Undercoating agent composition for layering inorganic substance layer, cured product thereof, and production method thereof

Abstract

The present invention is a primer composition for inorganic material lamination, which is coated on a resin substrate to deposit an inorganic material layer on the resin substrate by means of a dry film-forming method. It is characterized in that it contains a polysiloxane compound represented by the following formula (1), and a free radical polymerization initiator and / or a cationic polymerization initiator.

Description

[Technical Field]

[0001] This invention relates to a primer composition for inorganic material laminates, its cured form, and a method for manufacturing the same, and to a laminate comprising a cured form for inorganic material laminates, a resin substrate, and an inorganic material layer. More specifically, this invention relates to a primer composition for inorganic material laminates comprising a polysiloxane compound and a polymerization initiator. The cured form of this primer composition for inorganic material laminates is used as a base layer for inorganic material laminates in the fabrication of, for example, display substrates, touch panels, thin films with electrodes, and lenses. [Previous Technology]

[0002] In recent years, in order to impart or enhance various functions such as weather resistance, chemical resistance, hardness, scratch resistance, durability, heat resistance, conductivity, gas barrier properties, antifouling properties and antireflection properties to the surface of resin substrates, it has been proposed to use dry film-forming methods to deposit inorganic material layers.

[0003] Japanese Patent Application Publication No. 2009-178904 discloses a modified printed film laminate, characterized in that it comprises: a plastic film having a glass transition temperature of 70°C or higher; a transparent resin layer formed by curing a photocurable resin composition comprising a cage-type silsesquioxane resin having photocurability on the plastic film; and a surface modification film layer formed by further depositing it on the surface of the transparent resin layer by sputtering.

[0004] Japanese Patent Application Publication No. 2010-274562 discloses a gas barrier laminate characterized by having one or more of the following combinations: an organic compound layer; a layer containing polysilsesquioxane formed on the organic compound layer; and an oxide inorganic compound layer, which is further formed on the polysilsesquioxane-containing layer by chemical vapor deposition.

[0005] Japanese Patent Application Publication No. 2013-035274 discloses a laminate characterized in that it is formed by sequentially depositing a hardened coating layer and an inorganic material layer on a polycarbonate resin substrate. The hardened coating layer is formed from an active energy line-curing primer composition containing a silsesquioxane compound having (meth)acryloxy groups, a photopolymerization initiator, and a silicon-based surface modifier containing unsaturated groups. The inorganic material layer is formed by a dry film-forming method and contains a silicon oxide compound. [Summary of the Invention]

[0006] [The problem the invention aims to solve]

[0007] However, for the laminates disclosed in Japanese Patent Application Publication Nos. 2009-178904, 2010-274562 and 2013-035274, which use a hardened material containing a silsesquioxane composition as a primer layer, the adhesion between the laminate and the inorganic material layer laminated thereon is still insufficient, which poses a problem in practical application.

[0008] According to one embodiment of the present invention, a primer composition for inorganic material lamination, its cured form, a laminate using the same, and a method for manufacturing the above are provided, which can provide a cured form (primer layer) with good adhesion to an inorganic material layer laminated by a dry film-forming method. [Technical Means for Solving the Problem]

[0009] The present invention includes the following [1] to

[11] . [1] An inorganic material layering primer composition, which is coated on a resin substrate to deposit an inorganic material layer on the resin substrate by means of a dry film-forming method, characterized in that it comprises a polysiloxane compound represented by the following formula (1), and a free radical polymerization initiator and / or a cationic polymerization initiator.

[0010]

[0011] In formula (1), R1, R2 and R3 independently represent alkyl groups having 1 to 10 carbon atoms, aralkyl groups having 7 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, unsaturated hydrocarbon groups having 2 to 8 carbon atoms, or monovalent organic groups having (meth)acrylyl, epoxy or oxetyl groups. The alkyl, aralkyl, aryl, unsaturated hydrocarbon groups, (meth)acrylyl, epoxy and oxetyl groups can be selected from halogen atoms, hydroxyl, alkoxy, aromatic At least one of the group consisting of alkyloxy, aralkyloxy and oxy groups is substituted, and at least one of R1, R2 and R3 is a monovalent organic group having (meth)acrylyl, epoxy or oxacyclobutyl, and R1, R2 and R3 may be the same or different from each other; in formula (1), v, w, x and y respectively refer to the proportions in the total stoichiometry of v, w, x and y, w represents a positive number less than 1, and v, x and y respectively independently represent a positive number of 0 or less than 1. [2] An inorganic material laminate composition as described in [1] above, wherein x in formula (1) is a positive number. [3] An inorganic material laminate composition as described in [1] or [2] above, wherein the dry film formation method is a physical vapor deposition method. [4] An inorganic material laminate composition as described in any one of [1] to [3] above, wherein 0.3 ≦ {w / (v+w+x+y)} ≦ 1.0 and 0 ≦ {x / (v+w+x+y)} ≦ 0.7. [5] An inorganic material laminate composition as described in any one of [1] to [3] above, wherein 0.5 ≦ {w / (v+w+x+y)} ≦ 1.0 and 0 ≦ {y / (v+w+x+y)} ≦ 0.5. [6] An inorganic material laminate composition as described in any one of [1] to [5] above, wherein the polysiloxane compound has a viscosity of 10 to 1,000,000 mPa·s at 25°C. [7] A curable inorganic material for laminated layers, which is formed by curing an inorganic material for laminated layers primer composition as described in any one of [1] to [6] above. [8] A laminate comprising an inorganic material for laminated layers curable as described in [7] above, a resin substrate, and an inorganic material layer. [9] A laminate as described in [8] above, wherein, in a cross-cut peel test, the inorganic material layer peels off in 5 or fewer of 25 grids in an evaluation of the adhesion of the inorganic material for laminated layers curable to the inorganic material for laminated layers.

[10] A method for manufacturing an inorganic material for laminated layers curable as described in [7] above, comprising the step of irradiating an inorganic material for laminated layers primer composition as described in any one of [1] to [6] above with an active energy line to cure it.

[11] A method for manufacturing a laminate as described in [8] or [9] above, comprising the step of: irradiating an inorganic material laminate as described in any one of [1] to [6] above with an active energy line to harden it. (Effects of the Invention)

[0012] According to one embodiment of the present invention, an inorganic material lamination composition, its cured form, a laminate using the same, and a method for manufacturing the above are provided, which can provide a cured form (primer layer) with good adhesion to an inorganic material layer laminated by a dry film-forming method.

Implementation Method

[0013] Hereinafter, the present invention will be described in more detail. Furthermore, unless otherwise specified, "%" means "weight %", "parts" means "parts by weight", and "ppm" means "ppm by weight". In the present invention, the expression "lower limit to upper limit" indicating a numerical range means "above the lower limit and below the upper limit", and the expression "upper limit to lower limit" means "below the upper limit and above the lower limit". That is, it indicates a numerical range including both the upper and lower limits. Furthermore, in the present invention, a combination of two or more of the following preferred samples is also a preferred sample.

[0014] Hereinafter, the manufacturing methods of polysiloxane compounds, polymerization initiators, primer compositions for inorganic material lamination, cured materials, laminates, and the cured materials and laminates will be described.

[0015] 1. Polysiloxane Compounds The polysiloxane compounds of the present invention are represented by the following formula (1), having at least (meth)acrylyl, epoxy, or oxocyclobutyl groups, where w is a positive number less than or equal to 1. Here, (meth)acrylyl means acrylyl or methacrylyl, and the same meaning applies hereinafter.

[0016]

[0017] Each of the constituent units that the polysiloxane compound of the present invention may have is referred to as constituent units (a) to (d), and will be described below.

[0018] Constructing unit (a): (SiO4 / 2)v

[0019]

[0020] Constructing unit (b): (R1SiO3 / 2)w

[0021]

[0022] Constructing unit (c): (R22SiO2 / 2)x

[0023]

[0024] Constructing unit (d): (R33SiO1 / 2)y

[0025]

[0026] The polysiloxane compound of the present invention may comprise the above-described constituent units (a) to (d). In formula (1), v, w, x, and y respectively refer to the proportions in the total stoichiometry of v, w, x, and y, w represents a positive number less than 1, and v, x, and y each independently represent a positive number of 0 or less than 1. That is, v, w, x, and y in formula (1) represent the molar ratio of each constituent unit in constituent units (a) to (d). In other words, as described below. v / (v+w+x+y) represents the molar ratio of constituent unit (a) in constituent units (a) to (d), w / (v+w+x+y) represents the molar ratio of constituent unit (b) in constituent units (a) to (d), x / (v+w+x+y) represents the molar ratio of constituent unit (c) in constituent units (a) to (d), and y / (v+w+x+y) represents the molar ratio of constituent unit (d) in constituent units (a) to (d). Furthermore, in equation (1), v, w, x, and y represent the relative molar ratios of the constituent units contained in the polysiloxane compound of the present invention as expressed in equation (1). That is, the molar ratio is the relative ratio of the number of repetitions of each constituent unit as expressed in equation (1). The molar ratio can be obtained from the nuclear magnetic resonance (NMR) analysis value of the polysiloxane compound of the present invention. Furthermore, when the reaction rate of each raw material of the polysiloxane compound of the present invention is clear, or when the yield is 100%, it can be determined from the amount of the raw material added.

[0027] Regarding the constituent units (a), (b), (c), and (d) in formula (1), each may correspond to only one type of constituent unit or more than two types. For example, the constituent unit corresponding to constituent unit (a) may be one type or more types. Furthermore, the arrangement order in formula (1) indicates the composition of the constituent units, not their arrangement order. Therefore, the condensation form of the constituent units in the polysiloxane compound of the present invention does not necessarily have to be the arrangement order of formula (1).

[0028] 1-1. Constituent Unit (a): (SiO4 / 2)v Constituent unit (a) is a so-called Q unit comprising four O1 / 2 units (two in terms of oxygen atoms) relative to one silicon atom. Furthermore, a Q unit refers to a unit having four O1 / 2 units relative to one silicon atom. The proportion of constituent unit (a) in the polysiloxane compound of the present invention, i.e., (v / (v+w+x+y)), is a positive number of 0 or less than 1. Considering the viscosity of the polysiloxane compound of the present invention and the flexibility of its cured form, the molar ratio (v / (v+w+x+y)) in constituent units (a) to (d) is preferably 0.6 or less, more preferably 0.3 or less, and even more preferably 0. Here, a molar ratio of 0 means that the constituent unit is not present, and the same meaning applies below.

[0029] 1-2. Constituent Unit (b): (R1SiO3 / 2)w Constituent unit (b) is a T unit comprising three O1 / 2 (1.5 oxygen atoms) relative to one silicon atom and having R1 bonded to the silicon atom. R1 represents an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an unsaturated hydrocarbon group having 2 to 8 carbon atoms, or a monovalent organic group having (meth)acrylyl, epoxy, or oxetyl. The alkyl, aralkyl, aryl, unsaturated hydrocarbon group, (meth)acrylyl, epoxy, and oxetyl may be substituted by at least one of the group consisting of halogen atoms, hydroxyl, alkoxy, aryloxy, aralkyloxy, and oxygen. In the polysiloxane compound represented by formula (1), at least one of R1, R2, and R3 is a monovalent organic group having (meth)acryl, epoxy, or oxetyl. R1, R2, and R3 may be the same as or different from each other. When a plurality of groups corresponding to R1 exist in a molecule, the plurality of R1s may be the same as or different from each other. Furthermore, in the polysiloxane compound represented by formula (1), at least one of R1, R2, and R3 is a monovalent organic group having (meth)acryl, epoxy, or oxetyl, preferably at least one is a monovalent organic group having (meth)acryl or oxetyl, more preferably at least one is a monovalent organic group having acryl or oxetyl, and even more preferably at least one is a monovalent organic group having acryl. The alkyl groups with 1 to 10 carbon atoms, the aralkyl groups with 7 to 10 carbon atoms, and the unsaturated hydrocarbon groups with 2 to 8 carbon atoms in R1 can be straight-chain, branched, or have a ring structure.

[0030] The alkyl group having 1 to 10 carbon atoms in R1 is not particularly limited, but is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably methyl. The aralkyl group having 7 to 10 carbon atoms in R1 is not particularly limited, but is preferably phenylalkyl, and more preferably benzyl. The aryl group having 6 to 10 carbon atoms in R1 is not particularly limited, but is preferably phenyl. The unsaturated hydrocarbon group having 2 to 8 carbon atoms in R1 is not particularly limited, but is preferably vinyl, allyl, ethynyl, or styryl, and more preferably vinyl.

[0031] The monovalent organic group containing (meth)acrylyl in R1 is not particularly limited, but is preferably represented by the group in the following formula (2). Furthermore, in this invention, "(meth)acrylyl" means both acrylyl and methacrylyl.

[0032]

[0033] In formula (2), R4 represents a hydrogen atom or a methyl group, R5 represents an alkyl group with 1 to 10 carbon atoms, and ※ represents a bonding site.

[0034] R5 in formula (2) is not particularly limited, but is preferably an alkyl group with 2 to 8 carbon atoms, and more preferably a propenyl group. R1 is not particularly limited to a monovalent organic group containing an epoxy group, but is preferably a glycidyloxyalkyl group, and more preferably a glycidyloxypropyl group.

[0035] The monovalent organic group containing oxoheterobutyl in R1 is not particularly limited, but is preferably represented by the group in the following formula (3).

[0036]

[0037] In formula (3), R6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R7 represents an alkyl group having 1 to 10 carbon atoms, and ※ represents a bonding site.

[0038] R6 in formula (3) is not particularly limited, but is preferably a hydrogen atom, methyl or ethyl, and more preferably ethyl. R7 in formula (3) is not particularly limited, but is preferably an alkyl group having 2 to 8 carbon atoms, and more preferably propenyl.

[0039] The proportion of constituent unit (b) in the polysiloxane compound of the present invention is not particularly limited. However, considering the weather resistance, chemical resistance, hardness, scratch resistance, durability, heat resistance and / or oxidation resistance of the polysiloxane compound and its cured products of the present invention, the molar ratio (w / (v+w+x+y)) in constituent units (a) to (d) is a positive number of 1 or less, preferably 0.3 to 1.0, more preferably 0.5 to 0.95, and even more preferably 0.6 to 0.9.

[0040] 1-3. Constituent Unit (c): (R22SiO2 / 2)x Constituent unit (c) is a so-called D unit comprising two O1 / 2 (one for each oxygen atom) relative to one silicon atom. Furthermore, a D unit refers to a unit having two O1 / 2 relative to one silicon atom. R2 independently represents an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an unsaturated hydrocarbon group having 2 to 8 carbon atoms, or a monovalent organic group having (meth)acrylyl, epoxy, or oxetyl. This alkyl, aralkyl, aryl, unsaturated hydrocarbon, (meth)acrylyl, epoxy, and oxetyl group may be substituted by at least one of the group consisting of halogen atoms, hydroxyl groups, alkoxy groups, aryloxy groups, aralkyloxy groups, and oxygen groups. At least one of R1, R2, and R3 in the polysiloxane compound represented by formula (1) is a monovalent organic group having a (meth)acrylic, epoxy, or oxetyl group. R1, R2, and R3 may be the same as or different from each other, and R2 in a molecule may be the same as or different from each other. As substituents, substituents that are the same as those exemplified with respect to R1 in the above-described constitutive unit (b) can be listed. Constitutive unit (c) is a D unit, which helps to improve the low viscosity of the polysiloxane compound of the present invention and the flexibility, heat resistance, and / or oxidation resistance of its cured product. From the viewpoints of heat resistance, availability of raw materials, and imparting flexibility to the cured product, it is preferable that R2 independently represents methyl or phenyl, and more preferably methyl.

