JP6557522B2 - Hard coat layer forming curable composition, hard coat film, method for producing hard coat film, adhesive composition, cured product, adhesive sheet, laminate, and apparatus - Google Patents

Description

  The present invention relates to a polyorganosilsesquioxane, a curable composition containing the polyorganosilsesquioxane, and a cured product thereof. Moreover, this invention relates to the hard coat film which has the hard-coat layer formed from the hard-coat liquid (curable composition for hard-coat layer formation) containing the said polyorgano silsesquioxane. Moreover, this invention relates to the adhesive bond layer formed using the curable composition (adhesive composition) containing the said polyorgano silsesquioxane.

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

  On the other hand, glass is known as a material having a very high surface hardness, and in particular, glass having a surface pencil hardness of up to 9H by an alkali ion exchange treatment is known. ) And the processability is poor, and the roll-to-roll method cannot be used for manufacturing or processing, and it is necessary to manufacture or process using single wafers, resulting in high production costs.

  In addition, thermosetting adhesives containing benzocyclobutene (BCB), novolac epoxy resins, or epoxy group-containing polyorganosilsesquioxanes are known as adhesives used for semiconductor lamination and electronic component bonding. (For example, refer to Patent Document 2).

JP 2009-279840 A JP 2010-2226060 A

  However, it cannot be said that the hard coat film using the above-mentioned UV acrylic monomer still has a sufficient surface hardness. In general, in order to increase the hardness, it is conceivable to use a polyfunctional UV acrylic monomer or to increase the thickness of the hard coat layer. When such a method is adopted, the hard coat layer is cured. There is a problem that the shrinkage increases, and as a result, the hard coat film is curled and cracked. In addition, when nanoparticles are added to the hard coat layer, if the compatibility between the nanoparticles and the UV acrylic monomer is poor, there is a problem that the nanoparticles aggregate and the hard coat layer is whitened.

  Moreover, in order to cure the thermosetting adhesive containing BCB, it is necessary to heat at a high temperature, and the adherend may be damaged by being exposed to a high temperature. In addition, a thermosetting adhesive containing a novolac epoxy resin decomposes the adhesive when it is subjected to a high-temperature process (for example, 260 to 280 ° C.) such as lead-free solder reflow, thereby generating outgas. There is a problem that adhesiveness decreases.

  Accordingly, an object of the present invention is to provide a polyorganosilsesquioxane that can form a cured product having high surface hardness and excellent heat resistance by curing, and a curable composition containing the same. It is to provide. Another object of the present invention is to provide a hard coat film having flexibility (flexibility) while maintaining high surface hardness and capable of being manufactured and processed by a roll-to-roll method. . Another object of the present invention is a cured product that has excellent film forming properties, is cured at low temperature, and has excellent heat resistance, crack resistance (or cold shock resistance), adhesion to adherends, and adhesion. It is providing the curable composition (adhesive composition) which can form.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors cured a curable composition containing this by using a polyorganosilsesquioxane having an epoxy group containing a specific structure at a specific ratio. It was found that the cured product obtained by making it have particularly high surface hardness and flexibility, and excellent heat resistance and crack resistance. The present invention has been completed based on these findings.

［式（１）中、Ｒ¹は、エポキシ基を含有する基を示す。］

［式（Ｉ）中、Ｒ^aは、エポキシ基を含有する基、置換若しくは無置換のアリール基、置換若しくは無置換のアラルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、又は水素原子を示す。］

［式（II）中、Ｒ^bは、エポキシ基を含有する基、置換若しくは無置換のアリール基、置換若しくは無置換のアラルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、又は水素原子を示す。Ｒ^cは、水素原子又は炭素数１〜４のアルキル基を示す。］

［式（２−１）及び式（２−２）中のＲ²¹及びＲ²²は、それぞれ同一又は異なって、置換若しくは無置換のアルキレン基、又は置換若しくは無置換のアルケニレン基を示す。］

［式（５）中、Ｒ¹は、式（１）におけるものと同じ。Ｒ^cは、式（II）におけるものと同じ。］ That is, this invention has a structural unit represented by following formula (1), a structural unit represented by following formula (2-1), and / or a structural unit represented by following formula (2-2). The ratio of the structural unit represented by the following formula (I) and the structural unit represented by the following formula (II) [the structural unit represented by the formula (I) / the structural unit represented by the formula (II)] Is a sum of the structural unit represented by formula (I) and the structural unit represented by formula (II), the structural unit represented by formula (2-1), and formula (2-2) The total ratio of the structural units represented by [{the total of the structural units represented by formula (I) and the structural units represented by formula (II)} / the structural units represented by formula (2-1) and The total of the structural units represented by the formula (2-2)] is 99.9 / 0.1 to 80/20, and the structural unit represented by the formula (1) with respect to the total amount of the siloxane structural units and The proportion of the structural unit represented by the formula (5) provides a polyorganosilsesquioxane 50 to 99 mol%.

[In Formula (1), R < ¹ > shows group containing an epoxy group. ]

[In the formula (I), R ^a is a group containing an epoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group. Represents a substituted or unsubstituted alkenyl group or a hydrogen atom. ]

[In the formula (II), R ^b represents an epoxy group-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group. Represents a substituted or unsubstituted alkenyl group or a hydrogen atom. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

[R ²¹ and R ^{22 in} Formula (2-1) and Formula (2-2) are the same or different and each represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted alkenylene group. ]

[In formula (5), R ¹ is the same as that in formula (1). R ^c is the same as in formula (II). ]

  In the present invention, the polyorganosilsesquioxane has a number average molecular weight of 500 to 6000 and a molecular weight dispersity (weight average molecular weight / number average molecular weight) of 1.0 to 4.0. Provide silsesquioxane.

［式（１ａ）中、Ｒ^1aは、直鎖又は分岐鎖状のアルキレン基を示す。］
で表される基、下記式（１ｂ）

［式（１ｂ）中、Ｒ^1bは、直鎖又は分岐鎖状のアルキレン基を示す。］
で表される基、下記式（１ｃ）

［式（１ｃ）中、Ｒ^1cは、直鎖又は分岐鎖状のアルキレン基を示す。］
で表される基、及び、下記式（１ｄ）

［式（１ｄ）中、Ｒ^1dは、直鎖又は分岐鎖状のアルキレン基を示す。］
で表される基からなる群より選択される１種以上の基である前記のポリオルガノシルセスキオキサンを提供する。 In the present invention, the R ¹ is represented by the following formula (1a):

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

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

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

[In formula (1d), R ^1d represents a linear or branched alkylene group. ]
The polyorganosilsesquioxane is provided as one or more groups selected from the group consisting of groups represented by:

In the present invention, R ²¹ and R ^{22 in the} formulas (2-1) and (2-2) are the same or different and each is an unsubstituted C _2-20 alkylene group. Organosilsesquioxane is provided.

  The present invention also provides a curable composition comprising the polyorganosilsesquioxane and a leveling agent.

  Moreover, this invention provides the said curable composition further containing a curing catalyst.

  Moreover, this invention provides the said curable composition whose said curing catalyst is a photocationic polymerization initiator.

  Moreover, this invention provides the said curable composition whose said curing catalyst is a thermal cationic polymerization initiator.

  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 an adhesive composition.

  Moreover, this invention provides the hardened | cured material obtained by hardening the said curable composition.

  Further, the present invention is a hard coat film having a base material and a hard coat layer formed on at least one surface of the base material, wherein the hard coat layer is cured by the cured product. A hard coat film as a physical layer is provided.

  Moreover, this invention provides the said hard coat film whose thickness of the said hard coat layer is 1-200 micrometers.

  Moreover, this invention provides the said hard coat film manufactured by the roll toe roll system.

  Moreover, this invention applies the said curable composition to the process A which draws out the base material wound by roll shape, and at least one surface of the drawn-out base material, and then hardens this curable composition. A process B for forming a hard coat layer, and then a process C for winding the obtained hard coat film again on a roll, and a method for producing a hard coat film is provided in which steps A to C are continuously carried out. .

  The present invention also provides an adhesive sheet having a base material and an adhesive layer on the base material, wherein the adhesive layer is a layer of the curable composition. I will provide a.

  Further, the present invention is a laminate composed of three or more layers, and has two layers to be bonded and an adhesive layer between the layers to be bonded, and the adhesive layer has the curable property described above. Provided is a laminate, which is a layer of a cured product of the composition.

  Moreover, this invention provides the apparatus which has the said laminated body.

  Since the polyorganosilsesquioxane of this invention has the said structure, the hardened | cured material which has high surface hardness can be formed by hardening the curable composition which contains this polyorganosilsesquioxane as an essential component. Moreover, since the hard coat film of this invention has the said structure, it has flexibility (flexibility), maintaining high surface hardness, and manufacture and a process by a roll toe roll are possible. For this reason, the hard coat film of the present invention is excellent in both quality and cost.

  In addition, the cured product of the present invention cures the curable composition (adhesive composition) at a low temperature to form a cured product having excellent heat resistance, crack resistance, adhesion to an adherend, and adhesion. can do. Therefore, the curable composition of the present invention can be preferably used as an adhesive composition (adhesive). Moreover, an adhesive sheet and a laminated body can be obtained by using the said adhesive composition.

The ¹ H-NMR spectrum of the polyorganosilsesquioxane obtained in Example 1 is shown. The ²⁹ Si-NMR spectrum of the polyorganosilsesquioxane obtained in Example 1 is shown. The FT-IR spectrum of the polyorganosilsesquioxane obtained in Example 1 is shown. The ¹ H-NMR spectrum of the polyorganosilsesquioxane obtained in Example 2 is shown. The ²⁹ Si-NMR spectrum of the polyorganosilsesquioxane obtained in Example 2 is shown. The FT-IR spectrum of the polyorganosilsesquioxane obtained in Example 2 is shown. It is explanatory drawing (schematic diagram of a thermogravimetric analysis result) which shows the evaluation method of the heat resistance of hardened | cured material.

［式（１）中、Ｒ¹は、エポキシ基を含有する基を示す］

［式（Ｉ）中、Ｒ^aは、エポキシ基を含有する基、置換若しくは無置換のアリール基、置換若しくは無置換のアラルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、又は水素原子を示す］

［式（II）中、Ｒ^bは、エポキシ基を含有する基、置換若しくは無置換のアリール基、置換若しくは無置換のアラルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、又は水素原子を示す。Ｒ^cは、水素原子又は炭素数１〜４のアルキル基を示す］

［式（２−１）及び式（２−２）中のＲ²¹及びＲ²²は、それぞれ同一又は異なって、置換若しくは無置換のアルキレン基、又は置換若しくは無置換のアルケニレン基を示す］

［式（５）中、Ｒ¹は、式（１）におけるものと同じ。Ｒ^cは、式（II）におけるものと同じ］ [Polyorganosilsesquioxane]
The polyorganosilsesquioxane (silsesquioxane) of the present invention is a structural unit represented by the following formula (1), a structural unit represented by the following formula (2-1), and / or the following formula (2- 2) The ratio of the structural unit represented by the following formula (I) to the structural unit represented by the following formula (II) [the structural unit represented by the formula (I) / The structural unit represented by the formula (II)] is 5 or more, the total of the structural unit represented by the formula (I) and the structural unit represented by the formula (II), and the formula (2-1) Ratio of the structural unit represented and the structural unit represented by formula (2-2) [{total of the structural unit represented by formula (I) and the structural unit represented by formula (II)} / {formula The sum of the structural unit represented by (2-1) and the structural unit represented by formula (2-2)}] is 99.5 / 0.5 to 80/20, and the siloxane structural unit The proportion of the structural units relative to the total amount represented by the structural units and the following formula represented by the formula (1) (5) is 50 to 99 mol%.

