Laminate, thermosetting silicone resin composition, and laminate production method

Abstract

Provided are: a thermosetting silicone resin composition that has excellent adhesion to a cyclic olefin resin substrate (I) and is capable of imparting properties such as scratch resistance thereto; a laminate in which the substrate (I), a cured coating layer (II) formed from the composition, and an inorganic substance layer (III) are sequentially laminated; and a production method therefor.　In said laminate, the cured coating layer (II) contains a reactive silicone resin (A), a polyfunctional (meth)acrylate monomer (B), and an organic peroxide (C), and contains 34-80 parts by weight of (A), 19-65 parts by weight of (B), and 0.5-10 parts by weight of (C) with respect to 100 parts by weight of the total of (A), (B), and (C). The number of (meth)acrylic moles in (B) per 100 g of the composition is 0.20-0.60. (A) is obtained by hydrolyzing and condensing an alkoxysilane of formula (i) and a compound containing an alkyl silicate of formula (ii) or a partial hydrolysate thereof. The laminate is such that [moles of Si derived from (ii)-component-containing compound / moles of Si derived from (i) component] with respect to 100 moles of the total Si content satisfies the range of 0.2-4.0.

Description

Laminate, thermosetting silicone resin composition, and method for producing laminate

[0001] The present invention relates to a thermosetting silicone resin composition that has excellent adhesion to a cyclic olefin resin substrate and can impart properties such as scratch resistance; a laminate that has a cyclic olefin resin substrate, a cured coating layer made of the thermosetting silicone resin composition, and an inorganic substance layer laminated in that order, and that has properties such as excellent weather resistance; and a method for producing the same.

[0002] In recent years, cyclic olefin resins have been increasingly used as optical components for mobile phones, smartphones, liquid crystal displays, and the like due to their high transparency, low moisture absorption, and other functional properties. Cyclic olefin resins are easily scratched due to their relatively low surface hardness. Therefore, a hard coat layer is provided on the surface. However, the adhesion between the cyclic olefin resin and the cured coating layer has not always been sufficient. Therefore, prior to forming the cured coating layer, an adhesion-enhancing treatment step, such as corona discharge treatment, plasma treatment, ozone treatment, or application of an adhesion-enhancing primer composition, was required for the cyclic olefin resin surface (Patent Document 1).

[0003] In Patent Documents 2 and 3, as cured coatings of cyclic olefin resins that do not require the above-mentioned easy-adhesion treatment, active energy ray-curable compositions containing a diphenyl sulfide-based compound, a benzophenone-based compound, and a compound having a (meth)acryloyl group, and active energy ray-curable compositions containing a polyfunctional (meth)acrylate, a benzophenone-based compound, and a polysiloxane have been proposed. However, when attempting to form a cured coating layer on a molded product or film made of cyclic olefin resin having a complex shape such as a lens, it is difficult to uniformly irradiate the active energy ray with the active energy ray-curable composition, resulting in variations in the hardness and adhesion of the cured coating layer and making it difficult to fully exhibit performance.

[0004] On the other hand, forming an inorganic substance layer on a plastic substrate to impart mechanical, electrical, optical, or chemical functions has been conventionally practiced. In this case, in order to ensure sufficient interlayer adhesion between the plastic substrate and the inorganic substance layer, a laminate structure has been proposed in which a resin-cured layer made of a curable resin composition is interposed. For example, Patent Document 4 describes a surface-modified plastic plate for windows, in which a cured film of an active energy ray-curable primer composition is formed on a plastic plate, and an inorganic substance layer is formed thereon. However, when the substrate is a cyclic olefin resin, the interlayer adhesion between the substrate and the cured resin layer and / or the interlayer adhesion between the cured resin layer and the inorganic substance layer may be insufficient. Furthermore, in a laminate having a cyclic olefin resin, a cured coating layer, and an inorganic substance layer in this order, there are problems such as cracks occurring in the inorganic substance layer due to deterioration of the cured coating layer in a xenon weathering test, or the inorganic substance layer being easily peeled off from the cured coating, resulting in poor steel wool resistance.

[0005] JP-T-2008-518280A JP-A-2015-127102 JP-A-2016-105164 JP-A-4-202240

[0006] The present invention relates to a thermosetting silicone resin composition that has excellent adhesion to a cyclic olefin resin substrate (I) and can impart properties such as scratch resistance; a laminate that has the cyclic olefin resin substrate (I), a cured coating layer (II) made of the thermosetting silicone resin composition, and an inorganic substance layer (III) laminated in this order, and that has properties such as excellent weather resistance; and a method for producing the same.

[0007] The present inventors have discovered that the above-mentioned problems can be solved by forming a cured coating layer (II) on a cyclic olefin resin substrate (I) using a thermosetting silicone resin composition containing a polymerizable compound having a specific structure and an organic peroxide in a specific ratio, and have arrived at the present invention.