[0041] The proportion of the constituent unit (c) in the polysiloxane compound of the present invention, i.e. (x / (v+w+x+y)) is a positive number of 0 or less than 1. Considering the low viscosity of the polysiloxane compound of the present invention and the hardness, scratch resistance, weather resistance and / or flexibility of its cured product, the molar ratio (x / (v+w+x+y)) in constituent units (a) to (d) is preferably 0 ≤ {x / (v+w+x+y)} ≤ 0.7, more preferably 0.05 to 0.6, and even more preferably 0.1 to 0.5. Wherein, when x = 0, at least one of R1 in the above-mentioned constituent unit (b) and R3 in the following constituent unit (d) is a monovalent organic group having (meth)acrylic, epoxy or oxacyclobutyl groups. Especially when the value of x / (v+w+x+y) is in the range of 0.05~0.6, the adhesion between the hardened material and the inorganic material layer is particularly good, and the inorganic material layer of the obtained laminate also shows good scratch resistance, thus possessing both of these properties, which is better.

[0042] 1-4. Constituent Unit (d): (R33SiO1 / 2)z The constituent unit (d) is a so-called M unit comprising one O1 / 2 (0.5 oxygen atoms) relative to one silicon atom. Furthermore, an M unit refers to a unit having one O1 / 2 relative to one silicon atom. R3 independently represents an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an unsaturated hydrocarbon group having 2 to 8 carbon atoms, or a monovalent organic group having (meth)acrylyl, epoxy, or oxetyl. The alkyl, aralkyl, aryl, unsaturated hydrocarbon, (meth)acrylyl, epoxy, and oxetyl groups may be substituted by at least one of the group consisting of halogen atoms, hydroxyl groups, alkoxy groups, aryloxy groups, aralkyloxy groups, and oxygen groups. At least one of R1, R2, and R3 in the polysiloxane represented by formula (1) is a monovalent organic group having (meth)acrylic, epoxy, or oxetyl groups. R1, R2, and R3 may be the same as or different from each other, and R3 in a molecule may be the same as or different from each other. As these substituents, substituents that are the same as those exemplified with respect to R1 in the above-described constitutive unit (b) can be listed. The constitutive unit (d) is an M unit, which helps to improve the low viscosity of the polysiloxane compound of the present invention and the flexibility of its cured product. From the viewpoints of heat resistance, availability of raw materials, curing properties of the primer composition, and / or imparting flexibility to the cured product, it is preferable that R3 independently represents methyl, phenyl, or vinyl, and more preferably methyl or vinyl.

[0043] The proportion of the constituent unit (d) in the polysiloxane compound of the present invention, i.e. (y / (v+w+x+y)), is a positive number that is 0 or less than 1. Considering the low viscosity of the polysiloxane compound of the present invention and the hardness, weather resistance, and / or flexibility of its cured product, the molar ratio (y / (v+w+x+y)) in constituent units (a) to (d) is preferably 0 ≤ {y / (v+w+x+y)} ≤ 0.5, more preferably 0 to 0.4, and even more preferably 0 to 0.3. Wherein, when y = 0, at least one of R1 in the above-mentioned constituent unit (b) and R2 in the above-mentioned constituent unit (c) is a monovalent organic group having (meth)acrylic, epoxy, or oxacyclobutyl groups.

[0044] 1-5. Other Constituent Units (e) The polysiloxane compound of the present invention may further include (R8O1 / 2) as a Si-free constituent unit (hereinafter referred to as constituent unit (e)). Here, R8 is an alkyl group having 1 to 6 carbon atoms, and may be any one of aliphatic and alicyclic groups, and may be any one of linear and branched forms. Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl.

[0045] The constituent unit is an alkoxy group contained in the following raw material monomer, or an alkoxy group generated by replacing the hydrolyzable group of the raw material monomer with an alcohol contained in the reaction solvent, and is a group that does not undergo hydrolysis or polycondensation and remains in the molecule, or a hydroxyl group that does not undergo polycondensation and remains in the molecule after hydrolysis.

[0046] 1-6. Molecular Weight, etc. The weight-average molecular weight (hereinafter also referred to as "Mw") of the polysiloxane compound of the present invention is not particularly limited, but is preferably in the range of 300 to 10,000. The polysiloxane compound itself is a liquid and has low viscosity suitable for handling, is readily soluble in organic solvents, and its solution viscosity is easy to manage, exhibiting excellent storage stability. Mw is more preferably 500 to 8,000, more preferably 600 to 7,000, and even more preferably 700 to 6,000. Furthermore, Mw in the present invention refers to the value obtained by converting the molecular weight measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. Mw can be determined, for example, under the determination conditions described in the [Examples] below.

[0047] The state of the polysiloxane compound of the present invention is not particularly limited, and examples include liquid, solid, and semi-solid. The polysiloxane compound of the present invention is preferably a liquid, and its viscosity is not particularly limited. For example, the viscosity at 25°C is preferably 10 to 1,000,000 mPa·s, more preferably 100 to 100,000 mPa·s, further preferably 300 to 30,000 mPa·s, even more preferably 400 to 10,000 mPa·s, and even more preferably 500 to 5,000 mPa·s. Especially when it is below 10,000 mPa·s, it is preferred because it has excellent workability in solvent-free systems, does not release organic solvents into the environment, and has excellent environmental resistance. Furthermore, if the viscosity is low, the surface of the primer layer for inorganic material deposition, which is coated and hardened, tends to become smoother, and it is also better for the deposition of inorganic material layers. Moreover, the viscosity referred to in this invention means the value measured at 25°C using an E-type viscometer (cone-plate type viscometer, such as the TVE22H type viscometer from Toki Sangyo Co., Ltd.).

[0048] 2. Method for manufacturing the polysiloxane compound of the present invention The polysiloxane compound of the present invention can be manufactured by known methods. There are no particular limitations on the method for manufacturing the polysiloxane compound. For example, methods for manufacturing polysiloxanes are disclosed in detail in Japanese Patent Application Publication No. 11-116682, Japanese Patent Application Publication No. 2000-044689, International Publication No. WO2004 / 076534, International Publication No. WO2009 / 090916, International Publication No. WO2009 / 131038, International Publication No. WO2012 / 090707, and International Publication No. WO2013 / 031798.

[0049] The polysiloxane compound of the present invention can be manufactured, for example, by the following method. That is, the method for manufacturing the polysiloxane compound of the present invention may include a condensation step, which is a hydrolysis and polycondensation reaction of the raw material monomer providing the constituent unit in formula (1) by condensation in a suitable reaction solvent using a suitable acid or base as a reaction catalyst. In this condensation step, for example, the following can be used: a silicone compound having four siloxane bond generating groups to form constituent unit (a) (Q unit) (hereinafter referred to as "Q monomer"), a silicone compound having three siloxane bond generating groups to form constituent unit (b) (T unit) (hereinafter referred to as "T monomer"), a silicone compound having two siloxane bond generating groups to form constituent unit (c) (D unit) (hereinafter referred to as "D monomer"), and a silicone compound having one siloxane bond generating group to form constituent unit (d) (M unit) (hereinafter referred to as "M monomer").

[0050] The preferred method for manufacturing the polysiloxane compound of the present invention includes a distillation removal step, wherein the reaction solvent, byproducts, residual monomers, and water in the reaction solution are removed by distillation after the raw material monomers have undergone hydrolysis and polymerization condensation reactions in the presence of a reaction solvent. Furthermore, a washing step may also be suitably included to wash the reaction solution or reaction concentrate with water or the like.

[0051] 2-1. The siloxane bond generating groups contained in monomers Q, T, D, and M, which are used as raw material monomers, are hydroxyl and / or hydrolyzable groups. Among them, halogen groups, alkoxy groups, and silalkoxy groups can be listed as hydrolyzable groups. In the condensation step, in terms of good hydrolysis and no formation of acid byproducts, the hydrolyzable group is preferably alkoxy, and more preferably alkoxy with 1 to 3 carbon atoms. Furthermore, regarding monomer M, in terms of the availability of raw materials, the hydrolyzable group is preferably silalkoxy, and a disiloxane composed of two constituent units (d) can be used.

[0052] In the condensation step, the siloxane bond generating groups of monomers Q, T, and D corresponding to each constituent unit are preferably alkoxy groups, and the siloxane bond generating groups of monomer M are preferably alkoxy or silalkoxy groups. Furthermore, the monomers corresponding to each constituent unit can be used individually or in combination of two or more.

[0053] Examples of the Q monomers that provide the constituent unit (a) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.

[0054] Examples of T monomers providing constituent unit (b) include trimethoxyvinylsilane, triethoxyvinylsilane, trichlorovinylsilane, trimethoxyallylsilane, triethoxyethynylsilane, (p-styryl)trimethoxysilane, (p-styryl)triethoxysilane, (3-methacryloxypropyl)trimethoxysilane, and (3-methacryloxy)trimethoxysilane. (3-Propyleneoxypropyl)triethoxysilane, (3-propenyloxypropyl)trimethoxysilane, (3-propenyloxypropyl)triethoxysilane, (8-methpropenyloxyoctyl)trimethoxysilane, (8-propenyloxyoctyl)trimethoxysilane, 3-ethyl-3-[{3-(trimethoxysilyl)propoxy}methyl]oxetane, 3-ethyl-3-[{3-(triethoxy)propoxy]methyl]oxetane {3-{3-(triethoxysilyl)propoxy}methyl}oxetane, (3-glycidoxypropyl)trimethoxysilane, (3-glycidoxypropyl)triethoxysilane, {2-(3,4-epoxycyclohexyl)ethyl}trimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyl Benzyltriisopropoxysilane, methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, benzyltriethoxysilane, and benzyltrichlorosilane, etc.

[0055] Examples of monomers D providing constituent unit (c) include dimethoxymethyl vinyl silane, dimethoxyethyl vinyl silane, diethoxymethyl vinyl silane, methyl vinyl dichlorosilane, dimethoxyallyl methyl silane, dimethoxyallyl ethyl silane, diethoxyethynyl methyl silane, diethoxyethynyl ethyl silane, (p-styryl)dimethoxymethyl silane, (p-styryl)dimethoxyethyl silane, (p-styryl)diethoxymethyl silane, and (3-methacryloxypropyl)dimethoxy 3-methylsilane, (3-methpropenyloxypropyl)diethoxymethylsilane, (3-methpropenyloxypropyl)diethoxymethylsilane, (3-methpropenyloxypropyl)diethoxyethylsilane, (3-propenyloxypropyl)dimethoxymethylsilane, (3-propenyloxypropyl)diethoxymethylsilane, (3-propenyloxypropyl)diethoxymethylsilane, (8-methpropenyloxyoctyl)dimethoxymethylsilane, (8-propenyloxyoctyl)dimethoxymethylsilane, 3-ethyl-3-[{3-(dimethoxymethylsilyl)propoxy}methyl] Oxycyclobutane, 3-ethyl-3-[{3-(diethoxymethylsilyl)propoxy}methyl]oxycyclobutane, 3-{3-(diethoxymethylsilyl)propoxy}oxycyclobutane, (3-glycidoxypropyl)dimethoxymethylsilane, (3-glycidoxypropyl)dimethoxyethylsilane, (3-glycidoxypropyl)diethoxymethylsilane, {2-(3,4-epoxycyclohexyl)ethyl}dimethoxymethylsilane, dimethoxydimethylsilane, dimethoxydiethylsilane, diethoxydimethyl Silane, diethoxydiethylsilane, dipropoxydimethylsilane, dipropoxydiethylsilane, diisopropoxydimethylsilane, dichlorodimethylsilane, diethoxymethylpropylsilane, dimethoxybutylmethylsilane, diethoxyoctylmethylsilane, dimethoxydecylmethylsilane, dimethoxycyclohexylmethylsilane, diethoxycyclohexylmethylsilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, methylphenyldichlorosilane, dimethoxybenzylmethylsilane, diethoxybenzylmethylsilane, and benzylmethyldichlorosilane, etc. Furthermore, oligomers with D-units containing silanol groups and / or alkoxysilyl groups capable of hydrolysis and condensation reactions, known as polysiloxanes, can also serve as D monomers providing constitutive unit (c) in this invention, and as raw materials for manufacturing the polysiloxane compound represented by formula (1). Examples include terminal silanol type dimethyl polysiloxane, terminal methoxy type dimethyl polysiloxane, dimethyl polysiloxane with both silanol and methoxy groups at the end, terminal silanol type methylphenyl polysiloxane, terminal methoxy type methylphenyl polysiloxane, and methylphenyl polysiloxane with both silanol and methoxy groups at the end, etc., and their molecular weights can be arbitrarily selected. Moreover, these raw material polysiloxanes may also contain cyclic siloxanes.

[0056] As the monomer M providing the constituent unit (d), in addition to hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, which provide two constituent units (d) by hydrolysis, examples include methoxytrimethylsilane, ethoxytrimethylsilane, propoxytrimethylsilane, isopropoxytrimethylsilane, ethoxydimethylethylsilane, methoxydimethylphenylsilane, ethoxydimethylphenylsilane, and dimethylvinylsilane. Chlorosilane, trimethylchlorosilane, dimethylvinylsilane, trimethylsilane, triethylsilane, tripropylsilane, tributylsilane, ethoxydimethylpropylsilane, methoxybutyldimethylsilane, ethoxyoctyldimethylsilane, methoxydecyldimethylsilane, methoxycyclohexyldimethylsilane, methoxybenzyldimethylsilane, benzyldimethylchlorosilane, methoxydimethylvinylsilane, methoxydiethylvinylsilane, ethoxydimethylvinylsilane, dimethylvinylchlorosilane, methoxyallyl 3-Methoxydimethylsilane, ethoxyethynyldimethylsilane, (p-styryl)methoxydimethylsilane, (p-styryl)ethoxydimethylsilane, (3-methpropenyloxypropyl)methoxydimethylsilane, (3-methpropenyloxypropyl)ethoxydimethylsilane, (3-propenyloxypropyl)methoxydimethylsilane, (3-propenyloxypropyl)ethoxydimethylsilane, (8-methpropenyloxyoctyl)methoxydimethylsilane, (8-propenyloxyoctyl)methoxy Dimethylsilane, 3-ethyl-3-[{3-(methoxydimethylsilyl)propoxy}methyl]oxetane, 3-ethyl-3-[{3-(ethoxydimethylsilyl)propoxy}methyl]oxetane, 3-{3-(ethoxydimethylsilyl)propoxy}oxetane, (3-glycidoxypropyl)methoxydimethylsilane, (3-glycidoxypropyl)ethoxydimethylsilane, and {2-(3,4-epoxycyclohexyl)ethyl}methoxydimethylsilane, etc.

[0057] Examples of compounds that provide the constituent unit (e) by reacting with the raw material monomer include water, as well as alcohols such as methanol, ethanol, 1-propanol, 2-propanol and 2-butanol.

[0058] The addition ratio of the raw material monomers Q monomer, T monomer, D monomer and M monomer can be appropriately set according to the values ​​of v to y of the target formula (1) in the polysiloxane compound according to the present invention.

[0059] Furthermore, the polysiloxane compound represented by formula (1) may contain a ring-opening group derived from the side chain functional groups of the monomer used for manufacturing, such as a p-oxetane butyl group or an epoxy group, which is formed by the addition of an acid to the epoxy group; it may also contain a hydroxyalkyl group generated by the decomposition of a monovalent organic group having a (meth)acrylic acid group; and it may also contain a group that is formed by the addition of an acid to an unsaturated hydrocarbon group. As a specific example, for example, a part of formula (1) may contain a group with the structure represented by formula (A) and / or the structure represented by formula (B) below, the content of which is 50 mol% or less of the original monovalent organic group having an oxetane butyl group or a monovalent organic group having a (meth)acrylic acid group derived from the raw material, preferably 30 mol% or less, and more preferably 10 mol% or less. Regarding formulas (A) and (B), although T units are illustrated, D units and M units may also be used.

