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

Abstract

To provide polyorganosilsesquioxane that can form a cured material having high surface hardness and bending property while having high heat resistance and is suitable as a material of a hard coat film and an adhesive agent.SOLUTION: A polyorganosilsesquioxane containing a cage type silsesquioxane represented by the following formula (1), in which a peak area % of the cage type silsesquioxane represented by the following formula (1) relative to a peak area of an entire constituent components when detected with a liquid chromatography-vaporized emission scattering detector is 5% or more. Formula (1):[R1SiO3 / 2]8[R1SiO2 / 2(ORc)]1 (R1 in the formula (1) is, independently, a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one is a group containing a polymerizable functional group. Rc shows an alkyl group of C1 to C4 or a hydrogen atom.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to polyorganosilsesquioxane, a curable composition containing the polyorganosilsesquioxane and a cured product thereof, and a hard coat film made of the cured product. The present disclosure also relates to a composition containing the above polyorganosilsesquioxane (composition for an adhesive), and an adhesive sheet and a laminate using the composition.

Background Art

[0002] Polyorganosilsesquioxane (silsesquioxane) is a network polymer or polyhedral cluster obtained by hydrolyzing trifunctional silane. As polyorganosilsesquioxane, cage-type silsesquioxane is known together with random-type and ladder-type. Cage-type silsesquioxane has a three-dimensionally closed structure by siloxane bonds, and is a general term for substances having organic functional groups at each vertex around the cubic structure of silica. As the cubic structure, mainly, octamer silsesquioxane (T8) having a regular hexahedron structure and decamer silsesquioxane (T 10 ) having a side cone pentagonal prism structure are known. Also, regarding cage-type silsesquioxane, many studies have been made as those capable of obtaining cured products excellent in heat resistance, weather resistance, optical properties, dimensional stability, etc. Such cage-type silsesquioxane is described in, for example, Patent Documents 1 to 3 below.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, the cured product obtained from the above-described cage-type silsesquioxane has a tendency to have insufficient hardness and cannot be used for applications that require a high degree of hardness as a material for hard coats, so its use as a material for hard coats has been limited. Also, the pencil hardness of a hard coat film having a hard coat layer using a conventional UV acrylic monomer was about 2H, and it could not be said that it had sufficient surface hardness yet.

[0005] Generally, to increase the hardness, a method of making the UV acrylic monomer polyfunctional or thickening the hard coat layer can be considered. However, when such a method is adopted, the curing shrinkage of the hard coat layer becomes large, and as a result, there is a problem that the flexibility is inferior and cracks occur in the hard coat layer.

[0006] Therefore, an object of the invention of the present disclosure is to provide a polyorganosilsesquioxane suitable as a material for a hard coat film, which can form a hard coat layer that is a cured product having high surface hardness and flexibility while having high heat resistance and the like, which are characteristics of cage-type silsesquioxane. Another object of the invention of the present disclosure is to provide a curable composition containing the polyorganosilsesquioxane. Furthermore, another object of the invention of the present disclosure is to provide a cured product of the curable composition and a hard coat film having the hard coat layer that is the cured product. Furthermore, another object of the invention of the present disclosure is to provide an adhesive composition (adhesive) that can form a cured product (adhesive) excellent in high heat resistance and flexibility, and an adhesive sheet and a laminate using the same.

Means for Solving the Problems

[0007] The inventors of the present disclosure have found that a polyorganosilsesquioxane containing a cage-type silsesquioxane structure having a specific composition formula in an amount equal to or more than a certain amount provides a cured product of a curable composition containing the polyorganosilsesquioxane with excellent surface hardness and flexibility and is very useful as a hard coat layer in a hard coat film. Further, the inventors of the present disclosure have found that a curable composition containing the above polyorganosilsesquioxane can be preferably used as an adhesive composition (adhesive) capable of forming a cured product (adhesive) excellent in high heat resistance and flexibility. The present disclosure has been completed based on these findings.

[0008] That is, the present disclosure provides a polyorganosilsesquioxane containing a cage-type silsesquioxane (T9) represented by the following composition formula (1), wherein the peak area percentage of T9 with respect to the peak area of all components when detected using liquid chromatography-evaporative light scattering detector is 5% or more. · Formula (1): [R 1 SiO 3 / 2 8[R 1 SiO 2 / 2 (OR c )]1 (In formula (1), each R 1 is independently a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one is a group containing a polymerizable functional group. R c represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.)

[0009] Further, in the present disclosure, the group containing a polymerizable functional group is a group represented by the following formula (1a)

Chemical formula

[0010] Further, the present disclosure provides the polyorganosilsesquioxane in which, in the cage-type silsesquioxane represented by the composition formula (1), the ratio of the group containing a polymerizable functional group to the whole of R 1 is 30% or more.

[0011] Further, the present disclosure provides the polyorganosilsesquioxane in which the molar ratio of the structural unit represented by the following formula (I) to the structural unit represented by the following formula (II) [structural unit represented by formula (I) / structural unit represented by formula (II)] is 1 or more and 500 or less. [R a SiO 3 / 2 (I) [In formula (I), R a represents a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom] [R b SiO 2 / 2 (OR c )] (II) [In formula (II), R brepresents a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom. R c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms]

[0012] Further, the present disclosure provides the polyorganosilsesquioxane having a number average molecular weight of 1,000 to 50,000.

[0013] Further, the present disclosure provides the polyorganosilsesquioxane having a molecular weight dispersity (weight average molecular weight / number average molecular weight) of 1.0 to 4.0.

[0014] Further, the present disclosure provides the polyorganosilsesquioxane having a 5% weight loss temperature (T d5 ) of 330°C or higher.

[0015] Further, the present disclosure provides a curable composition containing the polyorganosilsesquioxane.

[0016] Further, the present disclosure provides the curable composition further containing a curing catalyst.

[0017] Further, the present disclosure provides the curable composition in which the curing catalyst is a photo- or thermopolymerization initiator.

[0018] Further, the present disclosure provides the curable composition which is a curable composition for forming a hard coat layer.

[0019] Furthermore, the present disclosure provides the above-mentioned curable composition which is a composition for an adhesive.

[0020] Further, the present disclosure provides a cured product of the curable composition.

[0021] In addition, the present disclosure provides a hard coat film in which a base material and a hard coat layer formed on at least one surface of the base material are laminated, and the hard coat layer is a cured product of the curable composition.

[0022] In addition, the present disclosure has a base material and an adhesive layer on the base material, and provides an adhesive sheet in which the adhesive layer is a layer of the curable composition.

[0023] In addition, the present disclosure is composed of three or more layers, has two adherend layers and an adhesive layer between the adherend layers, and provides a laminate in which the adhesive layer is a layer of a cured product of the curable composition.

Advantages of the Invention

[0024] The hard coat layer, which is a cured product obtained from the polyorganosilsesquioxane of the present disclosure, has high surface hardness and flexibility while having high heat resistance and the like, which are characteristics of cage-type silsesquioxane. Therefore, by using the hard coat film having the hard coat layer, a molded product (product) having high surface hardness and flexibility can be manufactured. Further, since the hard coat film containing the polyorganosilsesquioxane of the present disclosure is excellent in flexibility, it can be wound and handled in a roll shape, and since the film containing the hard coat layer can be handled in a roll-to-roll manner, it is excellent in both quality and cost aspects. Furthermore, the curable composition containing the polyorganosilsesquioxane of the present disclosure as an essential component can also be preferably used as an adhesive composition (adhesive) that can form a cured product (adhesive material) excellent in high heat resistance and flexibility. By using the adhesive composition, an adhesive sheet and a laminate can be obtained.

Brief Description of the Drawings

[0025]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Mode for Carrying Out the Invention

[0026] [Polyorganosilsesquioxane] The polyorganosilsesquioxane of the present disclosure contains a cage-type silsesquioxane represented by the following compositional formula (1) (hereinafter, may be simply referred to as "T9"), and when measured using liquid chromatography-evaporative light scattering detector (LC-ELSD), the peak area percentage of T9 with respect to the peak areas of all components is 5% or more (preferably 6% or more, more preferably 7% or more, more preferably 8% or more, more preferably 9% or more, more preferably 10% or more, more preferably 12% or more, more preferably 14% or more, more preferably 16% or more, more preferably 18% or more, more preferably 20% or more, more preferably 22% or more, more preferably 24% or more, more preferably 26% or more, more preferably 28% or more, more preferably 30% or more, more preferably 32% or more, more preferably 34% or more, more preferably 36% or more, more preferably 38% or more, more preferably 40% or more, still more preferably 45% or more). When the ratio is 5% or more, the proportion of T9 in the polyorganosilsesquioxane of the present disclosure increases, and the surface hardness of the cured product can be further improved. The peak area percentage of T9 is not particularly limited, but is preferably 90% or less, more preferably 80% or less. · Formula (1): [R 1 SiO 3 / 2 8[R 1 SiO 2 / 2 (OR c )]1

[0027] R in the compositional formula (1) 1 are each independently a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one is a group containing a polymerizable functional group. R in the compositional formula (1) c is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0028] In addition, the polyorganosilsesquioxane of the present disclosure is not particularly limited, but is a cage-type silsesquioxane (T9) represented by the above compositional formula (1) and a cage-type silsesquioxane having a structural unit represented by the following compositional formula (I-2) (hereinafter, simply referred to as "T 10 "), and the ratio of the peak area % (T9 / T 10 ) measured using liquid chromatography-evaporative light scattering detector (LC-ELSD) is preferably 0.4 or more, more preferably 0.5 or more, more preferably 0.6 or more, more preferably 0.7 or more, more preferably 0.8 or more, more preferably 0.9 or more, more preferably 1 or more, more preferably 1.2 or more, more preferably 1.4 or more, more preferably 1.6 or more, more preferably 1.8 or more, more preferably 2 or more, more preferably 2.2 or more, more preferably 2.4 or more, more preferably 2.6 or more, more preferably 2.8 or more, more preferably 3 or more, more preferably 3.5 or more, more preferably 4 or more, more preferably 4.5 or more, and even more preferably 5 or more. When the peak area % of the above T9 is 5% or more and the ratio of T9 / T 10 is 0.4 or more, the proportion of T9 in the polyorganosilsesquioxane of the present disclosure tends to be relatively large, and both the surface hardness and flexibility of the cured product tend to be further improved. T9 / T 10 is not particularly limited, but is preferably 10 or less, more preferably 9 or less.

[0029] [R a SiO 3 / 2 10 (I-2) In the above compositional formula (I-2), R a represents a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom.

[0030] ​The peak area percentage when detected using the above liquid chromatography-evaporative light scattering detector (LC-ELSD) can be measured, for example, by the method described in the examples shown below.

[0031] [R in the compositional formula (1) 1 SiO 3 / 2 The structural unit represented by, and [R in the compositional formula (I-2) a SiO 3 / 2 The structural unit represented by, and [R in the compositional formula (3) 3 SiO 3 / 2 The structural unit represented by is included in the structural unit represented by the following formula (I) (hereinafter, may be referred to as "T3 body" in this specification). [R a SiO 3 / 2 (I)

[0032] Also, the structural unit represented by [R 1 SiO 2 / 2 (OR c )] in the compositional formula (1) is included in the structural unit represented by the following formula (II) (hereinafter, may be referred to as "T2 body" in this specification). [R b SiO 2 / 2 (OR c )] (II)

[0033] R in the above formula (I) a , and R in the formula (II) b represents a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom. Also, R in the above formula (II) c represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.

