Polyorganosilsesquioxanes, curable compositions, cured products, hard coatings, adhesive sheets, and laminates

Abstract

This disclosure provides a polyorganosilsesquioxane that can form a cured product with high heat resistance, high surface hardness, and flexibility, suitable as a material for hard coatings and adhesives. A polyorganosilsesquioxane comprising a cage-like silsesquioxane represented by the following chemical formula (1), wherein the peak area of ​​the cage-like silsesquioxane represented by the following chemical formula (1), when detected using a liquid chromatography-evaporative light scattering detector, is 5% or more relative to the peak area of ​​all constituent components. Formula (1): [R] 1 SiO 3 / 2 ]8[R 1 SiO 2 / 2 (OR c )]1.

Description

Technical Field

[0001] This disclosure relates to a polyorganosilsesquioxane, a curable composition comprising the polyorganosilsesquioxane, a cured product thereof, and a hard coating film comprising the cured product. Furthermore, this disclosure relates to a composition comprising the aforementioned polyorganosilsesquioxane (an adhesive composition), and adhesive sheets and laminates using the composition. This application claims priority to Japanese Patent Application No. 2020-145083, filed on August 28, 2020, the contents of which are incorporated herein by reference. Background Technology

[0002] Polyorganosilsesquioxanes (silsesquioxanes) are network polymers or polyhedral clusters obtained by hydrolyzing trifunctional silanes. As polyorganosilsesquioxanes, atactic, ladder-like, and cage-like silsesquioxanes are known. Cage-like silsesquioxanes are a general term for substances with a three-dimensional closed-ring structure formed by siloxane bonds, centered on a cubic structure of silica with organic functional groups at each vertex. Among these cubic structures, the octamer silsesquioxane (T8) with a hexahedral structure and the decameric silsesquioxane (T...) with a lateral pyramidal pentagonal prism structure are primarily known. 10 Furthermore, cage-like silsesquioxanes have been extensively studied as substances that can produce cured products with excellent heat resistance, weather resistance, optical properties, and dimensional stability. Such cage-like silsesquioxanes are described, for example, in the following patent documents 1 to 3.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2000-334881

[0006] Patent Document 2: Japanese Patent Application Publication No. 2010-18664

[0007] Patent Document 3: Japanese Patent Application Publication No. 2014-101435 Summary of the Invention

[0008] The problem the invention aims to solve

[0009] However, the cured products obtained from the aforementioned conventional cage-type silsesquioxanes tend to have insufficient hardness, making them unsuitable for applications requiring very high hardness as materials for hard coatings, thus limiting their use as such materials. Furthermore, the pencil hardness of hard coatings with conventional UV acrylic monomers is only around 2H, which cannot be considered sufficient surface hardness.

[0010] Typically, to further improve hardness, one would consider making the UV acrylic monomer multifunctional or thickening the hard coating. However, when such methods are used, the curing shrinkage of the hard coating increases, resulting in problems such as poor flexibility and cracking of the hard coating.

[0011] Therefore, the object of the present invention is to provide a polyorganosilsesquioxane that can form a hard coating as a cured product with characteristics such as high heat resistance as a cage-like silsesquioxane, and high surface hardness and flexibility, and is suitable as a material for hard coating films.

[0012] Furthermore, another object of the present invention is to provide a curable composition comprising the polyorganosilsesquioxane.

[0013] Furthermore, another object of the present invention is to provide a cured product of the curable composition and a hard coating having a hard coating layer as the cured product.

[0014] Furthermore, another object of the present invention is to provide an adhesive composition (adhesive) capable of forming a cured product (adhesive material) with high heat resistance and excellent flexibility, as well as adhesive sheets and laminates using the adhesive composition.

[0015] Technical solution

[0016] The inventors of this disclosure have discovered that, based on a polyorganosilsesquioxane containing a certain amount or more of a cage-like silsesquioxane structure having a specific chemical formula, the cured product of a curable composition containing this polyorganosilsesquioxane exhibits excellent surface hardness and flexibility, making it very useful as a hard coating layer for hard coating films. Furthermore, the inventors of this disclosure have discovered that the curable composition containing the aforementioned polyorganosilsesquioxane can be preferably used as an adhesive composition (adhesive) capable of forming a cured product (adhesive material) with high heat resistance and excellent flexibility. This disclosure was made based on these insights.

[0017] That is, this disclosure provides a polyorganosilsesquioxane comprising a cage-like silsesquioxane (T9) represented by the following chemical formula (1), wherein the peak area of ​​T9 when detected by liquid chromatography-evaporative light scattering detector is 5% or more relative to the peak area of ​​all constituent components.

[0018] ·Formula (1): [R1SiO 3 / 2 ]8[R1SiO 2 / 2 (OR c )]1

[0019] (R in equation (1)) 1Each of the following 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, at least one of which is a group containing a polymerizable functional group. R c (representing alkyl groups or hydrogen atoms with 1 to 4 carbon atoms).

[0020] Furthermore, this disclosure provides the polyorganosilsesquioxane, wherein the group containing the polymerizable functional group is a group represented by formula (1a), a group represented by formula (1b), a group represented by formula (1c), or a group represented by formula (1d).

[0021] [Chemical Formula 1]

[0022]

[0023] In equation (1a), R 1a Indicates a straight-chain or branched alkylene group.

[0024] [Chemical Formula 2]

[0025]

[0026] In equation (1b), R 1b Indicates a straight-chain or branched alkylene group.

[0027] [Chemical Formula 3]

[0028]

[0029] In equation (1c), R 1c Indicates a straight-chain or branched alkylene group.

[0030] [Chemical Formula 4]

[0031]

[0032] In equation (1d), R 1d Indicates a straight-chain or branched alkylene group.

[0033] Furthermore, this disclosure provides the polyorganosilsesquioxane, wherein, in the cage-like silsesquioxane represented by the chemical formula (1), the groups containing polymerizable functional groups are relative to R. 1 The overall proportion is over 30%.

[0034] Furthermore, this disclosure provides the polyorganosilsesquioxane, wherein the molar ratio of the structural unit represented by formula (I) to the structural unit represented by formula (II) [structural unit represented by formula (I) / structural unit represented by formula (II)] is 1 or more and 500 or less.

[0035] [R a SiO 3 / 2 (I)

[0036] In formula (I), R a This indicates 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.

[0037] [R b SiO 2 / 2 (OR c (II)

[0038] In formula (II), R b R represents a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom. c [Refers to alkyl groups having 1 to 4 hydrogen atoms or carbon atoms].

[0039] Furthermore, this disclosure provides the polyorganosilsesquioxane, wherein the number average molecular weight is 1000 to 50000.

[0040] Furthermore, this disclosure provides the polyorganosilsesquioxane, wherein the molecular weight dispersion (weight-average molecular weight / number-average molecular weight) is 1.0 to 4.0.

[0041] Furthermore, this disclosure provides the polyorganosilsesquioxane, wherein a 5% weight reduction occurs at a temperature (T) d5 The temperature is above 330℃.

[0042] Furthermore, this disclosure provides a curable composition comprising the polyorganosilsesquioxane.

[0043] Furthermore, this disclosure provides the curable composition, wherein the curable composition further comprises a curing catalyst.

[0044] Furthermore, this disclosure provides the curable composition wherein the curing catalyst is a photopolymerization initiator or a thermal polymerization initiator.

[0045] Furthermore, this disclosure provides the curable composition, wherein the curable composition is a curable composition for hard coating formation.

[0046] Furthermore, the curable composition is provided, wherein the curable composition is an adhesive composition.

[0047] Furthermore, this disclosure provides a cured product, which is a cured product of the curable composition.

[0048] Furthermore, this disclosure provides a hard coating film, wherein the hard coating film is formed by laminating a substrate with a hard coating layer formed on at least one surface of the substrate, the hard coating layer being a cured product of the curable composition.

[0049] Furthermore, this disclosure provides an adhesive sheet having a substrate and an adhesive layer on the substrate, the adhesive layer being a layer of the curable composition.

[0050] Furthermore, this disclosure provides a laminate comprising three or more layers, having two bonded layers and an adhesive layer between the bonded layers, wherein the adhesive layer is a cured layer of the curable composition.

[0051] Invention Effects

[0052] The hard coating obtained as a cured product from the polyorganosilsesquioxane of this disclosure exhibits high heat resistance, characteristic of cage-like silsesquioxanes, and also possesses high surface hardness and flexibility. Therefore, by using a hard coating film containing this hard coating, molded articles (products) with high surface hardness and flexibility can be manufactured. Furthermore, the hard coating film containing the polyorganosilsesquioxane of this disclosure has excellent flexibility, thus it can be wound into rolls for processing, and the film containing this hard coating can be processed in a roll-to-roll manner, resulting in advantages in both quality and cost. Moreover, a curable composition containing the polyorganosilsesquioxane of this disclosure as an essential component can preferably be used as an adhesive composition (adhesive) capable of forming a cured product (adhesive material) with high heat resistance and excellent flexibility. By using this adhesive composition, adhesive sheets and laminates can be obtained. Attached Figure Description

[0053] Figure 1 It is the product (polyorganosilsesquioxane) obtained in Example 1. 1 H-NMR spectrum.

[0054] Figure 2 It is the product (polyorganosilsesquioxane) obtained in Example 1. 29 Si-NMR spectrum.

[0055] Figure 3 This is the HPLC-ELSD chromatogram of the product (polyorganosilsesquioxane) obtained in Example 1.

[0056] Figure 4 The results are from the mass spectrometry analysis of the extract obtained in Example 1.

[0057] Figure 5 It has the chemical formula C. 72 H 122 NO 23 Theoretical isotope map of Si9.

[0058] Figure 6 This is a schematic diagram (cross-sectional view) illustrating one embodiment of the hard coating of this disclosure.

[0059] Figure 7 This is a schematic diagram (cross-sectional view) illustrating one embodiment of the adhesive sheet of this disclosure.

[0060] Figure 8 This is a schematic diagram (cross-sectional view) illustrating one embodiment of the laminate of this disclosure. Detailed Implementation

[0061] [Polyorganosilsesquioxane]

[0062] The polyorganosilsesquioxane disclosed herein comprises a cage-like silsesquioxane (hereinafter, sometimes simply referred to as "T9") represented by the following chemical formula (1), wherein the peak area of ​​T9, when measured using a liquid chromatography-evaporative light scattering detector (LC-ELSD), 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, and even more preferably 45% or more). If the ratio is 5% or higher, the proportion of T9 in the polyorganosilsesquioxane disclosed herein increases, which can further improve the surface hardness when the cured product is formed. The peak area % of T9 is not particularly limited, but is preferably 90% or less, more preferably 80% or less.

[0063] Equation (1): [R] 1 SiO 3 / 2 ]8[R 1 SiO 2 / 2 (OR c )]1

[0064] R in chemical formula (1) 1Each of the following 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, at least one of which is a group containing a polymerizable functional group. R in chemical formula (1) c It is an alkyl group having 1 to 4 hydrogen atoms or carbon atoms.

[0065] Furthermore, the polyorganosilsesquioxanes disclosed herein are not particularly limited to cage-like silsesquioxanes (T9) represented by the above chemical formula (1) and cage-like silsesquioxanes having structural units represented by the following chemical formulas (I-2) (hereinafter, sometimes simply referred to as "T"). 10 The ratio of peak area % when measured using liquid chromatography-evaporative light scattering detector (LC-ELSD) (T9 / T) 10 Preferably, the value is 0.4 or higher, more preferably 0.5 or higher, more preferably 0.6 or higher, more preferably 0.7 or higher, more preferably 0.8 or higher, more preferably 0.9 or higher, more preferably 1 or higher, more preferably 1.2 or higher, more preferably 1.4 or higher, more preferably 1.6 or higher, more preferably 1.8 or higher, more preferably 2 or higher, more preferably 2.2 or higher, more preferably 2.4 or higher, more preferably 2.6 or higher, more preferably 2.8 or higher, more preferably 3 or higher, more preferably 3.5 or higher, more preferably 4 or higher, more preferably 4.5 or higher, and even more preferably 5 or higher. If the peak area % of T9 is 5% or higher and T9 / T 10 If the ratio of T9 to T9 is 0.4 or higher, then the proportion of T9 in the polyorganosilsesquioxane of this disclosure tends to increase, leading to a further increase in both the surface hardness and flexibility of the cured product. T9 / T 10 There are no particular limitations, but it is preferred to be 10 or less, and more preferably 9 or less.

[0066] [R a SiO 3 / 2 ] 10 (I-2)

[0067] R in the above chemical formula (I-2) a It indicates 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.

[0068] The percentage of peak area detected using the above-described liquid chromatography-evaporative light scattering detector (LC-ELSD) can be determined, for example, by the method described in the examples below.

[0069] Chemical formula (1) is composed of [R] 1 SiO3 / 2 The structural unit represented by ] and the chemical formula (I-2) consisting of [R] a SiO 3 / 2 The structural unit represented by ], and the chemical formula (3) consisting of [R] 3 SiO 3 / 2 The structural unit represented by ] is contained in the structural unit represented by the following formula (I) (hereinafter, sometimes referred to as "T3 body" in this specification).

