JP4681372B2 - Adhesive of transparent resin laminate having colored layer and metal frame - Google Patents

Description

  In the present invention, a polycarbonate resin used as a substitute for a window glass or sunroof of an aircraft, a vehicle, an automobile, etc., a window glass (skylight) of a construction machine, a window of a building, a house, a greenhouse, etc. The present invention relates to an adhesive body between a transparent resin laminate having a metal frame and a metal frame.

  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, Patent Document 1 and Patent Document 2 describe a coating composition comprising a trihydroxysilane partial condensate and colloidal silica. Furthermore, Patent Document 3 and Patent Document 4 describe a coating composition in which colloidal silica is added to a condensate of alkyltrialkoxysilane and tetraalkoxysilane.

  However, a laminate obtained by laminating a cured film obtained from these coating compositions on a transparent plastic substrate has a certain degree of abrasion resistance. Due to the difference in the thermal expansion coefficient of the layer formed by thermosetting the resin, the layer formed by thermosetting the organosiloxane resin may be pulled and cracks may occur in the coat layer. ing.

  In order to improve this point, many proposals have been made to provide a thermosetting acrylic resin layer between a plastic substrate and an organosiloxane resin layer. For example, Patent Document 5 proposes that an acrylic-urethane resin layer obtained from an acrylic polyol and an isocyanate compound is used as the thermosetting acrylic resin layer. However, since the reactivity of the isocyanate compound is high, the storage stability of the coating is low, and the coating tends to thicken or gel during use or storage. In addition, there is a disadvantage that side reaction is likely to occur during thermosetting and the physical properties of the coating film are not stable.

  On the other hand, a method of adding an ultraviolet absorber to a thermosetting acrylic resin layer is known for the purpose of improving weather resistance. For example, the present inventors have shown in Patent Document 6 that weather resistance is improved by adding a benzotriazole-based ultraviolet absorber to a thermosetting acrylic resin layer having a specific composition. However, the acrylic resin layer shown in this document does not have sufficient weather resistance that can withstand long-term outdoor use.

  Moreover, in recent years, the transparent resin laminate having a hard coating applied to the polycarbonate substrate surface as described above has been used as an alternative material for glass in applications such as automobile window glass, sunroof, and construction machine window glass. It is being considered. In these applications, it is desired to have a performance that can withstand long-term outdoor use.

  When used in such applications, it is produced by a method in which the peripheral portion of the transparent resin laminate and the metal frame of the window are directly joined with an adhesive, as in the case of a conventional glass material. In order to hide the adhesive portion from the outside, printing is often performed with black paint or the like. There are two types of printing methods: a method of performing a hard coat treatment after printing on a polycarbonate substrate, and a method of printing on the surface of a polycarbonate laminate subjected to the hard coat treatment.

  As a method for printing directly on a polycarbonate substrate, at least one colored layer selected from vinyl / acrylic resin, vinyl / methacrylic resin, and modified polyester resin is formed on the polycarbonate substrate, and the surface thereof is formed. A method of sequentially laminating a polymethyl methacrylate primer layer and a silicone hard coat layer has been proposed (Patent Document 7).

  As a method for printing on the surface of a polycarbonate laminate subjected to a hard coat treatment, Patent Document 8 and Patent Document 9 propose a structure in which an acrylic primer layer, a silicone hard coat layer, and a colored layer are sequentially formed on a polycarbonate substrate. ing. The primer layer in the configuration shown in these patent documents has poor coating film elasticity, and cannot provide sufficient weather resistance that can withstand long-term outdoor use.

Japanese Patent Laid-Open No. 51-002736 Japanese Patent Laid-Open No. 55-094971 Japanese Unexamined Patent Publication No. Sho 63-27879 Japanese Patent Laid-Open No. 01-306476 JP-A-62-169832 JP 2000-318106 A Japanese Patent Publication No. 07-106613 JP-A-11-348176 JP 2001-180265 A

  An object of the present invention is to laminate a transparent resin laminate in which a thermosetting film of an acrylic resin composition is laminated as a first layer on a polycarbonate substrate, an organosiloxane resin layer is laminated as a second layer, and a colored layer is formed thereon. Automotive window glass and sunroof that can provide weather resistance, environmental change and durability against high-temperature environments, wear resistance, and hot water resistance by joining the body and the metal frame at the colored part, and window glass for construction machinery It is providing the adhesive body of the transparent resin laminated body and metal frame which can be utilized as.

