Thermosetting silicone resin composition, laminate, and method for producing laminate

Abstract

Provided are: a thermosetting silicone resin composition that has exceptional 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) and a cured coating layer (II) formed from the composition are laminated; and a method for producing the laminate.　In the laminate: the cured coating layer (II) contains a reactive silicone resin (A), a polyfunctional (meth)acrylate monomer (B), an organic peroxide (C), and an ultraviolet absorber (D); the cured coating layer (II) contains 30-75 parts by weight of (A), 20-65 parts by weight of (B), 0.5-10 parts by weight of (C), and 0.1-30 parts by weight of (D) per 100 parts by weight in total of (A) through (D); the number of (meth)acrylic moles of (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 that contains an alkyl silicate of formula (ii) or a partial hydrolysate thereof; and [mol of Si derived from compound that contains component (ii) / mol of Si derived from component (i)] is 0.5-4.0 with respect to 100 mol in total of Si content.

Description

Thermosetting silicone resin composition, laminate, and method for manufacturing the 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 excellent light resistance, and a laminate using the same and a method for producing the same.

[0002] In recent years, cyclic olefin resins have been increasingly used as optical components in mobile phones, smartphones, and liquid crystal displays due to their high transparency, low moisture absorption, and other functional properties. However, cyclic olefin resins are prone to scratches due to their relatively low surface hardness. Therefore, a hard coat layer is typically applied to their surface. Despite this, the adhesion between the cyclic olefin resin and the cured film layer has not always been sufficient. Consequently, pre-treatment processes such as corona discharge, plasma treatment, ozone treatment, or application of an easy-adhesion primer composition to the cyclic olefin resin surface were necessary before forming the cured film layer (Patent Document 1).

[0003] Patent documents 2 and 3 propose active energy ray curable compositions containing diphenyl sulfide compounds, benzophenone compounds, and compounds having (meth)acryloyl groups as cured coatings of cyclic olefin resins that do not require the above-mentioned easy-adhesion treatment, as well as active energy ray curable compositions containing polyfunctional (meth)acrylates, benzophenone compounds, and polysiloxanes.

[0004] However, when attempting to form a cured coating layer on molded articles or films made of cyclic olefin resin with complex shapes such as lenses, it is difficult to uniformly irradiate the active energy ray-curable composition with active energy rays. This results in variations in the hardness and adhesion of the cured coating layer, making it difficult to fully exhibit its properties.

[0005] Furthermore, in xenon lightfastness tests, there was a problem where the adhesion between the cyclic olefin resin and the hard coat layer decreased due to the deterioration of the hard coat layer.

[0006] Japanese Patent Publication No. 2008-518280, Japanese Patent Publication No. 2015-127102, Japanese Patent Publication No. 2016-105164

[0007] The present invention relates to a thermosetting silicone resin composition that has excellent adhesion to a cyclic olefin resin substrate and excellent light resistance, and a laminate using the same.

[0008] The present inventors have found that the above problem can be solved by forming a cured film layer (II) on a cyclic olefin resin substrate (I) using a thermosetting silicone resin composition containing a polymerizable compound having a specific structure, an organic peroxide, and an ultraviolet absorber in specific proportions, and have arrived at the present invention.

[0009] In other words, the present invention is as follows: (1) A laminate comprising a cyclic olefin resin substrate (I) on which a cured film layer (II) formed from a thermosetting silicone resin composition is laminated, wherein the cured film layer (II) comprises a reactive silicone resin (A), a polyfunctional (meth)acrylate monomer (B), an organic peroxide (C), and an ultraviolet absorber (D), and contains 30 to 75 parts by weight of component (A), 20 to 65 parts by weight of component (B), 0.5 to 10 parts by weight of component (C), and 0.1 to 30 parts by weight of component (D) per 100 parts by weight of the total of components (A), (B), (C), and (D), and the total number of (meth)acrylic moles of 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 or a partial hydrolysate thereof represented by the following general formula (ii), and the laminate is characterized in that, in the blending ratio of component (i) represented by formula (i) and the compound containing component (ii), which is an alkyl silicate or a partial hydrolysate thereof, the ratio of [moles of Si from the compound containing component (ii) / moles of Si from component (i)] is in the range of 0.5 to 4.0 per 100 moles of the total Si content contained in both. １ Si ( OR ２ ) ３ ... (i) [However, in equation (i), R １ is an organic functional group having a (meth)acryloyl group, 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) [However, 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.〕

[0010] (2) The laminate according to (1), wherein the ultraviolet transmittance of the cured film layer (II) at a wavelength of 315 nm is 42% or less.

[0011] (3) The laminate according to (1), wherein the film thickness of the cured film layer (II) is in the range of 0.5 to 20 μm.