[In formula (1), R ¹ represents a group containing an epoxy group]

[In the formula (I), R ^a is a group containing an epoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group. Represents a substituted or unsubstituted alkenyl group or a hydrogen atom]

[In the formula (II), R ^b represents an epoxy group-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group. Represents a substituted or unsubstituted alkenyl group or a hydrogen atom. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms]

[R ²¹ and R ^{22 in} Formula (2-1) and Formula (2-2) are the same or different and each represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted alkenylene group]

[In formula (5), R ¹ is the same as that in formula (1). R ^c is the same as in formula (II)]

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

R ¹ in the formula (1) represents a group (monovalent group) containing an epoxy group. That is, the polyorganosilsesquioxane of the present invention is a cationic curable compound (cationic polymerizable compound) having at least an epoxy group in the molecule. Examples of the group containing an epoxy group include known or commonly used groups having an oxirane ring, and are not particularly limited. However, from the viewpoint of curability of the curable composition and heat resistance of the cured product, the following formula (1a) Group represented by the following formula (1b), a group represented by the following formula (1c), and a group represented by the following formula (1d) are preferable, and more preferably the following formula (1a): A group represented by the following formula (1c), more preferably a group represented by the following formula (1a).

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

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

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

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

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

  Even if the polyorganosilsesquioxane of the present invention has only one type of structural unit represented by the above formula (1), it has two or more types of structural units represented by the above formula (1). It may be.

The polyorganosilsesquioxane of the present invention further has a structural unit represented by the following formula (2-1) and / or the following formula (2-2) as a siloxane structural unit. The polyorganosilsesquioxane of the present invention may have only one of the structural unit represented by the formula (2-1) and the structural unit represented by the following formula (2-2), or both. You may do it.

R ²¹ and R ^{22 in} formula (2-1) and formula (2-2) are the same or different and each represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted alkenylene group. Examples of the alkylene group include methylene group, ethylene group, propylene group, isopropylene group, n-butylene group, isobutylene group, s-butylene group, t-butylene group, n-pentylene group, isopentylene group, and s-pentylene. Group, t-pentylene group, n-hexylene group, isohexylene group, s-hexylene group, t-hexylene group, n-heptylene group, isoheptylene group, s-heptylene group, t-heptylene group, n-octylene group, isooctylene group , A linear or branched alkylene group such as s-octylene group and t-octylene group. Examples of the alkenylene group include linear or branched alkenylene groups such as vinylene group, arylene group, and isopropenylene group. Note that R ²¹ is bonded to two Si, and R ²² is bonded to three Si.

  As the above-mentioned substituted alkylene group and substituted alkenylene group, the hydrogen atom or the main chain skeleton in each of the alkylene group and alkenylene group is ether group, ester group, carbonyl group, siloxane group, halogen atom (fluorine atom). Etc.), a group substituted with at least one selected from the group consisting of an acrylic group, a methacryl group, a mercapto group, an amino group, and a hydroxy group (hydroxyl group).

Especially, as R < ²¹ > and R _< ²² > in Formula (2-1) and Formula (2-2), an unsubstituted _C2-20 linear or branched alkylene group is preferable, More preferably A substituted C _2-12 linear or branched alkylene group, more preferably an unsubstituted C _2-8 linear or branched alkylene group, particularly preferably an unsubstituted n-butylene group. , N-pentylene group, n-hexylene group, n-heptylene group and n-octylene group.

The polyorganosilsesquioxane of the present invention is a structural unit represented by the above formula (1), a structural unit represented by the above formula (2-1), and a structural unit represented by the above formula (2-2). In addition, a structural unit represented by a silsesquioxane structural unit [R ₃ SiO _1/2 ] (so-called M unit), a structural unit represented by [R ₂ SiO _2/2 ] (so-called D unit), And at least one siloxane structural unit selected from the group consisting of structural units represented by [SiO _4/2 ] (formula (4)) (so-called Q units). In addition, as a structural unit represented by the above formula (1), a structural unit represented by the above formula (2-1), and a silsesquioxane structural unit other than the structural unit represented by the above formula (2-2) Examples include a structural unit represented by the following formula (2 ′) and a structural unit represented by the following formula (3).

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

In formula (2 ′), R ^{2 ′} represents a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted group. A substituted alkenyl group is shown. As said aryl group, a phenyl group, a tolyl group, a naphthyl group etc. are mentioned, for example. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the cycloalkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like. Examples of the alkyl group include linear or branched alkyl groups such as methyl group, ethyl group, propyl group, n-butyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, and isopentyl group. Groups. As said alkenyl group, linear or branched alkenyl groups, such as a vinyl group, an allyl group, and an isopropenyl group, are mentioned, for example.

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

Among these, R ^{2 ′} is preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, more preferably a substituted or unsubstituted aryl group, and even more preferably phenyl. It is a group.

  In the polyorganosilsesquioxane of the present invention, each of the above siloxane structural units [for example, a structural unit represented by the formula (1), a structural unit represented by the formula (2-1), and a formula (2-2) The ratio of the structural unit represented, the structural unit represented by formula (2 ′), the structural unit represented by formula (3), and the structural unit represented by formula (4)] forms these structural units. It is possible to adjust appropriately according to the composition of the raw material (hydrolyzable trifunctional silane, hydrolyzable tetrafunctional silane, etc.) for

  Ratio of the structural unit (T3 body) represented by the above formula (I) and the structural unit (T2 body) represented by the above formula (II) in the polyorganosilsesquioxane of the present invention [T3 body / T2 body] ] Is 5 or more as described above, preferably 5 to 18, more preferably 6 to 16, and still more preferably 7 to 14. By setting the ratio [T3 body / T2 body] to 5 or more, the surface hardness of the cured product or the hard coat layer is improved.

When the structural unit represented by the above formula (I) is described in more detail, it is represented by the following formula (I ′). Further, when the structural unit represented by the above formula (II) is described in more detail, it is represented by the following formula (II ′). Each of the three oxygen atoms bonded to the silicon atom shown in the structure represented by the following formula (I ′) is bonded to another silicon atom (a silicon atom not shown in the formula (I ′)). . On the other hand, two oxygen atoms located above and below the silicon atom shown in the structure represented by the following formula (II ′) are respectively replaced with other silicon atoms (silicon atoms not shown in the formula (II ′)). Are connected. That is, the T3 body and the T2 body are structural units (T units) formed by hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound.

R ^a in the above formula (I) (formula (I ') in the R ^a same) and formula (II) in the R ^b (wherein (II') in the R ^b versa), respectively, an epoxy group A group containing, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, or hydrogen atom Show.

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

  In the polyorganosilsesquioxane of the present invention, the total of the structural unit (T3 form) represented by the above formula (I) and the structural unit (T2 form) represented by the above formula (II), and the above formula (2- Ratio of the total of the structural unit represented by 1) and the structural unit represented by the above formula (2-2) [(T3 body + T2 body) / the structural unit represented by the formula (2-1) and the formula (2) -2)] is 99.9 / 0.1-80 / 20 as described above, preferably 99 / 1-85 / 15, more preferably 98/2. It is -88/12, More preferably, it is 97 / 3-90 / 10. By setting the ratio within the above range, it becomes difficult to form a three-dimensional cross-linked structure at the time of synthesis of polyorganosilsesquioxane, and it becomes a polymer soluble in a solvent, so that it can be easily applied in the state of a hard coat solution described later. In addition, the surface hardness of the cured product or hard coat layer is remarkably improved.

The said ratio [T3 body / T2 body] in the polyorganosilsesquioxane of this invention can be calculated | required by ²⁹ Si-NMR spectrum measurement, for example. ^{29 In the} Si-NMR spectrum, the silicon atom in the structural unit (T3 form) represented by the formula (I) is different from the silicon atom in the structural unit (T2 form) represented by the formula (II). In order to show a signal (peak) in (chemical shift), the ratio [T3 body / T2 body] can be obtained by calculating the integration ratio of these respective peaks. Specifically, for example, the polyorganosilsesquioxane of the present invention has a structural unit represented by the above formula (1) and R ¹ is a 2- (3 ′, 4′-epoxycyclohexyl) ethyl group. In the case, the signal of the silicon atom in the structure (T3 form) represented by the above formula (I) appears at −64 to −70 ppm, and the silicon atom in the structure (T2 form) represented by the above formula (II) The signal appears at −54 to −60 ppm. Therefore, in this case, the ratio [T3 body / T2 body] can be obtained by calculating the integral ratio of the signals of the T3 body and the T2 body.

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

The ratio [T3 body / T2 body] of the polyorganosilsesquioxane of the present invention is 5 or more. In the polyorganosilsesquioxane of the present invention, a certain amount or more of T2 bodies exist with respect to the T3 body. Means that Examples of such a T2 body include a structural unit represented by the following formula (5), a structural unit represented by the following formula (6), a structural unit represented by the following formula (7), and the like. Formula (5) R ² in R ¹ and the following formula (6) in the ^', R ¹ and the formula in each of the above formula (1) (2' are the same as R ^{2 'in).} R ^c in the formula (5) to (7), like the R ^c in Formula (II), a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In general, a complete cage silsesquioxane is a polyorganosilsesquioxane composed only of a T3 form, and no T2 form exists in the molecule. That is, the polyorganosilsesquioxane of the present invention when the above ratio [T3 / T2] is 5 or more and further has one intrinsic absorption peak in the vicinity of 1100 cm ⁻¹ in the FT-IR spectrum as described later. Is suggested to have an incomplete cage silsesquioxane structure.

The polyorganosilsesquioxane of the present invention has a cage-type (incomplete cage-type) silsesquioxane structure. The polyorganosilsesquioxane of the present invention has a FT-IR spectrum of around 1050 cm ⁻¹ and 1150 cm. respectively in the vicinity of ^-1 it does not have a specific absorption peak is confirmed by the fact that with a single specific absorption peak in the vicinity of 1100 cm ^-1 [ref: R. H. Raney, M.M. Itoh, A.D. Sakakibara and T. Suzuki, Chem. Rev. 95, 1409 (1995)]. On the other hand, in general, when the FT-IR spectrum has intrinsic absorption peaks near 1050 cm ⁻¹ and 1150 cm ⁻¹ , it is identified as having a ladder-type silsesquioxane structure. In addition, the FT-IR spectrum of the polyorganosilsesquioxane of this invention can be measured with the following apparatus and conditions, for example.
Measuring device: Trade name “FT-720” (manufactured by Horiba, Ltd.)
Measurement method: Transmission method Resolution: 4 cm ^-1
Measurement wavenumber range: 400 to 4000 cm ⁻¹
Integration count: 16 times

  The total amount of siloxane structural units in the polyorganosilsesquioxane of the present invention [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%). The proportion (total amount) of the structural unit represented and the structural unit represented by the above formula (5) is 50 to 99 mol%, preferably 55 to 98 mol%, more preferably 60 to 95 mol%. By setting the ratio, the curability of the curable composition is improved and the surface hardness of the cured product is remarkably increased. In addition, the ratio of each siloxane structural unit in the polyorganosilsesquioxane of this invention is computable by the composition of a raw material, NMR spectrum measurement, etc., for example.

