JP2005161600A - Polycarbonate resin laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarbonate resin laminate excellent in weatherability, durability, abrasion resistance and hot water resistance. <P>SOLUTION: This polycarbonate resin laminate is composed of a polycarbonate base material, a first layer and a second layer, and the first layer is formed on the surface of the polycarbonate base material while the second layer is formed on the surface of the first layer. The polycarbonate resin laminate shows an endothermic peak of 0.1 mJ/mg or above in a temperature range of 120-150°C. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a laminate comprising a polycarbonate substrate, a first layer and a second layer. More specifically, the present invention is a laminate comprising a polycarbonate substrate, a first layer and a second layer, and the polycarbonate substrate exhibits an endothermic peak within a temperature range of 120 to 150 ° C., and the endothermic peak is 0. More than 0.1 mJ / mg, the first layer is a crosslinked acrylic copolymer, and the second layer is an organosiloxane polymer, which relates to a laminate excellent in weather resistance, wear resistance, durability and hot water resistance.

  Polycarbonate resins are used in a variety of applications, taking advantage of their impact resistance, transparency, lightness, and processability. In particular, it is used as a substitute for glass taking advantage of its transparency. However, it is known that polycarbonate resin does not have sufficient weather resistance and is degraded and deteriorated in long-term outdoor use, so that physical properties and appearance are impaired. Polycarbonate resins also have drawbacks such as poor wear resistance, easily scratched surfaces, and easy attack by solvents.

  For the purpose of improving these defects, a thermosetting acrylic resin layer has been conventionally provided on the surface of a polycarbonate substrate, and a siloxane-based cured film is further coated thereon to improve weather resistance, durability, and wear resistance. Numerous proposals have been made regarding laminates.

  For example, the present inventors have proposed improving the weather resistance by adding an ultraviolet absorber having a specific structure to the thermosetting acrylic resin layer (see Patent Document 1). However, sufficient weather resistance that can withstand long-term outdoor use is not obtained.

  Moreover, the proposal which improves the durability with respect to the change of an environment is made | formed (refer patent document 2). However, since the storage stability of the paint is low, there is a disadvantage that the paint is thickened during storage or use and cannot be used stably. Further, since the isocyanate group has a high reactivity, there is a drawback that a side reaction is likely to occur at the time of heat curing, and a molded product having stable coating film properties cannot be obtained.

  On the other hand, for the purpose of improving wear resistance, a coating composition comprising a trihydroxysilane partial condensate and colloidal silica has been proposed (see Patent Documents 3 and 4). In addition, a coating composition mainly composed of a partial condensate of alkyltrialkoxysilane and tetraalkoxysilane has been proposed (see Patent Documents 5 and 6).

  Furthermore, a coating composition in which colloidal silica is added to a condensate of alkyltrialkoxysilane and tetraalkoxysilane has been proposed (see Patent Documents 7 and 8).

  However, a laminate obtained by laminating a cured film obtained from these coating compositions on a polycarbonate substrate has a certain level of excellent wear resistance, but is not sufficiently durable in environmental changes and high temperature environments.

  In addition, the laminate has a crack in the coating layer due to the difference between the thermal expansion coefficients of the polycarbonate base material and the organosiloxane resin layer. Or may occur at the polycarbonate substrate / acrylic resin layer interface or the acrylic resin / organosiloxane resin interface.

JP 2000-318106 A JP-A-62-169832 JP-A 51-2736 JP 55-94971 A JP 48-26822 A JP 51-33128 A Japanese Unexamined Patent Publication No. Sho 63-27879 JP-A-1-306476

  An object of this invention is to provide the laminated body which makes the base material the polycarbonate excellent in a weather resistance, durability, abrasion resistance, and hot water resistance.

  As a result of intensive studies to achieve this object, the present inventors conducted thermal relaxation by annealing the polycarbonate substrate under the condition of a glass transition temperature or lower, and a thermosetting type having a specific composition on its surface. By sequentially laminating a first layer mainly composed of an acrylic resin and a second layer obtained by thermally curing an organosiloxane resin containing colloidal silica and trialkoxysilane hydrolysis condensate from the first layer, a high level is obtained. Laminate molding that protects the surface with a cured coating that provides the weather resistance and wear resistance of the coating, has less cracking during coating, and poor adhesion, and has sufficient durability in environmental changes and high-temperature environments. It was found that a body was obtained and reached the present invention.

That is, according to the present invention: A laminate comprising a polycarbonate substrate, a first layer and a second layer, wherein the first layer is formed on the surface of the polycarbonate substrate, and the second layer is formed on the surface of the first layer, the polycarbonate substrate The material exhibits an endothermic peak within a temperature range of 120 to 150 ° C., the endothermic peak is 0.1 mJ / mg or more, the first layer is a thermosetting acrylic resin composition cured layer, and the second layer is , Comprising a crosslinked organosiloxane polymer, and the cured layer of the thermosetting acrylic resin composition is 50 mol% or more of the following formula (A-1)

（式中Ｒ^１はメチル基またはエチル基である。）で表される繰り返し単位、
５〜３０モル％の下記式（Ａ−２）

(Wherein R ¹ is a methyl group or an ethyl group),
5-30 mol% of following formula (A-2)

（式中Ｒ^２は炭素数２〜５のアルキレン基である。）で表される繰り返し単位、および
０〜３０モル％の下記式（Ａ−３）

(Wherein R ² is an alkylene group having 2 to 5 carbon atoms) and 0 to 30 mol% of the following formula (A-3)

（但し、式中Ｙは水素原子またはメチル基であり、Ｒ^３は水素原子、炭素数２〜５のアルキル基、紫外線吸収残基からなる群より選ばれる少なくとも一種の基である。但し、Ｙがメチル基であり、かつＲ^３がメチル基またはエチル基である場合を除く。）
で表される繰り返し単位からなるアクリル共重合体を、ポリイソシアネート化合物またはシロキサン樹脂を架橋剤として硬化させた硬化層であり、また、該架橋したオルガノシロキサン重合体は、下記式（ｂ−４）〜（ｂ−６）

(Wherein, Y is a hydrogen atom or a methyl group, and R ³ is at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 2 to 5 carbon atoms, and an ultraviolet absorbing residue. Except that is a methyl group and R ³ is a methyl group or an ethyl group.)
Is a cured layer obtained by curing a polyisocyanate compound or a siloxane resin as a crosslinking agent, and the crosslinked organosiloxane polymer has the following formula (b-4): ~ (B-6)

（式中、Ｑ^１、Ｑ^２は、それぞれ炭素数１〜４のアルキル基、ビニル基、またはメタクリロキシ基、アミノ基、グリシドキシ基および３，４−エポキシシクロヘキシル基からなる群より選ばれる少なくとも一種の基で置換された炭素数１〜３のアルキル基である。）
で表される繰り返し単位からなり、各繰り返し単位のモル比｛（ｂ−４）／（ｂ−５）／（ｂ−６）｝が、８０〜１００／０〜２０／０〜２０である架橋したオルガノシロキサン重合体であることを特徴とするポリカーボネート樹脂積層体。

(In the formula, Q ¹ and Q ² are each at least one selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a vinyl group, or a methacryloxy group, an amino group, a glycidoxy group, and a 3,4-epoxycyclohexyl group. A C 1-3 alkyl group substituted with a group.)
A cross-linking unit having a molar ratio {(b-4) / (b-5) / (b-6)} of each repeating unit of 80 to 100/0 to 20/0 to 20 A polycarbonate resin laminate characterized by being an organosiloxane polymer.

2. A polyisocyanate compound is used as the crosslinking agent, and the amount used thereof is 0.7 to 5 equivalents of the total amount of isocyanate groups generated and / or present with respect to 1 equivalent of hydroxyl groups of the repeating unit represented by the formula (A-2). 2. The polycarbonate resin laminate according to item 1 above.
3. 2. The polycarbonate resin laminate according to item 1, wherein the cured layer of the thermosetting acrylic resin composition contains 5 to 50 parts by weight of an ultraviolet absorber with respect to 100 parts by weight of the acrylic copolymer.
4). 2. The polycarbonate resin laminate according to item 1, wherein the polycarbonate substrate has a thickness of 1 to 10 mm, the first layer has a thickness of 2 to 15 μm, and the second layer has a thickness of 2 to 10 μm.
Is provided.

Hereinafter, the present invention will be described in detail.
The polycarbonate resin used as the substrate in the present invention is a polycarbonate resin obtained by reacting a dihydric phenol and a carbonate precursor by an interfacial polycondensation method or a melting method. Representative examples of the dihydric phenol include 2,2-bis (4-hydroxyphenyl) propane [commonly known as bisphenol A], 1,1-bis (4-hydroxyphenyl) ethane, and 1,1-bis (4-hydroxy). Phenyl) cyclohexane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone and the like can be mentioned, and among them, bisphenol A is preferable. These dihydric phenols can be used alone or in admixture of two or more.

  As the polycarbonate precursor, carbonyl halide, carbonate ester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.

  When producing polycarbonate resin by reacting the above dihydric phenol and carbonate precursor by interfacial polycondensation method or melting method, use catalyst, terminal terminator, dihydric phenol antioxidant, etc. as necessary May be. The polycarbonate resin may be a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, or may be a polyester carbonate resin copolymerized with an aromatic or aliphatic difunctional carboxylic acid, Moreover, the mixture which mixed 2 or more types of the obtained polycarbonate resin may be sufficient.