  As a result of intensive investigations to achieve this object, the inventors of the present invention have found that a first layer mainly composed of a thermosetting acrylic resin having a specific composition on the surface of a polycarbonate substrate, and further colloidal silica and alkoxysilane thereon. A second layer is formed by thermosetting an organosiloxane resin containing a hydrolyzed condensate, a colored layer is formed on the surface, and a colored portion and a metal frame are adhered to each other, thereby providing a high level of weather resistance. It has been found that a bonded body of a transparent resin laminate and a metal frame, which has a surface protected by a cured coating that imparts abrasion resistance, and also has sufficient durability under environmental changes and high temperature environments, has been found. The present invention has been reached.

（式中Ｒ^１はメチル基またはエチル基である。）
１〜１５モル％の下記式（２）で表される繰り返し単位（（Ａ−２）単位）

（式中Ｒ^２は炭素数２〜５のアルキレン基であり、Ｙは水素原子またはメチル基である。）
および、１〜３５モル％の下記式（４）で表される繰返し単位（（Ａ−３）単位）

（式中Ｒ ^６ はシクロアルキル基であり、Ｘは水素原子またはメチル基である。）
を含有するアクリル共重合体であって、該アクリル共重合体の全繰り返し単位１００モル％中、（Ａ−１）単位〜（Ａ−３）単位の合計が少なくとも７０モル％であるアクリル共重合体、
（Ｂ）成分は、ブロック化されたポリイソシアネート化合物であって、そのイソシアネート基の含有割合が５．５〜５０重量％で、且つ上記（Ａ−２）単位中のヒドロキシ基１当量に対して、イソシアネート基が０．８〜１．５当量となる量のブロック化されたポリイソシアネート化合物、
（Ｃ）成分は、（Ａ）成分および（Ｂ）成分の合計１００重量部に対して０．００１〜０．４重量部の硬化触媒、
（Ｄ）成分は、（Ａ）成分および（Ｂ）成分の合計１００重量部に対して１〜４０重量部の紫外線吸収剤、
該オルガノシロキサン樹脂層（第２層）は、下記（Ｅ）成分および（Ｆ）成分を含有するオルガノシロキサン樹脂組成物を熱硬化させてなるオルガノシロキサン樹脂層であり、
（Ｅ）成分は、コロイダルシリカ、
（Ｆ）成分は、下記式（３）で表わされるアルコキシシランの加水分解縮合物

（但し、式中Ｒ^３、Ｒ^４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、Ｒ^５は炭素数１〜４のアルキル基であり、ｍ、ｎはそれぞれ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。）
であって、（Ｅ）成分が１０〜６０重量％および（Ｆ）成分がＲ^３ _ｍＲ^４ _ｎＳｉＯ_{（４−ｍ−ｎ）／２}に換算して４０〜９０重量％である、ことを特徴とする着色層を有する透明樹脂積層体と金属枠との接着体。 That is, according to the present invention,
1. A first layer made of an acrylic resin layer on at least one surface of a polycarbonate substrate, a second layer made of an organosiloxane resin layer on the first layer, and a colored layer are laminated in order on a part or all of the second layer. A transparent resin laminate having a colored layer, wherein the transparent resin laminate and the metal frame are bonded via an adhesive between the portion of the transparent resin laminate on which the colored layer is formed and the metal frame. And a metal frame,
The acrylic resin layer (first layer) is an acrylic resin layer obtained by thermally curing an acrylic resin composition containing the following components (A) to (D):
(A) component is 50 mol% or more of the repeating unit ((A-1) unit) represented by the following formula (1),

(In the formula, R ¹ is a methyl group or an ethyl group.)
1 to 15 mol% of a repeating unit represented by the following formula (2) (unit (A-2))

(Wherein R ² is an alkylene group having 2 to 5 carbon atoms, and Y is a hydrogen atom or a methyl group.)
And 1 to 35 mol% of a repeating unit represented by the following formula (4) (unit (A-3))

(Wherein R ⁶ is a cycloalkyl group, and X is a hydrogen atom or a methyl group.)
Acrylic copolymer having a total of (A-1) units to (A-3) units of at least 70 mol% in 100 mol% of all repeating units of the acrylic copolymer Coalescence,
The component (B) is a blocked polyisocyanate compound, the isocyanate group content of which is 5.5 to 50% by weight, and relative to 1 equivalent of the hydroxy group in the unit (A-2). A blocked polyisocyanate compound in an amount such that the isocyanate group is 0.8 to 1.5 equivalents,
(C) component is a 0.001-0.4 weight part curing catalyst with respect to a total of 100 weight part of (A) component and (B) component,
(D) component is 1-40 weight part ultraviolet absorber with respect to a total of 100 weight part of (A) component and (B) component,
The organosiloxane resin layer (second layer) is an organosiloxane resin layer obtained by thermally curing an organosiloxane resin composition containing the following components (E) and (F):
(E) component is colloidal silica,
Component (F) is a hydrolysis-condensation product of alkoxysilane represented by the following formula (3)

(In the formula, R ³ and R ⁴ are each one or more 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. An alkyl group having 1 to 3 carbon atoms substituted with a group, R ⁵ 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 It is an integer of 0, 1, or 2.)
The component (E) is 10 to 60% by weight and the component (F) is 40 to 90% by weight in terms of R ³ _m R ⁴ _n SiO _{(4-mn) / 2.} An adhesive body of a transparent resin laminate having a colored layer and a metal frame.