  Formula (2-1) above with respect to the total amount of siloxane constituent units in the polyorganosilsesquioxane of the present invention [total siloxane constituent units; total amount of M units, D units, T units, and Q units] (100 mol%) The total (total amount) of the structural unit represented by formula (2-2) and the structural unit represented by formula (2-2) is, for example, 0.1 to 20 mol%, preferably 0.5 to 15 mol%. Preferably it is 1-10 mol%. By setting it as the above ratio, the surface hardness of the cured product is remarkably increased.

  Formula (2-1) above with respect to the total amount of siloxane constituent units in the polyorganosilsesquioxane of the present invention [total siloxane constituent units; total amount of M units, D units, T units, and Q units] (100 mol%) The ratio (total amount) of the structural unit represented by formula (2-2), the structural unit represented by formula (2-2), the structural unit represented by formula (2 ′), and the structural unit represented by formula (6) above. Is, for example, 0.5 to 60 mol%, preferably 1.0 to 50 mol%, more preferably 1.5 to 40 mol%, and still more preferably 2.0 to 30 mol%. . By setting the above ratio, the ratio of the structural unit represented by the formula (1) and the structural unit represented by the formula (5) can be relatively increased, so that the curability of the curable composition is high. More improved, hardness is improved.

  The total amount of siloxane structural units in the polyorganosilsesquioxane of the present invention [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%). The structural unit represented by the above formula (2-1), the structural unit represented by the above formula (2-2), the structural unit represented by the above formula (2 ′), the above formula (5) ) And the ratio (total amount) of the structural unit represented by the above formula (6) is, for example, 55 to 100 mol%, preferably 60 to 100 mol%, more preferably 65. ˜100 mol%. By setting it as the above ratio, the surface hardness of the cured product tends to be higher.

  The number average molecular weight (Mn) in terms of standard polystyrene by GPC of the polyorganosilsesquioxane of the present invention is, for example, 500 to 6000, preferably 1000 to 5500, and more preferably 1100 to 5000. By setting the number average molecular weight within the above range, the heat resistance and scratch resistance of the cured product are further improved, the compatibility with other components in the curable composition is improved, and the heat resistance of the cured product is further improved. improves.

  The molecular weight dispersity (Mw / Mn) in terms of standard polystyrene by GPC of the polyorganosilsesquioxane of the present invention is, for example, 1.0 to 4.0, preferably 1.1 to 3.7, more Preferably it is 1.2-3.0, More preferably, it is 1.3-2.5, Most preferably, it is 1.45-1.80. By setting the molecular weight dispersity within the above range, the surface hardness of the cured product becomes higher, and it tends to be liquid, and the handleability tends to be improved.

In addition, the number average molecular weight and molecular weight dispersity of the polyorganosilsesquioxane of this invention can be measured with the following apparatus and conditions.
Measuring device: Product name “LC-20AD” (manufactured by Shimadzu Corporation)
Columns: Shodex KF-801 × 2, KF-802, and KF-803 (manufactured by Showa Denko KK)
Measurement temperature: 40 ° C
Eluent: THF, sample concentration 0.1-0.2% by weight
Flow rate: 1 mL / min Detector: UV-VIS detector (trade name “SPD-20A”, manufactured by Shimadzu Corporation)
Molecular weight: Standard polystyrene conversion

The 5% weight loss temperature (T _d5 ) in the air atmosphere of the polyorganosilsesquioxane of the present invention is, for example, 330 ° C. or higher (eg, 330 to 450 ° C.), preferably 340 ° C. or higher, more preferably 350 ° C. or higher. When the 5% weight reduction temperature is 330 ° C. or higher, the heat resistance of the cured product tends to be further improved. In particular, the polyorganosilsesquioxane of the present invention has the above-mentioned ratio [T3 / T2] of 5 or more and has one intrinsic peak in the vicinity of 1100 cm ⁻¹ in the FT-IR spectrum. The weight reduction temperature is controlled to a certain temperature or higher. The 5% weight reduction temperature is a temperature at the time when 5% of the weight before heating is reduced when heated at a constant rate of temperature increase, and serves as an index of heat resistance. The 5% weight loss temperature can be measured by TGA (thermogravimetric analysis) under an air atmosphere at a temperature rising rate of 5 ° C./min.

  The polyorganosilsesquioxane of the present invention can be produced by a known or conventional polysiloxane production method, and is not particularly limited. However, one or two or more hydrolyzable silane compounds are hydrolyzed and condensed. It can be manufactured by a method. However, as the hydrolyzable silane compound, a hydrolyzable trifunctional silane compound (compound represented by the following formula (a)) for forming the structural unit represented by the above formula (1), a formula ( 2-1) or a hydrolyzable trifunctional silane compound (formula (b-1) or formula (b-2) below) for forming the structural unit represented by formula (2-2) Need to be used as an essential hydrolyzable silane compound.

More specifically, for example, a compound represented by the following formula (a) which is a hydrolyzable silane compound for forming a silsesquioxane structural unit (T unit) in the polyorganosilsesquioxane of the present invention. , A compound represented by the following formula (d) which is a hydrolyzable silane compound for forming the Q unit, and further, if necessary, the following formula (b-1), formula (b-2) and formula (b The polyorganosilsesquioxane of this invention can be manufactured by the method of hydrolyzing and condensing the compound represented by ') and the compound represented by the following formula (c).

  In the polyorganosilsesquioxane of the present invention, the total of the structural unit represented by formula (I) and the structural unit represented by formula (II), and the structural unit and formula represented by formula (2-1) In order to set the total proportion of the structural units represented by (2-2) to 99.5 / 0.5 to 80/20, the compound represented by the above formula (a) and the above formula (b ′) The ratio (mole) of the total (total molar amount) of the compounds represented by the formula (b-1) and the total (total molar amount) of the compounds represented by the above formula (b-2). Ratio) [{the total (total molar amount) of the compound represented by the formula (a) and the compound represented by the formula (b ′)} / {the compound represented by the formula (b-1) and the above formula (b -2), the total (total molar amount)}] of 99.5 / 0.5 to 80/20, and hydrolysis and condensation of these compounds It may be produced by a method of.

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

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

The compound represented by the above formula (b-1) is a compound which forms the structural unit represented by the formula (2-1) in the polyorganosilsesquioxane of the present invention, and two Sis each represent R ²¹ . And is a dimer (bis-isomer) compound. Further, the compound represented by the above formula (b-2) is a compound that forms the structural unit represented by the formula (2-2) in the polyorganosilsesquioxane of the present invention, and three Si are R It is a compound of trimer (tris form) which is bonded through ²² . R ²¹ and R ²² of formula (b-1) and Formula (b-2) is the same as R ²¹ and R ²² in the formula (2-1) and (2-2). Moreover, the compound represented by the said Formula (b ') is a compound which forms the structural unit represented by Formula (2') in the polyorgano silsesquioxane of this invention. R ^{2 ′} in formula (b ′) is the same as R ^{2 ′} in formula (2 ′).

X ² in the above formula (b-1), formula (b-2) and formula (b ′) is the same or different and represents an alkoxy group or a halogen atom. Specific examples of X ² include those exemplified as X ¹ . Among these, as X ^2, alkoxy groups are preferred, more preferably a methoxy group, an ethoxy group. X ² in each formula may be the same or different.

For example, when R ²¹ is a hexylene group and both X ² are methoxy groups, the compound represented by the formula (b-1) is a dimer (bis-form) compound [bis ( Trimethoxysyl) hexane] (BTH).

The compound represented by the above formula (c) is a compound that forms the structural unit represented by the formula (3) in the polyorganosilsesquioxane of the present invention. X ³ in the above formula (c) represents an alkoxy group or a halogen atom. Specific examples of X ³ include those exemplified as X ¹ . Among these, X ³ is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. The three X ³ may be the same or different.

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

  Examples of the hydrolyzable silane compound include compounds represented by the above formulas (a) to (d) (compounds represented by the formula (b ′), the formula (b-1), and the formula (b-2)). A hydrolyzable silane compound other than (including) may be used in combination. For example, hydrolyzability other than compounds represented by the above formulas (a) to (c) (including compounds represented by formula (b ′), formula (b-1), and formula (b-2)) Trifunctional silane compounds, hydrolyzable monofunctional silane compounds that form M units, hydrolyzable bifunctional silane compounds that form D units, and the like.

  The amount and composition of the hydrolyzable silane compound can be appropriately adjusted according to the desired structure of the polyorganosilsesquioxane of the present invention. For example, the amount of the compound represented by the above formula (a) is, for example, 50 to 99 mol%, preferably 55 to 98 mol, based on the total amount (100 mol%) of the hydrolyzable silane compound to be used. %, And more preferably 60 to 95 mol%.

  The total amount of the compound represented by the above formula (b-1) and the compound represented by the above formula (b-2) (ratio of the total amount) is the total amount of hydrolyzable silane compound to be used (100 Mol%), for example, 0.1 to 20 mol%, preferably 0.5 to 18 mol%, more preferably 1 to 15 mol%, still more preferably 2 to 10 mol%. is there.

  Moreover, the usage-amount (total amount) of the compound represented by Formula (b ') is 0-70 mol% with respect to the whole quantity (100 mol%) of the hydrolysable silane compound to be used, Preferably it is 0. It is -60 mol%, More preferably, it is 0.5-40 mol%, More preferably, it is 1-15 mol%.

  Moreover, the usage-amount of the compound represented by the said Formula (d) is although it does not specifically limit, For example, it is 0-50 mol% with respect to the whole quantity (100 mol%) of the hydrolysable silane compound to be used, Preferably Is 2 to 45 mol%, more preferably 5 to 40 mol%, still more preferably 5 to 30 mol%.

  Furthermore, the compound represented by the formula (a), the compound represented by the formula (b-1), the compound represented by the formula (b-2) with respect to the total amount (100 mol%) of the hydrolyzable silane compound to be used. And the ratio of the compounds represented by formula (b ′) (total ratio) is, for example, 50 to 100 mol%, preferably 60 to 99.5 mol%, more preferably 70 to 99 mol. %, More preferably 80 to 98 mol%.

  Furthermore, the compound represented by the formula (a), the compound represented by the formula (b-1), the compound represented by the formula (b-2) with respect to the total amount (100 mol%) of the hydrolyzable silane compound to be used. The total ratio (ratio of the total amount) of the compound represented by formula (b ′) and the compound represented by formula (d) is, for example, 60 mol% or more (60 to 100 mol%), preferably It is 70 mol% or more, More preferably, it is 80 mol% or more, More preferably, it is 90 mol% or more.

