TW202219182A - Polyorganosilsesquioxane, curable composition, cured object, hardcoat film, transfer film, and adhesive sheet - Google Patents

Abstract

Provided is a polyorganosilsesquioxane which can give cured objects having the high heat resistance characteristic of polyorganosilsesquioxanes and having high surface hardness and flexing characteristics and which is suitable as a material for hardcoat films. This polyorganosilsesquioxane includes a silsesquioxane which is a product of condensation of two or more cage silsesquioxanes that include at least one cage silsesquioxane selected from the group consisting of cage silsesquioxanes represented by the following empirical formulae (1), (2), (3), and (4) and which has a molecular weight of 8,000 or lower. Formula (1): [R1SiO3/2]8[R1SiO2/2(ORc)]1. Formula (2): [R2SiO3/2]6[R2SiO2/2(ORc)]2. Formula (3): [R3SiO3/2]8[R3SiO2/2(ORc)]2. Formula (4): [R4SiO3/2]10[R4SiO2/2(ORc)]2 [Symbols in the formulae are as described in the description.].

Description

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

The present invention relates to a polyorganosiloxane, a curable composition containing the polyorganosiloxane, a cured product thereof, and a hard coating film composed of the cured product. The present invention relates to a transfer film containing the curable composition as a hard coat layer. Furthermore, the present invention relates to an adhesive sheet containing the curable composition as an adhesive layer. This case claims the priority of Japanese Patent Application No. 2020-145085 filed in Japan on August 28, 2020, and the content is incorporated herein by reference.

Polyorganosiloxanes (silsesquioxanes) are network-structured polymers or polyhedral clusters obtained by hydrolyzing trifunctional silanes. As silsesquioxanes, those having a random structure, a ladder structure, and a cage structure are known. Most of the known high molecular weight silsesquioxanes with molecular weight above 3000 have random structure or ladder structure. Such a polymer silsesquioxane is described in Patent Document 1 below, for example.

In addition, the silsesquioxane of the cage structure has a structure in which a ring is three-dimensionally closed by a siloxane bond, and is a general term for substances having an organic functional group at each vertex with a cubic structure of silicon oxide as the center. As the cubic structure, octamer silsesquioxane (T ₈ ), which is a regular hexahedral structure, and decamer silsesquioxane (T ₁₀ ), which is a side pyramidal pentagonal structure, are mainly known. Such a cage silsesquioxane is described in Patent Document 2 below, for example. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2013-35918 [Patent Document 2] Japanese Patent Laid-Open No. 2000-334881

[The problem to be solved by the invention]

However, the hardened product obtained from the current high molecular weight polyorganosiloxane or cage silsesquioxane tends to be insufficient in hardness, and has a limit in flexibility during bending. Therefore, the current hardened product cannot be used for applications requiring high hardness and high bending resistance, and thus its use as a material suitable for hard coating is limited. In addition, as the molecular weight of the current polymer silsesquioxane increases, it is difficult to dissolve in solvents such as organic solvents, so it is difficult to process it into a material suitable for hard coating.

Therefore, the object of the invention of the present invention is to provide a polyorganosiloxane, which can be made into a polyorganosiloxane having high heat resistance, which is characteristic of polyorganosiloxane, and high surface hardness and bending resistance. Hardened product, and suitable as a material for hard coating. Moreover, it aims at providing the polyorganosiloxane sesquioxane which is a high molecular weight polyorganosiloxane and has high solubility in solvents, such as an organic solvent.

Another object of the present invention is to provide a curable composition containing the polyorganosiloxane silsesquioxane. Further, an object of the present invention is to provide a cured product of the curable composition, and a hard coat film having a hard coat layer as the cured product. Furthermore, another object of the present invention is to provide a transfer film having a hard coat layer containing the curable composition. Furthermore, another object of the present invention is to provide an adhesive sheet having an adhesive layer containing the curable composition. [Technical means to solve the problem]

The inventors of the present invention have found that a cured product of a curable composition containing a silsesquioxane having a structure in which two or more clathrate silsesquioxanes having a specific composition formula are condensed and having a molecular weight of 8,000 or less has both It has high heat resistance and excellent surface hardness and bending resistance, and is very useful as a hard coat layer in a hard coat film or a transfer film, and an adhesive layer in an adhesive sheet. In addition, it was found that the silsesquioxane has a high molecular weight and has high solubility in solvents such as organic solvents. The present invention has been completed based on such knowledge.

That is, the present invention provides a polyorganosiloxane containing silsesquioxane, and the silsesquioxane is selected from the following compositional formula (1), compositional formula (2), compositional formula (3) ) and at least one of the clathrate silsesquioxanes in the group consisting of the clathrate silsesquioxane represented by the composition formula (4) is a condensate obtained by condensing two or more pieces and having a molecular weight of 8,000 or less.・Formula (1): [R ¹ SiO _3/2 ] ₈ [R ¹ SiO _2/2 (OR ^c )] ₁ (in formula (1), R ¹ is each independently a polymerizable functional group-containing group, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or hydrogen atom, and at least one is a group containing a polymerizable functional group; R ^c represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (2): [R ² SiO _3/2 ] ₆ [R ² SiO _2/2 (OR ^c )] ₂ (in formula (2), R ² 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; R ^c respectively independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (3): [R ³ SiO _3/2 ] ₈ [R ³ SiO _2/2 (OR ^c )] ₂ (in formula (3), R ³ are 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 aryl group alkyl group, substituted or unsubstituted alkenyl group, or hydrogen atom, and at least one of them is a group containing a polymerizable functional group; R ^c independently represents an alkyl group with 1 to 4 carbon atoms or a hydrogen atom) ・Formula ( 4): [R ⁴ SiO _3/2 ] ₁₀ [R ⁴ SiO _2/2 (OR ^c )] ₂ (in formula (4), R ⁴ is independently a group containing a polymerizable functional group, substituted or unsubstituted Substituted aryl, substituted or unsubstituted aralkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or hydrogen atom , and at least one is a group containing a polymerizable functional group; R ^c independently represents an alkyl group with 1 to 4 carbon atoms or a hydrogen atom)

[式（1A）中，R ^1A表示直鏈或支鏈狀之伸烷基] 所表示之基、下述式（1B）

[式（1B）中，R ^1B表示直鏈或支鏈狀之伸烷基] 所表示之基、下述式（1C）

[式（1C）中，R ^1C表示直鏈或支鏈狀之伸烷基] 所表示之基、或下述式（1D）

[式（1D）中，R ^1D表示直鏈或支鏈狀之伸烷基] 所表示之基。 Furthermore, the present invention provides the above-mentioned polyorganosiloxane, wherein the polymerizable functional group-containing group is the following formula (1A)

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

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

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

A group represented by [in formula (1D), R ^1D represents a linear or branched alkylene group].

In addition, the present invention provides the above-mentioned polyorganosiloxane silsesquioxane, wherein, with respect to R ¹ in the composition formula (1), R ² in the composition formula (2), R ³ in the composition formula (3), And R ⁴ in the composition formula (4) as a whole, the ratio of the group containing a polymerizable functional group is 30% or more.

Furthermore, the present invention provides the above-mentioned polyorganosiloxane, wherein the molar ratio of the structural unit represented by the following formula (I) and the structural unit represented by the following formula (II) [represented by the formula (I) The structural unit represented by the structural unit represented by the formula (II)] is 1 or more and 500 or less. [R ^a SiO _3/2 ] (I) [In formula (I), R ^a represents a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, Substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or hydrogen atom] [R ^b SiO _2/2 (OR ^c )] (II) [In formula (II), R ^b represents a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, A substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom; R ^c represents a hydrogen atom or an alkyl group with 1 to 4 carbons]

Furthermore, the present invention provides the above-mentioned polyorganosiloxane sesquioxane having a number average molecular weight of 2,000 to 50,000.

Furthermore, the present invention provides the above-mentioned polyorganosiloxane sesquioxane having a molecular weight dispersion (weight average molecular weight/number average molecular weight) of 1.0 to 4.0.

Furthermore, the present invention provides a curable composition containing the above-mentioned polyorganosiloxane sesquioxane.

Moreover, this invention provides the said curable composition which further contains a hardening catalyst.

Moreover, this invention provides the said curable composition in which the said hardening catalyst is a photo- or thermal polymerization initiator.

Moreover, this invention provides the said curable composition which further contains a polymerization stabilizer.

Moreover, this invention provides the said curable composition which is a curable composition for hard-coat layer formation.

Moreover, this invention provides the said curable composition which is a curable composition for adhesives.

Furthermore, the present invention provides a cured product of the aforementioned curable composition.

Moreover, this invention provides the hard-coat film which laminated|stacked the base material, and the hard-coat layer which is the said hardened|cured material formed on at least one surface of this base material.

Further, the present invention provides a transfer film comprising a base material and a hard coat layer formed on a release layer formed on at least one surface of the base material, wherein the hard coat layer contains the above curable composition layer.

Moreover, this invention provides the said film for transcription|transfer which further laminated|stacked an anchor coat layer and an adhesive agent layer on the said hard coat layer in this order.

Furthermore, the present invention provides the above-mentioned transfer film further comprising at least one coloring layer.

Moreover, this invention provides the said film for transcription|transfer in which the thickness of the said hard-coat layer is 3-150 micrometers.

Furthermore, the present invention provides an adhesive sheet comprising a substrate and an adhesive layer, wherein the adhesive layer is located on at least one side of the substrate and is a layer containing the curable composition.

In addition, the present invention provides an adhesive sheet, which has a substrate, an adhesion-promoting coating and an adhesive layer, the adhesion-promoting coating and the adhesive layer are located on at least one side of the substrate, and the adhesion-promoting coating contains silane A mixture, the adhesive layer is a layer containing the above-mentioned curable composition; the above-mentioned adhesive layer is arranged on the surface of the above-mentioned adhesion-promoting coating. [Effect of invention]

The cured product (eg, hard coat layer) obtained from the curable composition containing the polyorganosiloxane sesquioxane of the present invention has high heat resistance, and has high surface hardness and bending resistance. Therefore, by using a hard coat film or a transfer film having the hard coat layer, a molded product (product) having high surface hardness and bending resistance can be produced. Moreover, the polyorganosiloxane sesquioxane of the present invention is a high molecular weight polyorganosiloxane sesquioxane, and has high solubility in solvents such as organic solvents. Therefore, the hard coat or transfer film containing the polyorganosiloxane of the present invention can reduce the amount of solvent used, and the uncured or semi-cured hard coat is not sticky and can be rolled into a roll for operation , the film containing the hard coat layer can be handled in a roll-to-roll manner, so it is excellent both in terms of quality and cost. Furthermore, the curable composition containing the polyorganosiloxane sesquioxane of the present invention as an essential component can form a cured product (adhesive material) with high heat resistance and flexibility, and thus can also be preferably used as an adhesive (For example, a curable composition for laminated semiconductors).

[Polyorganosiloxane] The polyorganosiloxane of the present invention contains silsesquioxane, which (hereinafter sometimes referred to as "condensed silsesquioxane of the present invention") It is a clathrate containing at least one selected from the group consisting of clathrate silsesquioxanes represented by the following compositional formula (1), compositional formula (2), compositional formula (3) and compositional formula (4). A condensate obtained by condensing two or more silsesquioxanes has a molecular weight of 8000 or less (preferably 1500-7500, more preferably 1800-7000, and still more preferably 2000-6500).・Formula (1): [R ¹ SiO _3/2 ] ₈ [R ¹ SiO _2/2 (OR ^c )] ₁ (in formula (1), R ¹ is each independently a polymerizable functional group-containing group, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or hydrogen atom, and at least one is a group containing a polymerizable functional group; R ^c represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (2): [R ² SiO _3/2 ] ₆ [R ² SiO _2/2 (OR ^c )] ₂ (in formula (2), R ² 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; R ^c respectively independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (3): [R ³ SiO _3/2 ] ₈ [R ³ SiO _2/2 (OR ^c )] ₂ (in formula (3), R ³ are 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 aryl group alkyl group, substituted or unsubstituted alkenyl group, or hydrogen atom, and at least one of them is a group containing a polymerizable functional group; R ^c independently represents an alkyl group with 1 to 4 carbon atoms or a hydrogen atom) ・Formula ( 4): [R ⁴ SiO _3/2 ] ₁₀ [R ⁴ SiO _2/2 (OR ^c )] ₂ (in formula (4), R ⁴ is independently a group containing a polymerizable functional group, substituted or unsubstituted Substituted aryl, substituted or unsubstituted aralkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or hydrogen atom , and at least one is a group containing a polymerizable functional group; R ^c independently represents an alkyl group with 1 to 4 carbon atoms or a hydrogen atom)

The structural unit represented by [R ¹ SiO _3/2 ] in the composition formula (1), the structural unit represented by [R 2 SiO 3/2 ] in the composition formula (2), and the [R ² SiO _3/2 ] in the composition formula (3) The structural unit represented by R ³ SiO _3/2 ] and the structural unit represented by [R ⁴ SiO _3/2 ] in the composition formula (4) are included in the structural unit represented by the following formula (I) (hereinafter, In this specification, it is sometimes referred to as "T3 body"). [R ^a SiO _3/2 ] (I)

In addition, the structural unit represented by [R ¹ SiO _2/2 (OR ^c )] in the composition formula (1), and the structure represented by [R ² SiO _2/2 (OR ^c )] in the composition formula (2) A unit, a structural unit represented by [R ³ SiO _2/2 (OR ^c )] in the composition formula (3), and a unit represented by [R ⁴ SiO _2/2 (OR ^c )] in the composition formula (4) The structural unit is included in the structural unit represented by the following formula (II) (hereinafter, it may be referred to as "T2 body" in this specification). [R ^b SiO _2/2 (OR ^c )] (II)

R a in the above formula (I) and R ^b in the formula (II ⁾ represent a polymerizable functional group-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a Substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or hydrogen atom. In addition, in the above formula (II), R ^c represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.

When the structural unit represented by the above formula (I) is described in more detail, it is represented by the following formula (I'). Moreover, if the structural unit represented by the said formula (II) is described in detail, it will be represented by the following formula (II'). In the structure represented by the following formula (I'), the three oxygen atoms shown to be bonded to the silicon atom are respectively bonded to another silicon atom (silicon atom not shown in the formula (I')). On the other hand, two oxygen atoms located above and below the silicon atom shown in the structure represented by the following formula (II') are respectively connected with another silicon atom (the silicon atom not shown in the formula (II')) bond. That is, the above-mentioned T3 body and T2 body are both silsesquioxane structural units (so-called T units) formed by the hydrolysis and condensation reactions of the corresponding hydrolyzable trifunctional silane compounds.

R ^a in the above formula (I'), and R ^b and R ^c in the formula (II') are the same groups as described above. In the formula (II), the alkyl group in R ^c is usually derived from the alkoxy group in the hydrolyzable silane compound used as the raw material of the polyorganosiloxane of the present invention (for example, as the following formula (A) ) to (C), the alkoxy groups of X ¹ to X ³ , etc.) alkyl groups.

The clathrate silsesquioxane represented by the above-mentioned composition formula (1) is composed of eight constituent units (T3 body) represented by [R ¹ SiO _3/2 ] and one [R ¹ SiO _2/2 (OR ^c ) ] The constituent units (T2 bodies) represented by silsesquioxane are bonded to each other through siloxane bonds (Si-O-Si) to form a cage-type silsesquioxane. The specific structure of the clathrate silsesquioxane represented by the above composition formula (1) is not particularly limited as long as it satisfies the above composition formula (1), for example, the clathrate silsesquioxane represented by the following formula (1') Hemioxane etc.

In formula (1'), R ^1a to R ¹ⁱ each independently have the same meaning as R ¹ in composition formula (1). R ^{c in formula (1') also has the same meaning as R c in} composition formula (1).

The clathrate silsesquioxane represented by the above composition formula (2) is composed of six constituent units (T3 body) represented by [R ² SiO _3/2 ] and two [R ² SiO _2/2 (OR ^c ) The constituent units (T2 bodies) represented by ] are bonded to each other through siloxane bonds (Si-O-Si) to form a silsesquioxane with a cage structure. The specific structure of the cage silsesquioxane represented by the above compositional formula (2) is not particularly limited as long as it satisfies the above compositional formula (2). Said cage silsesquioxane and so on.

R ^2a to R ^2h in the formula (2') and R ²ⁱ to R ^2p in the formula (2'') have the same meaning as R ² in the composition formula (2), respectively. R ^c in formulas (2') and (2'') also independently have the same meaning as R ^c in the composition formula (2).

The clathrate silsesquioxane represented by the above composition formula (3) is composed of eight constituent units (T3 body) represented by [R ³ SiO _3/2 ] and two [R ³ SiO _2/2 (OR ^c ) The constituent units (T2 bodies) represented by ] are bonded to each other through siloxane bonds (Si-O-Si) to form a silsesquioxane with a cage structure. The specific structure of the cage silsesquioxane represented by the above composition formula (3) is not particularly limited as long as it satisfies the above composition formula (3), for example, the following formulas (3'), (3'') or (3''') represents the cage silsesquioxane.

R ^3a to R ^3j in formula (3'), R ^3k to R ^3t in formula (3''), R ^3u to R ^3z and R ^3aa to R ^3dd in formula (3''') are respectively independently It has the same meaning as R ³ in the composition formula (3). R ^{c in formula (3'), (3''), and formula (3''') also independently have the same meaning as R c in} composition formula (3).

The clathrate silsesquioxane represented by the above composition formula (4) is composed of 10 constituent units (T3 body) represented by [R ⁴ SiO _3/2 ] and two [R ⁴ SiO _2/2 (OR ^c ) The constituent units (T2 bodies) represented by ] are bonded to each other through siloxane bonds (Si-O-Si) to form a silsesquioxane with a cage structure. The specific structure of the cage silsesquioxane represented by the above compositional formula (4) is not particularly limited as long as it satisfies the compositional formula (4). For example, the following formula (4′) or (4″) can be used The cage silsesquioxane.

R ^4a to R ^4l in the formula (4') and R ^4m to R ^4x in the formula (4'') have the same meaning as R ⁴ in the composition formula (4), respectively. R ^c in formulas (4') and (4'') also independently have the same meaning as R ^c in the composition formula (4).

The condensed silsesquioxane of the present invention may also include compositions other than the above-mentioned compositional formula (1), compositional formula (2), compositional formula (3) and compositional formula (4) within the range that does not impair the effects of the present invention Cage silsesquioxane represented by the formula. As a compositional formula other than the said compositional formula (1), compositional formula (2), compositional formula (3), and compositional formula (4), the following compositional formulae (5)-(8) are mentioned, for example.・Formula (5): [R ⁵ SiO _3/2 ] ₆ [R ⁵ SiO _2/2 (OR ^c )] ₃ (in formula (5), R ⁵ is each independently a polymerizable functional group-containing group, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or hydrogen atom, and at least one of them is a group containing a polymerizable functional group; R ^c independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (6): [R ⁶ SiO _3/2 ] ₈ [R ⁶ SiO _2/2 (OR ^c )] ₃ (in formula (6), R ⁶ is independently a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aralkane R ^c each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (7): [R ⁷ SiO _3/2 ] ₁₀ [R ⁷ SiO _2/2 (OR ^c )] ₁ (in formula (7) , R ⁷ 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 aryl group, A substituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one of which is a group containing a polymerizable functional group; R ^c represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula ( 8): [R ⁸ SiO _3/2 ] ₁₂ [R ⁸ SiO _2/2 (OR ^c )] ₁ (in formula (8), R ⁸ is independently a group containing a polymerizable functional group, substituted or unsubstituted Substituted aryl, substituted or unsubstituted aralkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or hydrogen atom , and at least one is a group containing a polymerizable functional group; R ^c represents an alkyl group with 1 to 4 carbon atoms or a hydrogen atom)

The condensed silsesquioxanes of the present invention also include those in which the cage silsesquioxanes represented by the above-mentioned composition formulae (1) to (8) are mixed. That is, the condensed silsesquioxane of the present invention may contain a composition selected from the above compositional formula (1), compositional formula (2), compositional formula (3), compositional formula (4), compositional formula (5), compositional formula ( 6) Condensates obtained by condensing at least one of the clathrate silsesquioxanes in the group consisting of the clathrate silsesquioxanes represented by the composition formula (7) and the composition formula (8) by condensing two or more .

Furthermore, even in the case of including a cage silsesquioxane having three hydroxyl groups represented by -OR ^c as shown in the above compositional formula (5) and compositional formula (6), two of them are condensed. The case is also included in the condensed silsesquioxane of the present invention. In addition, when all the hydroxyl groups represented by the three -OR ^c in the above-mentioned composition formula (5) and composition formula (6) are condensed, as long as the effect of the present invention is not impaired, the condensed silsesquioxane of the present invention is also considered to be included in the present invention. alkyl.

The "cationic polymerizable functional group" in the above-mentioned polymerizable functional group-containing group is not particularly limited as long as it has cationic polymerizability, and examples thereof include epoxy group, oxycyclobutyl group, vinyl ether group, vinylbenzene group Base et al. The "radical polymerizable functional group" in the above-mentioned polymerizable functional group-containing group is not particularly limited as long as it has radical polymerizability, and examples thereof include (meth)acryloyloxy, (meth)propylene amide group, vinyl group, vinylthio group, etc. As a polymerizable functional group, an epoxy group, a (meth)acryloyloxy group, etc. are preferable from a viewpoint of the surface hardness (for example, 4H or more) of hardened|cured material, and an epoxy group is more preferable.

As R ¹ in the above-mentioned composition formula (1), R ^1a to R ¹ⁱ in the formula (1'), R 2 in the composition formula (2), R ^2a to R ^2h in the formula ( ² '), and formula ( 2'') in R ²ⁱ -R ^2p , R ³ in the composition formula (3), R ^3a -R ^3j in the formula (3'), R ^3k -R ^3t in the formula (3''), R ^3u to R ^3z , R ^3aa to R ^3dd in (3'''), R ⁴ in formula (4), R ^4a to R ^4l in formula (4'), in formula (4'') R ^4m to R ^4x of composition formula (5), R ⁵ in composition formula (5), R ⁶ in composition formula (6), R ⁷ in composition formula (7), R ⁸ in composition formula (8), formula (I) ) in R ^a , and the polymerizable functional group-containing group in R ^b in the formula (II) are not particularly limited, but are preferably epoxy group-containing groups, and are based on the curability and curing properties of the curable composition. From the viewpoint of surface hardness or heat resistance of the object, the base represented by the following formula (1A), the base represented by the formula (1B), the base represented by the formula (1C), and the base represented by the formula (1D) are preferred. , more preferably a group represented by the following formula (1A), a group represented by the following formula (1C), and still more preferably a group represented by the following formula (1A).

In the above formula (1A), R ^1A represents a linear or branched alkylene group. Examples of linear or branched alkylene groups include methylene, methylmethylene, dimethylmethylene, ethylidene, propylidene, trimethylene, tetramethylene, Pentamethylene, hexamethylene, decamethylene and other linear or branched alkylene groups having 1 to 10 carbon atoms. Among them, from the viewpoint of the surface hardness or curability of the cured product, R ^1A is preferably a linear alkylene group having 1 to 4 carbon atoms, a branched alkylene group having 3 or 4 carbon atoms, more preferably Ethylene, trimethylene, and propylidene are more preferred, and ethylidene and trimethylene are more preferred.

In the above formula (1B), R ^1B represents a linear or branched alkylene group, and the same group as R ^1A can be exemplified. Among them, from the viewpoint of the surface hardness or hardenability of the cured product, R ^1B is preferably a straight-chain alkylene having 1 to 4 carbon atoms, or a branched alkylene having 3 or 4 carbon atoms, more preferably Ethylene, trimethylene, and propylidene are more preferred, and ethylidene and trimethylene are more preferred.