（式中Ｒ^７は、水素原子、炭素数１〜１４のアルキル基または炭素数１〜１４のアルコキシ基である。） 2 . The component (A) is 50 mol% or more of the (A-1) unit, 1 to 15 mol% of the (A-2) unit, 1 to 35 mol% of the (A-3) unit, and the following formula (5). An acrylic copolymer containing 0.1 to 10 mol% of the repeating unit ((A-4) unit) represented by (A-1) in 100 mol% of all repeating units of the acrylic copolymer The bonded body of a transparent resin laminate and a metal frame according to claim 1, which is an acrylic copolymer having a total of units to (A-4) units of at least 70 mol%.

(Wherein R ⁷ is a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an alkoxy group having 1 to 14 carbon atoms.)

3 . The bonded body of a transparent resin laminate and a metal frame according to claim 1, wherein the colored layer is a colored layer made of an epoxy resin.

4 . The adhesive body of a transparent resin laminate and a metal frame according to claim 1, wherein the adhesive is an adhesive made of a urethane resin.

(First layer: Acrylic resin layer)
In the present invention, the coating resin laminated on at least one surface of the polycarbonate substrate as the first layer is (A) 50 mol% of the repeating unit ((A-1) unit) represented by the formula (1). The acrylic copolymer containing 1 to 15 mol% of the repeating unit represented by the above formula (2) ((A-2) unit), in 100 mol% of all repeating units of the acrylic copolymer, (A-1) an acrylic copolymer having a total of at least 70 mol% of units and (A-2) units, and (B) a blocked polyisocyanate compound, wherein the isocyanate group content is 5. Blocked polyisocyanate compound in an amount of 5 to 50% by weight and 0.8 to 1.5 equivalents of isocyanate groups based on 1 equivalent of hydroxy groups in the unit (A-2), ( ) 0.001 to 0.4 parts by weight of the curing catalyst with respect to 100 parts by weight of the total of the components (A) and (B), and (D) the total of 100 parts by weight of the components (A) and (B). On the other hand, it is an acrylic resin layer obtained by thermosetting an acrylic resin composition containing 1 to 40 parts by weight of an ultraviolet absorber.

((A) Component Acrylic Copolymer)
The acrylic copolymer of the component (A) is a copolymer composed of at least the repeating units represented by the formula (1) and the formula (2), each of an alkyl methacrylate corresponding to the formula (1), and a formula It is an acrylic copolymer having a hydroxy group obtained by copolymerizing an acrylate and / or methacrylate monomer containing a hydroxy group corresponding to (2).

  Examples of the alkyl methacrylate corresponding to the formula (1) include methyl methacrylate and ethyl methacrylate, which can be used alone or in combination.

  Specific examples of the acrylate or methacrylate monomer having a hydroxy group corresponding to the formula (2) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3- Hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, and the like. These can be used alone or in admixture of two or more. Of these, 2-hydroxyethyl methacrylate is preferably employed.

  The acrylic copolymer used in the present invention has an acrylic copolymer containing 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more in total of the repeating units represented by the formula (1) and the formula (2). It is a polymer, and it is desirable that the molar ratio of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) is 99: 1 to 85:15. When the proportion of the repeating unit represented by the formula (1) is less than 85 mol%, the flexibility of the first layer is lowered, and cracks are likely to occur in the cured organosiloxane resin layer. Moreover, adhesiveness with a base material or a 2nd layer may fall. Moreover, when the ratio of the repeating unit represented by the formula (2) exceeds the above range, cracks are likely to occur in the coating film layer.