[0008] That is, the present invention is as follows: (1) A laminate comprising a cyclic olefin resin substrate (I) and, in that order, a cured coating layer (II) formed from a thermosetting silicone resin composition and an inorganic substance layer (III), wherein the cured coating layer (II) contains a reactive silicone resin (A), a polyfunctional (meth)acrylate monomer (B), and an organic peroxide (C), and contains 34 to 80 parts by weight of component (A), 19 to 65 parts by weight of component (B), and 0.5 to 10 parts by weight of component (C) per 100 parts by weight of components (A), (B), and (C), and the total number of (meth)acrylic moles of the polyfunctional (meth)acrylate monomer (B) contained in 100 g of the composition is 0.20 to 0.60, A laminate characterized in that the reactive silicone resin (A) is obtained by hydrolyzing and condensing an alkoxysilane represented by the following general formula (i) and a compound containing an alkyl silicate represented by the following general formula (ii) or a partial hydrolyzate thereof, and in that, in the blending ratio of the component (i) represented by formula (i) and the compound containing the component (ii), which is the alkyl silicate represented by formula (ii) or a partial hydrolyzate thereof, the ratio [moles of Si derived from the compound containing component (ii) / moles of Si derived from component (i)] satisfies the range of 0.2 to 4.0, relative to a total of 100 moles of Si contained in both components. １ Si(OR ２ ) ３ ...(i) [However, in formula (i), R １ is an organic functional group having a (meth)acryloyl group, and R ２ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.] Si ｎ O （ｎ－１） (OR ３ ) （２ｎ＋２） ...(ii) [wherein, in formula (ii), n represents a number from 1 to 20, and R ３ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0009] (2) The laminate is exposed to a xenon lamp with an illuminance of 2.4 W / m 2 at a temperature of 55° C. and a relative humidity of 30% Rh on the surface of the inorganic substance layer (III). ２In a weather resistance test in which light at 420 nm is irradiated for 150 hours, no cracks or peeling occurs after the weather resistance test, and the inorganic substance layer (III) surface is irradiated with #0000 steel wool at a pressure of 0.25 kg / cm ２ The laminate according to (1), characterized in that no scratches are visually observed after 10 reciprocating motions under a load of 1000 psi.

[0010] (3) The laminate according to (1), wherein the thickness of the cured coating layer (II) is within the range of 0.5 to 20 μm.

[0011] (4) The laminate according to (1), wherein the cyclic olefin resin substrate (I) is not subjected to an easy-adhesion treatment.

[0012] (5) A thermosetting silicone resin composition for forming the cured coating layer (II) of the laminate according to any one of (1) to (4), comprising a reactive silicone resin (A), a polyfunctional (meth)acrylate monomer (B), and an organic peroxide (C), wherein the composition contains 34 to 80 parts by weight of component (A), 19 to 65 parts by weight of component (B), and 0.5 to 10 parts by weight of component (C) relative to 100 parts by weight of the total of components (A), (B), and (C), and the total number of (meth)acrylic moles of the polyfunctional (meth)acrylate monomer (B) contained in 100 g of the composition is 0.20 to 0.60, A thermosetting silicone resin composition, characterized in that the reactive silicone resin (A) is obtained by hydrolysis and condensation of an alkoxysilane represented by the following general formula (i) and a compound containing an alkyl silicate represented by the following general formula (ii) or a partial hydrolyzate thereof, and in that the blending ratio of the component (i) represented by formula (i) and the compound containing the component (ii), which is the alkyl silicate represented by formula (ii) or a partial hydrolyzate thereof, is such that, relative to a total of 100 moles of Si contained in both, [moles of Si derived from the compound containing component (ii) / moles of Si derived from component (i)] is in the range of 0.2 to 4.0. １ Si(OR ２ ) ３ ...(i) [However, in formula (i), R １ is an organic functional group having a (meth)acryloyl group, and R ２represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.] Si ｎ O （ｎ－１） (OR ３ ) （２ｎ＋２） ...(ii) [wherein, in formula (ii), n represents a number from 1 to 20, and R ３ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0013] (6) A method for producing the laminate according to any one of (1) to (4) above, comprising the steps of: applying a thermosetting silicone resin composition onto a cyclic olefin resin substrate (I) to form a coating layer of the thermosetting silicone resin composition; curing the coating layer of the thermosetting silicone resin composition by heat to form a cured coating layer (II); and forming at least one inorganic substance layer (III) on the cured coating layer (II) by a dry film-forming method.

[0014] The present invention provides a thermosetting silicone resin composition that has excellent adhesion to a cyclic olefin resin substrate (I) and can impart properties such as scratch resistance; a laminate that has excellent properties such as weather resistance and is formed by sequentially laminating a cyclic olefin resin substrate (I), a cured coating layer (II) made of the thermosetting silicone resin composition, and an inorganic substance layer (III); and a method for producing the same.

[0015] Each element constituting the present invention will be described in detail below, but the following description is an example of an embodiment of the present invention, and the present invention is not limited to the following description as long as it does not deviate from the gist of the present invention. In this specification, when the expression "to" is used, it is used as an expression including the numerical values ​​or physical property values ​​before and after it. Furthermore, in the present invention, when the expression "(meth)acrylic" is used, it means one or both of "acrylic" and "methacrylic". The same applies to "(meth)acrylate" and "(meth)acryloyl".

[0016] The laminate of the present invention has, on at least one surface of a cyclic olefin resin substrate (I), a cured coating layer (II) formed from a thermosetting silicone resin composition and obtained by curing the composition, and is a laminate having an inorganic substance layer (III) sequentially laminated thereon.

[0017] From the viewpoint of shortening the process for producing the laminate, it is preferable that the cyclic olefin resin substrate (I) is not subjected to an easy-adhesion treatment. Examples of the easy-adhesion treatment include known easy-adhesion treatments such as corona discharge treatment, plasma treatment, ozone treatment, and coating with an easy-adhesion primer composition.

[0018] The cyclic olefin resin substrate (I) can be any homopolymer or copolymer obtained by polymerizing a cyclic olefin, without any particular limitations. Commercially available cyclic olefin resins include, for example, "ZEONOR" manufactured by Zeon Corporation, "ARTON" manufactured by JSR Corporation, "TOPAS" manufactured by Polyplastics Co., Ltd., and "APL" manufactured by Mitsui Chemicals, Inc. The shape of the cyclic olefin resin substrate (I) may be a molded body or a film, and the thickness is not particularly limited.