In the above formula (1C), R ^1C represents a linear or branched alkylene group, and the same group as R ^1A can be exemplified. Among them, from the viewpoint of the surface hardness or hardenability of the cured product, R ^1C is preferably a linear alkylene group having 1 to 4 carbon atoms, a branched alkylene group having 3 or 4 carbon atoms, and more preferably Ethylene, trimethylene, and propylidene are more preferred, and ethylidene and trimethylene are more preferred.

In the above formula (1D), R ^1D represents a linear or branched alkylene group, and the same group as that of R ^1A can be exemplified. Among them, from the viewpoint of the surface hardness or hardenability of the cured product, R ^1D is preferably a linear alkylene group having 1 to 4 carbon atoms, a branched alkylene group having 3 or 4 carbon atoms, and more preferably Ethylene, trimethylene, and propylidene are more preferred, and ethylidene and trimethylene are more preferred.

As R ¹ in the above-mentioned composition formula (1), R ^1a to R ¹ⁱ in the formula (1'), R 2 in the composition formula (2), R ^2a to R ^2h in the formula ( ² '), and formula ( 2'') in R ²ⁱ -R ^2p , R ³ in the composition formula (3), R ^3a -R ^3j in the formula (3'), R ^3k -R ^3t in the formula (3''), R ^3u to R ^3z , R ^3aa to R ^3dd in (3'''), R ⁴ in formula (4), R ^4a to R ^4l in formula (4'), in formula (4'') R ^4m to R ^4x of composition formula (5), R ⁵ in composition formula (5), R ⁶ in composition formula (6), R ⁷ in composition formula (7), R ⁸ in composition formula (8), formula (I) ) in R ^a , and the polymerizable functional group-containing group in R ^b in the formula (II), preferably an epoxy group-containing group, more preferably a group represented by the above formula (1A) and R ^1A It is an ethyl extension group [wherein, it is 2-(3',4'-epoxycyclohexyl)ethyl].

As R ¹ in the above-mentioned composition formula (1), R ^1a to R ¹ⁱ in the formula (1'), R 2 in the composition formula (2), R ^2a to R ^2h in the formula ( ² '), and formula ( 2'') in R ²ⁱ -R ^2p , R ³ in the composition formula (3), R ^3a -R ^3j in the formula (3'), R ^3k -R ^3t in the formula (3''), R ^3u to R ^3z , R ^3aa to R ^3dd in (3'''), R ⁴ in formula (4), R ^4a to R ^4l in formula (4'), in formula (4'') R ^4m to R ^4x of composition formula (5), R ⁵ in composition formula (5), R ⁶ in composition formula (6), R ⁷ in composition formula (7), R ⁸ in composition formula (8), formula (I) ) in R ^a and the aryl group in the substituted or unsubstituted aryl group of R ^b in the formula (II), for example, phenyl, tolyl, naphthyl and the like are exemplified.

As R ¹ in the above-mentioned composition formula (1), R ^1a to R ¹ⁱ in the formula (1'), R 2 in the composition formula (2), R ^2a to R ^2h in the formula ( ² '), and formula ( 2'') in R ²ⁱ -R ^2p , R ³ in the composition formula (3), R ^3a -R ^3j in the formula (3'), R ^3k -R ^3t in the formula (3''), R ^3u to R ^3z , R ^3aa to R ^3dd in (3'''), R ⁴ in formula (4), R ^4a to R ^4l in formula (4'), in formula (4'') R ^4m to R ^4x of composition formula (5), R ⁵ in composition formula (5), R ⁶ in composition formula (6), R ⁷ in composition formula (7), R ⁸ in composition formula (8), formula (I) ) in R ^a , and R ^b in the formula (II), as the above-mentioned aralkyl group in the substituted or unsubstituted aralkyl group, for example, a benzyl group, a phenethyl group and the like can be exemplified.

As R ¹ in the above-mentioned composition formula (1), R ^1a to R ¹ⁱ in the formula (1'), R 2 in the composition formula (2), R ^2a to R ^2h in the formula ( ² '), and formula ( 2'') in R ²ⁱ -R ^2p , R ³ in the composition formula (3), R ^3a -R ^3j in the formula (3'), R ^3k -R ^3t in the formula (3''), R ^3u to R ^3z , R ^3aa to R ^3dd in (3'''), R ⁴ in formula (4), R ^4a to R ^4l in formula (4'), in formula (4'') R ^4m to R ^4x of composition formula (5), R ⁵ in composition formula (5), R ⁶ in composition formula (6), R ⁷ in composition formula (7), R ⁸ in composition formula (8), formula (I) ) in R ^a and the cycloalkyl group in the substituted or unsubstituted cycloalkyl group of R ^b in the formula (II), for example, cyclobutyl, cyclopentyl, cyclohexyl, etc. can be mentioned.

As R ¹ in the above-mentioned composition formula (1), R ^1a to R ¹ⁱ in the formula (1'), R 2 in the composition formula (2), R ^2a to R ^2h in the formula ( ² '), and formula ( 2'') in R ²ⁱ -R ^2p , R ³ in the composition formula (3), R ^3a -R ^3j in the formula (3'), R ^3k -R ^3t in the formula (3''), R ^3u to R ^3z , R ^3aa to R ^3dd in (3'''), R ⁴ in formula (4), R ^4a to R ^4l in formula (4'), in formula (4'') R ^4m to R ^4x of composition formula (5), R ⁵ in composition formula (5), R ⁶ in composition formula (6), R ⁷ in composition formula (7), R ⁸ in composition formula (8), formula (I) ) in R ^a , and the alkyl group in the substituted or unsubstituted alkyl group of R ^b in formula (II), for example, methyl, ethyl, propyl, n-butyl, isopropyl , isobutyl, sec-butyl, tert-butyl, isopentyl and other linear or branched alkyl groups.

As R ¹ in the above-mentioned composition formula (1), R ^1a to R ¹ⁱ in the formula (1'), R 2 in the composition formula (2), R ^2a to R ^2h in the formula ( ² '), and formula ( 2'') in R ²ⁱ -R ^2p , R ³ in the composition formula (3), R ^3a -R ^3j in the formula (3'), R ^3k -R ^3t in the formula (3''), R ^3u to R ^3z , R ^3aa to R ^3dd in (3'''), R ⁴ in formula (4), R ^4a to R ^4l in formula (4'), in formula (4'') R ^4m to R ^4x , R ^a in formula (I), R ⁵ in composition formula (5), R ⁶ in composition formula (6), R ⁷ in composition formula (7), composition formula ( The alkenyl group in the substituted or unsubstituted alkenyl group of R ⁸ in 8) and R ^b in formula (II), for example, linear or branched vinyl, allyl, isopropenyl, etc. can be mentioned. Chain alkenyl.

The number of groups containing a polymerizable functional group in R ¹ in the above compositional formula (1) is preferably 3 to 9, more preferably 5 to 9, still more preferably 7 to 9, still more preferably 9 ( All are groups containing polymerizable functional groups). The number of the polymerizable functional group-containing groups in R ² in the above compositional formula (2) is preferably 3-8, more preferably 5-8, still more preferably 7-8, still more preferably 8 ( All are groups containing polymerizable functional groups). The number of groups containing a polymerizable functional group in R ³ in the above compositional formula (3) is preferably 3-10, more preferably 5-10, still more preferably 7-10, still more preferably 10 ( All are groups containing polymerizable functional groups). The number of groups containing polymerizable functional groups in R ⁴ in the above compositional formula (4) is preferably 3-12, more preferably 5-12, more preferably 7-12, still more preferably 12 ( All are groups containing polymerizable functional groups). The number of these polymerizable functional groups-containing groups is preferably larger from the viewpoints of curability when a curable composition is formed and surface hardness of a cured product.

Moreover, in the polyorganosiloxane sesquioxane of the present invention, with respect to R ¹ in the composition formula (1), R ² in the composition formula (2), R ³ in the composition formula (3), and composition R ⁴ in formula (4) as a whole, ratio of groups containing polymerizable functional groups (for example, groups containing epoxy groups) (number of groups containing polymerizable functional groups/number of total R ¹ to R ⁴ ) ) is, for example, 30% or more, preferably 50% or more, more preferably 80% or more. The ratio of the above-mentioned polymerizable functional group-containing group is more suitable from the viewpoint of the curability when a curable composition is formed and the surface hardness of the cured product, and more preferably the above-mentioned value or more.

Regarding the polyorganosiloxane of the present invention, the molar ratio of the structural unit (T3 form) represented by the above formula (I) and the structural unit (T2 form) represented by the above formula (II) [formula (I) The represented structural unit/the structural unit represented by the formula (II); T3 body/T2 body] is, for example, 1 or more and 500 or less. Furthermore, the structural unit represented by the above-mentioned formula (I) and the structural unit represented by the formula (II) include the above-mentioned compositional formula (1), compositional formula (2), compositional formula (3), and compositional formula (4) The T3 body and T2 body of the cage silsesquioxane represented, and further include all silsesquioxanes other than these (complete cage silsesquioxane, ladder silsesquioxane, random silsesquioxane) Silsesquioxane, etc.) T3 body and T2 body.

The lower limit value of the above ratio [T3 body/T2 body] is 1, preferably 2, more preferably 3, more preferably 4, more preferably 6, more preferably 7, more preferably 8, more preferably 6 as described above. 8 is preferable, 10 is more preferable, 20 is more preferable, and 40 is still more preferable. By setting the above ratio [T3 body/T2 body] to 1 or more, the surface of an uncured or semi-cured hard coat is easily made non-sticky, the blocking resistance is improved, and it is easy to be rolled into a roll. It can be preferably used as a component of a hard coat layer with bending resistance, and the surface hardness or adhesion of the hardened product or hard coat layer can be significantly improved. On the other hand, the upper limit of the ratio [T3 body/T2 body] 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 body/T2 body] to 500 or less, the compatibility with other components in the curable composition is improved, and the viscosity is also suppressed, so that it is easy to handle and coat as a hard coat layer.

The polyorganosiloxane of the present invention may further comprise a group selected from the group represented by [(R) ₃ SiO _1/2 ] in addition to the above-mentioned silsesquioxane structural unit [RSiO _3/2 ] (T unit). The constituent unit (so-called M unit), the constituent unit represented by [(R) ₂ SiO _2/2 ] (the so-called D unit), and the constituent unit represented by [SiO _4/2 ] (the so-called Q unit) At least one siloxane constituent unit in the formed group. In addition, as a silsesquioxane structural unit other than the structural unit represented by the said formula (I), the structural unit represented by [ _HSiO3/2 ] can also be mentioned. Furthermore, R in the above formula represents a hydrogen atom or a monovalent organic group.

The above-mentioned ratio [T3 form/T2 form] in the polyorganosiloxane of the present invention can be determined, for example, by measuring ²⁹ Si-NMR spectrum. In the ²⁹ Si-NMR spectrum, the silicon atom in the structural unit (T3 body) represented by the above formula (I) and the silicon atom in the structural unit (T2 body) represented by the above formula (II) are in different positions (chemical Displacement) shows a signal (peak), therefore, by calculating the integral ratio of these respective peaks, the above ratio [T3 body/T2 body] is obtained. The signal of the silicon atom in the structure (T3 body) represented by the above formula (I) appears at -64 to -70 ppm, and the signal of the silicon atom in the structure (T2 body) represented by the above formula (II) appears at - 54～-60ppm. Therefore, at this time, by calculating the integral ratio of the signal of -64 to -70 ppm (T3 body) and the signal of -54 to -60 ppm (T2 body), the above ratio [T3 body/T2 body] can be obtained.

The ²⁹ Si-NMR spectrum of the polyorganosiloxane of the present invention can be measured, for example, by the following apparatus and conditions. Measuring apparatus: "Brucker AVANCE (600 MHz)" (manufactured by Brucker Corporation) Solvent: Deuterochloroform Accumulated number of times: 8000 Measurement temperature: 25°C Sample: Polyorganosiloxane sesquioxane/Chromium(III) acetylacetonate/deuterochloroform (1% tetramethylsilane) = 2.0: 0.10: 4.0 (weight ratio)

The above-mentioned ratio [T3 body/T2 body] of the polyorganosiloxane sesquioxane of the present invention is 1 or more and 500 or less means that in the polyorganosiloxane sesquioxane of the present invention, the T2 body is present in an amount equal to or equal to the T3 body. Relatively few, further hydrolysis and condensation reactions of silanols are carried out.

The ratio of each silsesquioxane constituent unit in the polyorganosiloxane of the present invention can be appropriately adjusted by the composition of the raw material (hydrolyzable trifunctional silane) for forming these constituent units.

At least one selected from the group consisting of the clathrate silsesquioxanes represented by the above compositional formula (1), compositional formula (2), compositional formula (3) and compositional formula (4) is condensed with two or more The obtained condensate is the condensed silsesquioxane of the present invention, which refers to the clathrate silsesquioxane represented by the above compositional formula (1), compositional formula (2), compositional formula (3) and compositional formula (4). Among the alkanes, two or more condensed (for example, 2 to 5, preferably 2 to 3, more preferably 2), or two or more condensed (for example, 2 to 5, preferably 2 to 3). , more preferably 2). Here, "condensation" refers to the hydroxyl group represented by -OR ^c in the above compositional formula (1), compositional formula (2), compositional formula (3) and compositional formula (4) (when ^-ORc is an alkoxy group) The hydroxyl groups formed by hydrolysis) dehydrate each other to form siloxane bonds (Si-O-Si).

Since the clathrate silsesquioxanes represented by the above compositional formula (2), compositional formula (3) and compositional formula (4) have two groups represented by -OR ^c in the molecule, these condensation The inventive polyorganosiloxane has a structure in which these cage structures are connected in a straight line.

Since the cage-type silsesquioxane represented by the above-mentioned composition formula (1) has only one group represented by -OR ^c in the molecule, it is condensed at the end of the structure in which the cage-type structures are connected in a straight line. .

In addition, the condensed silsesquioxane of the present invention may not have a cage structure derived from the cage silsesquioxane represented by the above-mentioned compositional formula (2), compositional formula (3) and compositional formula (4). , which is obtained by condensing two cage-type silsesquioxanes represented by the above composition formula (1).

The condensed silsesquioxane of the present invention is derived from each cage of the clathrate silsesquioxane represented by the above-mentioned compositional formula (1), compositional formula (2), compositional formula (3) and compositional formula (4). The condensation form of the type constituting unit is not particularly limited, and may be a random type or a block type.

For example, when the condensed silsesquioxane of the present invention includes a cage structure derived from the cage silsesquioxane represented by the above formula (2'), it has the following formula (2a) in the molecule. The repeating structure of the cage silsesquioxane structure.

Each symbol in the above formula (2a) has the same meaning as the above formula (2'). Furthermore, when the condensed silsesquioxane of the present invention includes a cage structure derived from the cage silsesquioxane represented by the above formula (2″), the molecule has the following formula (2b) in the molecule. Represents the repeating structure of the cage silsesquioxane structure.

Each symbol in the above formula (2b) has the same meaning as the above formula (2″). For example, when the condensed silsesquioxane of the present invention includes a cage structure derived from the cage silsesquioxane represented by the above formula (3'), the molecule has the following formula (3a) in the molecule. The repeating structure of the cage silsesquioxane structure.

Each symbol in the above formula (3a) has the same meaning as the above formula (3'). In addition, when the condensed silsesquioxane of the present invention includes a cage structure derived from the cage silsesquioxane represented by the above formula (3″), the molecule has the following formula (3b) in the molecule. Represents the repeating structure of the cage silsesquioxane structure.

Each symbol in the above formula (3b) has the same meaning as the above formula (3″). Furthermore, when the condensed silsesquioxane of the present invention includes a cage-type structure derived from the cage-type silsesquioxane represented by the above formula (3″), it has the following formula (3c) in the molecule Repetition of the cage silsesquioxane structure represented.

Each symbol in the above formula (3c) has the same meaning as the above formula (3'''). For example, when the condensed silsesquioxane of the present invention includes a cage structure derived from the cage silsesquioxane represented by the above formula (4'), it has the following formula (4a) in the molecule. The repeating structure of the cage silsesquioxane structure.

The symbols in the above formula (4a) have the same meanings as those in the above formula (4'). Furthermore, when the condensed silsesquioxane of the present invention includes a cage structure derived from the cage silsesquioxane represented by the above formula (4″), the molecule has the following formula (4b) in the molecule. Represents the repeating structure of the cage silsesquioxane structure.

Each symbol in the above formula (4b) has the same meaning as the above (4″). For example, when the condensed silsesquioxane of the present invention includes a cage structure derived from the cage silsesquioxane represented by the above formula (1'), both ends or one end thereof has the following formula The cage silsesquioxane structure represented by (1a) and/or the cage silsesquioxane structure represented by the following formula (1b).

Each symbol in the above formula (1a) has the same meaning as the above (1'). R ^1j to R ^1r in the above formula (1b) have the same meanings as R ^1a to R ¹ⁱ in the above formula (1').

The condensed silsesquioxane of the present invention includes, for example, two or more condensates of one type, such as two condensates of clathrate silsesquioxanes represented by the composition formula (1), and two or more condensates of the above-mentioned composition formula (1). ) represented by the clathrate silsesquioxane and the clathrate silsesquioxane represented by the above-mentioned composition formula (2) are obtained by condensing two or more kinds of condensates of different types. Among them, the condensed silsesquioxane of the present invention is preferably one clathrate silsesquioxane represented by the above composition formula (1) and another clathrate silsesquioxane represented by the above composition formula (1) A condensate of alkane, or a clathrate silsesquioxane represented by the above compositional formula (1) and a clathrate silsesquioxane represented by the compositional formulas (2), (3) and (4) The condensate of any of the oxanes.

In the condensed silsesquioxane of the present invention, the combination of one clathrate silsesquioxane represented by the above composition formula (1) and one clathrate silsesquioxane represented by the above composition formula (2) As the silsesquioxane of the condensate, for example, a group represented by -OR ^c in the above formula (1') is condensed with one of the groups represented by two -OR ^c in the above formula (2'). And the condensed silsesquioxane represented by the following formula (1a-2a) is formed. In addition, the substituents (R ^1a to R ¹ⁱ and R ^2a to R ^2h ) in formula (1a-2b) are the same as those in formula (1a) and (2b).

In the condensed silsesquioxane of the present invention, one clathrate silsesquioxane represented by the above-mentioned composition formula (1) and another clathrate silsesquioxane represented by the above-mentioned composition formula (1) are used. Examples of the silsesquioxane of the condensate include: a condensed silsesquioxane represented by the following formula (1a-1b) formed by condensing two groups represented by -OR ^c in the above formula (1') with each other. alkyl. In addition, the substituents (R ^1a to R ^1r ) in the formulas (1a-1b) are the same as those in the formulas (1a) and (1b).

In the condensed silsesquioxane of the present invention, one clathrate silsesquioxane represented by the above-mentioned composition formula (2) and another clathrate silsesquioxane represented by the above-mentioned composition formula (2) are used. Examples of the silsesquioxane of the condensate include: a condensed silsesquioxane represented by the following formula (2a-2a) formed by condensing two groups represented by -OR ^c in the above formula (2') with each other. alkyl. In addition, the substituents (R ^2a to R ^2h ) in the formula (2a-2a) are the same as those in the formula (2a).

In addition to the condensed silsesquioxane of the present invention, the polyorganosiloxane silsesquioxane of the present invention may also include a cage-type (structure) silsesquioxane ( That is, complete clathrate silsesquioxane), and clathrate silsesquioxanes represented by the above-mentioned compositional formula (1), compositional formula (2), compositional formula (3), compositional formula (4), etc. Monomeric cage silsesquioxanes such as those that have been condensed (ie, incomplete cage silsesquioxanes). Furthermore, in this specification, both of the above-mentioned complete cage-type silsesquioxane and incomplete cage-type silsesquioxane are collectively referred to as monomer cage-type silsesquioxane. The content of the monomer cage silsesquioxane in the polyorganosiloxane of the present invention is, for example, 5% by weight or more, preferably 10% by weight relative to the total amount of the polyorganosiloxane of the present invention % or more, more preferably 20% by weight or more, for example, 50% by weight or less, preferably 40% by weight or less, more preferably 20% by weight or less. If the content of the above-mentioned monomeric cage silsesquioxane is in the above-mentioned range, the surface hardness of the cured product can be further improved.

The polyorganosiloxane of the present invention may also have cage silsesquioxanes other than the condensed silsesquioxane of the present invention. In addition, the polyorganosiloxane of the present invention may have a silsesquioxane structure such as a ladder type or random type in addition to the cage type silsesquioxane. Moreover, you may combine two or more of these silsesquioxane structures.

The content of the condensed silsesquioxane of the present invention in the polyorganosiloxane sesquioxane of the present invention is 20% by weight or more (preferably 25-90 wt % relative to the total amount of the polyorganosiloxane sesquioxane of the present invention). % by weight, more preferably 30 to 80% by weight, still more preferably 40 to 70% by weight). The content of cage silsesquioxane relative to the total amount of polyorganosiloxane of the present invention is, for example, 40-99.5 wt %, preferably 45-98 wt %, more preferably 50-96 wt % %.

The number average molecular weight (Mn) of the polyorganosiloxane of the present invention in terms of standard polystyrene conversion based on gel permeation chromatography is, for example, 2,000-50,000, preferably 2,500-40,000, more preferably 3,000-30,000 . By setting the number average molecular weight to 2000 or more, the surface of the uncured or semi-cured hard coat layer is easy to become non-adhesive, the blocking resistance is improved, and it is easy to be wound into a roll. Therefore, by setting the number average molecular weight to 2000 or more, it can be preferably used as a component of a 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 be 50,000 or less, the compatibility with other components in the curable composition is improved, and the heat resistance of the cured product is further improved.

The molecular weight dispersion (Mw/Mn) of the polyorganosiloxane of the present invention based on standard polystyrene conversion based on gel permeation chromatography is, for example, 1.0-4.0, preferably 1.1-3.0, more preferably 1.2 ~2.5. By making the molecular weight dispersity 4.0 or less, the solubility to a solvent becomes favorable, and the surface hardness or adhesiveness of a hardened|cured material improves further. On the other hand, by making the molecular weight dispersion degree 1.1 or more, it becomes easy to become a liquid state, and there exists a tendency for workability|operativity to improve.

Furthermore, the number average molecular weight and molecular weight dispersion of the polyorganosiloxane sesquioxane of the present invention can be determined by GPC measurement. In addition, the content of the above-mentioned monomer cage silsesquioxane and condensed silsesquioxane in the polyorganosiloxane of the present invention can be obtained from the area ratio of the area values of the corresponding peaks in the GPC measurement. GPC measurement can be performed by the following apparatus and conditions. Measuring device: Trade name "GPC Semi-Micro System" (manufactured by Shimadzu Corporation) Detector: RI detector (manufactured by Zhaoguang Science Co., Ltd.) Column: KF-G4A (guard column), KF-602, and KF-603 (manufactured by Zhaoguang Science Co., Ltd.) Flow rate: 0.6 mL/min Measurement temperature: 40℃ Measurement time: 13 min Injection volume: 20 μL Precipitate: THF, sample concentration 0.1 to 0.2 wt% Molecular weight: standard polystyrene conversion

The 5% weight reduction temperature (T _d5 ) of the polyorganosiloxane sesquioxane of the present invention in an air environment is not particularly limited. More preferably, it is 350 degreeC or more. When the temperature is 330° C. or higher by 5% weight reduction, the heat resistance of the cured product tends to be further improved. In the polyorganosiloxane sesquioxane of the present invention, the ratio [T3 body/T2 body] is 1 or more and 500 or less, the number average molecular weight is 2,000-50,000, and the molecular weight dispersity is 1.0-4.0, which is 5% of the cured product. The weight reduction temperature is 330°C or higher. Furthermore, the 5% weight reduction temperature is an index of heat resistance, and it is the temperature at which the weight is reduced by 5% compared to the weight before heating when heating is performed at a constant temperature increase rate. The above-mentioned 5% weight loss temperature can be measured by TGA (thermogravimetric analysis) under the condition of a temperature increase rate of 5°C/min in an air environment.