[0012] (4) A thermosetting silicone resin composition for forming the cured film layer (II) of the laminate according to any one of (1) to (3), comprising a reactive silicone resin (A), a polyfunctional (meth)acrylate monomer (B), an organic peroxide (C), and an ultraviolet absorber (D), wherein the (A) component is 30 to 75 parts by weight, the (B) component is 20 to 65 parts by weight, the (C) component is 0.5 to 10 parts by weight, and the (D) component is 0.1 to 30 parts by weight with respect to a total of 100 parts by weight of the (A) component, the (B) component, the (C) component, and the (D) component, 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 (i) component represented by the formula (i) and the compound containing the alkyl silicate represented by the formula (ii) or a partial hydrolyzate thereof, [(Si mole derived from the compound containing the (ii) component) / (Si mole derived from the (i) component)] satisfies the range of 0.5 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 equation (i), R １ is an organic functional group having a (meth)acryloyl group, 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 equation (ii), n represents a number from 1 to 20, and R ３ This represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0013] (5) The thermosetting silicone resin composition according to claim (4), wherein the ultraviolet absorber (D) is zinc oxide, which may have a modified surface.

[0014] (6) The thermosetting silicone resin composition according to (4), wherein the ultraviolet absorber (D) is a compound having a hydroxyphenyltriazine structure.

[0015] (7) A method for producing a laminate according to any one of (1) to (3), comprising the steps of: coating a thermosetting silicone resin composition onto a cyclic olefin resin substrate (I) to form a film layer of the thermosetting silicone resin composition; and curing the film layer of the thermosetting silicone resin composition by heat to form a cured film layer (II).

[0016] The present invention provides a thermosetting silicone resin composition that has excellent adhesion to a cyclic olefin resin substrate and can impart properties such as light resistance, as well as a laminate using the same and a method for producing the same.

[0017] The following describes in detail each element constituting the present invention. However, the following description is merely an example of an embodiment of the present invention, and the present invention is not limited to the following description unless it exceeds the gist of the invention. In this specification, when the expression "~" is used, it is used to include the numerical value or physical property value before and after it. Also, in this invention, when the expression "(meth)acrylic" is used, it means either or both "acrylic" and "methacrylic". The same applies to "(meth)acrylate" and "(meth)acryloyl".

[0018] The laminate of the present invention has a cured film layer (II) formed from a thermosetting silicone resin composition and cured on at least one side of a cyclic olefin resin substrate (I).

[0019] The cyclic olefin resin substrate (I) is preferably one that has not undergone any easy-adhesion treatment, in order to shorten the process for manufacturing the laminate. Examples of easy-adhesion treatments include known treatments such as corona discharge treatment, plasma treatment, ozone treatment, and coating with an easy-adhesion primer composition.

[0020] The cyclic olefin resin substrate (I) can be any polymer or copolymer of a polymerized cyclic olefin without any particular limitations. Examples of commercially available cyclic olefin resins include "ZEONOR" from Nippon Zeon Co., Ltd., "ARTON" from JSR Corporation, "TOPAS" from Polyplastics Co., Ltd., and "APL" from Mitsui Chemicals, Inc. The shape of the cyclic olefin resin substrate (I) may be a molded article or a film, and its thickness is not particularly limited.

[0021] As described above, the cured film layer (II) of the present invention is made of a thermosetting silicone composition containing components (A) to (D) described below, and is a cured product formed from said composition. The reactive silicone resin (A) in the thermosetting silicone resin composition that forms the cured film layer (II) of the present invention is preferably blended in an amount of 30 to 75 parts by weight per 100 parts by weight of the total of components (A), (B), (C), and (D). Preferably, it is in the range of 37 to 75 parts by weight, and more preferably 40 to 70 parts by weight. If the amount is too small, the cured film layer (II) may deteriorate in a lightfastness test after the lamination of the laminate, and the adhesion between the cyclic olefin resin substrate (I) and the cured film layer (II) may decrease, and the pencil hardness may decrease.

[0022] The reactive silicone resin (A) in the thermosetting silicone resin composition that forms the cured film layer (II) of the present invention is obtained by hydrolysis and condensation of a compound containing component (i), represented by formula (i) (alkoxysilane), and component (ii), which is an alkyl silicate or a partial hydrolysate thereof, represented by formula (ii). Here, in the blending ratio of these components (i) and the compound containing component (ii), the molar ratio expressed as [moles of Si from the compound containing component (ii) / moles of Si from component (i)] with respect to 100 moles of the total Si content contained in both should preferably be in the range of 0.5 to 4.0. Preferably, it is in the range of 0.7 to 3.7, and more preferably 0.9 to 3.2. If it is too low, the cured film layer (II) may deteriorate in a lightfastness test after lamination, and adhesion and pencil hardness may worsen. If it is too high, it may become brittle and crack or peel off.