[0034] 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 formula (I')). On the other hand, each of the two oxygen atoms located above and below the silicon atom shown in the structure represented by the following formula (II') is bonded to another silicon atom (a silicon atom not shown in formula (II')). That is, both the above T3 unit and T2 unit are silsesquioxane structural units (so-called T units) formed by hydrolysis and condensation reactions of the corresponding hydrolyzable trifunctional silane compounds.

Chemical formula

Chemical formula

[0035] R in the above formula (I') a , R in formula (II') b and R c are the same groups as described above. The alkyl group in R c in formula (II) generally originates from the alkyl group that forms the alkoxy group (for example, the alkoxy group as X 1 ~X 3 in the following formulas (a) to (c), etc.) in the hydrolyzable silane compound used as a raw material for the polyorganosilsesquioxane of the present disclosure.

[0036] The cage-type silsesquioxane (T9) represented by the above compositional formula (1) has a structure centered on nine Si (atoms), and each Si has an organic functional group (R 1 ) and a silanol group or its ester (OR c ) as substituents, and is a so-called incomplete cage-type silsesquioxane. R in the above compositional formula (1) 1The number of groups containing polymerizable functional groups is preferably 3 to 9, more preferably 5 to 9, still more preferably 7 to 9, and even more preferably 9 (all groups contain polymerizable functional groups).

[0037] The cage-type silsesquioxane represented by the above compositional formula (1) is composed of eight structural units (T3 units) represented by [R 1 SiO 3 / 2 and one structural unit (T2 unit) represented by [R 1 SiO 2 / 2 (OR c )], which are bonded to each other via siloxane bonds (Si-O-Si) to form a cage-type structure. The specific structure of the cage-type silsesquioxane represented by the above compositional formula (1) is not particularly limited as long as the above compositional formula (1) is satisfied. Examples of the presumed structure include a cage-type silsesquioxane represented by the following formula (1’).

[0038]

Chemical formula

[0039] R 1a to R 1i in formula (1’) are each independently synonymous with R 1 in the compositional formula (1). R c in formula (1’) is also synonymous with R c in the compositional formula (1).

[0040] The cage-type silsesquioxane having the structural unit represented by the above compositional formula (I-2) (T 10 ) has a structure centered on 10 Si (atoms), and each Si has an organic functional group (R a ) as a substituent and does not have a silanol group or its ester.

[0041] The cage-type silsesquioxane represented by the above compositional formula (I-2) is composed of ten [R a SiO 3 / 2The structural unit (T3 unit) represented by [ ] forms a cage-like structure by bonding to each other via siloxane bonds (Si-O-Si), which is a silsesquioxane. The specific structure of the cage-like silsesquioxane represented by the above compositional formula (I-2) is not particularly limited as long as the above compositional formula (I-2) is satisfied. Examples of the estimated structure include cage-like silsesquioxanes represented by the following formulae.

Chemical Formula

[0042] The polyorganosilsesquioxane of the present disclosure may contain other silsesquioxanes other than the above-mentioned T9 and T 10 Examples of other silsesquioxanes include incomplete cage-like silsesquioxanes other than T9, complete cage-like silsesquioxanes other than T 10 ladder-type silsesquioxanes, random-type silsesquioxanes, and the like.

[0043] The "cationic polymerizable functional group" in the group containing the above polymerizable functional group is not particularly limited as long as it has cationic polymerizability, and examples thereof include an epoxy group, an oxetane group, a vinyl ether group, a vinylphenyl group, and the like. The "radical polymerizable functional group" in the group containing the above polymerizable functional group is not particularly limited as long as it has radical polymerizability, and examples thereof include a (meth)acryloxy group, a (meth)acrylamide group, a vinyl group, a vinylthio group, and the like. From the viewpoint of the surface hardness of the cured product (for example, 5H or more), the polymerizable functional group is preferably an epoxy group, a (meth)acryloxy group, etc., and more preferably an epoxy group.

[0044] Also, in the above-mentioned T9, R 1The proportion of the group containing a polymerizable functional group with respect to the whole (the proportion based on the number of groups containing a polymerizable functional group) is, for example, 30% or more, preferably 50% or more, more preferably 80% or more. From the viewpoints of curability when made into a curable composition and the surface hardness of the cured product, it is better for the above proportion to be higher, and it is preferably at least the above value.

[0045] R in the above composition formula (1) 1 R in the composition formula (I-2) a R in the above formula (I) a R in the above formula (II) b The group containing a polymerizable functional group in [ID=4, ID=6, ID=8, ID=10] is not particularly limited, and examples thereof include known or commonly used groups having an oxirane ring. From the viewpoints of the curability of the curable composition, the surface hardness and heat resistance of the cured product, the group represented by the following formula (1a), the group represented by the following formula (1b), the group represented by the following formula (1c), and the group represented by the following formula (1d) are preferred, more preferably the group represented by the following formula (1a), the group represented by the following formula (1c), and even more preferably the group represented by the following formula (1a). [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula]

[0046] In the above formula (1a), R 1a represents a linear or branched alkylene group. Examples of the linear or branched alkylene group include linear or branched alkylene groups having 1 to 10 carbon atoms such as 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. Among them, R 1aFrom the viewpoints of the surface hardness and curability of the cured product, a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms is preferable, more preferably an ethylene group, a trimethylene group, a propylene group, and even more preferably an ethylene group or a trimethylene group.

[0047] In the above formula (1b), R 1b represents a linear or branched alkylene group, and groups similar to R 1a are exemplified. Among them, as R 1b From the viewpoints of the surface hardness and curability of the cured product, a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms is preferable, more preferably an ethylene group, a trimethylene group, a propylene group, and even more preferably an ethylene group or a trimethylene group.

[0048] In the above formula (1c), R 1c represents a linear or branched alkylene group, and groups similar to R 1a are exemplified. Among them, as R 1c From the viewpoints of the surface hardness and curability of the cured product, a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms is preferable, more preferably an ethylene group, a trimethylene group, a propylene group, and even more preferably an ethylene group or a trimethylene group.

[0049] In the above formula (1d), R 1d represents a linear or branched alkylene group, and groups similar to R 1a are exemplified. Among them, as R 1d From the viewpoints of the surface hardness and curability of the cured product, a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms is preferable, more preferably an ethylene group, a trimethylene group, a propylene group, and even more preferably an ethylene group or a trimethylene group.

[0050] Examples of the group containing the above polymerizable functional group include the group represented by the above formula (1a) in which R 1a is an ethylene group [among them, a 2-(3’,4’-epoxycyclohexyl)ethyl group] is preferable.

[0051] The R in the above composition formula (1) 1 , the R in the composition formula (I-2) a , the R in the above formula (I) a , and the R in the above formula (II) b Examples of the aryl group in the substituted or unsubstituted aryl group in R include a phenyl group, a tolyl group, a naphthyl group, and the like.

[0052] The R in the above composition formula (1) 1 , the R in the composition formula (I-2) a , the R in the above formula (I) a , and the R in the above formula (II) b Examples of the above aralkyl group in the substituted or unsubstituted aralkyl group in R include a benzyl group, a phenethyl group, and the like.

[0053] The R in the above composition formula (1) 1 , the R in the composition formula (I-2) a , the R in the above formula (I) a , and the R in the above formula (II) b Examples of the cycloalkyl group in the substituted or unsubstituted cycloalkyl group in R include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like.

[0054] The R in the above composition formula (1) 1 , the R in the composition formula (I-2) a , the R in the above formula (I) a , and the R in the above formula (II) b Examples of the alkyl group in the substituted or unsubstituted alkyl group in R include linear or branched alkyl groups such as a methyl group, an ethyl group, a propyl group, an n-butyl group, an isopropyl group, an isobutyl group, an s-butyl group, a t-butyl group, an isopentyl group, and the like.

[0055] The R in the above composition formula (1) 1 , the R in the composition formula (I-2) a , the R in the above formula (I) a , and the R in the above formula (II)b Examples of the alkenyl group in the substituted or unsubstituted alkenyl group in [0000116] include linear or branched alkenyl groups such as vinyl group, allyl group, and isopropenyl group.

[0056] R in the above compositional formula (1) and the above formula (II) c Examples of the alkyl group having 1 to 4 carbon atoms in [0000117] include linear or branched alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, and isobutyl group.

[0057] The above-mentioned T9, T8, T 10 and other silsesquioxanes that the polyorganosilsesquioxane of the present disclosure may contain all generally contain a silsesquioxane structural unit (so-called T unit) represented by [RSiO 3 / 2 . In the above formula, R represents a monovalent organic group, which is the same hereinafter. The silsesquioxane structural unit can be formed by hydrolysis and condensation reactions of the corresponding hydrolyzable trifunctional silane compound (specifically, for example, compounds represented by the following formulas (a) to (c)).

[0058] In the polyorganosilsesquioxane of the present disclosure, the molar ratio of the structural unit represented by the above formula (I) (T3 body) to the structural unit represented by the above formula (II) (T2 body) [structural unit represented by formula (I) / structural unit represented by formula (II); T3 body / T2 body] is not particularly limited, but is, for example, 1 or more and 500 or less. Note that T9 is composed of 8 T3 bodies and 1 T2 body, and T 10 is composed of 10 T3 bodies. The T3 body and the T2 body in the polyorganosilsesquioxane of the present disclosure each contain the T3 body and the T2 body that constitute T9 and T 10 and further contain the T3 body and the T2 body that constitute all other silsesquioxanes.

[0059] The lower limit of the above ratio [T3 body / T2 body] is 1 as described above, preferably 2, more preferably 3, more preferably 4, more preferably 5, more preferably 6, more preferably 7, more preferably 8, still more preferably 9, and even more preferably 10. By setting the above ratio [T3 body / T2 body] to 1 or more, the surface hardness and adhesiveness of the cured product and the hard coat layer are remarkably improved. On the other hand, the upper limit of the above ratio [T3 body / T2 body] is 500 as described above, preferably 100, more preferably 50, more preferably 40, more preferably 30, more preferably 25, more preferably 20, more preferably 18, and still more preferably 16. By setting the above ratio [T3 body / T2 body] to 500 or less, the compatibility with other components in the curable composition is improved, and the viscosity is also suppressed, so that it becomes easy to handle and easy to coat as a hard coat layer.

[0060] The polyorganosilsesquioxane of the present disclosure, in addition to the above silsesquioxane structural unit [RSiO 3 / 2 (T unit), may further have at least one siloxane structural unit selected from the group consisting of a structural unit represented by [(R)3SiO 1 / 2 (so-called M unit), a structural unit represented by [(R)2SiO 2 / 2 (so-called D unit), and a structural unit represented by [SiO 4 / 2 (so-called Q unit).