  In the interfacial polycondensation method using phosgene, the reaction is carried out in the presence of an acid binder and an organic solvent. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amine compounds such as pyridine, and examples of the solvent include halogenated hydrocarbons such as methylene chloride and chlorobenzene. In order to accelerate the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can also be used. The reaction temperature is usually 0 to 40 ° C., and the reaction time is several minutes to 5 hours.

  The melting method using diphenyl carbonate is carried out by a method in which a predetermined proportion of a dihydric phenol component and diphenyl carbonate are stirred with heating in an inert gas atmosphere to distill the alcohol or phenols produced. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed while distilling off the alcohol or phenol produced by reducing the pressure from the beginning. Moreover, in order to accelerate | stimulate reaction, the catalyst for normal transesterification can also be used.

The molecular weight of the polycarbonate resin is preferably 10,000 to 50,000, more preferably 15,000 to 35,000 in terms of viscosity average molecular weight (M). A polycarbonate resin having such a viscosity average molecular weight is preferable because sufficient strength is obtained and the melt fluidity during molding is good. The viscosity average molecular weight referred to in the present invention is obtained by inserting the specific viscosity (η _sp ) obtained from a solution obtained by dissolving 0.7 g of polycarbonate resin in 100 ml of methylene chloride at 20 ° C. into the following equation.
η _sp /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

  When producing such a polycarbonate resin, if necessary, stabilizers such as phosphites, phosphates, and phosphonates, low molecular weight polycarbonates of tetrabromobisphenol A, tetrabromobisphenol A, and flame retardants such as decabromodiphenol Coloring agents, lubricants and the like can be added.

  When the polycarbonate substrate used in the present invention is thermally analyzed by a differential operating calorimeter (DSC), an endothermic peak (abnormal specific heat) having a peak at 120 to 150 ° C. is observed. This endothermic peak is different from the peak indicating glass transition heat and the peak indicating crystal melting heat. The endothermic energy represented by the size of this endothermic peak is 0.1 mJ / mg or more, preferably 0.2 mJ / mg or more, and there is a limit to the densification that can be achieved by annealing treatment. Is less than 3 mJ / mg. A polycarbonate resin base material having an endothermic energy in the above range has a dense structure and little residual stress, so that the weather resistance, durability and hot water resistance of the laminate are improved.

  As a method for imparting an endothermic peak having a peak at 120 to 150 ° C. to the polycarbonate substrate, a method of annealing the polycarbonate substrate is preferably employed. The annealing treatment is preferably a method in which heat treatment is performed for 0.5 hour to 100 hours in the temperature range of the secondary transition temperature Tg to Tg-40 ° C. of the polycarbonate.

  The polycarbonate substrate preferably has a haze value of 10% or less. The thickness of the substrate is preferably 1 to 10 mm, more preferably 2 to 8 mm.

  In the present invention, the coating resin laminated on the polycarbonate substrate surface as the first layer is (A) 50 mol% or more of the repeating unit represented by the formula (A-1), and the formula (A-2). It is an acrylic copolymer containing 5 to 30 mol% of the repeating unit shown and 0 to 30 mol% of the repeating unit represented by the formula (A-3), and this coating resin is made of a polyisocyanate compound derivative or a siloxane resin. The cured layer cured as a cross-linking agent is the first layer.

  The methacrylate monomer corresponding to the repeating unit represented by the formula (A-1) is methyl methacrylate or ethyl methacrylate.

  Specific examples of the methacrylate monomer corresponding to the repeating unit represented by the formula (A-2) include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate. These can be used alone or in admixture of two or more. Of these, 2-hydroxyethyl methacrylate is preferably employed.

  A part of the repeating unit represented by the formula (A-2) is bonded to the repeating unit represented by the other formula (A-2) by using a polyisocyanate compound or a siloxane resin as a crosslinking agent at the position of —OH. , Forming a cross-linked structure. The degree of crosslinking is such that the molar ratio between the urethane bond or siloxane bond and the total amount of the repeating units represented by formulas (A-1) to (A-3) is in the range of 4/100 to 30/100. The molar ratio is particularly preferably in the range of 10/100 to 20/100.

Specific examples of the alkyl group having 2 to 5 carbon atoms of R ^{3 in} the repeating unit represented by the formula (A-3) include an ethyl group, a propyl group, a butyl group, and a pentyl group.

Specifically, methyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate as the (meth) acrylate monomer in the case where R ³ in the repeating unit represented by (A-3) is an alkyl group having 2 to 5 primes Propyl methacrylate, butyl methacrylate, and pentyl methacrylate, which can be used alone or in combination of two or more.

Further, as a (meth) acrylate monomer in the case where R ³ in the repeating unit represented by (A-3) is an ultraviolet absorption residue, the wavelength was measured with a chloroform solution having a concentration of 10 mg / L and an optical path length of 1.0 cm. The thing whose absorbance in 300nm is 0.25 or more is mentioned.

  Specific examples of such monomers include 2- (2'-hydroxy-5'-acryloxyethylphenyl) benzotriazole, 2- (2'-hydroxy-5'-acryloxyethoxyphenyl) benzotriazole, 2- (2 ' -Hydroxy-5'-acryloxypropylphenyl) benzotriazole, 2- (2'-hydroxy-5'-acryloxypropoxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-acryloxyethylphenyl)- 5-chlorobenzotriazole, 2- (2'-hydroxy-3'-acryloxyethyl-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-acryloxyethyl-5'- t-butylphenyl) -5-chlorobenzotriazole, 2-hydroxy-4- ( Acryloxyethoxy) benzophenone, 2-hydroxy-4- (acryloxypropoxy) benzophenone, 2,2′-dihydroxy-4- (acryloxyethoxy) benzophenone, 2-hydroxy-4- (acryloyloxyethyl) benzophenone, 2- (2'-hydroxy-5'-methacryloxyethylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methacryloxyethoxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-methacryloxypropyl) Phenyl) benzotriazole, 2- (2′-hydroxy-5′-methacryloxypropoxyphenyl) benzotriazole, 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -5-chlorobenzotriazole, 2- ( 2'-hi Loxy-3'-methacryloxyethyl-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-methacryloxyethyl-5'-t-butylphenyl) -5-chlorobenzotriazole, 2-hydroxy-4- (methacryloxyethoxy) benzophenone, 2-hydroxy-4- (methacryloxypropoxy) benzophenone, 2,2'-dihydroxy-4- (methacryloxyethoxy) benzophenone, 2-hydroxy-4- (methacryloyl) And oxyethyl) benzophenone.

  The ratio of the repeating unit represented by the formula (A-1) in the acrylic copolymer is 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more.

  The ratio of the repeating unit represented by (A-2) in the acrylic copolymer is 5 to 30 mol%, preferably 8 to 20 mol%, more preferably 10 to 20 mol%.

  The ratio of the repeating unit represented by (A-3) in the acrylic copolymer is 0 to 30 mol%.

  Component (A) is an acrylic copolymer comprising 70 to 95 mol% of the repeating unit represented by the formula (A-1) and 5 to 30 mol% of the repeating unit represented by the formula (A-2). Preferably there is.

In the component (A), R ¹ in the formula (A-1) is preferably an ethyl group, and R ^{2 in the} formula (A-2) is preferably an ethylene group.

  The molecular weight of the crosslinked acrylic copolymer is preferably 20,000 or more in terms of weight average molecular weight, more preferably 50,000 or more, and preferably 10 million or less in terms of weight average molecular weight. The acrylic resin having such a molecular weight range is preferable because the performance such as adhesion and strength as the first layer is sufficiently exhibited.

The thickness of the first layer is preferably 1 to 12 μm, more preferably 2 to 10 μm.
In the first layer, the coating film resin is cured using a polyisocyanate compound or a siloxane resin as a crosslinking agent.
As the siloxane resin, the following formula (1)

（但し、式中Ｒ¹²、Ｒ¹³はそれぞれ炭素数１〜４のアルキル基、ビニル基またはメタクリロキシ基、アミノ基、グリシドキシ基および３，４−エポキシシクロヘキシル基からなる群から選ばれる１以上の基で置換された炭素数１〜３のアルキル基であり、Ｒ¹⁴は炭素数１〜４のアルキル基であり、ｍ，ｎは夫々０，１，２のいずれかの整数であり、ｍ＋ｎは０，１，２のいずれかの整数である。）で表されるアルコキシシランの加水分解縮合物や市販のシロキサン樹脂を用いることもできる。市販のシロキサン樹脂としては、信越化学工業製ＫＰ８５０，ＫＰ８５１等が挙げられる。

Wherein R ¹² and R ¹³ are each one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a vinyl group or a methacryloxy group, an amino group, a glycidoxy group and a 3,4-epoxycyclohexyl group. And R ¹⁴ is an alkyl group having 1 to 4 carbon atoms, m and n are each an integer of 0, 1, or 2, and m + n is 0. , 1, 2 or an integer.) Hydroxy condensate of alkoxysilane represented by the following formula or a commercially available siloxane resin can also be used. Examples of commercially available siloxane resins include KP850 and KP851 manufactured by Shin-Etsu Chemical Co., Ltd.