[0023] Examples of alkoxysilanes represented by the general formula (i) include 3-(meth)acryloxypropyltrimethoxysilane, 2-(meth)acryloxyethyltrimethoxysilane, (meth)acryloxymethyltrimethoxysilane, (meth)acryloxymethyltriethoxysilane, and 3-(meth)acryloxypropyltriethoxysilane.

[0024] Examples of alkyl silicates 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, and acetyl silicate. In addition to the alkyl silicate represented by formula (ii) or component (ii), which is a partial hydrolysate thereof, the following general formula (iv) Si ｎ O ｎ (OR ３ ) ２ｎ ... (iv) [However, in equation (iv), n represents a number from 1 to 20, and R ３represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. A cyclic alkyl silicate represented by 〕 or a partial hydrolyzate thereof [(iv) component] may be included. That is, in the above-mentioned "compound containing the (ii) component which is an alkyl silicate represented by the formula (ii) or a partial hydrolyzate thereof", the (iv) component which is a cyclic alkyl silicate represented by the formula (iv) or a partial hydrolyzate thereof may be included. In that case, in the above molar ratio related to Si, the Si content of the (iv) component is added to the "Si mole derived from the compound containing the (ii) component". More preferably, methyl silicate or ethyl silicate or a partial hydrolyzate thereof is preferred in terms of the fast hydrolysis and condensation reaction.

[0025] As a method for obtaining the reactive silicone resin (A) by hydrolyzing and condensing the mixture containing the above (i) component and the compound containing the (ii) component, it is preferable to co-hydrolyze the mixture containing the above (i) and the compound containing the (ii) component with acidic water having a pH of 1 to 7, preferably pH 2 to 5. For this pH adjustment, organic acids 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. Also, a solid acid catalyst such as a cation exchange resin having a carboxylic acid group or a sulfonic acid group on the surface may be used as the catalyst. The usage amount of the above acid or acid catalyst is preferably 0.0001 to 20% by weight based on the product.

[0026] In the above hydrolysis reaction, the presence of water is necessary. The amount of water may be an amount sufficient to hydrolyze the hydrolyzable groups in the silicon compound in the mixture, and is preferably an amount corresponding to 0.5 to 2.0 times the molar amount of the theoretical amount (mole) of the number of hydrolyzable groups. When the above other silane compounds are included in the mixture, their hydrolyzable groups are added to the calculation. Also, when the acidic catalyst is added as an aqueous solution, the water is added to the calculation. When the amount of water is small, sufficient hydrolysis does not proceed, and when it is large, the coating property and drying efficiency are reduced due to the remaining water.

[0027] A dehydration condensation reaction of the silanol groups generated simultaneously with hydrolysis occurs, resulting in the reactive silicone resin (A). The temperature at which this condensation is carried out is normal temperature or heating at 120°C or lower, more preferably 30°C or higher and 100°C or lower. When the temperature is low, the time for the hydrolysis and condensation reactions is long, and the productivity is low. When the temperature exceeds the range and is too high, there is a risk of insolubilization.

[0028] There is no particular limitation on the weight average molecular weight (hereinafter also referred to as "Mw") of the reactive silicone resin (A), but it is preferably in the range of 200 to 10,000. Mw is more preferably 500 to 8,000, still more preferably 600 to 7,000, and particularly preferably 700 to 6,000. The resulting structure is composed of linear, branched, and cyclic forms, and becomes a mixture with a molecular weight distribution. If Mw is less than 200, the hydrolysis and condensation reactions do not proceed sufficiently, and if it exceeds 10,000, there is a risk of insolubilization or poor storage stability. Thus, the reactive silicone resin (A) in the present invention is obtained as a mixture having a wide range of structures and properties by the above reaction, and it is impossible to directly specify it only by its structure or properties, or there are some circumstances (so-called impossible and impractical circumstances) that are not very practical. Incidentally, Mw in the present disclosure means a value obtained by converting the molecular weight measured by GPC (gel permeation chromatography) using polystyrene as a standard substance.

[0029] The polyfunctional (meth)acrylic monomer (B) for forming the cured film layer (II) of the present invention is preferably blended in an amount of 20 to 65 parts by weight based on 100 parts by weight in total of the components (A), (B), (C), and (D). Preferably it is in the range of 20 to 60 parts by weight, more preferably 24 to 55 parts by weight.

[0030] The total number of (meth)acrylic moles of polyfunctional (meth)acrylate monomers (B) contained in 100 g of the thermosetting silicone composition that forms the cured film layer (II) should be between 0.20 and 0.60. Preferably, it should be 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, the adhesion to the cyclic olefin resin substrate (I) may decrease. If it is too high, the shrinkage stress of the cured film layer during curing will be large, which may cause cracks or decrease adhesion.