The polyorganosiloxane of the present invention can be produced by a known or conventional production method of polysiloxane without particular limitation. For example, it can be produced by hydrolyzing one or more hydrolyzable silane compounds Manufactured by the method of condensation. Among them, as the hydrolyzable silane compound, a hydrolyzable trifunctional silane compound (a compound represented by the following formula (A)) must be used as an essential hydrolyzable silane compound.

More specifically, for example, the hydrolyzable silane compound used to form the silsesquioxane constituent unit (T unit) in the polyorganosiloxane of the present invention is represented by the following formula (a). The compound, the compound represented by the following formula (b) and the compound represented by the following formula (c) are further hydrolyzed and condensed as necessary to generate the above-mentioned composition formula (1), composition formula (2), composition The clathrate silsesquioxane represented by the formula (3) and/or the compositional formula (4) can be further hydrolyzed and condensed to produce the polyorganic organic compound of the present invention containing the condensed silsesquioxane of the present invention Silsesquioxane, the condensed silsesquioxane of the present invention is the cage-type silsesquioxane represented by the above-mentioned compositional formula (1), compositional formula (2), compositional formula (3) and compositional formula (4). Among the alkanes, two or more are condensed in the case of one kind, or two or more are condensed in the case of two or more kinds.

The compound represented by the above formula (A) is a compound that forms a structural unit represented by [ ^RA SiO _3/2 ] or [ ^RA SiO _2/2 (OR ^c )] in the condensed silsesquioxane of the present invention . R ^A in the formula (A) and R 1 in the above-mentioned composition formula (1), R ² in the composition formula (2), R ³ in the composition formula (3), and R ⁴ in the composition formula ( ⁴ ) ( That is, the substituent in the cage silsesquioxane) similarly represents a polymerizable functional group-containing group. R ^A in the formula (A) is preferably a group represented by the above formula (1A), a group represented by the above formula (1B), or a group represented by the above formula (1C) as the group containing a polymerizable functional group. The base represented by the above formula (1D) is more preferably the base represented by the above formula (1A), the base represented by the above formula (1C), and more preferably the base represented by the above formula (1A), More preferably, it is a group represented by the above formula (1A) and R ^1A is a group of ethylidene [wherein, it is 2-(3′,4′-epoxycyclohexyl)ethyl].

X ¹ in the above formula (A) represents an alkoxy group or a halogen atom. Examples of the alkoxy group in X ¹ include alkoxy groups having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and an isobutoxy group. Moreover, as ^a halogen atom in X1, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, for example. Among them, X ¹ is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. Furthermore, the three X ^1s may be the same or different.

The compound represented by the above formula (B) is a compound that forms a constituent unit represented by [R ^B SiO _3/2 ] or [R ^B SiO _2/2 (OR ^c )] in the condensed silsesquioxane of the present invention . In formula (B), R ^B represents substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkyl , or substituted or unsubstituted alkenyl. In formula (B), R ^B is preferably substituted or unsubstituted aryl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, more preferably substituted or unsubstituted The aryl group is more preferably a phenyl group.

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

The compound represented by the above formula (C) is a compound that forms a constituent unit represented by [HSiO _3/2 ] or [HSiO _2/2 (OR ^c )] in the condensed silsesquioxane of the present invention. In the above formula (C), X ³ represents an alkoxy group or a halogen atom. Specific examples of X ³ include those exemplified as X ¹ . Among them, X ³ is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. Furthermore, the three X ^3s may be the same or different.

As the hydrolyzable silane compound, a hydrolyzable silane compound other than the compounds represented by the above formulae (A) to (C) may be used in combination. For example, hydrolyzable trifunctional silane compounds other than the compounds represented by the above formulae (A) to (C), hydrolyzable monofunctional silane compounds that form M units, hydrolyzable difunctional silane compounds that form D units, and Q units form Hydrolyzable tetrafunctional silane compounds, etc.

The usage amount or composition of the above-mentioned hydrolyzable silane compound can be appropriately adjusted according to the desired structure of the polyorganosiloxane silsesquioxane of the present invention. For example, the use amount of the compound represented by the above formula (A) is not particularly limited, but is preferably 30 to 100 mol % relative to the total amount (100 mol %) of the hydrolyzable silane compound used, more preferably It is 55-100 mol%, more preferably 65-100 mol%, and still more preferably 80-99 mol%.

In addition, the usage amount of the compound represented by the above formula (B) is not particularly limited, but is preferably 0 to 70 mol %, more preferably 0 to 70 mol % with respect to the total amount (100 mol %) of the hydrolyzable silane compound used. It is 0 to 60 mol %, more preferably 0 to 40 mol %, and still more preferably 1 to 15 mol %.

Furthermore, the ratio (total ratio) of the compound represented by the formula (A) and the compound represented by the formula (B) with respect to the total amount (100 mol %) of the hydrolyzable silane compound used is not particularly limited, Preferably it is 60-100 mol%, More preferably, it is 70-100 mol%, More preferably, it is 80-100 mol%.

Moreover, when two or more types are used together as the said hydrolyzable silane compound, the hydrolysis and condensation reaction of these hydrolyzable silane compounds may be performed simultaneously, and may be performed sequentially. When the above-mentioned reactions are carried out successively, the order of carrying out the reactions is not particularly limited.

The hydrolysis and condensation reaction of the hydrolyzable silane compound can be carried out in one stage or in two or more stages. In order to efficiently produce the polyorganosiloxane sesquioxane of the present invention, it is preferably carried out in two stages or more (preferably For 2 stages) hydrolysis and condensation reactions are carried out. Hereinafter, an aspect in which the hydrolysis and condensation reactions of the hydrolyzable silane compound are carried out in two steps will be described, but the method for producing the polyorganosiloxane of the present invention is not limited thereto.

In the case where the hydrolysis and condensation reaction of the present invention are carried out in two stages, it is preferable to obtain the above-mentioned ratio [T3 body/T2 body] in the hydrolysis and condensation reaction of the first stage to be 1 or more and less than 20, and the number average For example, polyorganosiloxane with a molecular weight of 1000-3000 (hereinafter referred to as "intermediate polyorganosiloxane"), in the second stage, the intermediate polyorganosiloxane is further hydrolyzed and Condensation reaction, thereby obtaining the polyorganosiloxane sesquioxane of the present invention.

烷等醚；丙酮、甲基乙基酮、甲基異丁基酮等酮；乙酸甲酯、乙酸乙酯、乙酸異丙酯、乙酸丁酯等酯；N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等醯胺；乙腈、丙腈、苯甲腈等腈；甲醇、乙醇、異丙醇、丁醇等醇等。其中，上述溶劑較佳為酮、醚。再者，溶劑既可單獨使用1種，亦可組合2種以上使用。The hydrolysis and condensation reaction of the first stage may be carried out in the presence or absence of a solvent. Among them, it is preferably carried out in the presence of a solvent. Examples of the above-mentioned solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; diethyl ether, dimethoxyethane, tetrahydrofuran, diethyl ether,

Ethers such as alkane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, etc.; N,N-dimethylformamide , N,N-dimethylacetamide and other amides; acetonitrile, propionitrile, benzonitrile and other nitriles; methanol, ethanol, isopropanol, butanol and other alcohols. Among them, the above-mentioned solvents are preferably ketones and ethers. In addition, a solvent may be used individually by 1 type, and may be used in combination of 2 or more types.

The amount of the solvent used in the hydrolysis and condensation reactions in the first stage is not particularly limited, and may be in the range of 0 to 2,000 parts by weight with respect to 100 parts by weight of the total amount of the hydrolyzable silane compound, depending on the required reaction time, etc. Appropriate adjustments.

The hydrolysis and condensation reactions in the first stage are preferably carried out in the presence of a catalyst and water. The above-mentioned catalyst may be an acid catalyst or an alkali catalyst, and in order to suppress the decomposition of polymerizable functional groups such as epoxy groups, an alkali catalyst is preferred. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid; phosphoric acid esters; carboxylic acids such as acetic acid, formic acid, and trifluoroacetic acid; methanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid. Sulfonic acid such as acid; solid acid such as activated clay; Lewis acid such as ferric chloride, etc. Examples of the above-mentioned alkali catalyst include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; and hydrogen of alkaline earth metals such as magnesium hydroxide, calcium hydroxide, and barium hydroxide. Oxides; carbonates of alkali metals such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate; carbonates of alkaline earth metals such as magnesium carbonate; lithium bicarbonate, sodium bicarbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate Alkaline metal bicarbonate such as lithium acetate, sodium acetate, potassium acetate, cesium acetate and other alkali metal organic acid salts (such as acetate); magnesium acetate and other alkaline earth metal organic acid salts (such as acetate); lithium methoxide , sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium ethoxide, potassium 3-butoxide and other alkali metal alkoxides; sodium phenoxide and other alkali metal phenolates; triethylamine, N-methylpiperidine, 1 ,8-Diazbicyclo[5.4.0]undec-7-ene, 1,5-diazbicyclo[4.3.0]non-5-ene and other amines (tertiary amines, etc.); pyridine, 2,2 '-bipyridine, 1,10-phenanthroline and other nitrogen-containing aromatic heterocyclic compounds, etc. In addition, a catalyst may be used individually by 1 type, and may be used in combination of 2 or more types. In addition, the catalyst may be used in a state of being dissolved or dispersed in water, a solvent, or the like.

The usage-amount of the said catalyst in the hydrolysis and condensation reaction of a 1st stage is not specifically limited, It can adjust suitably in the range of 0.002-0.200 mol with respect to 1 mol of the total amount of a hydrolyzable silane compound.

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

The method of adding the above-mentioned water in the hydrolysis and condensation reaction in the first stage is not particularly limited, and the total amount of the water used (total amount used) may be added at one time, or may be added sequentially. In the case of successive addition, it may be added continuously or intermittently.

As the reaction conditions for the hydrolysis and condensation reactions in the first stage, it is important to select the reaction conditions such that the above-mentioned ratio [T3 body/T2 body] of the intermediate polyorganosiloxane is 1 or more and less than 20. The reaction temperature of the hydrolysis and condensation reaction in the first stage is not particularly limited, but is preferably 40 to 100°C, more preferably 45 to 80°C. By controlling the reaction temperature within the above-mentioned range, the above-mentioned ratio [T3 body/T2 body] tends to be more efficiently controlled to 1 or more and less than 20. In addition, the reaction time of the hydrolysis and condensation reaction in the first stage is not particularly limited, but is preferably 0.1 to 10 hours, more preferably 1.5 to 8 hours. In addition, the hydrolysis and condensation reaction of the first stage may be carried out under normal pressure, under pressure or under reduced pressure. Furthermore, the environment in which the hydrolysis and condensation reactions of the first stage are carried out is not particularly limited. For example, it may be in an inert gas environment such as a nitrogen atmosphere, an argon atmosphere, or in the presence of oxygen such as air, etc., preferably inactive. in a gaseous environment.

Through the above-mentioned first-stage hydrolysis and condensation reaction, the intermediate polyorganosiloxane can be obtained. After completion of the hydrolysis and condensation reaction in the first stage, it is preferable to perform catalyst neutralization to suppress decomposition of polymerizable functional groups such as ring-opening of epoxy groups. In addition, the intermediate polyorganosiloxane sesquioxane can be separated by, for example, water washing, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or Separation and purification of these combined separation means, etc. are carried out. Also, the reaction solution containing the intermediate polyorganosiloxane sesquioxane can be used for the hydrolysis and condensation reactions in the first stage.

The polyorganosiloxane of the present invention can be produced by subjecting the intermediate polyorganosiloxane obtained by the hydrolysis and condensation reaction of the first stage to the hydrolysis and condensation reaction of the second stage. The hydrolysis and condensation reaction of the second stage can be carried out in the presence or absence of a solvent. When performing the hydrolysis and condensation reaction of the second stage in the presence of a solvent, the solvents listed in the hydrolysis and condensation reaction of the first stage can be used. As the solvent for the hydrolysis and condensation reaction in the second stage, polyorganosiloxane, an intermediate containing the reaction solvent and extraction solvent for the hydrolysis and condensation reaction in the first stage, can be used as it is, or a part or all of it can be used. The resultant was removed by distillation. In addition, a high-boiling solvent with a boiling point higher than the solvent used in the first-stage hydrolysis and condensation reactions is added to the reaction solution containing the intermediate polyorganosiloxane, followed by heating and distillation to remove, thereby replacing the solvent. In addition, a solvent may be used individually by 1 type, and may be used in combination of 2 or more types.

When the solvent is used in the hydrolysis and condensation reaction in the second stage, the amount of the solvent used is not particularly limited. According to the required reaction time, etc., it is 0 with respect to 100 parts by weight of the intermediate polyorganosiloxane sesquioxane. Appropriate adjustment within the range of ~2000 parts by weight.

The hydrolysis and condensation reactions in the second stage are preferably carried out in the presence of a catalyst and water. The catalysts listed in the hydrolysis and condensation reactions in the first stage can be used as the above-mentioned catalysts. In order to suppress the decomposition of polymerizable functional groups such as epoxy groups, alkali catalysts are preferred, and sodium hydroxide and hydroxide are more preferred. Hydroxides of alkali metals such as potassium and cesium hydroxide; carbonates of alkali metals such as lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate. In addition, a catalyst may be used individually by 1 type, and may be used in combination of 2 or more types. In addition, the catalyst may be used in a state of being dissolved or dispersed in water, a solvent, or the like. In addition, the catalyst used for the hydrolysis and condensation reaction in the first stage can be directly used for the hydrolysis and condensation reaction in the second stage.

The usage amount of the above-mentioned catalyst in the hydrolysis and condensation reaction of the second stage is not particularly limited, and it is preferably 0.01-10,000 ppm, more preferably 0.1 ppm relative to the intermediate polyorganosiloxane sesquioxane (1,000,000 ppm) Adjust appropriately within the range of ~1000 ppm.

The amount of water used in the hydrolysis and condensation reaction in the second stage is not particularly limited, but it is preferably 10-100,000 ppm, more preferably 100-20,000 ppm relative to the intermediate polyorganosiloxane sesquioxane (1,000,000 ppm). Adjust appropriately within the range of ppm. If the amount of water used exceeds 100,000 ppm, the ratio of polyorganosiloxane sesquioxane [T3 body/T2 body] or the number average molecular weight tends to be difficult to control within the specified range.

The method of adding the above-mentioned water in the hydrolysis and condensation reaction in the second stage is not particularly limited, and the total amount of the water used (the total amount used) may be added at one time, or may be added sequentially. In the case of successive addition, it may be added continuously or intermittently. Moreover, the water used for the hydrolysis and condensation reaction of the 1st stage may be used as it is, or the water remaining after a part of distillation may be used.

As the reaction conditions of the hydrolysis and condensation reaction in the second stage, it is important to select the above-mentioned ratio [T3 body/T2 body] of the polyorganosiloxane sesquioxane of the present invention to be 20 or more and 500 or less, and the number average molecular weight to be 2000 to 2000. 50,000 reaction conditions. The reaction temperature of the hydrolysis and condensation reaction in the second stage varies depending on the catalyst used, and is not particularly limited, but is preferably 5 to 200°C, more preferably 30 to 150°C, and still more preferably 80 to 120°C. By controlling the reaction temperature within the above-mentioned range, the above-mentioned ratio [T3 body/T2 body] and the number average molecular weight tend to be more efficiently controlled within the desired range. In addition, the reaction time of the hydrolysis and condensation reaction in the second stage is not particularly limited, but is preferably 0.5 to 1000 hours, more preferably 1 to 500 hours, and still more preferably 5 to 200 hours. In addition, the hydrolysis and condensation reactions are carried out in the range of the above-mentioned reaction temperature, and sampling is carried out in a timely manner, and the reaction is carried out while detecting the above-mentioned ratio [T3 body/T2 body] and the number average molecular weight. The ratio [T3 body/T2 body], the number average molecular weight of the polyorganosiloxane sesquioxane of the present invention.

The hydrolysis and condensation reaction in the second stage may be carried out under normal pressure, or under increased pressure or reduced pressure. In addition, the environment in which the hydrolysis and condensation reactions of the second stage are carried out is not particularly limited, and for example, it may be in an inert gas environment such as a nitrogen atmosphere, an argon atmosphere, or in the presence of oxygen such as air, etc., preferably inert. in a gaseous environment.

The polyorganosiloxane of the present invention can be obtained through the hydrolysis and condensation reaction in the second stage. After completion of the hydrolysis and condensation reaction in the second stage, it is preferable to perform catalyst neutralization to suppress decomposition of polymerizable functional groups such as ring-opening of epoxy groups. In addition, the polyorganosiloxane sesquioxane of the present invention can be separated by, for example, water washing, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or These combined separation means and the like are used for separation and purification.

Since the polyorganosiloxane of the present invention contains a condensed silsesquioxane in which two or more clathrate silsesquioxanes are condensed in a straight chain, it is considered to be different from the conventional polyorganosiloxane silsesquioxane. In contrast, there is a tendency to have excellent hardening properties. Therefore, the cured product of the curable composition containing the polyorganosiloxane sesquioxane of the present invention has high surface hardness and excellent heat resistance. Furthermore, the polyorganosiloxane sesquioxane of the present invention is excellent in solubility in solvents such as organic solvents. "Two or more clathrate silsesquioxanes are linearly condensed" means two or more of the above compositional formula (1), compositional formula (2), compositional formula (3), and/or compositional formula (4) ) represented by the cage-type silsesquioxane condensed in series rather than three-dimensional condensation, resulting in the formation of linear condensate. Also, even if the polyorganosiloxane of the present invention includes a cage silsesquioxane having three hydroxyl groups represented by -OR ^c as shown in the above-mentioned compositional formulas (5) and (6) When two of them are condensed, it is equivalent to "two or more cage-type silsesquioxanes are condensed in a straight chain". Furthermore, the above-mentioned mechanisms are merely presumptions and should not be construed as being limited to these mechanisms.

[hardenable composition] The curable composition of the present invention is a curable composition (curable resin composition) containing the above-described polyorganosilosilsesquioxane of the present invention as an essential component. As described below, the curable composition of the present invention may further contain a curing catalyst (for example, a photocationic polymerization initiator, a radical polymerization initiator), a surface conditioner or a surface modifier, a polymerization stabilizer, a silane Couplers and other ingredients. The curable composition of the present invention can be used as a curable composition for forming a hard coat layer or a curable composition for an adhesive (eg, a curable composition for laminated semiconductors), depending on the application. In the curable composition of the present invention, the polyorganosiloxane sesquioxane of the present invention may be used alone or in combination of two or more.

The content (compounding amount) of the polyorganosiloxane of the present invention in the curable composition of the present invention is not particularly limited, and it is more than the total amount (100% by weight) of the curable composition excluding the solvent. Preferably it is 70 weight% or more and less than 100 weight%, More preferably, it is 80 to 99.8 weight%, More preferably, it is 90 to 99.5 weight%. By setting the content of the polyorganosiloxane sesquioxane of the present invention to 70% by weight or more, the surface hardness or adhesiveness of the cured product tends to be further improved. On the other hand, by setting the content of the polyorganosiloxane sesquioxane of the present invention to be less than 100% by weight, a curing catalyst can be contained, whereby the curing of the curable composition tends to be more efficient. .

The ratio of the polyorganosiloxane sesquioxane of the present invention is not particularly limited with respect to the total amount (100% by weight) of the cationic curable compound or radical curable compound contained in the curable composition of the present invention, and is preferably It is 70-100 weight%, More preferably, it is 75-98 weight%, More preferably, it is 80-95 weight%. By setting the content of the polyorganosiloxane sesquioxane of the present invention to 70% by weight or more, the surface hardness or adhesiveness of the cured product tends to be further improved.

The curable composition of the present invention preferably further contains a curing catalyst. Among them, it is preferable to contain a photo- or thermal polymerization initiator as a hardening catalyst, and it is more preferable to contain a cationic polymerization initiator or a radical polymerization initiator from the viewpoint of being able to further shorten the curing time until it does not stick. In addition, in the curable composition of this invention, a hardening catalyst may be used individually by 1 type, and may be used in combination of 2 or more types.

The above-mentioned cationic polymerization initiator is a compound capable of initiating or accelerating the cationic polymerization reaction of the cationic curable compound such as the polyorganosiloxane sesquioxane of the present invention. Although the said cationic polymerization initiator is not specifically limited, For example, a photocationic polymerization initiator (photoacid generator), a thermal cationic polymerization initiator (thermal acid generator), etc. are mentioned.

As the above-mentioned photocationic polymerization initiator, known or conventional photocationic polymerization initiators can be used, and examples thereof include perium salts (salts of perionium ions and anions), iodonium salts (salts of iodonium ions and anions), selenium salts (salt of selenium ion and anion), ammonium salt (salt of ammonium ion and anion), phosphonium salt (salt of phosphonium ion and anion), transition metal complex ion and salt of anion, etc. These can be used individually or in combination of 2 or more types.

Examples of the above-mentioned perylium salts include [4-(4-biphenylthio)phenyl]-4-biphenylphenyl perylium tris(pentafluoroethyl)trifluorophosphate, and triphenyl perylium salts. , Tri-p-Toluene salt, Tri-o-Toluene salt, Tris (4-methoxyphenyl) Peri salt, 1-naphthyl diphenyl periyl salt, 2-naphthyl diphenyl periyl salt, Tris (4- Fluorophenyl) pericolium salt, tris-1-naphthyl pericanium salt, tris-2-naphthyl pericynium salt, tris(4-hydroxyphenyl) pericolium salt, diphenyl[4-(phenylthio)phenyl] Perylium salts, 4-(p-tolylthio) phenyl di(p-phenyl) pericynium salts and other triaryl pericynium salts; diphenylbenzyl methyl perylate, diphenyl 4-nitrobenzyl methyl Perylium salts, diphenylbenzyl periconium salts, diphenylmethyl perylium salts, and other diaryl periconium salts; Monoaryl periconium salts such as phenylmethylbenzyl perionium salt; dimethylbenzyl methyl perionium salt, benzyl methyl tetrahydrothiophenium salt (phenacyl tetrahydro thiophenium salt), dimethylbenzyl perionium salt Salts and other trialkyl perionate salts, etc.

As the above-mentioned diphenyl[4-(phenylthio)phenyl]perylium salt, for example, diphenyl[4-(phenylthio)phenyl]perylium hexafluoroantimonate, diphenyl[4-( Phenylthio) phenyl] perilinium hexafluorophosphate and the like.

Examples of the above-mentioned iodonium salt include: trade name "UV9380C" (manufactured by Momentive High-Tech Materials Japan Co., Ltd., bis(4-dodecylphenyl) iodonium=hexafluoroantimonate 45% alkylglycidyl ether solution), trade name "RHODORSIL PHOTOINITIATOR 2074" (manufactured by Rhodia Japan Co., Ltd., tetrakis(pentafluorophenyl)borate=[(1-methylethyl)phenyl](methylphenyl)idium), Trade name "WPI-124" (manufactured by Wako Pure Chemical Industries, Ltd.), diphenyl iodonium salt, di-p-toluene iodonium salt, bis(4-dodecylphenyl) iodonium salt, bis(4-methyl) oxyphenyl) iodonium salt, etc.

Examples of the selenium salt include triphenylselenide, tri-p-tolueneselenide, tri-o-tolueneselenide, tris(4-methoxyphenyl)selenide, 1-naphthyldiphenylselenide, and the like. Triaryl selenide; diaryl selenide such as diphenylbenzyl selenide, diphenylbenzyl selenide, diphenylmethyl selenide; monoaryl such as phenylmethyl benzyl selenide Selenium salts; trialkyl selenium salts such as dimethylbenzyl methyl selenium salt, etc.