  Furthermore, the acrylic copolymer (component (A)) in the present invention improves the compatibility of the acrylic copolymer and the triazine-based UV absorber when a triazine-based UV absorber is used as the UV absorber used in the first layer. Therefore, it is preferable to use the component (A-3) represented by the formula (4). When the component (A-3) is used, the component (A) is 50 mol% or more of the repeating unit (A-1), 1 to 15 mol% of the repeating unit (A-2), and (A- 3) An acrylic copolymer containing 1 to 35 mol% of the repeating units represented by the formula (4), wherein (A-1) to (A) in 100 mol% of all the repeating units of the acrylic copolymer. -3) It is desirable that the total of the repeating units of the component is an acrylic copolymer of at least 70 mol%, preferably at least 80 mol%, more preferably at least 90 mol%. When the proportion of the repeating unit represented by the formula (4) is 1 mol% or more, the dispersibility of the triazine-based ultraviolet absorber is good and the coating film is not whitened. Adhesiveness with the two layers is good, which is preferable.

  The acrylate or methacrylate monomer having a cycloalkyl group corresponding to the formula (4) is not particularly limited as long as it is an acrylate or methacrylate having at least one cycloalkyl group in the molecule.

  Specific examples include cyclohexyl acrylate, 4-methylcyclohexyl acrylate, 2,4-dimethylcyclohexyl acrylate, 2,4,6-trimethylcyclohexyl acrylate, 4-t-butylcyclohexyl acrylate, adamantyl acrylate, dicyclopentadienyl acrylate, cyclohexyl Methyl acrylate, 4-methylcyclohexylmethyl acrylate, 2,4-dimethylcyclohexylmethyl acrylate, 2,4,6-trimethylcyclohexylmethyl acrylate, 4-t-butylcyclohexylmethyl acrylate, cyclohexyl methacrylate, 4-methylcyclohexyl methacrylate, 2, 4-dimethylcyclohexyl methacrylate, 2,4,6-trimethylcyclohexylmeta Relate, 4-t-butylcyclohexyl methacrylate, adamantyl methacrylate, dicyclopentadienyl methacrylate, cyclohexylmethyl methacrylate, 4-methylcyclohexylmethyl methacrylate, 2,4-dimethylcyclohexylmethyl methacrylate, 2,4,6-trimethylcyclohexylmethyl methacrylate , 4-t-butylcyclohexylmethyl methacrylate, and the like, and these can be used alone or in admixture of two or more. Of these, cyclohexyl methacrylate is preferably employed.

  Furthermore, the acrylic copolymer (component (A)) in the present invention preferably uses the component (A-4) represented by the formula (5) for the purpose of further improving the weather resistance. When the component (A-4) is used, the component (A) is 50 mol% or more of the repeating unit (A-1), 1 to 15 mol% of the repeating unit (A-2), -3) an acrylic copolymer containing 1 to 35 mol% of repeating units of the component and (A-4) 0.1 to 10 mol% of repeating units represented by the formula (5), wherein the acrylic copolymer In 100 mol% of all repeating units of the coal, the total of repeating units of the components (A-1) to (A-4) is at least 70 mol%, preferably at least 80 mol%, more preferably at least 90 mol%. A polymer is desirable. By including the repeating unit represented by the formula (5), radical scavenging ability can be imparted, and weather resistance can be further improved. The ratio of the repeating unit represented by the formula (5) is more preferably in the range of 1 to 8 mol% in 100 mol% of all repeating units of the acrylic copolymer. If it exceeds 10 mol%, the adhesion to the substrate or the second layer tends to be lowered.

  The repeating unit represented by the formula (5) can be introduced by copolymerizing a corresponding acrylate and / or methacrylate monomer, and the corresponding monomer is 2,2,6,6-tetramethyl-4-piperidyl methacrylate. 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 1-ethyl-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1-propyl-2,2,6,6- Tetramethyl-4-piperidyl methacrylate, 1-t-butyl-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1-cyclohexyl-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1- (4-methylcyclohexyl) -2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1 t-octyl-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1-decyl-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1-dodecyl-2,2,6 6-tetramethyl-4-piperidyl methacrylate, 1-methoxy-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1-ethoxy-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1-propoxy-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1-t-butoxy-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1-cyclohexyloxy-2,2 , 6,6-tetramethyl-4-piperidyl methacrylate, 1- (4-methylcyclohexyloxy) -2,2,6,6-the Lamethyl-4-piperidyl methacrylate, 1-octoxy-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1-t-octoxy-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1 -Decyloxy-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1-dodecyloxy-2,2,6,6-tetramethyl-4-piperidyl methacrylate, etc., which may be used alone or in combination of two or more May be used in combination.

  The acrylic copolymer having a hydroxy group containing the repeating units (A-1) to (A-4) (component (A)) may further contain other repeating units for imparting functionality or the like. Good. The other repeating unit is preferably in the range of 30 mol% or less, more preferably in the range of 20 mol% or less, particularly preferably 10 mol% or less, based on 100 mol% of all repeating units of the acrylic copolymer of component (A). Range.