[0060]

[0061]

[0062] 2-2. Reaction Solvent In the condensation step, an alcohol may be used as the reaction solvent. An alcohol is a narrowly defined alcohol represented by the general formula R-OH, and is a compound that does not have any functional groups other than the alcoholic hydroxyl group. There are no particular limitations on the alcohol; specific examples include methanol, ethanol, 1-propanol, 2-propanol, 2-butanol, 2-pentanol, 3-pentanol, 2-methyl-2-butanol, 3-methyl-2-butanol, cyclopentanol, 2-hexanol, 3-hexanol, 2-methyl-2-pentanol, 3-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-3-pentanol, 2-ethyl-2-butanol, 2,3-dimethyl-2-butanol, cyclohexanol, and secondary or tertiary alcohols with 7 to 10 carbon atoms. Of these, secondary alcohols such as 2-propanol, 2-butanol, 2-pentanol, 3-pentanol, 3-methyl-2-butanol, cyclopentanol, 2-hexanol, 3-hexanol, 3-methyl-2-pentanol, and cyclohexanol are preferred. In the condensation step, one or more of these alcohols may be used in combination. More preferably, the alcohol is a compound that can dissolve the required concentration of water in the condensation step. This type of alcohol is a compound whose solubility in water is 10 g or more per 100 g of alcohol at 20°C.

[0063] Regarding the alcohol used in the condensation step, using 0.5% by mass or more relative to the total amount of all reaction solvents, including those added during the hydrolysis and polycondensation reactions, can suppress the gelation of the polysiloxane compound of the present invention. A preferred amount is 1% by mass or more and 60% by mass or less, and more preferably 3% by mass or more and 40% by mass or less.

[0064] The reaction solvent used in the condensation step may be only an alcohol, or it may be a mixture of an alcohol and at least one auxiliary solvent. The auxiliary solvent may be either a polar solvent or a non-polar solvent, or a combination of both. As a polar solvent, diols, ethers, amides, ketones, esters, and cellosols with 2 to 20 carbon atoms are preferred.

[0065] There are no particular limitations on the nonpolar solvent, and examples include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and chlorinated hydrocarbons. There are no particular limitations on this type of nonpolar solvent; for example, hexane, isohexane, cyclohexane, heptane, toluene, xylene, and dichloromethane are preferred as they azeotropically react with water. If these compounds are used together, water can be efficiently removed by distillation of the reaction mixture containing the polysiloxane compound after the condensation step. Xylene, as an aromatic hydrocarbon, is particularly preferred as a nonpolar solvent due to its relatively high boiling point.

[0066] 2-3. The hydrolysis and polymerization condensation reactions in the water and catalyst condensation steps used in the hydrolysis reaction are carried out in the presence of water. The amount of water used to hydrolyze the hydrolyzable groups contained in the raw material monomer is preferably 0.5 to 5 moles, more preferably 1 to 2 moles, relative to the hydrolyzable groups. Furthermore, the hydrolysis and polymerization condensation reactions of the raw material monomer can be carried out without a catalyst or with a catalyst. When a catalyst is used, an acid catalyst or a base catalyst can usually be used. There are no particular limitations on acid catalysts, and examples include inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid; and organic acids such as formic acid, acetic acid, oxalic acid, and p-toluenesulfonic acid. There are no particular limitations on base catalysts, and examples include ammonia, tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate. The amount of catalyst used relative to the total amount of silicon atoms contained in the raw material monomer is preferably equivalent to 0.01 to 20 mol%, more preferably equivalent to 0.1 to 10 mol%.

[0067] 2-4. The completion of the hydrolysis and polymerization condensation reactions in the condensation step of other additives can be appropriately detected by the methods described in the various publications. Furthermore, in the condensation step of the manufacture of the polysiloxane compound of the present invention, an auxiliary agent can be added to the reaction system. Examples of auxiliary agents include, for instance, defoamers that inhibit foaming of the reaction solution, scale control agents that prevent scale adhesion on the reaction vessel or stirring shaft, and polymerization inhibitors. The amount of such auxiliary agents used is arbitrary, but it is preferably about 1 to 100% by weight relative to the concentration of the polysiloxane compound of the present invention in the reaction mixture.

[0068] 2-5. Distillation Removal of Reaction Solvents, etc. By including a distillation removal step after the condensation step in the manufacture of the polysiloxane compound of the present invention, the stability of the generated polysiloxane compound of the present invention can be improved. This distillation removal step removes the reaction solvents, byproducts, residual monomers, water, and catalysts contained in the reaction solution obtained in the condensation step. Distillation removal can generally be carried out under normal or reduced pressure, and can generally be carried out at room temperature or under heating, or under cooling. Furthermore, residual catalysts can be neutralized before distillation removal of the reaction solvents, etc. Alternatively, the reaction solution or the neutralized reaction solution can be washed with water before distillation removal of the solvents, etc., or the reaction solution or the neutralized reaction solution can be concentrated before washing with water. Water washing can be performed using commonly used water media such as pure water and saturated saline solution.

[0069] 3. The polymerization initiator contained in the inorganic material layer primer composition of the present invention is not particularly limited. Known polymerization initiators used in polymerization reactions can be used, and active energy line polymerization initiators and / or thermal polymerization initiators can be selected arbitrarily depending on the application. From a productive point of view, active energy line polymerization initiators are preferred because they cause the polysiloxane compound represented by formula (1) to harden in a relatively short time. When the polymerizable group is a free radical polymerizable group such as (meth)acrylyl, a free radical polymerization initiator is preferred; when the polymerizable group is a cationic polymerizable group such as oxobutyl or epoxy, a cationic polymerization initiator is preferred.

[0070] The amount of polymerization initiator contained in the inorganic material layer primer composition of the present invention is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 1 to 5 parts by weight, relative to 100 parts by weight of the polysiloxane compound represented by formula (1).

[0071] 3-1. Active Energy Line Radical Polymerization Initiator There are no particular limitations on the active energy line radical polymerization initiator used in this invention. Examples include: benzodiazepine dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, oligomeric [2-hydroxy-2-methyl-1-[4-1-(methylvinyl)phenyl]propanone, 2-hydroxy-1-{4-[4- Acetophenone compounds including (2-hydroxy-2-methyl-propionic)benzyl]phenyl}-2-methylpropane-1-one, 2-methyl-1-[4-(methylthio)]phenyl]-2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butane-1-one, and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)butane-1-one; benzoin compounds including benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone. Benzyl ketone compounds, including 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, methyl-2-benzophenone, 1-[4-(4-benzoylphenylthio)phenyl]-2-methyl-2-(4-methylbenzenesulfonyl)propane-1-one, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone; bis(2,4,6-trimethyl... Acrylphosphine oxide compounds such as benzoylphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; and thioxanthone compounds such as 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3-[3,4-dimethyl-9-sideoxy-9H-thioxanthone-2-yl-oxy]-2-hydroxypropyl-N,N,N-trimethylammonium chloride, and fluorothioxanthone. Other compounds not listed above include benzyl, ethyl(2,4,6-trimethylbenzoyl)phenyl ester of phosphinocyanate, methyl benzoate, ethyl anthrone, phenanthrenequinone, and camphorquinone. Only one of these compounds may be used, or two or more may be used in combination.

[0072] 3-2. Thermal free radical polymerization initiator The thermal free radical polymerization initiator used in this invention is not particularly limited, and examples include peroxide and azo initiators.

[0073] Specific examples of peroxides include: hydrogen peroxide; inorganic peroxides such as sodium persulfate, ammonium persulfate, and potassium persulfate; 1,1-bis(tert-butylperoxy)-2-methylcyclohexane, 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)-2- ... (Peroxy)cyclohexane, 2,2-bis(4,4-dibutylperoxycyclohexyl)propane, 1,1-bis(tert-butylperoxy)cyclododecane, trihexyhexylperoxyisopropyl monocarbonate, tributyl maleate peroxide, tributyl peroxide of 3,5,5-trimethylhexanoate, tributyl peroxylaurate, 2,5-dimethyl-2,5-di(m-tolylperoxy)hexane, tributyl peroxyisopropyl monocarbonate, tributylperoxy 2-Ethylhexyl monocarbonate, trihexyl benzoate peroxide, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, tributyl peroxyacetate, 2,2-bis(tert-butylperoxy)butane, tributyl peroxybenzoate, n-butyl 4,4-bis(tert-butylperoxy)valerate, ditert-butyl peroxyisophthalate, α,α'-bis(tert-butylperoxy)diisopropylbenzene, diisopropylbenzene peroxide, 2,5-di Organic peroxides such as methyl-2,5-di(tert-butylperoxy)hexane, tert-butylisopropylphenyl peroxide, ditert-butylperoxide, hydroperoxide p-menthane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, diisopropylphenyl hydroperoxide, tert-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, hydroperoxide cumene, tert-hexyl hydroperoxide, and tert-butyl hydroperoxide. Only one of these peroxides may be used, or two or more may be used in combination.

[0074] Specific examples of azo initiators include 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-formonitrile), 2-(aminomethoxyazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylpentanenitrile, azobis(tert-octane), azobis(tert-butane), and other azo compounds. Only one of these compounds may be used, or two or more may be used in combination. Furthermore, a redox reaction can occur by combining it with a redox polymerization initiator, which is a combination of peroxides and reducing agents such as ascorbic acid, sodium ascorbate, sodium isoascorbate, tartaric acid, citric acid, metal salts of formaldehyde hyposulfite, sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium metabisulfite, and ferric chloride (III).

[0075] 3-3. Active Energy Line Cationic Polymerization Initiator The active energy line cationic polymerization initiator used in this invention is not particularly limited, and examples include monium salts, strontium salts, diazo-onium salts, selenium salts, pyridinium salts, ferrocene salts, and phosphonium salts. Among these, monium salts and strontium salts are preferred. When the active energy line cationic polymerization initiator is a monium salt or a strontium salt, examples of relative anions include BF4-, AsF6-, SbF6-, PF6-, and B(C6F5)4-.

[0076] Examples of the above-mentioned iron salts include tetra(pentafluorophenyl)boronic acid (triisopropylphenyl)iron, diphenyliron hexafluorophosphate, diphenyliron hexafluoroantimony, diphenyliron tetrafluoroboronic acid, diphenyliron tetra(pentafluorophenyl)boronic acid, bis(dodecylphenyl)iron hexafluorophosphate, bis(dodecylphenyl)iron hexafluoroantimony, bis(dodecylphenyl)iron tetrafluoroboronic acid, bis(dodecylphenyl)iron tetra(pentafluorophenyl)boronic acid, 4-methylphenyl-4-(1-methylethyl)phenyliron hexafluorophosphate, 4-methylphenyl-4-(1-methylethyl)phenyliron hexafluoroantimony, 4-methylphenyl-4-(1-methylethyl)phenyliron tetrafluoroboronic acid, and 4-methylphenyl-4-(1-methylethyl)phenyliron tetra(pentafluorophenyl)boronic acid. Furthermore, commercially available products can also be used as the aforementioned styrene salts. Specifically, examples include "UV-9380C" (trade name) manufactured by GE Toshiba Silicones Co., Ltd., "RHODOSIL PHOTOINITIATOR 2074" (trade name) manufactured by Rhodia Corp., and "WPI-116" (trade name) and "WPI-113" (trade name) manufactured by FUJIFILM Wako Pure Chemical Corporation. Only one of these can be used, or two or more can be used in combination.

[0077] As the above-mentioned strontium salts, examples include bis[4-(diphenylstrontium)phenyl]sulfide bis(hexafluorophosphate), bis[4-(diphenylstrontium)phenyl]sulfide bis(hexafluoroantimonate), bis[4-(diphenylstrontium)phenyl]sulfide bis(tetrafluoroborate), bis[4-(diphenylstrontium)phenyl]sulfide tetra(pentafluorophenyl)borate, diphenyl-4-(phenylthio)phenyl strontium hexafluorophosphate, diphenyl-4-(phenylthio)phenyl strontium hexafluoroantimonate, diphenyl-4-(phenylthio)phenyl strontium tetrafluoroborate, and diphenyl-4-(phenylthio)phenyl tetra(pentafluorophenyl)borate. Sirium, triphenyl strontium hexafluorophosphate, triphenyl strontium hexafluoroantimony, triphenyl strontium tetrafluoroborate, triphenyl strontium tetra(pentafluorophenyl)borate, bis[4-(di(4-(2-hydroxyethoxy))phenylstrontium)phenyl]sulfide bis(hexafluorophosphate), bis[4-(di(4-(2-hydroxyethoxy))phenylstrontium)phenyl]sulfide bis(hexafluoroantimony), bis[4-(di(4-(2-hydroxyethoxy))phenylstrontium)phenyl]sulfide bis(tetrafluoroborate), bis[4-(di(4-(2-hydroxyethoxy))phenylstrontium)phenyl]sulfide tetra(pentafluorophenyl)borate, etc. Furthermore, commercially available strontium salts can also be used. Specifically, examples include "Cyracure UVI-6990," "Cyracure UVI-6992," and "Cyracure UVI-6974" manufactured by Dow Chemical Japan Ltd., and "Adeka Optomer SP-150," "Adeka Optomer SP-152," "Adeka Optomer SP-170," and "Adeka Optomer SP-172" manufactured by ADEKA. Only one type can be used, or two or more can be used in combination.

[0078] Examples of the above-mentioned diazonium salts include benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, and benzenediazonium hexafluoroborate. Only one of these may be used, or two or more may be used together.

[0079] 3-4. Thermal cationic polymerization initiator There are no particular limitations on the thermal cationic polymerization initiator used in this invention, and examples include strontium salts, phosphonium salts, and quaternary ammonium salts. Among these, strontium salts are preferred. Examples of relative anions in thermal cationic polymerization initiators include AsF6-, SbF6-, PF6-, and B(C6F5)4-.

[0080] Examples of the aforementioned strontium salts include triphenylstrontium boron tetrafluoride, triphenylstrontium antimony hexafluoride, triphenylstrontium arsenic hexafluoride, tris(4-methoxyphenyl)strontium arsenic hexafluoride, and diphenyl(4-phenylthienyl)strontium arsenic hexafluoride. Furthermore, commercially available strontium salts may also be used, specifically, examples include "Adeka Opton CP-66" and "Adeka Opton CP-77" manufactured by ADEKA Corporation, and "San-Aid SI-60L," "San-Aid SI-80L," and "San-Aid SI-100L" manufactured by SANSHIN CHEMICAL INDUSTRY CO.,LTD. Only one of these salts may be used, or two or more may be used in combination.

[0081] Examples of the above-mentioned phosphonium salts include ethyltriphenylphosphonium antimony hexafluoride and tetrabutylphosphonium antimony hexafluoride. Examples of the above-mentioned quaternary ammonium salts include N,N-dimethyl-N-benzylphenylammonium antimony hexafluoride, N,N-diethyl-N-benzylphenylammonium boron tetrafluoride, N,N-dimethyl-N-benzylpyridinium antimony hexafluoride, N,N-diethyl-N-benzylpyridinium trifluoromethanesulfonate, N,N-dimethyl-N-(4-methoxybenzyl)pyridinium antimony hexafluoride, N,N-diethyl-N-(4-methoxybenzyl)pyridinium antimony hexafluoride, N,N-diethyl-N-(4-methoxybenzyl)tolueneammonium antimony hexafluoride, and N,N-dimethyl-N-(4-methoxybenzyl)tolueneammonium antimony hexafluoride. Only one of these salts may be used, or two or more may be used in combination.