[0061] The above ratio [T3 body / T2 body] in the polyorganosilsesquioxane of the present disclosure can be determined, for example, 29 by Si-NMR spectrum measurement. 29 In the Si-NMR spectrum, the silicon atom in the structural unit (T3 body) represented by the above formula (I) and the silicon atom in the structural unit (T2 body) represented by the above formula (II) show signals (peaks) at different positions (chemical shifts). Therefore, by calculating the integral ratio of these respective peaks, the above ratio [T3 body / T2 body] can be determined. In the polyorganosilsesquioxane of the present disclosure, R aIn the structure (T3 form) represented by the above formula (I) where is a 2-(3',4'-epoxycyclohexyl)ethyl group, the signal of the silicon atom appears at -64 to -70 ppm, and R b In the structure (T2 form) represented by the above formula (II) where is a 2-(3',4'-epoxycyclohexyl)ethyl group, the signal of the silicon atom appears at -54 to -60 ppm. Therefore, in this case, the ratio [T3 form / T2 form] can be determined by calculating the integral ratio of the signal at -64 to -70 ppm (T3 form) and the signal at -54 to -60 ppm (T2 form).

[0062] The 29 Si-NMR spectrum of the polyorganosilsesquioxane of the present disclosure can be measured, for example, using the following apparatus and conditions. Measuring apparatus: Trade name "Brucker AVANCE (600 MHz)" (manufactured by Brucker) Solvent: Deuterated chloroform Number of integrations: 8000 times Measurement temperature: 25 °C Sample: Polyorganosilsesquioxane / acetylacetone chromium(III) / deuterated chloroform (1% tetramethylsilane) = 2.0:0.10:4.0 (weight ratio)

[0063] The fact that the ratio [T3 form / T2 form] of the polyorganosilsesquioxane of the present disclosure is the above ratio such that it is 1 or more means that the abundance of the T2 form relative to the T3 form in the polyorganosilsesquioxane of the present disclosure is equal or relatively small, and the hydrolysis and condensation reaction of silanol is proceeding.

[0064] The number average molecular weight (Mn) in terms of standard polystyrene of the polyorganosilsesquioxane of the present disclosure by gel permeation chromatography is, for example, from 1000 to 50000, preferably from 1100 to 40000, more preferably from 1200 to 30000. By setting the number average molecular weight to be not less than the lower limit, the heat resistance, scratch resistance, and adhesiveness of the cured product are further improved. On the other hand, by setting the number average molecular weight to be not more than the upper limit, the compatibility with other components in the curable composition is improved, and the heat resistance of the cured product is further improved.

[0065] The molecular weight dispersity (Mw / Mn) in terms of standard polystyrene of the polyorganosilsesquioxane of the present disclosure by gel permeation chromatography is, for example, from 1.0 to 4.0, preferably from 1.1 to 3.0, more preferably from 1.2 to 2.5. By setting the molecular weight dispersity to be not more than 4.0, the surface hardness and adhesiveness of the cured product become higher. On the other hand, by setting the molecular weight dispersity to be not less than 1.0, it tends to become liquid and the handleability is improved.

[0066] Note that the number average molecular weight and molecular weight dispersity of the polyorganosilsesquioxane of the present disclosure can be measured by the following apparatus and conditions. Measuring apparatus: Trade name "LC-20AD" (manufactured by Shimadzu Corporation) Columns: Shodex KF-801 × 2, KF-802, and KF-803 (manufactured by Showa Denko K.K.) Measurement temperature: 40 °C Eluent: THF, sample concentration 0.1 to 0.2% by weight Flow rate: 1 mL / min Detector: RI detector (manufactured by Shoko Science Co., Ltd.) Molecular weight: In terms of standard polystyrene

[0067] The 5% weight loss temperature (T of the polyorganosilsesquioxane of the present disclosure in an air atmosphere d5) is not particularly limited, but is preferably 330°C or higher (for example, 330 - 450°C), more preferably 340°C or higher, and even more preferably 350°C or higher. When the 5% weight loss temperature is 330°C or higher, the heat resistance of the cured product tends to be further improved. When the polyorganosilsesquioxane of the present disclosure has the above ratio [T3 body / T2 body] of 1 or more and 500 or less, a number average molecular weight of 1000 - 50000, and a molecular weight dispersity of 1.0 - 4.0, its 5% weight loss temperature is 330°C or higher. The 5% weight loss temperature is the temperature at which 5% of the weight before heating has decreased when heated at a constant heating rate, and serves as an index of heat resistance. The above 5% weight loss temperature can be measured by TGA (thermogravimetric analysis) under an air atmosphere at a heating rate of 5°C / min.

[0068] The polyorganosilsesquioxane of the present disclosure can be produced by a known or conventional method for producing polysiloxanes, and is not particularly limited. For example, it can be produced by a method of hydrolyzing and condensing one or more hydrolyzable silane compounds. However, as the above hydrolyzable silane compound, a compound represented by the following formula (a) must be used as an essential hydrolyzable silane compound as a hydrolyzable trifunctional silane compound for forming the structural unit of T9 described above.

[0069] More specifically, for example, as a hydrolyzable silane compound for forming a silsesquioxane structural unit (T unit) in the polyorganosilsesquioxane of the present disclosure, a compound represented by the following formula (a), and, if necessary, further a compound represented by the following formula (b) and a compound represented by the following formula (c) can be hydrolyzed and condensed to produce the polyorganosilsesquioxane of the present disclosure.

Chemical formula

Chemical formula

Chemical formula

[0070] The compound represented by the above formula (a) is an essential compound for forming the constituent unit of T9 in the polyorganosilsesquioxane of the present disclosure, that is, R in formula (a) A is a group containing a polymerizable functional group. R in formula (a) A is preferably 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 a group represented by the above formula (1d), more preferably a group represented by the above formula (1a) or a group represented by the above formula (1c), still more preferably a group represented by the above formula (1a), and still more preferably a group represented by the above formula (1a), wherein R 1a is an ethylene group [among others, a 2-(3’,4’-epoxycyclohexyl)ethyl group].

[0071] X in the above formula (a) 1 represents an alkoxy group or a halogen atom. Examples of the alkoxy group in X 1 include alkoxy groups having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, and an isobutyloxy group. Examples of the halogen atom in X 1 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, X 1 is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. Note that the three X 1 may be the same or different from each other.

[0072] The compound represented by the above formula (b) is a compound for forming the constituent unit of T9 in the polyorganosilsesquioxane of the present disclosure. R in formula (b) B represents a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group. R in formula (b) 2Preferably, it is a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, more preferably a substituted or unsubstituted aryl group, and even more preferably a phenyl group.

[0073] X in the above formula (b) 2 represents an alkoxy group or a halogen atom. X 2 Specific examples of 1 include those exemplified as 2 Preferably, X is an alkoxy group, more preferably a methoxy group or an ethoxy group. Note that the three Xs 2 may be the same or different from each other.

[0074] The compound represented by the above formula (c) is a compound that forms a structural unit represented by [HSiO 3 / 2 in T9 of the polyorganosilsesquioxane of the present disclosure. X in the above formula (c) 3 represents an alkoxy group or a halogen atom. X 3 Specific examples of 1 include those exemplified as 3 Preferably, X is an alkoxy group, more preferably a methoxy group or an ethoxy group. Note that the three Xs 3 may be the same or different from each other.

[0075] In addition to the structural unit of T9, the compounds represented by the above formulas (a) to (c) are also raw material compounds that form structural units of other silsesquioxanes (for example, incomplete cage-type silsesquioxanes other than T9, complete cage-type silsesquioxanes such as T 10 , ladder-type silsesquioxanes, random-type silsesquioxanes) that the polyorganosilsesquioxane of the present disclosure may contain.

[0076] As the hydrolyzable silane compound, hydrolyzable silane compounds other than the compounds represented by the above formulas (a) to (c) may be used in combination. For example, hydrolyzable trifunctional silane compounds other than the compounds represented by the above formulas (a) to (c), hydrolyzable monofunctional silane compounds that form M units, hydrolyzable bifunctional silane compounds that form D units, hydrolyzable tetrafunctional silane compounds that form Q units, and the like can be mentioned.

[0077] The usage amount and composition of the hydrolyzable silane compound can be appropriately adjusted according to the structure of the desired polyorganosilsesquioxane of the present disclosure. For example, the usage amount of the compound represented by the above formula (a) is not particularly limited, but is preferably 30 to 100 mol%, more preferably 55 to 100 mol%, still more preferably 65 to 100 mol%, and even more preferably 80 to 99 mol% with respect to the total amount (100 mol%) of the hydrolyzable silane compound used.

[0078] Also, the usage amount of the compound represented by the above formula (b) is not particularly limited, but is preferably 0 to 70 mol%, more preferably 0 to 60 mol%, still more preferably 0 to 40 mol%, and particularly preferably 1 to 15 mol% with respect to the total amount (100 mol%) of the hydrolyzable silane compound used.

[0079] Furthermore, the ratio (total amount ratio) of the compound represented by formula (a) to the compound represented by formula (b) with respect to the total amount (100 mol%) of the hydrolyzable silane compound used is not particularly limited, but is preferably 60 to 100 mol%, more preferably 70 to 100 mol%, and still more preferably 80 to 100 mol%.

[0080] When two or more of the above hydrolyzable silane compounds are used in combination, the hydrolysis and condensation reactions of these hydrolyzable silane compounds can be carried out simultaneously or sequentially. When the above reactions are carried out sequentially, the order of the reactions is not particularly limited.

[0081] As reaction conditions for performing the hydrolysis and condensation reactions of the above hydrolyzable silane compound, it is important to select reaction conditions such that the peak area % of T9 in the polyorganosilsesquioxane of the present disclosure is 5% or more.

[0082] The hydrolysis and condensation reactions can be carried out in the presence or absence of a solvent. Among them, it is preferably carried out in the presence of a solvent. Examples of the above solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran, and dioxane; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, isopropyl acetate, and butyl acetate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; nitriles such as acetonitrile, propionitrile, and benzonitrile; alcohols such as methanol, ethanol, isopropyl alcohol, and butanol. From the viewpoint of easily controlling the peak area % of T9 described above to 5% or more, ketones, ethers, amides, and alcohols are preferred as the above solvent, methyl isobutyl ketone, acetone, tetrahydrofuran, N,N-dimethylacetamide, and isopropyl alcohol are more preferred, and methyl isobutyl ketone and tetrahydrofuran are even more preferred. Note that the solvent can be used alone or in combination of two or more.

[0083] The amount of the solvent used in the hydrolysis and condensation reactions is not particularly limited, and can be appropriately adjusted according to the desired reaction time, the type of the solvent used, etc. within the range of 0 to 2000 parts by weight with respect to 100 parts by weight of the total amount of the hydrolyzable silane compound. From the viewpoint of easily controlling the peak area % of T9 described above to 5% or more, 200 to 1500 parts by weight is preferred, and 300 to 1000 parts by weight is more preferred.