  Examples of the alkoxysilane represented by the formula (1) include tetramethoxysilane, tetraethoxysilane, tetra n-propoxy silane, tetraisopropoxy silane, tetra n-butoxy silane, tetraisobutoxy silane, methyltrimethoxy silane, Methyltriethoxysilane, ethyltrimethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ -Glycidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β Minoethyl) -γ-aminopropyltriethoxysilane, dimethyldimethoxysilane, vinylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, etc. Of these, alkyltrialkoxysilane is preferable, and methyltrimethoxysilane and methyltriethoxysilane are particularly preferable. These can be used alone or in combination.

  The hydrolysis-condensation product of alkoxysilane is usually 0.2 to 4 equivalents, preferably 0.5 to 2 equivalents, more preferably 1 to 1.5 equivalents per 1 equivalent of alkoxy group of alkoxysilane under acidic conditions. It is obtained by carrying out a hydrolysis condensation reaction at 20 to 40 ° C. for 1 hour to several days with water. An acid is used for the hydrolysis condensation reaction, and examples of the acid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, sulfamic acid, and other inorganic acids, formic acid, acetic acid, propionic acid, butyric acid, and oxalic acid. Organic acids such as succinic acid, maleic acid, lactic acid, and paratoluenesulfonic acid, and volatile acids such as acetic acid and hydrochloric acid are preferred. In the case of using an inorganic acid, the acid is usually used in a concentration of 0.0001 to 2 N, preferably 0.001 to 0.1 N. It is used in the range of 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight. The blending amount of the siloxane resin is 1 to 40% by weight, preferably 5 to 30% by weight of the coating resin.

  The polyisocyanate compound is a polyisocyanate compound and / or a blocked polyisocyanate compound.

  Examples of the polyisocyanate compound include polyisocyanate, an adduct of polyisocyanate and a polyhydric alcohol, an adduct of polyisocyanate and a low molecular weight polyester resin, a cyclized polymer of polyisocyanates, and an isocyanate burette.

  Polyisocyanates include tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, tolidine diisocyanate, xylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, hexamethylene diisocyanate, Examples include dicyclohexylmethane diisocyanate and isophorone diisocyanate.

  As the blocked polyisocyanate compound, an oxime such as acetooxime and methyl ethyl ketoxime on the isocyanate group of the polyisocyanate compound; active methylene compound such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone Alcohols such as methanol, ethanol, 2-propanol, n-butanol, sec-butanol and 2-ethyl-1-hexanol; a blocking agent represented by phenols such as phenol, cresol and ethylphenol is added; Examples include blocked isocyanate compounds that generate polyisocyanate compounds by thermal decomposition.

  This blocked isocyanate is the first to form an isocyanate group during the thermosetting reaction, so it has excellent storage stability of the coating composition, and the isocyanate group is hardly consumed in side reactions and is not easily affected by the coating environment. A cured film having the coated film properties can be obtained.

  The said polyisocyanate compound and the blocked polyisocyanate compound can be used individually or in mixture of 2 or more types. Among these, aliphatic and / or alicyclic polyisocyanate compounds are particularly preferable because of excellent weather resistance.

  Examples of such polyisocyanate compounds include adduct polyisocyanate compounds obtained by blocking adduct polyisocyanate compounds represented by the following formula (2) with a blocking agent.

（但し、式中Ｒ⁵、Ｒ⁶、Ｒ⁷は、同一または異なり、脂肪族および／または脂環族ジイソシアネート化合物よりイソシアネート基を除いた基を表す。またＲ⁸はヒドロキシ化合物からヒドロキシ基を除いた基を表し、ｎ¹は０または２以下の整数を表す。）

(However, in the formula, R ⁵ , R ⁶ and R ⁷ are the same or different and represent a group in which an isocyanate group is removed from an aliphatic and / or alicyclic diisocyanate compound. R ⁸ excludes a hydroxy group from a hydroxy compound. And n ¹ represents 0 or an integer of 2 or less.)

  Examples of the aliphatic diisocyanate compound include hexamethylene diisocyanate, and examples of the alicyclic diisocyanate compound include cyclohexyl diisocyanate.

  Moreover, the isocyanurate type | mold polyisocyanate compound which blocked the isocyanurate type | mold polyisocyanate compound represented by following formula (3) with the blocking agent is mentioned.

（但し、式中ｎ²はイソシアヌレートプレポリマーの核体数を表し、その統計的平均値は１．０〜４．０であり、Ｒ⁹〜Ｒ¹¹は同一または異なり、脂肪族および／または脂環族ジイソシアネート化合物よりイソシアネート基を除いた基を表す。）

(Wherein n ² represents the number of nuclei of the isocyanurate prepolymer, the statistical average value thereof is 1.0 to 4.0, R ^{9 to} R ¹¹ are the same or different, aliphatic and / or (Represents a group obtained by removing an isocyanate group from an alicyclic diisocyanate compound.)

  Examples of the aliphatic diisocyanate compound include hexamethylene diisocyanate, and examples of the alicyclic diisocyanate compound include cyclohexyl diisocyanate.

Since R ⁵ , R ⁶ , R ^{7 in} formula (2) and R ⁹ , R ¹⁰ , R ¹¹ in formula (3) are in the range of 2 to 10 in terms of durability, it is particularly excellent. preferable.

  The blocking agent is preferably used because it depends on the heat resistance of the polycarbonate substrate, but oximes and active methylene compounds can be thermally cured at a lower temperature.

  The isocyanate group content in the polyisocyanate compound and the blocked polyisocyanate compound is 5 to 60% by weight, preferably 6 to 55% by weight, and most preferably 6 to 50% by weight. When the isocyanate group content is less than 5% by weight, the blending amount of the polyisocyanate compound and the blocked polyisocyanate compound with respect to the acrylic resin increases, and the repetition represented by the formula (A-1) in the coating film resin Since the unit ratio decreases, the adhesion with the plastic substrate becomes poor. On the other hand, if it exceeds 60% by weight, the flexibility of the coating layer decreases, and the coating layer is cracked when the second layer is thermoset, and the durability against changes in the environment is impaired.

  The mixing amount ratio of the polyisocyanate compound is 0.7 to 5 equivalents, preferably 0.75 to 3 equivalents, and most preferably 0.7 to 5 equivalents of isocyanate groups generated and / or present with respect to 1 equivalent of the hydroxy group of the acrylic resin. 8 to 2 equivalents. By preparing to such a composition, the first layer can maintain good adhesion with the polycarbonate base material and the second-layer organosiloxane resin thermosetting layer, and has a high level of crosslinking density. Therefore, it is difficult to cause a decrease in crosslink density due to ultraviolet rays, water, and oxygen, and it can maintain long-term adhesion, environmental change, and durability under a high temperature environment and has excellent weather resistance.

  When the isocyanate group is less than 0.7 equivalent, the crosslinking is insufficient, resulting in insufficient durability in a high temperature environment, and the unreacted hydroxy group exhibits a high affinity with water molecules. Absorbs moisture, so that weather resistance and hot water resistance are also lowered. When there are more than 5 equivalents of isocyanate groups, the coating layer has a very high cross-linking density with allophanate bonds and becomes a hard and brittle layer, resulting in poor followability to environmental changes and poor adhesion to environmental changes.

  In the present invention, it is preferable that the thermosetting acrylic resin composition cured layer of the first layer contains an ultraviolet absorber.

  Examples of the ultraviolet absorber include benzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone. 2- (5'-methyl-2'-hydroxyphenyl) benzotriazole, 2- (3'-t-butyl-5'-methyl-2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5 Benzotriazoles such as' -di-t-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3 -Cyanoacrylates such as diphenyl acrylate, phenyl salicylate, p- Salicylates such as octylphenyl salicylate, benzylidene malonates such as diethyl-p-methoxybenzylidene malonate, bis (2-ethylhexyl) benzylidene malonate, 2- (4,6-diphenyl-1,3,5-triazine- 2-yl) -5-[(methyl) oxy] -phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(ethyl) oxy] -phenol, 2 -(4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(propyl) oxy] -phenol, 2- (4,6-diphenyl-1,3,5-triazine-2 -Yl) -5-[(butyl) oxy] -phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -fur Triazines such as diol, 2- (2′-hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and a copolymer of vinyl monomer copolymerizable with the monomer, 2- (2′-hydroxy -5-acryloxyethylphenyl) -2H-benzotriazole and a copolymer of vinyl monomer copolymerizable with the monomer, titanium cerium oxide, zinc oxide, tin oxide, tungsten oxide, zinc sulfide, cadmium sulfide. Examples include metal oxide fine particles. These agents may be used alone or in combination of two or more.

  The ultraviolet absorber is preferably used in an amount of 5 to 50 parts by weight, more preferably 10 to 50 parts by weight, and particularly preferably 15 to 45 parts by weight with respect to 100 parts by weight of the acrylic copolymer. By using the ultraviolet absorber, the ultraviolet ray transmittance is lowered, the yellowing of the base material does not occur, and the adhesion is improved, thereby improving the weather resistance. Moreover, there is almost no decrease in adhesion, which is preferable.