  The hydrolysis and condensation reaction of the hydrolyzable silane compound can be performed simultaneously or sequentially. When performing the said reaction sequentially, the order which performs reaction is not specifically limited.

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

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

  The hydrolysis and condensation reaction of the hydrolyzable silane compound is preferably allowed to proceed in the presence of a catalyst and water. The catalyst may be an acid catalyst or an alkali catalyst. Examples of the acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and boric acid; phosphoric acid esters; carboxylic acids such as acetic acid, formic acid and trifluoroacetic acid; methanesulfonic acid, trifluoromethanesulfonic acid, p -Sulfonic acids such as toluenesulfonic acid; solid acids such as activated clay; Lewis acids such as iron chloride. Examples of the alkali catalyst include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkaline earth metals such as magnesium hydroxide, calcium hydroxide, and barium hydroxide. Hydroxides; carbonates of alkali metals such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate; carbonates of alkaline earth metals such as magnesium carbonate; lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate Alkali metal bicarbonates such as lithium acetate, sodium acetate, potassium acetate, cesium acetate, etc. (for example, acetate); alkaline earth metal organic acid salts, such as magnesium acetate (for example, Acetate); lithium methoxide, sodium methoxide, sodium ethoxide Alkali metal alkoxides such as sodium phenoxide, sodium isopropoxide, potassium ethoxide, potassium t-butoxide; alkali metal phenoxides such as sodium phenoxide; triethylamine, N-methylpiperidine, 1,8-diazabicyclo [5.4.0] Amines such as undec-7-ene and 1,5-diazabicyclo [4.3.0] non-5-ene (tertiary amine and the like); pyridine, 2,2′-bipyridyl, 1,10-phenanthroline and the like And nitrogen-containing aromatic heterocyclic compounds. In addition, a catalyst can also be used individually by 1 type and can also be used in combination of 2 or more type. Further, the catalyst can be used in a state dissolved or dispersed in water, a solvent or the like.

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

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

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

  As the reaction conditions for carrying out the hydrolysis and condensation reaction of the hydrolyzable silane compound, in particular, the reaction in which the ratio [T3 body / T2 body] in the polyorganosilsesquioxane of the present invention is 5 or more. It is important to select the conditions. The reaction temperature of the hydrolysis and condensation reaction is, for example, 40 to 100 ° C, preferably 45 to 80 ° C. By controlling the reaction temperature within the above range, the ratio [T3 / T2] tends to be more efficiently controlled to 5 or more. Moreover, the reaction time of the said hydrolysis and condensation reaction is 0.1 to 10 hours, for example, Preferably it is 1.5 to 8 hours. The hydrolysis and condensation reaction can be performed under normal pressure, or can be performed under pressure or under reduced pressure. The atmosphere for performing the hydrolysis and condensation reaction may be, for example, an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere, or in the presence of oxygen such as air. An atmosphere is preferred.

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

  Since the polyorganosilsesquioxane of the present invention has the above-described configuration, a cured product having high surface hardness can be formed by curing a curable composition containing the polyorganosilsesquioxane as an essential component. In addition, a cured product having high heat resistance and excellent flexibility and workability can be formed.

[Curable composition]
The curable composition (adhesive composition) of the present invention is a curable composition (curable resin composition) containing the polyorganosilsesquioxane of the present invention as an essential component. As will be described later, the curable composition of the present invention may further contain other components such as a curing catalyst (particularly a photocationic polymerization initiator), a surface conditioner or a surface modifier.

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

  The content (blending amount) of the polyorganosilsesquioxane of the present invention in the curable composition of the present invention is, for example, 70% by weight or more and 100% with respect to the total amount (100% by weight) of the curable composition excluding the solvent. It is less than% by weight, preferably 80 to 99.8% by weight, and more preferably 90 to 99.5% by weight. By setting the content of the polyorganosilsesquioxane of the present invention to 70% by weight or more, the surface hardness of the cured product tends to be further improved. On the other hand, by setting the content of the polyorganosilsesquioxane of the present invention to less than 100% by weight, it is possible to contain a curing catalyst, thereby allowing the curing of the curable composition to proceed more efficiently. it can.

  The ratio of the polyorganosilsesquioxane of this invention with respect to the whole quantity (100 weight%) of the cationic curable compound contained in the curable composition of this invention is 70-100 weight%, for example, Preferably it is 75-98 weight. %, More preferably 80 to 95% by weight. By setting the content of the polyorganosilsesquioxane of the present invention to 70% by weight or more, the surface hardness of the cured product tends to be further improved.

  The curable composition of the present invention preferably further contains a curing catalyst. Especially, it is especially preferable to contain a photocationic polymerization initiator as a curing catalyst in that the curing time until it becomes more tack-free can be shortened.

  The said curing catalyst is a compound which can start thru | or accelerate | stimulate the cation polymerization reaction of cationic curable compounds, such as the polyorgano silsesquioxane of this invention. Although it does not specifically limit as said curing catalyst, For example, polymerization initiators, such as a photocationic polymerization initiator (photoacid generator) and a thermal cationic polymerization initiator (thermal acid generator), are mentioned.

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

Examples of the anion constituting the salt in the photocationic polymerization initiator include SbF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , (CF ₃ CF ₂ ) ₃ PF ₃ ⁻ , and (CF ₃ CF ₂ CF ₂ ) ₃ PF _{3. ^{-, (C 6 F 5)}} 4 B -, (C 6 F 5) 4 Ga -, a sulfonate anion (trifluoromethanesulfonic acid anion, pentafluoroethanesulfonate anion, nonafluorobutanesulfonic acid anion, methanesulfonic acid anion , Benzenesulfonate 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, hexafluorobismuth ion, carboxylate ion, arylborate ion, thiocyanate ion, nitrate ion, etc. Is mentioned.

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

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

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

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

  Examples of the ammonium salt include tetramethylammonium salt, ethyltrimethylammonium salt, diethyldimethylammonium salt, triethylmethylammonium salt, tetraethylammonium salt, trimethyl-n-propylammonium salt, and trimethyl-n-butylammonium salt. Pyrrolium salts such as alkyl ammonium salts; N, N-dimethylpyrrolidinium salts, N-ethyl-N-methylpyrrolidinium salts; N, N′-dimethylimidazolinium salts, N, N′-diethylimidazolinium salts, etc. Imidazolinium salts; tetrahydropyrimidinium salts such as N, N′-dimethyltetrahydropyrimidinium salt, N, N′-diethyltetrahydropyrimidinium salt; N, N-dimethylmorpholinium salt, N, N -Diethylmorpholini Morpholinium salts such as N salt, piperidinium salts such as N, N-dimethylpiperidinium salt and N, N-diethylpiperidinium salt; pyridinium salts such as N-methylpyridinium salt and N-ethylpyridinium salt; N, N '-Imidazolium salt such as dimethylimidazolium salt; Quinolium salt such as N-methylquinolium salt; Isoquinolium salt such as N-methylisoquinolium salt; Thiazonium salt such as benzylbenzothiazonium salt; And the like.

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

Examples of the salt of the transition metal complex ion include chromium such as (η ⁵ -cyclopentadienyl) (η ⁶ -toluene) Cr ⁺ and (η ⁵ -cyclopentadienyl) (η ⁶ -xylene) Cr ^+. Salts of complex cations; salts of iron complex cations such as (η ⁵ -cyclopentadienyl) (η ⁶ -toluene) Fe ⁺ and (η ⁵ -cyclopentadienyl) (η ⁶ -xylene) Fe ⁺ It is done.

  Examples of the cationic polymerization initiator include trade names “SP-66” and “SP-77” (manufactured by ADEKA Corporation); trade names “Sun Aid SI-60L”, “Sun Aid SI-80L”, “ Commercial products such as “Sun-Aid SI-100L” and “Sun-Aid SI-150L” (manufactured by Sanshin Chemical Industry Co., Ltd.) can be used.

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

  Examples of the anion constituting the salt in the thermal cationic polymerization initiator include the same examples as the anion constituting the salt in the above-mentioned photocationic polymerization initiator.

  In the curable composition of the present invention, one type of curing catalyst can be used alone, or two or more types can be used in combination.

  The content (blending amount) of the curing catalyst in the curable composition of the present invention is, for example, 0.01 to 3.0 parts by weight with respect to 100 parts by weight of the polyorganosilsesquioxane of the present invention, preferably Is 0.05 to 3.0 parts by weight, more preferably 0.1 to 1.0 parts by weight, and still more preferably 0.3 to 1.0 parts by weight. By setting the content of the curing catalyst in the above range, the curing reaction can be efficiently and sufficiently advanced, the surface hardness of the cured product tends to be further improved, and the storability of the curable composition is improved. There exists a tendency which improves further and the coloring of hardened | cured material is suppressed.

(Polymerization stabilizer)
When the curable composition of the present invention is an adhesive composition, it preferably contains a polymerization stabilizer in order to suppress the progress of cationic polymerization by trapping cations. The ability to trap cations by the polymerization stabilizer is lost due to saturation by heating. When the curable composition of the present invention contains a polymerization stabilizer together with a cationic polymerization initiator, after the coating and drying to form an adhesive layer, the progress of polymerization can be suppressed over a long period of time. It is possible to form an adhesive layer excellent in storage stability that can exhibit excellent adhesiveness by heating at a timing when is required.

  Examples of the polymerization stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, poly ([6- (1,1,3,3-tetramethylbutyl) imino-1, 3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) Imino]), tetrakis (2,2,6,6-tetramethyl-4-piperidyl) butane-1,2,3,4-tetracarboxylate, 2,2,6,6-tetramethyl-4-piperidi Nylbenzoate, (mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, 3,9-bis (2,3-di-t -Butyl-4-methylpheno Ii) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, mixed (2,2,6,6-tetramethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3-9- [2,4,8,10-tetraoxaspiro (5.5) undecane] diethyl) -1,2,3,4-butanetetracarboxylate, poly ([6- N-morpholyl-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetra Methyl-4-piperidyl) imino]), [N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl-2- (2,2,6,6-tetramethyl-4- Piperidyl) imino] propionamide, trade name “LA-77” ”,“ LA-67 ”,“ LA-57 ”(manufactured by ADEKA), hindered amine compounds such as trade names“ TINUVIN123 ”,“ TINUVIN152 ”(manufactured by Ciba Japan Co., Ltd.), (4- Hydroxyphenyl) sulfonium sulfate compounds such as dimethylsulfonium methylsulfite (Sun aid SI auxiliary, manufactured by Sanshin Chemical Industry Co., Ltd.), and phosphites such as trade name “PEP-36” (manufactured by ADEKA Corporation) Compounds and the like. These can be used alone or in combination of two or more.

  When the curable composition of this invention contains a cationic polymerization initiator, the usage-amount of a polymerization stabilizer is 1 weight part or more with respect to 100 weight part of cationic polymerization initiators, Preferably it is 3-20 weights. Part, more preferably 5 to 15 parts by weight.