[0019] The inorganic substance layer (III) in the present invention is not particularly limited as long as it is formed by a dry film-forming method, and can be selected depending on the properties to be imparted to the laminate. For example, a layer containing as a main component at least one or more of various metals containing elements such as Si, Ti, Zn, Al, Ga, In, Ce, Bi, Sb, B, Zr, Sn, and Ta, or metal oxides, nitrides, sulfides, etc., can be mentioned.

[0020] The inorganic substance layer (III) in the present invention may be at least one layer or may be multiple layers. When the inorganic substance layer (III) is multiple layers, the order of lamination thereof and the type of the inorganic substance layer (III) are not particularly limited. In addition, the inorganic substance layer (III) may be various functional layers such as an anti-reflection layer, an ultraviolet absorbing layer, or a functional layer.

[0021] Among these, the inorganic substance layer (III) is preferably a layer made of a metal oxide, particularly a silicon oxide compound, from the viewpoints of high hardness, low reflectivity, interlayer adhesion with the cured coating layer (II), and transparency of the laminate. Examples of silicon oxide compounds include silicon monoxide, silicon dioxide, and silicon suboxide.

[0022] The lamination method of the inorganic substance layer (III) in the present invention is not particularly limited as long as it is a dry film formation method, and examples thereof include physical vapor deposition methods (hereinafter also referred to as "PVD") such as resistance heating evaporation, electron beam evaporation, molecular beam epitaxy, ion beam deposition, ion plating, ion-assisted evaporation, and sputtering, and chemical vapor deposition methods (hereinafter also referred to as "CVD") such as thermal CVD, plasma CVD, photo CVD, epitaxial CVD, atomic layer CVD, and cat CVD, but ion-assisted evaporation is preferred because it can produce a highly adhesive, high-density, and stable film. The dry film formation method referred to here is a method in which the surface of a material is treated using a gas phase or a molten state, and is sometimes generally called a dry process.

[0023] The thickness of the inorganic substance layer (III) is preferably 10 nm or more from the viewpoint of scratch resistance, and more preferably 20 nm or more in order to maintain sufficient abrasion resistance. The upper limit of the thickness of each inorganic substance layer (III) is not particularly limited, but is preferably 5 μm or less, particularly preferably 2 μm or less. If the thickness of the inorganic substance layer (III) is less than 10 nm, sufficient scratch resistance may not be achieved.

[0024] As described above, the cured coating layer (II) of the present invention is a cured product formed from a thermosetting silicone resin composition containing the components (A) to (C) described below. The reactive silicone resin (A) in the thermosetting silicone resin composition forming the cured coating layer (II) of the present invention is blended in an amount of 34 to 80 parts by weight per 100 parts by weight of the total of components (A), (B), and (C). This amount is preferably 37 to 75 parts by weight, and more preferably 40 to 70 parts by weight. If the amount is too small, the cured coating layer (II) may deteriorate during weather resistance testing after laminate formation, resulting in poor adhesion to the inorganic substance layer (III) and poor steel wool resistance. If the amount is too large, the adhesion between the cyclic olefin resin substrate (I) and the cured coating layer (II) may be reduced.

[0025] The reactive silicone resin (A) in the thermosetting silicone resin composition forming the cured coating layer (II) of the present invention is obtained by hydrolysis and condensation of component (i) (alkoxysilane) represented by formula (i) above and a compound containing component (ii), which is an alkyl silicate represented by formula (ii) above or a partial hydrolyzate thereof. Here, the blending ratio of component (i) and the compound containing component (ii) is such that the molar ratio [moles of Si derived from the compound containing component (ii) / moles of Si derived from component (i)] is in the range of 0.2 to 4.0, based on the total 100 moles of Si contained in both components. Preferably, it is in the range of 0.5 to 4.0. More preferably, it is in the range of 0.7 to 3.7, and even more preferably, it is in the range of 0.9 to 3.2. If the amount is too small, the cured coating layer (II) may deteriorate during weathering tests after the laminate is formed, potentially reducing adhesion to the inorganic substance layer (III) and steel wool resistance. If the amount is too large, the laminate may become brittle, resulting in cracking and peeling.

[0026] Examples of alkoxysilanes represented by the general formula (i) include 3-(meth)acryloxypropyltrimethoxysilane, 2-(meth)acryloxyethyltrimethoxysilane, (meth)acryloxymethyltrimethoxysilane, (meth)acryloxymethyltriethoxysilane, and 3-(meth)acryloxypropyltriethoxysilane.

[0027] Examples of the alkyl silicate represented by the general formula (ii) include linear and branched alkyl silicates such as methyl silicate, ethyl silicate, isopropyl silicate, n-propyl silicate, isobutyl silicate, n-butyl silicate, n-pentyl silicate, acetyl silicate, etc. In addition to the component (ii) which is a compound containing the alkyl silicate represented by the formula (ii) or a partial hydrolyzate thereof, a compound represented by the following general formula (iv): Si ｎ O ｎ (OR ３ ) ２ｎ ...(iv) [wherein, in formula (iv), n represents a number from 1 to 20, and R ３ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ] or a partial hydrolyzate thereof [component (iv)] may be included. That is, the above-mentioned "compound containing component (ii), which is an alkyl silicate represented by formula (ii) or a partial hydrolyzate thereof," may contain component (iv), which is a cyclic alkyl silicate represented by formula (iv) or a partial hydrolyzate thereof. In this case, in the above-mentioned molar ratio of Si, the Si content of component (iv) is added to the "moles of Si derived from the compound containing component (ii)." Methyl silicate or ethyl silicate, or a partial hydrolyzate thereof, is more preferred in terms of rapid hydrolysis and condensation reactions.