[0031] Examples of the above-mentioned polyfunctional (meth)acrylate monomer (B) include pentaerythritol triacrylate, glycerin dimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dimethylol tricyclodecane diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, and the like. In addition to these, compounds obtained by modifying all the hydroxyl groups of pentaerythritol or dipentaerythritol with glycols such as ethylene or isopropylene, or γ-butyrolactone, and then modifying all the terminal hydroxyl groups of the skeleton with unsaturated groups can also be used. Alternatively, urethane acrylates and acrylic copolymer acrylates can be given as examples. Furthermore, these compounds may be used individually or in combination of two or more types.

[0032] Furthermore, as component (B), a polyfunctional (meth)acrylate monomer that absorbs ultraviolet light can be used in combination, as described later. The polyfunctional (meth)acrylate monomer that absorbs ultraviolet light is not limited, but examples include (4,4'-bisacryloyloxymethyl)biphenyl, 9,9-bis[4-(2-hydroxyethoxy)phenyl]ful orange acrylate, and bisphenol A ethoxylate diacrylate. The content of such a polyfunctional (meth)acrylate monomer that absorbs ultraviolet light can be adjusted as appropriate as long as it satisfies the number of (meth)acrylic moles for component (B) as described later and is within the scope of the objectives of the present invention. For example, in order to improve the mixability in the composition, it is preferable to use 1 to 15 parts by weight, and more preferably 1 to 10 parts by weight, per 100 parts by weight of the total of components (A) to (D).

[0033] The number of (meth)acrylic moles of polyfunctional (meth)acrylate monomer (B) contained in the above 100g is the number of (meth)acrylic moles of polyfunctional (meth)acrylate monomer (B) per 100g of thermosetting silicone composition (number of (meth)acrylic functional groups / molecular weight g・mol －１ This shows the sum of ).

[0034] The organic peroxide (C) that forms the cured film layer (II) of the present invention is preferably blended in an amount of 0.5 to 10 parts by weight per 100 parts by weight of the total of components (A), (B), (C), and (D). Preferably, it is in the range of 0.5 to 8, more preferably 1 to 6. If the amount is too little, crosslinking will be insufficient, reducing adhesion and elastic modulus, and the desired pencil hardness may not be obtained. If the amount is too much, the proportion of the polyfunctional (meth)acrylate monomer (B) component in the thermosetting silicone composition will decrease, resulting in insufficient crosslinking, reducing adhesion and elastic modulus, and the desired pencil hardness may not be obtained.

[0035] Examples of organic peroxides (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, as well as bis(1-phenyl-1-methylethyl)peroxide and 1,4-bis[(t-butylperoxy)isopropyl]benzene, t Examples of peroxides include, but are not limited to, dialkyl peroxides such as butyl-α-cumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, and 2,5-bis(t-butylperoxy)-2,5-dimethyl-3-hexine; 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 that 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 individually or in combination of two or more.

[0036] The ultraviolet absorber (D) that forms the cured film layer (II) of the present invention is preferably blended in an amount of 0.1 to 30 parts by weight per 100 parts by weight of the total of components (A), (B), (C), and (D). Preferably, it is in the range of 0.2 to 25 parts by weight, and more preferably in the range of 0.3 to 20 parts by weight. The ultraviolet absorption capacity of the ultraviolet absorber used at a wavelength of 315 nm affects the blending ratio, but if it is too little, a large amount of light reaches the adhesion interface between the cured film layer (II) and the cyclic olefin resin substrate (I), which may lead to deterioration and a decrease in adhesion. If it is too much, transparency may decrease, crosslinking may become insufficient, reducing adhesion and lowering the elastic modulus, which may prevent the desired pencil hardness from being obtained.

[0037] To reduce the UV transmittance of the cured film layer (II) at a wavelength of 315 nm, a UV absorber component (D) is used. However, by incorporating the aforementioned UV-absorbing polyfunctional (meth)acrylate monomer component (B), the amount of component (D) can be reduced. However, without the inclusion of component (D), adhesion may decrease after the lightfastness test.

[0038] As the ultraviolet absorber (D), conventionally known organic ultraviolet absorbers or inorganic ultraviolet absorbers can be selected and used. However, due to reasons such as the transparency of the cured film and not inhibiting the curing reaction, compounds having a zinc oxide or hydroxyphenyltriazine structure are preferred, and one type may be used alone, or two or more types may be used in combination.

[0039] The particle size of zinc oxide is generally 10 to 200 nm, preferably 15 to 150 nm, and particularly preferably 15 to 100 nm. Zinc oxide may also be surface-modified, with a particle size generally 10 to 210 nm, preferably 15 to 150 nm, and particularly preferably 15 to 100 nm. Here, the particle size can be determined, for example, by measuring the maximum diameter of particles in images obtained by observation with an electron microscope such as a TEM (transmission electron microscope) or SEM (scanning electron microscope). The average particle diameter can be determined by the arithmetic mean of the maximum diameters of any 50 particles. While there are no limitations on the surface modification method, it is preferable, for example, to use zinc oxide surface-modified with acryloyl groups.