[0084] The hydrolysis and condensation reactions are preferably carried out in the presence of a catalyst and water. The above catalyst may be an acid catalyst or an alkali catalyst, but an alkali catalyst is preferred in order to suppress the decomposition of polymerizable functional groups such as epoxy groups. Examples of the above acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid; phosphate esters; carboxylic acids such as acetic acid, formic acid, and trifluoroacetic acid; sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid; solid acids such as activated clay; and Lewis acids such as iron chloride. Examples of the above alkali catalyst include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; hydroxides of alkaline earth metals such as magnesium hydroxide, calcium hydroxide, and barium hydroxide; carbonates of alkali metals such as lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate; carbonates of alkaline earth metals such as magnesium carbonate; hydrogen carbonates of alkali metals such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and cesium hydrogen carbonate; organic acid salts of alkali metals (e.g., acetates) such as lithium acetate, sodium acetate, potassium acetate, and cesium acetate; organic acid salts of alkaline earth metals (e.g., acetates) such as magnesium acetate; alkoxides of alkali metals such as lithium methoxide, sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium ethoxide, and potassium t-butoxide; phenoxides of alkali metals such as sodium phenoxide; amines (tertiary amines, etc.) such as triethylamine, N-methylpiperidine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and 1,5-diazabicyclo[4.3.0]nona-5-ene; and nitrogen-containing aromatic heterocyclic compounds such as pyridine, 2,2'-bipyridyl, and 1,10-phenanthroline. From the viewpoint of easily controlling the peak area percentage of T9 described above to 5% or more, alkali metal carbonates, alkali metal hydroxides, and amines are preferred, alkali metal carbonates are more preferred, and potassium carbonate is even more preferred. In addition, the catalyst can be used alone or in combination of two or more. Further, the catalyst can be used in a state dissolved or dispersed in water, a solvent, or the like.

[0085] The amount of the catalyst used in the hydrolysis and condensation reactions is not particularly limited and can be appropriately adjusted within the range of 0.000001 to 0.200 mol per 1 mol of the total amount of the hydrolyzable silane compound. However, from the viewpoint of easily controlling the peak area percentage of T9 described above to 5% or more, 0.00001 to 0.10 mol is preferable, and 0.0001 to 0.05 mol is more preferable.

[0086] The amount of water used in the hydrolysis and condensation reactions is not particularly limited and can be appropriately adjusted within the range of 0.5 to 20 mol per 1 mol of the total amount of the hydrolyzable silane compound. However, from the viewpoint of easily controlling the peak area percentage of T9 described above to 5% or more, 1 to 15 mol is preferable, and 2 to 10 mol is more preferable.

[0087] The method of adding the water in the hydrolysis and condensation reactions is not particularly limited, and the total amount of water used (total usage amount) may be added all at once or sequentially. When adding sequentially, it may be added continuously or intermittently.

[0088] The reaction temperature of the hydrolysis and condensation reactions is not particularly limited. However, from the viewpoint of easily controlling the peak area percentage of T9 described above to 5% or more, 20 to 100 °C is preferable, more preferably 45 to 80 °C, still more preferably 30 to 80 °C, and still more preferably 40 to 70 °C. The reaction time of the hydrolysis and condensation reactions is not particularly limited, but 0.1 to 10 hours is preferable, and more preferably 1.5 to 8 hours. Further, the hydrolysis and condensation reactions can be carried out under normal pressure, or under pressure or reduced pressure. In addition, the atmosphere during the hydrolysis and condensation reactions is not particularly limited. For example, it may be any of an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere, or an oxygen presence such as under air, but an inert gas atmosphere is preferable.

[0089] Through the above hydrolysis and condensation reactions, polyorganosilsesquioxane is obtained. After the hydrolysis and condensation reactions are completed, it is preferable to neutralize the catalyst in order to suppress the decomposition of polymerizable functional groups such as the ring-opening of epoxy groups. Further, the obtained polyorganosilsesquioxane may be separated and purified by separation means such as, for example, washing with water, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or separation means combining these.

[0090] The polyorganosilsesquioxane of the present disclosure contains a large amount of the cage-type silsesquioxane (T9) represented by the above compositional formula (1), and thus tends to have a flexible structure while increasing the (number average) molecular weight compared to conventional polyorganosilsesquioxanes. Further, when the proportion of T9 in the polyorganosilsesquioxane of the present disclosure increases, the Si-OR c of T9 further condenses with Si-OR such as another T9, c and becomes a crosslinking point that reacts with polymerizable functional groups possessed by another T9, T8, T 10 etc., and it is considered that the crosslinking density increases. Therefore, the cured product of the curable composition containing the polyorganosilsesquioxane of the present disclosure has high surface hardness and heat resistance, and is excellent in flexibility and processability. However, these mechanisms are only presumptions, and the present disclosure should not be construed as being limited to these mechanisms.

[0091] [Curable Composition] The curable composition of the present disclosure is a curable composition (curable resin composition) containing the above-described polyorganosilsesquioxane of the present disclosure as an essential component. As will be described later, the curable composition of the present disclosure may further contain other components such as a curing catalyst (preferably a photo cationic polymerization initiator), a surface conditioner, or a surface modifier. In the curable composition of the present disclosure, the polyorganosilsesquioxane of the present disclosure can be used alone or in combination of two or more.

[0092] The content (blending amount) of the polyorganosilsesquioxane of the present disclosure in the curable composition of the present disclosure is not particularly limited, but is preferably 70% by weight or more and less than 100% by weight, more preferably 80 to 99.8% by weight, still more preferably 90 to 99.5% by weight, based on the total amount (100% by weight) of the curable composition excluding the solvent. By setting the content of the polyorganosilsesquioxane of the present disclosure to 70% by weight or more, the hardness of the cured product tends to be further improved. On the other hand, by setting the content of the polyorganosilsesquioxane of the present disclosure to less than 100% by weight, a curing catalyst can be contained, and thus the curing of the curable composition tends to proceed more efficiently.

[0093] The content of the polyorganosilsesquioxane of the present disclosure with respect to the total amount (100% by weight) of the cation-curable compound contained in the curable composition of the present disclosure is preferably 70 to 100% by weight, more preferably 75 to 98% by weight, still more preferably 80 to 95% by weight. By setting the content of the polyorganosilsesquioxane of the present disclosure to 70% by weight or more, the surface hardness and adhesiveness of the cured product tend to be further improved.

[0094] The curable composition of the present disclosure preferably further contains a curing catalyst. Among them, in terms of shortening the curing time until it becomes more tack-free, it is preferable to contain a photo- or thermopolymerization initiator as the curing catalyst, and it is more preferable to contain a cationic polymerization initiator. In the curable composition of the present disclosure, the curing catalyst can be used alone or in combination of two or more.

[0095] The above cationic polymerization initiator is a compound that can initiate or promote the cationic polymerization reaction of a cation-curable compound such as the polyorganosilsesquioxane of the present disclosure. The above cationic polymerization initiator is not particularly limited, and examples thereof include photo cationic polymerization initiators (photoacid generators), thermal cationic polymerization initiators (thermal acid generators), and the like.

[0096] As the above-mentioned photo cationic polymerization initiator, known or commonly used photo cationic polymerization initiators can be used. For example, sulfonium salts (salts of sulfonium ions and anions), iodonium salts (salts of iodonium ions and anions), selenium salts (salts of selenium ions and anions), ammonium salts (salts of ammonium ions and anions), phosphonium salts (salts of phosphonium ions and anions), salts of transition metal complex ions and anions, etc. can be mentioned. These can be used alone or in combination of two or more.

[0097] Examples of the above-mentioned sulfonium salts include [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium tris(pentafluoroethyl) trifluorophosphate, triphenylsulfonium salt, tri-p-tolylsulfonium salt, tri-o-tolylsulfonium salt, tris(4-methoxyphenyl) sulfonium salt, 1-naphthyldiphenylsulfonium salt, 2-naphthyldiphenylsulfonium salt, tris(4-fluorophenyl) sulfonium salt, tri-1-naphthylsulfonium salt, tri-2-naphthylsulfonium salt, tris(4-hydroxyphenyl) sulfonium salt, diphenyl[4-(phenylthio)phenyl]sulfonium salt, 4-(p-tolylthio)phenyl di-(p-phenyl)sulfonium salt and other triaryl sulfonium salts; diaryl sulfonium salts such as diphenylphenacylsulfonium salt, diphenyl 4-nitrophenacylsulfonium salt, diphenylbenzylsulfonium salt, diphenylmethylsulfonium salt; monoaryl sulfonium salts such as phenylmethylbenzylsulfonium salt, 4-hydroxyphenylmethylbenzylsulfonium salt, 4-methoxyphenylmethylbenzylsulfonium salt; trialkyl sulfonium salts such as dimethylphenacylsulfonium salt, phenacyltetrahydrothiophenium salt, dimethylbenzylsulfonium salt, etc.

[0098] Examples of the diphenyl[4-(phenylthio)phenyl]sulfonium salt include diphenyl[4-(phenylthio)phenyl]sulfonium hexafluoroantimonate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, and the like.

[0099] Examples of the iodonium salt include the product named "UV9380C" (manufactured by Momentive Performance Materials Japan LLC, 45% alkyl glycidyl ether solution of bis(4-dodecylphenyl)iodonium hexafluoroantimonate), the product named "RHODORSIL PHOTOINITIATOR 2074" (manufactured by Rhodia Japan Ltd., tetra kis(pentafluorophenyl)borate=[(1-methylethyl)phenyl](methylphenyl)iodonium), the product named "WPI-124" (manufactured by Wako Pure Chemical Industries, Ltd.), diphenyliodonium salt, di-p-tolyliodonium salt, bis(4-dodecylphenyl)iodonium salt, bis(4-methoxyphenyl)iodonium salt, and the like.

[0100] Examples of the selenium salt include triarylselenium salts such as triphenylselenium salt, tri-p-tolylselenium salt, tri-o-tolylselenium salt, tris(4-methoxyphenyl)selenium salt, 1-naphthyldiphenylselenium salt; diarylselenium salts such as diphenylphenacylselenium salt, diphenylbenzylselenium salt, diphenylmethylselenium salt; monoarylselenium salts such as phenylmethylbenzylselenium salt; trialkylselenium salts such as dimethylphenacylselenium salt, and the like.

[0101] Examples of the ammonium salt include tetraalkylammonium salts such as tetramethylammonium salt, ethyltrimethylammonium salt, diethyldimethylammonium salt, triethylmethylammonium salt, tetraethylammonium salt, trimethyl-n-propylammonium salt, trimethyl-n-butylammonium salt; pyrrolidinium salts such as N,N-dimethylpyrrolidinium salt, N-ethyl-N-methylpyrrolidinium salt; imidazolinium salts such as N,N'-dimethylimidazolinium salt, N,N'-diethylimidazolinium salt; tetrahydropyrimidinium salts such as N,N'-dimethyltetrahydropyrimidinium salt, N,N'-diethyltetrahydropyrimidinium salt; morpholinium salts such as N,N-dimethylmorpholinium salt, N,N-diethylmorpholinium salt; piperidinium salts such as N,N-dimethylpiperidinium salt, N,N-diethylpiperidinium salt; pyridinium salts such as N-methylpyridinium salt, N-ethylpyridinium salt; imidazolium salts such as N,N'-dimethylimidazolium salt; quinolinium salts such as N-methylquinolinium salt; isoquinolinium salts such as N-methylisoquinolinium salt; thiazonium salts such as benzylbenzothiazonium salt; acridinium salts such as benzylacridinium salt, and the like.