[0028] A suitable method for obtaining the reactive silicone resin (A) by hydrolyzing and condensing a mixture containing the above-mentioned component (i) and a compound containing the above-mentioned component (ii) is to co-hydrolyze the mixture containing the above-mentioned component (i) and a compound containing the above-mentioned component (ii) in acidic water having a pH of 1 to 7, preferably 2 to 5. To adjust the pH, organic or inorganic acids such as hydrogen fluoride, hydrochloric acid, nitric acid, formic acid, acetic acid, propionic acid, oxalic acid, citric acid, maleic acid, benzoic acid, malonic acid, glutaric acid, glycolic acid, methanesulfonic acid, and toluenesulfonic acid can be used. Alternatively, a solid acid catalyst such as a cation exchange resin having carboxylic acid or sulfonic acid groups on its surface can be used. The amount of the acid or acid catalyst used is preferably 0.0001 to 20 wt % of the product.

[0029] The hydrolysis reaction requires the presence of water. The amount of water is sufficient to hydrolyze the hydrolyzable groups in the silicon compound in the mixture, and is preferably an amount equivalent to 0.5 to 2.0 times the theoretical number (moles) of hydrolyzable groups. If the mixture contains other silane compounds, the hydrolyzable groups in those compounds are included in the calculation. If the acid catalyst is added as an aqueous solution, the water in that solution is included in the calculation. If there is not enough water, hydrolysis will not proceed sufficiently, and if there is too much water, the remaining water will reduce the coatability and drying efficiency.

[0030] Simultaneously with the hydrolysis, a dehydration condensation reaction of the silanol groups produced occurs to form a reactive silicone resin (A). The temperature at which this condensation is carried out is room temperature or under heating at 120°C or less, more preferably 30°C or more and 100°C or less. If the temperature is too low, the hydrolysis and condensation reactions take a long time, resulting in low productivity, while if the temperature is too high, the resin may become insoluble.

[0031] The weight-average molecular weight (hereinafter also referred to as "Mw") of the reactive silicone resin (A) is not particularly limited, but is preferably in the range of 200 to 10,000. Mw is more preferably 500 to 8,000, even more preferably 600 to 7,000, and particularly preferably 700 to 6,000. The resulting structure is linear, branched, and cyclic, resulting in a mixture with a molecular weight distribution. If Mw is less than 200, the hydrolysis and condensation reactions do not proceed sufficiently, and if Mw exceeds 10,000, the resin may become insoluble or its storage stability may deteriorate. As such, the reactive silicone resin (A) of the present invention is obtained as a mixture with a range of structures and properties through the above reaction, and there are some circumstances in which it is impossible or impractical to directly identify the resin based on its structure or properties alone (so-called impossible or impractical circumstances). In this disclosure, Mw refers to the molecular weight measured by GPC (gel permeation chromatography) converted using polystyrene as a standard substance.

[0032] The polyfunctional (meth)acrylate monomer (B) forming the cured coating layer (II) of the present invention is blended in an amount of 19 to 65 parts by weight, preferably 19 to 60 parts by weight, and more preferably 24 to 55 parts by weight, per 100 parts by weight of the total of components (A), (B), and (C).

[0033] The total number of (meth)acrylic moles of the polyfunctional (meth)acrylate monomers (B) contained in 100 g of the thermosetting silicone resin composition forming the cured coating layer (II) should be 0.20 to 0.60. It is preferably in the range of 0.23 to 0.57, and more preferably 0.24 to 0.55. If the number of (meth)acrylic moles is too low, adhesion to the cyclic olefin resin substrate (I) may be reduced. If the number is too high, peeling may occur between the cured coating layer (II) and the inorganic substance layer (III) after a weather resistance test.

[0034] Examples of the polyfunctional (meth)acrylate monomer (B) include difunctional or higher functional (meth)acrylate monomers, such as pentaerythritol triacrylate, glycerin dimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dimethyloltricyclodecane diacrylate, 1,6-hexanediol diacrylate, and 1,9-nonanediol diacrylate. In addition to these, compounds in which some or all of the hydroxy groups of pentaerythritol or dipentaerythritol are modified with glycols such as ethylene or isopropylene, or γ-butyrolactone, and all of the terminal hydroxy groups of the resulting skeleton are modified with unsaturated groups, can also be used. Other examples include urethane acrylate and acrylic copolymer acrylate. These compounds may be used either alone or in combination of two or more.

[0035] The number of (meth)acrylic moles of the polyfunctional (meth)acrylate monomer (B) contained in 100 g of the above-mentioned heat-curable silicone resin composition is the number of (meth)acrylic moles of the polyfunctional (meth)acrylate monomer (B) per 100 g of the heat-curable silicone resin composition (number of (meth)acrylic functional groups / molecular weight g mol －１ )

[0036] The organic peroxide (C) forming the cured coating layer (II) of the present invention is blended in an amount of 0.5 to 10 parts by weight per 100 parts by weight of the total of components (A), (B), and (C). This amount is preferably 0.5 to 8 parts by weight, and more preferably 1 to 6 parts by weight. If the amount is too small, crosslinking may be insufficient, resulting in reduced adhesion and a reduced modulus of elasticity, and the desired steel wool resistance and pencil hardness may not be achieved. If the amount is too large, the proportion of the polyfunctional (meth)acrylate monomer (B) component in the thermosetting silicone resin composition may be reduced, resulting in insufficient crosslinking, reduced adhesion, and a reduced modulus of elasticity, and the desired steel wool resistance and pencil hardness may not be achieved.