  As a method of forming the acrylic resin layer (first layer), the acrylic copolymer, the crosslinking agent, etc. are dissolved in a volatile solvent that does not react with or dissolve the polycarbonate as a base material. The coating composition is applied to the surface of a polycarbonate substrate, and then the solvent is removed by heating or the like, followed by further crosslinking by heating.

  Examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ethers such as tetrahydrofuran, 1,4-dioxane, and 1,2-dimethoxyethane, esters such as ethyl acetate and ethoxyethyl acetate, methanol, Ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 2-butoxy Examples include alcohols such as ethanol, hydrocarbons such as n-hexane, n-heptane, isooctane, benzene, toluene, xylene, gasoline, light oil, kerosene, acetonitrile, nitromethane, water, etc. 2 or more It may be used as a mixture.

  When an alcohol is used as a solvent for a composition comprising an acrylic resin having a hydroxy group and a polyisocyanate compound, it is expected that the polyisocyanate compound and the alcohol in the solvent react to cause the thermosetting acrylic resin to exhibit the expected performance. However, if the alcohol used in the solvent system is mainly a secondary or tertiary alcohol having a boiling point of 130 ° C. or less as described above, the alcohol in the solvent is removed by volatilization before reacting with the polyisocyanate compound in the system. There is no problem in the performance of the first layer made of the thermosetting acrylic resin of the invention.

  The concentration of the solid content composed of the coating film resin in the coating composition is preferably 1 to 50% by weight, and more preferably 3 to 30% by weight.

  Application of the coating composition to the plastic substrate is performed by a bar coating method, a dip coating method, a flow coating method, a spray coating method, a spin coating method, a roller coating method, or the like depending on the shape of the substrate to be coated. It can be selected appropriately. The base material coated with such a coating composition is usually cured by heating after the solvent is dried and removed at a temperature from room temperature to a temperature lower than the heat distortion temperature of the base material. Such thermosetting is preferably performed at a high temperature within a range where there is no problem in the heat resistance of the base material because the curing can be completed earlier. In addition, at normal temperature, thermosetting does not advance completely, and it does not become a coat layer having sufficient crosslink density required for the first layer. In the process of thermosetting, the crosslinkable group in the thermosetting acrylic resin composition reacts to increase the crosslink density of the coat layer, and the coat layer has excellent adhesion, hot water resistance, and durability in a high temperature environment. Become. The thermosetting is preferably in the range of 80 to 160 ° C, more preferably in the range of 100 to 140 ° C, most preferably in the range of 110 to 130 ° C, preferably 10 minutes to 3 hours, more preferably 20 minutes to 2 hours, Most preferably, a polycarbonate base material is obtained in which the crosslinkable group is crosslinked by heating for 30 minutes to 1 hour 30 minutes, and the coating film resin is laminated as the first layer. When the thermosetting time is 10 minutes or less, the crosslinking reaction does not proceed sufficiently, and a coating layer having poor durability and weather resistance in a high temperature environment may be obtained. Moreover, the heat curing time is sufficient within 3 hours in view of the performance of the coating film.

  If necessary, a curing catalyst, a light stabilizer, and a silane coupling agent can be added to the coating composition used for the first layer.

  Curing catalysts include di-n-butyltin dilaurate, di-n-butyltin acetate, di-n-butyltin dioctanoate, di-n-butyltin bis (2-ethylhexyl maleate), dimethylhydroxytin oleate, dimethyl Organic tin compounds such as tin dineodecanoate, di-n-octyltin dilaurate, di-n-octyltin dimaleate, n-butyltin tris (2-ethylhexanoate), dimethylethanolamine, triethylenediamine, etc. And tertiary amines. These agents may be used alone or in combination of two or more, and are preferably 0.001 to 3.0 parts by weight, more preferably 0.002 to 2.0 parts by weight with respect to 100 parts by weight of the acrylic copolymer. Used. When the curing catalyst is less than 0.001 part by weight, the effect of accelerating the crosslinking reaction cannot be obtained, and when it exceeds 3.0 parts by weight, the adhesion between the acrylic resin layer and the second layer is undesirably lowered.

  Examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (2,2 , 6,6-tetramethyl-4-piperidyl) sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-octanoyloxy-2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) diphenylmethane-p, p'-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) benzene-1,3-di Hindered amines such as sulfonate, bis (2,2,6,6-tetramethyl-4-piperidyl) phenyl phosphite, nickel bis (octylphenyl sulfide) Examples include nickel complexes such as nickel complex-3,5-di-t-butyl-4-hydroxybenzyl phosphate monoethylate, nickel dibutyldithiocarbamate, etc. These agents may be used alone or in combination of two or more. Preferably it is 0.01-50 weight part with respect to 100 weight part of copolymers, More preferably, 0.05-10 weight part is used.

  Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N -Vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, vinyltriacetoxysilane, γ-anilinopropyltrimethoxysilane, Examples include vinyltrimethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ-ureidopropyltriethoxysilane and the like, and partial hydrolysis condensates of the above silane coupling agents can also be used. By adding such an agent, the adhesion between the polycarbonate base material and the first layer and between the first layer and the second layer is maintained for a long time. These agents may be used alone or in combination of two or more, and are preferably used in an amount of 0.1 to 50 parts by weight, more preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the acrylic copolymer.

  By forming the first layer made of the coating resin mainly composed of the acrylic resin, the adhesion between the second layer and the polycarbonate substrate is improved, and a polycarbonate molded article having excellent wear resistance and weather resistance is obtained. be able to.

  In this invention, the 2nd layer laminated | stacked next on the said 1st layer consists of a crosslinked organosiloxane polymer.

The crosslinked organosiloxane polymer has the above formulas (b-4) to (b-6).
(In the formula, Q ¹ and Q ² are each at least one selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a vinyl group, or a methacryloxy group, an amino group, a glycidoxy group, and a 3,4-epoxycyclohexyl group. A C 1-3 alkyl group substituted with a group.)
Consisting of repeating units represented by
It is a cross-linked organosiloxane polymer in which the molar ratio {(b-4) / (b-5) / (b-6)} of each repeating unit is 80 to 100/0 to 20/0 to 20.
Examples of the alkyl group for Q ¹ and Q ² include a methyl group and an ethyl group.
The molar ratio {(b-4) / (b-5) / (b-6)} is preferably 85-100 / 0-15 / 0-15, and more preferably 85-100 / 0-10 /. 0-10.

  The second layer can be formed by laminating an organosiloxane resin composition containing the following components (a) to (d) on the first layer and then curing.

  The colloidal silica used as the component (a) is a colloidal dispersion of silica fine particles having a diameter of 5 to 200 nm, preferably 5 to 40 nm, in water or an organic solvent. The colloidal silica can be used in either a water dispersion type or an organic solvent dispersion type, but a water dispersion type is preferably used. In the case of water-dispersed colloidal silica, there are a large number of hydroxyl groups on the surface of the silica fine particles, which are strongly bonded to the alkoxysilane hydrolysis condensate, so that a plastic laminate having more excellent wear resistance can be obtained. Conceivable.

  The water-dispersed colloidal silica is further divided into an acidic aqueous dispersion type and a basic aqueous dispersion type. The water-dispersed colloidal silica can be used in either an acidic aqueous dispersion type or a basic aqueous dispersion type. However, in view of the diversity of curing catalyst selection, appropriate hydrolysis of methyltrialkoxysilane, and the realization of a condensed state, Type colloidal silica is preferably used.

  As such colloidal silica, specifically, as a product dispersed in an acidic aqueous solution, as a product dispersed in a basic aqueous solution, Snowtex O of Nissan Chemical Industry Co., Ltd., Cataloid SN of Catalytic Chemical Industry Co., Ltd. Nissan Chemical Industries, Ltd. Snowtex 30, Snowtex 40, Catalytic Chemical Industry Co., Ltd. Cataloid S30, Cataloid S40, Nissan Chemical Industries, Ltd. MA-ST, IPA-ST , NBA-ST, IBA-ST, EG-ST, XBA-ST, NPC-ST, DMAC-ST, OSCAL1132, OSCAL1232, OSCAL1332, OSCAL1432, OSCAL1532, OSCAL1632, OSCAL1732, etc.

Component (b) is represented by the following formulas (b-1) to (b-3).
Q ¹ Si (OQ ³ ) ₃ (b-1)
Q ¹ Q ² Si (OQ ³ ) ₂ (b-2)
Si (OQ ³ ) ₄ (b-3)
(Wherein Q ¹ and Q ² are one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a vinyl group, or a methacryloxy group, an amino group, a glycidoxy group, and a 3,4-epoxycyclohexyl group. And Q ³ is an alkyl group having 1 to 4 carbon atoms.
The alkoxysilane which is formed from the alkoxysilane represented by this, and the ratio of each component, (b-1) / (b-2) / (b-3) is 80-100 / 0-20 / 0-20 Hydrolyzate and / or condensate thereof.
Specific examples of the alkyl group for Q ¹ , Q ² , and Q ³ include a methyl group and an ethyl group.

  As the alkoxysilane of the formula (b-1), methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ -Aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltriethoxysilane, and the like.

  Examples of the alkoxysilane of the formula (b-2) include dimethyldimethoxysilane, vinylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-aminopropylmethyldiethoxysilane. It is done.