[0070] [R a SiO 3 / 2 (I)

[0071] Furthermore, in chemical formula (1), [R] 1 SiO 2 / 2 (OR c The structural unit represented by )] is contained in the structural unit represented by the following formula (II) (hereinafter, sometimes referred to as "T2 body" in this specification).

[0072] [R b SiO 2 / 2 (OR c (II)

[0073] R in the above formula (I) a R in formula (II) b This indicates 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. Furthermore, R in formula (II) above... c It represents alkyl groups or hydrogen atoms with 1 to 4 carbon atoms.

[0074] If the structural unit represented by the above formula (I) is described in more detail, it is represented by the following formula (I'). Furthermore, if the structural unit represented by the above formula (II) is described in more detail, it is represented by the following formula (II'). The three oxygen atoms bonded to the silicon atom shown in the structure represented by the following formula (I') are bonded to other silicon atoms (silicon atoms not shown in formula (I')). On the other hand, the two oxygen atoms located above and below the silicon atom shown in the structure represented by the following formula (II') are bonded to other silicon atoms (silicon atoms not shown in formula (II')). That is, both the above-described T3 and T2 bodies are sesquioxane structural units (so-called T units) formed by the hydrolysis and condensation reactions of the corresponding hydrolytic trifunctional silane compounds.

[0075] [Chemical Formula 5]

[0076]

[0077] [Chemical Formula 6]

[0078]

[0079] R in the above formula (I') a R in equation (II') b and R c For the same group as described above. Generally, R in formula (II) is... c The alkyl group in the alkyl group is derived from the alkoxy group in the hydrolyzable silane compound that forms the raw material for the polyorganosilsesquioxanes used in this disclosure (e.g., as X in formulas (a) to (c) as described later). 1 ~X 3 Alkyl groups (such as alkoxy groups).

[0080] The cage-like silsesquioxane (T9) represented by the above chemical formula (1) is a structure with nine Si (atoms) as the center, each Si having an organic functional group (R). 1 ) and silanol group or its ester (OR c The structure of the substituent is that of a so-called incomplete cage-like silsesquioxane. The R in the above chemical formula (1) 1 The number of groups containing polymerizable functional groups is preferably 3 to 9, more preferably 5 to 9, even more preferably 7 to 9, and even more preferably 9 (all of which are groups containing polymerizable functional groups).

[0081] The cage-like silsesquioxane represented by the above chemical formula (1) consists of eight [R] 1 SiO 3 / 2 The structural unit (T3 body) represented by ] and a unit composed of [R 1 SiO 2 / 2 (OR c The structural unit (T2 body) represented by )] is a silsesquioxane with a cage-like structure formed by the bonding of the structural units (T2 body) through siloxane bonds (Si-O-Si). The specific structure of the cage-like silsesquioxane represented by the above chemical formula (1) is not particularly limited as long as it satisfies the above chemical formula (1). As a presumptive structure, for example, cage-like silsesquioxanes represented by the following formula (1') can be listed.

[0082] [Chemical Formula 7]

[0083]

[0084] R in equation (1') 1a ~R 1i Each independently of R in chemical formula (1) 1 The meanings are the same. R in equation (1') c Also related to R in chemical formula (1) c They have the same meaning.

[0085] Cage-type silsesquioxanes (T) having structural units represented by the above chemical formula (I-2) 10 It is a structure with 10 Si (atoms) as the center, and each Si atom has an organic functional group (R). a The structure of the substituent does not have a silanol group or its ester.

[0086] The cage-like silsesquioxane represented by the above chemical formula (I-2) consists of ten [R] molecules. a SiO 3 / 2 The structural unit (T3 body) represented by ] is a silsesquioxane with a cage-like structure formed by the bonding of siloxane bonds (Si-O-Si). The specific structure of the cage-like silsesquioxane represented by the above chemical formula (I-2) is not particularly limited as long as it satisfies the above chemical formula (I-2). For example, cage-like silsesquioxanes represented by the following formula can be listed as presumptive structures.

[0087] [Chemical Formula 8]

[0088]

[0089] The polyorganosilsesquioxane disclosed herein may contain the aforementioned T9 and T. 10 Other silsesquioxanes besides T9. Examples of other silsesquioxanes include, for instance, incomplete cage-like silsesquioxanes other than T9, and others besides T9. 10 In addition to the above, there are fully cage-like silsesquioxanes, ladder-like silsesquioxanes, random silsesquioxanes, etc.

[0090] The term "cationic polymerizable functional group" in the above-mentioned groups containing polymerizable functional groups is not particularly limited as long as it has cationic polymerizability. Examples include epoxy groups, oxetane groups, vinyl ether groups, vinyl phenyl groups, etc.

[0091] As for the "free radical polymerizable functional group" among the aforementioned groups containing polymerizable functional groups, there are no particular limitations as long as it has free radical polymerizability. Examples include (meth)acryloyloxy, (meth)acrylamide, vinyl, vinyl thio, etc.

[0092] From the viewpoint of surface hardness of the cured product (e.g., 5H or higher), epoxy groups, (meth)acryloyloxy groups, etc., are preferred as polymerizable functional groups, and epoxy groups are even more preferred.

[0093] Furthermore, in the aforementioned T9, the group containing polymerizable functional groups is relative to R. 1The overall proportion (based on the number of groups containing polymeric functional groups) is, for example, 30% or more, preferably 50% or more, and more preferably 80% or more. From the viewpoint of curability when the curable composition is prepared and surface hardness of the cured product, a higher of the above proportion is preferable, and preferably the above value or above.

[0094] As R in the above chemical formula (1) 1 R in chemical formula (I-2) a R in the above formula (I) a And R in equation (II) above b The group containing polymerizable functional groups is not particularly limited, and known or conventional groups having an ethylene oxide ring can be listed. From the viewpoint of curability of the curable composition, surface hardness of the cured product and heat resistance, the group represented by formula (1a), formula (1b), formula (1c) and formula (1d) are preferred, more preferably the group represented by formula (1a) and formula (1c), and even more preferably the group represented by formula (1a).

[0095] [Chemical Formula 9]

[0096]

[0097] [Chemical Formula 10]

[0098]

[0099] [Chemical Formula 11]

[0100]

[0101] [Chemical Formula 12]

[0102]

[0103] In equation (1a) above, R 1a This refers to straight-chain or branched alkylene groups. Examples of straight-chain or branched alkylene groups include: methylene, methylmethylene, dimethylmethylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decamethylene, and other straight-chain or branched alkylene groups with 1 to 10 carbon atoms. Among these, R... 1a From the viewpoint of surface hardness and curability of the cured product, it is preferable to use straight-chain alkylene compounds with 1 to 4 carbon atoms or branched alkylene compounds with 3 or 4 carbon atoms, more preferably ethylene, trimethylene, or propylene, and even more preferably ethylene or trimethylene.

[0104] In equation (1b) above, R1b This refers to straight-chain or branched alkylene groups, exemplified by R. 1a The same group. Wherein, as R... 1b From the viewpoint of surface hardness and curability of the cured product, it is preferable to use straight-chain alkylene compounds with 1 to 4 carbon atoms or branched alkylene compounds with 3 or 4 carbon atoms, more preferably ethylene, trimethylene, or propylene, and even more preferably ethylene or trimethylene.

[0105] In equation (1c) above, R 1c This refers to straight-chain or branched alkylene groups, exemplified by R. 1a The same group. Wherein, as R... 1c From the viewpoint of surface hardness and curability of the cured product, it is preferable to use straight-chain alkylene compounds with 1 to 4 carbon atoms or branched alkylene compounds with 3 or 4 carbon atoms, more preferably ethylene, trimethylene, or propylene, and even more preferably ethylene or trimethylene.

[0106] In the above equation (1d), R 1d This refers to straight-chain or branched alkylene groups, exemplified by R. 1a The same group. Wherein, as R... 1d From the viewpoint of surface hardness and curability of the cured product, it is preferable to use straight-chain alkylene compounds with 1 to 4 carbon atoms or branched alkylene compounds with 3 or 4 carbon atoms, more preferably ethylene, trimethylene, or propylene, and even more preferably ethylene or trimethylene.

[0107] As the group containing the polymerizable functional group mentioned above, it is preferably a group represented by the above formula (1a), R. 1a The group is an ethylene group [wherein it is 2-(3',4'-epoxycyclohexyl)ethyl].

[0108] As R in the above chemical formula (1) 1 R in chemical formula (I-2) a R in the above formula (I) a And R in equation (II) above b Aryl groups in substituted or unsubstituted aryl groups, such as phenyl, tolyl, naphthyl, etc.

[0109] As R in the above chemical formula (1) 1 R in chemical formula (I-2) a R in the above formula (I) a And R in equation (II) above b Aryl groups, whether substituted or unsubstituted, include, for example, benzyl, phenethyl, etc.

[0110] As R in the above chemical formula (1) 1 R in chemical formula (I-2) a R in the above formula (I) a And R in equation (II) above b The substituted or unsubstituted cycloalkyl group in the cycloalkyl group can be exemplified by cyclobutyl, cyclopentyl, cyclohexyl, etc.

[0111] As R in the above chemical formula (1) 1 R in chemical formula (I-2) a R in the above formula (I) a And R in equation (II) above b The alkyl group in the substituted or unsubstituted alkyl group can be exemplified by straight-chain or branched alkyl groups such as methyl, ethyl, propyl, n-butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, and isopentyl.

[0112] As R in the above chemical formula (1) 1 R in chemical formula (I-2) a R in the above formula (I) a And R in equation (II) above b The substituted or unsubstituted alkenyl group in the group, such as vinyl, allyl, isopropenyl and other straight-chain or branched alkenyl groups.

[0113] R in the above chemical formula (1) and above formula (II) c Alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, etc., which are straight-chain or branched alkyl groups having 1 to 4 carbon atoms.

[0114] The polyorganosilsesquioxane disclosed herein may contain the aforementioned T9, T8, and T 10 Other silsesquioxanes contain all of the components typically composed of [RSiO 3 / 2 The ] represents the silsesquioxane structural unit (the so-called T unit). It should be noted that R in the above formula represents a monovalent organic group, and the same applies below. The silsesquioxane structural unit can be formed by the hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound (specifically, for example, the compound represented by formulas (a) to (c) described below).

[0115] In the polyorganosilsesquioxane disclosed herein, the molar ratio of the structural unit (T3 body) represented by formula (I) above to the structural unit (T2 body) represented by formula (II) above [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. It should be noted that T9 is composed of eight T3 bodies and one T2 body, T... 10 It is composed of ten T3 bodies. The T3 and T2 bodies in the disclosed polyorganosilsesquioxane respectively contain components constituting T9 and T... 10 The T3 and T2 forms, as well as the T3 and T2 forms of all sesquioxanes that constitute them.

[0116] The lower limit of the above-mentioned ratio [T3 body / T2 body] is 1, preferably 2, more preferably 3, more preferably 4, more preferably 5, more preferably 6, more preferably 7, more preferably 8, even more preferably 9, and even more preferably 10. By making the above-mentioned ratio [T3 body / T2 body] 1 or more, the surface hardness and adhesion of the cured product and the hard coating are significantly improved. On the other hand, the upper limit of the above-mentioned ratio [T3 body / T2 body] is 500, preferably 100, more preferably 50, more preferably 40, more preferably 30, more preferably 25, more preferably 20, more preferably 18, and even more preferably 16. By making the above-mentioned ratio [T3 body / T2 body] 500 or less, the compatibility of the curable composition with other components is improved, the viscosity is also suppressed, and therefore processing becomes easier, and it is easier to apply as a hard coating.

[0117] The disclosed polyorganosilsesquioxane, in addition to possessing the aforementioned silsesquioxane structural unit [RSiO], also exhibits... 3 / 2 In addition to the (T unit), it can also have the option to select [(R)3SiO] 1 / 2 The structural unit represented by ] (the so-called M-unit), [(R)2SiO 2 / 2 The structural unit represented by ] (the so-called D unit) and [SiO] 4 / 2 The structural unit represented by ] is at least one siloxane structural unit in the group consisting of the so-called Q unit.

[0118] The above-mentioned ratio [T3 body / T2 body] in the polyorganosilsesquioxanes disclosed herein can be, for example, by... 29 The result is determined by Si-NMR spectroscopy. 29 In Si-NMR spectra, silicon atoms in the structural unit (T3 body) represented by formula (I) and silicon atoms in the structural unit (T2 body) represented by formula (II) exhibit signals (peaks) at different positions (chemical shifts). Therefore, the ratio [T3 body / T2 body] can be determined by calculating the integral ratio of these individual peaks. In the polyorganosilsesquioxane disclosed herein, Ra The signal for silicon atoms in the structure (T3 body) of 2-(3',4'-epoxycyclohexyl)ethyl represented by formula (I) above appears in the range of -64 to -70 ppm. b The signal of silicon atoms in the structure (T2 body) represented by the above formula (II) for 2-(3',4'-epoxycyclohexyl)ethyl appears at -54 to -60 ppm. Therefore, in this case, the above ratio [T3 body / T2 body] can be obtained by calculating the integral ratio of the signal (T3 body) at -64 to -70 ppm to the signal (T2 body) at -54 to -60 ppm.