啉鎓鹽、N,N-二乙基

啉鎓鹽等

啉鎓鹽（morpholinium salt）；N,N-二甲基哌啶鎓鹽、N,N-二乙基哌啶鎓鹽等哌啶鎓鹽（piperidinium salt）；N-甲基吡啶鎓鹽、N-乙基吡啶鎓鹽等吡啶鎓鹽（pyridinium salt）；N,N'-二甲基咪唑鎓鹽等咪唑鎓鹽（imidazolium salt）；N-甲基喹啉鎓鹽等喹啉鎓鹽（quinolium salt）；N-甲基異喹啉鎓鹽等異喹啉鎓鹽；苄基苯并噻唑鎓鹽等噻唑鎓鹽（thiazonium salt）；苄基吖啶鎓鹽等吖啶鎓鹽（acridinium）等。As said ammonium salt, tetramethyl ammonium salt, ethyl trimethyl ammonium salt, diethyl dimethyl ammonium salt, triethyl methyl ammonium salt, tetraethyl ammonium salt, trimethyl ammonium salt, trimethyl ammonium salt, for example Tetraalkylammonium salts such as propylammonium salt, trimethyl-n-butylammonium salt; N,N-dimethylpyrrolidinium salt, N-ethyl-N-methylpyrrolidinium salt and other pyrrolidinium salts (pyrrolidinium salt); N,N'-dimethylimidazolinium salt, N,N'-diethylimidazolinium salt and other imidazolinium salts (imidazolinium salt); N,N'-dimethyl tetrahydro Pyrimidinium salts, N,N'-diethyltetrahydropyrimidinium salts and other tetrahydropyrimidinium salts (tetrahydro pyrimidinium salt); N,N-dimethyl

Linonium salt, N,N-diethyl

phosphonium salts, etc.

Morpholinium salts (morpholinium salts); N,N-dimethylpiperidinium salts, N,N-diethylpiperidinium salts and other piperidinium salts (piperidinium salts); N-methylpyridinium salts, N-methylpyridinium salts -Pyridinium salts such as ethylpyridinium salts (pyridinium salts); N,N'-dimethylimidazolium salts and other imidazolium salts (imidazolium salts); salt); isoquinolinium salts such as N-methyl isoquinolinium salts; thiazonium salts such as benzyl benzothiazolium salts (thiazonium salts); benzyl acridinium salts and other acridinium salts (acridinium), etc. .

Examples of the phosphonium salts include tetraarylphosphonium salts such as tetraphenylphosphonium salts, tetra-p-toluenephosphonium salts, and tetrakis(2-methoxyphenyl)phosphonium salts; and triarylphosphonium salts such as triphenylbenzylphosphonium salts. Phosphonium salts; tetraalkylphosphonium salts such as triethylbenzylphosphonium salt, tributylbenzylphosphonium salt, tetraethylphosphonium salt, tetrabutylphosphonium salt, triethylbenzylmethylphosphonium salt, etc.

Examples of the salts of the transition metal complex ions include (η5-cyclopentadienyl)(η6-toluene)Cr ⁺ , (η5-cyclopentadienyl)(η6-xylene)Cr ⁺ and the like Salts of chromium complex cations; salts of iron complex cations such as (η5-cyclopentadienyl) (η6-toluene) Fe ⁺ , (η5-cyclopentadienyl) (η6-xylene) Fe ⁺ Wait.

Examples of anions constituting the above salts include SbF ₆ ^- , PF ₆ ^- , BF ₄ ^- , (CF ₃ CF ₂ ) ₃ PF ₃ ^- , (CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ^- , (C ₆ ). F ₅ ) ₄ B ^- , (C ₆ F ₅ ) ₄ Ga ^- , sulfonate anion (trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, nonafluorobutanesulfonate anion, mesylate anion, benzenesulfonate anion anion, p-toluenesulfonate anion, etc.), (CF ₃ SO ₂ ) ₃ C ^- , (CF ₃ SO ₂ ) ₂ N ^- , perhalogenate ion, halogenated sulfonate ion, sulfate ion, carbonate ion, aluminate ion ion, hexafluorobismuthate ion, carboxylate ion, arylborate ion, thiocyanate ion, nitrate ion, etc.

Examples of the thermal cationic polymerization initiator include aryl perionium salts, aryl iodonium salts, aromatic hydrocarbon-ion complexes, quaternary ammonium salts, aluminum chelates, boron trifluoride amine complexes, and the like.

As said aryl perionium salt, hexafluoroantimonate etc. are mentioned, for example. In the curable composition of the present invention, for example, trade names "SP-66" and "SP-77" (the above are manufactured by ADEKA Corporation); trade names "San-Aid SI-60L", "San-Aid SI-60L", "San-Aid SI-60L" -Aid SI-80L", "San-Aid SI-100L", "San-Aid SI-150L" (the above are manufactured by Sanxin Chemical Industry Co., Ltd.) and other commercial products. As said aluminum chelate compound, ethyl aluminum diisopropyl acetoacetate, Tris (ethyl acetoacetato) aluminum, etc. are mentioned, for example. Moreover, as said boron trifluoride amine complex, a boron trifluoride monoethylamine complex, a boron trifluoride imidazole complex, a boron trifluoride piperidine complex, etc. are mentioned, for example.

The above-mentioned radical polymerization initiator is a compound capable of initiating or accelerating the radical polymerization reaction of radically curable compounds such as polyorganosiloxane of the present invention. As said radical polymerization initiator, a photo radical polymerization initiator, a thermal radical polymerization initiator, etc. are mentioned, for example.

（日本化藥（股）製造，商品名「kayacure DETX」等）、2-甲基-1-[4-(甲基)苯基]-2-

啉基丙酮-1（Ciba-Geigy（股）製造，商品名「Irgacure 907」等）、1-羥基環己基苯基酮（Ciba-Geigy（股）製造，商品名「Irgacure 184」等）、2-二甲基胺基-2-(4-

啉基)苯甲醯基-1-苯基丙烷等之2-胺基-2-苯甲醯基-1-苯基烷烴化合物、四(第三丁基過氧基羰基)二苯甲酮、二苯乙二酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、4,4-雙二乙基胺基二苯甲酮等胺基苯衍生物、2,2'-雙(2-氯苯基)-4,5,4',5'-四苯基-1,2'-聯咪唑（保土谷化學（股）製造，商品名「B-CIM」等）等咪唑化合物、2,6-雙(三氯甲基)-4-(4-甲氧基萘-1-基)-1,3,5-三

等鹵甲基化三

化合物、2-三氯甲基-5-(2-苯并呋喃-2-基-乙烯基)-1,3,4-

二唑等鹵甲基

二唑化合物等。又，視需要可添加光敏劑。Examples of the photoradical polymerization initiator include benzophenone, acetophenone diacetophenone, benzoin dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl Ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyldisulfide, methyl o-benzoic acid benzoate, 4-dimethylamine Ethyl benzoate (manufactured by Nippon Kayaku Co., Ltd., trade name "kayacure EPA", etc.), 2,4-diethyl-9-oxothioate

(manufactured by Nippon Kayaku Co., Ltd., trade name "kayacure DETX", etc.), 2-methyl-1-[4-(methyl)phenyl]-2-

Linoacetone-1 (manufactured by Ciba-Geigy Co., Ltd., trade name "Irgacure 907", etc.), 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba-Geigy Co., Ltd., trade name "Irgacure 184", etc.), 2 -Dimethylamino-2-(4-

2-Amino-2-benzyl-1-phenyl alkane compounds such as olinyl)benzyl-1-phenylpropane, tetrakis(tert-butylperoxycarbonyl)benzophenone, Aminobenzene derivatives such as benzophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 4,4-bisdiethylaminobenzophenone, 2,2 '-Bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole (manufactured by Hodogaya Chemical Co., Ltd., trade name "B-CIM", etc.) Isoimidazole compound, 2,6-bis(trichloromethyl)-4-(4-methoxynaphthalen-1-yl)-1,3,5-tris

isohalomethylated tris

Compound, 2-trichloromethyl-5-(2-benzofuran-2-yl-vinyl)-1,3,4-

Halomethyl such as oxadiazole

oxadiazole compounds, etc. Moreover, a photosensitizer may be added as needed.

Examples of thermal radical polymerization initiators include hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides, peroxydicarbonates, peroxyketals, and ketone peroxides. (specifically, benzalkonium peroxide, (-2-ethylhexanoic acid) tert-butyl peroxide, 2,5-dimethyl-2,5-bis(2-ethyl) Hexyl) peroxyhexane, tert-butyl peroxybenzoate, tert-butyl peroxide, cumene hydroperoxide, bisisophenylpropyl peroxide, di-tert-butyl peroxide compound, 2,5-dimethyl-2,5-dibutylperoxyhexane, 2,4-dichlorobenzyl peroxide, 1,4-bis(2-tert-butylperoxy isopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, methyl ethyl ketone peroxide, (2-ethyl peroxide) hexanoic acid)-1,1,3,3-tetramethylbutyl ester, etc.) and other organic peroxides.

The content (compounding amount) of the above-mentioned hardening catalyst in the curable composition of the present invention is 100 parts by weight in total with respect to the polyorganosiloxane sesquioxane of the present invention and the following other cationic curable compounds. Preferably it is 0.01-3.0 weight part, More preferably, it is 0.05-3.0 weight part, More preferably, it is 0.1-1.0 weight part (for example, 0.3-1.0 weight part). By setting the content of the hardening catalyst to be 0.01 part by weight or more, the hardening reaction can be efficiently and sufficiently advanced, and the surface hardness and adhesiveness of the hardened product tend to be further improved. On the other hand, by setting the content of the hardening catalyst to be 3.0 parts by weight or less, the preservability of the curable composition is further improved, or the coloring of the hardened material tends to be suppressed.

The curable composition of the present invention may further contain cationic curable compounds other than the polyorganosiloxane of the present invention (sometimes referred to as "other cationic curable compounds") and/or the polyorganosiloxane of the present invention Radical hardening compounds other than hemioxanes (sometimes referred to as "other free radical hardening compounds"). As other cationic curable compounds, well-known or conventional cationic curable compounds can be used, and examples thereof include epoxy compounds, oxetane compounds, vinyl ether compounds, and the like other than the polyorganosiloxane of the present invention. Furthermore, in the curable composition of the present invention, other cationic curable compounds may be used alone or in combination of two or more.

As the epoxy compound, well-known or conventional compounds having one or more epoxy groups (ethylene oxide ring) in the molecule can be used, and are not particularly limited, and examples thereof include alicyclic epoxy compounds (alicyclic epoxy compounds). epoxy resin), aromatic epoxy compound (aromatic epoxy resin), aliphatic epoxy compound (aliphatic epoxy resin), etc.

The above-mentioned alicyclic epoxy compound includes known or customary compounds having one or more alicyclic rings and one or more epoxy groups in the molecule, and is not particularly limited. For example, (1) having a constituent lipid in the molecule Compounds with epoxy groups (called "alicyclic epoxy groups") formed by two adjacent carbon atoms and oxygen atoms adjacent to the ring; (2) compounds with epoxy groups directly bonded to the alicyclic ring with a single bond; (3) Compounds having alicyclic and glycidyl ether groups in the molecule (glycidyl ether type epoxy compounds) and the like.

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

In the above formula (i), Y represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the above-mentioned linking group include a divalent hydrocarbon group, an alkenylene group in which a part or all of a carbon-carbon double bond is epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, The basis etc. which are formed by connecting a plurality of these.

As said divalent hydrocarbon group, a C1-C18 linear or branched alkylene group, a divalent alicyclic hydrocarbon group, etc. are mentioned. Examples of linear or branched alkylene groups having 1 to 18 carbon atoms include methylene, methylmethylene, dimethylmethylene, ethylidene, propylidene, and trimethylene. Wait. Examples of the above-mentioned divalent alicyclic hydrocarbon group include 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylene, 1,2-cyclohexylene, 1,3-cyclopentylene Cyclohexyl, 1,4-cyclohexylene, cyclohexylene and other divalent cycloalkylene groups (including cycloalkylene), etc.

Examples of alkenylene groups in alkenylene groups in which a part or the whole of the carbon-carbon double bond is epoxidized (sometimes referred to as "epoxidized alkenylene groups") include vinylidene groups, propenylene groups, 1 -Butenylene, 2-butenyl, butadienyl, pentenyl, hexenyl, heptenyl, octenyl and other straight or branched chains with 2 to 8 carbon atoms Alkenyl and so on. The epoxidized alkenylene group is preferably an alkenylene group in which all carbon-carbon double bonds are epoxidized, and more preferably an alkenylene group with 2 to 4 carbon atoms in which all carbon-carbon double bonds are epoxidized.

Typical examples of the alicyclic epoxy compound represented by the above formula (i) include (3,4,3',4'-diepoxy)bicyclohexane and the following formula (i-1) The compounds represented by ~(i-10), etc. In addition, l and m in following formula (i-5) and (i-7) each represent the integer of 1-30. In the following formula (i-5), R' is an alkylene group having 1 to 8 carbon atoms, and among them, preferably a methylene group, an ethylidene group, a propylidene group, an isopropylidene group and the like having 1 to 3 carbon atoms straight-chain or branched-chain alkylene. In the following formulae (i-9) and (i-10), n1 to n6 each represent an integer of 1 to 30. Moreover, as an alicyclic epoxy compound represented by the said formula (i), for example, 2,2-bis(3,4-epoxycyclohexyl)propane, 1,2-bis(3,4- Epoxycyclohexyl)ethane, 2,3-bis(3,4-epoxycyclohexyl)ethylene oxide, bis(3,4-epoxycyclohexylmethyl)ether, etc.

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

In formula (ii), R'' is a group obtained by removing p hydroxyl groups (-OH) from the structural formula of p-valent alcohol (a p-valent organic group), and p and n represent natural numbers, respectively. Examples of the p-valent alcohol [R''(OH) _p ] include polyhydric alcohols such as 2,2-bis(hydroxymethyl)-1-butanol (alcohols having 1 to 15 carbon atoms, etc.), and the like. p is preferably 1-6, and n is preferably 1-30. When p is 2 or more, n in the bases within each ( ) (within the outer brackets) may be the same or different. Specific examples of the compound represented by the above formula (ii) include: 1,2-epoxy-4-(2-oxiranyl) of 2,2-bis(hydroxymethyl)-1-butanol Cyclohexane adduct [for example, trade name "EHPE3150" (manufactured by Daicel Co., Ltd.), etc.] and the like.

As a compound which has an alicyclic ring and a glycidyl ether group in the molecule of said (3), the glycidyl ether of an alicyclic alcohol (for example, an alicyclic polyol) is mentioned, for example. More specifically, for example, 2,2-bis[4-(2,3-glycidoxy)cyclohexyl]propane, 2,2-bis[3,5-dimethyl-4- (2,3-glycidoxy)cyclohexyl]propane and other bisphenol A-type epoxy compounds hydrogenated compounds (hydrogenated bisphenol A-type epoxy compounds); bis[o,o-(2,3 -Glycidoxy)cyclohexyl]methane, bis[o,p-(2,3-glycidoxy)cyclohexyl]methane, bis[p,p-(2,3-glycidoxy) ) cyclohexyl]methane, bis[3,5-dimethyl-4-(2,3-glycidoxy)cyclohexyl]methane and other bisphenol F-type epoxy compounds hydrogenated compounds (hydrogenated bisphenol F type epoxy compound); Hydrogenated biphenol type epoxy compound; Hydrogenated phenol novolac type epoxy compound; Hydrogenated cresol novolac type epoxy compound; Hydrogenated cresol novolac type epoxy compound of bisphenol A; Hydrogenated naphthalene type epoxy compounds; hydrogenated epoxy compounds of epoxy compounds obtained from trisphenol methane; hydrogenated epoxy compounds of the following aromatic epoxy compounds, etc.

Examples of the above-mentioned aromatic epoxy compound include epi-bis-type glycidyl ether-type epoxy resins obtained by condensation reaction of bisphenols and epihalohydrin; Epibis-glycidyl ether-type epoxy resin is a high molecular weight epibis-glycidyl ether-type epoxy resin obtained by further addition reaction of the above-mentioned bisphenols; Polyols are obtained, and the polyols are further subjected to condensation reaction with epihalohydrin to obtain a novolac-alkyl glycidyl ether type epoxy resin; 2 phenols are bonded to the 9-position of the perylene ring The skeleton is directly bonded to the oxygen atom after removing the hydrogen atom from the hydroxyl group of the phenol skeleton, or an epoxy compound bonded with a glycidyl group through an alkyleneoxy group, and the like.

Examples of the above-mentioned aliphatic epoxy compound include: glycidyl ether of an alcohol (q is a natural number) of q-valent alcohol without a cyclic structure; glycidyl ester of monovalent or polyvalent carboxylic acid; epoxidized linseed Oil, epoxidized soybean oil, epoxidized castor oil and other epoxidized oils and fats with double bonds; epoxidized epoxidized of polyolefins (including polydiene) such as epoxidized polybutadiene, etc.

As said oxetane compound, the well-known or conventional compound which has one or more oxetane rings in a molecule|numerator is mentioned. As said vinyl ether compound, the well-known or conventional compound which has one or more vinyl ether groups in a molecule|numerator is mentioned.

As another radical curable compound, a well-known or conventional radical curable compound can be used, and it does not specifically limit, For example, the (meth)acrylic compound other than the polyorganosiloxane of this invention is mentioned. As said (meth)acrylic compound, the well-known or usual compound which has one or more (meth)acrylic groups in a molecule|numerator is mentioned.

The content (blending amount) of other cationic curable compounds and/or other radical curable compounds in the curable composition of the present invention is not particularly limited. The total amount of the curable compound and other radical curable compounds (100% by weight; the total amount of the cation curable compound and the radical curable compound) is preferably 50% by weight or less (for example, 0 to 50% by weight), more Preferably it is 30 weight% or less (for example, 0 to 30 weight%), More preferably, it is 10 weight% or less.

The curable composition of the present invention may further contain a polymerization stabilizer. The polymerization stabilizer is a compound having the function of inhibiting the progress of cationic polymerization by trapping cations, saturating the cation-capturing ability of the polymerization stabilizer, and enabling the polymerization to proceed at the stage of deactivation. By including the polymerization stabilizer in the curable composition of the present invention, after coating and drying to form an adhesive layer, the progress of the polymerization can be suppressed for a long time, and the adhesive layer can be heated by heating at a point in time when the adhesiveness is obtained. An adhesive layer with excellent adhesiveness and excellent storage stability. When the curable composition of the present invention is a curable composition for an adhesive, it is preferable to contain a polymerization stabilizer.

-2,4-二基][(2,2,6,6-四甲基-4-哌啶基)亞胺基]六亞甲基[(2,2,6,6-四甲基-4-哌啶基)亞胺基])、1,2,3,4-丁烷四羧酸四(2,2,6,6-四甲基-4-哌啶基)酯、苯甲酸2,2,6,6-四甲基-4-哌啶基酯、(混合2,2,6,6-四甲基-4-哌啶基/十三烷基)-1,2,3,4-丁烷四羧酸酯、3,9-雙(2,3-二第三丁基-4-甲基苯氧基)-2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、混合(2,2,6,6-四甲基-4-哌啶基/β,β,β',β'-四甲基-3-9-[2,4,8,10-四氧雜螺[5.5]十一烷]二乙基)-1,2,3,4-丁烷四羧酸酯、聚([6-N-

啉基-1,3,5-三

-2,4-二基][(2,2,6,6-四甲基-4-哌啶基)亞胺基]六亞甲基[(2,2,6,6-四甲基-4-哌啶基)亞胺基])、[N-(2,2,6,6-四甲基-4-哌啶基)-2-甲基-2-(2,2,6,6-四甲基-4-哌啶基)亞胺基]丙醯胺、商品名「LA-77」、「LA-67」、「LA-57」（以上由ADEKA（股）製造）、商品名「TINUVIN123」、「TINUVIN152」（以上由Ciba Japan（股）公司製造）等受阻胺（hindered amine）系化合物；或(4-羥基苯基)二甲基鋶甲基亞硫酸鹽（例如商品名「San-Aid SI助劑」，三新化學工業（股）公司製造）等鋶硫酸鹽系化合物、商品名「Adekastab PEP-36」（ADEKA（股）製造）等亞磷酸鹽系化合物等。其中，基於更不易產生接著劑於乾燥過程中之局部硬化，硬化物對被接著體之接著性更優異之觀點，較佳為鋶硫酸鹽系化合物、亞磷酸鹽系化合物。As the above-mentioned polymerization stabilizer, for example, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, poly([6-(1,1,3,3-tetramethyl) Methylbutyl)imino-1,3,5-tris

-2,4-Diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]hexamethylene[(2,2,6,6-tetramethyl- 4-Piperidinyl)imino]), 1,2,3,4-butanetetracarboxylic acid tetrakis(2,2,6,6-tetramethyl-4-piperidinyl)ester, benzoic acid 2 ,2,6,6-Tetramethyl-4-piperidinyl ester, (mixed 2,2,6,6-tetramethyl-4-piperidinyl/tridecyl)-1,2,3, 4-Butanetetracarboxylate, 3,9-bis(2,3-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9- Diphosphaspiro[5.5]undecane, mixed (2,2,6,6-tetramethyl-4-piperidinyl/β,β,β',β'-tetramethyl-3-9-[ 2,4,8,10-Tetraoxaspiro[5.5]undecane]diethyl)-1,2,3,4-butanetetracarboxylate, poly([6-N-

Lino-1,3,5-tris

-2,4-Diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]hexamethylene[(2,2,6,6-tetramethyl- 4-Piperidinyl)imino]), [N-(2,2,6,6-tetramethyl-4-piperidinyl)-2-methyl-2-(2,2,6,6 -Tetramethyl-4-piperidinyl)imino]propionamide, trade name "LA-77", "LA-67", "LA-57" (the above are manufactured by ADEKA Corporation), trade name Hindered amine compounds such as "TINUVIN123" and "TINUVIN152" (manufactured by Ciba Japan Co., Ltd.); San-Aid SI Additives", bisulfite-based compounds such as Sanshin Chemical Industry Co., Ltd.), and phosphite-based compounds such as trade name "Adekastab PEP-36" (manufactured by ADEKA Co., Ltd.). Among them, from the viewpoint that local hardening of the adhesive during the drying process is less likely to occur, and the adhesiveness of the cured product to the adherend is more excellent, perylene sulfate-based compounds and phosphite-based compounds are preferred.

The said polymerization stabilizer may be used individually by 1 type, and may be used in combination of 2 or more types. In the curable composition for adhesives of the present invention, it is preferable to contain two or more kinds of polymerization stabilizers in particular. Thereby, the storage stability of the curable composition for adhesives is remarkably excellent, and local hardening of the adhesive during the drying process is less likely to occur, and the adhesiveness of the cured product to the adherend tends to be further excellent. As the above-mentioned two or more kinds of polymerization stabilizers, it is preferable to contain at least a permanyl sulfate-based compound and a phosphite-based compound.

When the curable composition of the present invention contains the above-mentioned polymerization stabilizer, its content (compounding amount) is not particularly limited. is the total amount of polyorganosiloxane sesquioxane and other cationic curable compounds) 100 parts by weight, preferably 0.005 parts by weight or more, preferably 0.01-10 parts by weight, and more preferably 0.02-1 part by weight. When the above-mentioned content is 0.005 parts by weight or more, local hardening of the adhesive during the drying process is more difficult to occur, and the adhesiveness of the hardened product to the adherend tends to be more excellent. In the case of using two or more kinds of polymerization stabilizers, the total amount of the polymerization stabilizers is relative to the polyorganosiloxane sesquioxane of the present invention (when other cationic curable compounds are contained, the polyorganosiloxane sesquioxane and other The total amount of the cationic curable compound) is 100 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.2 to 1 part by weight.