  Examples of the alkoxysilane of formula (b-3) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, and tetraisobutoxysilane.

  The ratio of each component {(b-1) / (b-2) / (b-3)} is preferably 85 to 100/0 to 15/0 to 15, more preferably 85 to 95/5. 15 / 5-15.

The molar ratio (Si ^a / Si ^b ) of Si derived from component (a) to Si derived from component (b) in the resin composition is 2/8 to 4/6, preferably 2.5 / 7. .5 to 3.5 / 6.5.

  A curing catalyst is further contained as component (c). Such catalysts include formic acid, propionic acid, butyric acid, lactic acid, tartaric acid, lithium salts of aliphatic carboxylic acids such as succinic acid, alkali metal salts such as sodium salt and potassium salt, benzyltrimethylammonium salt, choline salt, tetramethylammonium salt And quaternary ammonium salts such as salts and tetraethylammonium salts. Specifically, sodium acetate, potassium acetate, choline acetate, and benzyltrimethylammonium acetate are preferably used.

  When a basic water-dispersed colloidal silica is used as the colloidal silica and an aliphatic carboxylic acid is used as the acid during the hydrolysis of the alkoxysilane, a curing catalyst is already contained in the organosiloxane resin composition. Will be.

  The required content varies depending on the composition of the organosiloxane resin, the degree of hydrolysis, the progress of the condensation reaction, and the thermosetting conditions, but the content of the curing catalyst with respect to 100 parts by weight of the total of component (a) and component (b). Is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight. When the content is less than 0.01 parts by weight, a sufficient curing rate cannot be obtained, and when the content is more than 10 parts by weight, the storage stability of the organosiloxane resin composition is lowered or a precipitate is generated, which is not preferable.

  As the solvent used as component (d), it is necessary for component (a) and component (b) to be stably dissolved. For this purpose, at least 20% by weight, preferably 50% by weight or more is alcohol. Is desirable.

  Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-ethoxyethanol, 4-methyl-2-pentanol, and 2-butoxy. Ethanol etc. are mentioned, C1-C4 low boiling point alcohol is preferable, and 2-propanol is especially preferable at the point of solubility, stability, and coating property. When water in the water-dispersed colloidal silica is used in the solvent, water that does not participate in the hydrolysis reaction, lower alcohol generated by hydrolysis of alkoxysilane, and organic solvent-dispersed colloidal silica are used. An organic solvent for the dispersion medium and an acid added for adjusting the pH of the organosiloxane resin composition are also included.

  Acids used for pH adjustment include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, sulfamic acid and other inorganic acids, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, maleic acid Examples thereof include organic acids such as acid, lactic acid, and paratoluenesulfonic acid, and organic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, and maleic acid are preferable from the viewpoint of easy control of pH.

  Other solvents must be miscible with water / alcohol, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethers such as tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, acetic acid Examples thereof include esters such as ethyl and ethoxyethyl acetate. A solvent is 50-900 weight part with respect to 100 weight part of organosiloxane resin solid content, Preferably it is 150-700 weight part.

  The organosiloxane resin composition of the present invention is desirably prepared to have a pH of 3.0 to 6.0, preferably 4.0 to 5.5 by adjusting the contents of the acid and the curing catalyst. Thereby, gelatinization of the organosiloxane resin composition at room temperature can be prevented, and the storage stability can be increased. The organosiloxane resin composition usually becomes a stable composition by further aging for several hours to several days.

  Furthermore, a known leveling agent can be blended in the organosiloxane resin composition of the present invention for the purpose of improving the coatability and the smoothness of the resulting coating film. The blending amount is preferably in the range of 0.01 to 2 parts by weight with respect to 100 parts of the organosiloxane resin composition. Moreover, you may add a ultraviolet absorber, dye, a pigment, a filler, etc. in the range which does not impair the objective of this invention.

  The organosiloxane resin composition thus prepared can be preferably applied to a molded body in which an acrylic resin layer is formed as a primer layer on a polycarbonate resin.

The organosiloxane resin composition is prepared, for example, through the following process.
In the colloidal silica dispersion, the alkoxysilanes of formulas (b-1), (b-2), and (b-3) are subjected to a hydrolytic condensation reaction under acidic conditions.

  Here, water required for the hydrolysis reaction of alkoxysilane is supplied from this dispersion when a water-dispersed colloidal silica dispersion is used, and water may be added if necessary. Usually, 1 to 10 equivalents, preferably 1.5 to 7 equivalents, more preferably 3 to 5 equivalents of water are used per 1 equivalent of alkoxysilane.

  As described above, the hydrolysis and condensation reaction of alkoxysilane needs to be performed under acidic conditions. In order to perform hydrolysis under such conditions, an acid is generally used as a hydrolyzing agent. Such an acid may be added in advance to the alkoxysilane or colloidal silica dispersion, or both may be added after mixing. Moreover, this addition can also be divided into 1 time or 2 times or more. When acidic aqueous dispersion type colloidal silica is used, it is not always necessary to use an acid because the acid in the colloidal silica keeps the reaction solution under acidic conditions.

  Such acids include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, sulfamic acid, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, maleic acid, lactic acid, paratoluene sulfone. Organic acids such as acids can be mentioned.

  When an inorganic acid is used as such an acid, it is usually used at a concentration of 0.0001 to 2 mol / l, preferably 0.001 to 0.1 mol / l. When an organic acid is used, 100 parts by weight of methyltrialkoxysilane The amount is 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight.

  The conditions for the hydrolysis and condensation reaction of the alkoxysilane cannot be unconditionally changed depending on the type of alkoxysilane used, the type and amount of colloidal silica coexisting in the system, but the system temperature is usually 20 to 40 ° C. The reaction time is 1 hour to several days. Although the hydrolysis reaction of alkoxysilane is an exothermic reaction, it is desirable that the temperature of the system does not exceed 60 ° C. at the maximum. It is also preferable to allow the hydrolysis reaction to proceed sufficiently under such conditions and to allow the condensation reaction to proceed at 40 to 80 ° C. for 1 hour to several days in order to stabilize the coating agent.

In this reaction, the alkoxysilanes of the above formulas (b-1), (b-2), and (b-3) are hydrolyzed to give the following formula Q ¹ Si (OH) ₃
Q ¹ Q ² Si (OH) ₂
Si (OH) ₄
(Wherein Q ¹ and Q ² are the same as in formulas (b-1) to (b-3)).
The produced Si-OH is subjected to a condensation reaction with Si-OH in colloidal silica or Si-OH of a trialkoxysilane hydrolyzate molecule different from this molecule to form a Si-O- A Si bond is formed, and the resulting condensate also undergoes a condensation reaction with another Si—OH to form a Si—O—Si bond. This hydrolysis reaction and condensation reaction proceed partially but not completely.

When the reaction liquid was measured for a silicon nuclear magnetic resonance spectrum ( ²⁹ Si-NMR), the chemical shift of the organosiloxane resin composition was found to be the silicon atom peak of the trialkoxysilane dimer condensate with the silicon atom of tetramethylsilane being 0 ppm. From -46.5 ppm to -48.5 ppm, a peak based on a silicon atomic group derived from a terminal trialkoxysilane by a silicone oligomer and a condensation reaction of only one hydroxyl group is from -52.5 ppm to -61.0 ppm. The peak of the oligomer derived from trialkoxysilane and based on the silicon atomic group obtained by condensation reaction of two hydroxyl groups is from -61.0 ppm to -70.0 ppm, the silicone oligomer is derived from trialkoxysilane, and the three hydroxyl groups are Condensed silicon group And a peak based on a silicon atomic group bonded to colloidal silica is changed from -95 ppm to -130 ppm. Moreover, the peak based on the silicon atom of tetraalkoxysilane and dialkoxysilane appears in a region other than the aforementioned region.

  Organosiloxane resin compositions have favorable hydrolysis and condensation ratios. If the hydrolysis reaction is not progressing sufficiently, hair cracks may occur due to transpiration of the starting trialkoxysilane, rapid progress of the curing reaction, etc. May occur. In addition, if the condensation reaction proceeds too much, the particle size in the sol becomes too large and an appropriate crosslinking reaction becomes impossible, which may reduce the wear resistance.

Organosiloxane resin composition, using heavy water _(D 2 O) as a measurement solvent, observation frequency 79MH _Z, observation pulse 6.0Myuesu, repetition time 30 seconds, silicon nuclear magnetic resonance spectra in terms of broadening factor 5H _Z ⁽²⁹ Si-NMR) When measured, the chemical shift of the silicon atom of the organosiloxane resin composition is the integrated value of all peaks in the range of -46.5 ppm to -70.0 ppm, assuming that the silicon atom of tetramethylsilane is 0 ppm. [S], peak integration value [X] in the range of −46.5 ppm to −48.5 ppm in the peak integration value, and peak integration value in the range of −52.5 ppm to −61.0 ppm in [Y], − When the peak value in the range of 61.0 ppm to −70.0 ppm is expressed as [Z], 0.002 ≦ [X] / [ ] A ≦ 0.2, and is preferably 0.6 ≦ [Y] / [Z] ≦ 3. Such an organosiloxane resin composition has sufficient wear resistance without cracking during thermosetting.