  Other repeating units can be introduced by copolymerizing vinyl monomers copolymerizable with acrylate or methacrylate monomers. Other vinyl monomers include acrylic acid, methacrylic acid, acrylic acid amide, methacrylic acid amide, methyl acrylate, ethyl acrylate, propyl acrylate, propyl methacrylate, butyl acrylate, in terms of durability such as adhesion or weather resistance. Butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl acrylate, dodecyl methacrylate, 2- (2′-hydroxy-5′-acryloxyethylphenyl) benzotriazole, 2- (2′-hydroxy-5′-acrylic) Loxyethoxyphenyl) benzotriazole, 2- (2′-hydroxy-5′-acryloxypropylphenyl) benzotriazole, 2- (2′-hydroxy-5′-acryloxypropoxyphene) ) 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′- Droxy-5′-methacryloxyethoxyphenyl) benzotriazole, 2- (2′-hydroxy-5′-methacryloxypropylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methacryloxypropoxyphenyl) benzotriazole 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-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 Examples include '-dihydroxy-4- (methacryloxyethoxy) benzophenone and 2-hydroxy-4- (methacryloyloxyethyl) benzophenone, and these can be used alone or in combination of two or more. Moreover, it is not necessary to use an acrylic resin having a single composition alone, and two or more kinds of acrylic resins may be mixed and used.

  The molecular weight of the acrylic copolymer as the component (A) 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 copolymer having such a molecular weight range is preferable because it exhibits sufficient performance such as adhesion and strength as the first layer.

(About the blocked polyisocyanate compound of component (B))
Examples of the blocked polyisocyanate compound of the component (B) include oximes such as acetooxime and methyl ethyl ketoxime on the isocyanate group of the polyisocyanate compound, dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone Blocking typified by active methylene compounds such as methanol, ethanol, 2-propanol, n-butanol, sec-butanol, alcohols such as 2-ethyl-1-hexanol, and phenols such as phenol, cresol, and ethylphenol And a blocked isocyanate compound having a function of producing a polyisocyanate compound by thermal decomposition, which is obtained by adding an agent.

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

  Examples of 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.

  Since the blocked isocyanate is the first isocyanate group to form during the thermal curing reaction, it is excellent in storage stability of the coating composition, and the isocyanate group is hardly consumed in the side reaction, and is stable and hardly affected by the coating environment. A cured film having physical properties can be obtained. These blocked isocyanates can be used alone or in admixture of two or more.

  Of the blocked isocyanates, blocked aliphatic and / or alicyclic polyisocyanate compounds are particularly preferable because of excellent weather resistance. The blocked aliphatic and / or alicyclic polyisocyanate compound is an adduct type obtained by reacting a hydroxy compound having 2 to 4 hydroxy groups with an aliphatic and / or alicyclic diisocyanate compound. Particularly preferred are adduct-type polyisocyanate compounds obtained by blocking polyisocyanate compounds with a blocking agent, isocyanurate-type polyisocyanate compounds derived from aliphatic and / or alicyclic diisocyanate compounds, and isocyanurate-type polyisocyanate compounds blocked with a blocking agent. Preferably used. Among them, aliphatic diisocyanate compounds and / or alicyclic diisocyanate compounds having 4 to 20 carbon atoms are preferable, and those having 4 to 15 carbon atoms are more preferable. By setting the number of carbon atoms of the isocyanate compound in such a range, a coating film having excellent durability is formed.

  Moreover, in the blocked polyisocyanate compound, the content ratio of the isocyanate group to be generated is 5.5 to 50% by weight, preferably 6.0 to 40% by weight, and most preferably 6.5 to 30% by weight. When the isocyanate group content is less than 5.5% by weight, the blended amount of the blocked polyisocyanate compound relative to the acrylic resin increases, and the adhesion to the plastic substrate becomes poor. If the isocyanate group content exceeds 50% 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 environmental changes is impaired. This is not preferable.

  The mixing ratio of the acrylic copolymer having a hydroxy group of the component (A) and the blocked polyisocyanate compound of the component (B) is 1 equivalent of the hydroxy group of the acrylic copolymer of the component (A). (B) It mixes so that the isocyanate group which the (B) component produces | generates will be 0.8-1.5 equivalent, Preferably it is 0.8-1.3 equivalent, Most preferably, it is 0.9-1.2 equivalent. By preparing such a composition, the layer made of such an acrylic copolymer can maintain good adhesion to the polycarbonate base material and the second-layer organosiloxane resin thermosetting layer, Since it has a crosslink density, it is difficult to cause a decrease in crosslink density due to ultraviolet rays, water, or oxygen, and it can maintain long-term adhesion, environmental changes and durability under high temperature environments, and has excellent weather resistance.