When the curable composition of the present invention contains the above-mentioned polymerization stabilizer and hardening catalyst, the content (compounding amount) of the polymerization stabilizer is not particularly limited, but is preferably 1 weight part relative to 100 parts by weight of the hardening catalyst part or more, more preferably 3 to 200 parts by weight, still more preferably 5 to 150 parts by weight. When the above-mentioned content is 1 part by weight or more, local hardening of the adhesive during the drying process is more difficult to occur, and the adhesiveness of the hardened product to the adherend tends to be more excellent. When two or more kinds of polymerization stabilizers are used, the total amount of the polymerization stabilizers is preferably 100 to 200 parts by weight, more preferably 110 to 150 parts by weight, relative to 100 parts by weight of the hardening catalyst.

Preferably, the curable composition of the present invention may further contain a solvent. Examples of the solvent include water, organic solvents, and the like, and are not particularly limited as long as they can dissolve the polyorganosiloxane sesquioxane of the present invention and an optional additive, and do not inhibit polymerization.

It is preferable to use one or more solvents whose boiling point (at 1 atmosphere) is 170°C or lower (such as toluene, butyl acetate, methyl isobutyl ketone, xylene, 1,3,5-trimethylbenzene) , propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, etc.).

The solvent may be used in an appropriate amount according to the application of the curable composition. The amount of the solvent used is, for example, about 30 to 80% by weight, preferably 40 to 70% by weight, and more preferably 50 to 60% by weight, based on the concentration of the nonvolatile matter contained in the curable composition of the present invention. When the amount of the solvent used is excessive, the viscosity of the curable composition tends to decrease, and it tends to be difficult to form a layer with an appropriate film thickness. On the other hand, when the usage-amount of a solvent is too small, the viscosity of a curable composition becomes too high, and there exists a tendency for it to become difficult to apply|coat uniformly.

The curable composition of the present invention may further contain the following conventional additives as other optional components: precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, alumina, glass, Inorganic fillers such as quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate, carbon black, silicon carbide, silicon nitride, boron nitride; Inorganic fillers obtained by processing organosilicon compounds such as siloxanes and organosilazanes; fine powders of organic resins such as polysiloxanes, epoxy resins and fluororesins; fillers such as conductive metal powders such as silver and copper, hardened Additives, stabilizers, flame retardants, flame retardant additives, reinforcing materials, nucleating agents, lubricants, waxes, plasticizers, mold release agents, impact modifiers, hue modifiers, clearing agents, rheology Conditioner, processability improver, colorant, antistatic agent, dispersant, surface conditioner, surface modifier, matting agent, antifoaming agent, antifoaming agent, antifoaming agent, antibacterial agent, preservative, viscosity adjustment agent, tackifier, photosensitizer, foaming agent, etc. These additives may be used alone or in combination of two or more.

The curable composition of the present invention is not particularly limited, and can be prepared by stirring and mixing the above-mentioned components at room temperature or as necessary while heating. Furthermore, the curable composition of the present invention can be used in the form of a single-liquid composition that is obtained by mixing the components in advance and used as it is. It is used in the form of a multi-liquid system (eg 2-liquid system) composition that is mixed and used.

The curable composition of the present invention is not particularly limited, but is preferably liquid at normal temperature (about 25°C). More specifically, regarding the curable composition of the present invention, as a solution diluted to a solvent of 20% [for example, a curable composition (solution) with a ratio of 20% by weight of methyl isobutyl ketone] at 25°C. The viscosity is preferably 300 to 20000 mPa·s, more preferably 500 to 10000 mPa·s, and still more preferably 1000 to 8000 mPa·s. By setting the above viscosity to 300 mPa·s or more, the heat resistance of the cured product tends to be further improved. On the other hand, by setting the viscosity to 20,000 mPa·s or less, the preparation and handling of the curable composition are easy, and there is a tendency that air bubbles are less likely to remain in the cured product. In addition, the viscosity of the curable composition of the present invention is determined by using a viscometer (trade name "MCR301", manufactured by Anton Paar Corporation) under the conditions of a swing angle of 5%, a frequency of 0.1 to 100 (1/s), and a temperature of 25°C to measure.

[hardened product] By polymerizing the cationic curable compound or the radical curable compound in the curable composition of the present invention, the curable composition can be cured, and a cured product (sometimes referred to as "the cured product of the present invention") can be obtained. ”). A hardening method can be suitably selected from a well-known method, and it does not specifically limit, For example, the method of irradiation of an active energy ray and/or heating is mentioned. As the above-mentioned active energy rays, for example, any of infrared rays, visible rays, ultraviolet rays, X rays, electron beams, alpha rays, beta rays, and gamma rays can be used. Among them, ultraviolet rays are preferable in terms of excellent handleability.

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

On the other hand, the conditions at the time of hardening the curable composition of this invention by heating are not specifically limited, For example, 30-200 degreeC is preferable, and 50-190 degreeC is more preferable. The hardening time can be set appropriately.

As described above, the curable composition of the present invention can be cured to form a cured product having high surface hardness and heat resistance, and excellent in bending resistance and workability. Therefore, the curable composition of the present invention can be used as a "hard coat layer forming curable composition" (sometimes referred to as "hard coat liquid" or "hard coat agent") for forming a hard coat layer in a hard coat film. etc.) or adhesives for laminated semiconductors are suitably used. Using the curable composition of the present invention as a curable composition for forming a hard coat layer and having a hard coat layer formed from the composition can maintain high hardness and high heat resistance, and has flexibility, and is suitable for use in rolls. Manufactured or processed in roll form. In addition, when the curable composition of the present invention is used as the adhesive curable composition, it can be cured at a low temperature, and it is possible to form a product with excellent crack resistance, heat resistance, adhesion to the adherend, and adhesion. Therefore, even if a thermal shock is given, the adhesive layer will not be cracked or peeled off, and a reliable device can be formed.

In addition, the surface of the uncured or semi-cured hard coat layer obtained by coating and drying the curable composition of the present invention on the release layer provided on the substrate becomes non-sticky, and the blocking resistance is improved, Therefore, it can be wound up and handled in a roll shape, and further, by transferring and hardening the hard coat layer on the surface of the molded product, a hard coat layer having a high surface hardness can be formed. Therefore, the curable composition of the present invention can also be suitably used as a hard coat layer forming curable composition for forming a hard coat layer having excellent bending resistance.

[Hard coat] The hard coat film of the present invention is formed by laminating a substrate and a hard coat layer formed on at least one surface of the substrate, and the hard coat layer is composed of the curable composition of the present invention (hard coat layer for forming a hard coat layer) The hard coat layer (hardened layer of the curable composition of the present invention) formed. FIG. 9 is a schematic diagram (cross-sectional view) showing one embodiment of the hard coat film of the present invention. 1 represents a hard coat film, 11 represents a hard coat layer, and 12 represents a base material.

Furthermore, the hard coat layer in the hard coat film of the present invention may be formed only on one surface (one side) of the above-mentioned substrate, or may be formed on both surfaces (both sides).

Moreover, the hard-coat layer in the hard-coat film of this invention may be formed in only a part of each surface of the said base material, and may be formed in the whole surface.

The base material in the hard coat film of the present invention is the base material of the hard coat film, and refers to a portion other than the hard coat layer. As the above-mentioned substrates, known plastic substrates, metal substrates, ceramic substrates, semiconductor substrates, glass substrates, paper substrates, wood substrates (wood substrates), and substrates whose surfaces are painted surfaces can be used. Or the commonly used base material is not particularly limited. Among them, plastic substrates (substrates composed of plastic materials) are preferred.

The plastic material constituting the plastic base material is not particularly limited, for example, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyimide; polycarbonate Ester; polyamide; polyacetal; polyphenylene ether; polyphenylene sulfide; polyether; polyether ether ketone; ), copolymers of norbornene-based monomers and olefin-based monomers such as copolymers of norbornene and ethylene (addition polymers or cyclic olefin copolymers such as ring-opening polymers, etc.), their derivatives, etc. Cyclic polyolefins; vinyl polymers (such as acrylic resins such as polymethyl methacrylate (PMMA), polystyrene, polyvinyl chloride, acrylonitrile-styrene-butadiene resin (ABS resin), etc.); Vinylidene-based polymers (eg, polyvinylidene chloride, etc.); cellulose-based resins such as triacetyl cellulose (TAC); epoxy resins; phenol-based resins; melamine resins; urea resins; maleic diarylene Amine resin; polysiloxane and other plastic materials. Furthermore, the above-mentioned plastic base material may be composed of only one kind of plastic material, or may be composed of two or more kinds of plastic materials.

Among them, as the above-mentioned plastic substrate, in the case of obtaining a hard coat film with excellent transparency as the hard coat film of the present invention, it is preferable to use a substrate (transparent substrate) with excellent transparency, more preferably a polymer Ester films (eg PET, PEN), cyclic polyolefin films, polycarbonate films, TAC films, PMMA films.

The above plastic substrates may also contain antioxidants, ultraviolet absorbers, light-resistant stabilizers, heat stabilizers, crystal nucleating agents, flame retardants, flame retardant additives, fillers, plasticizers, impact resistance improvers, Reinforcing agent, dispersing agent, antistatic agent, foaming agent, antibacterial agent and other additives. In addition, an additive may be used individually by 1 type, and may be used in combination of 2 or more types.

The above-mentioned plastic base material may have a single-layer structure or a multi-layer (lamination) structure, and the structure (structure) is not particularly limited. For example, the above-mentioned plastic substrate may also have a layer other than the hard coat layer of the present invention (sometimes referred to as "other layer") formed on at least one surface of the plastic film, that is, "plastic film/other layer" or "other layer" /plastic film/other layers" and other laminated plastic substrates. As said other layer, the hard coat layer other than the hard coat layer of this invention, etc. are mentioned, for example. In addition, as a material which comprises the said other layer, the said plastic material etc. are mentioned, for example.

Roughening treatment, easy bonding treatment, antistatic treatment, sandblasting treatment (sand matt treatment), corona discharge treatment, plasma treatment, chemical etching can also be applied to a part or all of the surface of the above-mentioned plastic substrate Treatment, water matt treatment, flame treatment, acid treatment, alkali treatment, oxidation treatment, ultraviolet irradiation treatment, silane coupling agent treatment and other well-known or conventional surface treatments. Furthermore, the above-mentioned plastic substrate may be an unstretched film or a stretched film.

The above-mentioned plastic base material can be manufactured by, for example, the following well-known or conventional methods: a method of forming the above-mentioned plastic material into a film shape to make a plastic base material (plastic film); if necessary, further appropriate layers are formed on the above-mentioned plastic film (such as the above-mentioned other layers, etc.), or the method of applying appropriate surface treatment to the above-mentioned plastic film, etc. In addition, a commercial item can also be used for the said plastic base material.

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

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

The thickness of the hard coat layer of the present invention (the thickness of each hard coat layer when the substrate has a hard coat layer on both surfaces) is not particularly limited, but is preferably 1 to 200 μm, more preferably 3 to 150 μm. Even when the hard coat layer of the present invention is thin (for example, the thickness is 5 μm or less), the high hardness of the surface can be maintained (for example, the pencil hardness is set to 3H or more). In addition, even when the hard coat layer of the present invention is thick (for example, the thickness is 50 μm or more), inconveniences such as cracks caused by hardening shrinkage and the like are less likely to occur. Therefore, the thickening of the film can still significantly improve the pencil lead. Hardness (for example, make pencil hardness 9H or more).

The haze of the hard coat layer is not particularly limited, but when the thickness is 50 μm, it is preferably 1.5% or less, more preferably 1.0% or less. In addition, 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 applications requiring very high transparency (for example, surface protection sheets for displays such as touch panels). The haze of the hard coat layer of the present invention can be measured according to JIS K7136.

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

The hard coat film of the present invention may further have a surface protective film on the surface of the hard coat layer of the present invention. By making the hard coat film of this invention have a surface protective film, there exists a tendency for the punching workability of a hard coat film to further improve. In the case of such a surface protection film, for example, even if the hardness of the hard coating is very high, peeling or cracking from the substrate is likely to occur during punching, and such problems will not occur, and Thomson blades can be used. (Thomson blade) for punching. As the above-mentioned surface protection film, a well-known or conventional surface protection film can be used.

The hard coat film of the present invention can be manufactured according to a known or conventional manufacturing method of a hard coat film, and the manufacturing method is not particularly limited. For example, the curable composition of the present invention can be coated on at least one surface of the above-mentioned substrate. (The curable composition for hard-coat layer formation) is produced by hardening the curable composition (curable composition layer) after removing the solvent by drying if necessary. The conditions for curing the curable composition are not particularly limited, and can be appropriately selected, for example, from the above-mentioned conditions for forming the cured product.

The hard coat layer of the present invention in the hard coat film of the present invention is formed from the curable composition of the present invention (curable composition for forming a hard coat layer) capable of forming a cured product excellent in bending resistance and workability Therefore, the hard coating film of the present invention can be produced in a roll-to-roll manner. By producing the hard coat film of the present invention in a roll-to-roll manner, the productivity can be remarkably improved. As a method for producing the hard coat film of the present invention by a roll-to-roll method, a well-known or conventional roll-to-roll method can be used, and it is not particularly limited. For example, the following steps (steps A to C) are included as necessary steps. , and continuously implement the methods of these steps (steps A to C), etc.: step A, unrolling the rolled substrate; step B, coating the present invention on at least one surface of the rolled substrate The curable composition (curable composition for forming a hard coat layer), and then, if necessary, the solvent is removed by drying and then the curable composition (curable composition layer) is cured, thereby forming the hard coating of the present invention. coating; and step C, after which the hard coat film obtained is rewound into a roll. Furthermore, the method may also include steps other than steps A to C.

The thickness of the hard coat film of the present invention is not particularly limited, and can be appropriately selected from the range of 1 to 10000 μm.

The pencil hardness of the hard coat surface of the hard coat film of the present invention is preferably 4H or more, more preferably 5H or more, and still more preferably 6H or more. In addition, the pencil hardness can be evaluated according to the method described in JIS K5600-5-4.

The haze of the hard coat film of the present invention is not particularly limited, but is preferably 1.5% or less, more preferably 1.0% or less. In addition, 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 applications requiring very high transparency (for example, surface protection sheets for displays such as touch panels). The haze of the hard coat film of the present invention can be easily controlled within the above-mentioned range by using, for example, the above-mentioned transparent base material as a base material. In addition, haze can be measured based on JISK7136.

The total light transmittance of the hard coat film of the present invention is not particularly limited, but is preferably 85% or more, more preferably 90% or more. Furthermore, the upper limit of the total light transmittance is not particularly limited, for example, it is 99%. By setting the total light transmittance to 90% or more, it tends to be suitable for applications requiring very high transparency (such as surface protection sheets for displays such as touch panels, etc.). The total light transmittance of the hard coat film of the present invention can be easily controlled within the above-mentioned range, for example, by using the above-mentioned transparent base material as a base material. In addition, the total light transmittance can be measured according to JIS K7361-1.

The hard coat film of the present invention has flexibility while maintaining high hardness and high heat resistance, and can be produced or processed in a roll-to-roll system, and therefore has high quality and excellent productivity. In the case where the hard coat layer of the present invention has a surface protective film, punching workability is also excellent. Therefore, it can be preferably used for all applications requiring such properties. The hard coating film of the present invention can be used, for example, as a surface protective film in various products, a surface protective film in various products or components, and the like, and can also be used as a constituent material for 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 household electrical appliances; various electrical and electronic products; , input boards, smart phones, mobile phones, etc.) various electrical and electronic products; various optical machines, etc. Moreover, as an aspect of using the hard coat film of the present invention as a constituent material of various products or its members or parts, for example, an aspect of a laminate of a hard coat film and a transparent conductive film used in a touch panel, etc. can be mentioned. Wait.

[Film for transfer] The film for transfer (hard coat film for transfer) of the present invention is a film having a base material and an uncured or semi-cured hard coat layer on a release layer formed on at least one surface of the base material, and The above-mentioned uncured or semi-cured hard coat layer is a layer containing the curable composition of the present invention (curable composition for forming a hard coat layer (hereinafter sometimes referred to as "the hard coat agent of the present invention"). Here, Uncured refers to a state in which the polymerizable functional group of the polyorganosiloxane sesquioxane of the present invention contained in the curable composition (hard coat agent) for forming a hard coat layer of the present invention has not undergone a polymerization reaction. It refers to a state in which a part of the polymerizable functional group undergoes a polymerization reaction and an unreacted polymerizable functional group remains. In addition, in this specification, the unreacted polymer formed by the curable composition (hard coat agent) of the present invention may be used. A hardened or semi-hardened hard coat is abbreviated as "hard coat", and a hard coat obtained by transferring and hardening to a molded product is called "hardened hard coat". Fig. 10 shows the transfer film of the present invention Schematic diagram (cross-sectional view) of one embodiment. 2 denotes a transfer film, 21 denotes a substrate, 22 denotes a release layer, 23 denotes a hard coat (uncured or semi-cured hard coat), and 24 denotes a tackifier Coating, 25 denotes a colored layer, and 26 denotes an adhesive layer.

The base material in the film for transfer of the present invention is the base of the film for transfer, and refers to a portion other than the transfer layer that constitutes the hard coat layer of the present invention. Here, the transfer layer refers to a layer other than the base material on which the mold release layer is formed in the transfer film of the present invention, and refers to a portion transferred to the surface of a molded product.

As the above-mentioned base material, the base material exemplified by the above-mentioned hard coating film can be used, and among them, a plastic base material (plastic film) is preferably used as the base material. The thickness of the above-mentioned base material can be appropriately selected from, for example, a range of 0.01 to 10,000 μm, and from the viewpoints of moldability, shape followability, workability, etc., preferably 2 to 250 μm, more preferably 5 to 100 μm, still more preferably 20 to 100 μm.

The mold release layer in the transfer film of the present invention is a layer that constitutes at least one surface layer of the substrate in the transfer film of the present invention, and the layer is provided to make the transfer layer easy to peel from the substrate . By providing the mold release layer, the transfer layer can be surely and easily transferred from the transfer film to the transfer target body (molded article), and the base material can be surely peeled off.

In the transfer film of the present invention, the peeling strength between the release layer and the hard coat layer is not particularly limited, but is preferably 30-500 mN/24 mm, more preferably 40-300 mN/24 mm, and more preferably 50 to 200 mN/24 mm. When the peel strength is within this range, the hard coat layer tends to be easily peeled off at the time of transfer to a molded product without peeling off the hard coat layer during normal handling. The peel strength of the hard coat layer and the mold release layer of the present invention can be measured according to JIS Z0237.

Furthermore, the mold release layer in the transfer film of the present invention may be formed only on one surface (one side) of the above-mentioned substrate, or may be formed on both surfaces (both sides). In addition, the mold release layer in the film for transfer of the present invention may be formed only on a part of each surface of the above-mentioned base material, or may be formed on the entire surface.

As a component for forming the release layer, a publicly known release agent can be used without particular limitation. For example, a release agent selected from the group consisting of unsaturated ester resin, epoxy resin, epoxy-melamine resin, and amino alkyd resin can be used. , At least one of acrylic resin, melamine resin, silicone resin, fluorine resin, cellulose resin, urea resin, polyolefin resin, paraffin resin and cycloolefin resin. From the viewpoint of releasability between the hard coat layer of the present invention and the above-mentioned mold release layer in contact with the transfer layer, the above-mentioned mold release layer is preferably a melamine-based resin or a cycloolefin-based resin, and more preferably 2-norcambe Cyclic olefin copolymer resins (COC resins) such as olefin-ethylene copolymers.

As the method of forming the mold release layer on the surface of the base material, a publicly known mold release treatment method may be used without particular limitation. For example, the above-mentioned resin can be dispersed or dissolved in a solvent (for example, alcohols such as methanol and butanol, aromatic hydrocarbons such as toluene and xylene, tetrahydrofuran, etc.), and can be applied by bar coating, Meyer bar coating, gravure coating, A mold release layer can be formed by a known coating method such as roll coating, drying, and heating at 80 to 200°C. The thickness of the mold release layer is also not particularly limited, and can be usually selected from the range of 0.01 to 5 μm, preferably 0.1 to 3.0 μm.

The hard coat layer in the transfer film of the present invention is a layer constituting at least one surface layer of the above-mentioned mold release layer, and is an uncured layer obtained by drying the curable composition (hard coat agent) of the present invention, Or a semi-hardened layer obtained by partial hardening. The semi-hardened hard coat layer can be formed by irradiating or heating the unhardened hard coat layer with the above-mentioned active energy rays to locally advance hardening. The uncured or semi-cured hard coat layer of the present invention has low viscosity and excellent blocking resistance, and can be wound into a roll for operation without resin adhering to the surface when fingers touch the surface.

Furthermore, the hard coat layer in the transfer film of the present invention may be formed only on one release layer (one side) of the above-mentioned base material, or may be formed on both release layers (both sides). Moreover, the hard-coat layer of this invention in the film for transcription|transfer of this invention may be formed in only one part of each surface of the said mold release layer, and may be formed in the whole surface.

The method for laminating the hard coat layer on the mold release layer of the transfer film of the present invention is not particularly limited, and examples include the following method: apply the curable composition (hard coat layer) of the present invention on the mold release layer by a known method. agent) and make it dry to form an unhardened hard coating; or further irradiate or heat the unhardened hard coating with active energy rays to form a semi-hardened hard coating. As the coating method of the curable composition (hard coat agent) of the present invention, known coating methods can be used without limitation, for example, bar coater coating, Meyer bar coating, air knife coating, and gravure coating are exemplified Coating, offset printing, flexographic printing, screen printing, etc. The heating temperature at the time of forming the hard coat layer is not particularly limited, but it is preferably appropriately selected from 50 to 200°C. The heating time is also not particularly limited, but it is preferably appropriately selected from 1 to 60 minutes. The conditions for irradiating the active energy ray to the hard coat layer are not particularly limited, and can be appropriately selected, for example, from the above-mentioned conditions at the time of forming the cured product.

The thickness of the hard coat layer in the transfer film of the present invention (in the case of having a hard coat layer on both sides of the substrate, the thickness of each hard coat layer) is not particularly limited, but is preferably 1-200 μm, more Preferably, it is 3 to 150 μm. Even when the hard coat layer is thin (for example, the thickness is less than 5 μm), the high hardness of the surface can be maintained (for example, the pencil hardness is more than 5H). In addition, even when the hard coat layer is thick (for example, the thickness is more than 50 μm), it is not easy to cause problems such as cracks caused by hardening shrinkage. Therefore, the pencil hardness can still be significantly improved by thickening the film (for example Make the pencil hardness 9H or more).

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

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

The transfer film of the present invention is preferably formed by sequentially laminating an adhesion-promoting coating layer and an adhesive layer on the hard coating layer. Furthermore, in the case of using the transfer film of the present invention as a decorative film, at least one coloring layer is laminated. The lamination position of the colored layer is not particularly limited, but it is preferably a state in which one layer or two or more layers are laminated between the tackifier coating layer and the adhesive layer.

The adhesion-promoting coating layer in the transfer film of the present invention is provided in order to improve the adhesion between the hard coat layer and the adhesive layer, the coloring layer, and the like. The adhesion-promoting coating is preferably a transparent or translucent layer, so that the patterns and patterns of the colored layer can be clearly transferred. Phenol resin, alkyd resin, melamine resin (such as methylated melamine resin, butyl resin, etc.) can be used. melamine resin, methyl etherified melamine resin, butyl etherified melamine resin, methyl butyl mixed etherified melamine resin, etc.), epoxy resins (such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, Multifunctional 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 polymer Ester resins, urethane resins [for example, polyisocyanate compounds with two or more isocyanate groups (O=C=NRN=C=O) and polyol compounds with two or more hydroxyl groups (HO -R'-OH), polyamine (H ₂ N-R''-NH ₂ ), or water and other compounds with active hydrogen (-NH ₂ , -NH, -CONH-, etc.) ester resin], thermosetting polyimide, polysiloxane and other thermosetting resins; or vinyl chloride-vinyl acetate copolymer resin, acrylic resin (such as acrylic polyol-based resin, etc.), chlorinated rubber, poly The amide resin, nitrocellulose resin, and thermoplastic resins such as cyclic polyolefin-based resins are used alone or in combination of two or more, preferably epoxy-based resins.