  The range of each integral value is preferably 0.003 ≦ [X] / [S] ≦ 0.150, and 0.75 ≦ [Y] / [Z] ≦ 2.25, most preferably 0.003 ≦ [X] / [S] ≦ 0.150 and 0.75 ≦ [Y] / [Z] ≦ 2.00.

  When colloidal silica is not used for the organosiloxane resin composition, scratch resistance and the like may be insufficient even in the range of the silicon nuclear magnetic resonance spectrum of the present invention.

In the present invention, the mixing ratio of the component (a) and the component (b) is the stability of the organosiloxane resin composition, the transparency of the resulting cured film, the wear resistance, the scratch resistance, the adhesion and the presence or absence of cracks, etc. When the total of component (a) and component (b) is 100% by weight, the preferred mixing ratio of these two components is 10 to 60% by weight for component (a) and Q for component (b). 40 to 90% by weight in terms of ¹ _m Q ² _n SiO _{(4-mn) / 2} , preferably 10 to 40% by weight of component (a), and component (b) of Q ¹ _m Q ² _n SiO It is 60 to 90% by weight in terms of _{(4-mn) / 2} .

  The organosiloxane resin composition is desirably adjusted to a pH of 3.0 to 6.0, preferably 4.0 to 5.5 by adjusting the contents of the acid and the curing catalyst. Thereby, gelatinization of the organosiloxane resin composition at room temperature can be prevented, and the storage stability can be increased. The organosiloxane resin composition usually becomes a stable composition by further aging for several hours to several days.

  Moreover, a known leveling agent can be mix | blended with the organosiloxane resin composition in order to improve coating property and the smoothness of the coating film obtained. The blending amount is preferably in the range of 0.01 to 2 parts by weight with respect to 100 parts of the organosiloxane resin composition. Moreover, you may add a ultraviolet absorber, dye, a pigment, a filler, etc. in the range which does not impair the objective of this invention.

  The thus-obtained polycarbonate resin laminate of the present invention, which is obtained as described above, comprises a first layer mainly composed of a thermosetting acrylic resin layer on a polycarbonate resin substrate having an endothermic peak by annealing or the like, colloidal silica, trialkoxy. By having a second layer formed by thermosetting an organopolysiloxane resin composed of a silane hydrolyzed condensate, it has unprecedented high levels of weather resistance and wear resistance, and sufficient durability in high temperature environments It becomes a molded body.

  Such polycarbonate resin moldings are used for window glass for aircraft, vehicles, automobiles, window glass for construction machinery, window glass for buildings, houses, greenhouses, garages, arcade roofs, headlamp lenses, optical lenses, mirrors. , Glasses, goggles, sound barriers, traffic light lenses, curve mirrors, motorcycle windshields, nameplates, various other sheets, films, and the like.

  In addition, the polycarbonate molded body obtained by the present invention uses a CS-10F wear wheel manufactured by Calibrase, performs a Taber abrasion test (ASTM D1044) of 1000 rotations under a load of 500 g, and the change in haze value before and after the test is 6 % Or less is preferable.

  The polycarbonate resin laminate of the present invention has good appearance, hot water resistance, adhesion, and abrasion resistance, has a high level of weather resistance, and is excellent in durability against environmental changes and high-temperature environments. It is suitably used for window glass of construction machines, window glass of construction machinery, etc., and the industrial effect produced is exceptional.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to this from the first. In addition, the obtained polycarbonate molded object was evaluated by the following method. Moreover, the part and% in an Example mean a weight part and weight%.
(1) Appearance evaluation: The coat layer appearance (presence of foreign matter) of the test piece and the presence or absence of cracks (cracks) were visually confirmed.
(2) Adhesion: 100 grids with a 1 mm interval are made on the coating layer with a cutter knife, and Nichiban adhesive tape (trade name “Cerotape”) is pressure-bonded and peeled off vertically and left on the substrate. The number of eyes was evaluated (based on JIS K5400).
(3) Scratch resistance: After the test piece was rubbed with # 0000 steel wool, the scratched surface condition was visually evaluated in five stages.
1: No damage even when rubbed 10 times at 500 g load 2: Slightly damaged when rubbed 10 times at 500 g load 3: Slightly damaged when rubbed 10 times at 500 g load 4: Damaged when rubbed 10 times at 500 g load 5: 100 g load (4) Wear resistance: A CS-10F wear wheel manufactured by Calibrase was used, and a 1000-rotor Taber wear test was performed at a load of 500 g. The haze after the Taber wear test and the haze before the Taber wear test The difference ΔH was measured and evaluated (based on ASTM D1044).
(Haze = Td / Tt × 100, Td: scattered light transmittance, Tt: total light transmittance)
(5) Hot water resistance: Appearance change and adhesion of the coating layer after the test piece was immersed in boiling water for 3 hours and 8 hours were evaluated.
(6) Environmental cycle test: Specimens at 80 ° C. in 80% RH environment for 4 hours, 25 ° C. in 50% RH environment for 1 hour, −15 ° C. environment in 4 hours, and 25 ° C. in 50% RH environment A cycle that was allowed to stand for 1 hour was defined as 1 cycle, and after such a cycle was repeated 20 times, a test piece was taken out and the appearance and adhesion were evaluated.
(7) Endothermic energy ΔHK (mJ / mg)
A polycarbonate resin molded plate 10 mg was set in a thermal analysis system (differential scanning calorimeter) SSC5200 and DSC220 manufactured by Seiko Electronics Industry Co., Ltd., and heated at a rate of temperature increase of 20 ° C./min in a nitrogen stream to obtain the endothermic energy of the film. It calculated | required from the endothermic side area on a corresponding DSC chart. This area shifts from the baseline to the endothermic side as the temperature rises, and after the endothermic peak continues to rise and then returns to the baseline position, from the endothermic start temperature position to the end temperature position The area (A) was obtained by connecting the above to a straight line. In (indium) was measured under the same DSC measurement conditions, and the area (B) was determined to be 28.5 mJ / mg from the following equation.
(A / B) × 28.5 = ΔHK (mJ / mg)

(Synthesis of acrylic resins (I) to (VI))
[Reference Example 1]
A flask equipped with a reflux condenser and a stirrer and purged with nitrogen, 80.1 parts of methyl methacrylate (hereinafter abbreviated as MMA), 13 parts of 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA), azobisisobutyronitrile 0.14 parts (hereinafter abbreviated as AIBN) and 200 parts of 1,2-dimethoxyethane were added, mixed and dissolved. Subsequently, it was made to react under stirring at 70 degreeC in nitrogen stream for 6 hours. The obtained reaction solution was added to n-hexane and purified by reprecipitation to obtain 80 parts of a copolymer (acrylic resin (I)) having a MMA / HEMA composition ratio of 90/10 (molar ratio). The hydroxyl value of the copolymer was 54.3 mgKOH / g, and the weight average molecular weight was 180,000 in terms of polystyrene from the measurement of GPC (column; Shodex GPCA-804, eluent: THF).

[Reference Example 2]
MMA / HEMA composition ratio 80/20 (molar ratio) copolymer (acrylic resin (II)) 90 parts were obtained in the same manner as in Reference Example 1 except that MMA 80.1 parts, HEMA 26 parts, and AIBN 0.18 parts were used. . The copolymer had a hydroxyl value of 101.8 mgKOH / g and a weight average molecular weight of 80,000 in terms of polystyrene.

[Reference Example 3]
A copolymer (acrylic resin) having an EMA / HEMA composition ratio of 90/10 (molar ratio) in the same manner as in Reference Example 1 except that 102.7 parts of ethyl methacrylate (hereinafter abbreviated as EMA), 13 parts of HEMA, and 0.18 part of AIBN are used. (III)) 100 parts were obtained. The copolymer had a hydroxyl value of 46.7 mgKOH / g and a weight average molecular weight of 80000 in terms of polystyrene.

[Reference Example 4]
Except for using 97 parts of EMA, 19.5 parts of HEMA, and 0.18 part of AIBN, 100 parts of a copolymer (acrylic resin (IV)) having an EMA / HEMA composition ratio of 85/15 (molar ratio) was obtained in the same manner as in Reference Example 1. . The copolymer had a hydroxyl value of 72.1 mg KOH / g and a weight average molecular weight of 80,000 in terms of polystyrene.

[Reference Example 5]
The composition ratio of MMA / MPTMS is 95/5 in the same manner as in Reference Example 1 except that 95.1 parts of MMA, 12.4 parts of 3-methacryloxypropyltrimethoxysilane (hereinafter abbreviated as MPTMS) and 0.2 part of AIBN are used. The molar ratio of the copolymer (acrylic resin (V)) 85 parts. The weight average molecular weight of the copolymer was 80,000 in terms of polystyrene.

[Reference Example 6]
MMA / HEMA composition ratio 55/45 (molar ratio) copolymer (acrylic resin (VI)) 90 parts was obtained in the same manner as Reference Example 1 except that MMA 55 parts, HEMA 58.5 parts, and AIBN 0.18 parts were used. . The copolymer had a hydroxyl value of 221.8 mgKOH / g and a weight average molecular weight of 100,000 in terms of polystyrene.

[Reference Example 7]
MMA / MA composition ratio 90/10 (molar ratio) copolymer (acrylic resin) in the same manner as in Reference Example 1 except that 90 parts of MMA, 8.6 parts of methacrylic acid (hereinafter abbreviated as MA), and 0.18 part of AIBN were used. (VII)) 90 parts were obtained. The weight average molecular weight of the copolymer was 100,000 in terms of polystyrene.