[0102] Examples of the phosphonium salt include tetraarylphosphonium salts such as tetraphenylphosphonium salt, tetra-p-tolylphosphonium salt, tetrakis(2-methoxyphenyl)phosphonium salt; triarylphosphonium salts such as triphenylbenzylphosphonium salt; tetraalkylphosphonium salts such as triethylbenzylphosphonium salt, tributylbenzylphosphonium salt, tetraethylphosphonium salt, tetrabutylphosphonium salt, triethylphenacylphosphonium salt, and the like.

[0103] Examples of the salt of the transition metal complex ion include salts of chromium complex cations such as (η5-cyclopentadienyl)(η6-toluene)Cr + , (η5-cyclopentadienyl)(η6-xylene)Cr + and the like; salts of iron complex cations such as (η5-cyclopentadienyl)(η6-toluene)Fe+ 、(η5-Cyclopentadienyl)(η6-xylene)Fe + Salts of iron complex cations such as the above, etc. can be mentioned.

[0104] Examples of the anion constituting the above salt include, for example, SbF6 - 、PF6 - 、BF4 - 、(CF3CF2)3PF3 - 、(CF3CF2CF2)3PF3 - 、(C6F5)4B - 、(C6F5)4Ga - 、Sulfonic acid anions (trifluoromethanesulfonic acid anion, pentafluoroethanesulfonic acid anion, nonafluorobutanesulfonic acid anion, methanesulfonic acid anion, benzenesulfonic acid anion, p-toluenesulfonic acid anion, etc.), (CF3SO2)3C - 、(CF3SO2)2N - 、Perhalate ions, halogenated sulfonate ions, sulfate ions, carbonate ions, aluminate ions, hexafluorobismuthate ions, carboxylate ions, arylborate ions, thiocyanate ions, nitrate ions, etc. can be mentioned.

[0105] Examples of the above thermal cationic polymerization initiator include, for example, arylsulfonium salts, aryliodonium salts, allene-ion complexes, quaternary ammonium salts, aluminum chelates, boron trifluoride amine complexes, etc.

[0106] Examples of the arylsulfonium salt include hexafluoroantimonate salts. In the curable composition of the present disclosure, for example, commercially available products such as the trade names "SP-66" and "SP-77" (manufactured by ADEKA Corporation); the trade names "Sun-Aid SI-60L", "Sun-Aid SI-80L", "Sun-Aid SI-100L", and "Sun-Aid SI-150L" (manufactured by Sanshin Chemical Industry Co., Ltd.) can be used. Examples of the aluminum chelate include aluminum diisopropylate ethylacetoacetate and aluminum tris(ethylacetoacetate). Examples of the boron trifluoride amine complex include boron trifluoride monoethylamine complex, boron trifluoride imidazole complex, and boron trifluoride piperidine complex.

[0107] The content (blending amount) of the curing catalyst in the curable composition of the present disclosure is not particularly limited, but is preferably 0.01 to 3.0 parts by weight, more preferably 0.05 to 3.0 parts by weight, and still more preferably 0.1 to 1.0 parts by weight (for example, 0.3 to 1.0 parts by weight) with respect to 100 parts by weight of the total amount of the polyorganosilsesquioxane of the present disclosure and other cationically curable compounds described below. By setting the content of the curing catalyst to 0.01 part by weight or more, the curing reaction can proceed efficiently and sufficiently, and the surface hardness and adhesiveness of the cured product tend to be further improved. On the other hand, by setting the content of the curing catalyst to 3.0 parts by weight or less, the storage stability of the curable composition tends to be further improved, and the coloring of the cured product tends to be suppressed.

[0108] The curable composition of the present disclosure may further contain a cationically curable compound other than the polyorganosilsesquioxane of the present disclosure (which may be referred to as "other cationically curable compound"). As the other cationically curable compound, known or commonly used cationically curable compounds can be used, and examples include epoxy compounds, oxetane compounds, and vinyl ether compounds other than the polyorganosilsesquioxane of the present disclosure. In the curable composition of the present disclosure, the other cationically curable compound can be used alone or in combination of two or more.

[0109] As the above epoxy compound, known or commonly used compounds having one or more epoxy groups (oxirane rings) in the molecule can be used, and there is no particular limitation. For example, alicyclic epoxy compounds (alicyclic epoxy resins), aromatic epoxy compounds (aromatic epoxy resins), aliphatic epoxy compounds (aliphatic epoxy resins), etc. can be mentioned.

[0110] As the above alicyclic epoxy compound, known or commonly used compounds having one or more alicyclic rings and one or more epoxy groups in the molecule can be mentioned, and there is no particular limitation. For example, compounds having an epoxy group (referred to as an "alicyclic epoxy group") composed of two adjacent carbon atoms and an oxygen atom constituting the alicyclic ring in the molecule, compounds in which the epoxy group is directly bonded to the alicyclic ring by a single bond, compounds having an alicyclic ring and a glycidyl ether group in the molecule (glycidyl ether type epoxy compounds), etc. can be mentioned.

[0111] Examples of the compound having the above alicyclic epoxy group include compounds represented by the following formula (i).

Chemical formula

[0112] 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 a divalent hydrocarbon group, an alkenylene group in which part or all of the carbon-carbon double bond is epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, a group in which a plurality of these are linked, etc.

[0113] Examples of the divalent hydrocarbon group include linear or branched alkylene groups having 1 to 18 carbon atoms, divalent alicyclic hydrocarbon groups, etc. 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, a trimethylene group, etc. Examples of the divalent alicyclic hydrocarbon group include divalent cycloalkylene groups (including cycloalkylidene groups) such as a 1,2-cyclopentylene group, a 1,3-cyclopentylene group, a cyclopentylidene group, a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group, a cyclohexylidene group, etc.

[0114] Examples of the alkenylene group in the alkenylene group in which some or all of the carbon-carbon double bonds are epoxidized (sometimes referred to as an "epoxidized alkenylene group") include linear or branched alkenylene groups having 2 to 8 carbon atoms such as a vinylene group, a propenylene group, a 1-butenylene group, a 2-butenylene group, a butadienylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group, etc. As the epoxidized alkenylene group, an alkenylene group in which all of the carbon-carbon double bonds are epoxidized is preferable, and more preferably an alkenylene group having 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized.

[0115] Typical examples of the alicyclic epoxy compound represented by the above formula (i) include (3,4,3’,4’-diepoxy)bicyclohexyl, compounds represented by the following formulas (i-1) to (i-10), etc. In the following formulas (i-5) and (i-7), l and m each represent an integer of 1 to 30. R’ in the following formula (i-5) is an alkylene group having 1 to 8 carbon atoms, and among them, a linear or branched alkylene group having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group, and an isopropylene group is preferable. In the following formulas (i-9) and (i-10), n1 to n6 each represent an integer of 1 to 30. Further, as the alicyclic epoxy compound represented by the above formula (i), for example, 2,2-bis(3,4-epoxycyclohexyl)propane, 1,2-bis(3,4-epoxycyclohexyl)ethane, 2,3-bis(3,4-epoxycyclohexyl)oxirane, bis(3,4-epoxycyclohexylmethyl)ether, etc. can be mentioned. [Chemical formula] [Chemical formula]

[0116] Examples of the compound in which an epoxy group is directly bonded to the above alicyclic ring by a single bond include compounds represented by the following formula (ii), etc. [Chemical formula]

[0117] In formula (ii), R” is a group obtained by removing p hydroxyl groups (-OH) from the structural formula of a p-valent alcohol (p-valent organic group), and p and n each represent a natural number. The p-valent alcohol [R”(OH) pExamples thereof include polyhydric alcohols such as 2,2-bis(hydroxymethyl)-1-butanol (alcohols having 1 to 15 carbon atoms, etc.). p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or more, n in the groups within each () (within the outer parentheses) may be the same or different. Specific examples of the compound represented by the above formula (ii) include the 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol [e.g., product name "EHPE3150" (manufactured by Daicel Corporation), etc.].

[0118] Examples of the compound having an alicyclic ring and a glycidyl ether group in the molecule include glycidyl ethers of alicyclic alcohols (preferably alicyclic polyhydric alcohols). Examples of glycidyl ethers of alicyclic alcohols include compounds obtained by hydrogenating bisphenol A type epoxy compounds (hydrogenated bisphenol A type epoxy compounds), compounds obtained by hydrogenating bisphenol F type epoxy compounds (hydrogenated bisphenol F type epoxy compounds), hydrogenated biphenyl type epoxy compounds, hydrogenated phenol novolak type epoxy compounds, hydrogenated cresol novolak type epoxy compounds, hydrogenated cresol novolak type epoxy compounds of bisphenol A, hydrogenated naphthalene type epoxy compounds, hydrogenated epoxy compounds of epoxy compounds obtained from trisphenol methane, hydrogenated epoxy compounds of aromatic epoxy compounds, and the like.

[0119] Examples of the aromatic epoxy compound include an epibis type glycidyl ether type epoxy resin obtained by a condensation reaction of bisphenols and epihalohydrin; a high molecular weight epibis type glycidyl ether type epoxy resin obtained by further addition reaction of these epibis type glycidyl ether type epoxy resins with the bisphenols; a novolak alkyl type glycidyl ether type epoxy resin obtained by a condensation reaction of phenols and aldehydes to obtain polyhydric alcohols and further condensation reaction with epihalohydrin; an epoxy compound in which two phenol skeletons are bonded to the 9-position of a fluorene ring, and glycidyl groups are bonded to the oxygen atoms obtained by removing hydrogen atoms from the hydroxy groups of these phenol skeletons, directly or via an alkyleneoxy group, and the like.

[0120] Examples of the aliphatic epoxy compound include glycidyl ethers of alcohols having no q-valent cyclic structure (q is a natural number); glycidyl esters of monovalent or polyvalent carboxylic acids [e.g., acetic acid, propionic acid, butyric acid, stearic acid, adipic acid, sebacic acid, maleic acid, itaconic acid, etc.]; epoxidized products of oils and fats having double bonds such as epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil; epoxidized products of polyolefins (including polyalkadienes) such as epoxidized polybutadiene, and the like.

[0121] Examples of the oxetane compound include known or commonly used compounds having one or more oxetane rings in the molecule. As the vinyl ether compound, known or commonly used compounds having one or more vinyl ether groups in the molecule can be used.

[0122] The content (blending amount) of other cation-curable compounds in the curable composition of the present disclosure is preferably 50% by weight or less (for example, 0 to 50% by weight), more preferably 30% by weight or less (for example, 0 to 30% by weight), and still more preferably 10% by weight or less, based on the total amount of the polyorganosilsesquioxane of the present disclosure and other cation-curable compounds. By setting the content of other cation-curable compounds to 50% by weight or less (preferably 10% by weight or less), the scratch resistance of the cured product tends to be further improved. On the other hand, by setting the content of other cation-curable compounds to 10% by weight or more, desired properties (for example, fast curability and viscosity adjustment for the curable composition) may be imparted to the curable composition or the cured product.