The above-mentioned resin for tackifying coating may further contain wax, silicon oxide, plasticizer, leveling agent, surfactant, dispersant, defoamer, ultraviolet absorber, ultraviolet stabilizer, etc. Agents, antioxidants and other commonly used additives are used as other optional ingredients. These additives may be used alone or in combination of two or more.

The tackifying coating can be applied to the hard coating of the present invention by a known coating method such as bar coating, Meyer bar coating, gravure coating, roll coating, etc. The coating is applied and dried, optionally heated to form. The temperature at the time of heating during the formation of the tackifier coating is not particularly limited, and it is preferably appropriately selected from 50 to 200°C. The heating time is also not particularly limited, but it is preferably appropriately selected from 10 seconds to 60 minutes.

The thickness of the adhesion-promoting coating is usually about 0.1-20 μm, preferably in the range of 0.5-5 μm.

The tackifying coating of the present invention can be formed using a commercially available tackifying coating agent. As a commercially available tackifier coating agent, for example, K468HP Anchor (Epoxy resin based tackifier coating agent manufactured by Toyo Ink Co., Ltd.), TM-VMAC (Acrylic polyamide manufactured by Dainisei Chemical Co., Ltd.) Alcohol resin-based tackifying coating agent), etc.

The adhesive layer in the transfer film of the present invention is provided to transfer the transfer layer (including a hard coat layer, an adhesion-promoting coat layer if necessary, and a coloring layer) to a molded article with good adhesion. As an adhesive layer, what consists of a heat sensitive adhesive, a pressure adhesive, etc. is mentioned, In this invention, the heat sealing layer which expresses adhesiveness to a molded article by heating and pressurization as needed is preferable. As resins used for the adhesive layer, for example, acrylic resins, vinyl chloride-based resins, vinyl acetate-based resins, vinyl chloride-vinyl acetate-based copolymer resins, styrene-acrylic copolymer resins, polyester-based resins, poly Among resins such as amide-based resins, one kind alone or a mixture of two or more kinds thereof is preferably an acrylic-based resin and a vinyl chloride-vinyl acetate-based copolymer resin.

As the acrylic resin used for the adhesive layer of the present invention, for example, polymethyl(meth)acrylate, polyethyl(meth)acrylate, polybutyl(meth)acrylate, and (meth)acrylic acid may be mentioned. Acrylic resins such as methyl ester-(meth)butyl acrylate copolymer, methyl (meth)acrylate-styrene copolymer, etc.; modified acrylic resins modified with fluorine, etc., these can be 1 type or 2 types Use in the form of a mixture of the above. In addition, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, etc. can also be used. Alkyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, etc. Acrylic polyol esters obtained by copolymerizing (meth)acrylates with hydroxyl groups. Moreover, as a vinyl chloride-vinyl acetate type copolymer resin, the vinyl acetate content of about 5-20 mass % and the average degree of polymerization of about 350-900 can be used normally. If necessary, vinyl chloride-vinyl acetate-based copolymer resin may be further copolymerized with carboxylic acids such as maleic acid and fumaric acid. In addition, other resins such as thermoplastic polyester-based resin, thermoplastic urethane-based resin, chlorinated polyethylene, chlorinated polypropylene and other resins such as chlorinated polyolefin-based resins can also be appropriately mixed as the subcomponent resin as necessary.

For the adhesive layer, a solution or emulsion of one or more of the above-mentioned resins can be made into a form that can be applied. Well-known coating methods such as bar coating, Meyer bar coating, gravure coating, and roll coating are used. The cloth method is applied, dried, and formed by heating if necessary. The temperature at the time of heating at the time of forming an adhesive bond layer can be suitably selected from 50-200 degreeC suitably. The heating time can be suitably selected from 10 seconds to 60 minutes.

The thickness of the adhesive layer is preferably about 0.1 to 10 μm, and more preferably 0.5 to 5 μm, because the film for transfer can be efficiently transferred to a molded product with good adhesion.

The adhesive layer can be blended with organic ultraviolet absorbers such as benzophenone-based compounds, benzotriazole-based compounds, oxanilide-based compounds, cyanoacrylate-based compounds, and salicylate-based compounds ; Or, such as oxides of zinc, titanium, cerium, tin, iron, etc., inorganic microparticle additives with ultraviolet absorbing ability. Moreover, as an additive, a coloring pigment, a white pigment, an extender, a filler, an antistatic agent, an antioxidant, a fluorescent whitening agent, etc. may be used suitably as needed.

A commercial item can also be used for the said adhesive agent. Examples of commercially available adhesives include K588HP Adhesive gloss A varnish (vinyl chloride-vinyl acetate copolymer resin adhesive manufactured by Toyo Ink Co., Ltd.), PSHP780 (acrylic resin type manufactured by Toyo Ink Co., Ltd.) then agent) etc.

The coloring layer in the transfer film of the present invention is provided when the decorative film for transferring the design layer and/or the concealment layer to the molded product is formed. Here, the pattern layer is a layer provided for expressing patterns, characters, etc. and pattern-like patterns, and the concealing layer is usually a solid layer, which is provided for masking the coloring of the injection resin, etc. . The concealment layer is sometimes arranged inside the pattern layer to make the pattern of the pattern layer obvious, and the decorative layer is also formed only by the concealment layer.

The pattern layer of the present invention is a layer provided for expressing patterns, characters, etc. and pattern-like patterns. The pattern of the pattern layer is arbitrary, and examples thereof include patterns composed of wood grains, stone grains, cloth grains, grain patterns, geometric patterns, characters, and the like.

The coloring layer is usually printed with ink on the above-mentioned hard coating or tackifying coating, and is printed by well-known printing such as gravure printing, offset printing, screen printing, transfer printing of self-transfer sheet, sublimation transfer printing, inkjet printing, etc. It is formed by the method, whereby it can be formed between the hard coat layer and the adhesive layer, or between the tackifying coating and the adhesive layer. From the viewpoint of designability, the thickness of the colored layer is preferably 3 to 40 μm, more preferably 10 to 30 μm.

Preferable examples of binder resins for printing inks for forming the colored layer include polyester-based resins, polyurethane-based resins, acrylic-based resins, vinyl acetate-based resins, vinyl chloride-vinyl acetate-based copolymer resins, fibers It is preferable that a plain resin etc. contain only an acrylic resin as a main component, or a mixture of an acrylic resin and a vinyl chloride-vinyl acetate type copolymer resin as a main component. Among these, when an acrylic resin, a vinyl chloride-vinyl acetate-based copolymer resin, or other acrylic resin is mixed, the printing suitability and the molding suitability become more favorable, which is preferable. Here, as acrylic resin, polymethyl (meth)acrylate, polyethyl (meth)acrylate, polybutyl (meth)acrylate, methyl (meth)acrylate-(methyl) Acrylic resins such as butyl acrylate copolymer, methyl (meth)acrylate-styrene copolymer, etc., and modified acrylic resins modified with fluorine, etc., may be one of these or a mixture of two or more of them. use. In addition, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, etc. can also be used. Alkyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, etc. An acrylic polyol ester obtained by copolymerizing a (meth)acrylate having a hydroxyl group. Moreover, as a vinyl chloride-vinyl acetate type copolymer resin, the vinyl acetate content of about 5-20 mass % and the average degree of polymerization of about 350-900 are generally used. If necessary, vinyl chloride-vinyl acetate-based copolymer resin may be further copolymerized with carboxylic acids such as maleic acid and fumaric acid. The mixing ratio of the acrylic resin and the vinyl chloride-vinyl acetate copolymer resin is about acrylic resin/vinyl chloride-vinyl acetate copolymer resin=1/9 to 9/1 (mass ratio). In addition, other resins such as thermoplastic polyester-based resins, thermoplastic urethane-based resins, chlorinated polyethylene, chlorinated polypropylene and other chlorinated polyolefin-based resins can be appropriately mixed as the subcomponent resins as necessary.

As the colorant used in the above-mentioned coloring layer, a scaly foil powder composed of metals, alloys, or metal compounds such as aluminum, chromium, nickel, tin, titanium, iron phosphide, copper, gold, silver, and brass can be used. Metallic pigments; pearlescent (pearl) consisting of mica-like iron oxide, titanium dioxide-coated mica, titanium dioxide-coated bismuth oxychloride, bismuth oxychloride, titanium dioxide-coated talc, fish scale foil, colored titanium dioxide-coated mica, alkaline lead carbonate, etc. ) pigments; fluorescent pigments such as strontium aluminate, calcium aluminate, barium aluminate, zinc sulfide, calcium sulfide; white inorganic pigments such as titanium dioxide, zinc white, antimony trioxide; zinc white, red red, vermilion, ultramarine, cobalt Inorganic pigments such as blue, titanium yellow, yellow lead, carbon black; isoindolinone yellow, Hansa yellow A, quinacridone red, permanent red 4R, phthalocyanine blue, indanthrene blue RS , nigrosine and other organic pigments (including dyes) 1 type or a mixture of 2 or more types.

Such a coloring layer is a layer provided to give designability to the transfer film of the present invention, and further, a metal thin film layer or the like may be formed in order to improve designability. For the formation of the metal thin film layer, metals such as aluminum, chromium, gold, silver, and copper can be used, and the film can be formed by methods such as vacuum evaporation and sputtering. The metal thin film layer can be arranged on the entire surface, or can be partly arranged in a pattern.

In addition to the above-mentioned components, the printing ink used to form the coloring layer may be appropriately added with a precipitation inhibitor, a hardening catalyst, an ultraviolet absorber, an antioxidant, a leveling agent, a tackifier, a defoaming agent, a lubricant, and the like. Printing inks can be provided in the form of dissolving or dispersing the above components in common solvents. As a solvent, what is necessary is just to melt|dissolve or disperse|distribute a binder resin, and an organic solvent and/or water can be used. Examples of the organic solvent include hydrocarbons such as toluene and xylene, ketones such as acetone and methyl ethyl ketone, ethyl acetate, esters such as cellulose acetate and butyl cellulose acetate, and alcohols.

In addition to the above-mentioned base material, mold release layer, hard coat layer, tackifier coat layer, adhesive layer, and coloring layer, the transfer film of the present invention may be further laminated with a low-reflection layer and an antistatic layer in an arbitrary order if necessary. , UV absorbing layer, near-infrared blocking layer, electromagnetic wave absorbing layer, etc.

The thickness of the transfer film of the present invention is not particularly limited, and can be appropriately selected from the range of 1 to 10,000 μm, and is preferably 2 to 250 μm, more preferably 2 to 250 μm, from the viewpoints of formability, shape followability, and workability. 5 to 150 μm, more preferably 25 to 150 μm.

Since the hard coat layer of the transfer film of the present invention is non-adhesive and has excellent blocking resistance, it can be wound into a roll and handled, so it is suitable for use as a transfer film for in-mold injection molding. For example, in a mold composed of a fixed mold and a movable mold, the transfer film of the present invention is continuously conveyed by a conveying roller or the like, the base film side is brought into contact with the surface of the fixed mold, and the movable mold is moved after the position is appropriately adjusted. to lock the mold. Then, the pre-heated thermoplastic resin is injected and filled into the mold from the transfer layer side of the transfer film under high temperature and high pressure. After rapid cooling, the mold is opened, and the hard coat layer of the present invention can be taken out and transferred to the outermost surface. The molded product (in-mold molded product).

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

After the transfer layer of the transfer film of the present invention is transferred to the molded product, the hardened hard coat layer of the present invention is formed on the outermost surface of the molded product. Therefore, the pencil hardness of the surface of the molded product can be very high, preferably 5H or more, more preferably 6H or more. In addition, the pencil hardness can be evaluated according to the method described in JIS K5600-5-4.

The molded product (in-mold molded product) produced by the in-mold injection molding method using the transfer film of the present invention has a very high surface hardness, and the pattern and pattern are vividly transferred, so it can be preferably used for the required application. All moldings of this characteristic. The transfer film of the present invention is suitable for various exterior moldings requiring high surface hardness, scratch resistance, design, and durability, such as interior and exterior trim parts such as dashboards of automobiles, and housings of home appliances.

[continued film] By using the curable composition of the present invention (curable composition for adhesives, curable composition for laminated semiconductors), it is possible to obtain a substrate having an adhesive layer formed of the curable composition of the present invention on at least one side of the substrate. Next film. FIG. 11 is a schematic diagram (sectional view) of one embodiment of the adhesive sheet of the present invention. 3 denotes an adhesive sheet, 31 denotes an adhesive layer, 32 denotes a substrate, and 33 denotes an adhesion promoting coating.

The said adhesive sheet can be obtained by apply|coating the curable composition (curable composition for adhesiveness, curable composition for laminated semiconductors) of this invention to a base material, and drying as needed, for example. The coating method is not particularly limited, and well-known and conventional means can be used. In addition, the drying means and conditions are not particularly limited either, and the conditions can be set to remove volatile components such as solvents as much as possible, and well-known and conventional means can be used. In the case where the curable composition of the present invention contains a polymerization initiator whose thermosetting time at 130° C. is 3.5 minutes or more for the composition obtained by adding 1 part by weight to 100 parts by weight of Celloxide 2021P (manufactured by Daicel Co., Ltd.) At the time of heating and drying, the progress of the curing reaction can be suppressed, and the volatile matter such as the solvent can be quickly removed, thereby forming an adhesive layer. The adhesive layer obtained in this way has the characteristics of not having adhesiveness at a temperature lower than 50° C., showing adhesiveness by heating at a temperature capable of suppressing damage to electronic components such as semiconductor wafers, and then rapidly curing. The above-mentioned adhesive sheet includes not only a sheet shape, but also a form similar to a sheet shape such as a film shape, a tape shape, and a plate shape.

The above-mentioned adhesive sheet may be a single-sided adhesive sheet having an adhesive layer only on one side of the substrate, or a double-sided adhesive sheet having an adhesive layer on both sides of the substrate. When the above-mentioned adhesive sheet is a double-sided adhesive sheet, at least one adhesive layer may be an adhesive layer formed from the curable composition of the present invention, and the other may be the adhesive layer or the adhesive. Adhesive layers other than layers (other adhesive layers).

The substrate in the adhesive sheet of the present invention can be a well-known and conventional substrate (the substrate used for the adhesive sheet), which is not particularly limited, for example, plastic substrates, metal substrates, ceramic substrates, semiconductor substrates , glass substrates, paper substrates, wood substrates, substrates whose surfaces are painted surfaces, etc. In addition, the base material in the adhesive sheet of the present invention may be a so-called release liner. In addition, the adhesive sheet of this invention may have only 1 layer of base material, and may have 2 or more layers. In addition, the thickness of the said base material is not specifically limited, For example, it can select suitably from the range of 1-10000 micrometers.

The above-mentioned adhesive sheet may have only one adhesive layer formed of the curable composition of the present invention, or may have two or more layers of the adhesive layer. In addition, the thickness of the adhesive layer in the said adhesive sheet is not specifically limited, For example, it can select suitably from the range of 0.1-10000 micrometers.

In addition, as another aspect of the above-mentioned adhesive sheet, by using a silane coupling agent and the polyorganosiloxane sesquioxane of the present invention, crack resistance, heat resistance, adhesion to an adherend, and adhesion can be obtained Excellent sticker. Specifically, at least one side of the substrate has an adhesion-promoting coating layer containing a silane coupling agent and an adhesive layer formed from a curable composition containing the polyorganosiloxane sesquioxane of the present invention, and the adhesive is The adhesive sheet in which the layer is provided on the surface of the tackifier coating layer is excellent in crack resistance, heat resistance, adhesiveness to the adherend, and adhesion.

Moreover, in another aspect of the above-mentioned adhesive sheet, the adhesive sheet may have only one layer of the above-mentioned tackifying coating layer, or may have two or more layers of the tackifying coating layer. In addition, the thickness of the tackifier coating can be appropriately selected from, for example, a range of 0.001 to 10,000 μm.

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

By using the said adhesive sheet, the laminated body which adhered the to-be-adhered layer (to-be-adhered body) to the adhesive bond layer of an adhesive sheet can be obtained. In addition, when the laminate obtained by using the above-mentioned adhesive sheet is a three-dimensional laminate of semiconductor wafers, compared with conventional semiconductors, the laminate is highly integrated and power-saving, so using the laminate can improve the Packing density and provide smaller and high-performance electronic machines.

The various aspects disclosed in this specification can be combined with any other feature disclosed in this specification. The respective configurations and combinations thereof in each embodiment are examples, and additions, omissions, substitutions, and other modifications of the configurations can be appropriately made within the scope of not departing from the gist of the present invention. The present invention is limited only by the scope of the patent application and is not limited by the embodiments. [Example]

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

The number-average molecular weight and molecular weight dispersion of the product were measured under the following GPC conditions. In addition, the content of monomeric cage silsesquioxane and condensed silsesquioxane in the product was obtained according to the area ratio of the area values of the corresponding peaks in the GPC measurement. In addition, the measurement of the ratio of T2 form and T3 form in the product [T3 form/T2 form] was carried out by measuring ²⁹ Si-NMR spectrum using NMR (600 MHz) manufactured by Brucker Corporation.

[GPC conditions] Measuring device: Trade name "GPC Semi-Micro system" (manufactured by Shimadzu Corporation) Detector: RI detector (manufactured by Zhaoguang Science Co., Ltd.) Column: KF-G4A (guard column), KF-602, and KF-603 (manufactured by Zhaoguang Science Co., Ltd.) Flow rate: 0.6 mL/min Measurement temperature: 40℃ Measurement time: 13 min Injection volume: 20 μL Precipitate: THF, sample concentration 0.1 to 0.2 wt% Molecular weight: standard polystyrene conversion

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

[MS condition] Measuring device: Xevo-G2XS QTOFMS (manufactured by Waters) Ionization mode: ESI+ (sensitivity mode) Measurement method: MSE Capillary voltage: 3.2 kV Cone voltage: 30 V Source compensation voltage: 80 V Desolvation gas: 1000 L/hr (200℃) Cone gas: 50 L/hr Ion source heater: 80℃ Scanning range: m/z=100～3000 Scan time: 0.4 sec Collision energy: 30～50 eV (MSE high energy) Lock in quality: Leucine Enkephalin

Example 1 : Manufacture of the epoxy-containing polyorganosiloxane sesquioxane of the present invention ( 1 ) 1000 units equipped with a thermometer, a stirring device, a reflux condenser, a nitrogen introduction pipe, and a Dean-Stark pipe 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane 277.2 mmol (68.30 g), phenyltrimethoxysilane 3.0 mmol, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane 277.2 mmol (68.30 g), 3.0 mmol of phenyltrimethoxysilane were added to a ml flask (reaction vessel) under nitrogen flow. (0.56 g), and 275.4 g of acetone, and heated up to 50 degreeC. To the thus obtained mixture, 7.74 g of a 5% aqueous potassium carbonate solution (2.8 mmol as potassium carbonate) was added over 5 minutes, and then 2800.0 mmol (50.40 g) of water was added over 20 minutes. In addition, during the addition period, the temperature was not significantly increased. Then, the polycondensation reaction was carried out under nitrogen flow for 5 hours while maintaining at 50°C. Then, 230.5 g of methyl isobutyl ketone was added, the temperature was raised from 50°C to 90°C under reduced pressure, and the acetone (0.0%) and methyl isobutyl ketone (30.32%) in the system were removed by distillation. , water (0.23%). After that, the mixture was stirred at 90° C. for 11 hours, 273.2 g of methyl isobutyl ketone was added, washed with 273.2 g of water 5 times, and concentrated to a conductivity of 1.5 uS/cm or less to obtain 61.1 g of a colorless and transparent liquid. The product was analyzed, and the results showed that the number average molecular weight was 4736, the molecular weight dispersion was 2.54, the content of monomer cage silsesquioxane (retention time 7.6 to 8.3 minutes) was 6.7%, and the condensed cage silsesquioxane ( Retention time 4.9 to 7.6 minutes) was 93.3%, and [T3 body/T2 body] was 46.5. The ²⁹ Si-NMR spectrum is shown in FIG. 1 , and the GPC diagram is shown in FIG. 2 .

The epoxy-containing polyorganosiloxane obtained in Example 1 was measured under the above-mentioned UPLC-MS conditions. The MS spectra detected at the retention times of 3.86 minutes and 1.81 minutes are shown in Fig. 3 and Fig. 4, respectively. According to the comparison between the MS simulation diagram of the molecular formula C ₁₄₄ H ₂₃₄ O ₄₅ Si ₁₈ (Z=2) shown in FIG. 5 and the MS simulation diagram of the molecular formula C ₁₂₈ H ₂₁₀ O ₄₁ Si ₁₆ (Z=2) shown in FIG. 6 , the silsesquioxane with the peak of retention time of 3.86 minutes can be identified as the cage type represented by the composition formula (1) (all R ¹ are 2-(3',4'-epoxycyclohexyl)ethyl) The condensed silsesquioxane obtained by condensing two silsesquioxanes, and the silsesquioxane with the peak of the retention time of 1.81 minutes is the composition formula (1) (all R ¹ are 2-(3',4'- Cage silsesquioxane represented by epoxycyclohexyl)ethyl) and cage represented by composition formula (2) (all R ² are 2-(3',4'-epoxycyclohexyl)ethyl) Condensed silsesquioxane obtained by condensation of silsesquioxane. The estimated structure of the condensed silsesquioxane at the peaks of residence time 3.86 minutes and 1.81 minutes is shown below.・Silsesquioxane with peak retention time of 3.86 minutes

上述式中之全部R ¹及R ²為2-(3',4'-環氧環己基)乙基。 All R ¹ in the above formula are 2-(3',4'-epoxycyclohexyl)ethyl.・Silsesquioxane with peak retention time of 1.81 minutes

All of R ¹ and R ² in the above formula are 2-(3',4'-epoxycyclohexyl)ethyl.

Example 2 : Manufacture of the epoxy-containing polyorganosiloxane sesquioxane of the present invention ( 2 ) 1000 meters equipped with a thermometer, a stirring device, a reflux condenser, a nitrogen introduction pipe, and a Dean-Stark pipe 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane 277.2 mmol (68.30 g), phenyltrimethoxysilane 3.0 mmol, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane 277.2 mmol (68.30 g), 3.0 mmol of phenyltrimethoxysilane were added to a ml flask (reaction vessel) under nitrogen flow. (0.56 g), and 275.4 g of acetone, and heated up to 50 degreeC. To the thus obtained mixture, 7.74 g of a 5% aqueous potassium carbonate solution (2.8 mmol as potassium carbonate) was added over 5 minutes, and then 2800.0 mmol (50.40 g) of water was added over 20 minutes. In addition, during the addition period, the temperature was not significantly increased. After that, the polycondensation reaction was carried out under nitrogen flow for 5 hours while maintaining at 50°C. Then, 230.5 g of methyl isobutyl ketone was added, the temperature was raised from 50°C to 90°C under reduced pressure, and the acetone (0.0%) and methyl isobutyl ketone (20.58%) in the system were removed by distillation. , water (0.35%). Then, the mixture was stirred at 90° C. for 42 hours, 273.2 g of methyl isobutyl ketone was added, washed 6 times with 273.2 g of water, and concentrated to a conductivity of 1.5 uS/cm or less to obtain 50.0 g of a colorless and transparent liquid. The product was analyzed, and the results showed that the number average molecular weight was 9843, the molecular weight dispersion was 2.89, the content of monomer cage silsesquioxane (retention time 7.6-8.3 minutes) was 1.9%, and condensed silsesquioxane (retention time 7.6-8.3 minutes) was 1.9%. 4.7 to 7.6 minutes) was 98.1%, and [T3 body/T2 body] was 196.2. The ²⁹ Si-NMR spectrum is shown in FIG. 7 , and the GPC diagram is shown in FIG. 8 .