[0119] The disclosed polyorganosilsesquioxane 29 Si-NMR spectra can be measured, for example, using the following apparatus and conditions.

[0120] Measurement device: Trade name "Brucker AVANCE (600MHz)" (Brucker).

[0121] Solvent: deuterated chloroform.

[0122] Total number of times: 8000.

[0123] Measurement temperature: 25℃.

[0124] Sample: Polyorganosilsesquioxane / Chromium acetylacetone (III) / Deuterated chloroform (1% tetramethylsilane) = 2.0:0.10:4.0 (weight ratio).

[0125] The aforementioned ratio [T3 body / T2 body] of the polyorganosilsesquioxane disclosed herein being 1 or more means that the amount of T2 body present in the polyorganosilsesquioxane disclosed herein is equal to or relatively less than that of T3 body, and the hydrolysis / condensation reaction of silanol has been carried out.

[0126] The number-average molecular weight (Mn) of the polyorganosilsesquioxane disclosed herein, obtained by gel permeation chromatography from standard polystyrene, is, for example, 1000 to 50000, preferably 1100 to 40000, and more preferably 1200 to 30000. By setting the number-average molecular weight above the lower limit, the heat resistance, scratch resistance, and adhesion of the cured product are further improved. On the other hand, by setting the number-average molecular weight below the upper limit, the compatibility of the cured composition with other components is improved, and the heat resistance of the cured product is further improved.

[0127] The molecular weight dispersion (Mw / Mn) of the polyorganosilsesquioxane disclosed herein, obtained by gel permeation chromatography from standard polystyrene, is, for example, 1.0 to 4.0, preferably 1.1 to 3.0, and more preferably 1.2 to 2.5. By making the molecular weight dispersion 4.0 or less, the surface hardness and adhesion of the cured product are further improved. On the other hand, by making the molecular weight dispersion 1.0 or more, there is a tendency for it to easily become liquid and for workability to be improved.

[0128] It should be noted that the number-average molecular weight and molecular weight dispersion of the polyorganosilsesquioxanes disclosed herein can be determined using the following apparatus and conditions.

[0129] Measuring device: Trade name "LC-20AD" (manufactured by Shimadzu Corporation).

[0130] Chromatographic columns: two Shodex KF-801 columns, KF-802 columns, and KF-803 columns (manufactured by Showa Denko Co., Ltd.).

[0131] Measurement temperature: 40℃.

[0132] Eluent: THF, sample concentration 0.1–0.2% by weight.

[0133] Flow rate: 1 mL / min.

[0134] Detector: RI detector (manufactured by Shoko Science Co., Ltd.).

[0135] Molecular weight: converted from standard polystyrene.

[0136] The disclosed polyorganosilsesquioxane exhibits a 5% weight loss at an air atmosphere at the temperature (T). d5 There is no particular limitation, but it is preferably 330°C or higher (e.g., 330–450°C), more preferably 340°C or higher, and even more preferably 350°C or higher. By setting the temperature for a 5% weight loss to 330°C or higher, there is a tendency to further improve the heat resistance of the cured product. For the polyorganosilsesquioxane disclosed herein, the above-mentioned ratio [T3 body / T2 body] is 1 or higher and 500 or lower, the number average molecular weight is 1000–50000, the molecular weight dispersion is 1.0–4.0, and the temperature for a 5% weight loss is 330°C or higher. It should be noted that the 5% weight loss temperature is the temperature at which 5% of the weight before heating is reduced when heated at a fixed heating rate, and is an indicator of heat resistance. The above-mentioned 5% weight loss temperature can be determined by TGA (thermogravimetric analysis) in an air atmosphere at a heating rate of 5°C / min.

[0137] The polyorganosilsesquioxane disclosed herein can be manufactured by known or conventional methods for manufacturing polysiloxanes, without particular limitation. For example, it can be manufactured by hydrolyzing and condensing one or more hydrolyzable silane compounds. Wherein, as the aforementioned hydrolyzable silane compound, the hydrolyzable trifunctional silane compound used to form the structural unit T9 described above, i.e., the compound represented by the following formula (a), is required as the hydrolyzable silane compound.

[0138] More specifically, for example, the polyorganosilsesquioxane of the present disclosure can be manufactured by a method of hydrolytic silane compound representing the silsesquioxane structural unit (T unit) in forming the polyorganosilsesquioxane of the present disclosure, namely the compound represented by formula (a) below, and, as needed, the compound represented by formula (b) below, and the compound represented by formula (c) below, through hydrolysis and condensation.

[0139] [Chemical Formula 13]

[0140] R A Si(X 1 )3 (a)

[0141] [Chemical Formula 14]

[0142] R B Si(X 2 )3 (b)

[0143] [Chemical Formula 15]

[0144] HSi(X 3 )3 (c)

[0145] The compound represented by formula (a) above is a necessary compound for forming the T9 structural unit in the polyorganosilsesquioxane of this disclosure, i.e., R in formula (a) A It is a group containing polymerizable functional groups. As R in formula (a) A Preferably, it is a group represented by formula (1a), a group represented by formula (1b), a group represented by formula (1c), or a group represented by formula (1d). More preferably, it is a group represented by formula (1a) or a group represented by formula (1c). Even more preferably, it is a group represented by formula (1a). Furthermore, it is a group represented by formula (1a) and R 1a The group is an ethylene group [wherein it is 2-(3',4'-epoxycyclohexyl)ethyl].

[0146] X in equation (a) above 1 This represents an alkoxy or halogen atom. As X... 1Alkoxy groups, for example, include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, and other alkoxy groups with 1 to 4 carbon atoms. Furthermore, as X... 1 Halogen atoms in the form of halogen atoms include, for example, fluorine, chlorine, bromine, and iodine atoms. Among them, X... 1 Preferably, it is alkoxy, and more preferably methoxy or ethoxy. It should be noted that the three X's... 1 They can be the same or different.

[0147] The compound represented by formula (b) above is a compound that forms the T9 structural unit in the polyorganosilsesquioxane of this disclosure. R in formula (b) B This indicates 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) B Preferably, it is a substituted or unsubstituted aryl, substituted or unsubstituted alkyl, or substituted or unsubstituted alkenyl group, more preferably a substituted or unsubstituted aryl group, and even more preferably a phenyl group.

[0148] X in equation (b) above 2 This represents an alkoxy or halogen atom. As X... 2 Specific examples can be listed as X 1 The example shown is where X is... 2 Preferably, it is alkoxy, and more preferably methoxy or ethoxy. It should be noted that the three X's... 2 They can be the same or different.

[0149] The compound represented by formula (c) above is the [HSiO] that forms T9 in the polyorganosilsesquioxane of this disclosure. 3 / 2 Compounds whose structural unit is represented by ] . X in formula (c) above 3 This represents an alkoxy or halogen atom. As X... 3 Specific examples can be listed as X 1 The example shown is where X is... 3 Preferably, it is alkoxy, and more preferably methoxy or ethoxy. It should be noted that the three X's... 3 They can be the same or different.

[0150] The compounds represented by formulas (a) to (c) above, in addition to forming the structural unit T9, are also other silsesquioxanes that can be contained in the formation of the polyorganosilsesquioxanes of this disclosure (e.g., incomplete cage-like silsesquioxanes other than T9, T...). 10 Raw material compounds consisting of structural units such as complete cage-like silsesquioxanes, ladder-like silsesquioxanes, and random silsesquioxanes.

[0151] As the aforementioned hydrolyzable silane compounds, hydrolyzable silane compounds other than those represented by formulas (a) to (c) above can be used. Examples include hydrolyzable trifunctional silane compounds other than those represented by formulas (a) to (c) above, hydrolyzable monofunctional silane compounds forming M units, hydrolyzable difunctional silane compounds forming D units, and hydrolyzable tetrafunctional silane compounds forming Q units.

[0152] The amount and composition of the above-mentioned hydrolyzable silane compound can be appropriately adjusted according to the desired structure of the polyorganosilsesquioxane of this disclosure. For example, the amount of the compound represented by the above formula (a) is not particularly limited, but is preferably 30 to 100 mol%, preferably 55 to 100 mol%, more preferably 65 to 100 mol%, and even more preferably 80 to 99 mol%, relative to the total amount (100 mol%) of the hydrolyzable silane compound used.

[0153] Furthermore, the amount of the compound represented by formula (b) above is not particularly limited, but is preferably 0 to 70 mol% relative to the total amount (100 mol%) of the hydrolyzable silane compound used, more preferably 0 to 60 mol%, even more preferably 0 to 40 mol%, and particularly preferably 1 to 15 mol%.

[0154] Furthermore, the ratio (total percentage) of the compound represented by formula (a) and the compound represented by formula (b) relative to the total amount (100 mol%) of the hydrolyzable silane compound used is not particularly limited, but is preferably 60 to 100 mol%, more preferably 70 to 100 mol%, and even more preferably 80 to 100 mol%.

[0155] Furthermore, when two or more of the above-mentioned hydrolyzable silane compounds are used together, the hydrolysis and condensation reactions of these hydrolyzable silane compounds can occur simultaneously or sequentially. When the reactions are carried out sequentially, the order of the reactions is not particularly limited.

[0156] As for the reaction conditions for carrying out the hydrolysis and condensation reactions of the above-mentioned hydrolyzable silane compounds, it is important to select reaction conditions such that the peak area % of T9 in the polyorganosilsesquioxane of this disclosure is 5% or more.

[0157] Hydrolysis and condensation reactions can be carried out in the presence or absence of a solvent. Preferably, they are carried out in the presence of a solvent. Examples of such solvents include: aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran, and dioxane; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, isopropyl acetate, and butyl acetate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; nitriles such as acetonitrile, propionitrile, and benzonitrile; and alcohols such as methanol, ethanol, isopropanol, and butanol. From the viewpoint of easily controlling the peak area % of T9 to 5% or more, ketones, ethers, amides, and alcohols are preferred as solvents; methyl isobutyl ketone, acetone, tetrahydrofuran, N,N-dimethylacetamide, and isopropanol are more preferred; and methyl isobutyl ketone and tetrahydrofuran are even more preferred. It should be noted that a single solvent or a combination of two or more solvents can be used.

[0158] The amount of solvent used in the hydrolysis and condensation reactions is not particularly limited. It can be in the range of 0 to 2000 parts by weight relative to the total amount of hydrolyzable silane compound (100 parts by weight), and can be appropriately adjusted according to the desired reaction time, the type of solvent used, etc. However, from the viewpoint that it is easy to control the peak area % of T9 to more than 5%, it is preferably 200 to 1500 parts by weight, and more preferably 300 to 1000 parts by weight.

[0159] Hydrolysis and condensation reactions are preferably carried out in the presence of a catalyst and water. The catalyst can be either an acid catalyst or a base catalyst, but a base catalyst is preferred to suppress the decomposition of polymerizable functional groups such as epoxy groups. Examples of acid catalysts include: inorganic 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 ferric chloride. Examples of base catalysts 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; bicarbonates of alkali metals such as lithium bicarbonate, sodium bicarbonate, sodium bicarbonate, potassium bicarbonate, and cesium bicarbonate; and organic acid salts of alkali metals such as lithium acetate, sodium acetate, potassium acetate, and cesium acetate (e.g., Acetates; organic acid salts of alkaline earth metals such as magnesium acetate (e.g., acetates); alkali metal alkoxides such as lithium methoxide, sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium ethoxide, potassium tert-butoxide; alkali metal phenolates such as sodium phenolate; amines (tertiary amines, etc.) such as triethylamine, N-methylpiperidine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene; nitrogen-containing aromatic heterocyclic compounds such as pyridine, 2,2'-bipyridine, 1,10-phenanthroline, etc. From the viewpoint that it is easy to control the peak area % of T9 to 5% or more, alkali metal carbonates, alkali metal hydroxides, and amines are preferred, more preferably alkali metal carbonates, and even more preferably potassium carbonate. It should be noted that a single catalyst or a combination of two or more catalysts can be used. In addition, the catalyst can also be used in a state in which it is dissolved or dispersed in water, solvent, etc.

[0160] The amount of the catalyst used in the hydrolysis and condensation reactions is not particularly limited. It can be appropriately adjusted in the range of 0.000001 to 0.200 moles relative to the total amount of hydrolyzable silane compound (1 mole). However, from the viewpoint that it is easy to control the peak area % of T9 to 5% or more, it is preferably 0.00001 to 0.10 moles, and more preferably 0.0001 to 0.05 moles.

[0161] The amount of water used in the hydrolysis and condensation reactions is not particularly limited. It can be appropriately adjusted in the range of 0.5 to 20 moles relative to the total amount of hydrolyzable silane compound (1 mole). However, considering that it is easy to control the peak area % of T9 above to 5% or more, it is preferred to be 1 to 15 moles, and more preferably 2 to 10 moles.

[0162] There are no particular limitations on the method of adding water in the hydrolysis and condensation reactions. The total amount of water used can be added all at once or added gradually. When adding water gradually, it can be added continuously or intermittently.