  When the isocyanate group is less than 0.8 equivalent, the crosslinking is insufficient, resulting in insufficient durability in a high temperature environment, and the unreacted hydroxy group has a high affinity with water molecules. As a result, the weather resistance and hot water resistance deteriorate. When there are more than 1.5 equivalents of isocyanate groups, the coating layer has a very high cross-linking density with allophanate bonds, it becomes a hard and brittle layer, the followability to environmental changes becomes worse, and the adhesiveness to environmental changes is improved. Inferior and undesirable.

(About curing catalyst of component (C))
In the present invention, in order to promote dissociation of the blocking agent of the blocked polyisocyanate compound of component (B) and the urethanization reaction between the regenerated isocyanate group and the hydroxy group of the acrylic copolymer of component (A), ( C) Component curing catalyst is used. Examples of the curing catalyst include organic tin compounds, quaternary ammonium salt compounds, tertiary amine compounds, and the like, and these compounds are used alone or in admixture of two or more. Among these curing catalysts, organotin compounds are preferably used, and particularly, organotin compounds represented by the following formula (6) are preferably used.

ここで、Ｒ^８は炭素数が１〜８個の炭化水素基、好ましくは炭素数が１〜８個のアルキル基、より好ましくは炭素数が４〜８個のアルキル基である。Ｒ^９は炭素数が１〜１７個の置換あるいは非置換の炭化水素基、好ましくは炭素数が１〜１７個の置換あるいは非置換のアルキル基である。置換基としては、炭素数１〜４のアルキル基が好ましい。ｍは０〜３の整数である。

Here, R ⁸ is a hydrocarbon group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 4 to 8 carbon atoms. R ⁹ is a substituted or unsubstituted hydrocarbon group having 1 to 17 carbon atoms, preferably a substituted or unsubstituted alkyl group having 1 to 17 carbon atoms. As the substituent, an alkyl group having 1 to 4 carbon atoms is preferable. m is an integer of 0-3.

  Typical examples of such organotin compounds include monobutyltin tris (2-ethylhexanoate), dimethyltin dineodecanoate, dibutyltin bis (2-ethylhexanoate), monobutyltin tris ( n-butylpropionate), dibutyltin dilaurate, monohexyltin trioctoate, dihexyltin dioctoate, trihexyltin monooctoate, monohexyltin tris (methyl maleate), dioctyltin diacetate, trioctyltin monoacetate , Dioctyltin bis (methyl maleate), monooctyltin tris (methylpropionate), dioctyltin dipropionate), trioctyltin monopropionate, monooctyltin trioctate, dioctyltin diocteo , Tri-octyl tin mono octoate, and the like. These compounds may be used alone or in admixture of two or more.

  Representative examples of the quaternary ammonium salt compounds include, for example, 2-hydroxyethyl tri-n-butylammonium 2,2-dimethylpropionate, 2-hydroxyethyl tri-n-butylammonium 2,2-dimethyl. Examples include butanoate, 2-hydroxypropyl · tri-n-butylammonium · 2,2-dimethylpropionate, and 2-hydroxypropyl · tri-n-butylammonium · 2,2-dimethylbutanoate. Examples of tertiary amines include dimethylethanolamine and triethylenediamine. These quaternary ammonium salt compounds and tertiary amine compounds are preferably used in combination with the above organotin compounds.

  The curing catalyst for component (C) is in the range of 0.001 to 0.4 parts by weight, preferably 0.002 to 0.3 parts by weight, based on 100 parts by weight of the total of components (A) and (B). used. If the amount of the curing catalyst is less than 0.001 part by weight, the effect of promoting the crosslinking reaction cannot be obtained, and if it exceeds 0.4 part by weight, the adhesion between the acrylic resin layer and the second layer is undesirably lowered.

((D) Component UV absorber)
Examples of the component (D) UV absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2'-dihydroxy-4,4'- Benzophenones such as dimethoxybenzophenone, 2- (5'-methyl-2'-hydroxyphenyl) benzotriazole, 2- (3'-t-butyl-5'-methyl-2'-hydroxyphenyl) benzotriazole, 2- Benzotriazoles such as (3 ', 5'-di-t-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl-2- Cyanoacrylates such as cyano-3,3-diphenylacrylate, phenyl salici , Salicylates such as p-octylphenyl salicylate, benzylidene malonates such as diethyl-p-methoxybenzylidene malonate, bis (2-ethylhexyl) benzylidene malonate, 2- (4,6-diphenyl-1,3 , 5-Triazin-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-Triazin-2-yl) -5-[(butyl) oxy] -phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) Triazines such as xyl] -phenol, copolymers of 2- (2′-hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and vinyl monomers copolymerizable with the monomers, 2- (2 Copolymer of '-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole and vinyl monomer copolymerizable with the monomer, titanium oxide, cerium oxide, zinc oxide, tin oxide, tungsten oxide, zinc sulfide And metal oxide fine particles such as cadmium sulfide.