(Preparation of organosiloxane resin solution)
[Reference Example 8]
142 parts of methyltrimethoxysilane, 72 parts of distilled water and 20 parts of acetic acid were mixed with ice water while cooling. This mixed solution was stirred at 25 ° C. for 1 hour and diluted with 116 parts of isopropanol to obtain 350 parts of a methyltrimethoxysilane hydrolysis condensate solution (X).

[Example 1]
(Composition for the first layer) 8.9 parts of the acrylic resin (I) and 2.5 parts of 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole were 20 parts of methyl ethyl ketone and 30 parts of methyl isobutyl ketone. And 1.1 parts of hexamethylene diisocyanate so that the isocyanate group is 1.5 equivalents relative to 1 equivalent of the hydroxy group of the acrylic resin (I). Was added and stirred at 25 ° C. for 5 minutes to prepare a coating composition (i-1).

  (Composition for the second layer) Water dispersion type colloidal silica dispersion (Nissan Chemical Industry Co., Ltd. Snowtex 30 solid content concentration 30 wt%) 100 parts, 2 parts distilled water and 20 parts acetic acid were added and stirred. To this dispersion, 130 parts of methyltrimethoxysilane was added while cooling in an ice-water bath. The reaction solution obtained by stirring this mixed solution at 25 ° C. for 1 hour was mixed with 2 parts of sodium acetate as a curing catalyst under cooling with ice water, diluted with 200 parts of isopropanol, and coated composition (ii-1). Got.

  A polycarbonate resin (L-1225 manufactured by Teijin Chemicals) was used as the thermoplastic resin. A thermoplastic resin was injected and injected into the cavity of the mold under the conditions of a resin temperature of 285 ° C., a mold temperature of 60 ° C., and an injection pressure (gauge pressure) of 160 MPa to obtain a molded plate of 300 mm length × 300 mm width × 4 mm thickness. . This molded plate was heated to 130 ° C. over 2 hours, held for 8 hours, and then annealed (heat treatment) to decrease the temperature to 25 ° C. over 24 hours. Table 3 shows endothermic peak values of the molded plate. The coating composition (i-1) was applied on the molded plate by a dip coating method, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 1 hour. Next, the coating composition (ii-1) was applied on the coating surface of the sheet by a dip coating method (bar coating method), allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 1 hour. The evaluation results of the obtained PC resin molded product are shown in Table 3.

  The coating composition (i-1) was solidified after 2 weeks of preparation at 23 ° C. and could not be used for coating.

[Example 2]
(Composition for the first layer) 8.3 parts of the acrylic resin (II) and 2 parts of 2,4-dihydroxybenzophenone were mixed with 30 parts of methyl ethyl ketone, 30 parts of methyl isobutyl ketone and 30 parts of 2-methyl-2-propanol. After dissolving in a solvent, 1.7 parts of isophorone diisocyanate was added to this solution so that the isocyanate group was 1 equivalent to 1 equivalent of the hydroxy group of the acrylic resin (II), and the mixture was stirred at 25 ° C. for 5 minutes. A coating composition (i-2) was prepared.

  (Composition for the second layer) Water dispersion type colloidal silica dispersion (Snowtex 30 solids concentration 30% by weight, manufactured by Nissan Chemical Industries, Ltd.) 100 parts, acetic acid 20 parts, and stirred, ice water Under cooling in a bath, 122 parts of methyltrimethoxysilane was added. The reaction mixture obtained by stirring this mixture at 25 ° C. for 1 hour was mixed with 1 part of potassium acetate as a curing catalyst under cooling with ice water, diluted with 408 parts of isopropanol, and coated composition (ii-2). Got.

  The PC resin molded plate obtained by the same method as in Example 1 was heated to 130 ° C. over 2 hours, held for 8 hours, and then annealed to cool down to 25 ° C. over 24 hours. The coating composition (i-2) was applied by a dip coating method, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 1 hour. The film thickness of the first layer was 1.5 μm. Next, the coating composition (ii-3) was applied on the coating surface of the molded plate by a dip coating method, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 2 hours. The film thickness of the second layer was 5.0 μm. The evaluation results of the obtained PC resin molded product are shown in Table 3.

  The coating composition (i-2) solidified after 2 months of preparation at 23 ° C. and could not be used for coating.

[Example 3]
(Composition for the first layer) 7.5 parts of the acrylic resin (I) and 2 parts of 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole were mixed with 20 parts of methyl ethyl ketone, 30 parts of methyl isobutyl ketone and 2 parts. -Dissolve in a mixed solvent consisting of 30 parts of propanol, and further add 12.5 parts of the methyltrimethoxysilane hydrolysis condensate solution (X) obtained in Reference Example 7 to this solution and stir at 25 ° C for 5 minutes. A coating composition (i-3) was prepared.

  The PC resin molding plate obtained by the same method as in Example 1 was heated to 130 ° C. over 2 hours, held for 8 hours, and then annealed to cool down to 25 ° C. over 24 hours. The coating composition (i-3) was applied on the molded plate by a dip coating method, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 1 hour. The film thickness of the first layer was 4.0 μm. Next, the coating composition (ii-1) was applied on the coating surface of the sheet by dip coating, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 1 hour. The film thickness of the second layer was 5.0 μm. The evaluation results of the obtained PC resin molded product are shown in Table 3.

[Example 4]
(Composition for the first layer) 7.7 parts of the acrylic resin (III) and 1.5 parts of 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole were 40 parts of methyl ethyl ketone and 20 parts of methyl isobutyl ketone. In a mixed solvent consisting of 24 parts of isopropanol and 3.2 parts of 1-methoxy-2-propanol, the isocyanate group in this solution is 1 equivalent to 1 equivalent of the hydroxy group of the acrylic resin (I). VESTANATB 1358/100 (Degussa Japan polyisocyanate compound precursor) 2.3 parts, di-n-butyltin dilaurate 0.001 part was added and stirred at 25 ° C. for 5 minutes to form a coating composition (i- 4) was prepared.

  (Composition for second layer) Water-dispersed colloidal silica dispersion (Nissan Chemical Industry Co., Ltd. Snowtex 30 solid content concentration 30 wt%) 60 parts distilled water 28 parts and acetic acid 20 parts were added and stirred, To this dispersion, 130 parts of methyltrimethoxysilane was added while cooling in an ice-water bath. The reaction mixture obtained by stirring this mixture at 25 ° C. for 1 hour was mixed with 4 parts of benzyltrimethylammonium acetate as a curing catalyst under cooling with ice water, diluted with 172 parts of isopropanol, and coated with a coating composition (ii- 3) was prepared.

  The PC resin molded plate obtained by the same method as in Example 1 was heated to 120 ° C. over 2 hours, held for 24 hours, and then annealed to cool down to 25 ° C. over 24 hours. The coating composition (i-4) was applied by a dip coating method, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 1 hour. The film thickness of the first layer was 4.0 μm. Next, the coating composition (ii-3) was applied on the coating surface of the molded plate by a dip coating method, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 2 hours. The film thickness of the second layer was 4.0 μm. The evaluation results of the obtained PC resin molded product are shown in Table 3.

  The coating composition (i-4) was stored at 23 ° C. and could be used for coating without problems even after 3 months of preparation.

[Example 5]
(Composition for the first layer) 5.8 parts of the acrylic resin (IV) and 2- (4,6diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol 2.5 parts are dissolved in a mixed solvent consisting of 40 parts of methyl ethyl ketone, 20 parts of methyl isobutyl ketone, and 25 parts of 2-methyl-2-propanol, and then this solution is added to 1 equivalent of the hydroxy group of the acrylic resin (IV). Takenate XB-72-H6 (Mitsui Takeda Chemical Polyisocyanate Compound Precursor) 4.0 parts, APZ-6633 (Nihon Unicar Silane Coupling Agent) 0.1 parts Was added and stirred at 25 ° C. for 5 minutes to prepare a coating composition (i-5).

  (Composition for the second layer) Water dispersion type colloidal silica dispersion (Snowtex 30 solid content concentration 30% by weight, manufactured by Nissan Chemical Industries, Ltd.) 100 parts, 12 parts distilled water and 20 parts acetic acid were added and stirred. To this dispersion, 134 parts of methyltrimethoxysilane was added while cooling in an ice water bath. To the reaction liquid obtained by stirring this mixed liquid at 25 ° C. for 1 hour, 1 part of sodium acetate as a curing catalyst was added and diluted with 200 parts of isopropanol to prepare a coating composition (ii-4).

  The PC resin molded plate obtained by the same method as in Example 1 was heated to 130 ° C. over 2 hours, held for 12 hours, and then annealed to cool down to 25 ° C. over 24 hours. The coating composition (i-5) was applied on the molded plate by a flow coating method, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 130 ° C. for 1 hour. Next, the coating composition (ii-4) was applied on the coating surface of the sheet by a flow coating method, allowed to stand at 25 ° C for 20 minutes, and then thermally cured at 120 ° C for 2 hours. The evaluation results of the obtained PC resin molded product are shown in Table 3.