[0163] The reaction temperature for the hydrolysis and condensation reactions is not particularly limited, but from the viewpoint of easily controlling the peak area % of T9 to 5% or more, 20–100°C is preferred, more preferably 45–80°C, further preferably 30–80°C, and even more preferably 40–70°C. The reaction time for the hydrolysis and condensation reactions is not particularly limited, but is preferably 0.1–10 hours, more preferably 1.5–8 hours. Furthermore, the hydrolysis and condensation reactions can be carried out under normal pressure, or under pressure or reduced pressure. It should be noted that the atmosphere for carrying out the hydrolysis and condensation reactions is not particularly limited; for example, it can be any atmosphere containing nitrogen, an inert gas such as argon, or oxygen such as air, but an inert gas atmosphere is preferred.

[0164] Polyorganosilsesquioxanes can be obtained through the above-described hydrolysis and condensation reactions. After the hydrolysis and condensation reactions are completed, it is preferable to neutralize the catalyst to suppress the decomposition of polymeric functional groups such as ring-opening of the epoxy groups. Furthermore, the obtained polyorganosilsesquioxanes can be separated and purified by methods such as water washing, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or combinations thereof.

[0165] The polyorganosilsesquioxane disclosed herein contains a large amount of cage-like silsesquioxanes (T9) represented by the above chemical formula (1), and therefore tends to have a higher (number average) molecular weight and a more flexible structure compared to conventional polyorganosilsesquioxanes. Furthermore, it is believed that if the proportion of T9 in the polyorganosilsesquioxane of this disclosure increases, it will become the Si-OR structure possessed by T9. c Further, compared with other Si-ORs such as T9 c Condensation, or with other T9, T8, T 10 The crosslinking points of the polymerizable functional groups in the composition increase the crosslinking density. Therefore, cured compositions containing the polyorganosilsesquioxanes of this disclosure exhibit high surface hardness, excellent heat resistance, flexibility, and processability. However, these mechanisms are merely presumptions, and this disclosure should not be construed as limiting itself to these mechanisms.

[0166] [Curing composition]

[0167] The curable composition disclosed herein is a curable composition (curable resin composition) comprising the aforementioned polyorganosilsesquioxane as an essential component. As described below, the curable composition of this disclosure may also contain other components such as a curing catalyst (preferably a photocationic polymerization initiator), a surface modifier, or a surface conditioner. In the curable composition of this disclosure, the polyorganosilsesquioxane may be used alone or in combination of two or more.

[0168] The content (composition amount) of the disclosed polyorganosilsesquioxane in the curable composition is not particularly limited, but is preferably 70% by weight or more and less than 100% by weight relative to the total amount (100% by weight) of the curable composition excluding the solvent, more preferably 80 to 99.8% by weight, and even more preferably 90 to 99.5% by weight. By making the content of the disclosed polyorganosilsesquioxane 70% by weight or more, there is a tendency to further increase the hardness of the cured product. On the other hand, by making the content of the disclosed polyorganosilsesquioxane less than 100% by weight, it can contain a curing catalyst, thereby having a tendency to cure the curable composition more effectively.

[0169] The content of the polyorganosilsesquioxane disclosed herein is preferably 70 to 100% by weight relative to the total amount (100% by weight) of the cationic curable compound contained in the curable composition of the present invention, more preferably 75 to 98% by weight, and even more preferably 80 to 95% by weight. By making the content of the polyorganosilsesquioxane disclosed herein 70% by weight or more, there is a tendency to further improve the surface hardness and adhesion of the cured product.

[0170] Preferably, the curable composition of this disclosure further comprises a curing catalyst. From the viewpoint of further shortening the curing time until it becomes non-sticky, it is preferable to include a photopolymerization initiator as a curing catalyst, and more preferably, a cationic polymerization initiator as a curing catalyst. In the curable composition of this disclosure, a single curing catalyst may be used, or two or more may be used in combination.

[0171] The aforementioned cationic polymerization initiator is a compound capable of initiating or even promoting the cationic polymerization reaction of cationic curable compounds such as polyorganosilsesquioxanes disclosed herein. There are no particular limitations on the aforementioned cationic polymerization initiator; examples include photocationic polymerization initiators (photoacid generators) and thermal cationic polymerization initiators (thermal acid generators).

[0172] As the aforementioned photocationic polymerization initiators, known or commonly used photocationic polymerization initiators can be used, such as: sulfonium salts (salts formed by sulfonium ions and anions), iodonium salts (salts formed by iodonium ions and anions), selenium salts (salts formed by selenium ions and anions), ammonium salts (salts formed by ammonium ions and anions), phosphonium salts (salts formed by phosphonium ions and anions), salts formed by transition metal complex ions and anions, etc. They can be used alone or in combination of two or more.

[0173] Examples of the aforementioned sulfonium salts include: [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium tris(pentafluoroethyl)trifluorophosphate, triphenylsulfonium salt, tri-p-tolylsulfonium salt, tri-o-tolylsulfonium salt, tris(4-methoxyphenyl)sulfonium salt, 1-naphthyldiphenylsulfonium salt, 2-naphthyldiphenylsulfonium salt, tris(4-fluorophenyl)sulfonium salt, tri-1-naphthylsulfonium salt, tri-2-naphthylsulfonium salt, tris(4-hydroxyphenyl)sulfonium salt, and diphenyl[4-(phenylthio)phenyl] Triaryl sulfonium salts such as 4-(p-toluenethio)phenyl di-(p-phenyl)sulfonium salt; diaryl sulfonium salts such as diphenylbenzoylmethyl sulfonium salt, diphenyl-4-nitrobenzoylmethyl sulfonium salt, diphenylbenzyl sulfonium salt, and diphenylmethyl sulfonium salt; monoaryl sulfonium salts such as phenylmethylbenzyl sulfonium salt, 4-hydroxyphenylmethylbenzyl sulfonium salt, and 4-methoxyphenylmethylbenzyl sulfonium salt; and trialkyl sulfonium salts such as dimethylbenzoylmethyl sulfonium salt, benzoylmethyltetrahydrothiophenonium salt, and dimethylbenzyl sulfonium salt.

[0174] As the above-mentioned diphenyl[4-(phenylthio)phenyl]sulfonium salt, for example, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluoroantimonate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, etc. can be used.

[0175] Examples of the aforementioned iodonium salts include: "UV9380C" (manufactured by Momentive Performance Materials Japan Co., Ltd., bis(4-dodecylphenyl)iodonium = hexafluoroantimonate 45% alkyl glycidyl ether solution), "RHODORSIL PHOTOINITIATOR 2074" (manufactured by Rhodia Japan Co., Ltd., tetra(pentafluorophenyl)borate = [(1-methylethyl)phenyl](methylphenyl)iodonium), "WPI-124" (manufactured by Wako Pure Chemical Industries Co., Ltd.), diphenyliodonium salt, di-p-tolyliodonium salt, bis(4-dodecylphenyl)iodonium salt, bis(4-methoxyphenyl)iodonium salt, etc.

[0176] Examples of the aforementioned selenium salts include: triphenylseleno ...

[0177] Examples of the aforementioned ammonium salts include: tetramethylammonium salt, ethyltrimethylammonium salt, diethyldimethylammonium salt, triethylmethylammonium salt, tetraethylammonium salt, trimethyl-n-propylammonium salt, trimethyl-n-butylammonium salt, and other tetraalkylammonium salts; pyrrolomonium salts such as N,N-dimethylpyrrolomonium salt and N-ethyl-N-methylpyrrolomonium salt; imidazolinemonium salts such as N,N'-dimethylimidazolinemonium salt and N,N'-diethylimidazolinemonium salt; and N,N'-dimethyltetrahydropyrimidinemonium salt and N,N'-diethyltetrahydropyrimidinemonium salt. Tetrahydropyrimidine onion salts such as pyridinium salts; morpholine onion salts such as N,N-dimethylmorpholine onion salt and N,N-diethylmorpholine onion salt; piperidine onion salts such as N,N-dimethylpiperidine onion salt and N,N-diethylpiperidine onion salt; pyridine onion salts such as N-methylpyridinium onion salt and N-ethylpyridinium onion salt; imidazole onion salts such as N,N'-dimethylimidazolium onion salt; quinoline onion salts such as N-methylquinoline onion salt; isoquinoline onion salts such as N-methylisoquinoline onion salt; thiazolium onion salts such as benzylbenzothiazolium onion salt; acridine onion salts such as benzyl acridine onion salt, etc.

[0178] Examples of the aforementioned phosphonium salts include: tetraphenylphosphonium salt, tetra-p-tolylphosphonium salt, tetra(2-methoxyphenyl)phosphonium salt, and other tetraarylphosphonium salts; triphenylbenzylphosphonium salt, and other triarylphosphonium salts; and tetraalkylphosphonium salts such as triethylbenzylphosphonium salt, tributylbenzylphosphonium salt, tetraethylphosphonium salt, tetrabutylphosphonium salt, and triethylbenzoylmethylphosphonium salt.

[0179] Salts of the aforementioned transition metal complex ions include, for example, (η5-cyclopentadienyl)(η6-toluene)Cr. + (η5-cyclopentadienyl)(η6-xylene)Cr + Salts of chromium complex cations; (η5-cyclopentadienyl)(η6-toluene)Fe + (η5-cyclopentadienyl)(η6-xylene)Fe + Salts of iron complex cations, etc.

[0180] Examples of anions that constitute the salts described above include: SbF. 6- PF 6- BF 4- (CF3CF2)3PF3 - (CF3CF2CF2)3PF3 - (C6F5)4B- (C6F5)4Ga - Sulfonate anions (trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, nonafluorobutanesulfonate anion, methanesulfonate anion, benzenesulfonate anion, p-toluenesulfonate anion, etc.), (CF3SO2)3C - (CF3SO2)2N - Perhalide ions, halosulfonic acid ions, sulfate ions, carbonate ions, aluminate ions, hexafluorobismuthate ions, carboxylate ions, arylborate ions, thiocyanate ions, nitrate ions, etc.

[0181] Examples of initiators for the aforementioned thermo-cationic polymerization include: aryl sulfonium salts, aryl iodonium salts, propadiene-ion complexes, quaternary ammonium salts, aluminum chelates, and boron trifluoride amine complexes.

[0182] Examples of the aforementioned arylsulfonate salts include hexafluoroantimonate. In the curable compositions disclosed herein, commercially available products such as "SP-66" and "SP-77" (manufactured by ADEKA Co., Ltd.) and "San-Aid SI-60L," "San-Aid SI-80L," "San-Aid SI-100L," and "San-Aid SI-150L" (manufactured by Sanshin Chemical Industry Co., Ltd.) can be used. Examples of the aforementioned aluminum chelates include ethylaluminum diisopropyl acetoacetate and tris(ethylacetoacetyl)aluminum. Furthermore, examples of the aforementioned boron trifluoride amine complexes include boron trifluoride monoethylamine complex, boron trifluoride imidazole complex, and boron trifluoride piperidine complex.

[0183] The content (combination amount) of the curing catalyst in the curable composition disclosed herein is not particularly limited. It is preferably 0.01 to 3.0 parts by weight, more preferably 0.05 to 3.0 parts by weight, and even more preferably 0.1 to 1.0 parts by weight (e.g., 0.3 to 1.0 parts by weight) relative to 100 parts by weight of the total amount of the polyorganosilsesquioxane of this disclosure and the other cationic curable compounds described later. By making the content of the curing catalyst 0.01 parts by weight or more, the curing reaction can be effectively and sufficiently carried out, and there is a tendency to further improve the surface hardness and adhesion of the cured product. On the other hand, by making the content of the curing catalyst 3.0 parts by weight or less, there is a tendency to further improve the shelf life of the curable composition or to suppress the coloring of the cured product.

[0184] The curable compositions disclosed herein may also contain cationic curable compounds other than the polyorganosilsesquioxanes disclosed herein (sometimes referred to as "other cationic curable compounds"). As other cationic curable compounds, known or conventional cationic curable compounds may be used, including epoxy compounds, oxetane compounds, vinyl ether compounds, etc., other than the polyorganosilsesquioxanes disclosed herein. It should be noted that in the curable compositions disclosed herein, one or more other cationic curable compounds may be used alone or in combination.

[0185] As the aforementioned epoxy compound, any known or conventional compound having one or more epoxy groups (ethylene oxide rings) within its molecule can be used, without particular limitation. Examples include: alicyclic epoxy compounds (alicyclic epoxy resins), aromatic epoxy compounds (aromatic epoxy resins), and aliphatic epoxy compounds (aliphatic epoxy resins).

[0186] As for the aforementioned alicyclic epoxides, examples include well-known or conventional compounds having one or more alicyclic rings and one or more epoxy groups within the molecule, without particular limitation. Examples include: compounds having an epoxy group (called "alicyclic epoxy group") composed of two adjacent carbon atoms and an oxygen atom constituting the alicyclic ring; compounds where the epoxy group is directly bonded to the alicyclic ring by a single bond; and compounds having an alicyclic ring and a glycidyl ether group within the molecule (glycidyl ether type epoxides), etc.

[0187] Examples of compounds having alicyclic epoxy groups include those represented by formula (i).