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

  As said other epoxy compound, the well-known thru | or usual compound which has 1 or more epoxy groups (oxirane ring) in a molecule | numerator can be used, Although it does not specifically limit, An alicyclic epoxy compound (alicyclic epoxy resin) ), Aromatic epoxy compounds (aromatic epoxy resins), aliphatic epoxy compounds (aliphatic epoxy resins), and the like.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  In addition, as the other cationic curable compound, particularly when a vinyl ether compound having one or more hydroxyl groups in the molecule is used, the surface hardness is higher, and further, heat-resistant yellowing (yellowing due to heating hardly occurs). There is an advantage that a cured product having excellent properties can be obtained. For this reason, the hardened | cured material and hard coat film of higher quality and durability are obtained. The number of hydroxyl groups in the molecule of the vinyl ether compound having one or more hydroxyl groups in the molecule is, for example, 1 to 4, preferably 1 or 2. Specifically, examples of the vinyl ether compound having one or more hydroxyl groups in the molecule include 2-hydroxyethyl vinyl ether (ethylene glycol monovinyl ether), 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl. Vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl vinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl Vinyl ether, 1-hydroxymethylpropyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 1,6-hexa Diol monovinyl ether, 1,8-octanediol divinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,2-cyclohexanedimethanol monovinyl ether, p-xylene glycol monovinyl ether, m-xylene glycol monovinyl ether, o-xylene glycol monovinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, pentaethylene glycol monovinyl ether, oligoethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, tripropylene glycol Monovinyl ether, tetra B propylene glycol monomethyl ether, pentaethylene glycol monomethyl ether, oligo propylene glycol monomethyl ether, polypropylene glycol monovinyl ether, pentaerythritol trivinyl ether, dipentaerythritol penta vinyl ether.

  The content (blending amount) of the other cation curable compound in the curable composition of the present invention is the total amount of the polyorganosilsesquioxane of the present invention and the other cation curable compound (100% by weight; cation curable compound). For example, 50% by weight or less (0 to 50% by weight), preferably 30% by weight or less, and more preferably 10% by weight or less. By setting the content of other cationic curable compounds to 50% by weight or less (particularly 10% by weight or less), the scratch resistance of the cured product tends to be further improved. On the other hand, by setting the content of other cationic curable compounds to 10% by weight or more, desired performance for the curable composition or the cured product (for example, quick curability or viscosity adjustment for the curable composition). May be granted.

  The content (blending amount) of the vinyl ether compound (particularly, the vinyl ether compound having one or more hydroxyl groups in the molecule) in the curable composition of the present invention is the same as that of the polyorganosilsesquioxane of the present invention and other cationic curability. For example, 0.01 to 10% by weight, preferably 0.05 to 9% by weight, more preferably 1 to 8% by weight, based on the total amount of the compound (100% by weight; the total amount of the cationic curable compound). It is. By controlling the content of the vinyl ether compound within the above range, the surface hardness of the cured product becomes higher, and the surface hardness is extremely high even when the irradiation amount of active energy rays (for example, ultraviolet rays) is lowered. There is a tendency to get things. In particular, by controlling the content of the vinyl ether compound having one or more hydroxyl groups in the molecule within the above range, in addition to particularly high surface hardness of the cured product, there is a tendency to further improve its heat-resistant yellowing. is there.

  The curable composition of the present invention further includes, as other optional components, precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate. Inorganic fillers such as carbon black, silicon carbide, silicon nitride, boron nitride, etc., inorganic fillers obtained by treating these fillers with organosilicon compounds such as organohalosilanes, organoalkoxysilanes, organosilazanes; silicone resins, epoxy resins , Organic resin fine powder such as fluororesin; filler such as conductive metal powder such as silver and copper, curing agent (amine curing agent, polyaminoamide curing agent, acid anhydride curing agent, phenol curing agent, etc. ), Curing aids, curing accelerators (imidazoles, alkali metal or alkaline earth metal alkoxides, Fins, amide compounds, Lewis acid complex compounds, sulfur compounds, boron compounds, condensable organometallic compounds, etc.), solvents (water, organic solvents, etc.), stabilizers (antioxidants, UV absorbers, light stabilizers, Heat stabilizers, heavy metal deactivators, etc.), flame retardants (phosphorous flame retardants, halogen flame retardants, inorganic flame retardants, etc.), flame retardant aids, reinforcing materials (other fillers, etc.), nucleating agents , Coupling agents (silane coupling agents, etc.), lubricants, waxes, plasticizers, mold release agents, impact modifiers, hue modifiers, clearing agents, rheology modifiers (fluidity modifiers, etc.), processability improvement Agents, colorants (dyes, pigments, etc.), antistatic agents, dispersants, surface conditioners (leveling agents, anti-waxing agents, etc.), surface modifiers (slip agents, etc.), matting agents, antifoaming agents, suppression Foaming agent, defoaming agent, antibacterial agent, preservative, viscosity modifier, thickener, photosensitizer, foaming agent, heavy It may contain conventional additives such as stabilizers. These additives can be used individually by 1 type or in combination of 2 or more types. These additives can be used individually by 1 type or in combination of 2 or more types. The content (blending amount) of the additive is, for example, 100 parts by weight or less, preferably 30 parts by weight or less (for example, 0.01 to 30) with respect to 100 parts by weight of the polyorganosilsesquioxane of the present invention. Parts by weight), more preferably 10 parts by weight or less (for example, 0.1 to 10 parts by weight).

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

  Although the curable composition of this invention is not specifically limited, It is preferable that it is a liquid at normal temperature (about 25 degreeC). More specifically, the curable composition of the present invention has a viscosity at 25 ° C. of a liquid diluted to 20% of a solvent [particularly, a curable composition (solution) in which the proportion of methyl isobutyl ketone is 20% by weight]. For example, it is 300-20000 mPa * s, Preferably it is 500-10000 mPa * s, More preferably, it is 1000-8000 mPa * s. There exists a tendency for the heat resistance of hardened | cured material to improve more by making the said viscosity into 300 mPa * s or more. On the other hand, when the viscosity is 20000 mPa · s or less, preparation and handling of the curable composition are facilitated, and air bubbles tend not to remain in the cured product. The viscosity of the curable composition of the present invention was measured using a viscometer (trade name “MCR301”, manufactured by Anton Paar Co., Ltd.) with a swing angle of 5%, a frequency of 0.1 to 100 (1 / s), and temperature: It is measured at 25 ° C.

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

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

  Since the curable composition of this invention contains the polyorgano silsesquioxane of this invention, it can form hardened | cured material rapidly by heating at the low temperature of 200 degrees C or less. That is, it has low temperature curability. The conditions for curing the curable composition of the present invention by heating are, for example, 30 to 200 ° C, and preferably 50 to 190 ° C. The curing time can be appropriately set.

  As described above, the curable composition of the present invention can be cured to form a cured product having a high surface hardness. Further, glass is known as a material having a very high surface hardness, and in particular, glass having a surface pencil hardness of up to 9H by an alkali ion exchange treatment is known. However, flexibility and workability are known. Therefore, it is impossible to manufacture and process by roll-to-roll method, and it is necessary to manufacture and process by a single wafer, which requires high production cost. On the other hand, the hardened | cured material of this invention can form the hardened | cured material excellent in the flexibility and workability compared with glass. Accordingly, the curable composition of the present invention particularly includes a “curable composition for forming a hard coat layer” (“hard coat liquid”, “hard coat agent” and the like for forming a hard coat layer in a hard coat film. And may be particularly preferably used. The curable composition of the present invention is used as a curable composition for forming a hard coat layer, and a hard coat film having a hard coat layer formed from the composition has flexibility while maintaining high hardness. Can be manufactured and processed by roll-to-roll.

  Moreover, the hardened | cured material obtained by hardening the curable composition of this invention is excellent in heat resistance, and thermal decomposition temperature is 200 degreeC or more (for example, 200-500 degreeC), for example, Preferably it is 260 degreeC or more. .

  A cured product obtained by curing the curable composition of the present invention has heat resistance, crack resistance, and excellent adhesion and adhesion to an adherend. Therefore, the curable composition of the present invention can be preferably used as an adhesive (sometimes referred to as “adhesive composition”), particularly as a thermosetting adhesive, and by curing it, heat resistance, crack resistance The adhesive can be converted into an adhesive having excellent properties, adhesion to an adherend, and adhesion.

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

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

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

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

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

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

  Among these, as the plastic substrate, a substrate having excellent transparency (transparent substrate) is used when the hard coat film of the present invention is intended to obtain a hard coat film having excellent transparency. It is preferably a polyester film (particularly PET, PEN), a cyclic polyolefin film, a polycarbonate film, a TAC film, or a PMMA film.

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

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

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

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

  The thickness of the said base material can be suitably selected from the range of 0.01-10000 micrometers, for example.

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

  The thickness of the hard coat layer of the present invention (when the hard coat layer of the present invention is provided on both surfaces of the substrate, the thickness of each hard coat layer) is, for example, 1 to 200 μm, preferably 3 to 150 μm. In particular, even when the hard coat layer of the present invention is thin (for example, when the thickness is 5 μm or less), it is possible to maintain a high surface hardness (for example, the pencil hardness is set to H or more). . In addition, even when the thickness is thick (for example, when the thickness is 50 μm or more), it is difficult to cause defects such as cracks due to curing shrinkage, etc. 9H or higher).

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

  The total light transmittance of the hard coat layer of the present invention is, for example, 85% or more, preferably 90% or more in the case of a thickness of 50 μm. Note that the upper limit of the total light transmittance is, for example, 99%. By setting the total light transmittance to 85% or more, there is a tendency to be suitable for use in applications that require very high transparency (for example, surface protection sheets for displays such as touch panels). The total light transmittance of the hard coat layer of the present invention can be measured according to JIS K7361-1.

  The hard coat film of the present invention may further have a surface protective film on the surface of the hard coat layer of the present invention. When the hard coat film of the present invention has a surface protective film, the punchability of the hard coat film tends to be further improved. When having a surface protective film in this way, the hardness of the hard coat layer is very high, and even if it is prone to peeling or cracking from the substrate during punching, it may cause such problems. It is possible to perform punching using a Thomson blade.

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

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

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

  In particular, the hard coat layer of the present invention in the hard coat film of the present invention is a hard coat layer formed from the curable composition of the present invention (the curable composition for forming a hard coat layer). The coat film can be manufactured by a roll-to-roll method. By producing the hard coat film of the present invention by a roll-to-roll method, the productivity can be remarkably increased. As a method for producing the hard coat film of the present invention by a roll-to-roll method, a known or conventional roll-to-roll method can be employed. For example, a step of feeding a substrate wound in a roll shape (step) A) and, after applying the curable composition of the present invention (curable composition for forming a hard coat layer) on at least one surface of the fed substrate, and then removing the solvent by drying as necessary, A step of forming the hard coat layer of the present invention by curing the curable composition (curable composition layer) (step B), and then a step of winding the obtained hard coat film again on a roll (step) C) as an essential step, and a method of continuously performing these steps (steps A to C) and the like. In addition, the said method may include processes other than process AC.