[0082] 4. Primer Composition for Inorganic Material Lamination Layers The primer composition for inorganic material lamination layers of the present invention (hereinafter also referred to as "the composition of the present invention") comprises the polysiloxane compound of the present invention, and a free radical polymerization initiator and / or a cationic polymerization initiator. The polysiloxane compound of the present invention has excellent flowability and curability, and the inorganic material layer formed by lamination onto the surface of a cured material using a dry film-forming method as described below has excellent adhesion, and the cured material has excellent heat resistance, scratch resistance, and / or hardness. Therefore, the composition of the present invention can be used as a primer, applied to a resin substrate, to laminate an inorganic material layer onto the resin substrate using a dry film-forming method. The composition of the present invention comprises the polysiloxane compound, and a free radical polymerization initiator and / or a cationic polymerization initiator, but various components (hereinafter referred to as "other components") may be formulated as needed. Other components are preferably polymerizable compounds capable of co-polymerizing with polysiloxane compounds, such as (meth)acrylate compounds, cationic polymerizable compounds, compounds having vinyl unsaturated groups, free radical polymerization inhibitors, antioxidants, solvents, heat resistance enhancers, and polysiloxanes. The other components will be described below.

[0083] 4-1. (Meth)acrylate compounds The composition of the present invention contains a polysiloxane compound represented by formula (1), and further, compounds having acrylonitrile or methacrylonitrile (hereinafter referred to as (meth)acrylate compounds) can be formulated to adjust the scratch resistance and hardness of the hardened material formed by the composition of the present invention, or to adjust the viscosity and hardness of the composition of the present invention.

[0084] There are no particular limitations on the (meth)acrylate compound, and examples include compounds having one (meth)acrylic group (hereinafter referred to as "monofunctional (meth)acrylate") and compounds having two or more (meth)acrylic groups (hereinafter referred to as "polyfunctional (meth)acrylate").

[0085] Examples of monofunctional (meth)acrylates include: alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate; monofunctional (meth)acrylates having alicyclic groups such as cyclohexyl methacrylate, tributylcyclohexyl methacrylate, isoborneol methacrylate, and tricyclodecane hydroxymethyl methacrylate; and monofunctional (meth)acrylates having aromatic groups such as benzyl methacrylate and phenyl methacrylate. (Meth)acrylates of phenol ethylene oxide adducts, (Meth)acrylates of phenol propylene oxide adducts, (Meth)acrylates of modified nonylphenol ethylene oxide adducts, (Meth)acrylates of nonylphenol propylene oxide adducts, (Meth)acrylates of p-cumylphenol alkyl oxide adducts, (Meth)acrylates of o-phenylphenol (Meth)acrylates, and (Meth)acrylates of o-phenylphenol alkyl oxide adducts, etc., are alkyl oxide adducts of phenol derivatives; monofunctional (Meth)acrylates with alkoxyalkyl groups, such as 2-ethylhexylcarbitol (Meth)acrylate; tetrahydrofurfuryl (Meth)acrylate and N-(2-(meth)acryloxyethyl)hexahydrophthalimide, etc., are heterocyclic monofunctional (Meth)acrylates; Hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, and hydroxyhexyl methacrylate, etc., are all hydroxyalkyl methacrylates; monofunctional methacrylates with hydroxyl and aromatic groups, such as 2-hydroxy-3-phenoxypropyl methacrylate; alkyl glycol monomethacrylates such as diethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, triethylene glycol monomethacrylate, and tripropylene glycol monomethacrylate; and monofunctional methacrylates with carboxyl groups, such as ω-carboxylated polycaprolactone monomethacrylate and phthalic acid monohydroxyethyl methacrylate.Examples of multifunctional (meth)acrylates include diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene oxide-modified neopentyl glycol dimethacrylate, and ethylene oxide-modified bisphenol A dimethacrylate. Acrylates, propylene oxide-modified bisphenol A di(meth)acrylate, ethylene oxide-modified hydrogenated bisphenol A di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane allyl ether di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexaacrylate, etc.

[0086] As a polyfunctional (meth)acrylate, (meth)acrylate aminocarbamate can also be used. Examples of (meth)acrylate aminocarbamates include compounds obtained by adding organic polyisocyanates to hydroxyl-containing (meth)acrylates, and compounds obtained by adding organic polyisocyanates, polyols, and hydroxyl-containing (meth)acrylates. Only one of these compounds may be used, or two or more may be used in combination, or different types of compounds may be used in combination.

[0087] Here, examples of polyols include low molecular weight polyols, polyether polyols, polyester polyols, and polycarbonate polyols. Examples of low molecular weight polyols include ethylene glycol, propylene glycol, neopentyl glycol, cyclohexanediol, and 3-methyl-1,5-pentanediol. Examples of polyether polyols include polypropylene glycol and poly1,4-butanediol. Examples of polyester polyols include reactions of such low molecular weight polyols and / or polyether polyols with dicarboxylic acids such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid, and terephthalic acid, or their anhydrides. Only one of these compounds may be used, or two or more may be used in combination, or different types of compounds may be used in combination.

[0088] Examples of organic polyisocyanates include toluene diisocyanate, phenyl diisocyanate, tetramethylphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,6-hexane diisocyanate, and isoflavone diisocyanate. Examples of hydroxyl-containing (meth)acrylates include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate, as well as hydroxyl-containing polyfunctional (meth)acrylates such as pentaerythritol trimethacrylate, dimethacrylates of 3-molar adducts of isocyanuric acid epoxy esters, and dipentaerythritol pentaacrylate. Only one of these compounds may be used, or two or more may be used in combination, or different types of compounds may be used in combination.

[0089] When the composition of the present invention further includes a (meth)acrylate compound, there is no particular limitation on its mixing ratio. The mixing ratio of the (meth)acrylate compound is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, and even more preferably 20 parts by weight or less, relative to 100 parts by weight of the polysiloxane compound represented by formula (1). From the viewpoint of adhesion to the inorganic material layer, the mixing ratio of the (meth)acrylate compound is preferably lower, preferably 10% by weight or less, more preferably 5% by weight or less, and even more preferably 1% by weight or less.

[0090] 4-2. Compounds with an vinyl unsaturated group other than (meth)acrylate compounds may be added to the composition of the present invention for purposes such as reducing viscosity or improving adhesion to the adherend when used under solvent-free conditions. Preferably, the vinyl unsaturated group is (meth)acrylyl, maleic anhydride, (meth)acrylamide, or vinyl. Specific examples of compounds with an vinyl unsaturated group include (meth)acrylic acid, a macomer of acrylic acid, N-(2-hydroxyethyl)limoneneimide, N,N-dimethylacrylamide, acrylmorpholine, N-vinylpyrrolidone, and N-vinylcaprolactone. Only one of these compounds may be used, or two or more may be used in combination.

[0091] Furthermore, when the compound having an ethylene unsaturated group is included in the composition of the present invention, from the viewpoint of the adhesion and weather resistance of the inorganic material layer, the proportion of the compound having an ethylene unsaturated group is preferably 10% by weight or less, more preferably 5% by weight or less, and even more preferably 1% by weight or less, relative to the total weight of the polysiloxane compound represented by formula (1).

[0092] 4-3. Cationic Polymerizable Compounds When the polysiloxane represented by formula (1) comprises a monovalent organic group having an epoxy group or an oxetyl group, the composition of the present invention is preferably a cationic polymerizable compound other than the polysiloxane, in order to improve the hardness of the hardened material or the adhesion to the adhered material. The cationic polymerizable compound is a cationic polymerizable compound other than the polysiloxane compound represented by formula (1), and examples include epoxy compounds (compounds having an epoxy group), other compounds having an oxetyl group (other compounds containing an oxetyl group), compounds having a vinyl ether group (vinyl ether compounds), etc. Such compounds may be used alone or in combination of two or more. When the epoxy compound has at least an oxetyl group in the polysiloxane compound represented by formula (1), it is particularly preferred because it facilitates the cationic polymerization of the oxetyl group in the polysiloxane compound represented by formula (1).

[0093] Examples of such epoxy compounds include monofunctional epoxy compounds and polyfunctional epoxy compounds. Examples of polyfunctional epoxy compounds include dicyclopentadiene dioxide, limonene dioxide, 4-vinylcyclohexene dioxide, and methyl 3,4-epoxycyclohexylcarboxylic acid (3,4-epoxycyclohexyl) (e.g., Celloxide manufactured by Diacel Corporation). 2021P (trade name), di(3,4-epoxycyclohexyl) adipic acid ester, bisphenol A type epoxy resin, halogenated bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S diglycidyl ether, bisphenol F type epoxy resin, 1,6-hexanediol diglycidyl ether, poly1,4-butanediol diglycidyl ether, compounds of polybutadiene with glycidyl etherification at both ends, o-cresol phenolic varnish type epoxy resin, m-cresol phenolic varnish type epoxy resin, p-cresol phenolic varnish type epoxy resin, phenolic varnish type epoxy resin, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, internal epoxides of polybutadiene, and styrene-butadiene copolymers such as "Epofriend" (trade name) manufactured by Daicel Co., Ltd. The compounds include compounds with partially epoxidized double bonds, compounds with partially epoxidized isoprene polymer portions in block copolymers comprising ethylene-butene copolymer portions and isoprene polymer portions such as "L-207" (trade name) manufactured by KRATON, compounds with partially epoxidized isoprene polymer portions, compounds with an epoxidized vinyl structure in ring-opening polymers of 4-vinylcyclohexene oxide such as "Q-4" (Q8 series) manufactured by Mayaterials, cage-like silsesquioxanes with glycidyl groups such as "Q-5" (Q8 series) manufactured by Mayaterials, alicyclic cage-like silsesquioxanes with epoxy groups, epoxidized silsesquioxane compounds, and epoxidized vegetable oils. From the viewpoint of weather resistance, the compositions of the present invention are preferably those containing polyfunctional epoxy compounds.

[0094] Furthermore, examples of monofunctional epoxy compounds include α-olefin epoxides such as 1,2-epoxyhexadecane, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, and glycidyl methacrylate.

[0095] Other compounds containing oxocyclic butyl groups include monofunctional and polyfunctional oxocyclic butyl compounds. Examples of polyfunctional oxocyclic butyl compounds include 1,4-bis{[(3-ethyl-3-oxetane-3-yl)methoxy]methyl}benzene (XDO), di[2-(3-oxetane-3-yl)butyl]ether (DOX), 1,4-bis[(3-ethyloxetane-3-yl)methoxy]benzene (HQOX), 1,3-bis[(3-ethyloxetane-3-yl)methoxy]benzene (RSOX), 1,2-bis[(3-ethyloxetane-3-yl)methoxy]benzene (CTOX), 4,4'-bis[(3-ethyloxetane-3-yl)methoxy]biphenyl (4,4'-BPOX), 2,2'-bis[(3-ethyl-3-oxetane-3-yl)methoxy]methyl}benzene (HQOX), 1,4-bis[(3-ethyloxetane-3-yl)methoxy]benzene (RSOX), 1,2-bis[(3-ethyloxetane-3-yl)methoxy]benzene (CTOX), 4,4'-bis[(3-ethyloxetane-3-yl)methoxy]biphenyl (4,4'-BPOX), 2,2'-bis[(3-ethyl-3-oxetane-3-yl)methoxy]benzene (HQOX), 1,4-bis[(3-ethyl ...-3-oxetane-3-yl)methoxy]benzene (HQOX), 1, [4,4'-bis(3-ethyloxetane-3-yl)methoxy]biphenyl (2,2'-BPOX), 3,3',5,5'-tetramethyl[4,4'-bis(3-ethyloxetane-3-yl)methoxy]biphenyl (TM-BPOX), 2,7-bis[(3-ethyloxetane-3-yl)methoxy]naphthalene (2,7-NpDOX), 1,6-bis[(3-ethyloxetane-3-yl)methoxy]-2,2,3,3,4,4,5,5-octafluorohexane (OFH-DOX), 3(4),8(9)-bis[(1-ethyl-3-oxetane-butyl)methoxymethyl]-tricyclo[5.2.1.02.6]decane, 1,2-bis[2-[(1-ethyl-3-oxetane-butyl)methoxy]methoxy] [Ethylthio]ethane, 4,4'-bis[(1-ethyl-3-oxetane-3-yl)methyl]thiodiphenyl sulfide, 2,3-bis[(3-ethyloxetane-3-yl)methoxymethyl]norbornene (NDMOX), 2-ethyl-2-[(3-ethyloxetane-3-yl)methoxymethyl]-1,3-O-bis[(1-ethyl-3-oxetane-3-yl)methyl]-propane-1,3-diol (TMPTOX), 2,2-dimethyl-1,3-O-bis[(3-ethyloxetane-3-yl)methyl]-propane-1,3-diol (NPGOX), 2-butyl-2-ethyl-1,3-O-bis[(3-ethyloxetane-3-yl)methyl]-propane-1,3-diol [3-ethyloxetane-1,3-diol, 1,4-O-bis[(3-ethyloxetane-3-yl)methyl]butane-1,4-diol, 2,4,6-O-tris[(3-ethyloxetane-3-yl)methyl]cyanuric acid, ethers of bisphenol A and 3-ethyl-3-chloromethyloxetane (hereinafter referred to as "OXC") (BisAOX), ethers of bisphenol F and OXC (BisFOX), ethers of phenolic varnish and OXC (PNOX), ethers of cresol varnish and OXC (CNOX), oxetane-butylsilsesquioxane (OX-SQ), and silane oxides of 3-ethyl-3-hydroxymethyloxetane (OX-SC), etc.

[0096] Furthermore, examples of monofunctional oxetane compounds include 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane (EHOX), 3-ethyl-3-(dodecylsiloxymethyl)oxetane (OXR-12), 3-ethyl-3-(octadecylsiloxymethyl)oxetane (OXR-18), 3-ethyl-3-(phenoxymethyl)oxetane (POX), and 3-ethyl-3-hydroxymethyloxetane (OXA).

[0097] Among these, dicyclopentadiene dioxide, limonene dioxide, 4-vinylcyclohexene dioxide, 3,4'-epoxycyclohexanecarboxylic acid methyl ester, di(3,4-epoxycyclohexyl) adipic acid, and epoxy-containing silsesquioxane compounds are preferred; more preferably, 3,4-epoxycyclohexanecarboxylic acid methyl ester and the following epoxy-containing silsesquioxane compounds are preferred. Furthermore, from the viewpoint of improving the adhesion of the inorganic material layer, epoxy-containing silsesquioxane compounds and epoxy-containing polysiloxane compounds, and other organic-inorganic mixed compounds with epoxy groups, are particularly preferred.

[0098]

[0099] Examples of the aforementioned vinyl ether compounds include monofunctional vinyl ether compounds and polyfunctional vinyl ether compounds. Examples of polyfunctional vinyl ether compounds include cyclohexanediethanol divinyl ether, triethylene glycol divinyl ether, and phenolic varnish-type divinyl ether. Examples of monofunctional vinyl ether compounds include hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, dodecyl vinyl ether, allyl ether propylene glycol carbonate, and cyclohexyl vinyl ether.

[0100] When the cationic curable composition of the present invention contains the cationic polymeric compound, the content of the cationic polymeric compound is not particularly limited. It is preferably 0.1 to 100 parts by weight, more preferably 0.1 to 50 parts by weight, and even more preferably 1 to 25 parts by weight, relative to 100 parts by weight of the polysiloxane compound represented by formula (1). If the content of the cationic polymeric compound is within this range, the curability of the composition of the present invention and the hardness of the obtained cured product are excellent. Furthermore, when the composition of the present invention contains a cationic polymeric compound other than the polysiloxane compound represented by formula (1), from the viewpoint of the adhesion of the inorganic material layer, the content is preferably 25% by weight or less, more preferably 10% by weight or less, and even more preferably 5% by weight or less, relative to the total weight of the polysiloxane compound represented by formula (1).