[0037] Examples of the organic peroxide (C) include ketone peroxides such as ethyl methyl ketone peroxide and 2,4-pentanedione peroxide, peroxyketals such as 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, and 4,4-bis[(t-butyl)peroxy]butyl pentanoate, hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, [2-(4-methylcyclohexyl)propan-2-yl]hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide, bis(1-phenyl-1-methylethyl)peroxide, 1,4-bis[(t-butylperoxy)isopropyl]benzene, and t Examples of peroxides that can be used include, but are not limited to, dialkyl peroxides such as 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane and 2,5-bis(t-butylperoxy)-2,5-dimethyl-3-hexyne, peroxyesters such as 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 2-methylpentan-2-yl benzoperoxoate, t-butylperoxy-2-ethylhexanoate and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, and peroxydicarbonates such as bis(isopropoxycarbonyl)peroxide, peroxybis(2-ethylhexyl formate) and bis(1-methylpropyloxycarbonyl)peroxide. Although not an organic peroxide, 2,3-dimethyl-2,3-diphenylbutane can also be used as a peroxide. Among these, those which generate t-butoxy radicals with high radical reactivity are preferred, and 1,1-di(t-butylperoxy)cyclohexane is preferably used. These organic peroxides may be used alone or in combination of two or more.

[0038] The thickness of the cured coating layer (II) made from the thermosetting silicone resin composition is preferably in the range of 0.5 to 20 μm, more preferably 1 to 10 μm, and even more preferably 3 to 7 μm. If the amount is too small, the desired pencil hardness and steel wool resistance will not be obtained, while if the amount is too large, the contraction stress of the cured coating layer (II) during curing will be so great that cracks may occur or adhesion may decrease.

[0039] The thermosetting silicone resin composition used in the present invention may further contain various additives as needed, and may be diluted with a solvent if desired. Examples of additives that can be used include ultraviolet absorbers, light stabilizers, antioxidants, rheology control agents, surface conditioners (silicon-based surface conditioners, acrylic-based surface conditioners, fluorine-based surface conditioners, vinyl-based surface conditioners, etc.), surfactants, resin particles, lubricants, defoamers, mold release agents, silane coupling agents, antistatic agents, antifogging agents, and colorants.

[0040] The ultraviolet absorber may be any of the conventionally known organic and inorganic ultraviolet absorbers, such as benzotriazole-based absorbers, triazine-based absorbers, salicylic acid derivative-based absorbers, benzophenone-based absorbers, and other compounds (hydroxyphenyltriazines, oxalic acid anilide, cyanoacrylate, etc.). Examples of inorganic ultraviolet absorbers include fine particle titanium oxide, fine particle zinc oxide, and fine particle iron oxide. The ultraviolet absorber may also have a polymerizable unsaturated group. When the ultraviolet absorber is contained, the content of the ultraviolet absorber is within a range of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on the total cured coating-forming components.

[0041] The light stabilizer is not particularly limited, and a wide variety of conventionally known light stabilizers can be used, but preferred examples include hindered piperidine compounds. The hindered piperidine compound is a compound having at least one hindered piperidine group in one molecule. Examples of the hindered piperidine compound include monomer-type compounds such as bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, and bis(1,2,2,6,6-pentamethyl-4-piperidyl){[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl}butylmalonate; Examples of the light stabilizer include, but are not limited to, oligomer types such as (1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl)[(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)iminol]}; and polyester bond types such as a polyesterification product of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and succinic acid. Also usable as the light stabilizer are known polymerizable light stabilizers.

[0042] Commercially available light stabilizers include, for example, TINUVIN 123, TINUVIN 152, TINUVIN 292, and TINUVIN 479 (trade names, manufactured by BASF), HOSTAVIN 3050, HOSTAVIN 3052, and HOSTAVIN 3058 (trade names, manufactured by Clariant), and Adekastab LA-82 (trade name, manufactured by ADEKA). These may be used alone or in combination of two or more. When the light stabilizer is contained, the content thereof is within a range of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on all cured coating-forming components.

[0043] The cured coating layer (II) may be obtained either in an oxygen-blocking atmosphere or in the air. However, since the composition of the present invention provides a good cured film even when polymerized and cured in the air, the cured coating layer (II) is preferably obtained in the air. For example, the cured coating layer (II) can be formed by coating the thermosetting silicone resin composition of the present invention on a cyclic olefin resin substrate (I) or by diluting the composition with various organic solvents and then applying heat after a drying process. Coating methods include, for example, the flow coating method, roller coating, bar coating, spray coating, inkjet coating, air knife coating, spin coating, flow coating, curtain coating, and dipping. The coating thickness is adjusted by the solids concentration, taking into account the film thickness formed after drying and thermal curing. If an organic solvent is used to adjust the solids concentration, it is preferable to remove the organic solvent by drying or the like after coating. The drying temperature should be set so as not to deform the substrate used, and the drying time should be 1 hour or less from the viewpoint of productivity. The thermal curing temperature is not limited, but is preferably 100 to 125°C, more preferably 110 to 120°C. The thermal curing time is also not limited, but is preferably 1 to 10 hours, more preferably 2 to 6 hours. If the curing temperature is higher than 125°C, the cyclic olefin resin substrate (I) may soften, while if it is lower than 100°C, crosslinking may not proceed sufficiently, resulting in a decrease in hardness and adhesion.

[0044] Specific examples of the organic solvent include known organic solvents, such as aromatic organic solvents such as toluene and xylene, ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester organic solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate and isobutyl acetate, alcohol organic solvents such as methanol, ethanol, n-propanol, isopropanol and n-butanol, and glycol ether organic solvents such as propylene glycol monomethyl ether. In particular, it is preferable to use a glycol organic solvent.