[0123] The content (blending amount) of the vinyl ether compound (preferably a vinyl ether compound having one or more hydroxyl groups in the molecule) in the curable composition of the present disclosure is not particularly limited, but is preferably 0.01 to 10% by weight, more preferably 0.05 to 9% by weight, and still more preferably 1 to 8% by weight, based on the total amount of the polyorganosilsesquioxane of the present disclosure and other cation-curable compounds. By controlling the content of the vinyl ether compound within the above range, the surface hardness of the cured product becomes higher, and there is a tendency to obtain a cured product having a very high surface hardness even when the irradiation amount of active energy rays (for example, ultraviolet rays) is low. Preferably, 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 increasing the surface hardness of the cured product, the heat-resistant yellowing property also tends to be further improved.

[0124] The curable composition of the present disclosure may further contain, as optional other components, inorganic fillers such as precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate, carbon black, silicon carbide, silicon nitride, boron nitride, etc., inorganic fillers treated with organosilicon compounds such as organohalosilanes, organoalkoxysilanes, organosilazanes; organic resin fine powders such as silicone resins, epoxy resins, fluororesins; fillers such as conductive metal powders of silver, copper, etc., curing aids, solvents (such as organic solvents), stabilizers (such as antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, heavy metal deactivators), flame retardants (such as phosphorus-based flame retardants, halogen-based flame retardants, inorganic flame retardants), flame retardant aids, reinforcing materials (such as other fillers), nucleating agents, coupling agents (such as silane coupling agents), lubricants, waxes, plasticizers, mold release agents, impact resistance improvers, hue improvers, clarifying agents, rheology modifiers (such as fluidity improvers), processability improvers, colorants (such as dyes, pigments), antistatic agents, dispersants, surface modifiers (such as defoamers, leveling agents, anti-cissing agents), surface treatment agents (such as slip agents), matting agents, defoamers, foam suppressants, degassing agents, antibacterial agents, preservatives, viscosity adjusters, thickeners, photosensitizers, foaming agents, and other conventional additives. These additives can be used alone or in combination of two or more kinds.

[0125] The curable composition of the present disclosure is not particularly limited, but can be prepared by stirring and mixing the above components at room temperature or while heating as necessary. Note that the curable composition of the present disclosure can also be used as a one-component composition in which the components are pre-mixed and used as they are, or, for example, as a multi-component (e.g., two-component) composition in which two or more components stored separately are mixed at a predetermined ratio before use.

[0126] The curable composition of the present disclosure is preferably liquid at normal temperature (about 25°C), although not particularly limited. More specifically, the viscosity at 25°C of the liquid [preferably, a curable composition (solution) in which the proportion of methyl isobutyl ketone is 20% by weight] obtained by diluting the curable composition of the present disclosure with 20% of a solvent is preferably 300 to 20,000 mPa·s, more preferably 500 to 10,000 mPa·s, and even more preferably 1000 to 8000 mPa·s. By setting the above viscosity to 300 mPa·s or more, the heat resistance of the cured product tends to be further improved. On the other hand, by setting the above viscosity to 20,000 mPa·s or less, the preparation and handling of the curable composition become easy, and bubbles tend not to remain in the cured product. The viscosity of the curable composition of the present disclosure is measured using a viscometer (trade name "MCR301", manufactured by Anton Paar) under the conditions of a swing angle of 5%, a frequency of 0.1 to 100 (1 / s), and a temperature of 25°C.

[0127] [Cured product] By advancing the polymerization reaction of the cation-curable compound (such as the polyorganosilsesquioxane of the present disclosure) in the curable composition of the present disclosure, the curable composition can be cured, and a cured product (which may be referred to as "the cured product of the present disclosure") can be obtained. The curing method can be appropriately selected from well-known methods and is not particularly limited. For example, methods such as irradiation with active energy rays and / or heating can be mentioned. As the above active energy rays, for example, any of infrared rays, visible light rays, ultraviolet rays, X-rays, electron beams, α-rays, β-rays, γ-rays, etc. can be used. Among them, ultraviolet rays are preferable in terms of excellent handleability.

[0128] The conditions (such as the irradiation conditions of active energy rays) when curing the curable composition of the present disclosure by irradiation with active energy rays can be appropriately adjusted according to the type and energy of the active energy rays to be irradiated, the shape and size of the cured product, etc., and are not particularly limited. However, when irradiating with ultraviolet rays, for example, 1 to 1000 mJ / cm 2It is preferably at such a level. For the irradiation of active energy rays, for example, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, sunlight, an LED lamp, a laser, etc. can be used. After the irradiation of active energy rays, further heat treatment (annealing, aging) can be performed to further advance the curing reaction.

[0129] On the other hand, the conditions for curing the curable composition of the present disclosure by heating are not particularly limited. For example, 30 to 200 °C is preferable, and more preferably 50 to 190 °C. The curing time can be set as appropriate.

[0130] As described above, the curable composition of the present disclosure can form a cured product having high surface hardness and heat resistance and excellent flexibility and processability by curing. Therefore, the curable composition of the present disclosure is preferably used as a "curable composition for forming a hard coat layer" (which may be referred to as a "hard coat liquid" or a "hard coat agent", etc.) for forming a hard coat layer in a hard coat film. Further, when the curable composition of the present disclosure is used as a curable composition for forming a hard coat layer, a hard coat film having a hard coat layer formed from the composition has flexibility while maintaining high hardness and high heat resistance, and is suitable for roll-to-roll production and processing.

[0131] [Hard coat film] The hard coat film of the present disclosure is a hard coat film in which a substrate and a hard coat layer formed on at least one surface of the substrate are laminated, and the hard coat layer is a hard coat layer (a cured product layer of the curable composition of the present disclosure) formed by the curable composition of the present disclosure (curable composition for forming a hard coat layer). FIG. 6 is a schematic diagram (cross-sectional view) showing an embodiment of the hard coat film of the present disclosure. 1 represents the hard coat film, 11 represents the hard coat layer, and 12 represents the substrate.

[0132] In addition, the hard coat layer of the hard coat film of the present disclosure may be formed only on one surface (single side) of the above-mentioned base material, or may be formed on both surfaces (both sides).

[0133] Also, the hard coat layer of the hard coat film of the present disclosure may be formed only on a part or on the entire surface of each surface of the above-mentioned base material.

[0134] The base material in the hard coat film of the present disclosure refers to the base material of the hard coat film and constitutes the part other than the hard coat layer of the present disclosure. As the above-mentioned base material, known or commonly used base materials such as plastic base materials, metal base materials, ceramic base materials, semiconductor base materials, glass base materials, paper base materials, wood base materials (wooden base materials), and base materials with a painted surface can be used, and there is no particular limitation. Among them, a plastic base material (a base material composed of a plastic material) is preferable. In addition, commercially available products can also be used as the above-mentioned base materials such as plastic base materials.

[0135] Among them, as the above-mentioned plastic base material, it is preferable to use a base material excellent in heat resistance, moldability, and mechanical strength, and more preferably a polyester film (preferably PET, PEN), a cyclic polyolefin film, a polycarbonate film, a TAC film, or a PMMA film.

[0136] The thickness of the above-mentioned base material is not particularly limited, but can be appropriately selected from the range of, for example, 0.01 to 10000 μm.

[0137] The hard coat layer of the hard coat film of the present disclosure is a layer that constitutes at least one surface layer of the hard coat film of the present disclosure, and is a layer (cured product layer) formed by a cured product (resin cured product) obtained by curing the curable composition of the present disclosure (curable composition for forming a hard coat layer).

[0138] The thickness of the hard coat layer of the present disclosure (when the hard coat layers of the present disclosure are provided on both sides of the substrate, the thickness of each hard coat layer) is not particularly limited, but is preferably 1 to 200 μm, more preferably 3 to 150 μm. Preferably, even when the hard coat layer of the present disclosure is thin (for example, when the thickness is 5 μm or less), it is possible to maintain a high hardness on the surface (for example, making the pencil hardness H or higher). Also, even when it is thick (for example, when the thickness is 50 μm or more), problems such as crack generation due to curing shrinkage are less likely to occur, so it is possible to significantly increase the pencil hardness by thickening the film (for example, making the pencil hardness 9H or higher).

[0139] The haze of the hard coat layer of the present disclosure is not particularly limited, but in the case of a thickness of 50 μm, it is preferably 1.5% or less, more preferably 1.0% or less. The lower limit of the haze is not particularly limited, but is, for example, 0.1%. By preferably setting the haze to 1.0% or less, it tends to be suitable for use in applications that require very high transparency (for example, surface protection sheets for displays such as touch panels). The haze of the hard coat layer of the present disclosure can be measured in accordance with JIS K7136.

[0140] The total light transmittance of the hard coat layer of the present disclosure is not particularly limited, but in the case of a thickness of 50 μm, it is preferably 85% or more, more preferably 90% or more. The upper limit of the total light transmittance is not particularly limited, but is, for example, 99%. By setting the total light transmittance to 85% or more, it tends to be suitable for use in applications that require very high transparency (for example, surface protection sheets for displays such as touch panels). The total light transmittance of the hard coat layer of the present disclosure can be measured in accordance with JIS K7361-1.

[0141] The hard coat film of the present disclosure may further have a surface protection film on the surface of the hard coat layer of the present disclosure.

[0142] The hard coat film of the present disclosure can be manufactured in accordance with known or conventional manufacturing methods for hard coat films, and the manufacturing method is not particularly limited. For example, the curable composition of the present disclosure (curable composition for forming a hard coat layer) is applied to at least one surface of the above-mentioned base material, and after removing the solvent by drying as necessary, the curable composition (curable composition layer) can be manufactured by curing it. The conditions for curing the curable composition are not particularly limited, and can be appropriately selected, for example, from the conditions for forming the above-mentioned cured product.

[0143] Preferably, the hard coat layer of the present disclosure in the hard coat film of the present disclosure is a hard coat layer formed from the curable composition of the present disclosure (curable composition for forming a hard coat layer) that can form a cured product excellent in flexibility and processability. Therefore, the hard coat film of the present disclosure can be manufactured by a roll-to-roll method. By manufacturing the hard coat film of the present disclosure by a roll-to-roll method, its productivity can be significantly increased. As a method for manufacturing the hard coat film of the present disclosure by a roll-to-roll method, known or conventional roll-to-roll manufacturing methods can be adopted, and it is not particularly limited. For example, a step of feeding out a base material wound in a roll (step A), applying the curable composition of the present disclosure (curable composition for forming a hard coat layer) to at least one surface of the fed-out base material, and then, after removing the solvent by drying as necessary, curing the curable composition (curable composition layer) to form the hard coat layer of the present disclosure (step B), and then, a step of winding the obtained hard coat film around a roll again (step C) are included as essential steps, and methods of continuously performing these steps (steps A to C) and the like can be mentioned. In addition, the method may include steps other than steps A to C.