[0101] 4-4. Organic polymers Based on the aim of reducing hardening shrinkage with inexpensive components, organic polymers may also be incorporated into the composition of the present invention. Suitable polymers include (meth)acrylic acid polymers, and suitable constituent monomers include methyl methacrylate, cyclohexyl (meth)acrylate, and N-(2-(meth)acryloxyethyl)tetrahydrophthalimide, etc.

[0102] Furthermore, when the organic polymer is included in the composition of the present invention, from the viewpoint of the adhesion and weather resistance of the inorganic material layer, the content is preferably 10% by weight or less, more preferably 5% by weight or less, and even more preferably 1% by weight or less, relative to the total weight of the polysiloxane compound represented by formula (1).

[0103] 4-5. Free Radical Polymerization Inhibitors and Antioxidants For the purpose of improving storage stability or thermal stability, free radical polymerization inhibitors or antioxidants may also be added to the composition of the present invention. There are no particular limitations on the polymerization inhibitors or antioxidants used, and known free radical scavengers may be used. Specific examples of free radical polymerization inhibitors include phenolic compounds such as hydroquinone or hydroquinone monomethyl ether. Specific examples of antioxidants include hindered phenolic antioxidants such as 2,6-di-tert-butyl-4-methylphenol or 2,4-dimethyl-6-tert-butylphenol, pentaerythritol tetra(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), and 3-hydroxythiophenol. Furthermore, α-nitroso-β-naphthol, p-benzoquinone, and copper salts may also be included. Furthermore, aluminum salts of N-nitrosophenylhydroxylamine manufactured by Fujifilm and Koujun Pharmaceutical Co., Ltd., or 2-[1-(2-hydroxy-3,5-diterpentylphenyl)ethyl]-4,6-diterpentylphenyl ester manufactured by Sumitomo Chemical Co., Ltd., may also be used. Only one of these can be used, or two or more can be used in combination. Additionally, sulfur-based secondary antioxidants such as 4,6-bis(octylthiomethyl)o-cresol, or phosphorus-based secondary antioxidants, may also be added.

[0104] 4-6. Solvent When the composition of the present invention is in liquid form, it can be directly coated onto the surface of a substrate, or it can be diluted with a solvent as needed. When using a solvent, it is preferable to use a solvent that dissolves the polysiloxane compound of the present invention. Examples include various organic solvents such as aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, chlorinated hydrocarbon solvents, alcohol solvents, ether solvents, amide solvents, ketone solvents, ester solvents, and cellosolve solvents. There are no particular limitations on the organic solvent; examples include: alcohols such as methanol, ethanol, isopropanol, and isobutanol; alkyl glycol monoalkyl ethers such as propylene glycol monomethyl ether; aromatic compounds such as toluene and xylene; esters such as propylene glycol monomethyl ether acetate, ethyl acetate, and butyl acetate; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethers such as dibutyl ether; and N-methylpyrrolidone, etc. Only one of these can be used, or two or more can be used in combination. When using a solvent, it is preferable to allow the solvent contained in the coated film to evaporate before the composition of the present invention hardens. Solvent evaporation can occur in air or in an inert gas atmosphere. Heating can be performed to allow the solvent to evaporate; the preferred heating temperature is below 100°C.

[0105] 4-7. Heat Resistance Enhancer The composition of the present invention may include a heat resistance enhancer. There are no particular limitations on the heat resistance enhancer; known compounds may be used, such as ferric 2-ethylhexanoate (e.g., tri(2-ethylhexanoate)ferric(III)), cerium 2-ethylhexanoate (e.g., tri(2-ethylhexanoate)cerium(III)), and organocarboxylic acid metal salts such as zirconium(IV) tetra(2-ethylhexanoate) and zirconium(IV) bis(2-ethylhexanoate), as well as metal oxides such as iron oxide, cerium oxide, and zirconium oxide. There are no particular limitations on the proportion of the heat resistance enhancer used; for example, it may be 0 to 10,000 ppm by weight, 1 to 1,000 ppm by weight, 5 to 500 ppm by weight, or 10 to 300 ppm by weight relative to 100 parts by weight of the polysiloxane compound of the present invention. By adding heat resistance enhancers, it is possible to suppress the rise or fall of thermal weight reduction due to temperature, suppress the decrease of dielectric constant when used and stored under heating and at room temperature, suppress the decrease of insulation, suppress the occurrence of cracks, and suppress coloring.

[0106] 4-8. Polysiloxane The composition of the present invention may include polysiloxane. There are no particular limitations on the polysiloxane used; known compounds may be used, such as polydimethylpolysiloxane, polydiphenylpolysiloxane, polymethylphenylpolysiloxane, etc., and functional groups may be present at its ends and / or side chains. There are no particular limitations on the aforementioned functional groups; examples include (meth)acrylic acid, epoxy, oxetyl, vinyl, hydroxyl, carboxyl, amino, mercapto, etc. There are no particular limitations on the proportion of polysiloxane used; for example, 0 to 100 parts by weight, 1 to 50 parts by weight, 5 to 40 parts by weight, or 5 to 30 parts by weight relative to the total amount of the polysiloxane compound of the present invention.

[0107] 4-9. Other Components Besides the Above Other components may be added to the composition of the present invention as needed. Specifically, it may also contain surfactants, antistatic agents (e.g., conductive polymers), leveling agents such as polysiloxane polymers and polymers containing fluorine atoms, photosensitizers, ultraviolet absorbers, stabilizers, lubricants, pigments, dyes, plasticizers, suspending agents, nanoparticles, nanofibers, nanosheets, and various fillers such as silica or alumina, and any other auxiliary agents. Furthermore, it may also contain silane-based reactive diluents such as tetraalkoxysilanes, trialkoxysilanes, dialkoxysilanes, monoalkoxysilanes, and disiloxanes.

[0108] 5. The resin substrate used for laminating the inorganic material layer of the present invention is not particularly limited. Examples include polyethylene resin, polypropylene resin, acrylonitrile butadiene styrene (ABS) resin, polyamide resin, acrylic resin, vinylidene chloride resin, polycarbonate resin (PC), polyurethane resin, epoxy resin, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene phthalate (PBT) and other polyester resins, polystyrene resin, polyvinyl chloride resin, polyacrylonitrile resin, polyimide resin, polyacrylate and polymethyl methacrylate (PMMA) and other acrylic resins, cyclic olefin polymers (Cyclo-Olefin Polymer, Resins such as COP, cycloolefin copolymers (Cyclo Olefin Copolymer, COC), acetate resins, fluoroethylene resins, polyarylates, cellophane, polyether ether, norcamphene resins, and acetylated cellulose resins such as triacetyl cellulose (TAC), or various fiber-reinforced plastics (FRP), etc. Furthermore, as a resin base material, it is preferable to have appropriate physical properties according to the intended use. For example, from the viewpoint of heat resistance, melting point is preferably 150°C or higher, more preferably 200°C or higher. From the viewpoint of optical properties, turbidity (haze), birefringence, refractive index, etc. are preferred. For example, haze (ASTM D1003) is preferably 2% or less, more preferably 0.5% or less. For example, retardation (parallel polarizer rotation method) is preferably 30 or less, more preferably 20 or less, and even more preferably 5 or less. For example, a refractive index of 1.48 or higher is preferred. From an optical property perspective, polycarbonate resin and polymethyl methacrylate are suitable. From a gas barrier property perspective, polyethylene terephthalate is suitable. Furthermore, as such a resin substrate, it is ideal to use a resin substrate with excellent coatability and adhesion to the primer composition of the present invention. To further improve the adhesion of the cured inorganic material laminate of the present invention, for example, a surface-active treatment such as corona discharge treatment, ultraviolet irradiation treatment, and plasma treatment can be used.Furthermore, the shape of the resin substrate used in this invention is not particularly limited; for example, films, sheets, lenses, and plates can be arbitrarily selected depending on the application.

[0109] 6. Inorganic material layer As the inorganic material layer in this invention, it can be formed by dry film formation method, without any particular limitation. Examples include layers with various metals or metal oxides, nitrides and sulfides as the main components, having at least one of the elements such as Si, Ti, Zn, Al, Ga, In, Ce, Bi, Sb, B, Zr, Sn, Ta, Ag and Pt. As materials for forming inorganic layers, specifically, examples of low-refractive-index materials include sodium fluoride, cryolite, chiolite, lithium fluoride, magnesium fluoride, aluminum fluoride, calcium fluoride, strontium fluoride, zirconium fluoride, silicon dioxide, barium fluoride, and yttrium fluoride; examples of medium-refractive-index materials include OL-B (a mixture of silicon dioxide and aluminum oxide), lanthanum fluoride, neodymium fluoride, thiocyanate fluoride, cerium fluoride, aluminum oxide, tungsten oxide, magnesium oxide, lead fluoride, silicon monoxide, lanthanum oxide, yttrium oxide, and others. Scandium, europium oxide, molybdenum oxide, samarium fluoride, and tungsten oxide are examples of high refractive index materials. Other examples include indium oxide, tin oxide, hafnium oxide, tantalum oxide, zirconium oxide, antimony oxide, zinc oxide, cerium oxide, OS-5 (a mixture of zirconium oxide and titanium dioxide), neodymium oxide, niobium oxide, zinc sulfide, titanium trioxide, titanium pentoxide, titanium monoxide, titanium dioxide, silicon, and germanium. Metals include silver, aluminum, gold, chromium, copper, hafnium, indium, molybdenum, nickel, platinum, tantalum, titanium, and tungsten. Furthermore, germanium oxide, indium tin oxide (ITO), MS-DC100, and MS-SY are examples of other functional agents. Additionally, high-hardness and highly insulating diamond-like carbon (DLC) films are also examples. DLC film is an amorphous carbon film with sp3 bonds between carbon atoms. It is very hard and has a low coefficient of friction, wear resistance, corrosion resistance and gas barrier properties. It is a diamond-shaped carbon film with excellent insulation properties.

[0110] As an inorganic material layer in this invention, it is acceptable to have at least one layer, and there may be multiple layers. When there are multiple inorganic material layers, there are no particular restrictions on the stacking order or the type of inorganic material layer. Furthermore, the inorganic material layer may be a variety of functional layers such as an ultraviolet absorption layer or a functional layer.

[0111] When an inorganic material layer is used as the DLC layer, it is preferable that the metal oxide layer is stacked and the stacked layer is the outermost layer in terms of having the above-mentioned properties.

[0112] The inorganic material layer is arbitrarily selected according to the intended use.

[0113] The deposition method of the inorganic material layer in this invention is not particularly limited as long as it is a dry film formation method. Examples include vacuum evaporation such as resistance heating evaporation, electron beam heating evaporation, and high-frequency induction heating evaporation; physical vapor deposition methods such as molecular beam epitaxy, ion beam deposition, ion plating, sputtering, and laser ablation (hereinafter also referred to as "PVD" or physical vapor deposition); or chemical vapor deposition methods such as thermal CVD, plasma CVD, photo-CVD, epitaxial CVD, atomic layer CVD, catCVD, and organometallic CVD (hereinafter also referred to as "CVD" or chemical vapor deposition). Physical vapor deposition is preferred. The dry film formation method referred to here means treating the material surface in a gaseous or molten state, which is also commonly referred to as a dry process.

[0114] The thickness of the inorganic material layer is not particularly limited and can be arbitrarily set according to the purpose or application. For example, from the viewpoint of scratch resistance of the inorganic material layer, it is preferable to be 5 nm or more, more preferably 50 nm or more, and even more preferably 100 nm or more, and even more preferably 150 nm or more. The upper limit of the inorganic material layer thickness is not particularly limited, but it is preferably 25 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less. The thickness of the inorganic material layer can be adjusted by adjusting the processing time, etc., during physical vapor deposition.

[0115] Since the inorganic material layer formed by the above-described manner in the laminate of the present invention is inorganic, it can have excellent appearance, weather resistance and scratch resistance that organic film does not possess, and has excellent adhesion to the hardened material used for lamination of the inorganic material layer, and its weather resistance, water resistance and scratch resistance are very excellent.

[0116] 8. Method for manufacturing a primer composition for inorganic material lamination layers and its cured form. The curable composition of the present invention can be obtained by mixing raw material components. A known mixer or similar equipment can be used for mixing. Specifically, reaction flasks, changeover mixers, planetary mixers, dispersers, Henschel mixers, kneaders, ink rollers, extruders, three-roll mills, sand mills, etc., can be used. The composition of the present invention is cured by coating the composition onto a suitable resin substrate, etc., and then causing a polymerizable reaction by methods such as irradiation with active energy lines, heating, or irradiation with active energy lines and heating. The composition of the present invention may contain a solvent or may not contain a solvent. When it contains a solvent, it is usually used for curing after the solvent is removed, as described above.

[0117] 8-1. Curable Composition The composition of the present invention comprises the polysiloxane compound represented by formula (1), and the free radical polymerization initiator and / or cationic polymerization initiator. Other components may also be included. When a solvent is included as another component, the solvent is usually removed by drying or other means before the composition of the present invention is cured to obtain a cured product and thus form a base coating. Therefore, in the composition of the present invention, the proportion of the polysiloxane compound represented by formula (1) among all components other than the solvent is preferably 50 parts by weight or more, more preferably 70 parts by weight or more, and even more preferably 90 parts by weight or more. By setting the above preferred range, a cured product with good adhesion to the inorganic material layer can be obtained. When mixing solvents, the amount used can be set arbitrarily according to the purpose and there is no particular limitation. For example, relative to 100 parts by weight of the polysiloxane compound represented by formula (1), it can be set to 1 to 20,000 parts by weight, more preferably 10 to 1,000 parts by weight, and even more preferably 50 to 500 parts by weight.

[0118] 8-2. Coating Method There are no particular limitations on the method of coating the composition of the present invention onto the resin substrate, and it can be appropriately selected according to the constituent materials and shape of the substrate. For example, conventional coating methods such as casting, spin coating, rod coating, dip coating, spraying, roller coating, flow coating, and gravure coating can be used. There are no particular limitations on the coating thickness of the composition of the present invention, and it can be arbitrarily set according to the purpose, preferably 0.1 to 100 μm, more preferably 0.5 to 50 μm, and even more preferably 1 to 10 μm.

[0119] 8-3. Curing Method In this invention, the curing method and curing conditions are selected according to whether the curable composition is heat-curable and / or thermo-curable. Furthermore, the curing conditions (for heat-curing, such as the type and amount of light source, and for thermo-curing, such as heating temperature and heating time) are suitably selected based on the type and amount of polymerization initiator and other polymerizable compounds contained in the composition according to this invention.

[0120] (1) Active Energy Line Curing Method When the composition of the present invention is an active energy line curing composition, the curing method is to irradiate it with an active energy line using a known active energy line irradiation device. Examples of active energy lines include electron beams, ultraviolet light, visible light, and X-rays, with light being preferred. Ultraviolet light is preferred because inexpensive devices can be used. Examples of ultraviolet irradiation devices include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, ultraviolet (UV) electrodeless lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, and light-emitting diodes (LEDs). The light irradiation intensity of the film coated with the composition of the present invention can be selected according to the purpose or application. The light irradiation intensity in the effective activation wavelength region of the active energy line polymerization initiator (called a photopolymerization initiator when photocuring) (which varies depending on the type of photopolymerization initiator, preferably using light with a wavelength of 220–460 nm) is preferably 0.1–1000 mW / cm². Furthermore, the irradiation energy should be appropriately set according to the type and formulation of the active energy line, and the light irradiation time of the film can also be selected according to the purpose or application. Preferably, the cumulative light intensity, expressed as the product of the light irradiation intensity and the light irradiation time in the wavelength region, is set to 10–7,000 mJ / cm². More preferably, it is 200–5,000 mJ / cm², and even more preferably, it is 500–3500 mJ / cm². If the cumulative light intensity is within this range, the curing of the composition will proceed smoothly, and a uniform cured product can be easily obtained.