[0040] Specific examples of compounds having a hydroxyphenyltriazine structure include 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (BASF, trade name "TINUVIN 479"), BASF, trade name "TINUVIN 477", and the reaction product of 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-hydroxyphenyl with oxirane {especially [(C10-C16, mainly C12-C13 alkyloxy)methyl]oxirane} (BASF, trade name "TINUVIN 477"). Examples include the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester (BASF, trade name "TINUVIN 405"), and 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine (BASF, trade name "TINUVIN 460"). 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (BASF, trade name "TINUVIN 479") is preferred because it can impart sufficient lightfastness with a small amount of additive.

[0041] When using a compound having the hydroxyphenyltriazine structure as component (D), it is preferable to use 0.1 to 2 parts by weight, and more preferably 0.1 to 1 part by weight, per 100 parts by weight of the total of components (A) to (D), in order to improve miscibility in the composition and to exert the effect of ultraviolet absorption (to reduce the ultraviolet transmittance at an ultraviolet wavelength of 315 nm). In this case, although not limited, it is a preferred embodiment to use in combination with the aforementioned ultraviolet-absorbing polyfunctional (meth)acrylate monomer component (B).

[0042] The cured film layer (II) preferably has an ultraviolet transmittance of 42% or less at a wavelength of 315 nm. If it exceeds 42%, the amount of light reaching the adhesion interface between the cured film layer (II) and the cyclic olefin resin substrate (I) will be high in the lightfastness test, which may lead to a decrease in adhesion due to degradation. The ultraviolet transmittance is more preferably 34% or less, and even more preferably 30% or less.

[0043] The thickness of the cured film layer (II) made from the thermosetting silicone resin composition is preferably in the range of 0.5 to 20 μm. Preferably, it is in the range of 1 to 10 μm, and more preferably 3 to 7 μm. If it is too small, the ultraviolet transmittance of the cured film layer (II) at a wavelength of 315 nm is high, and in the lightfastness test, a large amount of light reaches the adhesion interface between the cured film layer (II) and the cyclic olefin resin substrate (I), causing deterioration and a decrease in adhesion. If it is too large, the shrinkage stress of the cured film layer during curing is large, which may cause cracks or a decrease in adhesion.

[0044] The cured film layer (II) may be obtained under either an oxygen-barrier atmosphere or an air atmosphere. However, since the composition of the present invention provides a good cured film layer even when polymerized and cured under an air atmosphere, it is preferable to carry out the process under an air atmosphere. For example, the cured film layer (II) can be formed by coating the thermosetting silicone resin composition of the present invention onto a cyclic olefin resin substrate, or by diluting it with various organic solvents and coating it, then curing it by applying heat after a drying process. Examples of coating methods include the drip method, roller coating method, bar coating method, spray coating method, inkjet method, air knife coating method, spin coating method, flow coating method, curtain coating method, and dipping method. The coating film thickness is adjusted by the solid content concentration, taking into account the film thickness formed after drying and curing by heat. If an organic solvent is used to adjust the solid content concentration, it is preferable to remove the organic solvent by drying or other means after coating. The drying temperature should be such that the substrate used does not deform, and the drying time is preferably one hour or less from the viewpoint of productivity. Furthermore, while there are no restrictions on the heat curing temperature, 90 to 125°C is preferred, and 100 to 120°C is more preferred. Similarly, while there are no restrictions on the heat curing time, 1 to 10 hours is preferred, and 2 to 6 hours is more preferred. If the curing temperature is higher than 125°C, the cyclic olefin resin substrate may soften, and if it is lower than 90°C, crosslinking may not proceed sufficiently, potentially leading to a decrease in hardness and adhesion.

[0045] Specific examples of organic solvents include 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. Known organic solvents can be used. It is particularly preferable to include a glycol organic solvent.

[0046] Examples of glycol ether-based 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, as well as propylene glycols such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and butoxypropanol. Among these, propylene glycol monomethyl ether is preferred.

[0047] The laminate of the present invention can be obtained by forming a cured film layer (II) made of a thermosetting silicone resin composition on a cyclic olefin substrate (I) in the manner described above. Furthermore, an inorganic material layer can be formed on the cured film layer (II) to impart mechanical, electrical, optical, or chemical functions. The inorganic material layer is not particularly limited as long as it is formed by a dry film formation method, and can be selected according to the properties to be imparted to the laminate. For example, a layer mainly composed of at least one of various metals or metal oxides, nitrides and sulfides having elements such as Si, Ti, Zn, Al, Ga, In, Ce, Bi, Sb, B, Zr, Sn, and Ta can be cited.