[0188] [Chemical Formula 16]

[0189]

[0190] In formula (i) above, Y represents a single bond or a linking group (a divalent group having one or more atoms). Examples of such linking groups include: divalent hydrocarbon groups, alkenyl groups formed by partial or complete epoxidation of carbon-carbon double bonds, carbonyl groups, ether bonds, ester bonds, carbonate groups, amide groups, and groups formed by multiple linkages of these groups.

[0191] Examples of divalent hydrocarbon groups include straight-chain or branched alkylene groups with 1 to 18 carbon atoms, and divalent alicyclic hydrocarbon groups. Examples of straight-chain or branched alkylene groups with 1 to 18 carbon atoms include methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene. Examples of divalent alicyclic hydrocarbon groups include 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, and divalent cyclohexylene (including cycloalkylene groups).

[0192] Examples of alkenyl groups formed by epoxidation of part or all of the carbon-carbon double bonds (sometimes called "epoxidized alkenyl groups") include: vinylidene, propenide, 1-butenide, 2-butenide, butadiene, pentenide, hexenide, heptenide, octene, and other straight-chain or branched alkenyl groups with 2 to 8 carbon atoms. Among these epoxidized alkenyl groups, alkenyl groups formed by epoxidation of all carbon-carbon double bonds are preferred, and alkenyl groups with 2 to 4 carbon atoms formed by epoxidation of all carbon-carbon double bonds are more preferred.

[0193] Representative examples of alicyclic epoxy compounds represented by formula (i) above include (3,4,3',4'-diepoxy)bicyclohexyl and compounds represented by formulas (i-1) to (i-10) below. It should be noted that in formulas (i-5) and (i-7) below, l and m represent integers from 1 to 30. In formula (i-5) below, R' is an alkylene group having 1 to 8 carbon atoms, preferably a straight-chain or branched alkylene group having 1 to 3 carbon atoms, such as methylene, ethylene, propylene, or isopropylene. In formulas (i-9) and (i-10) below, n1 to n6 represent integers from 1 to 30. In addition, other examples of alicyclic epoxy compounds represented by the above formula (i) include: 2,2-bis(3,4-epoxycyclohexyl)propane, 1,2-bis(3,4-epoxycyclohexyl)ethane, 2,3-bis(3,4-epoxycyclohexyl)ethylene oxide, bis(3,4-epoxycyclohexylmethyl) ether, etc.

[0194] [Chemical Formula 17]

[0195]

[0196] [Chemical Formula 18]

[0197]

[0198] Compounds in which the aforementioned epoxy group is directly bonded to an alicyclic ring by a single bond include, for example, compounds represented by the following formula (ii).

[0199] [Chemical Formula 19]

[0200]

[0201] In formula (ii), R” is a group (a p-valent organic group) obtained by removing p hydroxyl groups (-OH) from the structural formula of a p-hydronic alcohol, where p and n represent natural numbers. As a p-hydronic alcohol [R””OH] p Examples of compounds represented by formula (ii) include polyols such as 2,2-bis(hydroxymethyl)-1-butanol (alcohols with 1 to 15 carbon atoms). p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or more, n in the groups within the parentheses (outer) of each compound may be the same or different. Specifically, examples of compounds represented by formula (ii) include 1,2-epoxy-4-(2-epoxyethylene)cyclohexane adducts of 2,2-bis(hydroxymethyl)-1-butanol [e.g., trade name "EHPE3150" (manufactured by DAICL Co., Ltd.)].

[0202] Examples of compounds containing both alicyclic and glycidyl ether groups within their molecules include glycidyl ethers of alicyclic alcohols (preferably alicyclic polyols). 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 biphenol type epoxy compounds, hydrogenated phenol phenolic varnish type epoxy compounds, hydrogenated cresol phenolic varnish type epoxy compounds, hydrogenated cresol phenolic varnish type epoxy compounds of bisphenol A, hydrogenated naphthalene type epoxy compounds, hydrogenated epoxy compounds of epoxy compounds obtained from triphenolmethane, and hydrogenated epoxy compounds of aromatic epoxy compounds.

[0203] Examples of the aforementioned aromatic epoxy compounds include: epididymated glycidyl ether epoxy resins obtained by condensation reaction of bisphenols with epihaloalcohols; high molecular weight epididymated glycidyl ether epoxy resins obtained by further addition reaction of these epididymated glycidyl ether epoxy resins with the aforementioned bisphenols; varnish / alkyl glycidyl ether epoxy resins obtained by further condensation reaction of polyols obtained by condensation reaction of phenols with aldehydes with epihaloalcohols; and epoxy compounds in which two phenol skeletons are bonded at the 9-position of the fluorene ring, and glycidyl groups are directly or via alkylene oxides bonded to the oxygen atoms obtained by removing hydrogen atoms from the hydroxyl groups of these phenol skeletons.

[0204] Examples of the aforementioned aliphatic epoxides include: glycidyl ethers of alcohols (q being a natural number) that do not have a cyclic structure; glycidyl esters of mono- or polycarboxylic acids [such as acetic acid, propionic acid, butyric acid, stearic acid, adipic acid, sebacic acid, maleic acid, itaconic acid, etc.]; epoxides of oils and fats with double bonds, such as epoxidized linseed oil, epoxidized soybean oil, and epoxidized castor oil; and epoxides of polyolefins (including polydienes) such as epoxidized polybutadiene.

[0205] As the aforementioned oxetane compounds, known or conventional compounds having one or more oxetane rings within the molecule can be listed. As the aforementioned vinyl ether compounds, known or conventional compounds having one or more vinyl ether groups within the molecule can be used.

[0206] The content (compounding amount) of other cationic curable compounds in the curable composition of this disclosure is preferably 50% by weight or less (e.g., 0 to 50% by weight) relative to the total amount of the polyorganosilsesquioxane and other cationic curable compounds of this disclosure, more preferably 30% by weight or less (e.g., 0 to 30% by weight), and even more preferably 10% by weight or less. By making the content of other cationic curable compounds 50% by weight or less (preferably 10% by weight or less), there is a tendency to further improve the scratch resistance of the cured product. On the other hand, by making the content of other cationic curable compounds 10% by weight or more, it is sometimes possible to impart desired properties (e.g., rapid curing of the curable composition, viscosity adjustment, etc.) to the curable composition and the cured product.

[0207] The content (compounding amount) of the vinyl ether compound (preferably a vinyl ether compound having one or more hydroxyl groups in the molecule) in the curable composition disclosed herein is not particularly limited, but is preferably 0.01 to 10% by weight, more preferably 0.05 to 9% by weight, and even more preferably 1 to 8% by weight, relative to the total amount of the polyorganosilsesquioxane and other cationic curable compounds of this disclosure. By controlling the content of the vinyl ether compound within the above range, there is a tendency to further increase the surface hardness of the cured product, and even with reduced exposure to active energy rays (e.g., ultraviolet light), a cured product with very high surface hardness can be obtained. Preferably, by controlling the content of the vinyl ether compound having one or more hydroxyl groups in the molecule within the above range, there is a tendency to increase the surface hardness of the cured product, and in addition, its heat resistance to yellowing is also further improved.

[0208] The curable composition disclosed herein may also contain the following conventional additives as other optional components: inorganic fillers such as precipitated silica, wet silica, fumed silica, calcined silica, titanium dioxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate, carbon black, silicon carbide, silicon nitride, and boron nitride; inorganic fillers obtained by treating these fillers with organosilicon compounds such as organohalosilanes, organoalkoxysilanes, and organosilazanes; organic resin micropowders such as silicone resins, epoxy resins, and fluororesins; fillers such as conductive metal powders such as silver and copper; curing aids; solvents (organic solvents, etc.); stabilizers (antioxidants, ultraviolet absorbers, etc.). Light stabilizers, heat stabilizers, heavy metal passivators, etc.; flame retardants (phosphorus-based flame retardants, halogen-based flame retardants, inorganic flame retardants, etc.); flame retardant additives; reinforcing materials (other fillers, etc.); nucleating agents; coupling agents (silane coupling agents, etc.); lubricants; waxes; plasticizers; release agents; impact modifiers; color modifiers; transparentizing agents; rheology modifiers (flowability modifiers, etc.); processability modifiers; colorants (dyes, pigments, etc.); antistatic agents; dispersants; surface modifiers (defoamers, leveling agents, antifoaming agents, etc.); surface modifiers (slip agents, etc.); matting agents; defoamers; foam suppressants; defoaming agents; antibacterial agents; preservatives; viscosity modifiers; tackifiers; photosensitizers; foaming agents, etc. These additives can be used alone or in combination of two or more.

[0209] The curable compositions disclosed herein are not particularly limited and can be prepared by stirring / mixing the above-mentioned components at room temperature or while heating as needed. It should be noted that the curable compositions disclosed herein can be prepared as a single-liquid composition for direct use of a substance premixed from the components, or as a multi-liquid composition (e.g., a two-liquid composition) for use, for example, by mixing two or more separately stored components in a prescribed ratio before use.

[0210] The curable composition disclosed herein is not particularly limited, but is preferably a liquid at room temperature (approximately 25°C). More specifically, for the curable composition disclosed herein, the viscosity at 25°C as a liquid diluted to 20% solvent [preferably a curable composition (solution) with a methyl isobutyl ketone content of 20% by weight] is preferably 300 to 20,000 mPa·s, more preferably 500 to 10,000 mPa·s, and even more preferably 1,000 to 8,000 mPa·s. By setting the above viscosity to 300 mPa·s or higher, there is a tendency to further improve the heat resistance of the cured product. On the other hand, by setting the above viscosity to 20,000 mPa·s or lower, there is a tendency to make the preparation and handling of the curable composition easier, and to reduce the likelihood of residual air bubbles in the cured product. It should be noted that the viscosity of the curable composition disclosed herein was measured using a viscometer (trade name "MCR301", manufactured by Anton-Paar) at a swing angle of 5%, a frequency of 0.1 to 100 (1 / s), and a temperature of 25°C.

[0211] [cured material]

[0212] By polymerizing the cationic curable compound (such as the polyorganosilsesquioxane of this disclosure) in the curable composition, the curable composition can be cured to obtain a cured product (sometimes referred to as "the cured product of this disclosure"). The curing method can be suitably selected from known methods and is not particularly limited; for example, methods such as irradiation with active energy rays and / or heating can be listed. As such active energy rays, examples include any one of infrared rays, visible light, ultraviolet light, X-rays, electron beams, alpha rays, beta rays, gamma rays, etc. Among these, ultraviolet light is preferred from the viewpoint of excellent operability.

[0213] The conditions for curing the curable composition of this disclosure by irradiation with active energy rays (irradiation conditions of active energy rays, etc.) can be appropriately adjusted according to the type and energy of the active energy rays irradiated, the shape and size of the cured product, etc., and are not particularly limited. In the case of irradiation with ultraviolet light, it is preferably, for example, 1 to 1000 mJ / cm 2 It should be noted that for irradiation with active energy rays, various types of lamps can be used, such as high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, carbon arc lamps, metal halide lamps, sunlight, LED lamps, and lasers. Further curing can be achieved by heat treatment (annealing, aging) after irradiation with active energy rays.

[0214] On the other hand, the conditions for curing the curable composition of this disclosure by heating are not particularly limited, but are preferably 30 to 200°C, more preferably 50 to 190°C. The curing time can be set appropriately.

[0215] Regarding the curable compositions of this disclosure, as described above, curing them can form a cured product with high surface hardness and excellent heat resistance, flexibility, and processability. Therefore, it is preferable that the curable compositions of this disclosure be used as a "curable composition for forming a hard coating layer" (sometimes referred to as a "hard coating liquid," "hard coating agent," etc.) for forming a hard coating layer in a hard coating film. Furthermore, when the curable compositions of this disclosure are used as curable compositions for forming hard coating layers, the hard coating film having a hard coating layer formed by the composition maintains high hardness and high heat resistance, and is flexible, suitable for roll-to-roll manufacturing and processing.

[0216] [Hard coating]

[0217] The hard coating film disclosed herein is a hard coating film formed by laminating a substrate and a hard coating layer formed on at least one surface of the substrate, wherein the hard coating layer is a hard coating layer (cured layer of the hard coating composition disclosed herein) formed by the curable composition disclosed herein (curable composition for forming hard coating). Figure 6 This is a schematic diagram (cross-sectional view) illustrating one embodiment of the hard coating film of this disclosure. 1 represents the hard coating film, 11 represents the hard coating layer, and 12 represents the substrate.

[0218] It should be noted that the hard coating of this disclosure in the hard coating film may be formed on only one surface (single side) of the above-mentioned substrate, or it may be formed on two surfaces (both sides).

[0219] Furthermore, the hard coating of this disclosure in the hard coating film may be formed only on a portion of each surface of the aforementioned substrate, or it may be formed on the entire surface of each surface of the aforementioned substrate.

[0220] The substrate in the hard coating film of this disclosure refers to the portion other than the hard coating layer of this disclosure. As such a substrate, known or conventional substrates such as plastic substrates, metal substrates, ceramic substrates, semiconductor substrates, glass substrates, paper substrates, wood substrates (wood-based substrates), and substrates with a coated surface can be used, without particular limitation. Among these, a plastic substrate (a substrate made of plastic material) is preferred. It should be noted that commercially available products can also be used as the aforementioned plastic substrates and other substrates.