[0121] Furthermore, heat curing can also be appropriately combined before and / or after light curing. For example, two-stage curing can be performed, in which the substrate having areas that become shadowed when exposed to light is impregnated with the composition of the present invention and then exposed to light, so that the composition of the present invention in the light-exposed areas is cured first, and then heated to cure the composition of the present invention in the areas not exposed to light. There are no particular limitations on such substrates, and examples include substrates with complex shapes such as cloth-like, fibrous, powdery, porous, and uneven surfaces, or shapes formed by combining two or more of these shapes.

[0122] (2) Thermosetting Method When the composition of the present invention is a thermosetting composition, the curing method and curing conditions are not particularly limited. The curing temperature is preferably 80°C to 200°C, more preferably 100°C to 180°C, and even more preferably 110°C to 150°C. Furthermore, the curing temperature can be set to a fixed temperature or can be increased. In addition, heating and cooling can also be combined. The curing time is appropriately selected according to the type of thermopolymerization initiator and the content ratio of other components, preferably 10 to 360 minutes, more preferably 30 to 300 minutes, and even more preferably 60 to 240 minutes. By curing the film under these preferred conditions, a uniformly cured film that does not bulge, crack, etc., can be formed.

[0123] 8-4. Properties of the Cured Material The cured material obtained by curing the components of the present invention (also referred to as "the cured material of the present invention" in this specification) exhibits excellent adhesion to the resin substrate and to the inorganic material layer. There are no particular limitations on the adhesion index; known indicators can be used, such as the cross-cut method. When using the cross-cut method, the adhesion of the inorganic material layer of the laminate can be evaluated according to JIS K5600-5-6 (ISO-2409). Furthermore, the cured material of the present invention exhibits excellent hardness. There are no particular limitations on the hardness index; known indicators can be used, such as the pencil hardness test and the scratch resistance test. Furthermore, the cured material of the present invention exhibits excellent transparency, colorfastness, UV resistance, flexibility, resin substrate conformability, weather resistance, chemical resistance, scratch resistance, durability, and heat resistance. The cured product of the present invention is obtained by curing a composition mainly composed of a polysiloxane compound represented by formula (1). The polysiloxane compound of the present invention contains T units, preferably D units and / or M units. Therefore, the SiO content in the cured product, i.e., the content of inorganic components contained in the cured product, is relatively high, resulting in excellent adhesion to the inorganic material layer deposited thereon. The cured product of the present invention containing D units and / or M units has better flexibility or resin substrate conformability, which is preferred. Furthermore, the cured product of the present invention containing D units and / or M units has better surface smoothness, which is preferred. By appropriately adjusting the proportions of each component of the polysiloxane of the present invention, especially the proportions of constituent units (b) and (c), according to the purpose or use, the cured product of the present invention obtained by curing the polysiloxane compound of the present invention can exhibit a good balance of physical properties such as adhesion to the resin substrate, adhesion to the inorganic material layer, hardness, flexibility, and resin substrate conformability.

[0124] 9. Laminated Body The laminate of the present invention comprises the cured material, resin substrate, and inorganic material layer of the present invention described above. Preferably, the laminate of the present invention comprises at least one layer of the resin substrate, a cured material for inorganic material layering formed by curing the inorganic material layering primer composition of the present invention onto the substrate, and at least one layer of the aforementioned inorganic material layer onto the substrate. Its composition is not particularly limited and can be arbitrarily selected according to purpose or use. For example, when the resin substrate is a film, the cured material and inorganic material layer of the present invention can be sequentially laminated on one side of the film, and the cured material and inorganic material layer of the present invention can also be sequentially laminated on both sides of the film respectively.

[0125] 10. Applications The applications of the laminate of the present invention are not particularly limited, but can be listed as follows: outer panels of automobile bodies such as buses, trucks, motorcycles, and public buses; automobile parts; outer panels of household electrical products such as mobile phones and voice communication devices; among which, outer panels of automobile bodies and automobile parts are preferred. Furthermore, it can be used as packaging material for moisture-proof parts or components in various devices such as optical components, liquid crystal displays or organic EL displays, semiconductor devices, and thin-film solar cells, as well as for packaging food, clothing, electronic components, etc. Furthermore, it can be used as a decorative printed film laminate for use as a decorative film for display substrates, touch panels, films with transparent electrodes, lenses, waveguides, solar cell substrates, optical discs, and various transparent substrates. There are no particular limitations on the functions of inorganic material layers and laminates. Examples include anti-reflective properties, anti-fogging properties, gas barrier properties, hard coating, scratch resistance, abrasion resistance, design properties, antistatic properties, conductivity, moisture resistance, weather resistance, light resistance, waterproofing, oil resistance, stain resistance, antibacterial properties, antiviral properties, anti-biological activity, UV resistance, cosmic radiation resistance, plasma resistance, and atomic oxygen resistance. [Example]

[0126] Hereinafter, the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to the following examples. Furthermore, the weight-average molecular weight (hereinafter also referred to as Mw) was calculated by separation using gel permeation chromatography (hereinafter referred to as "GPC") in isopropanol solvent at 40°C using connected GPC columns "TSK gel G4000HX" and "TSK gel G2000HX" (manufactured by Tosoh Co., Ltd.), and by residence time using standard polystyrene. Furthermore, the molar ratio of each constituent unit of the obtained polysiloxane compound was calculated by dissolving the sample in dichloroform and performing 1H-NMR analysis, and, if necessary, 29Si-NMR analysis. The alkoxysilane monomer was quantitatively introduced into the polysiloxane compound through a reaction, but the introduction rate of the M unit derived from the disodium siloxane monomer was not quantitatively introduced according to the composition of the polysiloxane compound. Viscosity was measured using a cone plate at 25°C using TVE22H manufactured by Toki Industries, Ltd.

[0127] [Synthesis of Polysiloxane Compounds] <Synthesis Example 1> 3-Acryloxypropyltrimethoxysilane was used as the T monomer in the silane raw material reaction. Isopropanol was used as the reaction solvent and hydrochloric acid as the catalyst. After hydrolysis and polycondensation reactions according to known methods, the solvent was removed, and polysiloxane compound 1 was obtained in the form of a colorless and transparent liquid. The composition ratio, Mw, and viscosity (25°C) of polysiloxane compound 1 are shown in Table 1.

[0128] <Synthesis Example 2> The raw material silane monomers used were 3-acryloxypropyltrimethoxysilane as the T monomer and two-terminated silyl alcohol type polydimethylsiloxane as the D monomer. Isopropanol was used as the reaction solvent and tetramethylammonium hydroxide was used as the catalyst. After hydrolysis and polycondensation reactions according to known methods, the solvent and other components were removed, and polysiloxane compound 2 was obtained in the form of a colorless and transparent liquid. The composition ratio, Mw and viscosity (25°C) of polysiloxane compound 2 are shown in Table 1.

[0129] <Synthesis Examples 3-7> The raw material silane monomers used were 3-acryloxypropyltrimethoxysilane as monomer T and dimethoxydimethylsilane as monomer D. Isopropanol was used as the reaction solvent and hydrochloric acid as the catalyst. After hydrolysis and polycondensation reactions according to known methods, the solvent was removed, and polysiloxane compounds 3-7 were obtained in the form of colorless and transparent liquids. The molar ratio of each constituent unit of the generated polysiloxane compounds was the same as the addition ratio of the raw material monomers. The composition ratio, Mw, and viscosity (25°C) of each polysiloxane compound are shown in Table 1.

[0130] <Synthesis Example 8> The raw material silane monomers used were 3-acryloxypropyltrimethoxysilane as monomer T and 1,1,3,3-tetramethyl-1,3-divinyldisiloxane as monomer M. Isopropanol was used as the reaction solvent and hydrochloric acid was used as the catalyst. After hydrolysis and polycondensation reactions according to known methods, the solvent was removed, and polysiloxane compound 8 was obtained in the form of a colorless and transparent liquid. 1,1,3,3-tetramethyl-1,3-divinyldisiloxane was quantitatively introduced into polysiloxane compound 8 by the reaction. The composition ratio, Mw, and viscosity (25°C) of polysiloxane compound 8 are shown in Table 1.

[0131] <Synthesis Example 9> 3-Methylpropenyloxypropyltrimethoxysilane was used as the T monomer in the silane raw material reaction. Isopropanol was used as the reaction solvent and hydrochloric acid was used as the catalyst. After hydrolysis and polycondensation reactions according to known methods, the solvent was removed, and polysiloxane compound 9 was obtained in the form of a colorless and transparent liquid. The composition ratio, Mw, and viscosity (25°C) of polysiloxane compound 9 are shown in Table 1.

[0132] <Synthesis Example 10> The raw material silane monomers used were 3-methacryloxypropyltrimethoxysilane as the T monomer and two-terminated silyl alcohol type polydimethylsiloxane as the D monomer. Isopropanol was used as the reaction solvent and tetramethylammonium hydroxide was used as the catalyst. After hydrolysis and polycondensation reactions according to known methods, the solvent and other components were removed, and polysiloxane compound 10 was obtained in the form of a colorless and transparent liquid. The composition ratio, Mw and viscosity (25°C) of polysiloxane compound 10 are shown in Table 1.

[0133] <Synthesis Example 11> The raw material silane monomers used were 3-methacryloxypropyltrimethoxysilane as monomer T and dimethoxydimethylsilane as monomer D. Isopropanol was used as the reaction solvent and hydrochloric acid was used as the catalyst. After hydrolysis and polycondensation reactions according to known methods, the solvent and other components were removed, and polysiloxane compound 11 was obtained in the form of a colorless and transparent liquid. The composition ratio, Mw and viscosity (25°C) of polysiloxane compound 11 are shown in Table 1.

[0134] <Synthesis Example 12> 3-ethyl-3-[{3-(trimethoxysilyl)propoxy}methyl]oxetane was used as the T monomer in the silane reaction. Isopropanol was used as the reaction solvent, tetramethylammonium hydroxide was used as the catalyst, and hydrolysis and polycondensation reactions were carried out according to known methods. After removing the solvent, etc., polysiloxane compound 12 was obtained in the form of a colorless and transparent liquid. The composition ratio, Mw, and viscosity (25°C) of polysiloxane compound 12 are shown in Table 1.

[0135] <Synthesis Example 13> The raw material silane monomers used were 3-ethyl-3-[{3-(trimethoxysilyl)propoxy}methyl]oxetane as the T monomer and a two-terminated silyl alcohol type polydimethylsiloxane as the D monomer. Isopropanol was used as the reaction solvent and tetramethylammonium hydroxide was used as the catalyst. After hydrolysis and polycondensation reactions according to known methods, the solvent and other components were removed, and polysiloxane compound 13 was obtained in the form of a colorless and transparent liquid. The composition ratio, Mw, and viscosity (25°C) of polysiloxane compound 13 are shown in Table 1.

[0136] <Synthesis Example 14> The raw material silane monomers used were tetramethoxysilane as monomer Q and 3-methacryloxypropyltrimethoxysilane as monomer T. The reaction solvent was 1-propanol, and the catalyst was tetramethylammonium hydroxide. After hydrolysis and polycondensation reactions according to known methods, the reaction solution was neutralized, and the product was subjected to liquid-liquid extraction to remove the solvent, etc., to obtain polysiloxane compound 14 as a colorless solid. The composition ratio and Mw of polysiloxane compound 14 are shown in Table 1. Furthermore, since it is a solid, the viscosity was not measured.

[0137] The composition, molar ratio, Mw and viscosity (25°C) of each polysiloxane compound obtained in Synthesis Examples 1 to 14 are summarized in Table 1.

[0138] [Table 1] combine become example Q Single Yuan structure Unit (a) T unit Constituent Unit (b) Unit D Constituent Unit (c) M unit Constituent Unit (d) v / (v + w + x + y) w / (v + w + x + y) x / (v + w + x + y) y / (v + w + x + y) Mw viscosity mPa·s (25℃) Si-AC Si-MAC Si-OX SiMe2 SiMe2Vi 1 - 1 - - - - 0 1 0 0 2330 5990 2 - 0.64 - - 0.36 - 0 0.64 0.36 0 4800 2920 3 - 0.90 - - 0.10 - 0 0.90 0.10 0 1200 1350 4 - 0.80 - - 0.20 - 0 0.80 0.20 0 1160 1080 5 - 0.64 - - 0.36 - 0 0.64 0.36 0 1970 550 6 - 0.51 - - 0.49 - 0 0.51 0.49 0 1740 500 7 - 0.31 - - 0.69 - 0 0.31 0.69 0 1440 190 8 - 0.72 - - - 0.28 0 0.72 0 0.28 1250 390 9 - - 1 - - - 0 1 0 0 1840 3370 10 - - 0.62 - 0.38 - 0 0.62 0.38 0 5290 1430 11 - - 0.62 - 0.38 - 0 0.62 0.38 0 1680 1250 12 - - - 1 - - 0 1 0 0 2300 30000 13 - - - 0.59 0.41 - 0 0.59 0.41 0 1900 4400 14 0.50 - 0.50 - - - 0.50 0.50 0 0 19200 - AC: 3-Acryloyloxypropyl MAC: 3-Methylacryloyloxypropyl OX: 3-[(3-ethyloxocyclobutane-3-yl)methoxy]propyl Me: Methyl Vi: Vinyl

[0139] <Reference Example 1> Directly use Aronix M-405 (dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate) manufactured by Toagosei Company, Limited.

[0140] <Example 1> (1) Preparation of photocurable primer composition 1 10 g of the polysiloxane compound obtained in Synthesis Example 1, 0.3 g of 1-hydroxycyclohexylphenyl ketone (Omnirad 184 manufactured by IGM RESINS BV, hereinafter also referred to as Om184) as a photoradical polymerization initiator, and 10 g of propylene glycol monobutyl ether acetate (hereinafter also referred to as PGB) as a solvent were weighed and placed in a 50 mL vial. The mixture was stirred and dissolved using a rotation-revolution mixer to prepare the photocurable primer composition. (2) Coating and photocuring on a resin substrate: On a polycarbonate (hereinafter also referred to as PC) board (Iupilon NF-2000 manufactured by Mitsubishi Gas Chemical Co., Inc., 1 mm thick) used as the resin substrate, the photocurable composition prepared in (1) above is coated using a bar coater to form a film with a thickness of about 5 μm. The film is then dried at 65°C for 5 minutes to remove the solvent. Then, the cured material is produced by ultraviolet irradiation under the following conditions. [Ultraviolet irradiation conditions] Lamp: 80 W / cm high-pressure mercury lamp Lamp height: 10 cm Conveyor belt speed: 5.7 m / min Light irradiation intensity: 700 mW / cm2 Cumulative light amount per pass: 360 mJ / cm2 Atmosphere: Atmosphere Number of passes: 9 (3) Deposition of an inorganic layer: Platinum is deposited by sputtering on the photocurable material produced in (2) above using the following apparatus and conditions. The thickness of the platinum layer is about 10 nm. [Platinum Sputtering Conditions] MSP-1S magnetron sputtering machine manufactured by VACUUM DEVICE CO.,LTD.: Discharge current: 30 mA, Processing time: 20 seconds (4) Adhesion test of inorganic material layer: Adhesion (crosscut method) Adhesion of inorganic material layer of the laminate prepared by (1) to (3) above was evaluated according to JIS K5600-5-6 (ISO-2409). The number of peelings out of 25 cells was used for evaluation. The fewer the peelings, the higher the adhesion. In Example 1, the number of peelings was 2. Furthermore, in this evaluation, no peelings occurred between the resin substrate and the photocured product of the primer composition. The results of this example are summarized in Table 2.