[0048] Among these, the inorganic material layer of the optical component is preferably a layer made of metal oxides, particularly silicon oxide compounds, from the viewpoint of high hardness, low reflectivity, and transparency. Examples of silicon oxide compounds include silicon monoxide, silicon dioxide, and silicon dioxide.

[0049] The method for laminating inorganic material layers is not particularly limited as long as it is a dry deposition method. Examples include physical vapor deposition (PVD) methods such as resistance heating deposition, electron beam deposition, molecular beam epitaxy, ion beam deposition, ion plating, ion-assisted deposition, and sputtering, as well as chemical vapor deposition (CVD) methods such as thermal CVD, plasma CVD, photo-CVD, epitaxial CVD, atomic layer CVD, and catCVD. However, ion-assisted deposition is preferred as it provides high adhesion, high density, and a stable film. A dry deposition method, as used here, involves treating the material surface using a gas phase or molten state, and is sometimes generally referred to as a dry process.

[0050] The thermosetting silicone resin composition of the present invention can also be used as a material for forming a cured film layer on substrates such as polycarbonate and polymethyl methacrylate.

[0051] 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 light stabilizers, antioxidants, rheology control agents, surface modifiers (silicone-based surface modifiers, acrylic-based surface modifiers, fluorine-based surface modifiers, vinyl-based surface modifiers, etc.), surfactants, resin particles, lubricants, defoaming agents, mold release agents, silane coupling agents, antistatic agents, antifogging agents, colorants, and the like.

[0052] The laminate of the present invention can be manufactured 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 of the thermosetting silicone resin composition; and curing the coating layer of the thermosetting silicone resin composition by heat to form a cured coating layer (II). Here, the thermosetting silicone resin composition, as described above, comprises a reactive silicone resin (A), a polyfunctional (meth)acrylate monomer (B), an organic peroxide (C), and an ultraviolet absorber (D), and contains 30 to 75 parts by weight of component (A), 20 to 65 parts by weight of component (B), 0.5 to 10 parts by weight of component (C), and 0.1 to 30 parts by weight of component (D) per 100 parts by weight of the total of components (A), (B), (C), and (D), and the total number of (meth)acrylic moles of 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 or a partial hydrolysate thereof represented by the following general formula (ii), characterized in that, in the blending ratio of component (i) represented by formula (i) and the compound containing component (ii), which is an alkyl silicate or a partial hydrolysate thereof, the ratio of [moles of Si from the compound containing component (ii) / moles of Si from component (i)] satisfies the range of 0.5 to 4.0 per 100 moles of the total Si content contained in both. １ Si ( OR ２ ) ３ ... (i) [However, in equation (i), R １ is an organic functional group having a (meth)acryloyl group, 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 equation (ii), n represents a number from 1 to 20, and R ３ This represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0053] The thermosetting silicone resin composition used in the present invention allows for the formation of laminates that exhibit excellent adhesion to cyclic olefin resin substrates and have excellent pencil hardness. For example, the pencil hardness (according to JIS K 5600) is preferably F or higher, and more preferably H or higher.

[0054] The present invention will be described more specifically below based on examples and comparative examples, but the present invention is not limited to the following.

[0055] [Synthesis of A-1] In a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer, (i) component 3-methacryloxypropyltrimethoxysilane (XIAMETER OFS-6030 Silane, manufactured by Dow Toray Industries, Inc.) 30.0 g and (ii) component methyl silicate 13.6 g of (Corcoat Co., Ltd., trade name: Methyl Silicate 53A) was added and stirred. 11.7 g of 0.05% hydrochloric acid aqueous solution was added to a dropping funnel and stirred at room temperature. After the dropwise addition was complete, the temperature was raised to 60°C and stirred for 1 hour. After cooling, 14.4 g of propylene glycol monomethyl ether was added to obtain reactive silicone resin (A-1) with a ratio of 1.0 [silica moles from the compound containing (ii) / silica moles from component (i)] relative to the total 100 moles of Si contained in component (A), which is the target product with a solid content of 50 wt%.

[0056] [Synthesis of A-2] In a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer, 37.5 g of component (i), the aforementioned 3-methacryloxypropyltrimethoxysilane (XIAMETER OFS-6030 Silane, manufactured by Dow Toray Industries, Inc.), and 51.1 g of component (ii), the aforementioned methyl silicate (manufactured by Colcoat, trade name: Methyl Silica 53A), were added and stirred. 27.3 g of 0.05% aqueous hydrochloric acid solution was added to the dropping funnel and added while stirring at room temperature. After the addition was complete, the temperature was raised to 60°C and stirred for 1 hour, then cooled, and 20.5 g of propylene glycol monomethyl ether was added to obtain reactive silicone resin (A-2) with a ratio of 3.0 [silica moles from the compound containing component (ii) / silica moles from component (i)] relative to the total 100 moles of Si contained in component (A), which has a solid content of 50% by weight (wt%).