Comparative Example 1 : Manufacture of epoxy-containing polyorganosiloxane sesquioxane in a 1000 ml flask (reaction vessel) equipped with a thermometer, a stirring device, a reflux condenser, and a nitrogen introduction tube and a Dean-Stark tube In the middle, 3.0 mmol (0.56 g) of phenyltrimethoxysilane and 275.4 g of acetone were added under nitrogen flow, and the temperature was raised to 50°C. To the thus obtained mixture, 7.74 g of a 5% aqueous potassium carbonate solution (2.8 mmol as potassium carbonate) was added over 5 minutes, and then 2800.0 mmol (50.40 g) of water was added over 20 minutes. Furthermore, 277.2 mmol (68.30 g) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane was started dropwise at the same time as the dropwise addition of potassium carbonate was started, and the dropwise addition was terminated after 2 hours. In addition, during the addition period, the temperature was not significantly increased. After that, the polycondensation reaction was carried out under nitrogen flow for 5 hours while maintaining at 50°C. Then, 230.5 g of methyl isobutyl ketones were added, and it washed with water (273.2 g) 6 times. It was concentrated so that the conductivity was 1.5 uS/cm or less to obtain 50.0 g of a cloudy liquid.

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

[Table 1] (Table 1) sample acetone Chloroform Example 1 completely dissolved completely dissolved Example 2 completely dissolved completely dissolved Comparative Example 1 cloudy cloudy

Reference Example 1 : Manufacture of hard coating film 100 parts by weight of epoxy-containing polyorganosiloxane obtained in Example 1, 20 parts by weight of methyl isobutyl ketone (manufactured by Kanto Chemical Co., Ltd.) , and a mixed solution of 1 part by weight of hardening catalyst 1 ([diphenyl[4-(phenylthio)phenyl]permanium tris(pentafluoroethyl)trifluorophosphate]), which was used as a hard coating solution (hardening composition). The hard coating solution obtained above was cast-coated on a PET film (trade name "KEB03W", manufactured by DuPont Teijin Film Co., Ltd.) using a wire bar coater so that the thickness of the hard coating layer after hardening became 5 μm. After the coating, it was placed in an oven at 70° C. (pre-baking) for 10 minutes, and then irradiated with ultraviolet rays (irradiation conditions (irradiation amount): 312 mJ/cm ² , irradiation intensity: 80 W/cm ² ). Finally, heat treatment (aging) was performed at 80° C. for 2 hours to harden the coating film of the above-mentioned hard coating liquid, and a hard coating film having a hard coating layer was produced.

About the hard coat film obtained above, various evaluations were performed by the following method. (1) Haze and total light transmittance The haze and total light transmittance of the hard coat film obtained above were measured using HAZE METER (NDH-300A, manufactured by Nippon Denshoku Kogyo Co., Ltd.).

(2) Surface hardness (pencil hardness) According to JIS K5600-5-4, the pencil hardness of the hard coat surface of the hard coat film obtained above was evaluated.

(3) Heat resistance (5% weight reduction temperature (T _d5 )) About 5 mg of the hard coat layer of the hard coat film obtained by the same method as above was cut out using a cutter except that a glass plate was used instead of the PET film , as a sample. Using a differential thermogravimetric analyzer (manufactured by Seiko Instruments Co., Ltd., TG/DTA6300), the 5% weight loss temperature of the above-mentioned sample was measured under the following conditions. Measurement temperature range: 25 to 550°C Heating rate: 10°C/min Gas environment: nitrogen

(4) Scratch resistance: Make #0000 steel wool reciprocate 100 times on the hard coat surface of the hard coat film obtained above with a load of 1000 g/cm ² , and check whether there are scratches on the hard coat surface and the number of lines. , and the scratch resistance was evaluated according to the following criteria. ◎ (excellent scratch resistance): 0 scratches ○ (good scratch resistance): 1 to 10 scratches × (poor scratch resistance): more than 10 scratches

(5) Bending resistance (cylindrical mandrel method); according to mandrel test The bending resistance of the hard coat film obtained above was evaluated according to JIS K5600-5-1 using a cylindrical mandrel.

[式（1A）中，R ^1A表示直鏈或支鏈狀之伸烷基] 所表示之基、下述式（1B）

[式（1B）中，R ^1B表示直鏈或支鏈狀之伸烷基] 所表示之基、下述式（1C）

[式（1C）中，R ^1C表示直鏈或支鏈狀之伸烷基] 所表示之基、或下述式（1D）

[式（1D）中，R ^1D表示直鏈或支鏈狀之伸烷基] 所表示之基。 [附記7]如附記6記載之聚有機矽倍半氧烷，其中，上述式（1A）、（1B）、（1C）、及（1D）中，R ^1A、R ^1B、R ^1C、及R ^1D分別為碳數1～4之直鏈狀之伸烷基、或碳數3或4之支鏈狀之伸烷基（較佳為伸乙基、三亞甲基、或伸丙基，更佳為伸乙基、或三亞甲基）。 [附記8]如附記1至7中任一項記載之聚有機矽倍半氧烷，其中，上述組成式（1）中，R ¹中之含有聚合性官能基之基之個數為3～9（較佳為5～9，更佳為7～9，進而較佳為9）。 [附記9]如附記1至8中任一項記載之聚有機矽倍半氧烷，其中，上述組成式（2）中，R ²中之含有聚合性官能基之基之個數為3～8（較佳為5～8，更佳為7～8，進而較佳為8）。 [附記10]如附記1至9中任一項記載之聚有機矽倍半氧烷，其中，上述組成式（3）中，R ³中之含有聚合性官能基之基之個數為3～10（較佳為5～10，更佳為7～10，進而較佳為10）。 [附記11]如附記1至10中任一項記載之聚有機矽倍半氧烷，其中，上述組成式（4）中，R ⁴中之含有聚合性官能基之基之個數較佳為3～12（較佳為5～12，更佳為7～12，進而較佳為12）。 [附記12]如附記1至11中任一項記載之聚有機矽倍半氧烷，其中，相對於上述組成式（1）中之R ¹、組成式（2）中之R ²、組成式（3）中之R ³、及組成式（4）中之R ⁴之整體，含有聚合性官能基之基之比率為30%以上（較佳為50%以上，更佳為80%以上）。 [附記13]如附記1至12中任一項記載之聚有機矽倍半氧烷，其中，下述式（I）所表示之構成單元（T3體）與下述式（II）所表示之構成單元（T2體）之莫耳比[式（I）所表示之構成單元/式（II）所表示之構成單元；T3體/T2體]為1以上（較佳為2以上，更佳為3以上，更佳為4以上，更佳為6以上，更佳為7以上，更佳為8以上，更佳為10以上，更佳為15以上，進而較佳為20以上）。 [R ^aSiO _3/2]                （I） [式（I）中，R ^a表示含有聚合性官能基之基、經取代或未經取代之芳基、經取代或未經取代之芳烷基、經取代或未經取代之環烷基、經取代或未經取代之烷基、經取代或未經取代之烯基、或氫原子] [R ^bSiO _2/2(OR ^c)]        （II） [式（II）中，R ^b表示含有聚合性官能基之基、經取代或未經取代之芳基、經取代或未經取代之芳烷基、經取代或未經取代之環烷基、經取代或未經取代之烷基、或者經取代或未經取代之烯基；R ^c表示氫原子或碳數1～4之烷基] [附記14]如附記13記載之聚有機矽倍半氧烷，其中，上述（T3體）與（T2體）之莫耳比[T3體/T2體]為500以下（較佳為400以下，更佳為300以下，更佳為100以下，更佳為50以下，更佳為40以下，更佳為30以下，進而較佳為25以下）。 [附記15]如附記1至14中任一項記載之聚有機矽倍半氧烷，其為上述組成式（1）、組成式（2）、組成式（3）及組成式（4）所表示之籠型矽倍半氧烷中，1種時縮合2～5（較佳為2～3，更佳為2）、或者2種以上時縮合2～5（較佳為2～3，更佳為2）而得者。 [附記16]如附記1至15中任一項記載之聚有機矽倍半氧烷，其含有單體籠型矽倍半氧烷。 [附記17]如附記1至16中任一項記載之聚有機矽倍半氧烷，其中，單體籠型矽倍半氧烷之含量相對於上述聚有機矽倍半氧烷總量為5重量%以上（較佳為10重量%以上，更佳為20重量%以上）。 [附記18]如附記17中記載之聚有機矽倍半氧烷，其中，上述單體籠型矽倍半氧烷之含量相對於上述聚有機矽倍半氧烷總量為50重量%以下（較佳為40重量%以下，更佳為20重量%以下）。 [附記19]如附記1至18中任一項記載之聚有機矽倍半氧烷，其中，上述聚有機矽倍半氧烷中之縮合矽倍半氧烷之含量相對於上述聚有機矽倍半氧烷總量為20重量%以上（較佳為25～90重量%，更佳為30～80重量%，進而較佳為40～70重量%）。 [附記20]如附記19中記載之聚有機矽倍半氧烷，其中，上述縮合矽倍半氧烷之基於凝膠滲透層析法之標準聚苯乙烯換算之數量平均分子量（Mn）為2000～50000（較佳為2500～40000，更佳為3000～30000）。 [附記21]如附記1至20中任一項記載之聚有機矽倍半氧烷，其中，基於凝膠滲透層析法之標準聚苯乙烯換算之數量平均分子量（Mn）為2000～50000（較佳為2500～40000，更佳為3000～30000）。 [附記22]如附記1至21中任一項記載之聚有機矽倍半氧烷，其中，基於凝膠滲透層析法之標準聚苯乙烯換算之分子量分散度（Mw/Mn）為1.0～4.0（較佳為1.1～3.0，更佳為1.2～2.5）。 [附記23]如附記1至22中任一項記載之聚有機矽倍半氧烷，其中，空氣環境下之5%重量減少溫度（T _d5）為330℃以上（例如為330～450℃，較佳為340℃以上，進而較佳為350℃以上）。 [附記24]一種硬化性組成物，其含有附記1至23中任一項記載之聚有機矽倍半氧烷。 [附記25]如附記24中記載之硬化性組成物，其中，聚有機矽倍半氧烷之含量相對於溶劑除外之硬化性組成物之總量（100重量%）為70重量～100重量%（較佳為80～99.8重量%，進而較佳為90～99.5重量%）。 [附記26]如附記22或23中記載之硬化性組成物，其中，相對於陽離子硬化性化合物或自由基硬化性化合物之總量（100重量%），上述聚有機矽倍半氧烷之比率為70～100重量%（較佳為75～98重量%，更佳為80～95重量%）。 [附記27]如附記24至26中任一項記載之硬化性組成物，其含有硬化觸媒。 [附記28]如附記27記載之硬化性組成物，其含有光聚合起始劑或熱聚合起始劑作為上述硬化觸媒。 [附記29]如附記27或28中記載之硬化性組成物，其含有陽離子聚合起始劑或自由基聚合起始劑作為上述硬化觸媒。 [附記30]如附記29記載之硬化性組成物，其中，上述陽離子聚合起始劑為光陽離子聚合起始劑、或熱陽離子聚合起始劑。 [附記31]如附記30記載之硬化性組成物，其中，上述光陽離子聚合起始劑係選自由鋶鹽、錪鹽、硒鹽、銨鹽、鏻鹽、及過渡金屬錯合物離子與陰離子之鹽所組成之群中之一種以上之光陽離子聚合起始劑。 [附記32]如附記30記載之硬化性組成物，其中，上述熱陽離子聚合起始劑係選自由芳基鋶鹽、芳基錪鹽、芳烴-離子錯合物、四級銨鹽、鋁螯合物、及三氟化硼胺錯合物所組成之群中之一種以上之化合物。 [附記33]如附記29記載之硬化性組成物，其中，上述自由基聚合起始劑為光自由基聚合起始劑、熱自由基聚合起始劑。 [附記34]如附記33記載之硬化性組成物，其中，上述光自由基聚合起始劑係選自由2-胺基-2-苯甲醯-1-苯基烷烴化合物、咪唑化合物、鹵甲基化三

化合物、及鹵甲基

二唑化合物所組成之群中之1種以上之光自由基聚合起始劑。 [附記35]如附記33記載之硬化性組成物，其中，上述熱自由基聚合起始劑為有機過氧化物類。 [附記36]如附記27至35中任一項記載之硬化性組成物，其含有上述聚有機矽倍半氧烷以外之其他陽離子硬化性化合物及/或上述聚有機矽倍半氧烷以外之其他自由基硬化性化合物。 [附記37]如附記36記載之硬化性組成物，其中，上述硬化觸媒之含量相對於上述聚有機矽倍半氧烷及上述其他之陽離子硬化性化合物之總量100重量份為0.01～3.0重量份（較佳為0.05～3.0重量份，更佳為0.1～1.0重量份，進而較佳為0.3～1.0重量份）。 [附記38]如附記36或37中記載之硬化性組成物，其中，上述其他陽離子硬化性化合物包含上述聚有機矽倍半氧烷以外之環氧化合物、氧環丁烷化合物、或乙烯醚化合物。 [附記39]如附記38記載之硬化性組成物，其中，上述環氧化合物為脂環式環氧化合物、芳香族環氧化合物、或脂肪族環氧化合物。 [附記40]如附記36至39中任一項記載之硬化性組成物，其含有上述聚有機矽倍半氧烷以外之(甲基)丙烯酸化合物作為上述其他自由基硬化性化合物。 [附記41]如附記36至40中任一項記載之硬化性組成物，其中，上述其他陽離子硬化性化合物及/或上述其他自由基硬化性化合物之含量（摻合量）相對於上述聚有機矽倍半氧烷、上述其他陽離子硬化性化合物、及上述其他自由基硬化性化合物之總量為50重量%以下（較佳為30重量%以下，更佳為10重量%以下）。 [附記42]如附記24至41中任一項記載之硬化性組成物，其含有聚合穩定劑。 [附記43]如附記42記載之硬化性組成物，其中，上述聚合穩定劑為選自由受阻胺系化合物、鋶硫酸鹽系化合物、及亞磷酸鹽系化合物所組成之群中之1種以上之聚合穩定劑。 [附記44]如附記42或43中記載之硬化性組成物，其中，上述聚合穩定劑之含量相對於上述聚有機矽倍半氧烷100重量份為0.005重量份以上（較佳為0.01～10重量份，進而較佳為0.02～1重量份）。 [附記45]如附記42至44中任一項記載之硬化性組成物，其含有上述聚合穩定劑及硬化觸媒，聚合穩定劑之含量相對於硬化觸媒100重量份為1重量份以上（較佳為3～200重量份，更佳為5～150重量份）。 [附記44]如附記24至45中任一項記載之硬化性組成物，其含有溶劑。 [附記45]如附記44記載之硬化性組成物，其中，上述溶劑之沸點為170℃以下。 [附記46]如附記44或45中記載之硬化性組成物，其中，上述溶劑之使用量以上述硬化性組成物所含之不揮發分之濃度計為30～80重量%（較佳為40～70重量%，更佳為50～60重量%）。 [附記47]如附記24至46中任一項記載之硬化性組成物，其於常溫（約25℃）為液體。 [附記48]如附記24至47中任一項記載之硬化性組成物，其於25℃之黏度為300～20000 mPa・s（較佳為500～10000 mPa・s，更佳為1000～8000 mPa・s）。 [附記49]如附記24至48中任一項記載之硬化性組成物，其為硬塗層形成用硬化性組成物。 [附記50]如附記24至48中任一項記載之硬化性組成物，其為接著劑用硬化性組成物。 [附記51]一種硬化物，其為附記24至50中任一項記載之硬化性組成物之硬化物。 [附記52]一種硬塗膜，其積層有基材、及為附記51記載之硬化物之硬塗層。 [附記53]如附記52記載之硬塗膜，其中，上述基材為塑膠基材、金屬基材、陶瓷基材、半導體基材、玻璃基材、紙基材、木基材、或表面為塗裝表面之基材。 [附記54]如附記52或53中記載之硬塗膜，其中，上述基材之厚度為0.01～10000 μm。 [附記55]如附記52至54中任一項記載之硬塗膜，其中，上述硬塗層之厚度為1～200 μm（較佳為3～150 μm）。 [附記56]如附記52至55中任一項記載之硬塗膜，其中，上述硬塗層之厚度為50 μm時之霧度為1.5%以下（較佳為1.0%以下）。 [附記57]如附記52至56中任一項記載之硬塗膜，其中，上述硬塗層之厚度為50 μm時之霧度為0.1%以上。 [附記58]如附記52至57中任一項記載之硬塗膜，其中，上述硬塗層之厚度為50 μm時之全光線穿透率為85%以上（較佳為90%以上）。 [附記59]如附記52至58中任一項記載之硬塗膜，其於上述硬塗層表面具有表面保護膜。 [附記60]如附記52至59中任一項記載之硬塗膜，其厚度為1～10000 μm。 [附記61]一種轉印用膜，其積層有基材、及位於形成於該基材之至少一表面之脫模層上之硬塗層，該硬塗層為含有附記49記載之硬化性組成物之層。 [附記62]如附記61記載之轉印用膜，其中，上述脫模層與上述硬塗層之剝離強度為30～500 mN/24 mm（較佳為40～300 mN/24 mm，更佳為50～200 mN/24 mm）。 [附記63]如附記61或62中記載之轉印用膜，其於上述硬塗層上依序進而積層增黏塗層及接著劑層。 [附記64]如附記63記載之轉印用膜，其中，上述增黏塗層之厚度為0.1～20 μm（較佳為0.5～5 μm）之範圍。 [附記65]如附記61至64中任一項記載之轉印用膜，其中，接著劑層之厚度為0.1～10 μm（較佳為0.5～5 μm）。 [附記66]如附記61至65中任一項記載之轉印用膜，其進而含有至少一層之著色層。 [附記67]如附記66記載之轉印用膜，其中，上述著色層係於製成用以將圖樣層及/或隱蔽層轉印至成型品之加飾膜時所設置者。 [附記68]一種接著片，其具有基材及接著劑層，該接著劑層位於該基材之至少一面，且為含有附記50記載之硬化性組成物之層。 [附記69]一種附記50記載之硬化性組成物之用途，其用於具有基材、及位於該基材之至少一面之接著劑層之接著片中之接著劑層。 [附記70]一種接著片，其具有基材、增黏塗層及接著劑層，該增黏塗層及該接著劑層位於該基材之至少一面，該增黏塗層含有矽烷偶合劑，該接著劑層為含有附記50記載之硬化性組成物之層；上述接著劑層設置於上述增黏塗層之表面上。 [附記71]一種附記22至48中任一項記載之硬化性組成物之用途，其用作硬塗層形成用硬化性組成物。 [附記72]一種附記22至48中任一項記載之硬化性組成物之用途，其用作接著劑用硬化性組成物。 [附記73]一種附記51記載之硬化物之用途，其用於具有基材與硬塗層之硬塗膜中之硬塗層。 [附記74]一種附記49記載之硬化性組成物之用途，其用於具有基材、且在形成於該基材之至少一表面之脫模層上形成有硬塗層之轉印用膜中之硬塗層。 [附記75]一種附記50記載之硬化性組成物之用途，其用於具有基材、增黏塗層及接著劑層的接著片中之接著劑層，該增黏塗層及該接著劑層位於該基材之至少一面，該增黏塗層含有矽烷偶合劑，且該接著劑層設置於該增黏塗層之表面上。 [產業上之可利用性] Hereinafter, the invention changes related to this invention are described. [Supplementary Note 1] A polyorganosiloxane containing silsesquioxane, the silsesquioxane containing a compound selected from the following compositional formula (1), compositional formula (2), compositional formula (3) A condensate obtained by condensing at least one clathrate silsesquioxane of at least one of the group consisting of the clathrate silsesquioxane represented by the composition formula (4) and having a molecular weight of 8,000 or less.・Formula (1): [R ¹ SiO _3/2 ] ₈ [R ¹ SiO _2/2 (OR ^c )] ₁ (in formula (1), R ¹ is each independently a polymerizable functional group-containing group, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or hydrogen atom, and at least one is a group containing a polymerizable functional group; R ^c represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (2): [R ² SiO _3/2 ] ₆ [R ² SiO _2/2 (OR ^c )] ₂ (in formula (2), R ² 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; R ^c respectively independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (3): [R ³ SiO _3/2 ] ₈ [R ³ SiO _2/2 (OR ^c )] ₂ (in formula (3), R ³ are 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 aryl group alkyl group, substituted or unsubstituted alkenyl group, or hydrogen atom, and at least one of them is a group containing a polymerizable functional group; R ^c independently represents an alkyl group with 1 to 4 carbon atoms or a hydrogen atom) ・Formula ( 4): [R ⁴ SiO _3/2 ] ₁₀ [R ⁴ SiO _2/2 (OR ^c )] ₂ (in formula (4), R ⁴ is independently a group containing a polymerizable functional group, substituted or unsubstituted Substituted aryl, substituted or unsubstituted aralkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or hydrogen atom , and at least one is a group containing a polymerizable functional group; R ^c independently represents an alkyl group with 1 to 4 carbon atoms or a hydrogen atom) [Supplementary Note 2] The polyorganosiloxane sesquioxane as described in Supplementary Note 1, wherein, The above-mentioned silsesquioxane is a condensate obtained by condensing at least one selected from the group consisting of clathrate silsesquioxanes represented by the following composition formulae (5) to (8).・Formula (5): [R ⁵ SiO _3/2 ] ₆ [R ⁵ SiO _2/2 (OR ^c )] ₃ (in formula (5), R ⁵ is each independently a polymerizable functional group-containing group, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or hydrogen atom, and at least one of them is a group containing a polymerizable functional group; R ^c independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (6): [R ⁶ SiO _3/2 ] ₈ [R ⁶ SiO _2/2 (OR ^c )] ₃ (in formula (6), R ⁶ is independently a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aralkane R ^c each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (7): [R ⁷ SiO _3/2 ] ₁₀ [R ⁷ SiO _2/2 (OR ^c )] ₁ (in formula (7) , R ⁷ 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 aryl group, A substituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one of which is a group containing a polymerizable functional group; R ^c represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula ( 8): [R ⁸ SiO _3/2 ] ₁₂ [R ⁸ SiO _2/2 (OR ^c )] ₁ (in formula (8), R ⁸ is independently a group containing a polymerizable functional group, substituted or unsubstituted Substituted aryl, substituted or unsubstituted aralkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or hydrogen atom , and at least one is a group containing a polymerizable functional group; R ^c represents an alkyl group with 1 to 4 carbon atoms or a hydrogen atom) [Appendix 3] The polyorganosiloxane as described in appendix 1 or 2, wherein, The above-mentioned polymerizable functional group-containing group is a cationically polymerizable functional group (preferably an epoxy group, an oxycyclobutyl group, a vinyl ether group, or a vinyl phenyl group). [Supplementary Note 4] The polyorganosiloxane sesquioxane according to any one of Supplementary Notes 1 to 3, wherein the polymerizable functional group-containing group is a radically polymerizable functional group (preferably (meth)acrylonitrile) oxy, (meth)acrylamido, vinyl, or vinylthio). [Supplementary Note 5] The polyorganosiloxane sesquioxane according to any one of Supplementary Notes 1 to 4, wherein the polymerizable functional group is an epoxy group or a (meth)acryloyloxy group. [Supplementary Note 6] The polyorganosiloxane sesquioxane according to any one of Supplementary Notes 1 to 5, wherein the polymerizable functional group-containing group is the following formula (1A)