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

  The pencil hardness of the hard coat layer surface of the present invention of the hard coat film of the present invention is, for example, H or more, preferably 2H or more, more preferably 6H or more. The pencil hardness can be evaluated according to the method described in JIS K5600-5-4.

  The haze of the hard coat film of the present invention is, for example, 1.5% or less, and preferably 1.0% or less. In addition, the minimum of haze is 0.1%, for example. By setting the haze to 1.0% or less in particular, there is a tendency to be suitable for use in applications that require very high transparency (for example, surface protection sheets for displays such as touch panels). The haze of the hard coat film of the present invention can be easily controlled within the above range by using, for example, the above-mentioned transparent substrate as a substrate. The haze can be measured according to JIS K7136.

  The total light transmittance of the hard coat film of the present invention is, for example, 85% or more, and preferably 90% or more. Note that the upper limit of the total light transmittance is, for example, 99%. By setting the total light transmittance to 90% or more in particular, there is a tendency to be suitable for use in applications that require very high transparency (for example, surface protection sheets for displays such as touch panels). The total light transmittance of the hard coat film of the present invention can be easily controlled within the above range by using, for example, the above-mentioned transparent substrate as the substrate. The total light transmittance can be measured according to JIS K7361-1.

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

[Adhesive sheet]
By using the curable composition (adhesive composition) of the present invention, an adhesive sheet having at least a base material and an adhesive layer on the base material, wherein the adhesive layer is curable according to the present invention. An adhesive sheet (sometimes referred to as “the adhesive sheet of the present invention”) that is a layer of the composition (sometimes referred to as “the adhesive layer of the present invention”) is obtained. The adhesive sheet of the present invention includes not only a sheet shape but also a form similar to a sheet shape such as a film shape, a tape shape, and a plate shape.

  The adhesive sheet of the present invention can be obtained, for example, by applying the curable composition of the present invention to a substrate and further drying as necessary. The method of application is not particularly limited, and well-known and commonly used means can be used. Also, the means and conditions for drying are not particularly limited, and conditions under which volatile components such as solvents can be removed as much as possible can be set, and well-known and commonly used means can be used. In particular, the thermosetting time at 130 ° C. of the composition obtained by adding 1 part by weight of the curable composition of the present invention to 100 parts by weight of the above-mentioned Celoxide 2021P (manufactured by Daicel Corporation) is 3.5 minutes. When the polymerization initiator as described above is contained, the adhesive layer can be formed by quickly removing volatile components such as a solvent while suppressing the progress of the curing reaction by heating and drying. The adhesive layer thus obtained does not have an adhesive property at a temperature lower than 50 ° C., so that the cutting can be performed without adhering the glue to the cutting blade, and the temperature at which damage to the adherend can be suppressed. It has the property of exhibiting adhesiveness when heated with and then rapidly curing.

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

  As a base material in the adhesive sheet of the present invention, a well-known and commonly used base material (a base material used for the adhesive sheet) can be used, and is not particularly limited. However, a plastic base material, a metal base material, a ceramic base material, Examples thereof include a semiconductor substrate, a glass substrate, a paper substrate, a wood substrate, and a substrate whose surface is a painted surface. The base material in the adhesive sheet of the present invention may be a so-called release liner. In addition, the adhesive sheet of the present invention may have only one layer of the base material, or may have two or more layers. Moreover, the thickness of the said base material is not specifically limited, It can select suitably in the range of 1-10000 micrometers.

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

  The adhesive sheet of the present invention may have other layers (for example, an intermediate layer and an undercoat layer) in addition to the base material and the adhesive layer.

[Laminate]
By using the curable composition (adhesive composition) of the present invention, it is a laminate (laminate) composed of three or more layers, and between the two adherend layers and these adherend layers. At least an adhesive layer (a layer for adhering the adherend layers to each other), and the adhesive layer is sometimes referred to as a layer of a cured product of the curable composition of the present invention (the “adhesive layer of the present invention”). A laminate (which may be referred to as “the laminate of the present invention”). The laminate of the present invention is not particularly limited, but the adhesive layer of the present invention is formed on one adherend layer (for example, it can be formed in the same manner as the adhesive layer in the adhesive sheet of the present invention), and further the adhesion It can be obtained by bonding the other adherend layer to the adhesive layer and then curing the adhesive layer of the present invention by heat treatment. In addition, the laminate of the present invention is, for example, when the adhesive sheet of the present invention is a single-sided adhesive sheet, the adhesive sheet of the present invention is bonded to an adherend layer, and then subjected to heat treatment. It can be obtained by curing the adhesive layer of the present invention inside. In this case, a laminate in which the substrate in the adhesive sheet of the present invention hits the adherend layer is obtained. Furthermore, the laminate of the present invention is, for example, when the adhesive sheet of the present invention is a double-sided adhesive sheet and a release liner as a base material is adhered to both surfaces of the adhesive layer. The adhesive layer of the invention is bonded to the layer to be bonded to the adhesive layer exposed by peeling one of the release liners, and then the other adhesive layer exposed by peeling the other release liner The adhesive layer of the present invention can be obtained by bonding the adherend layer and then heat-treating the adhesive layer. However, the manufacturing method of the laminate of the present invention is not limited to these methods.

  The adherend forming the adherend layer in the laminate of the present invention is not particularly limited, and is a plastic substrate, a metal substrate, a ceramic substrate, a semiconductor substrate (including a semiconductor chip, a semiconductor wafer, etc.), a glass substrate. , Paper base material, wood base material, base material whose surface is a painted surface, and the like. The laminate of the present invention may have only two layers to be bonded, or may have three or more layers. Moreover, the thickness of a to-be-adhered layer is not specifically limited, It can select suitably in the range of 1-100,000 micrometers. The adherend layer may not have a strict layered form.

  The laminate of the present invention may have only one adhesive layer of the present invention, or may have two or more layers. Moreover, the thickness of the adhesive layer of the present invention can be appropriately selected within a range of, for example, 0.1 to 10,000 μm.

  The laminate of the present invention may have other layers (for example, an intermediate layer, an undercoat layer, and other adhesive layers) in addition to the adherend layer and the adhesive layer of the present invention.

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

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

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

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The molecular weight of the product was measured using Alliance HPLC system 2695 (manufactured by Waters), Refractive Index Detector 2414 (manufactured by Waters), column: Tskel GMH _HR- M × 2 (manufactured by Tosoh Corporation), guard column: Tskel guard column H _HR L (manufactured by Tosoh Corporation), column oven: COLUMN HEATER U-620 (manufactured by Sugai), solvent: THF, measurement conditions: 40 ° C., standard polystyrene conversion. Moreover, the ratio of the T3 body / T2 body in the product was measured by ²⁹ Si-NMR spectrum measurement with JEOL ECA500 (500 MHz). In addition, the unit of the compounding quantity of each raw material of Table 1 and 2 is a weight part.

[Example 1]
(Preparation of epoxy group-containing polyorganosilsesquioxane (curable resin A))
A 1000 ml flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube was charged with 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (hereinafter, “EMS” under a nitrogen stream. ) 392.0 mmol (96.58 g), bis (trimethoxysyl) hexane (hereinafter referred to as “BTH”) 4.0 mmol (1.31 g), and acetone 391.5 g were charged at 50 ° C. The temperature was raised to. To the mixture thus obtained, 11.06 g of 5% aqueous potassium carbonate solution (4.0 mmol as potassium carbonate) was added dropwise over 5 minutes, and then 4000.0 mmol (72.00 g) of water was added over 20 minutes. It was dripped. Note that no significant temperature increase occurred during the dropping. Thereafter, the polycondensation reaction was carried out under a nitrogen stream for 5 hours while maintaining the temperature at 50 ° C.
Thereafter, simultaneously with cooling the reaction solution, 195.8 g of methyl isobutyl ketone (MIBK) and 143.1 g of 5% saline were added. This solution was transferred to a 1 liter separatory funnel, and 195.8 g of MIBK was added again, followed by washing with water. After separation of the aqueous phase, washing was performed until the lower layer solution (aqueous phase) became neutral, and the upper layer solution was collected, and then the upper layer solution was concentrated under the conditions of 1 mmHg and 50 ° C., and MIBK was 24.06 wt. 91.7 g of a colorless and transparent liquid product (epoxy group-containing polyorganosilsesquioxane) was obtained.
When the product was analyzed, the number average molecular weight was 2012 and the molecular weight dispersity was 2.0. Moreover, as shown in FIG. 1, as a result of ¹ H-NMR measurement, a peak derived from an epoxy group (3.15 ppm, broad singlet), a peak derived from a cyclohexyl group (1 to 2.2 ppm), a methylene group adjacent to Si. A peak derived from (0.53 ppm, broad singlet) was confirmed. Furthermore, as shown in FIG. 2, ²⁹ Si-NMR measurement was performed, and as a result, a peak derived from T2 form was observed near −55 to −60 ppm, and a peak derived from T3 form was observed near −65 to −70 ppm. The ratio [T3 body / T2 body] of T2 body and T3 body calculated from the integrated value was 10.5. Moreover, as shown in FIG. 3, in the FT-IR spectrum, one intrinsic absorption peak was confirmed near 1100 cm ⁻¹ . Hereinafter, the obtained epoxy group-containing polyorganosilsesquioxane is referred to as “curable resin A”. In addition, the weight ratio of the ratio of EMS and BTH in preparation of the curable resin A was 99/1, and the molar ratio was 99/1.

(Preparation of hard coat film)
As shown in Table 1, a mixed solution of 100 parts by weight of the curable resin A obtained above, 1 part by weight of the curing catalyst, and 0.5 parts by weight of the leveling agent was prepared, and this was used as a hard coat solution (hardening for forming a hard coat layer). Composition).
The obtained hard coat solution was applied to the surface of the PET film using a wire bar # 30, and then left (prebaked) in an oven at 120 ° C. for 5 minutes, and then a high-pressure mercury lamp (manufactured by Mitsui Graphics Co., Ltd.). ) Was irradiated with ultraviolet rays for 5 seconds at a dose of 400 mJ / cm ² . Thereafter, the coating film of the hard coat solution was cured by heat treatment (aging process) at 120 ° C. for 1 hour, and a hard coat film having a hard coat layer was produced. At this time, the thickness of the hard coat layer was 38 μm.