[0057] [Example 1] The reactive silicone resin (A) component was (A-1): 126.2 parts by weight (solids: 63.1 parts by weight), the polyfunctional (meth)acrylic monomer (B) component was a mixture of dipentaerythritol hexaacrylate (Mw = 578.57, number of acrylic groups = 6) and dipentaerythritol pentaacrylate (Mw = 524.52, number of acrylic groups = 5) in a 65:35 (weight ratio) (product name DPHA, manufactured by Kyoeisha Chemical Co., Ltd.) (B-1): 26.7 parts by weight, the organic peroxide (C) component was 1,1-di(t-butylperoxy)cyclohexane (C-1) having the chemical structure shown below (product name Perhexa C, manufactured by NOF Corporation): 2.9 parts by weight, and the ultraviolet absorber (D) component was unmodified zinc oxide with a particle size of 15 to 30 nm (product name, manufactured by CIK Nanotech Corporation) A thermosetting silicone resin composition 1 was obtained by mixing ZnDNA 15WT%-G0) (D-1): 49 parts by weight (solid content: 7.3 parts by weight). For the obtained thermosetting silicone resin composition 1, the number of (meth)acrylic moles of component (B) per 100 g was {[100 × (6 / 578.57) × 0.65] + [100 × (5 / 524.52) × 0.35]} × (26.7 / 100.0) = 0.27.

[0058] Next, the obtained thermosetting silicone resin composition 1 was diluted with propylene glycol monomethyl ether to a solid content of 40 parts by weight, and 0.5 parts by weight of an acrylic surface modifier (product name WS-314, manufactured by Kyoeisha Co., Ltd.) was mixed in. This mixture was then coated onto one side of a cyclic olefin copolymer resin substrate (thickness 3 mm, length 65 mm, width 35 mm, product name APL5014, manufactured by Mitsui Chemicals Co., Ltd.) in air using a spin coater to achieve a film thickness of 4 μm after drying, and dried at 80°C for 5 minutes to form a film layer. Subsequently, the film layer was cured by heating at 120°C for 2 hours to obtain a laminate test piece in which a cured film layer (II) of the thermosetting silicone resin composition was formed on the surface of the cyclic olefin copolymer resin substrate.

[0059] [Examples 2-5, 14-15, Comparative Examples 1-6] Thermosetting silicone resin compositions and laminate test pieces were obtained using the same procedure as in Example 1, except that the raw materials and composition ratios listed in Tables 1-2 were used. Other abbreviations in the tables are as follows.

[0060] Polyfunctional (meth)acrylic monomers (B) 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: (4,4'-bisacryloyloxymethyl)biphenyl (Mw = 322.36, number of acrylic groups = 2)

[0061] (Meth)acrylic monomers other than polyfunctional (meth)acrylic monomer (B) B'-4: Isovonyl acrylate (Mw = 208.3, number of acrylic groups = 1, product name Light Acrylate IB-XA manufactured by Kyoeisha Chemical Co., Ltd.) For the convenience of comparison, B'-4 is listed as (B) in Tables 1 and 2.

[0062] Organic peroxide (C) C-2: t-butylperoxy-2-ethylhexanoate (product name Perbutyl O, manufactured by NOF Corporation)

[0063] UV absorbers (D) D-2: Surface-modified zinc oxide with a particle size of 15-30 nm (CIK Nanotech product name UC-Z53) D-3: Hydroxyphenyltriazine-based UV absorber (BASF product name Tinuvin 479) D-4: Hydroxyphenyltriazine-based UV absorber (BASF product name Tinuvin 477)

[0064] [Examples 6-11, Comparative Example 7] Using the raw materials and composition ratios listed in Tables 1-2, thermosetting silicone resin compositions and laminate test pieces were obtained in the same procedure as in Example 1, except that the curing conditions for the thermosetting silicone resin composition were set to 110°C for 4 hours.

[0065] [Examples 12-13] Using the raw materials and composition ratios listed in Table 1, thermosetting silicone resin compositions and laminate test pieces were obtained in the same procedure as in Example 1, except that the thickness of the cured film (II) made of the thermosetting silicone resin composition was set to 7 μm and the curing conditions for the thermosetting silicone resin composition were set to 110°C for 4 hours.

[0066] The following evaluations were performed using the thermosetting silicone resin composition and laminate test specimens obtained above. The evaluation results are shown in Tables 1 and 2. In the tables, the ratio of [moles of Si from the compound containing component (ii) / moles of Si from component (i)] to 100 moles of total Si in component (A) is abbreviated as "moles of Si from component (ii) / moles of Si from component (i)". Also, the number of (meth)acrylic moles of component (B) per 100 g of the composition is abbreviated as "number of (meth)acrylic moles of component (B)".