[0144] The thickness of the hard coat film of the present disclosure is not particularly limited, and can be appropriately selected from the range of 1 to 10,000 μm.

[0145] The pencil hardness of the hard coat layer surface of the hard coat film of the present disclosure is preferably 5H or more, more preferably 6H or more, and even more preferably 7H or more. The pencil hardness can be evaluated according to the method described in JIS K5600-5-4.

[0146] The haze of the hard coat film of the present disclosure is not particularly limited, but is preferably 1.5% or less, more preferably 1.0% or less. The lower limit of the haze is not particularly limited, but is, for example, 0.1%. By setting the haze to preferably 1.0% or less, for example, it tends to be suitable for use in applications that require very high transparency (such as surface protection sheets for displays such as touch panels). The haze of the hard coat film of the present disclosure can be easily controlled within the above range, for example, by using the above-described transparent substrate as the substrate. The haze can be measured in accordance with JIS K7136.

[0147] The total light transmittance of the hard coat film of the present disclosure is not particularly limited, but is preferably 85% or more, more preferably 90% or more. The upper limit of the total light transmittance is not particularly limited, but is, for example, 99%. By setting the total light transmittance to 90% or more, for example, it tends to be suitable for use in applications that require very high transparency (such as surface protection sheets for displays such as touch panels). The total light transmittance of the hard coat film of the present disclosure can be easily controlled within the above range, for example, by using the above-described transparent substrate as the substrate. The total light transmittance can be measured in accordance with JIS K7361-1.

[0148] The hard coat film of the present disclosure has high hardness and flexibility while maintaining high heat resistance, and can be manufactured and processed by a roll-to-roll method. Therefore, it has high quality and excellent productivity. Preferably, when the hard coat film of the present disclosure has a surface protection film on the surface of the hard coat layer, it also has excellent punching processability. For this reason, it can be preferably used in any application that requires such characteristics. The hard coat film of the present disclosure can be used, for example, as a surface protection film for various products, a surface protection film for members or parts of various products, etc., and can also be used as a constituent material for various products and their members or parts. Examples of the above products include display devices such as liquid crystal displays and organic EL displays; input devices such as touch panels; solar cells; various household appliances; various electrical and electronic products; various electrical and electronic products of portable electronic terminals (for example, game devices, personal computers, tablets, smartphones, mobile phones, etc.); various optical devices, etc. In addition, examples of the mode in which the hard coat film of the present disclosure is used as a constituent material for various products and their members or parts include a mode in which it is used in a laminate of a hard coat film and a transparent conductive film in a touch panel, etc.

[0149] The cured product obtained by curing the curable composition of the present disclosure is not only excellent in terms of the above-mentioned surface hardness, heat resistance, flexibility, and processability, but also exhibits excellent adhesiveness and adhesion to the adherend. Therefore, the curable composition of the present disclosure can also be preferably used as an adhesive (sometimes referred to as an "adhesive composition"). The adhesive obtained by using the curable composition of the present disclosure as an adhesive composition can be converted into an adhesive excellent in surface hardness, heat resistance, flexibility, processability, adhesiveness, and adhesion by curing. The above adhesive can be used, for example, as a photocurable adhesive when the curable composition of the present disclosure contains a photo cationic polymerization initiator as a curing catalyst, and as a thermosetting adhesive when it contains a thermal cationic polymerization initiator.

[0150] By using the curable composition (composition for adhesives) of the present disclosure, an adhesive sheet having at least a base material and an adhesive layer on the base material can be obtained, wherein the adhesive layer is a layer of the curable composition of the present disclosure (sometimes referred to as "the adhesive layer of the present disclosure") (sometimes referred to as "the adhesive sheet of the present disclosure"). FIG. 7 is a schematic diagram (cross-sectional view) showing an embodiment of the adhesive sheet of the present disclosure. 2 denotes the adhesive sheet, 21 denotes the adhesive layer, and 22 denotes the base material.

[0151] The adhesive sheet of the present disclosure includes not only a sheet form but also forms similar to a sheet form such as a film form, a tape form, and a plate form. The adhesive sheet of the present disclosure is not particularly limited. For example, it can be obtained by applying the curable composition of the present disclosure to a base material and further drying it as necessary. The coating method is not particularly limited, and well-known and commonly used means can be used. Also, the drying means and conditions are not particularly limited, and conditions can be set to remove as much volatile matter such as a solvent as possible, and well-known and commonly used means can be used.

[0152] The adhesive sheet of the present disclosure may be a single-sided adhesive sheet having an adhesive layer only on one side of the base material, or a double-sided adhesive sheet having adhesive layers on both sides of the base material. When the adhesive sheet of the present disclosure is a double-sided adhesive sheet, at least one of the adhesive layers may be the adhesive layer of the present disclosure, and the other may be the adhesive layer of the present disclosure or another adhesive layer.

[0153] As the base material in the adhesive sheet of the present disclosure, well-known and commonly used base materials (base materials used in adhesive sheets) can be used, and there is no particular limitation. For example, plastic base materials, metal base materials, ceramic base materials, semiconductor base materials, glass base materials, paper base materials, wood base materials, base materials with a painted surface, etc. can be mentioned. Specifically, those similar to the base material in the hard coat film of the present disclosure are exemplified. Further, the base material in the adhesive sheet of the present disclosure may be a so-called release liner. For example, those similar to the surface protection film in the hard coat film of the present disclosure can also be used. Note that the adhesive sheet of the present disclosure may have only one layer of the base material or may have two or more layers. Further, the thickness of the above base material is not particularly limited and can be appropriately selected, for example, in the range of 1 to 10,000 μm.

[0154] The adhesive sheet of the present disclosure may have only one layer of the adhesive layer of the present disclosure or may have two or more types. Further, the thickness of the adhesive layer of the present disclosure is not particularly limited and can be appropriately selected, for example, in 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 disclosure).

[0155] The adhesive sheet of the present disclosure may have other layers (for example, an intermediate layer, an undercoat layer, etc.) in addition to the base material and the adhesive layer.

[0156] By using the curable composition (composition for adhesive) of the present disclosure, a laminate (laminated body) composed of three or more layers (at least three layers), having at least two adherend layers and an adhesive layer (a layer that adheres the above adherend layers to each other) located between these adherend layers, and the above adhesive layer is a layer of a cured product of the curable composition of the present disclosure (sometimes referred to as "the adhesive layer of the present disclosure") can be obtained. FIG. 8 is a schematic diagram (cross-sectional view) showing an embodiment of the adhesive sheet of the present disclosure. 3 is a laminate, 31 is an adhesive layer (cured product), and 32 and 33 are adherend layers.

[0157] The laminate of the present disclosure is not particularly limited. For example, an adhesive layer of the present disclosure 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 disclosure), and further, the other adherend layer is bonded to the adhesive layer, and then, the adhesive layer of the present disclosure is cured by light irradiation, heating, etc., whereby it can be obtained. Further, the laminate of the present disclosure can be obtained, for example, when the adhesive sheet of the present disclosure is a single-sided adhesive sheet, by bonding the adhesive sheet of the present disclosure to the adherend layer and then curing the adhesive layer of the present disclosure in the adhesive sheet by light irradiation, heating, etc. In this case, a laminate in which the base material in the adhesive sheet of the present disclosure hits the adherend layer is obtained. Further, the laminate of the present disclosure can be obtained, for example, when the adhesive sheet of the present disclosure is a double-sided adhesive sheet and the base material is a release liner, by bonding the adhesive sheet of the present disclosure to one adherend layer, peeling the release liner, and then bonding the other adherend layer to the exposed adhesive layer, and then curing the adhesive layer of the present disclosure by light irradiation, heating, etc. However, the manufacturing method of the laminate of the present disclosure is not limited to these methods.

[0158] The adherend in the laminate of the present disclosure is not particularly limited, and examples thereof include the same as the base material in the hard coat film of the present disclosure. Note that the laminate of the present disclosure may have only two adherends or may have three or more adherends. Further, the thickness of the adherend is not particularly limited, and can be appropriately selected, for example, in the range of 1 to 100,000 μm. The adherend does not necessarily have a strict layered form.

[0159] The laminate of the present disclosure may have only one adhesive layer of the present disclosure or may have two or more types. Further, the thickness of the adhesive layer of the present disclosure is not particularly limited, and can be appropriately selected, for example, in the range of 0.1 to 10,000 μm.

[0160] The laminate of the present disclosure may have other layers (for example, an intermediate layer, a primer layer, other adhesive layers, etc.) in addition to the above adherend and the adhesive layer of the present disclosure.

[0161] The curable composition (composition for adhesives) of the present disclosure is not limited to the use for obtaining the adhesive sheet and the laminate of the present disclosure described above, and can be used for various applications for adhering desired articles (such as parts) to each other.

[0162] Each aspect disclosed in this specification can be combined with any other features disclosed in this specification. Each configuration and their combinations in each embodiment are examples, and within the scope not departing from the gist of the present invention, addition, omission, substitution, and other changes of the configuration can be made as appropriate. The present disclosure is not limited by the embodiments, but is limited only by the claims.

Examples

[0163] Hereinafter, the present disclosure will be described in more detail based on examples, but the present disclosure is not limited by these examples. The number average molecular weight and molecular weight dispersity of the product were measured under the following GPC conditions. The 1 1H-NMR spectrum of the product was measured under the following conditions. Note that Examples 8 and 9 shall be read as Reference Examples 1 and 2, respectively.

[0164] Also, the area percentage of the cage-type silsesquioxane (T9) represented by the composition formula (1) in the product, and the cage-type silsesquioxane (T 10 ) having a structural unit represented by the composition formula (I-2) were measured under the following HPLC-ELSD conditions, and further fractionation was performed with respect to the largest peak on the chart obtained by HPLC-ELSD. The measurement of the ratio [T3 body / T2 body] of the T2 body and the T3 body in the product was performed by 29 Si-NMR spectrum measurement using Brucker AVANCE (600 MHz). Further, mass spectrometry of the above-mentioned fraction was performed using a quadrupole-time-of-flight mass spectrometer (manufactured by Waters, product name "Xevo G2-XS QTof").