[0221] Among them, the plastic substrate is preferably a substrate with excellent heat resistance, formability and mechanical strength, and more preferably a polyester film (preferably PET or PEN), cyclic polyolefin film, polycarbonate film, TAC film or PMMA film.

[0222] The thickness of the substrate is not particularly limited, and can be appropriately selected from the range of 0.01 to 10000 μm.

[0223] The hard coating layer of this disclosure is a layer constituting at least one surface layer in the hard coating film of this disclosure, and is a layer (cured layer) formed by curing a cured product (resin cured product) obtained by curing the curable composition of this disclosure (curable composition for hard coating formation).

[0224] The thickness of the hard coating disclosed herein (the thickness of each hard coating when the hard coating of this disclosure is present on both sides of the substrate) is not particularly limited, but is preferably 1 to 200 μm, more preferably 3 to 150 μm. Preferably, the hard coating of this disclosure can maintain high surface hardness (e.g., a pencil hardness of H or higher) even when it is thin (e.g., a thickness of 5 μm or less). Furthermore, even when it is thick (e.g., a thickness of 50 μm or more), it is not prone to defects such as cracks caused by curing shrinkage, and therefore, pencil hardness can be significantly improved (e.g., a pencil hardness of 9H or higher) by thickening the film.

[0225] The haze of the hard coating disclosed herein is not particularly limited, but for a thickness of 50 μm, it is preferably 1.5% or less, more preferably 1.0% or less. It should be noted that the lower limit of haze is not particularly limited, for example, it is 0.1%. By preferably setting the haze to 1.0% or less, it tends to be suitable for applications requiring, for example, very high transparency (e.g., surface protection sheets for displays such as touch panels). The haze of the hard coating disclosed herein can be measured according to JIS K7136.

[0226] The total light transmittance of the hard coating disclosed herein is not particularly limited, but with a thickness of 50 μm, it is preferably 85% or more, more preferably 90% or more. It should be noted that the upper limit of the total light transmittance is not particularly limited, for example, it is 99%. By achieving a total light transmittance of 85% or more, it tends to be suitable for applications requiring, for example, very high transparency (e.g., surface protection sheets for displays such as touch panels). The total light transmittance of the hard coating disclosed herein can be measured according to JIS K7361-1.

[0227] The hard coating of this disclosure may also have a surface protective film on the surface of the hard coating of this disclosure.

[0228] The hard coating film disclosed herein can be manufactured according to known or conventional methods for manufacturing hard coating films. The manufacturing method is not particularly limited; for example, it can be manufactured by applying the curable composition (curable composition for hard coating formation) disclosed herein to at least one surface of the aforementioned substrate, removing the solvent by drying as needed, and then curing the curable composition (curable composition layer). The conditions for curing the curable composition are not particularly limited; for example, they can be appropriately selected from the conditions used to form the aforementioned cured product.

[0229] Preferably, the hard coating layer of the present disclosure in the hard coating film is a hard coating layer formed by a curable composition (curable composition for hard coating formation) of the present disclosure that can form a cured product with excellent flexibility and processability. Therefore, the hard coating film of the present disclosure can be manufactured in a roll-to-roll manner. The productivity of the hard coating film of the present disclosure can be significantly improved by manufacturing it in a roll-to-roll manner. As a method for manufacturing the hard coating film of the present disclosure in a roll-to-roll manner, a known or conventional roll-to-roll manufacturing method can be used, without particular limitation. For example, the following steps can be listed as necessary steps: a step of feeding a substrate rolled into a roll (step A); a step of forming the hard coating layer of the present disclosure by coating at least one surface of the fed substrate with the curable composition (curable composition for hard coating formation), and then, as needed, removing the solvent by drying, curing the curable composition (curable composition layer); and then, a step of rewinding the obtained hard coating film into a roll (step C), and a method of continuously performing these steps (steps A to C), etc. It should be noted that this method may include processes other than A to C.

[0230] The thickness of the hard coating film disclosed herein is not particularly limited and can be appropriately selected from the range of 1 to 10000 μm.

[0231] The pencil hardness of the surface of the hard coating film disclosed herein is preferably 5H or higher, more preferably 6H or higher, and even more preferably 7H or higher. It should be noted that the pencil hardness can be evaluated according to the method described in JIS K5600-5-4.

[0232] The haze of the hard coating film disclosed herein is not particularly limited, but is preferably 1.5% or less, more preferably 1.0% or less. It should be noted that the lower limit of haze is not particularly limited, for example, it is 0.1%. By preferably setting the haze to 1.0% or less, it tends to be suitable for applications requiring, for example, very high transparency (e.g., surface protectors for displays such as touch panels). The haze of the hard coating film disclosed herein can be easily controlled to the above range, for example, by using the aforementioned transparent substrate as the substrate. It should be noted that the haze can be measured according to JIS K7136.

[0233] The total light transmittance of the hard coating film disclosed herein is not particularly limited, but is preferably 85% or more, more preferably 90% or more. It should be noted that the upper limit of the total light transmittance is not particularly limited, for example, it is 99%. By achieving a total light transmittance of 90% or more, it tends to be suitable for applications requiring, for example, very high transparency (e.g., surface protective films for displays such as touch panels). The total light transmittance of the hard coating film disclosed herein can be easily controlled to the above range, for example, by using the aforementioned transparent substrate as the substrate. It should be noted that the total light transmittance can be measured according to JIS K7361-1.

[0234] The hard coating of this disclosure maintains high heat resistance and possesses high hardness and flexibility, allowing for roll-to-roll manufacturing and processing, thus resulting in high quality and excellent productivity. Preferably, when the surface of the hard coating of this disclosure has a surface protective film, its die-cutting processability is also excellent. Therefore, it is preferably used for all applications requiring such characteristics. The hard coating of this disclosure can also be used, for example, as a surface protective film in various products, a surface protective film in components or parts of various products, and further, as a constituent material of various products, their components, or parts. Examples of such products include: display devices such as liquid crystal displays and organic EL displays; input devices such as touch panels; solar cells; various home appliances; various electrical / electronic products; portable electronic terminals (e.g., gaming devices, personal computers, tablet computers, smartphones, mobile phones, etc.); various electrical / electronic products; and various optical devices. Furthermore, as an example of using the hard coating of this disclosure as a constituent material of various products, their components, or parts, examples include laminations of hard coatings and transparent conductive films in touch panels.

[0235] The cured product obtained by curing the curable composition of this disclosure not only exhibits excellent surface hardness, heat resistance, flexibility, and processability as described above, but also demonstrates excellent adhesion and bonding properties to the adhered objects. Therefore, the curable composition of this 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 this disclosure as an adhesive composition can be transformed into an adhesive material with excellent surface hardness, heat resistance, flexibility, processability, adhesion, and bonding properties by curing it. For example, the above-mentioned adhesive can be used as a photocurable adhesive when the curable composition of this disclosure contains a photocationic polymerization initiator as a curing catalyst, and can be used as a thermosetting adhesive when it contains a thermal cationic polymerization initiator.

[0236] By using the curable composition (adhesive composition) of this disclosure, an adhesive sheet having at least a substrate and an adhesive layer on the substrate can be obtained, that is, an adhesive sheet (sometimes referred to as "adhesive layer of this disclosure") having the adhesive layer being a layer of the curable composition of this disclosure (sometimes referred to as "adhesive layer of this disclosure"). Figure 7 This is a schematic diagram (cross-sectional view) illustrating one embodiment of the adhesive sheet of this disclosure. 2 represents the adhesive sheet, 21 represents the adhesive layer, and 22 represents the substrate.

[0237] The adhesive sheet disclosed herein includes not only sheet-like forms but also film-like, tape-like, plate-like, and other sheet-like forms. The adhesive sheet of this disclosure is not particularly limited; for example, it can be obtained by coating a substrate with the curable composition of this disclosure and then drying it as needed. The coating method is not particularly limited; conventionally known methods can be used. Furthermore, the drying method and conditions are not particularly limited; conditions can be set to remove volatile components such as solvents as much as possible, and conventionally known methods can be used.

[0238] The adhesive sheet disclosed herein can be a single-sided adhesive sheet having an adhesive layer on only one side of the substrate, or a double-sided adhesive sheet having adhesive layers on both sides of the substrate. In the case of a double-sided adhesive sheet, at least one adhesive layer can be the adhesive layer of this disclosure, while the other can be the adhesive layer of this disclosure or another type of adhesive layer.

[0239] As the substrate in the adhesive sheet of this disclosure, commonly known substrates (substrates for adhesive sheets) can be used, without particular limitation. Examples include: plastic substrates, metal substrates, ceramic substrates, semiconductor substrates, glass substrates, paper substrates, wood substrates, and substrates with a coated surface. Specifically, examples can be given of substrates similar to those in the hard coating film of this disclosure. Furthermore, the substrate in the adhesive sheet of this disclosure can be a so-called release liner, for example, the same substrate as the surface protective film in the hard coating film of this disclosure can be used. It should be noted that the adhesive sheet of this disclosure may have only one substrate layer or two or more substrate layers. Furthermore, the thickness of the aforementioned substrate is not particularly limited, and can be appropriately selected within the range of 1 to 10000 μm.

[0240] The adhesive sheet of this disclosure may have only one adhesive layer of this disclosure, or it may have two or more adhesive layers of this disclosure. Furthermore, the thickness of the adhesive layer of this disclosure is not particularly limited, and may be appropriately selected in the range of 0.1 to 10000 μm. The same applies to other adhesive layers (adhesive layers other than those of this disclosure).

[0241] In addition to the substrate and adhesive layer, the adhesive sheet disclosed herein may also have other layers (e.g., intermediate layer, primer layer, etc.).

[0242] By using the curable composition (adhesive composition) of this disclosure, a laminate (laminate) consisting of three or more layers (at least three layers) can be obtained, that is, a laminate (sometimes referred to as "laminate of this disclosure") having at least two bonded layers and an adhesive layer (a layer that bonds the bonded layers to each other) located between these bonded layers and the adhesive layer being a cured product of the curable composition of this disclosure (sometimes referred to as "adhesive layer of this disclosure"). Figure 8 This is a schematic diagram (cross-sectional view) illustrating one embodiment of the adhesive sheet of this disclosure. 3 represents a laminate, 31 represents an adhesive layer (cured product), and 32 and 33 represent layers to be bonded.

[0243] The laminates disclosed herein are not particularly limited, and can be obtained, for example, by forming an adhesive layer of this disclosure (e.g., similar to the adhesive layer in the adhesive sheet of this disclosure) on one bonded layer, then bonding another bonded layer to the adhesive layer, and subsequently curing the adhesive layer of this disclosure by light irradiation, heating, or the like. Furthermore, regarding the laminates of this disclosure, for example, if the adhesive sheet of this disclosure is a single-sided adhesive sheet, it can be obtained by bonding the adhesive sheet of this disclosure to the bonded layer, and then curing the adhesive layer of this disclosure in the adhesive sheet by light irradiation, heating, or the like. In this case, a laminate in which the substrate of the adhesive sheet of this disclosure is in contact with the bonded layer can be obtained. Furthermore, regarding the laminates of this disclosure, for example, when the adhesive sheet of this disclosure is a double-sided adhesive sheet and the substrate is a release liner, it can be obtained by bonding the adhesive sheet of this disclosure to one bonded layer, peeling off the release liner, then bonding another bonded layer to the exposed adhesive layer, and then curing the adhesive layer of this disclosure by light irradiation, heating, or the like. However, the manufacturing method of the laminates of this disclosure is not limited to these methods.

[0244] The adherend in the laminates disclosed herein is not particularly limited; for example, the adherend may be the same as the substrate in the hard coating film of this disclosure. It should be noted that the laminates of this disclosure may have only two adherends or may have three or more adherends. Furthermore, the thickness of the adherend is not particularly limited, and may be appropriately selected within the range of 1 to 100,000 μm. The adherend may not have a strictly layered morphology.

[0245] The laminates disclosed herein may have only one adhesive layer of this disclosure, or they may have two or more adhesive layers of this disclosure. Furthermore, the thickness of the adhesive layers of this disclosure is not particularly limited, and may be appropriately selected within the range of 0.1 to 10000 μm.

[0246] In addition to the bonded body and the adhesive layer of this disclosure, the laminate may also have other layers (e.g., intermediate layer, primer layer, other adhesive layers, etc.).

[0247] The curable compositions (adhesive compositions) disclosed herein are not limited to the use of obtaining the adhesive sheets and laminates of the present disclosure described above, but can be used for various purposes of bonding desired articles (parts, etc.) to each other.

[0248] The various schemes disclosed in this specification can be combined with any other features disclosed in this specification.

[0249] The various components and combinations thereof in each embodiment are merely examples, and appropriate additions, omissions, substitutions, and other modifications to the components may be made without departing from the spirit of this disclosure. This disclosure is not limited by the embodiments, but only by the claims.

[0250] Example

[0251] The present disclosure will now be described in more detail based on embodiments, but the disclosure is not limited to these embodiments. The number-average molecular weight and molecular weight dispersion of the products were determined under the following GPC conditions. The products'... 1 The H-NMR spectra were measured under the following conditions.