[0067] [UV transmittance at a wavelength of 315 nm] A thermosetting silicone resin composition was applied to one side of a glass substrate (0.7 mm thick, 125 mm long, 125 mm wide; AGC product name AN100) using a spin coater so that the film thickness after drying and curing was 4 μm or 7 μm. The coating layer was dried at 80°C for 5 minutes. Subsequently, the coating was cured under the curing conditions described in Tables 1 and 2 to obtain a laminate test specimen in which a cured coating layer of the thermosetting silicone resin composition was formed on the surface of the glass substrate. The UV transmittance of the laminate test specimen at a wavelength of 315 nm was measured using a spectrophotometer (Shimadzu UV3600).

[0068] [Appearance] The laminate was visually inspected for cracks and delamination, and judged according to the following criteria: ○: No cracks or delamination present ×: Cracks or delamination present

[0069] [Adhesion] 100 1mm x 1mm grids were created on the hardened film surface of each laminate test specimen in accordance with JIS K 5600-5-6 (1990). Adhesive tape was applied to the surface, and after being rapidly peeled off, this process was repeated a total of three times. The degree of peeling was evaluated according to the remaining grid state based on the following criteria: ◎: 100 grids remain, with no chipping. 〇: 100 grids remain, but some chipping has occurred. △: 90-99 grids remain. ×: 0-89 grids remain.

[0070] [Pencil Hardness] In accordance with JIS K 5600, the surface of the cured film layer (II) of the thermosetting silicone resin composition of each laminate test piece was scratched with a Mitsubishi Uni pencil under a 500g load at a 45-degree angle, and the hardness at which the surface could not be scratched was visually determined.

[0071] [Lightfastness Test] Using a xenon weather meter (X75, manufactured by Suga Test Instruments Co., Ltd.), the surface of the cured film layer (II) made of thermosetting silicone resin composition was subjected to a xenon lamp irradiance of 2.4 W / m² under conditions of a temperature of 55°C and a relative humidity of 30% Rh. ２ The samples were irradiated with light at 420 nm for 150 hours, and their appearance, adhesion, and pencil hardness were evaluated after the test.

[0072]

[0073]

Claims

1. A laminate comprising a cured film layer (II) formed of a thermosetting silicone resin composition laminated on a cyclic olefin resin substrate (I), wherein the cured film layer (II) contains a reactive silicone resin (A), a polyfunctional (meth)acrylate monomer (B), an organic peroxide (C), and an ultraviolet absorber (D), and contains 30 to 75 parts by weight of the component (A), 20 to 65 parts by weight of the component (B), 0.5 to 10 parts by weight of the component (C), and 0.1 to 30 parts by weight of the component (D) with respect to a total of 100 parts by weight of the components (A), (B), (C), and (D), 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 0.5 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.] 2. The laminate according to claim 1, characterized in that the cured film layer (II) has an ultraviolet transmittance of 42% or less at a wavelength of 315 nm.

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

4. A thermosetting silicone resin composition for forming a cured film layer (II) of a laminate according to any one of claims 1 to 3, comprising a reactive silicone resin (A), a polyfunctional (meth)acrylate monomer (B), an organic peroxide (C), and an ultraviolet absorber (D), wherein the composition contains 30 to 75 parts by weight of component (A), 20 to 65 parts by weight of component (B), 0.5 to 10 parts by weight of component (C), and 0.1 to 30 parts by weight of component (D) per 100 parts by weight of the total of components (A), (B), (C), and (D), and the total number of (meth)acrylic moles of 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 or a partial hydrolysate thereof represented by the following general formula (ii), and in the blending ratio of component (i) represented by formula (i) and the compound containing component (ii), which is an alkyl silicate or a partial hydrolysate thereof, the ratio of [moles of Si from the compound containing component (ii) / moles of Si from component (i)] to 100 moles of Si content in both satisfies the range of 0.5 to 4.

0. １ Si ( OR ２ ) ３ ... (i) [However, in equation (i), R １ is an organic functional group having a (meth)acryloyl group, 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 equation (ii), n represents a number from 1 to 20, and R ３ This represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

5. The thermosetting silicone resin composition according to claim 4, wherein the ultraviolet absorber (D) is zinc oxide, which may have a modified surface.

6. The thermosetting silicone resin composition according to claim 4, wherein the ultraviolet absorber (D) is a compound having a hydroxyphenyltriazine structure.

7. A method for producing a laminate according to any one of claims 1 to 3, comprising the steps of: coating a thermosetting silicone resin composition onto a cyclic olefin resin substrate (I) to form a film layer of the thermosetting silicone resin composition; and curing the film layer of the thermosetting silicone resin composition by heat to form a cured film layer (II).

Images