[0045] Examples of glycol ether organic solvents include ethylene glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol dipropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol dibutyl ether, ethylene glycol isoamyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, methoxyethoxyethanol, and ethylene glycol monoallyl ether; and propylene glycols such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and butoxypropanol, with propylene glycol monomethyl ether being preferred.

[0046] The laminate according to the present invention can be produced by a method comprising the steps of applying a thermosetting silicone resin composition onto a cyclic olefin resin substrate (I) to form a coating layer made of the thermosetting silicone resin composition, curing the coating layer made of the thermosetting silicone resin composition by heat to form a cured coating layer (II), and forming at least one inorganic substance layer (III) on the cured coating layer (II) by a dry film formation method. Here, as described above, the thermosetting silicone resin composition comprises a reactive silicone resin (A), a polyfunctional (meth)acrylate monomer (B), and an organic peroxide (C), and contains 34 to 80 parts by weight of component (A), 19 to 65 parts by weight of component (B), and 0.5 to 10 parts by weight of component (C) relative to 100 parts by weight of the total of components (A), (B), and (C), and the total number of (meth)acrylic moles of the polyfunctional (meth)acrylate monomer (B) contained in 100 g of the composition is 0.20 to 0.60, The reactive silicone resin (A) is obtained by hydrolysis and condensation of an alkoxysilane represented by the following general formula (i) and a compound containing an alkyl silicate represented by the following general formula (ii) or a partial hydrolyzate thereof, and is characterized in that, in the blending ratio of the component (i) represented by formula (i) and the compound containing the component (ii), which is the alkyl silicate represented by formula (ii) or a partial hydrolyzate thereof, the ratio [moles of Si derived from the compound containing component (ii) / moles of Si derived from component (i)] satisfies the range of 0.2 to 4.0, relative to a total of 100 moles of Si contained in both components. １ Si(OR ２ ) ３ ...(i) [However, in formula (i), R １ is an organic functional group having a (meth)acryloyl group, and R ２ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.] Si ｎ O （ｎ－１） (OR ３ ) （２ｎ＋２） ...(ii) [wherein, in formula (ii), n represents a number from 1 to 20, and R ３ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0047] The thermosetting silicone resin composition used in the present invention can provide a cured coating layer (II) that has excellent adhesion to both the cyclic olefin resin substrate (I) and the inorganic substance layer (III), and can form a laminate that exhibits no cracking or peeling in a weather resistance test using a xenon lamp under the specified conditions in the examples described above and below, and that has excellent steel wool resistance and pencil hardness. For example, the pencil hardness (according to JIS K 5600) is preferably F or higher, more preferably H or higher, and even more preferably 2H or higher.

[0048] The present invention will be described in more detail below based on examples and comparative examples, but the present invention is not limited to the following.

[0049] [Synthesis of A-1] In a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer, 3-methacryloxypropyltrimethoxysilane (i) was added. (XIAMETER.OFS-6030 Silane manufactured by Dow Toray Co., Ltd.) 12.0 g, and methyl silicate (ii) 16.3 g of methyl silicate 53A (manufactured by Colcoat Co., Ltd.) was added and stirred, and 8.7 g of a 0.05% aqueous hydrochloric acid solution was placed in the dropping funnel and added with stirring at room temperature. After completion of the dropwise addition, the mixture was heated to 60°C and stirred for 1 hour, then cooled, and 6.6 g of propylene glycol monomethyl ether was added, yielding the target reactive silicone resin (A-1) with a solids content of 50 wt% (wt%) and a ratio of [moles of Si derived from compounds containing component (ii) / moles of Si derived from component (i)] of 3.0 per 100 moles of total Si content in component (A).

[0050] [Synthesis of A-2] 4.5 g of 3-methacryloxypropyltrimethoxysilane (XIAMETER.OFS-6030 Silane, manufactured by Dow-Toray Industries, Inc.) as component (i) and 10.0 g of methyl silicate (manufactured by Colcoat Co., Ltd., trade name: Methyl Silicate 53A) as component (ii) were placed in a reaction vessel equipped with a stirrer, dropping funnel, and thermometer and stirred. 3.9 g of 0.05% aqueous hydrochloric acid solution was placed in the dropping funnel and added with stirring at room temperature. After completion of the dropping, the temperature was raised to 60°C and stirred for 1 hour, then cooled, and 4.8 g of propylene glycol monomethyl ether was added to obtain the target reactive silicone resin (A-2) with a solids content of 50 wt% and a ratio of [moles of Si derived from compounds containing component (ii) / moles of Si derived from component (i)] of 1.0 per 100 moles of total Si content contained in component (A).

[0051] [Synthesis of A-3] 3.8 g of 3-methacryloxypropyltrimethoxysilane (XIAMETER.OFS-6030 Silane, manufactured by Dow-Toray Industries, Inc.) as component (i) and 12.0 g of methyl silicate (trade name: Methyl Silicate 53A, manufactured by Colcoat Co., Ltd.) were placed in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer and stirred. 3.3 g of 0.05% aqueous hydrochloric acid solution was placed in the dropping funnel and added with stirring at room temperature. After completion of the dropping, the temperature was raised to 60°C and stirred for 1 hour, then cooled, and 5.5 g of propylene glycol monomethyl ether was added to obtain the target reactive silicone resin (A-3) with a solids content of 50 wt% and a ratio of [moles of Si derived from compounds containing component (ii) / moles of Si derived from component (i)] of 0.3 per 100 moles of total Si content contained in component (A).