[0252] Furthermore, the area % of the cage-like silsesquioxane (T9) represented by the chemical formula (1) in the product, and the cage-like silsesquioxane (T) having the structural unit represented by the chemical formula (I-2) 10 The area percentage of the product was determined under the following HPLC-ELSD conditions, and the largest peak in the HPLC-ELSD spectrum was then separated. The ratio of T2 to T3 components [T3 / T2] was determined using a Brucker Avance (600 MHz). 29 Si-NMR spectroscopy was performed. Furthermore, for the mass spectrometry analysis of the aforementioned extracts, a quadrupole-time-of-flight mass spectrometer (Waters Corporation, product name "Xevo G2-XS QTof") was used.

[0253] [GPC Conditions]

[0254] Measurement device: Trade name "GPC Semi-micro system" (manufactured by Shimadzu Corporation).

[0255] Detector: RI detector (manufactured by Shoko Science Co., Ltd.).

[0256] Chromatographic columns: KF-G4A (guard column), KF-602, and KF-603 (manufactured by Shoko Science Co., Ltd.).

[0257] Flow rate: 0.6 mL / min.

[0258] Measurement temperature: 40℃.

[0259] Measurement time: 13 min.

[0260] Injection volume: 20 μL.

[0261] Eluent: THF, sample concentration 0.1–0.2% by weight.

[0262] Molecular weight: converted from standard polystyrene.

[0263] [ 1 H-NMR conditions

[0264] Measurement device: Trade name "ECA-500 (500MHz)" (Nippon Electronics).

[0265] Solvent: Deuterated chloroform.

[0266] Total number of times: 16.

[0267] Measurement temperature: 25℃.

[0268] [HPLC-ELSD conditions]

[0269] Measuring apparatus: Alliance 2695 (manufactured by Waters Corporation).

[0270] Detector: PL-ELS2100 (manufactured by Polymer Laboratories).

[0271] Detection conditions: ELSD (Evap: 70℃, Neb: 50℃, Gas: 1.60).

[0272] Chromatographic column:

[0273] Eluent: (A) Ultrapure water, (B) THF / ACN = 4 / 6.

[0274] Gradient condition: (A) / (B)=30 / 70(0min)→30min→(A) / (B)=0 / 100(10min).

[0275] Flow rate: 1 mL / min.

[0276] Column temperature: 25℃.

[0277] Injection volume: 10 μL.

[0278] Analysis time: 30 min.

[0279] [Example 1: Manufacturing of epoxy-containing polyorganosilsesquioxanes]

[0280] In a 1000 mL flask (reaction vessel) equipped with a thermometer, stirrer, reflux condenser, and 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) under a nitrogen atmosphere, and 73.2 parts by weight of water were added. The mixture was heated to 60 °C under a nitrogen atmosphere, and 11.2 parts by weight of a 5% potassium carbonate aqueous solution was added dropwise over 5 minutes. After reacting at 60 °C for 5 hours, MIBK and a 5% NaCl aqueous solution were added, and the mixture was separated by liquid-liquid extraction to separate the organic layer. After washing the organic layer six times with water, the solvent was removed by distillation under reduced pressure to obtain a colorless and transparent product. The product was analyzed under the GPC conditions described above, and the results showed that the number-average molecular weight (Mn) was 1561 and the molecular weight dispersion (Mw / Mn) was 1.52. Furthermore, the product was analyzed under the HPLC-ELSD conditions described above, and the results showed that the peak with a retention time of approximately 5.8 seconds corresponded to T9, and the peak with a retention time of approximately 7.5 seconds corresponded to T... 10 Based on the area % value of each peak area relative to the whole, the area % of the cage-like silsesquioxane (T9) represented by chemical formula (1) is 25.3%, and the cage-like silsesquioxane (T) with the structural unit represented by chemical formula (I-2) is... 10 The area percentage of T9 / T is 4.45%. 10 It is 5.69. Based on the above products... 29 The ratio of T2 to T3 bodies [T3 body / T2 body] calculated from Si-NMR spectra is 6.00.

[0281] The obtained product 1 The H-NMR spectrum is shown in Figure 1 ,Will 29 The Si-NMR spectrum is shown in Figure 2 The chromatogram of HPLC-ELSD analysis is shown in Figure 3 Furthermore, the obtained product was subjected to HPLC-ELSD conditions described above, and the peak with a retention time of approximately 5.8 seconds was separated. The mass spectrometry analysis results (ESI-MS spectrum) of the separated precipitate are shown below. Figure 4 Regarding the obtained fraction, it will be assumed that the chemical formula is C. 72 H 122 NO 23 Si9 (equivalent to all R)1 The theoretical isotopic spectrum for the chemical formula (1) of 2-(3,4-epoxycyclohexyl)ethyl is shown in Figure 5 Based on comparison with theoretical isotope patterns, the peak with a retention time of approximately 5.8 seconds can be identified as T9.

[0282] [Examples 2-12, Comparative Examples 1 and 2]

[0283] As shown in Table 1, the type and amount of catalyst, reaction solvent, amount of water, and reaction temperature were changed, but the synthesis was carried out in the same manner as in Example 1. Table 1 shows the catalyst, reaction solvent and their amounts (parts by weight), amount of water (parts by weight), reaction temperature (°C), number average molecular weight (Mn), molecular weight distribution, area % of the cage-like silsesquioxane (T9) represented by the above chemical formula (1), and cage-like silsesquioxane (T9) having the structural unit represented by the above chemical formula (I-2). 10 ) area % and [T9 / T 10 It should be noted that in the reaction solvents in Table 1, DMAc is dimethylacetamide, THF is tetrahydrofuran, IPA is isopropanol, DBU in the catalyst is 1,8-diazabicyclo[5.4.0]undec-7-ene, and TMAOH is trimethylammonium hydroxide.

[0284] [Preparation of Hard Coating]

[0285] A mixed solution of 0.5 parts by weight of leveling agent (trade name "S-243", manufactured by AGCSeimiChemical Co., Ltd.) and 1 part by weight of photocationic polymerization initiator (trade name "CPI-210S", manufactured by San-Apro Co., Ltd.) was prepared by adding methyl isobutyl ketone (MIBK) (manufactured by Kanto Chemical Co., Ltd.) to a concentration of 60 parts by weight of the polyorganosilsesquioxane obtained in Examples 1 to 12 and Comparative Examples 1 and 2, and this solution was used as a curable composition.

[0286] The curable compositions obtained above were coated onto a PEN (polyethylene naphthalate) film (trade name "Teonex" (registered trademark), manufactured by Teijin DuPont Film Co., Ltd., thickness 50 μm) with a cured hard coating thickness of 30 or 10 μm. The film was then placed in an oven at 120°C for 10 minutes (pre-baking), followed by irradiation with ultraviolet light (120 W / cm²). 2 The process involves a speed of 4.5 m / min, a USHIO electric motor, and the product name is "UVH-0251C-2200". Finally, a heat treatment (aging) is performed at 120°C for 30 minutes to produce a film with various hard coatings (hard coating film).

[0287] [evaluate]

[0288] The hard coatings obtained from Examples 1-12 and Comparative Examples 1 and 2 described above were evaluated for bending resistance and pencil hardness using the following methods. The evaluation results are shown in Table 1.

[0289] (Bending resistance: Cylindrical mandrel method)

[0290] The flexural strength of the hard coating (10 μm thickness) obtained above was evaluated using a cylindrical mandrel according to JIS K5600-5-1. Tests were conducted using mandrels with diameters of 2 mm, 3 mm, and 5 mm, with the hard coating on the inside (infold) and outside (outfold) sides. For the inside (infold) test, a 2 mm diameter mandrel was used; no cracks were observed in the hard coating (○), and cracks were observed (×). For the outside (outfold) test, mandrels with diameters of 3 mm and 5 mm were used; no cracks were observed in the hard coating (○), and cracks were observed (×). The results are shown in Table 1.

[0291] (Surface hardness: pencil hardness)

[0292] The pencil hardness of the surface (surface of the hard coating layer) of the obtained hard coating film (30 μm thick) was evaluated according to JIS K5600-5-4. It should be noted that a load of 750 g was used. The results are shown in Table 1.

[0293] (Heat resistance: Temperature at which 5% weight loss occurs (T) d5 ))

[0294] T of the product d5 (At a temperature where weight loss is 5%), the determination was performed using TGA (thermogravimetric analysis) under the following conditions.

[0295] (Measurement conditions)

[0296] Measurement device: TG-DTA 6200 / Hitachi High-Tech Science.

[0297] Atmosphere: N2.

[0298] Temperature range: 25℃~550℃.

[0299] Heating rate: 10℃ / min.

[0300] Sample tray: A1.

[0301]

[0302] The following describes variations of the invention disclosed herein.

[0303] [Appendix 1] A polyorganosilsesquioxane comprising a cage-like silsesquioxane represented by the following chemical formula (1), wherein the peak area of ​​the cage-like silsesquioxane represented by the following chemical formula (1) when detected by a liquid chromatography-evaporative light scattering detector 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, and even more preferably 45% or more).

[0304] Equation (1): [R] 1 SiO 3 / 2 ]8[R 1 SiO 2 / 2 (OR c )]1

[0305] (R in equation (1)) 1 Each of the following 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, at least one of which is a group containing a polymerizable functional group. R c (representing alkyl groups or hydrogen atoms with 1 to 4 carbon atoms).

[0306] [Note 2] The polyorganosilsesquioxane according to Note 1, wherein the above peak area % is 90% or less (preferably 80% or less).

[0307] [Appendix 3] According to Appendix 1 or 2, the polyorganosilsesquioxane, wherein the cage-like silsesquioxane (T9) represented by the above chemical formula (1) and the cage-like silsesquioxane (T) having structural units represented by the following chemical formulas (I-2) 10 The ratio of peak area % when measured using liquid chromatography-evaporative light scattering detector (LC-ELSD) (T9 / T) 10The value is 0.4 or higher, (preferably 0.5 or higher, more preferably 0.6 or higher, more preferably 0.7 or higher, more preferably 0.8 or higher, more preferably 0.9 or higher, more preferably 1 or higher, more preferably 1.2 or higher, more preferably 1.4 or higher, more preferably 1.6 or higher, more preferably 1.8 or higher, more preferably 2 or higher, more preferably 2.2 or higher, more preferably 2.4 or higher, more preferably 2.6 or higher, more preferably 2.8 or higher, more preferably 3 or higher, more preferably 3.5 or higher, more preferably 4 or higher, more preferably 4.5 or higher, and even more preferably 5 or higher).

[0308] [R a SiO 3 / 2 ] 10 (I-2)

[0309] (R in equation (I-2)) a This refers to a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom.

[0310] [Note 4] According to the polyorganosilsesquioxane described in Note 3, wherein the ratio of the above peak area % (T9 / T) 10 The value is 10 or less (preferably 9 or less).

[0311] [Note 5] The polyorganosilsesquioxane according to any one of Notes 1 to 4, wherein R in the above chemical formula (1) 1 The number of groups containing polymerizable functional groups is 3 to 9 (preferably 5 to 9, more preferably 7 to 9, and even more preferably 9).

[0312] [Note 6] The polyorganosilsesquioxane according to any one of Notes 1 to 5, wherein the groups containing polymerizable functional groups include cationic polymerizable functional groups (preferably epoxy, oxetyl, vinyl ether or vinylphenyl).

[0313] [Appendix 7] The polyorganosilsesquioxane according to any one of Appendices 1 to 6, wherein the groups containing polymerizable functional groups include free radical polymerizable functional groups (preferably (meth)acryloyloxy, (meth)acrylamido, vinyl or vinyl thio).

[0314] [Note 8] The polyorganosilsesquioxane according to any one of Notes 1 to 7, wherein the polymeric functional group comprises an epoxy group or (meth)acryloyloxy group.

[0315] [Appendix 9] The polyorganosilsesquioxane according to any one of Appendices 1 to 8, wherein, in the above T9, the group containing the polymerizable functional group is relative to R. 1 The overall proportion is 30% or more (preferably 50% or more, more preferably 80% or more).

[0316] [Appendix 10] The polyorganosilsesquioxane according to any one of Appendices 1 to 9, wherein the group containing the polymerizable functional group is a group represented by formula (1a), a group represented by formula (1b), a group represented by formula (1c), or a group represented by formula (1d).

[0317] [Chemical Formula 1]

[0318]

[0319] In equation (1a), R 1a Indicates a straight-chain or branched alkylene group.

[0320] [Chemical Formula 2]

[0321]

[0322] In equation (1b), R 1b Indicates a straight-chain or branched alkylene group.

[0323] [Chemical Formula 3]

[0324]

[0325] In equation (1c), R 1c Indicates a straight-chain or branched alkylene group.

[0326] [Chemical Formula 4]

[0327]

[0328] In equation (1d), R 1d Indicates a straight-chain or branched alkylene group.

[0329] [Note 11] According to the polyorganosilsesquioxane described in Note 10, wherein R in formulas (1a), (1b), (1c) and (1d) above 1a R 1b R 1c and R 1d It is a straight-chain or branched alkylene (preferably a straight-chain alkylene with 1 to 4 carbon atoms, or a branched alkylene with 3 or 4 carbon atoms, more preferably ethylene, trimethylene, or propylene, and even more preferably ethylene or trimethylene).