[Example 2]
(Preparation of epoxy group-containing polyorganosilsesquioxane (curable resin B))
A 1000 ml flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube was charged with 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (hereinafter, “EMS” under a nitrogen stream. 360.0 mmol (88.70 g), BTH 20.0 mmol (6.53 g), and acetone 380.9 g were charged, and the temperature was raised to 50 ° C. To the mixture thus obtained, 11.06 g of 5% aqueous potassium carbonate solution (4.0 mmol as potassium carbonate) was added dropwise over 5 minutes, and then 4000.0 mmol (72.00 g) of water was added over 20 minutes. It was dripped. Note that no significant temperature increase occurred during the dropping. Thereafter, the polycondensation reaction was performed for 2 hours under a nitrogen stream while maintaining the temperature at 50 ° C.
Thereafter, simultaneously with cooling the reaction solution, 190.5 g of methyl isobutyl ketone (MIBK) and 139.8 g of 5% saline were added. This solution was transferred to a 1 liter separatory funnel, and 190.5 g of MIBK was added again, followed by washing with water. After separation of the aqueous phase, washing was performed until the lower layer solution (aqueous phase) became neutral, and the upper layer solution was collected, and then the upper layer solution was concentrated under the conditions of 1 mmHg and 50 ° C., and MIBK was 21.86 wt. As a result, 88.2 g of a colorless and transparent liquid product (epoxy group-containing polyorganosilsesquioxane) was obtained.
When the product was analyzed, the number average molecular weight was 2725 and the molecular weight dispersity was 3.7. Moreover, as shown in FIG. 4, as a result of ¹ H-NMR measurement, a peak derived from an epoxy group (3.14 ppm, broad singlet), a peak derived from a cyclohexyl group (1 to 2.2 ppm), a methylene group adjacent to Si A peak derived from (0.53 ppm, broad singlet) was confirmed. Furthermore, as a result of ²⁹ Si-NMR measurement as shown in FIG. 5, a peak derived from T2 body was observed near −55 to −60 ppm, and a peak derived from T3 body was observed near −65 to −70 ppm. The ratio of T2 body and T3 body [T3 body / T2 body] calculated from the integrated value was 8.4. Further, as shown in FIG. 6, one intrinsic absorption peak was confirmed in the vicinity of 1100 cm ⁻¹ in the FT-IR spectrum. Hereinafter, the obtained epoxy group-containing polyorganosilsesquioxane is referred to as “curable resin B”. In addition, the weight ratio of the ratio of EMS and BTH in preparation of the curable resin B was 93/7, and the molar ratio was 95/5.

(Preparation of hard coat film)
As shown in Table 1, a mixed solution of 100 parts by weight of the curable resin B obtained above, 1 part by weight of the curing catalyst, and 0.5 parts by weight of the leveling agent was prepared, and this was used as a hard coat solution (hardening for hard coat layer formation). Composition). About the obtained hard coat liquid, the hard coat film which has a hard-coat layer by the same method as Example 1 was produced. At this time, the thickness of the hard coat layer was 36 μm.

[Comparative Examples 1-4]
As shown in Table 1, a hard coat solution was prepared in the same manner as in Example 1 except that a mixture (composition) was prepared. A hard coat film was produced in the same manner as in Example 1 except that the hard coat liquid was used and the thickness of the hard coat layer was changed as shown in Table 1.

[Evaluation]
(Pencil hardness (surface hardness))
The pencil hardness of the hard coat layer surface in the hard coat film obtained above was evaluated according to JIS K5600-5-4. The results are shown in Table 1.

(Bending (flexibility))
The bending (bending resistance) of the hard coat film obtained above was evaluated according to JIS K5600-5-1 using a cylindrical mandrel. The results are shown in Table 1.

(appearance)
The appearance of the hard coat film obtained above was visually observed and evaluated according to the following criteria. The results are shown in Table 1.
A (appearance is good): surface is smooth and gloss is excellent B (appearance is bad): surface is uneven in thickness and gloss is dull

The abbreviations shown in Table 1 are as follows.
(Curable resin)
PETIA: A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, trade name “PETIA” (manufactured by Daicel Ornex Co., Ltd.)
IRR214K: Tricyclodecane dimethanol diacrylate, trade name “IRR214K” (manufactured by Daicel Ornex Co., Ltd.)
TA-100: acrylic silicone resin, trade name “SQ TA-100” (manufactured by Toagosei Co., Ltd.)
SI-20: Acrylic silicone resin, trade name “SQ SI-20” (manufactured by Toagosei Co., Ltd.)
(Curing catalyst)
Curing catalyst A: [4- (4-biphenylthio) phenyl] -4-biphenylphenylsulfonium Tris (pentafluoroethyl) trifluorophosphate in propylene glycol methyl ether acetate 50% solution Irgacure 184: Photopolymerization initiator, trade name “ IRGACURE 184 "(manufactured by BASF Japan Ltd.)
(Leveling agent)
Surflon S-243: Ethylene oxide adduct of fluorine compound, trade name “Surflon S-243” (manufactured by AGC Seimi Chemical Co., Ltd.)

[Example 3]
(Preparation of epoxy group-containing polyorganosilsesquioxane (curable resin C))
In a 300 mL flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube, EMS 161.5 mmol (39.79 g), BTH 1.65 mmol (0.54 g) under a nitrogen stream, And 161.31 g of acetone were charged and the temperature was raised to 50 ° C. To the mixture thus obtained, 4.51 g of 5% potassium carbonate aqueous solution was dropped over 5 minutes, and then 29.63 g of water was dropped over 20 minutes. Note that no significant temperature increase occurred during the dropping. Thereafter, the polycondensation reaction was carried out for 4 hours under a nitrogen stream while maintaining the temperature at 50 ° C.
Thereafter, the reaction solution is cooled, washed with water until the lower layer solution becomes neutral, and after the upper layer solution is separated, the solvent is distilled off from the upper layer solution under conditions of 1 mmHg and 40 ° C. to produce a colorless transparent liquid The product (epoxy group-containing polyorganosilsesquioxane) was obtained. Hereinafter, the obtained epoxy group-containing polyorganosilsesquioxane is referred to as “curable resin C”. In addition, the weight ratio of the ratio of EMS and BTH in preparation of the curable resin C was 99/1, and the molar ratio was 99/1.
When the product was analyzed, the weight average molecular weight in terms of polystyrene was 3500, and the number average molecular weight was 2000 (molecular weight dispersity: 1.75).

(Preparation of adhesive composition (1))
100 parts by weight of curable resin C, 100 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, an antimony sulfonium salt (trade name “SI-150L”, Sanshin Chemical Co., Ltd., Celoxide 2021P (as a curing catalyst) (Daicel Co., Ltd.) 0.45 parts by weight of a composition obtained by adding 1 part by weight to 100 parts by weight of the composition obtained at 130 ° C .: 5.4 minutes) and (4-hydroxy) as a polymerization stabilizer Phenyl) dimethylsulfonium methylsulfite (SI auxiliary agent) (trade name “Sun aid SI auxiliary agent”, Sanshin Chemical Industry Co., Ltd.) 0.05 part by weight was mixed to obtain an adhesive composition (1). . In addition, the compounding quantity of brand name "SI-150L" was shown by the quantity of solid content conversion.

(Preparation of adhesive layer (1))
Spin coating a silane coupling agent (trade name “KBE403”, manufactured by Shin-Etsu Chemical Co., Ltd.) on a silicon plate (size: 2 cm × 5 cm, obtained by dicing a silicon wafer with a diameter of 100 mm, manufactured by SUMCO Corporation) And heated at 120 ° C. for 5 minutes to obtain a silicon plate with a silane coupling agent layer.
The adhesive composition (1) is applied to the surface of the silane coupling agent layer of the silicon plate with the silane coupling agent layer by spin coating, and the residual solvent is removed by heating at 80 ° C. for 4 minutes and then at 100 ° C. for 2 minutes. Thus, a silicon plate [adhesive layer (1) / silane coupling agent layer / silicon plate] with an adhesive layer (1) was obtained. The film thickness of the adhesive layer (1) was 5 to 6 μm.

(Preparation of laminate (1))
A silane coupling agent (trade name “KBE403”, manufactured by Shin-Etsu Chemical Co., Ltd.) is applied to a glass plate (4 inches, manufactured by SCHOTT Japan Co., Ltd.) by spin coating, heated at 120 ° C. for 5 minutes, and silane A glass plate with a coupling agent layer was obtained.
The adhesive for the silicon plate with the adhesive layer (1) obtained in the above (Preparation of the adhesive layer (1)) is performed on the silane coupling agent layer surface of the obtained glass plate with the silane coupling agent layer under reduced pressure. The laminate was laminated with the surface of the layer (1) by applying a pressure of 200 g / cm ² while heating to 60 ° C., heating at 150 ° C. for 30 minutes, and then heating at 170 ° C. for 30 minutes. (1) [silicon plate / silane coupling agent layer / adhesive layer (1) / silane coupling agent layer / glass plate] was obtained.

  The following evaluation was performed about the adhesive composition (1), adhesive layer (1), and laminate (1) obtained in Example 3. The results are shown in Table 2.

[Evaluation]
(Heat-resistant)
The cured product obtained by heating the adhesive composition (1) at 150 ° C. for 30 minutes and then heating at 170 ° C. for 30 minutes was subjected to thermal analysis equipment (trade name “TG-DTA6300”, Seiko Instruments Inc. The pyrolysis temperature (T) was determined by thermogravimetric analysis using Note that, as shown in FIG. 7, the thermal decomposition temperature (T) is a tangential line where there is no initial weight decrease or is gradually decreasing (range indicated by A in the figure), and a sudden weight decrease. It is the temperature at which the tangent of the inflection point where it is occurring (range indicated by B in the figure) intersects. The heat resistance was evaluated as follows.
A (excellent in heat resistance): Thermal decomposition temperature (T) is 260 ° C. or higher.
B (Inferior in heat resistance): Thermal decomposition temperature (T) is less than 260 ° C.

(Adhesion)
The adhesive layer (1) in the silicon plate with the adhesive layer (1) was heated at 150 ° C. for 30 minutes and then heated at 170 ° C. for 30 minutes to be cured. About the hardened | cured material of the obtained adhesive bond layer (1), the adhesiveness to a silicon plate was evaluated as follows by the cross cut tape test (JISK5400-8.5 conformity).
A (excellent adhesion): no peeling from the silicon plate.
B (inferior in adhesion): Peeling from the silicon plate is observed.

(Adhesiveness)
Insert a razor blade (trade name “single-blade trimming razor”, manufactured by Nissin EM Co., Ltd.) into the adhesive interface of the laminate (1) and see if peeling occurs at the interface (adhesiveness) as follows: evaluated.
A (excellent adhesiveness of the adhesive layer): no peeling at the interface occurs.
B (Inferior to adhesiveness of adhesive layer): Peeling occurs at the interface.

(Crack resistance)
The cured product of the adhesive layer obtained by heating the adhesive layer in the silicon plate with the adhesive layer (1) was subjected to a thermal shock (heating at 170 ° C. for 30 minutes and then rapidly cooling to room temperature) to Whether it was excellent in cracking property was evaluated as follows.
A (excellent in crack resistance): No crack is generated by a thermal shock.
B (Inferior to crack resistance): Cracks are generated by thermal shock.