[0052] [Synthesis of A-4] 12.0 g of 3-methacryloxypropyltrimethoxysilane (XIAMETER.OFS-6030 Silane, manufactured by Dow-Toray Industries, Inc.), component (i), was placed in a reaction vessel equipped with a stirrer, dropping funnel, and thermometer and stirred. 2.7 g of 0.05% aqueous hydrochloric acid solution was placed in the dropping funnel and added with stirring at room temperature. Component (ii) was not used. After the dropwise addition was completed, the temperature was raised to 60°C and the mixture was stirred for 1 hour, then cooled, and 5.4 g of propylene glycol monomethyl ether was added to obtain a reactive silicone resin (A-4) with a solids content of 50 wt% containing no Si moles derived from a compound containing component (ii) in component (A).

[0053] Example 1 A thermosetting silicone resin composition (II)-1 was obtained by mixing 150 parts by weight (solid content: 75 parts by weight) of (A-1) as the reactive silicone resin component (A), 25 parts by weight of a 65:35 (weight ratio) mixture of dipentaerythritol hexaacrylate (Mw=578.57, number of acrylic groups=6) and dipentaerythritol pentaacrylate (Mw=524.52, number of acrylic groups=5) (manufactured by Kyoeisha Chemical Co., Ltd., product name DPHA) (B-1) as the polyfunctional (meth)acrylic monomer component (B), and 3 parts by weight of 1,1-di(t-butylperoxy)cyclohexane (C-1) (manufactured by NOF Corporation, product name PERHEXA C) having the chemical structure shown below as the organic peroxide (C). With regard to the resulting thermosetting silicone resin composition (II)-1, the ratio [moles of Si derived from compounds containing component (ii) / moles of Si derived from component (i)] per 100 moles of total Si content in component (A) was 3.0, and the number of moles of (meth)acrylic acid of component (B) per 100 g of the composition was {[100 × (6 / 578.57) × 0.65] + [100 × (5 / 524.52) × 0.35]} × (25 / 103.0) = 0.24.

[0054] Next, the obtained thermosetting silicone resin composition (II)-1 was diluted with propylene glycol monomethyl ether to a solids content of 40 parts by weight, and 0.5 parts by weight of an acrylic surface conditioner (manufactured by BYK Corporation, trade name BYK3440) was mixed therewith. This mixture was applied to one surface of a cyclic olefin copolymer resin substrate (thickness 3 mm, length 65 mm, width 35 mm, manufactured by Mitsui Chemicals, trade name APL5014) using a spin coater in the atmosphere, dried and cured, and then coated to a film thickness of 5 μm after curing. The mixture was then dried at 80°C for 5 minutes to form a coating layer. The coating layer was then cured by heating at 120°C for 2 hours, forming a cured coating layer (II) made of the thermosetting silicone resin composition on the surface of the cyclic olefin copolymer resin substrate. Next, an inorganic substance layer (III) shown in Table 1 was coated thereon to a film thickness of 400 nm using SiO ２ was formed by ion-assisted deposition to obtain the laminate of Example 1. The inorganic substance layer (III) was silicon dioxide represented by SiOx (x: 2). The results are shown in Table 1. In the table, the ratio [moles of Si derived from compounds containing component (ii) / moles of Si derived from component (i)] relative to 100 moles of total Si content in component (A) is abbreviated as "moles of Si derived from component (ii) / moles of Si derived from component (i)." Furthermore, the number of moles of (meth)acrylic acid in component (B) per 100 g of the composition is abbreviated as "moles of (meth)acrylic acid in component (B)."

[0055] [Examples 2 to 13, Comparative Examples 1 to 6] Thermosetting silicone resin compositions (II)-2 to (II)-13, (II)-17 to (II)-22, and their respective laminates were obtained in the same manner as in Example 1, except that the raw materials and compositional ratios shown in Tables 1 to 3 were used. Note that other abbreviations in the tables refer to the following: B-2: Trimethylolpropane triacrylate (Mw = 296.32, number of acrylic groups = 3) (manufactured by Kyoeisha Chemical Co., Ltd., product name: Light Acrylate TMP-A) B-3: Dimethyloltricyclodecane diacrylate (Mw = 304.39, number of acrylic groups = 2) (manufactured by Kyoeisha Chemical Co., Ltd., product name: Light Acrylate DCP-A)

[0056] C-2: t-butylperoxy-2-ethylhexanoate (manufactured by NOF Corporation, product name Perbutyl O) C-3: 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (manufactured by NOF Corporation, product name Perocta O)

[0057] [Examples 14 to 16] Using the raw materials and compositional ratios shown in Table 2, thermosetting silicone resin compositions (II)-14 to (II)-16 and their respective laminates were obtained in the same manner as in Example 1, except that the curing conditions for the thermosetting silicone resin compositions were changed to 110°C for 8 hours or 4 hours.

[0058] The laminate test pieces obtained above were subjected to the following evaluations, and the evaluation results are shown in Tables 1 to 3.

[0059] [Adhesion] One hundred 1 mm x 1 mm squares were made on the surface of the inorganic substance layer (III) of each laminate test piece in accordance with JIS K 5600-5-6 (1990), adhesive tape was applied to the surface, and the tape was rapidly peeled off. This process was repeated three times, and the degree of peeling was evaluated based on the remaining state of the squares according to the following criteria. For the peel layer, the peel interface was measured using microscopic FT-IR. If there was a peak derived from acrylic groups, it was considered to be peeling between the cured coating layer (II) and the inorganic substance layer (III), and if there was a peak derived from the cyclic olefin resin substrate (I), it was considered to be peeling between the cyclic olefin resin substrate (I) and the cured coating layer (II). The adhesion between the cyclic olefin resin substrate (I) and the cured coating layer (II) and the adhesion between the cured coating layer (II) and the inorganic substance layer (III) were evaluated, respectively. In the table, the results are represented as "(I) / (II)" and "(II) / (III)," respectively. ◯: The number of remaining squares is 100. △: The number of remaining squares is 90 to 99. ×: The number of remaining squares is 0 to 89.