[0141] <Example 2> A polymethyl methacrylate (PMMA) sheet (Acrylite L, 1 mm thick, manufactured by Mitsubishi Chemical Co., Inc.) was used instead of polycarbonate as the resin substrate. Otherwise, a laminate was prepared in the same manner as in Example 1, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0142] <Example 3> SiO2 was deposited by ion plating instead of platinum as the inorganic material layer. Otherwise, the deposited body was fabricated in the same manner as in Example 1, and the adhesion of the inorganic material layer was evaluated. The thickness of the SiO2 layer was approximately 200 nm. The results are shown in Table 2.

[0143] <Example 4> ZrO2 was deposited by ion plating instead of platinum as the inorganic material layer. Otherwise, the deposited material was fabricated in the same manner as in Example 1, and the adhesion of the inorganic material layer was evaluated. The thickness of the ZrO2 layer was approximately 200 nm. The results are shown in Table 2.

[0144] <Example 5> Polysiloxane compound 2 obtained in Synthesis Example 2 was used instead of polysiloxane compound 1 obtained in Synthesis Example 1. Otherwise, the laminate was prepared in the same manner as in Example 1, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0145] <Example 6> Polysiloxane compound 2 obtained in Synthesis Example 2 was used instead of polysiloxane compound 1 obtained in Synthesis Example 1. Otherwise, the laminate was prepared in the same manner as in Example 4, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0146] <Example 7> Polysiloxane compound 2 obtained in Synthesis Example 2 was used instead of polysiloxane compound 1 obtained in Synthesis Example 1. Otherwise, the laminate was prepared in the same manner as in Example 3, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0147] <Example 8> Polysiloxane compound 3 obtained in Synthesis Example 3 was used instead of polysiloxane compound 1 obtained in Synthesis Example 1. Otherwise, the laminate was prepared in the same manner as in Example 1, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0148] <Example 9> Polysiloxane compound 4 obtained in Synthesis Example 4 was used instead of polysiloxane compound 1 obtained in Synthesis Example 1. Otherwise, the laminate was prepared in the same manner as in Example 1, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0149] <Example 10> Polysiloxane compound 5 obtained in Synthesis Example 5 was used instead of polysiloxane compound 1 obtained in Synthesis Example 1. Otherwise, the laminate was prepared in the same manner as in Example 1, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0150] <Example 11> A sheet made of polyethylene terephthalate (hereinafter also referred to as PET) (manufactured by CI TAKIRON Corporation, 1 mm thick) was used instead of polycarbonate as the resin substrate. Otherwise, a laminate was made in the same manner as in Example 10, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0151] <Example 12> A sheet made of Nylon 6 (hereinafter also referred to as Nylon 6) (manufactured by TP Giken Co., Ltd., 1 mm thick) was used instead of polycarbonate as the resin substrate. Otherwise, a laminate was made in the same manner as in Example 10, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0152] <Example 13> Polysiloxane compound 5 obtained in Synthesis Example 5 was used instead of polysiloxane compound 1 obtained in Synthesis Example 1. Otherwise, the laminate was prepared in the same manner as in Example 3, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0153] <Example 14> Polysiloxane compound 5 obtained in Synthesis Example 5 was used instead of polysiloxane compound 1 obtained in Synthesis Example 1. Otherwise, the laminate was prepared in the same manner as in Example 4, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0154] <Example 15> Polysiloxane compound 6 obtained in Synthesis Example 6 was used instead of polysiloxane compound 1 obtained in Synthesis Example 1. Otherwise, the laminate was prepared in the same manner as in Example 1, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0155] <Example 16> Polysiloxane compound 7 obtained in Synthesis Example 7 was used instead of polysiloxane compound 1 obtained in Synthesis Example 1. Otherwise, the laminate was prepared in the same manner as in Example 1, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0156] <Example 17> Polysiloxane compound 8 obtained in Synthesis Example 8 was used instead of polysiloxane compound 1 obtained in Synthesis Example 1. Otherwise, the laminate was prepared in the same manner as in Example 1, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0157] <Example 18> Polysiloxane compound 9 obtained in Synthesis Example 9 was used instead of polysiloxane compound 1 obtained in Synthesis Example 1. Otherwise, the laminate was prepared in the same manner as in Example 1, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0158] <Example 19> Polymethyl methacrylate was used instead of polycarbonate as the resin substrate. Otherwise, the laminate was prepared in the same manner as in Example 18, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0159] <Example 20> Polysiloxane compound 9 obtained in Synthesis Example 9 was used instead of polysiloxane compound 1 obtained in Synthesis Example 1. Otherwise, the laminate was prepared in the same manner as in Example 4, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0160] <Example 21> Polysiloxane compound 10 obtained in Synthesis Example 10 was used instead of polysiloxane compound 1 obtained in Synthesis Example 1. Otherwise, the laminate was prepared in the same manner as in Example 1, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0161] <Example 22> Polysiloxane compound 10 obtained in Synthesis Example 10 was used instead of polysiloxane compound 1 obtained in Synthesis Example 1. Otherwise, the laminate was prepared in the same manner as in Example 3, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0162] <Example 23> Polysiloxane compound 10 obtained in Synthesis Example 10 was used instead of polysiloxane compound 1 obtained in Synthesis Example 1. Otherwise, the laminate was prepared in the same manner as in Example 4, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0163] <Example 24> Polysiloxane compound 11 obtained in Synthesis Example 11 was used instead of polysiloxane compound 1 obtained in Synthesis Example 1. Otherwise, the laminate was prepared in the same manner as in Example 1, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0164] <Example 25> Polyethylene terephthalate was used instead of polycarbonate as the resin substrate. Otherwise, the laminate was prepared in the same manner as in Example 24, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0165] <Example 26> Nylon 6 was used instead of polycarbonate as the resin substrate. Otherwise, the laminate was prepared in the same manner as in Example 24, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0166] <Example 27> Polysiloxane compound 11 obtained in Synthesis Example 11 was used instead of polysiloxane compound 1 obtained in Synthesis Example 1. Otherwise, the laminate was prepared in the same manner as in Example 3, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0167] <Example 28> Polysiloxane compound 11 obtained in Synthesis Example 11 was used instead of polysiloxane compound 1 obtained in Synthesis Example 1. Otherwise, the laminate was prepared in the same manner as in Example 4, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0168] <Example 29> 9 g of the polysiloxane compound 12 obtained in Synthesis Example 12, 1 g of Celloxide 2021P (3,4-epoxycyclohexanecarboxylic acid 3',4'-epoxycyclohexylmethyl ester, hereinafter also referred to as CEL2021P) manufactured by Caillo Corporation, 0.2 g of PHOTO INITIATOR 2074 (manufactured by Solvay Japan, Ltd., hereinafter also referred to as PI2074) as a photocationic polymerization initiator, and 10 g of PGB as a solvent were weighed and placed in a 50 mL vial. The mixture was stirred and dissolved using a rotation-revolution mixer to prepare a photocurable primer composition. Using this composition, a laminate was prepared in the same manner as in (2) to (4) of Example 1, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0169] <Example 30> Polysiloxane compound 13 obtained in Synthesis Example 13 was used instead of polysiloxane compound 12 obtained in Synthesis Example 12. Otherwise, the laminate was prepared in the same manner as in Example 29, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0170] <Example 31> Polysiloxane compound 9 obtained in Synthesis Example 9 was used instead of polysiloxane compound 1 obtained in Synthesis Example 1. Otherwise, the laminate was prepared in the same manner as in Example 3, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0171] <Example 32> SiO2 was deposited by ion plating instead of platinum as the inorganic material layer. Otherwise, the deposited body was fabricated in the same manner as in Example 29, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0172] <Example 33> Polysiloxane compound 14 obtained in Synthesis Example 14 was used instead of polysiloxane compound 1 obtained in Synthesis Example 1. Otherwise, the laminate was prepared in the same manner as in Example 3, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0173] <Example 34> (1) Preparation of thermosetting primer composition 10 g of polysiloxane compound 11 obtained in Synthesis Example 11, 0.1 g of 2-ethylperoxyhexanoate tributyl ester (Perbutyl O manufactured by NOF CORPORATION., hereinafter also referred to as PBO) as a thermal free radical polymerization initiator, and 10 g of PGB as a solvent were weighed and placed in a 50 mL vial and stirred and mixed using a rotation-revolution mixer to dissolve them, thereby preparing a thermosetting primer composition. (2) Coating and thermosetting on resin substrate A thermosetting composition prepared in (1) was coated on a polycarbonate (hereinafter also referred to as PC) board (Iupilon NF-2000 manufactured by Mitsubishi Gas Chemical Co., Ltd., 1 mm thick) as the resin substrate using a bar coater to form a film with a thickness of about 5 μm, and then dried at 65°C for 5 minutes to remove the solvent. Then, the product is heated at 120°C for 1 hour in a constant temperature machine to produce a hardened product. (3) Deposition of inorganic material layer: ZrO2 is deposited on the thermocured product produced in (2) above by ion plating. (4) Adhesion test of inorganic material layer: Adhesion (crosscut method) Adhesion of inorganic material layer of the product produced by (1) to (3) above is evaluated according to JIS K5600-5-6 (ISO-2409). The number of peelings out of 25 cells is used for evaluation. The fewer the number of peelings, the higher the adhesion. In Example 34, no peelings occurred, which is 0 cells. Furthermore, in this evaluation, no peelings occurred between the resin substrate and the thermocured product of the primer composition. The results of this example are summarized in Table 2.

[0174] <Example 35> 9 g of the polysiloxane compound 13 obtained in Synthesis Example 13, 1 g of CEL2021P, 0.1 g of San-Aid SI-100L (manufactured by San-Shin Chemical Industry Co., Ltd., hereinafter also referred to as SI100L) as a thermo-cationic polymerization initiator, and 10 g of PGB as a solvent were weighed and placed in a 50 mL vial. The mixture was stirred and dissolved using a rotation-revolution mixer to prepare a thermosetting primer composition. Using this composition, the inorganic layer was set as SiO2. Otherwise, a laminate was prepared in the same manner as in (2) to (4) of Example 34, and the adhesion of the inorganic layer was evaluated. The results are shown in Table 2.

[0175] <Comparative Example 1> Using M-405 as described in Reference Example 1 instead of the polysiloxane compound 1 obtained in Synthesis Example 1, a laminate was prepared in the same manner as in Example 1, and the adhesion of the inorganic material layers was evaluated. The results are shown in Table 2.

[0176] <Comparative Examples 2-4> Polymethyl methacrylate, polyethylene terephthalate, or nylon 6 were used instead of polycarbonate as the resin substrate. Otherwise, laminates were prepared in the same manner as in Comparative Example 1, and the adhesion of each inorganic layer was evaluated. The results are shown in Table 2.

[0177] <Comparative Example 5> Using M-405 as described in Reference Example 1 instead of the polysiloxane compound 1 obtained in Synthesis Example 1, a laminate was prepared in the same manner as in Example 3, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0178] <Comparative Example 6> Using M-405 as described in Reference Example 1 instead of the polysiloxane compound 1 obtained in Synthesis Example 1, a laminate was prepared in the same manner as in Example 4, and the adhesion of the inorganic material layers was evaluated. The results are shown in Table 2.

[0179] <Comparative Examples 7-10> Polycarbonate, polymethyl methacrylate, polyethylene terephthalate, or nylon 6 were used as the resin substrate. No primer layer for inorganic material lamination was provided. Otherwise, the laminates were fabricated in the same manner as in Example 1, and the adhesion of each inorganic material layer was evaluated. The results are shown in Table 2.

[0180] <Comparative Example 11> No primer layer for inorganic material lamination was provided. Otherwise, the laminate was prepared in the same manner as in Example 3, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0181] <Comparative Example 12> No primer layer for inorganic material lamination was provided. Otherwise, the laminate was prepared in the same manner as in Example 4, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0182] (5) Adhesion test of inorganic material layers after warm water treatment: Adhesion (crosscut method) <Examples 36-41> The laminates prepared in the manner of Examples 3, 31, 22, 27, 32 and 33 were immersed in warm water at 90°C for 2 hours and then dried at room temperature for 17 hours (hereinafter also referred to as "after warm water treatment"). The adhesion of each inorganic material layer was evaluated in the same manner as in Example 1(4). The results are shown in Table 3.

[0183] <Comparative Examples 13 and 14> The laminates prepared in the manner of Comparative Examples 5 and 11 were immersed in warm water at 90°C for 2 hours and then dried at room temperature for 17 hours. After that, the adhesion of each inorganic material layer was evaluated in the same manner as in Example 1 (4). The results are shown in Table 3.

[0184] (6) Scratch resistance test of inorganic material layer: Scratch test <Example 42> For the inorganic material layer of the laminate made in the manner described in Example 3 above using polysiloxane compound 1, PC as resin substrate, and SiO2 as inorganic material layer, a scratch test was performed under the following conditions to determine the critical load value, thereby evaluating the scratch resistance of the inorganic material layer. Apparatus used: CSR-5000 micro-scratch tester manufactured by RHESCA Co., LTD. Stylus (tip needle) diameter: 25 μm Scratch speed: 10 μm / sec Amplitude: 100 μm Imprint load: 10 mN / sec The result was that the critical load value was 42.1 mN. The results are shown in Table 4. The larger the value, the higher the scratch resistance.

[0185] <Examples 43-56> Using polysiloxane compounds 1, 5, 9 or 11, PC, PMMA or PET as the resin substrate, and SiO2 or ZrO2 as the inorganic material layer, the laminate was prepared in the same manner as in Example 42, and the scratch resistance of each inorganic material layer was evaluated. The results are shown in Table 4.

[0186] <Example 57> Using polysiloxane compound 12 and PC as the resin substrate, an inorganic material laminate was formed on PC in the manner described in Example 29 above, followed by SiO2 lamination by ion plating. The scratch resistance of the inorganic material layer was evaluated for the fabricated laminate in the same manner as in Example 42. The result was a critical load value of 51.1 mN. The results are shown in Table 4.

[0187] <Example 58> Using polysiloxane compound 13, the scratch resistance of the inorganic layer of the prepared laminate was evaluated in the same manner as in Example 57. The result was a critical load value of 69.3 mN. The results are shown in Table 4.

[0188] <Example 59> Using polysiloxane compound 11 and PC as the resin substrate, an inorganic material laminate was formed on PC in the manner described in Example 34 above, followed by ZrO2 lamination by ion plating. The scratch resistance of the inorganic material layer was evaluated for the fabricated laminate in the same manner as in Example 42. The result was a critical load value of 63.9 mN. The results are shown in Table 4.

[0189] <Example 60> Using polysiloxane compound 13 and PC as the resin substrate, an inorganic material laminate was formed on PC in the manner described in Example 35 above, followed by SiO2 lamination by ion plating. The scratch resistance of the inorganic material layer was evaluated for the fabricated laminate in the same manner as in Example 42. The result was a critical load value of 68.7 mN. The results are shown in Table 4.

[0190] <Comparative Examples 15-19> Using M-405 as described in Reference Example 1 instead of the polysiloxane compound, and using PMMA or PET as the resin substrate, laminates with PC, PMMA, or PET as the resin substrate and SiO2 or ZrO2 as the inorganic material layer were prepared in the same manner as in Comparative Examples 5 or 6 above. The scratch resistance of each inorganic material layer was evaluated in the same manner as in Example 42 above. The results are shown in Table 4.

[0191] <Comparative Examples 20-24> Without using M-405 as described in Reference Example 1, the scratch resistance of each inorganic material layer was evaluated in the same manner as in Comparative Examples 15-19. The results are shown in Table 4.