[0330] [Appendix 12] The polyorganosilsesquioxane according to any one of Appendices 1 to 11, wherein the molar ratio of the structural unit (T3 body) represented by the following formula (I) to the structural unit (T2 body) represented by the following formula (II) [structural unit represented by formula (I) / structural unit represented by formula (II); T3 body / T2 body] is 1 or more (preferably 2 or more, more preferably 3 or more, more preferably 4 or more, more preferably 5 or more, more preferably 6 or more, more preferably 7 or more, more preferably 8 or more, more preferably 9 or more, and even more preferably 10 or more).

[0331] [R a SiO 3 / 2 (I)

[0332] In formula (I), R a This indicates 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.

[0333] [R b SiO 2 / 2 (OR c (II)

[0334] In formula (II), R b This indicates 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, or a substituted or unsubstituted alkenyl group. R c [Refers to alkyl groups having 1 to 4 hydrogen atoms or carbon atoms].

[0335] [Appendix 13] According to Appendix 12, the polyorganosilsesquioxane, wherein the molar ratio of (T3 body) to (T2 body) [T3 body / T2 body] is 500 or less (preferably 100 or less, more preferably 50 or less, more preferably 40 or less, more preferably 30 or less, more preferably 25 or less, more preferably 20 or less, more preferably 18 or less, and even more preferably 16 or less).

[0336] [Note 14] The polyorganosilsesquioxane according to any one of Notes 1 to 13, wherein the number-average molecular weight (Mn) of the standard polystyrene obtained by gel permeation chromatography is 1,000 to 50,000 (preferably 1,100 to 40,000, more preferably 1,200 to 30,000).

[0337] [Note 15] The polyorganosilsesquioxane according to any one of Notes 1 to 14, wherein the molecular weight dispersion (Mw / Mn) of the standard polystyrene obtained by gel permeation chromatography is 1.0 to 4.0 (preferably 1.1 to 3.0, more preferably 1.2 to 2.5).

[0338] [Note 16] The polyorganosilsesquioxane according to any one of Notes 1 to 15, wherein the weight loss at a temperature (T) of 5% under air atmosphere. d5 The temperature is 330°C or higher (e.g., 330–450°C, preferably 340°C or higher, more preferably 350°C or higher).

[0339] [Note 17] A curable composition comprising a polyorganosilsesquioxane as described in any one of Notes 1 to 16.

[0340] [Note 18] According to the curable composition described in Note 17, the content (combination amount) of the above-mentioned polyorganosilsesquioxane is 70 to 100% by weight (preferably 80 to 99.8% by weight, more preferably 90 to 99.5% by weight) relative to the total amount (100% by weight) of the curable composition excluding the solvent.

[0341] [Note 19] According to the curable composition described in Note 17 or 18, the content of the above-mentioned polyorganosilsesquioxane is 70 to 100% by weight (preferably 75 to 98% by weight, more preferably 80 to 95% by weight) relative to the total amount (100% by weight) of the cationic curable compound.

[0342] [Note 20] The curable composition according to any one of Notes 17 to 19, wherein the curable composition comprises a curing catalyst.

[0343] [Note 21] The curable composition according to Note 20 contains a photopolymerization initiator or a thermal polymerization initiator as the curing catalyst described above.

[0344] [Note 22] The curable composition according to Note 20 or 21 contains a cationic polymerization initiator as the curing catalyst described above.

[0345] [Note 23] The curable composition according to Note 22, wherein the above-mentioned cationic polymerization initiator is a photocationic polymerization initiator or a thermal cationic polymerization initiator.

[0346] [Note 24] According to the curable composition described in Note 23, the photocationic polymerization initiator is one or more photocationic polymerization initiators selected from the group consisting of sulfonium salts, iodonium salts, selenium salts, ammonium salts, phosphonium salts, and salts of transition metal complex ions and anions.

[0347] [Note 25] According to the curable composition described in Note 23, the above-mentioned thermo-cationic polymerization initiator is one or more thermo-cationic polymerization initiators selected from the group consisting of aryl sulfonium salts, aryl iodonium salts, propylene-ion complexes, quaternary ammonium salts, aluminum chelates, and boron trifluoride amine complexes.

[0348] [Note 26] In any one of Notes 20 to 25, the curing composition wherein the content of the curing catalyst is 0.01 to 3.0 parts by weight relative to 100 parts by weight of the total amount of the cationic curing compound (preferably 0.05 to 3.0 parts by weight, more preferably 0.1 to 1.0 parts by weight, and even more preferably 0.3 to 1.0 parts by weight).

[0349] [Note 27] The curable composition according to any one of Notes 17 to 26 contains other cationic curable compounds besides the polyorganosilsesquioxanes described above.

[0350] [Appendix 28] According to the curable composition of Appendix 27, the other cationic curable compounds mentioned above are one or more compounds selected from the group consisting of epoxy compounds other than the polyorganosilsesquioxanes mentioned above, oxetane compounds and vinyl ether compounds.

[0351] [Note 29] The curable composition according to Note 28, wherein the epoxy compound is an alicyclic epoxy compound, an aromatic epoxy compound or an aliphatic epoxy compound.

[0352] [Note 30] The curable composition according to any one of Notes 27 to 29, wherein the content of the other cationic curable compounds is 50% by weight or less (preferably 30% by weight or less, more preferably 10% by weight or less) relative to the total amount of the polyorganosilsesquioxane and the other cationic curable compounds.

[0353] [Note 31] The curable composition according to any one of Notes 17 to 30, wherein the curable composition is a liquid at room temperature (about 25°C).

[0354] [Appendix 32] The curable composition according to any one of Appendices 17 to 31, wherein the viscosity of the liquid diluted to 20% solvent [preferably, the curable composition (solution) in the proportion of 20% by weight of methyl isobutyl ketone] at 25°C is 300 to 20000 mPa·s (preferably 500 to 10000 mPa·s, more preferably 1000 to 8000 mPa·s).

[0355] [Note 33] The curable composition according to any one of Notes 17 to 32, wherein the curable composition is a curable composition for hard coating formation.

[0356] [Note 34] Use of a curable composition, which is the use of a curable composition as described in any one of Notes 17 to 32 as a curable composition for forming a hard coating.

[0357] [Note 35] The curing composition according to any one of Notes 17 to 32, wherein the curing composition is a curing composition for adhesives.

[0358] [Note 36] Use of a curing composition, which is the use of a curing composition as an adhesive, as described in any one of Notes 17 to 32.

[0359] [Note 37] A cured product is a cured product of a curable composition as described in any one of Notes 17 to 33 or 35.

[0360] [Appendix 38] A hard coating film, wherein the hard coating film is formed by laminating a substrate and a hard coating layer formed on at least one surface of the substrate, wherein the hard coating layer is a cured product of the curable composition as described in Appendix 33.

[0361] [Note 39] According to the hard coating film described in Note 38, the substrate is a plastic substrate, a metal substrate, a ceramic substrate, a semiconductor substrate, a glass substrate, a paper substrate, a wood substrate, or a substrate with a coated surface.

[0362] [Note 40] According to Note 38 or 39, the thickness of the hard coating layer is 1 to 200 μm (preferably 3 to 150 μm).

[0363] [Note 41] The hard coating film according to any one of Notes 38 to 40, wherein the haze is 1.5% or less (preferably 1.0% or less) when the thickness of the hard coating film is 50 μm.

[0364] [Note 42] The hard coating film according to any one of Notes 38 to 41, wherein the haze is 0.1% or more when the thickness of the hard coating film is 50 μm.

[0365] [Note 43] The hard coating film according to any one of Notes 38 to 42, wherein the total light transmittance is 85% or more (preferably 90% or more) when the thickness of the hard coating is 50 μm.

[0366] [Note 44] The hard coating according to any one of Notes 38 to 43, wherein a surface protective film is provided on the surface of the hard coating.

[0367] [Note 45] According to any one of Notes 38 to 44, the hard coating film has a pencil hardness of 5H or higher (preferably 6H or higher, more preferably 7H or higher) on the surface of the hard coating film.

[0368] [Appendix 46] An adhesive sheet, wherein the adhesive sheet has a substrate and an adhesive layer on the substrate, the adhesive layer being a layer of the curable composition as described in Appendix 35.

[0369] [Note 47] Use of a curable composition for use as an adhesive layer in an adhesive sheet having a substrate and an adhesive layer thereon, wherein the curable composition described in Note 35 serves as the adhesive layer.

[0370] [Appendix 48] A laminate comprising three or more layers, having two bonded layers and an adhesive layer between the bonded layers, wherein the adhesive layer is a cured layer of the curable composition as described in Appendix 35.

[0371] Industrial availability

[0372] The disclosed polyorganosilsesquioxane can be used as a raw material for hard coatings or adhesive sheets.

[0373] Explanation of reference numerals in the attached figures

[0374] 1: Hard coating;

[0375] 11: Hard coating;

[0376] 12: Substrate;

[0377] 2: Adhesive sheet;

[0378] 21: Adhesive layer;

[0379] 22: Substrate;

[0380] 3: Stacked objects;

[0381] 31: Adhesive layer (cured product);

[0382] 32, 33: Adhesive layer.

Claims

1. A polyorganosilsesquioxane comprising a cage-like silsesquioxane T9 represented by the following chemical formula (1) and a cage-like silsesquioxane T having structural units represented by the following chemical formulas (I-2). 10 When detected using a liquid chromatography-evaporative light scattering detector, the peak area of ​​the cage-like silsesquioxane represented by the following chemical formula (1) is more than 5% relative to the peak area of ​​all constituent components. ·Formula (1): [R 1 SiO 3 / 2 8[R 1 SiO 2 / 2 (OR c )]1 R in equation (1) 1 Each of the following 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, at least one of which is a group containing a polymerizable functional group, R c Indicates alkyl groups or hydrogen atoms having 1 to 4 carbon atoms. [R 2 SiO 3 / 2 ] 10 (I-2) R in equation (I-2) 2 This indicates 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. The polymerizable functional group is an epoxy group. The T9 and the T measured using liquid chromatography-evaporative light scattering detector 10 The ratio of peak area % is T9 / T 10 It is 1 or higher.

2. The polyorganosilsesquioxane according to claim 1, wherein, The group containing the polymerizable functional group is a group represented by formula (1a), a group represented by formula (1b), a group represented by formula (1c), or a group represented by formula (1d). [Chemical Formula 1] In equation (1a), R 1a Indicates a straight-chain or branched alkylene group. [Chemical Formula 2] In equation (1b), R 1b Indicates a straight-chain or branched alkylene group. [Chemical Formula 3] In equation (1c), R 1c Indicates a straight-chain or branched alkylene group. [Chemical Formula 4] In equation (1d), R 1d Indicates a straight-chain or branched alkylene group.

3. The polyorganosilsesquioxane according to claim 1 or 2, wherein, In the cage-like silsesquioxane represented by the chemical formula (1), the group containing the polymerizable functional group is relative to R. 1 The overall proportion is over 30%.

4. The polyorganosilsesquioxane according to claim 1 or 2, wherein, The molar ratio of the structural unit represented by equation (I) to the structural unit represented by equation (II), i.e., the ratio of the structural unit represented by equation (I) to the structural unit represented by equation (II), is 1 or more and 500 or less. [R a SiO 3 / 2 ](I) In equation (I), R a This indicates 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 equation (II), R b R represents a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group. c Indicates an alkyl group having 1 to 4 hydrogen atoms or carbon atoms. The polymerizable functional group is an epoxy group.

5. The polyorganosilsesquioxane according to claim 1 or 2, wherein, The number average molecular weight is 1,000 to 50,000.

6. The polyorganosilsesquioxane according to claim 1 or 2, wherein, The molecular weight dispersion, i.e., the weight-average molecular weight / number-average molecular weight, is 1.0 to 4.

0.

7. The polyorganosilsesquioxane according to claim 1 or 2, wherein, Temperature T that results in a 5% weight loss d5 It is above 330℃.

8. A curable composition comprising a polyorganosilsesquioxane as described in any one of claims 1 to 7.

9. The curable composition according to claim 8, wherein, The curing composition also includes a curing catalyst.

10. The curable composition according to claim 9, wherein, The curing catalyst is a photopolymerization initiator or a thermal polymerization initiator.

11. The curable composition according to any one of claims 8 to 10, wherein, The curing composition is a curing composition for forming a hard coating.

12. The curable composition according to any one of claims 8 to 10, wherein, The curing composition is an adhesive composition.

13. A cured product, which is a cured product of the curable composition as described in any one of claims 8 to 12.

14. A hard coating film, wherein, The hard coating is formed by laminating a substrate with a hard coating layer formed on at least one surface of the substrate, wherein the hard coating layer is a cured product of the curable composition as described in claim 11.

15. An adhesive sheet, wherein, The adhesive sheet has a substrate and an adhesive layer on the substrate. The adhesive layer is a layer of the curable composition as described in claim 12.

16. A layered material, wherein, The laminate consists of three or more layers. It has two bonded layers and an adhesive layer between the bonded layers. The adhesive layer is a cured layer of the curable composition as described in claim 12.

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