[0165] [GPC conditions] Measuring device: Trade name "GPC Semi-micro System" (manufactured by Shimadzu Corporation) Detector: RI detector (manufactured by Shoko Science Co., Ltd.) Columns: KF-G4A (guard column), KF-602, and KF-603 (manufactured by Shoko Science Co., Ltd.) Flow rate: 0.6 mL / min Measurement temperature: 40 °C Measurement time: 13 min Injection volume: 20 μL Eluent: THF, sample concentration 0.1 - 0.2 wt% Molecular weight: in terms of standard polystyrene

[0166] 1 1H-NMR conditions Measuring device: Trade name "ECA-500 (500 MHz)" (manufactured by JEOL Ltd.) Solvent: deuterated chloroform Number of integrations: 16 times Measurement temperature: 25 °C

[0167] [HPLC-ELSD conditions] Measuring device: Alliance 2695 (manufactured by Waters) Detector: PL-ELS2100 (manufactured by Polymer Laboratories) Detection conditions: ELSD (Evap: 70 °C, Neb: 50 °C, Gas: 1.60) Column: YMC-TriartPFP 3μm 4.6φ×150mm + SunShell RP Guard Filter Eluent: (A) ultrapure water, (B) THF / ACN = 4 / 6 Gradient conditions: (A) / (B) = 30 / 70 (0 min) → 30 min → (A) / (B) = 0 / 100 (10 min) Flow rate: 1 mL / min Column temperature: 25 °C Injection volume: 10 μL Analysis time: 30 min

[0168] ​[Example 1: Production of Epoxy Group-Containing Polyorganosilsesquioxane] In a 1000 milliliter flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube, 99.2 parts by weight of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (hereinafter referred to as "EMS") and 0.806 parts by weight of phenyltrimethoxysilane (hereinafter referred to as "PMS") were dissolved in 400 parts by weight of methyl isobutyl ketone (MIBK), and 73.2 parts by weight of water was added. After heating this mixture to 60 °C under a nitrogen atmosphere, 11.2 parts by weight of a 5% aqueous potassium carbonate solution was added dropwise over 5 minutes. After reacting at 60 °C for 5 hours, MIBK and a 5% aqueous NaCl solution were added and separated by liquid-liquid extraction, and the organic layer was separated. This organic layer was washed with water 6 times, and then the solvent was distilled off under reduced pressure to obtain a colorless and transparent product. When the obtained product was analyzed under the above GPC conditions, the number average molecular weight (Mn) was 1561 and the molecular weight dispersity (Mw / Mn) was 1.52. Also, when the obtained product was analyzed under the above HPLC-ELSD conditions, a peak with a retention time of about 5.8 seconds in the chromatogram corresponded to T9, and a peak with a retention time of about 7.5 seconds corresponded to T 10 . From the area% values with respect to the total peak area of each, the area% of the cage-type silsesquioxane (T9) represented by the compositional formula (1) was 25.3%, and the area% of the cage-type silsesquioxane (T 10 ) having a structural unit represented by the compositional formula (I-2) was 4.45%, and T9 / T 10 was 5.69. The ratio [T3 body / T2 body] of the T2 body and the T3 body calculated from the 29 Si-NMR spectrum of the above product was 6.00. The 1 H-NMR chart of the obtained product is shown in Figure 1, 29 the Si-NMR chart is shown in Figure 2, and the chromatogram chart of the HPLC-ELSD analysis is shown in Figure 3, respectively. Also, the peak with a retention time of about 5.8 seconds under the above HPLC-ELSD conditions of the obtained product was fractionated, and the mass spectrometry result (ESI-MS spectrum) of the obtained fraction is shown in Figure 4. For the obtained fraction, the molecular formula is C 72 H 122 NO 23Si9 (assuming that all R 1 is the 2-(3,4-epoxycyclohexyl)ethyl group, corresponding to the compositional formula (1)), the theoretical isotope patterns are shown in Fig. 5 respectively. From the comparison with the theoretical isotope patterns, the peak with a retention time of about 5.8 seconds can be identified as T9.

[0169] [Examples 2 to 12, Comparative Examples 1 and 2] Synthesis was carried out in the same manner as in Example 1 except that the type and amount of the catalyst, reaction solvent, amount of water, and reaction temperature were changed as shown in Table 1. Table 1 shows the catalyst, reaction solvent and its amount (parts by weight), amount of water (parts by weight), reaction temperature (°C), number average molecular weight (Mn), molecular weight distribution, area percentage of the cage-type silsesquioxane (T9) represented by the above compositional formula (1), area percentage of the cage-type silsesquioxane (T 10 ) having a structural unit represented by the compositional formula (I-2), and [T9 / T 10 . In addition, DMAc in the reaction solvent in Table 1 is dimethylacetamide, THF is tetrahydrofuran, IPA is isopropyl alcohol, DBU in the catalyst is 1,8-diazabicyclo[5.4.0]undec-7-ene, and TMAOH is trimethylammonium hydroxide.

[0170] [Preparation of Hard Coat Film] After adding methyl isobutyl ketone (MIBK) (manufactured by Kanto Chemical Co., Inc.) so that the concentration of the polyorganosilsesquioxane obtained in the above Examples 1 to 12 and Comparative Examples 1 and 2 becomes 60 parts by weight, a mixed solution of 0.5 part by weight of a leveling agent (trade name "S-243", manufactured by AGC Seimi Chemical Co., Ltd.) and 1 part by weight of a photo cationic polymerization initiator (trade name "CPI-210S", manufactured by San-Apro Ltd.) was prepared, and this was used as a curable composition. Each of the curable compositions obtained above was applied onto a PEN (polyethylene naphthalate) film (trade name "Teonex" (registered trademark), manufactured by Teijin DuPont Films Ltd., thickness 50 μm) so that the thickness of the cured hard coat layer became 30 or 10 μm, then left in an oven at 120 °C for 10 minutes (pre-baked), and then irradiated with ultraviolet rays (irradiance 120 W / cm 2, speed 4.5M / min, manufactured byUSHIO ELECTRIC, product name "UVH-0251C-2200"). Finally, by performing heat treatment (aging) at 120 ° C for 30 minutes, a film having each hard coat layer (hard coat film) was produced.

[0171] [Evaluation] Regarding the hard coat films obtained from Examples 1 to 12 and Comparative Examples 1 and 2 obtained above, the flexural resistance and pencil hardness were evaluated by the following methods. The evaluation results are shown in Table 1.

[0172] (Flexural resistance: cylindrical mandrel method) The flexural resistance of the hard coat film (thickness 10 μm) obtained above was evaluated by performing a test in accordance with JIS K5600-5-1 using a cylindrical mandrel. Tests were conducted using mandrels with diameters of 2, 3, and 5 mm, with the hard coat layer on the inside (infold) and outside (outfold). For the inside (infold), the test was conducted using a mandrel with a diameter of 2 mm, and when no cracks were observed in the hard coat layer, it was marked as ○, and when cracks were observed, it was marked as ×. For the outside (outfold), the test was conducted using mandrels with diameters of 3 mm and 5 mm, and when no cracks were observed in the hard coat layer, it was marked as ○, and when cracks were observed, it was marked as ×. The results are shown in Table 1.

[0173] (Surface hardness: pencil hardness) The pencil hardness of the surface (the surface of the hard coat layer) of the hard coat film (thickness 30 μm) obtained above was evaluated in accordance with JIS K5600-5-4. The load was applied at 750 g. The results are shown in Table 1.

[0174] (Heat resistance: 5% weight loss temperature (T d5 )) The T of the product d5 (5% weight loss temperature) was measured by TGA (thermogravimetric analysis) under the following measurement conditions. (Measurement conditions) Measuring device: TG-DTA 6200 / Hitachi High-Tech Science Atmosphere: N2 Temperature range: 25°C to 550°C Heating rate: 10°C / min Sample pan: Al

[0175]

Table 1

Explanation of symbols

[0176] 1 Hard coat film 11 Hard coat layer 12 Substrate 2 Adhesive sheet 21 Adhesive layer 22 Substrate 3 Laminate 31 Adhesive layer (cured product) 32, 33 Adherend layer

Claims

1. A polyorganosilsesquioxane represented by the following compositional formula (1) and a polyorganosilsesquioxane represented by the following compositional formula (I-2), wherein the peak area percentage of the polyorganosilsesquioxane represented by the compositional formula (1) with respect to the peak areas of all the components when detected using liquid chromatography-evaporative light scattering detector is 5% or more, The cage-type silsesquioxane (T) represented by the above compositional formula (1) ９ ), and the cage-type silsesquioxane (T) having a structural unit represented by the above compositional formula (I-2) １０ ), the ratio of the peak area % (T ９ / T １０ ) measured using liquid chromatography-evaporative light scattering detector is 1 or more, A polyorganosilsesquioxane in which a 10-μm-thick hard coat layer containing the polyorganosil sesquioxane is laminated on a substrate having a thickness of 50 μm, and in a test conducted in accordance with JIS K5600-5-1 using a cylindrical mandrel with the hard coat layer on the inside, the diameter at which cracks are observed in the hard coat layer is 2 mm or less. ・ Formula (1): [R 1 SiO 3 / 2 8 8 [R 1 SiO 2 / 2 (OR c )] 1 1 (R in formula (1) 1 are each independently a group containing an epoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one is a group containing an epoxy group. R c represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.) [R ａ SiO ３／２ １０ (I - 2)​ R in the above compositional formula (I-2) a represents a group containing an epoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom.

2. The group containing an epoxy group is a group represented by the following formula (1a) 【Chemical 1】 [In formula (1a), R 1a represents a linear or branched alkylene group. ] A group represented by the following formula (1b) 【Chemical 2】 [In formula (1b), R 1b represents a linear or branched alkylene group.] A group represented by the following formula (1c) 【Chemical Formula 3】 [In formula (1c), R 1c represents a linear or branched alkylene group.] A group represented by the following formula (1d) 【Chemical 4】 [In formula (1d), R 1d represents a linear or branched alkylene group.] Or a group represented by the following formula (1d), The polyorganosilsesquioxane according to claim 1.

3. In the cage-type silsesquioxane represented by the above compositional formula (1), R 1 The polyorganosilsesquioxane according to claim 1 or 2, wherein the proportion of the group containing an epoxy group in the whole is 30% or more.

4. The molar ratio of the structural unit represented by the following formula (I) to the structural unit represented by the following formula (II) [structural unit represented by formula (I) / structural unit represented by formula (II)] is 1 or more and 500 or less. The polyorganosilsesquioxane according to any one of claims 1 to 3. [R a SiO 3 / 2 (I) [In formula (I), R a represents a group containing an epoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom] [R b SiO 2 / 2 (OR c )](II) [In formula (II), R b represents a group containing an epoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group. R c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms]

5. The polyorganosilsesquioxane according to any one of claims 1 to 4, having a number average molecular weight of 1,000 to 50,000.

6. The polyorganosilsesquioxane according to any one of claims 1 to 5, having a molecular weight dispersity (weight average molecular weight / number average molecular weight) of 1.0 to 4.

0.

7. The 5% weight loss temperature (T d5 ) is 330 °C or higher, and the polyorganosilsesquioxane according to any one of claims 1 to 6.

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

9. The curable composition according to claim 8, wherein the curing catalyst is a photo or heat polymerization initiator.

10. The curable composition according to claim 8 or 9, which is a curable composition for forming a hard coat layer.

11. The curable composition according to claim 8 or 9, which is a composition for an adhesive.

12. A cured product of the curable composition according to any one of claims 8 to 11.

13. A hard coat film in which a substrate and a hard coat layer formed on at least one surface of the substrate are laminated, and the hard coat layer is a cured product of the curable composition according to claim 10.

14. Having a substrate and an adhesive layer on the substrate, An adhesive sheet in which the adhesive layer is a layer of the curable composition according to claim 11.

15. Composed of three or more layers, Having two adherend layers and an adhesive layer between the adherend layers, A laminate in which the adhesive layer is a layer of a cured product of the curable composition according to claim 11.

Images