogen stream for 5 hours. Subsequently, 230.5 g of methyl isobutyl ketone was added, and the temperature was raised from 50°C to 90°C under reduced pressure until acetone (0.0%), methyl isobutyl ketone (20.58%), and water (0.35%) were removed from the system. The mixture was then stirred at 90°C for 42 hours, 273.2 g of methyl isobutyl ketone was added, and the mixture was washed six times with 273.2 g of water until the electrical conductivity was 1.5 uS / cm or less. The mixture was then concentrated to obtain 50.0 g of a colorless, transparent liquid. Analysis of the product revealed a number-average molecular weight of 9843, a molecular weight dispersion of 2.89, a monomeric cage-type silsesquioxane content (retention time 7.6-8.3 mins) of 1.9%, a condensed silsesquioxane content (retention time 4.7-7.6 mins) of 98.1%, and a [T3 / T2] ratio of 196.2. 29 The Si-NMR spectrum is shown in Figure 7, and the GPC chart is shown in Figure 8.

[0260] Comparative Example 1: Production of epoxy group-containing polyorganosylsesquioxane A 1000 ml flask (reaction vessel) equipped with a thermometer, stirrer, reflux condenser, nitrogen inlet tube, and Dean-Stark tube was charged with 3.0 mmol (0.56 g) of phenyltrimethoxysilane and 275.4 g of acetone under a nitrogen stream, and the temperature was raised to 50°C. To the mixture obtained in this way, 7.74 g of 5% potassium carbonate aqueous solution (2.8 mmol as potassium carbonate) was added over 5 minutes, followed by the addition of 2800.0 mmol (50.40 g) of water over 20 minutes. Simultaneously with the start of the potassium carbonate addition, 277.2 mmol (68.30 g) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane was added dropwise, and the addition was completed over 2 hours. No significant temperature increase occurred during the addition. Subsequently, the polycondensation reaction was carried out at 50°C under a nitrogen stream for 5 hours. Subsequently, 230.5 g of methyl isobutyl ketone was washed six times with 273.2 g of water. The solution was concentrated to an electrical conductivity of 1.5 uS / cm or less, yielding 50.0 g of a cloudy white liquid.

[0261] [Evaluation of solvent solubility] 50-60 g of the product obtained in the above examples and comparative examples was mixed with 2 L of acetone or chloroform to evaluate its solvent solubility. "Completely soluble" was defined as a clear solution, while "turbid" was defined as a cloudy solution due to partial dissolution. The results are shown in Table 1.

[0262] [Table 1]

[0263] Example 1: Manufacturing of hard coat film A mixed solution was prepared using 100 parts by weight of epoxy group-containing polyorganosylsesquioxane obtained in Example 1, 20 parts by weight of methyl isobutyl ketone (manufactured by Kanto Chemical Co., Ltd.), and 1 part by weight of curing catalyst 1 ([diphenyl[4-(phenylthio)phenyl]sulfonium tris(pentafluoroethyl)trifluorophosphate]), and this was used as a hard coat liquid (curable composition). The hard coat solution obtained above is cast onto a PET film (product name "KEB03 W", manufactured by Teijin DuPont Films Ltd.) using a wire bar so that the hard coat layer thickness after curing is 5 μm. Then, it is left in a 70°C oven for 10 minutes (pre-bake), and then irradiated with ultraviolet light (irradiation conditions (irradiation dose): 312 mJ / cm²). 2 , Irradiation intensity: 80W / cm 2 Finally, the coating film of the hard coat liquid is cured by heat treatment (aging) at 80°C for 2 hours, thereby producing a hard coat film having a hard coat layer.

[0264] The hard coat film obtained as described above will be evaluated using the following methods. (1) Haze and total light transmittance The haze and total light transmittance of the hard coat film obtained as described above are measured using a haze meter (NDH-300A, manufactured by Nippon Denshoku Industries Co., Ltd.).

[0265] (2) Surface hardness (pencil hardness) The pencil hardness of the hard coat layer surface in the hard coat film obtained as described above is evaluated in accordance with JIS K5600-5-4.