  These agents may be used alone or in combination of two or more, and are 1 to 40 parts by weight, preferably 2 to 35 parts by weight, more preferably 100 parts by weight of the total of component (A) and component (B). 5 to 30 parts by weight are used. When the ultraviolet absorber is less than 1 part by weight, the ultraviolet ray transmittance is increased, yellowing of the base material is caused, and the adhesion is reduced, resulting in poor weather resistance. Moreover, when it exceeds 40 weight part, adhesiveness falls and it is unpreferable.

(About other components that can be used in the acrylic resin layer)
In the present invention, the acrylic resin composition containing the components (A) to (D) can further contain a silane coupling agent and / or a hydrolysis condensate of the silane coupling agent. By including such a silane coupling agent and / or a hydrolysis condensate of the silane coupling agent, the adhesion between the polycarbonate substrate and the first layer and between the first layer and the second layer is further improved, and over a long period of time. Since the adhesiveness is maintained, it is preferably used.

  Such silane coupling agents 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 , Vinyltrimethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ-ureidopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxy Silane and the like.

  The silane coupling agent and / or the hydrolysis condensate of the silane coupling agent may be used alone or in combination of two or more, and preferably 0 with respect to 100 parts by weight of the total of component (A) and component (B). 0.1 to 10 parts by weight, more preferably 0.2 to 8 parts by weight.

  In the present invention, a light stabilizer can be further added to the acrylic resin composition containing the components (A) to (D). 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 light stabilizers may be used alone or in combination of two or more. The component (A) and the component (B) are preferably used in an amount of 0.01 to 50 parts by weight, more preferably 0.05 to 10 parts by weight, based on a total of 100 parts by weight.

(About the thickness of the acrylic resin layer)
1-15 micrometers is preferable and, as for the film thickness of the acrylic resin layer formed by thermosetting the acrylic resin composition for coating containing the said (A) component-(D) component, 2-10 micrometers is more preferable.

  When the film thickness is less than 1 μm, the transmittance of ultraviolet rays increases, yellowing of the plastic base material occurs, or the adhesiveness is lowered, so that the weather resistance becomes poor. When the film thickness exceeds 15 μm, the internal stress is increased and the crosslinking reaction does not proceed sufficiently at the time of thermosetting, so that the coating layer has poor durability under a high temperature environment. In addition, the solvent used for dissolving the acrylic resin composition for coating containing the components (A) to (D) described later is insufficiently evaporated, the solvent remains in the coating film, Weather resistance will be impaired.

(About the method of forming the acrylic resin layer)
In the present invention, an acrylic resin layer (first layer) is formed by reacting an acrylic resin composition containing the components (A) to (D) with a polycarbonate as a base material or dissolving the polycarbonate. This is dissolved in a non-volatile volatile solvent, and this coating acrylic resin paint is applied to the polycarbonate substrate surface. Then, the solvent is removed by heating and the like, and further heated to generate hydroxyl groups and isocyanate groups formed by heating. It is formed by reacting and crosslinking.

  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.

  In the acrylic resin coating material for coating, the concentration of the acrylic resin composition (solid component) containing the components (A) to (D) is preferably 1 to 50% by weight, more preferably 3 to 30% by weight.

  Application of the acrylic resin coating material for coating to a plastic substrate is performed by applying 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 to the shape of the substrate to be coated. It can be appropriately selected depending on the case. The base material coated with such an acrylic resin paint 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 heat-curing is preferably performed at a high temperature within a range where there is no problem in the heat resistance of the substrate because curing can be completed more quickly. 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.

  Heat curing 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. Thus, a cross-linkable group is cross-linked, and a polycarbonate base material on which the acrylic resin layer is laminated as the first layer is obtained. 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.

  By forming the acrylic resin layer (first layer) by thermosetting the acrylic resin composition, the adhesion between the second layer and the polycarbonate base material is improved, and the polycarbonate molding is excellent in wear resistance and weather resistance. You can get a body.