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

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

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

A group represented by [in formula (1D), R ^1D represents a linear or branched alkylene group]. [Supplementary Note 7] The polyorganosiloxane sesquioxane according to Supplementary Note 6, wherein in the above formulae (1A), (1B), (1C), and (1D), R ^1A , R ^1B , R ^1C , and R ^1D is respectively a straight-chain alkylene with 1 to 4 carbon atoms, or a branched alkylene with 3 or 4 carbons (preferably ethylidene, trimethylene, or propylidene, more preferably For ethylene, or trimethylene). [Supplementary Note 8] The polyorganosiloxane sesquioxane according to any one of Supplementary Notes 1 to 7, wherein, in the above compositional formula (1), the number of groups containing a polymerizable functional group in R ¹ is 3 to 3 9 (preferably 5 to 9, more preferably 7 to 9, still more preferably 9). [Supplementary Note 9] The polyorganosiloxane sesquioxane according to any one of Supplementary Notes 1 to 8, wherein, in the above compositional formula (2), the number of groups containing a polymerizable functional group in R ² is 3 to 3 8 (preferably 5 to 8, more preferably 7 to 8, still more preferably 8). [Supplementary Note 10] The polyorganosiloxane sesquioxane according to any one of Supplementary Notes 1 to 9, wherein, in the above compositional formula (3), the number of groups containing a polymerizable functional group in R ³ is 3 to 3 10 (preferably 5-10, more preferably 7-10, still more preferably 10). [Supplementary Note 11] The polyorganosiloxane sesquioxane according to any one of Supplementary Notes 1 to 10, wherein, in the above compositional formula (4), the number of groups containing a polymerizable functional group in R ⁴ is preferably 3 to 12 (preferably 5 to 12, more preferably 7 to 12, further preferably 12). [Supplementary Note 12] The polyorganosiloxane according to any one of Supplementary Notes 1 to 11, wherein, with respect to R ¹ in the composition formula (1), R ² in the composition formula (2), and composition formula R ³ in (3) and R ⁴ in the compositional formula (4) as a whole have a ratio of groups containing a polymerizable functional group of 30% or more (preferably 50% or more, more preferably 80% or more). [Supplementary Note 13] The polyorganosiloxane according to any one of Supplementary Notes 1 to 12, wherein the structural unit (T3 body) represented by the following formula (I) and the compound represented by the following formula (II) The molar ratio of the constituent unit (T2 body) [constituent unit represented by formula (I)/constituent unit represented by formula (II); T3 body/T2 body] is 1 or more (preferably 2 or more, more preferably 3 or more, more preferably 4 or more, more preferably 6 or more, more preferably 7 or more, more preferably 8 or more, more preferably 10 or more, more preferably 15 or more, still more preferably 20 or more). [R ^a SiO _3/2 ] (I) [In formula (I), R ^a represents a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, Substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or hydrogen atom] [R ^b SiO _2/2 (OR ^c )] (II) [In formula (II), R ^b represents a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, Substituted or unsubstituted alkyl group, or substituted or unsubstituted alkenyl group; R ^c represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms] [Supplementary Note 14] Polyorganosilicon sesquises as described in Supplementary Note 13 Oxane, wherein the molar ratio of the above (T3 body) and (T2 body) [T3 body/T2 body] is 500 or less (preferably 400 or less, more preferably 300 or less, more preferably 100 or less, more preferably 50 or less, more preferably 40 or less, more preferably 30 or less, still more preferably 25 or less). [Supplementary Note 15] The polyorganosiloxane silsesquioxane according to any one of Supplementary Notes 1 to 14, which is represented by the above compositional formula (1), compositional formula (2), compositional formula (3) and compositional formula (4). Among the cage-type silsesquioxanes indicated, one type of silsesquioxane condenses 2-5 (preferably 2-3, more preferably 2), or two or more types condense 2-5 (preferably 2-3, more The best is the winner of 2). [Supplementary Note 16] The polyorganosiloxane according to any one of Supplementary Notes 1 to 15, which contains monomeric cage silsesquioxane. [Supplementary Note 17] The polyorganosiloxane silsesquioxane according to any one of Supplementary Notes 1 to 16, wherein the content of the monomer cage silsesquioxane relative to the total amount of the polyorganosiloxane silsesquioxane is 5 % by weight or more (preferably 10% by weight or more, more preferably 20% by weight or more). [Supplementary Note 18] The polyorganosiloxane silsesquioxane according to Supplementary Note 17, wherein the content of the monomer cage silsesquioxane is 50% by weight or less relative to the total amount of the polyorganosiloxane silsesquioxane ( Preferably it is 40 weight% or less, More preferably, it is 20 weight% or less). [Supplementary Note 19] The polyorganosiloxane according to any one of Supplementary Notes 1 to 18, wherein the content of the condensed silsesquioxane in the above-mentioned polyorganosiloxane is two times that of the above-mentioned polyorganosiloxane. The total amount of hemioxane is 20% by weight or more (preferably 25 to 90% by weight, more preferably 30 to 80% by weight, and still more preferably 40 to 70% by weight). [Supplementary Note 20] The polyorganosiloxane sesquioxane as described in Supplementary Note 19, wherein the number-average molecular weight (Mn) of the above-mentioned condensed silsesquioxane in terms of standard polystyrene based on gel permeation chromatography is 2000 ~50000 (preferably 2500 to 40000, more preferably 3000 to 30000). [Supplementary Note 21] The polyorganosiloxane sesquioxane according to any one of Supplementary Notes 1 to 20, wherein the number average molecular weight (Mn) in terms of standard polystyrene conversion based on gel permeation chromatography is 2000 to 50000 ( Preferably it is 2500-40000, More preferably, it is 3000-30000). [Supplementary Note 22] The polyorganosiloxane sesquioxane according to any one of Supplementary Notes 1 to 21, wherein the molecular weight dispersion (Mw/Mn) in terms of standard polystyrene based on gel permeation chromatography is 1.0～ 4.0 (preferably 1.1 to 3.0, more preferably 1.2 to 2.5). [Supplementary Note 23] The polyorganosiloxane sesquioxane according to any one of Supplementary Notes 1 to 22, wherein the 5% weight reduction temperature (T _d5 ) in an air environment is 330°C or higher (for example, 330 to 450°C, Preferably it is 340 degreeC or more, More preferably, it is 350 degreeC or more). [Supplementary Note 24] A curable composition containing the polyorganosiloxane sesquioxane according to any one of Supplementary Notes 1 to 23. [Supplementary Note 25] The curable composition according to Supplementary Note 24, wherein the content of the polyorganosiloxane sesquioxane is 70 to 100% by weight relative to the total amount (100% by weight) of the curable composition excluding the solvent (80-99.8weight% is preferable, More preferably, it is 90-99.5weight%). [Supplementary Note 26] The curable composition according to Supplementary Note 22 or 23, wherein the ratio of the polyorganosiloxane sesquioxane to the total amount (100% by weight) of the cationic curable compound or the radical curable compound It is 70 to 100 weight% (preferably 75 to 98 weight%, more preferably 80 to 95 weight%). [Supplementary Note 27] The curable composition according to any one of Supplementary Notes 24 to 26, which contains a hardening catalyst. [Supplementary Note 28] The curable composition according to Supplementary Note 27, which contains a photopolymerization initiator or a thermal polymerization initiator as the curing catalyst. [Supplementary Note 29] The curable composition according to Supplementary Note 27 or 28, which contains a cationic polymerization initiator or a radical polymerization initiator as the curing catalyst. [Supplementary Note 30] The curable composition according to Supplementary Note 29, wherein the cationic polymerization initiator is a photocationic polymerization initiator or a thermal cationic polymerization initiator. [Supplementary Note 31] The curable composition according to Supplementary Note 30, wherein the photocationic polymerization initiator is selected from the group consisting of pernium salts, iodonium salts, selenium salts, ammonium salts, phosphonium salts, and transition metal complex ions and anions One or more photocationic polymerization initiators in the group consisting of salts. [Supplementary Note 32] The curable composition as described in Supplementary Note 30, wherein the thermal cationic polymerization initiator is selected from the group consisting of aryl perionium salts, aryl iodonium salts, aromatic hydrocarbon-ion complexes, quaternary ammonium salts, and aluminum chelate One or more compounds in the group consisting of boron trifluoride amine complex and boron trifluoride amine complex. [Supplementary Note 33] The curable composition according to Supplementary Note 29, wherein the radical polymerization initiator is a photoradical polymerization initiator or a thermal radical polymerization initiator. [Supplementary Note 34] The curable composition according to Supplementary Note 33, wherein the photoradical polymerization initiator is selected from the group consisting of 2-amino-2-benzyl-1-phenylalkane compounds, imidazole compounds, halomethyl compounds base three

Compounds, and halomethyl

One or more photo-radical polymerization initiators in the group consisting of oxadiazole compounds. [Supplementary Note 35] The curable composition according to Supplementary Note 33, wherein the thermal radical polymerization initiator is an organic peroxide. [Supplementary Note 36] The curable composition according to any one of Supplementary Notes 27 to 35, which contains other cationic curable compounds other than the above-mentioned polyorganosilosilsesquioxane and/or other than the above-mentioned polyorganosilsesquioxane Other free radical hardening compounds. [Appendix 37] The curable composition according to appendix 36, wherein the content of the hardening catalyst is 0.01 to 3.0 parts by weight relative to 100 parts by weight of the total amount of the polyorganosiloxane and the other cationic curable compounds. parts by weight (preferably 0.05 to 3.0 parts by weight, more preferably 0.1 to 1.0 parts by weight, still more preferably 0.3 to 1.0 parts by weight). [Supplementary Note 38] The curable composition according to Supplementary Note 36 or 37, wherein the other cationic curable compound comprises an epoxy compound, an oxetane compound, or a vinyl ether compound other than the above-mentioned polyorganosiloxane . [Supplementary Note 39] The curable composition according to Supplementary Note 38, wherein the epoxy compound is an alicyclic epoxy compound, an aromatic epoxy compound, or an aliphatic epoxy compound. [Supplementary Note 40] The curable composition according to any one of Supplementary Notes 36 to 39, which contains a (meth)acrylic compound other than the polyorganosiloxane sesquioxane as the other radical curable compound. [Supplementary Note 41] The curable composition according to any one of Supplementary Notes 36 to 40, wherein the content (compounding amount) of the above-mentioned other cationic curable compound and/or the above-mentioned other radical curable compound is relative to the above-mentioned polyorganic The total amount of silsesquioxane, the above-mentioned other cation-curable compound, and the above-mentioned other radical-curable compound is 50% by weight or less (preferably 30% by weight or less, more preferably 10% by weight or less). [Supplementary Note 42] The curable composition according to any one of Supplementary Notes 24 to 41, which contains a polymerization stabilizer. [Supplementary Note 43] The curable composition according to Supplementary Note 42, wherein the polymerization stabilizer is at least one selected from the group consisting of hindered amine-based compounds, perylene sulfate-based compounds, and phosphite-based compounds Polymeric stabilizer. [Supplementary Note 44] The curable composition according to Supplementary Note 42 or 43, wherein the content of the polymerization stabilizer is 0.005 parts by weight or more (preferably 0.01 to 10 parts by weight relative to 100 parts by weight of the polyorganosiloxane sesquioxane) parts by weight, more preferably 0.02 to 1 part by weight). [Supplementary Note 45] The curable composition according to any one of Supplementary Notes 42 to 44, which contains the above-mentioned polymerization stabilizer and hardening catalyst, and the content of the polymerization stabilizer is 1 part by weight or more relative to 100 parts by weight of the hardening catalyst ( Preferably it is 3-200 weight part, More preferably, it is 5-150 weight part). [Supplementary Note 44] The curable composition according to any one of Supplementary Notes 24 to 45, which contains a solvent. [Supplementary Note 45] The curable composition according to Supplementary Note 44, wherein the boiling point of the solvent is 170°C or lower. [Supplementary Note 46] The curable composition according to Supplementary Note 44 or 45, wherein the amount of the solvent used is 30 to 80% by weight (preferably 40% by weight) based on the concentration of the nonvolatile matter contained in the curable composition. to 70% by weight, more preferably 50 to 60% by weight). [Supplementary Note 47] The curable composition according to any one of Supplementary Notes 24 to 46, which is liquid at normal temperature (about 25°C). [Supplementary Note 48] The curable composition according to any one of Supplementary Notes 24 to 47, wherein the viscosity at 25°C is 300 to 20000 mPa·s (preferably 500 to 10000 mPa·s, more preferably 1000 to 8000 mPa·s). mPa·s). [Supplementary Note 49] The curable composition according to any one of Supplementary Notes 24 to 48, which is a curable composition for forming a hard coat layer. [Supplementary Note 50] The curable composition according to any one of Supplementary Notes 24 to 48, which is a curable composition for an adhesive. [Supplementary Note 51] A hardened product, which is the hardened product of the curable composition according to any one of Supplementary Notes 24 to 50. [Supplementary Note 52] A hard coat film comprising a base material and a hard coat layer which is the cured product according to Supplementary Note 51 in layers. [Supplementary Note 53] The hard coating film as described in Supplementary Note 52, wherein the substrate is a plastic substrate, a metal substrate, a ceramic substrate, a semiconductor substrate, a glass substrate, a paper substrate, a wood substrate, or a surface of The substrate for the coated surface. [Supplementary Note 54] The hard coat film according to Supplementary Note 52 or 53, wherein the base material has a thickness of 0.01 to 10000 μm. [Supplementary Note 55] The hard coat film according to any one of Supplementary Notes 52 to 54, wherein the thickness of the hard coat layer is 1 to 200 μm (preferably 3 to 150 μm). [Supplementary Note 56] The hard coat film according to any one of Supplementary Notes 52 to 55, wherein the haze when the thickness of the hard coat layer is 50 μm is 1.5% or less (preferably 1.0% or less). [Supplementary Note 57] The hard coat film according to any one of Supplementary Notes 52 to 56, wherein the haze when the thickness of the hard coat layer is 50 μm is 0.1% or more. [Supplementary Note 58] The hard coat film according to any one of Supplementary Notes 52 to 57, wherein the total light transmittance when the thickness of the hard coat layer is 50 μm is 85% or more (preferably 90% or more). [Supplementary Note 59] The hard coat film according to any one of Supplementary Notes 52 to 58, which has a surface protection film on the surface of the hard coat layer. [Supplementary Note 60] The hard coat film according to any one of Supplementary Notes 52 to 59, which has a thickness of 1 to 10000 μm. [Supplementary Note 61] A transfer film comprising a base material and a hard coat layer formed on a release layer formed on at least one surface of the base material, the hard coat layer having the curable composition described in Supplementary Note 49 layer of things. [Supplementary Note 62] The transfer film according to Supplementary Note 61, wherein the peel strength between the mold release layer and the hard coat layer is 30 to 500 mN/24 mm (preferably 40 to 300 mN/24 mm, more preferably 40 to 300 mN/24 mm). 50 to 200 mN/24 mm). [Supplementary Note 63] The transfer film according to Supplementary Note 61 or 62, wherein an adhesion promoter coating layer and an adhesive layer are further laminated on the hard coat layer in this order. [Supplementary Note 64] The transfer film according to Supplementary Note 63, wherein the thickness of the tackifier coating layer is in the range of 0.1 to 20 μm (preferably 0.5 to 5 μm). [Supplementary Note 65] The transfer film according to any one of Supplementary Notes 61 to 64, wherein the adhesive layer has a thickness of 0.1 to 10 μm (preferably 0.5 to 5 μm). [Supplementary Note 66] The transfer film according to any one of Supplementary Notes 61 to 65, further comprising at least one coloring layer. [Supplementary Note 67] The transfer film according to Supplementary Note 66, wherein the colored layer is provided when a decorative film for transferring the design layer and/or the concealment layer to a molded article is formed. [Supplementary Note 68] An adhesive sheet comprising a substrate and an adhesive layer, the adhesive layer being located on at least one side of the substrate and containing the curable composition described in Supplementary Note 50. [Supplementary Note 69] A use of the curable composition according to Supplementary Note 50, which is used for an adhesive layer in an adhesive sheet having a substrate and an adhesive layer on at least one side of the substrate. [Supplementary Note 70] An adhesive sheet comprising a substrate, an adhesion-promoting coating and an adhesive layer, the adhesion-promoting coating and the adhesive layer being located on at least one side of the substrate, and the adhesion-promoting coating containing a silane coupling agent, The adhesive layer is a layer containing the curable composition described in Supplementary Note 50; the adhesive layer is provided on the surface of the adhesion-promoting coating. [Supplementary Note 71] Use of the curable composition according to any one of Supplementary Notes 22 to 48 as a curable composition for forming a hard coat layer. [Supplementary Note 72] Use of the curable composition according to any one of Supplementary Notes 22 to 48, as a curable composition for an adhesive. [Supplementary Note 73] Use of the cured product according to Supplementary Note 51, which is used as a hard coat layer in a hard coat film having a base material and a hard coat layer. [Supplementary Note 74] A use of the curable composition described in Supplementary Note 49, which is used in a transfer film having a base material and a hard coat layer formed on a release layer formed on at least one surface of the base material hard coating. [Supplementary Note 75] A use of the curable composition described in Supplementary Note 50, which is used for an adhesive layer in an adhesive sheet having a substrate, an adhesion-promoting coating and an adhesive layer, the adhesion-promoting coating and the adhesive layer On at least one side of the substrate, the adhesion-promoting coating contains a silane coupling agent, and the adhesive layer is disposed on the surface of the adhesion-promoting coating. [Industrial Availability]

The polyorganosiloxane sesquioxane of the present invention can be used as a raw material for a hard coating film or an adhesive sheet.

1: Hard coating 11: Hard coating 12: Substrate 2: Film for transfer 21: Substrate 22: Release layer 23: Hard coating (unhardened or semi-hardened hard coating) 24: Tackifier coating 25: Shading Layer 26: Adhesive layer 3: Next film 31: Adhesive layer 32: Substrate 33: Tackifier coating

Fig. 1 is a ²⁹ Si-NMR spectrum of the epoxy group-containing condensed silsesquioxane of the present invention obtained in Example 1. [Fig. FIG. 2 is a GPC chart of the epoxy group-containing condensed silsesquioxane of the present invention obtained in Example 1. FIG. FIG. 3 is a UPLC-MS chart of the epoxy group-containing condensed silsesquioxane of the present invention obtained in Example 1. FIG. FIG. 4 is a UPLC-MS chart of the epoxy group-containing condensed silsesquioxane of the present invention obtained in Example 1. FIG. [ Fig. 5 ] It is an MS simulation diagram of the molecular formula C ₁₄₄ H ₂₃₄ O ₄₅ Si ₁₈ (Z=2). [ Fig. 6 ] It is an MS simulation diagram of the molecular formula C ₁₂₈ H ₂₁₀ O ₄₁ Si ₁₆ (Z=2). FIG. 7 is a ²⁹ Si-NMR spectrum of the epoxy group-containing condensed silsesquioxane of the present invention obtained in Example 2. FIG. FIG. 8 is a GPC chart of the epoxy group-containing condensed silsesquioxane of the present invention obtained in Example 2. FIG. It is a schematic diagram (sectional drawing) which shows one Embodiment of the hard-coat film of this invention. 10 is a schematic view (sectional view) showing one embodiment of the transfer film of the present invention. Fig. 11 is a schematic view (sectional view) showing one embodiment of the adhesive sheet of the present invention.

Claims (20)

A polyorganosiloxane containing silsesquioxane, the silsesquioxane is selected from the following compositional formula (1), compositional formula (2), compositional formula (3) and compositional formula ( 4) A condensate obtained by condensing at least one of the clathrate silsesquioxanes in the group consisting of the indicated clathrate silsesquioxane 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), R ¹ is each independently a polymerizable functional group-containing group, a substituted or unsubstituted aryl group , substituted or unsubstituted aralkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or hydrogen atom, and at least one is a group containing a polymerizable functional group; R ^c represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (2): [R ² SiO _3/2 ] ₆ [R ² SiO _2/2 (OR ^c ) ] ₂ (in formula (2), R ² 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 aralkyl group, Cycloalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or hydrogen atom, and at least one of them is a group containing a polymerizable functional group; R ^c independently represents carbon number 1-4 alkyl group or hydrogen atom) ・Formula ( ³ ): [ _R3SiO3/2 ^] ₈ [R3SiO2 _/2 ^{( ORc} )] ₂ functional group, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted an unsubstituted alkenyl group or a hydrogen atom, and at least one of which is a group containing a polymerizable functional group; R ^c independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (4): [R ⁴ SiO _3/2 ] ₁₀ [R ⁴ SiO _2/2 (OR ^c )] ₂ (in formula (4), R ⁴ is independently a polymerizable functional group-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, or hydrogen atom, and at least one of which is polymer-containing group of sexual functional groups; R ^c independently represents an alkyl group with 1 to 4 carbon atoms or a hydrogen atom). The polyorganosiloxane as claimed in claim 1, wherein the above-mentioned polymerizable functional group-containing group is the following formula (1A)

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

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

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

A group represented by [in formula (1D), R ^1D represents a linear or branched alkylene group]. The polyorganosiloxane sesquioxane of claim 1 or 2, wherein, with respect to R 1 in the above composition formula (1), R ² in the composition formula (2), R ³ in the composition formula ( ³ ), And the whole of R ⁴ in the composition formula (4), the ratio of the group containing a polymerizable functional group is 30% or more. The polyorganosiloxane sesquioxane of claim 1 or 2, wherein the following formula (I) [R ^a SiO _3/2 ] (I) [in formula (I), R ^a represents a polymer containing a polymerizable functional group aryl, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted The structural unit represented by the alkenyl group or hydrogen atom] is the same as the following formula (II) [R ^b SiO _2/2 (OR ^c )] (II) [In formula (II), R ^b represents a polymerizable functional group , substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted A substituted alkenyl group, or a hydrogen atom; R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms] Molar ratio of the constituent unit represented by [the constituent unit represented by formula (I)/represented by formula (II)] The constituent unit] is 1 or more and 500 or less. For example, the polyorganosiloxane sesquioxane of claim 1 or 2 has a number-average molecular weight of 2,000 to 50,000. As claimed in claim 1 or 2, the polyorganosiloxane sesquioxane has a molecular weight dispersion (weight average molecular weight/number average molecular weight) of 1.0 to 4.0. A curable composition containing the polyorganosiloxane of any one of claims 1 to 6. The curable composition according to claim 7, which further contains a curable catalyst. The curable composition according to claim 8, wherein the curing catalyst is a photo- or thermal polymerization initiator. The curable composition according to claim 7, which further contains a polymerization stabilizer. The curable composition according to claim 7, which is a curable composition for forming a hard coat layer. The curable composition according to claim 7, which is a curable composition for an adhesive. A cured product, which is the cured product of the curable composition of any one of claims 7 to 12. A hard coat film comprising a base material and a hard coat layer which is the hardened product of claim 13 in layers. A transfer film comprising a substrate and a hard coat layer formed on a release layer formed on at least one surface of the substrate, wherein the hard coat layer is a layer containing the curable composition of claim 11. The transfer film of claim 15, wherein an anchor coat layer and an adhesive layer are sequentially laminated on the hard coat layer. The transfer film according to claim 15, further comprising at least one coloring layer. The transfer film according to claim 15, wherein the thickness of the hard coat layer is 3 to 150 μm. An adhesive sheet comprising a base material and an adhesive layer, wherein the adhesive layer is located on at least one side of the base material and is a layer containing the curable composition of claim 12. An adhesive sheet, which has a base material, an adhesion-promoting coating and an adhesive layer, the adhesion-promoting coating and the adhesive layer are located on at least one side of the base material, the adhesion-promoting coating contains a silane coupling agent, and the adhesive agent The layer is a layer containing the curable composition of claim 12; the above-mentioned adhesive layer is provided on the surface of the above-mentioned adhesion-promoting coating.

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