[0060] [Steel wool resistance] Using #0000 steel wool, a reciprocating abrasion tester (Type: 30S manufactured by HEIDON) was used under a load of 0.25 kg / cm. ２ The inorganic substance layer (III) surface was abraded 10 times with abrasive cloth. The presence or absence of scratches was visually observed and judged according to the following criteria: ○: 0 scratches △: 1 or more but less than 5 scratches ×: 5 or more scratches

[0061] [Appearance] The laminate was visually inspected for cracks and peeling, and judged according to the following criteria: ◯: No cracks or peeling occurred ×: Cracks or peeling occurred

[0062] [Pencil Hardness] According to JIS K 5600, the inorganic substance layer (III) surface of each laminate test piece was scratched at an angle of 45 degrees with a Mitsubishi Pencil Uni under a load of 750 g, and the hardness at which scratches were not produced was visually determined.

[0063] [Weather Resistance Test] Using a xenon weather meter tester (X75, manufactured by Suga Test Instruments Co., Ltd.), a xenon lamp illuminance of 2.4 W / m was applied from the surface of the inorganic substance layer (III) under conditions of a temperature of 55°C and a relative humidity of 30% Rh. ２ The coating was irradiated with light at 420 nm for 150 hours, and the appearance, adhesion, steel wool resistance, and pencil hardness were evaluated after the test.

[0064]

[0065]

[0066]

Claims

1. A laminate in which a cured film layer (II) formed of a thermosetting silicone resin composition and an inorganic substance layer (III) are sequentially laminated on a cyclic olefin resin substrate (I), The cured film layer (II) contains a reactive silicone resin (A), a polyfunctional (meth)acrylate monomer (B), and an organic peroxide (C), and the component (A) is 34 to 80 parts by weight, the component (B) is 19 to 65 parts by weight, and the component (C) is 0.5 to 10 parts by weight with respect to a total of 100 parts by weight of the components (A), (B), and (C), And the total number of (meth)acrylic moles of the polyfunctional (meth)acrylate monomer (B) contained in 100 g of the composition is 0.20 to 0.60, The reactive silicone resin (A) is obtained by hydrolyzing and condensing an alkoxysilane represented by the following general formula (i) and a compound containing an alkyl silicate represented by the following general formula (ii) or a partial hydrolyzate thereof. In the blending ratio of the component (i) represented by the formula (i) and the compound containing the alkyl silicate or its partial hydrolyzate represented by the formula (ii) which is the component (ii), based on 100 moles of the total Si content contained in both, [(Si moles derived from the compound containing the component (ii)) / (Si moles derived from the component (i))] satisfies the range of 0.2 to 4.

0. R １ Si(OR ２ ) ３ ...(i) [However, in the formula (i), R １ is an organic functional group having a (meth)acryloyl group, and R ２ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.] Si ｎ O （ｎ－１） (OR ３ ) （２ｎ＋２） ...(ii) [However, in the formula (ii), n represents a number from 1 to 20, and R ３ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.] 2. In the weather resistance test in which the laminate is irradiated with light at an illuminance of 2.4 W / m ２ (420 nm) from a xenon lamp for 150 hours under the conditions of a temperature of 55°C and a relative humidity of 30% Rh on the surface of the inorganic substance layer (III), no cracks or peeling occur after the weather resistance test, and no damage is visually confirmed after reciprocating 10 times with a load of 0.25 kg / cm ２ on the surface of the inorganic substance layer (III) using #0000 steel wool. The laminate according to claim 1, characterized by this.

3. The laminate according to claim 1, wherein the film thickness of the cured film layer (II) is in the range of 0.5 to 20 μm.

4. The laminate according to claim 1, wherein the cyclic olefin resin substrate (I) has not been subjected to an adhesion-improving treatment.

5. A thermosetting silicone resin composition for forming a cured film layer (II) of the laminate according to any one of claims 1 to 4, comprising a reactive silicone resin (A), a polyfunctional (meth)acrylate monomer (B), and an organic peroxide (C), wherein the component (A) is 34 to 80 parts by weight, the component (B) is 19 to 65 parts by weight, and the component (C) is 0.5 to 10 parts by weight based on a total of 100 parts by weight of the components (A), (B), and (C), and the total number of (meth)acrylic moles of the polyfunctional (meth)acrylate monomer (B) contained in 100 g of the composition is 0.20 to 0.60, and the reactive silicone resin (A) is obtained by hydrolyzing and condensing an alkoxysilane represented by the following general formula (i) and a compound containing an alkyl silicate represented by the following general formula (ii) or a partial hydrolyzate thereof, and in the blending ratio of the component (i) represented by the formula (i) and the compound containing the alkyl silicate or its partial hydrolyzate represented by the formula (ii), [Si mole derived from the compound containing the component (ii) / Si mole derived from the component (i)] satisfies the range of 0.2 to 4.0 with respect to a total of 100 moles of Si contained in both. R １ Si(OR ２ ) ３ ...(i) [However, in the formula (i), R １ is an organic functional group having a (meth)acryloyl group, and R ２ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.] Si ｎ O （ｎ－１） (OR ３ ) （２ｎ＋２） ...(ii) [However, in the formula (ii), n represents a number from 1 to 20, and R ３ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.] 6. A method for producing the laminate according to any one of claims 1 to 4, comprising: a step of applying a thermosetting silicone resin composition onto a cyclic olefin resin substrate (I) to form a coating layer of the thermosetting silicone resin composition; a step of curing the coating layer of the thermosetting silicone resin composition by heat to form a cured film layer (II); and a step of forming at least one layer of an inorganic material layer (III) on the cured film layer (II) by a dry film-forming method.

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