  The coating composition (i-5) could be used for coating without problems even after 3 months of preparation at 23 ° C.

[Example 6]
(First layer composition) 6.4 parts of the acrylic resin (III) and 1.8 parts of 2,4-dihydroxybenzophenone were 40 parts of methyl ethyl ketone, 20 parts of methyl isobutyl ketone, and 25 parts of 2-methyl-2-propanol. Then, Duranate MF20-B (Asahi Kasei Polyisocyanate Compound Precursor) is used so that the isocyanate group is 0.9 equivalent to 1 equivalent of the hydroxy group of the acrylic resin (III). 3.6 parts was added and stirred for 5 minutes at 25 ° C. to prepare a coating composition (i-6).

  The PC resin molded plate obtained by the same method as in Example 1 was heated to 110 ° C. over 2 hours, maintained for 24 hours, and then annealed to 25 ° C. over 12 hours. The coating composition (i-6) was applied on the molded plate by a dip coating method, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 130 ° C. for 1 hour. The film thickness of the first layer was 4.0 μm. Next, the coating composition (ii-1) was applied on the coating surface of the molded plate by a dip coating method, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 2 hours. The film thickness of the second layer was 6.0 μm. The evaluation results of the obtained PC resin molded product are shown in Table 3.

  The coating composition (i-6) could be used for coating without problems even after 3 months of preparation at 23 ° C.

[Example 7]
(Composition for the first layer) 5.4 parts of the acrylic resin (II) and 1.6 parts of 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole were 40 parts of methyl ethyl ketone and 20 parts of methyl isobutyl ketone. Takenate XB-72 is dissolved in a mixed solvent consisting of 25 parts of 2-methyl-2-propanol, and then 1 equivalent of isocyanate group is added to 1 equivalent of hydroxy group of the acrylic resin (II) in this solution. 4.6 parts of -H6 (polyisocyanate compound precursor manufactured by Mitsui Takeda Chemical Co., Ltd.) was added and stirred at 25 ° C for 5 minutes to prepare a coating composition (i-7).

  (Composition for the second layer) 2 parts of distilled water was added to 100 parts of water-dispersed colloidal silica dispersion (Cataloid SN30, solid content concentration 30% by weight, manufactured by Catalytic Chemicals Co., Ltd.) and stirred. Then, 130 parts of methyltrimethoxysilane was added under cooling. The reaction mixture obtained by stirring this mixture at 25 ° C. for 1 hour was mixed with 2 parts of sodium acetate as a curing catalyst under cooling with ice water, diluted with 200 parts of isopropanol, and coated composition (ii-5). Got.

  The PC resin molded plate obtained in the same manner as in Example 1 was heated to 130 ° C. over 2 hours, held for 6 hours, and then annealed to lower the temperature to 25 ° C. over 12 hours. The coating composition (i-7) was applied on the molded plate by a dip coating method, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 130 ° C. for 1 hour. The film thickness of the first layer was 4.0 μm. Next, the coating composition (ii-5) was applied on the coating surface of the molded plate by a dip coating method, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 2 hours. The film thickness of the second layer was 4.0 μm. The evaluation results of the obtained PC resin molded product are shown in Table 3.

  The coating composition (i-7) could be used for coating without problems even after 3 months of preparation at 23 ° C.

[Comparative Example 1]
The PC resin molded plate obtained by the same method as in Example 1 was applied with the coating composition (i-1) as it was without annealing treatment, and allowed to stand at 25 ° C. for 20 minutes. Heat cured at 1 ° C. for 1 hour. The film thickness of the first layer was 4.0 μm. Next, the coating composition (ii-1) was applied on the coating surface of the molded plate by a dip coating method, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 1 hour. The film thickness of the second layer was 3.5 μm. The evaluation results of the obtained PC resin molded product are shown in Table 3.

[Comparative Example 2]
(Composition for the first layer) 10 parts of the acrylic resin (V) and 1.5 parts of 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 20 parts of methyl ethyl ketone, 30 parts of methyl isobutyl ketone and It melt | dissolved in the mixed solvent which consists of 30 parts of 2-propanol, and prepared the composition for coating (i-8).

  The PC resin molding plate obtained by the same method as in Example 1 was heated to 130 ° C. over 2 hours, held for 8 hours, and then annealed to cool down to 25 ° C. over 24 hours. The coating composition (i-8) was applied on the molded plate by a dip coating method, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 1 hour. The film thickness of the first layer was 4.0 μm. Next, the coating composition (ii-1) was applied on the coating surface of the molded plate by a dip coating method, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 1 hour. The film thickness of the second layer was 5.0 μm. The evaluation results of the obtained PC resin molded product are shown in Table 3.

[Comparative Example 3]
(Composition for the first layer) 7.5 parts of the acrylic resin (VII) and 1.5 parts of 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole were mixed with 20 parts of methyl ethyl ketone and 30 parts of methyl isobutyl ketone. 1 part, 2-propanol 20 parts and 1-methoxy-2-propanol 10 parts in a mixed solvent, and then this solution is added to this solution with an epoxy group with respect to 1 equivalent of the carboxylic acid group of the acrylic resin (VII). 0.83 part of isocyanuric acid tripropylene oxide was added to give 1.1 equivalent, and the mixture was stirred at 25 ° C. for 5 minutes to prepare a coating composition (i-9).

  The PC resin molding plate obtained by the same method as in Example 1 was heated to 130 ° C. over 2 hours, held for 8 hours, and then annealed to cool down to 25 ° C. over 24 hours. The coating composition (i-9) was applied on the molded plate by a dip coating method, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 1 hour. The film thickness of the first layer was 4.0 μm. Next, the coating composition (ii-1) was applied on the coating surface of the molded plate by a dip coating method, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 1 hour. The film thickness of the second layer was 5.0 μm. The evaluation results of the obtained PC resin molded product are shown in Table 3.

In Table 1 and Table 2,
(1) DBTDL; di-n-butyltin dilaurate (2) APZ-6633; silane coupling agent (manufactured by Nihon Unicar)
(3) MTMOS; methyltrimethoxysilane (4) TEOS: tetraethoxysilane (5) S-30; water-dispersed colloidal silica dispersion (Snowtex 30 manufactured by Nissan Chemical Industries, Ltd., solid content concentration: 30% by weight, average Particle size 20nm)
(6) SN30; water-dispersed colloidal silica dispersion (catalyst SN30, solid content concentration 30% by weight, average particle diameter 10 nm, manufactured by Catalyst Chemicals Co., Ltd.)
The weight part of trialkoxysilane indicates a value converted to RSiO3 / 2, and the weight part of tetraalkoxysilane indicates a value converted to SiO2.

Moreover, as a kind of ultraviolet absorber,
(a) UV-1; 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole
(b) UV-2; 2,4-dihydroxybenzophenone
(c) UV-3; represents 2- (4,6diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol.

7

7

Claims (4)

A laminate comprising a polycarbonate substrate, a first layer and a second layer, wherein the first layer is formed on the surface of the polycarbonate substrate, and the second layer is formed on the surface of the first layer, the polycarbonate substrate The material exhibits an endothermic peak within a temperature range of 120 to 150 ° C., the endothermic peak is 0.1 mJ / mg or more, the first layer is a thermosetting acrylic resin composition cured layer, and the second layer is , Comprising a crosslinked organosiloxane polymer, and the cured layer of the thermosetting acrylic resin composition is 50 mol% or more of the following formula (A-1)

(Wherein R ¹ is a methyl group or an ethyl group),
5-30 mol% of following formula (A-2)

(Wherein R ² is an alkylene group having 2 to 5 carbon atoms) and 0 to 30 mol% of the following formula (A-3)

(Wherein, Y is a hydrogen atom or a methyl group, and R ³ is at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 2 to 5 carbon atoms, and an ultraviolet absorbing residue. Except that is a methyl group and R ³ is a methyl group or an ethyl group.)
Is a cured layer obtained by curing a polyisocyanate compound or a siloxane resin as a crosslinking agent, and the crosslinked organosiloxane polymer has the following formula (b-4): ~ (B-6)

(In the formula, Q ¹ and Q ² are each at least one selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a vinyl group, or a methacryloxy group, an amino group, a glycidoxy group, and a 3,4-epoxycyclohexyl group. A C 1-3 alkyl group substituted with a group.)
A cross-linking unit having a molar ratio {(b-4) / (b-5) / (b-6)} of each repeating unit of 80 to 100/0 to 20/0 to 20 A polycarbonate resin laminate characterized by being an organosiloxane polymer.   A polyisocyanate compound is used as the crosslinking agent, and the amount used thereof is 0.7 to 5 equivalents of the total amount of isocyanate groups generated and / or present with respect to 1 equivalent of hydroxyl groups of the repeating unit represented by the formula (A-2). The polycarbonate resin laminate according to claim 1.   The polycarbonate resin laminate according to claim 1, wherein the cured layer of the thermosetting acrylic resin composition contains 5 to 50 parts by weight of an ultraviolet absorber with respect to 100 parts by weight of the acrylic copolymer.   The polycarbonate resin laminate according to claim 1, wherein the polycarbonate substrate has a thickness of 1 to 10 mm, the first layer has a thickness of 2 to 15 µm, and the second layer has a thickness of 2 to 10 µm.