[0266] (3) Heat resistance (5% weight loss temperature (T d5 )) Except for using a glass plate instead of PET film, the hard coat layer of the hard coat film obtained by the same method as above is scraped off using a cutter to be used as a sample. The 5% weight loss temperature of the above sample is measured using a differential thermogravimetric analyzer (Seiko Instruments Inc., TG / DTA 6300) under the following conditions. Measurement temperature range: 25~550℃ Heating rate: 10°C / min Gas atmosphere: Nitrogen

[0267] (4) Scratch resistance Apply a load of 1000 g / cm² of #0000 steel wool to the surface of the hard coat layer in the hard coat film obtained above.2 The device is run back and forth 100 times, and the presence and number of scratches on the surface of the hard coat layer are checked. Scratch resistance is then evaluated according to the following criteria. ◎(Excellent scratch resistance): 0 scratches ○ (Good scratch resistance): Number of scratches: 1 to 10 × (Poor scratch resistance): More than 10 scratches

[0268] (5) Flexural resistance (cylindrical mandrel method); by mandrel test The bending resistance of the hard coat film obtained above is evaluated using a cylindrical mandrel in accordance with JIS K5600-5-1. [Explanation of symbols]

[0269] 1. Hard coat film 11. Hard court layer 12 Base material 2. Transfer film 21 Base material 22 Release layer 23. Hard coat layer (uncured or semi-cured hard coat layer) 24 Anchor Coat Layer 25 Colored layer 26 Adhesive layer 3 Adhesive sheet 31 Adhesive layer 32 Base material 33 Anchor Coat Layer

Claims

1. A condensed silsesquioxane is formed by the condensation of two or more cage-type silsesquioxanes, each containing at least one selected from the group consisting of cage-type silsesquioxanes represented by the following compositional formulas (1), (2), (3), and (4), and having a molecular weight of 8000 or less. The molecular weight dispersion (weight-average molecular weight / number-average molecular weight) is between 2.54 and 4.

0. The monomeric cage-type silsesquioxane content is 5% by weight or more relative to the total amount of polyorganosilsesquioxane. A polyorganosilsesquioxane in which the content of the condensed silsesquioxane is 20% by weight or more relative to the total amount of polyorganosilsesquioxane. ・Formula (1): [R 1 SiO 3 / 2 8 8 [R 1 SiO 2 / 2 (OR c )] 1 1 (R in formula (1) 1 is, independently of each other, 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 equation (2)) 2 Each of these is independently 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 of them is an epoxy group. c Each of these 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 equation (3)) 3 Each of these is independently 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 of them is an epoxy group. c Each of these 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 equation (4)) 4 Each of these is independently 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 of them is an epoxy group. c Each of these independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.

2. The epoxy group mentioned above is the following formula (1A) 【Chemistry 1】 [In formula (1A), R 1A This represents a linear or branched alkylene group. The base represented by the following formula (1B) 【Chemistry 2】 [In formula (1B), R 1B This represents a linear or branched alkylene group. The base represented by the following formula (1C) 【Transformation 3】 [In formula (1C), R 1C This represents a linear or branched alkylene group. A base represented by the following formula (1D) 【Chemistry 4】 [In formula (1D), R 1D This represents a linear or branched alkylene group. The polyorganosilsesquioxane according to claim 1, wherein the group is represented by [the specified group].

3. R in the above composition formula (1) 1 , R in composition formula (2) 2 , R in the composition formula (3) 3 , and R in composition formula (4) 4 The polyorganosilsesquioxane according to claim 1 or 2, wherein the proportion of epoxy group-containing groups to the total is 30% or more.

4. The following formula (I) [R ａ SiO ３／２ ] (I) [In formula (I), R a This refers to 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. The constituent units are represented by the following formula (II) [R ｂ SiO ２／２ (OR c )] (II) [In formula (II), R b R represents 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. c [This represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.] A polyorganosilsesquioxane according to any one of claims 1 to 3, wherein the molar ratio of the constituent units represented by [constituent units represented by formula (I) / constituent units represented by formula (II)] is 1 or more and 500 or less.

5. A polyorganosilsesquioxane according to any one of claims 1 to 4, wherein the number average molecular weight is 2,000 to 50,000.

6. A curable composition comprising a polyorganosilsesquioxane according to any one of claims 1 to 5, and at least one other component selected from the group consisting of a curing catalyst, a surface modifier, a surface alterant, other cationic 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 agent, 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 foaming agent, an antibacterial agent, a preservative, a viscosity modifier, a thickener, a photosensitizer, and a foaming agent.

7. Furthermore, the curable composition according to claim 6, further comprising a curing catalyst.

8. The curable composition according to claim 7, wherein the curing catalyst is a photopolymerization initiator.

9. Furthermore, the curable composition according to any one of claims 6 to 8, further containing a polymerization stabilizer.

10. A curable composition for forming a hard coat layer, as described in any one of claims 6 to 9.

11. A curable composition for use as an adhesive, according to any one of claims 6 to 9.

12. A cured product of a curable composition according to any one of claims 6 to 11.

13. A hard coat film comprising a substrate and a hard coat layer which is a cured product according to claim 12, laminated together.

14. A transfer film comprising a base material and a hard coat layer laminated on a release layer formed on at least one surface of the base material, the hard coat layer being a layer containing the curable composition described in claim 10.

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 that order.

16. Furthermore, 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 thickness of the hard coat layer is 3 to 150 μm.

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

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

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