[0192] [Table 2] Inorganic material lamination primer composition resin Substrate Inorganic Material layer Tightness test Polysiloxane compounds Aggregation compound polymerization Initiator solvent Number of cells that were stripped out out of 25 Polymerization group constitute unit Example 1 Polysiloxane compound 1 AC T - Om184 PGB PC Pt 2 Example 2 Polysiloxane compound 1 AC T - Om184 PGB PMMA Pt 3 Example 3 Polysiloxane compound 1 AC T - Om184 PGB PC SiO2 5 Example 4 Polysiloxane compound 1 AC T - Om184 PGB PC ZiO2 4 Example 5 Polysiloxane compound 2 AC T,D - Om184 PGB PC Pt 0 Example 6 Polysiloxane compound 2 AC T,D - Om184 PGB PC SiO2 1 Example 7 Polysiloxane compound 2 AC T,D - Om184 PGB PC ZiO2 0 Example 8 Polysiloxane compound 3 AC T,D - Om184 PGB PC Pt 1 Example 9 Polysiloxane compound 4 AC T,D - Om184 PGB PC Pt 1 Example 10 Polysiloxane compound 5 AC T,D - Om184 PGB PC Pt 1 Example 11 Polysiloxane compound 5 AC T,D - Om184 PGB PET Pt 0 Example 12 Polysiloxane compound 5 AC T,D - Om184 PGB Nylon 6 Pt 1 Example 13 Polysiloxane compound 5 AC T,D - Om184 PGB PC SiO2 1 Example 14 Polysiloxane compound 5 AC T,D - Om184 PGB PC ZiO2 0 Example 15 Polysiloxane compound 6 AC T,D - Om184 PGB PC Pt 1 Example 16 Polysiloxane compound 7 AC T,D - Om184 PGB PC Pt 3 Example 17 Polysiloxane compound 8 AC T,M - Om184 PGB PC Pt 2 Example 18 Polysiloxane compound 9 MAC T - Om184 PGB PC Pt 4 Example 19 Polysiloxane compound 9 MAC T - Om184 PGB PMMA Pt 3 Example 20 Polysiloxane compound 9 MAC T - Om184 PGB PC ZiO2 4 Example 21 Polysiloxane compound 10 MAC T,D - Om184 PGB PC Pt 0 Example 22 Polysiloxane compound 10 MAC T,D - Om184 PGB PC SiO2 0 Example 23 Polysiloxane compound 10 MAC T,D - Om184 PGB PC ZiO2 0 Example 24 Polysiloxane compound 11 MAC T,D - Om184 PGB PC Pt 0 Example 25 Polysiloxane compound 11 MAC T,D - Om184 PGB PET Pt 1 Example 26 Polysiloxane compound 11 MAC T,D - Om184 PGB Nylon 6 Pt 2 Example 27 Polysiloxane compound 11 MAC T,D - Om184 PGB PC SiO2 1 Example 28 Polysiloxane compound 11 MAC T,D - Om184 PGB PC ZiO2 0 Example 29 Polysiloxane compound 12 OX T CEL2021P PI2074 PGB PC Pt 2 Example 30 Polysiloxane compound 13 OX T,D CEL2021P PI2074 PGB PC Pt 0 Example 31 Polysiloxane compound 9 MAC T - Om184 PGB PC SiO2 5 Example 32 Polysiloxane compound 12 OX T CEL2021P PI2074 PGB PC SiO2 2 Example 33 Polysiloxane compound 14 MAC Q,T - Om184 PGB PC SiO2 5 Example 34 Polysiloxane compound 11 MAC T,D - PBO PGB PC ZiO2 0 Example 35 Polysiloxane compound 13 OX T,D CEL2021P SI100L PGB PC SiO2 0 Comparative Example 1 - - - M-405 Om184 PGB PC Pt 11 Comparative Example 2 - - - M-405 Om184 PGB PMMA Pt 6 Comparative Example 3 - - - M-405 Om184 PGB PET Pt 11 Comparative Example 4 - - - M-405 Om184 PGB Nylon 6 Pt 6 Comparative Example 5 - - - M-405 Om184 PGB PC SiO2 12 Comparative Example 6 - - - M-405 Om184 PGB PC ZiO2 7 Comparative Example 7 - - - - - - PC Pt 14 Comparative Example 8 - - - - - - PMMA Pt 9 Comparative Example 9 - - - - - - PET Pt 14 Comparative Example 10 - - - - - - Nylon 6 Pt 13 Comparative Example 11 - - - - - - PC SiO2 17 Comparative Example 12 - - - - - - PC ZiO2 10

[0193] [Table 3] Inorganic material lamination primer composition resin Substrate Inorganic Material layer Close contact test Table 2 Correspondence Polysiloxane compounds Aggregation compound polymerization Initiator solvent Occurring in 25 squares Number of cells stripped polymerization Sex base constitute unit warm water Before processing warm water After processing Example 36 Example 3 Polysiloxane compound 1 AC T - Om184 PGB PC SiO2 5 4 Example 37 Example 31 Polysiloxane compound 9 MAC T - Om184 PGB PC SiO2 5 5 Example 38 Example 22 Polysiloxane compound 10 MAC T,D - Om184 PGB PC SiO2 0 0 Example 39 Example 27 Polysiloxane compound 11 MAC T,D - Om184 PGB PC SiO2 1 1 Example 40 Example 32 Polysiloxane compound 12 OX T CEL2021P PI2074 PGB PC SiO2 2 0 Example 41 Example 33 Polysiloxane compound 14 MAC Q,T - Om184 PGB PC SiO2 5 5 Comparative Example 13 Comparative Example 5 - - - M-405 Om184 PGB PC SiO2 12 25 Comparative Example 14 Comparative Example 11 - - - - - - PC SiO2 17 25

[0194] [Table 4] Inorganic material lamination primer composition resin Substrate Inorganic Material layer Scratch resistant Harmful Polysiloxane compounds Aggregation compound polymerization Initiator solvent Critical load value mN polymerization Sex base constitute unit Example 42 Polysiloxane compound 1 AC T - Om184 PGB PC SiO2 42.1 Example 43 Polysiloxane compound 1 AC T - Om184 PGB PMMA SiO2 95.2 Example 44 Polysiloxane compound 1 AC T - Om184 PGB PET SiO2 59.2 Example 45 Polysiloxane compound 5 AC T,D - Om184 PGB PC SiO2 62.3 Example 46 Polysiloxane compound 5 AC T,D - Om184 PGB PMMA SiO2 138.8 Example 47 Polysiloxane compound 5 AC T,D - Om184 PGB PET SiO2 88.9 Example 48 Polysiloxane compound 5 AC T,D - Om184 PGB PMMA ZrO2 114.1 Example 49 Polysiloxane compound 9 MAC T - Om184 PGB PC SiO2 49.4 Example 50 Polysiloxane compound 9 MAC T - Om184 PGB PMMA SiO2 134.6 Example 51 Polysiloxane compound 9 MAC T - Om184 PGB PET SiO2 78.3 Example 52 Polysiloxane compound 11 MAC T,D - Om184 PGB PC SiO2 71.1 Example 53 Polysiloxane compound 11 MAC T,D - Om184 PGB PMMA SiO2 146.4 Example 54 Polysiloxane compound 11 MAC T,D - Om184 PGB PET SiO2 81.5 Example 55 Polysiloxane compound 11 MAC T,D - Om184 PGB PC ZrO2 64.1 Example 56 Polysiloxane compound 11 MAC T,D - Om184 PGB PMMA ZrO2 132.1 Example 57 Polysiloxane compound 12 OX T CEL2021P PI2074 PGB PC SiO2 51.1 Example 58 Polysiloxane compound 13 OX T,D CEL2021P PI2074 PGB PC SiO2 69.3 Example 59 Polysiloxane compound 11 MAC T,D - PBO PGB PC ZiO2 63.9 Example 60 Polysiloxane compound 13 OX T,D CEL2021P SI100L PGB PC SiO2 68.7 Comparative Example 15 - - - M-405 Om184 PGB PC SiO2 95.6 Comparative Example 16 - - - M-405 Om184 PGB PMMA SiO2 152.2 Comparative Example 17 - - - M-405 Om184 PGB PET SiO2 64.4 Comparative Example 18 - - - M-405 Om184 PGB PC ZrO2 56.0 Comparative Example 19 - - - M-405 Om184 PGB PMMA ZrO2 299.0 Comparative Example 20 - - - - - - PC SiO2 18.4 Comparative Example 21 - - - - - - PMMA SiO2 43.5 Comparative Example 22 - - - - - - PET SiO2 16.9 Comparative Example 23 - - - - - - PC ZrO2 50.8 Comparative Example 24 - - - - - - PMMA ZrO2 80.5

[0195] As clearly shown in Table 2, the primer coatings for inorganic material laminates of the present invention all exhibit good adhesion to the resin substrate and the inorganic material layer. The adhesion (0-5) to the inorganic material layer in Examples 1-35 shows superior adhesion to various resin substrates and various inorganic material layers compared to the adhesion (6-12) of Comparative Examples 1-6 using a primer coating without polysiloxane and the adhesion (9-17) of Comparative Examples 7-12 without a primer coating. Furthermore, as shown in Table 2, the primer coating containing a polysiloxane compound having T-units and D-units as constituent units exhibits superior adhesion to the inorganic material layer compared to the primer coating containing a polysiloxane compound composed only of T-units. This situation becomes clearer by comparing cases where all conditions except for the polysiloxane compound are met, for example, comparing Examples 1, 3, and 4 with Examples 5-10 and 13-15, comparing Examples 18 and 20 with Examples 21, 23, and 24, and comparing Example 29 with Example 30. Furthermore, although Example 16 has an excellent adhesion to the inorganic layer of "3", it is slightly inferior to cases including other T units and D units. Therefore, it is known that the proportion of D units, i.e., x / (v+w+x+y), is preferably less than 0.69 when the polysiloxane compound 7 contained in Example 16 is present.

[0196] As can be clearly seen from Table 3, the primer coating for the inorganic material laminate of the present invention exhibits good adhesion to the resin substrate and the inorganic material layer even after warm water treatment. The adhesion (0-5) to the inorganic material layer in Examples 36-41 is superior to the adhesion (25) of Comparative Example 13 using a primer coating without polysiloxane and the adhesion (25) of Comparative Example 14 without a primer coating, after warm water treatment.

[0197] As can be clearly seen from Tables 2 to 4, the primer coatings for inorganic material laminates of the present invention can achieve both good adhesion to the resin substrate and the inorganic material layer, as well as good scratch resistance to the inorganic material layer of the laminate, resulting in excellent practicality. This is evident, for example, from the results of Example 42 of the same laminate as Example 3 in Table 2, and Examples 43 to 60 as variations thereof. In contrast, Comparative Examples 15 to 19 in Table 4 are all formed by curing a curable composition containing a polyfunctional monomer that does not contain a polysiloxane compound. While the scratch resistance is sometimes high, the adhesion to the inorganic material layer is insufficient, making it impractical. This is evident, for example, from the results of Comparative Examples 15 and 18 of the same laminate as Comparative Examples 5 and 6 in Table 2. Furthermore, as shown in Table 4, the primer coating containing polysiloxane compounds with T-units and D-units as constituent units exhibits superior scratch resistance of the inorganic layer deposited on it compared to a primer coating containing polysiloxane compounds composed only of T-units. This is further demonstrated by comparing cases where all conditions except for the polysiloxane compound are met, such as comparing Examples 42-44 with Examples 45-47, Examples 49-51 with Examples 52-54, and Example 57 with Example 58. Therefore, the primer coating containing polysiloxane compounds with T-units and D-units as constituent units exhibits superior adhesion to the inorganic layer and superior scratch resistance of the deposited inorganic layer, resulting in superior practicality. [Industrial Applicability]

[0198] Examples of applications for the laminate of the present invention include: outer panels of automobile bodies such as buses, trucks, motorcycles, and public buses; automobile parts; and outer panels of household electrical products such as mobile phones and voice communication devices. Furthermore, it can be used as packaging material for moisture-proof parts or components in various devices such as optical elements, liquid crystal displays or organic EL displays, semiconductor devices, and thin-film solar cells, as well as for packaging food, clothing, and electronic components. It can also be used as a decorative printed film laminate for decorative films used as display substrates, touch panels, films with transparent electrodes, lenses, waveguides, solar cell substrates, optical discs, and various transparent substrates. Regarding the functions of the inorganic material layer or laminate, examples include anti-reflection, anti-fogging, gas barrier, hard coating, scratch resistance, wear resistance, design, antistatic properties, conductivity, moisture resistance, weather resistance, light resistance, waterproofing, oil resistance, stain resistance, antibacterial properties, antiviral properties, anti-biological activity, ultraviolet resistance, cosmic radiation resistance, oxygen plasma resistance, and atomic oxygen resistance.

[0199] The contents disclosed in Japanese Patent Application No. 2021-017829 filed on February 5, 2021, are incorporated herein by reference in their entirety. All documents, patent applications and technical specifications described in this specification are incorporated herein by reference to the same extent that each document, patent application and technical specification is specifically and individually described and incorporated herein by reference.

Claims

1. A primer composition for an inorganic material layering process, which is coated on a resin substrate to deposit an inorganic material layer on the resin substrate using a dry film-forming method, characterized in that it comprises a polysiloxane compound represented by the following formula (1), and a free radical polymerization initiator and / or a cationic polymerization initiator: In formula (1), R1, R2 and R3 independently represent an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an unsaturated hydrocarbon group having 2 to 8 carbon atoms, or a monovalent organic group having (meth)acrylyl, epoxy or oxetyl, wherein the alkyl, aralkyl, aryl, unsaturated hydrocarbon group, (meth)acrylyl, epoxy and oxetyl may be substituted by at least one of the group consisting of halogen atoms, hydroxyl, alkoxy, aryloxy, aralkyloxy and oxygen, and at least one of R1, R2 and R3 is The formula contains a monovalent organic group having (meth)acryl, epoxy, or oxetyl, and R1, R2, and R3 may be the same or different from each other; in formula (1), v, w, x, and y respectively refer to the proportions in the total stoichiometry of v, w, x, and y. When at least one of R1, R2, and R3 is a monovalent organic group having an epoxy or oxetyl, w represents a positive number less than 1. When at least one of R1, R2, and R3 is a monovalent organic group having (meth)acryl, w represents a positive number less than 1. v, x, and y each independently represent a positive number of 0 or less than 1.

2. The primer composition for inorganic material laminates as described in claim 1, wherein, In equation (1), x is a positive number less than 1.

3. The primer composition for inorganic material laminates as described in claim 1, wherein, This dry film formation method is a physical vapor deposition method.

4. The primer composition for inorganic material laminates as described in claim 1, wherein, It satisfies 0.3≦{w / (v+w+x+y)}≦1.0 and 0≦{x / (v+w+x+y)}≦0.

7.

5. The primer composition for inorganic material laminates as described in claim 1, wherein, Satisfies 0.5≦{w / (v+w+x+y)}≦1.0 and 0≦{y / (v+w+x+y)}≦0.

5.

6. The primer composition for inorganic material laminates as described in claim 1, wherein, The viscosity of this polysiloxane compound at 25°C is 10–1,000,000 mPa·s.

7. A hardener for an inorganic material laminate, which is formed by hardening an inorganic material laminate composition as described in any one of claims 1 to 6.

8. A laminate comprising a curing material for laminating an inorganic material layer as described in claim 7, a resin substrate, and an inorganic material layer.

9. The stack as described in claim 8, wherein, In the cross-cut peel test, the inorganic material layer was evaluated for its adhesion to the hardened material in the cross-cut peel test, with less than 5 out of 25 layers peeling off.

10. A method for manufacturing a hardened inorganic material laminate as described in claim 7, comprising the following steps: The inorganic material laminate as described in any one of claims 1 to 6 is hardened by irradiating an active energy line with a primer composition.

11. A method for manufacturing a laminate as described in claim 8 or 9, comprising the following steps: The inorganic material laminate as described in any one of claims 1 to 6 is hardened by irradiating an active energy line with a primer composition.