[Example 4]
(Preparation of epoxy group-containing polyorganosilsesquioxane (curable resin D))
In a 300 mL flask (reaction vessel) equipped with a thermometer, stirrer, reflux condenser, and nitrogen inlet tube, EMS 161.5 mmol (39.79 g), BTH 9 mmol (2.93 g), and acetone under a nitrogen stream 170.88 g was charged and heated to 50 ° C. To the resulting mixture, 4.70 g of 5% aqueous potassium carbonate solution was added dropwise over 5 minutes, and then 30.60 g of water was added dropwise over 20 minutes. Note that no significant temperature increase occurred during the dropping. Thereafter, the polycondensation reaction was carried out for 4 hours under a nitrogen stream while maintaining the temperature at 50 ° C.
Thereafter, the reaction solution is cooled, washed with water until the lower layer solution becomes neutral, and after the upper layer solution is separated, the solvent is distilled off from the upper layer solution under conditions of 1 mmHg and 40 ° C. to produce a colorless transparent liquid The product (epoxy group-containing polyorganosilsesquioxane) was obtained. Hereinafter, the obtained epoxy group-containing polyorganosilsesquioxane is referred to as “curable resin D”. In addition, the weight ratio of the ratio of EMS and BTH in preparation of the curable resin D was 93/7, and the molar ratio was 95/5.
When the product was analyzed, the weight average molecular weight in terms of polystyrene was 3900, and the number average molecular weight was 2100 (molecular weight dispersity: 1.86).

(Preparation of adhesive composition (2))
An adhesive composition (2) was obtained in the same manner as in Example 3 except that the curable resin D was used in place of the curable resin C.

(Preparation of adhesive layer (2))
A silicon plate with an adhesive layer (2) was obtained in the same manner as in Example 3 except that the adhesive composition (2) was used in place of the adhesive composition (1). The film thickness of the adhesive layer (2) was 5 to 6 μm.

(Preparation of laminate (2))
Silicone with adhesive layer (2) obtained in the above (Preparation of adhesive layer) is obtained by applying the silane coupling agent layer surface of the glass plate with a silane coupling agent layer produced in the same manner as in Example 3 under reduced pressure. Combine with the surface of the adhesive layer (2) of the plate, apply the pressure of 200 g / cm ² while heating to 60 ° C, and then heat at 150 ° C for 30 minutes, then heat at 170 ° C for 30 minutes Thus, a laminate (2) [silicon plate / silane coupling agent layer / adhesive layer (2) / silane coupling agent layer / glass plate] was obtained.

  The adhesive composition (2), adhesive layer (2), and laminate (2) obtained in Example 4 were evaluated in the same manner as in Example 3. The results are shown in Table 2.

[Comparative Example 5]
(Preparation of epoxy group-containing polyorganosilsesquioxane (curable resin E))
A 300 mL flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen introduction tube was charged with EMS 162.35 mmol (40.0 g) and acetone 40.0 g under a nitrogen stream, and the temperature was adjusted to 50 ° C. The temperature rose. To the mixture thus obtained, 4.49 g of 5% aqueous potassium carbonate solution (1.62 mmol as potassium carbonate) was added dropwise over 5 minutes, and then 163.51 mmol (29.48 g) of water was added dropwise over 20 minutes. . Note that no significant temperature increase occurred during the dropping. Thereafter, the polycondensation reaction was carried out under a nitrogen stream for 3 hours while maintaining the temperature at 50 ° C.
Subsequently, after adding methyl isobutyl ketone and brine, the reaction solution was cooled, and the upper layer solution was separated. Thereafter, washing is performed until the lower layer solution becomes neutral, and the solvent is distilled off from the upper layer solution until the amount of the solvent reaches 25% by weight under the conditions of 1 mmHg and 50 ° C. Oxane) was obtained. Hereinafter, the obtained epoxy group-containing polyorganosilsesquioxane is referred to as “curable resin E”. In addition, the weight ratio and molar ratio of the ratio of EMS and BTH in preparation of the curable resin E were 100/0.
When the product was analyzed, the weight average molecular weight in terms of polystyrene was 14400, and the number average molecular weight was 4000 (molecular weight dispersity: 3.60).

(Preparation of adhesive composition (3))
An adhesive composition (3) was obtained in the same manner as in Example 3 except that the curable resin E was used instead of the curable resin C.

(Preparation of adhesive layer (3))
A silicon plate with an adhesive layer (3) was obtained in the same manner as in Example 3 except that the adhesive composition (3) was used in place of the adhesive composition (1). The film thickness of the adhesive layer (3) was 5 to 6 μm.

  The resulting adhesive layer (3) was evaluated for crack resistance in the same manner as in Example 3.

  As shown in Table 1, the hard coat films (Examples 1 and 2) using the polyorganosilsesquioxane of the present invention had no problem in appearance, and both had high surface hardness and flexibility. . Moreover, as shown in Table 2, the adhesive composition (Examples 3 and 4) using the polyorganosilsesquioxane of the present invention has excellent heat resistance, crack resistance, adhesion, and adhesion. Had.

Claims (22)

A structural unit represented by the following formula (1), and further a structural unit represented by the following formula (2-1) and / or a structural unit represented by the following formula (2-2), The ratio of the structural unit represented by I) and the structural unit represented by the following formula (II) [the structural unit represented by the formula (I) / the structural unit represented by the formula (II)] is 5 or more. Yes, the sum of the structural unit represented by formula (I) and the structural unit represented by formula (II), and the structural unit represented by formula (2-1) and represented by formula (2-2). Ratio of total structural units [{total of structural units represented by formula (I) and structural unit represented by formula (II)} / {structural units represented by formula (2-1) and formula (2 -2) is a total of 99.9 / 0.1-80 / 20, the structural unit represented by the formula (1) and the following formula with respect to the total amount of the siloxane structural unit: Forming a hard coat layer curable composition for the amount of the structural unit represented comprises a polyorganosilsesquioxane 50 to 99 mole% 5).

[In Formula (1), R < ¹ > shows group containing an epoxy group. ]

[In the formula (I), R ^a is a group containing an epoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group. Represents a substituted or unsubstituted alkenyl group or a hydrogen atom. ]

[In the formula (II), R ^b represents an epoxy group-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group. Represents a substituted or unsubstituted alkenyl group or a hydrogen atom. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

[R ²¹ in the formula (2-1) may be the same or different, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted alkenylene group, R ²² in the formula (2-2) are the same Or differently, a substituted or unsubstituted alkane-triyl group, or a substituted or unsubstituted alkene-triyl group. ]

[In formula (5), R ¹ is the same as that in formula (1). R ^c is the same as in formula (II). ]   2. The hard coat layer formation according to claim 1, wherein the polyorganosilsesquioxane has a number average molecular weight of 500 to 6000 and a molecular weight dispersity (weight average molecular weight / number average molecular weight) of 1.0 to 4.0. Curable composition. R ¹ is represented by the following formula (1a)

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

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

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

[In formula (1d), R ^1d represents a linear or branched alkylene group. ]
The curable composition for forming a hard coat layer according to claim 1, which is one or more groups selected from the group consisting of groups represented by the formula: R ²¹ in the formula (2-1) is the same or different and is an unsubstituted C _2-20 alkylene group, and R ²² in the formula (2-2) is the same or different and is unsubstituted. The curable composition for forming a hard coat layer according to claim 1, which is a C _2-20 alkane-triyl group.   The curable composition for forming a hard coat layer according to any one of claims 1 to 4, comprising a leveling agent.   Furthermore, the curable composition for hard-coat layer formation of any one of Claims 1-5 containing a curing catalyst.   The curable composition for forming a hard coat layer according to claim 6, wherein the curing catalyst is a cationic photopolymerization initiator.   The curable composition for forming a hard coat layer according to claim 6, wherein the curing catalyst is a thermal cationic polymerization initiator. It is a hard-coat film which has a base material and the hard-coat layer formed in the at least one surface of this base material, Comprising: The said hard-coat layer is a hard-coat of any one of Claims 1-8. The hard coat film which is a hardened | cured material layer formed with the hardened | cured material of the curable composition for layer formation . The hard coat film according to claim 9 , wherein the hard coat layer has a thickness of 1 to 200 μm. The hard coat film according to claim 9 or 10 produced by a roll-to-roll method.   Applying the curable composition for forming a hard coat layer according to any one of claims 1 to 8 on the surface A of the rolled-out substrate A and at least one surface of the rolled-out substrate; The process B includes a process B for forming a hard coat layer by curing the curable composition, and a process C for winding the obtained hard coat film again on a roll. A method for producing a hard coat film. A structural unit represented by the following formula (1), and further a structural unit represented by the following formula (2-1) and / or a structural unit represented by the following formula (2-2), The ratio of the structural unit represented by I) and the structural unit represented by the following formula (II) [the structural unit represented by the formula (I) / the structural unit represented by the formula (II)] is 5 or more. Yes, the sum of the structural unit represented by formula (I) and the structural unit represented by formula (II), and the structural unit represented by formula (2-1) and represented by formula (2-2). Ratio of total structural units [{total of structural units represented by formula (I) and structural unit represented by formula (II)} / {structural units represented by formula (2-1) and formula (2 -2) is a total of 99.9 / 0.1-80 / 20, the structural unit represented by the formula (1) and the following formula with respect to the total amount of the siloxane structural unit: Adhesive composition the amount of the structural unit represented by 5) comprises a polyorganosilsesquioxane 50 to 99 mol%.

[In Formula (1), R < ¹ > shows group containing an epoxy group. ]

[In the formula (I), R ^a is a group containing an epoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group. Represents a substituted or unsubstituted alkenyl group or a hydrogen atom. ]

[In the formula (II), R ^b represents an epoxy group-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group. Represents a substituted or unsubstituted alkenyl group or a hydrogen atom. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

[R ²¹ in the formula (2-1) may be the same or different, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted alkenylene group, R ²² in the formula (2-2) are the same Or differently, a substituted or unsubstituted alkane-triyl group, or a substituted or unsubstituted alkene-triyl group. ]

[In formula (5), R ¹ is the same as that in formula (1). R ^c is the same as in formula (II). ] The adhesive composition according to claim 13 , wherein the polyorganosilsesquioxane has a number average molecular weight of 500 to 6000 and a molecular weight dispersity (weight average molecular weight / number average molecular weight) of 1.0 to 4.0. . R ¹ is represented by the following formula (1a)

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

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

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

[In formula (1d), R ^1d represents a linear or branched alkylene group. ]
The adhesive composition according to claim 13 or 14 , which is one or more groups selected from the group consisting of groups represented by: R ²¹ in the formula (2-1) is the same or different and is an unsubstituted C _2-20 alkylene group, and R ²² in the formula (2-2) is the same or different and is unsubstituted. The adhesive composition according to any one of claims 13 to 15 , which is a _C2-20 alkane-triyl group. Furthermore, the adhesive composition according to any one of claims 13 to 16 including a curing catalyst. The adhesive composition according to claim 17 , wherein the curing catalyst is a photocationic polymerization initiator. The adhesive composition according to claim 17 , wherein the curing catalyst is a thermal cationic polymerization initiator. An adhesive sheet having a substrate and an adhesive layer on the substrate,
Adhesive sheet the adhesive layer, characterized in that a layer of the adhesive composition according to any one of claims 13-19. A laminate composed of three or more layers,
Having two layers to be adhered and an adhesion layer between the layers to be adhered;
Laminates of the adhesive layer, characterized in that a layer of the cured product of the adhesive composition according to any one of claims 13-19. An apparatus comprising the laminate according to claim 21 .

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