(Second layer; thermosetting coating layer of organosiloxane resin composition)
In the present invention, the second layer laminated on the first layer comprises an organosiloxane resin composition containing (E) colloidal silica and (F) a hydrolytic condensate of alkoxysilane represented by the formula (3). It is a coating layer formed by thermosetting a product. Such an organosiloxane resin composition is composed of an organosiloxane resin component and, if desired, other components such as a curing catalyst, and the organosiloxane resin component substantially comprises the above component (E) and the above component (F).

  The second layer is preferably formed using a coating paint comprising an organosiloxane resin component (solid content) comprising the colloidal silica and alkoxysilane hydrolyzed condensate, an acid, a curing catalyst, and a solvent.

(About the colloidal silica of (E) component)
As the colloidal silica as the component (E), silica fine particles having a diameter of preferably 5 to 200 nm, more preferably 5 to 40 nm are dispersed in water or an organic solvent in a colloidal form.

  As such colloidal silica, specifically, as a product dispersed in an acidic aqueous solution, Snowtex O of Nissan Chemical Industry Co., Ltd., Cataloid SN35 of Catalytic Chemical Industry Co., Ltd., a product dispersed in a basic aqueous solution. 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 and the like.

  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, a large number of hydroxyl groups exist on the surface of the silica fine particles, which are firmly bonded to the alkoxysilane hydrolyzed condensate, so that a plastic molded article with higher wear resistance can be obtained. Conceivable. The water-dispersed colloidal silica can be used in either an acidic aqueous dispersion type or a basic aqueous dispersion type. However, the aqueous dispersion type colloidal silica is acidic in terms of diversity of selection of curing catalyst, appropriate hydrolysis of trialkoxysilane, and realization of a condensed state. An aqueous dispersion type colloidal silica is preferably used.

(About the hydrolysis condensate of alkoxysilane as component (F))
The hydrolyzed condensate of alkoxysilane which is the component (F) of the present invention is a product obtained by subjecting the alkoxysilane of formula (3) to a hydrolytic condensation reaction.

  Specific examples of the alkoxysilane include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, methyltrimethoxysilane, methyltrimethoxysilane. Ethoxysilane, ethyltrimethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycine Sidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl)- γ-aminopropyltriethoxysilane, dimethyldimethoxysilane, vinylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, etc. However, alkyltrialkoxysilane is preferable, and methyltrimethoxysilane and methyltriethoxysilane are particularly preferable. These can be used alone or in combination. Furthermore, in order to impart flexibility to the cured film depending on the application, it is also preferable to use a mixture of bifunctional alkoxysilanes such as dimethyldimethoxysilane.

  Moreover, in order to obtain the coating composition which forms the coating layer excellent in especially abrasion resistance, it is preferable that 70 to 100 weight% in alkoxysilane is methyl trialkoxysilane.

  The component (F) is a mixture such as a product obtained by hydrolyzing part or all of the alkoxysilane and a condensate obtained by subjecting part or all of the hydrolyzate to a condensation reaction. These components can be obtained by a sol-gel reaction. It is what

(Regarding organosiloxane resin composition containing component (E) and component (F))
The organosiloxane resin composition containing the component (E) and the component (F) can be prepared through the following processes, and it is preferable to employ a coating layer that has no precipitation and is more excellent in wear resistance. Is done.

  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 of water is used per 1 equivalent of alkoxysilane.

  The hydrolysis-condensation reaction of alkoxysilane needs to be performed under acidic conditions, and an acid is generally used as a hydrolysis agent in order to perform hydrolysis under such conditions. 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. 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. Examples thereof include organic acids such as acids, and organic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, and maleic acid are preferable, and acetic acid is particularly preferable from the viewpoint of easy control of pH.

  When an inorganic acid is used as such an acid, it is usually used in a concentration of 0.0001 to 2 N, preferably 0.001 to 0.1 N, and when an organic acid is used, it is usually based on 100 parts by weight of alkoxysilane. It is used in the range of 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 generally determined because they vary 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 70 ° C. The reaction time is 1 hour to several days.

In the present invention, the mixing ratio of the (E) component and the (F) component in the organosiloxane resin composition is the stability of the organosiloxane resin composition, the transparency of the resulting cured film, the wear resistance, the scratch resistance, and the adhesion. When the total of the (E) component and the (F) component is 100% by weight, the preferable mixing ratio of these two components is that the (E) component is 10 to 60% by weight. , (F) component is 40 to 90 wt% in terms of ^{_{R 3 m R 4 n SiO (}} 4-m-n) / 2, and more preferably component (E) is 10 to 40 wt%, (F ) component is 60 to 90 wt% in terms of ^{_{R 3 m R 4 n SiO (}} 4-m-n) / 2.

  The organosiloxane resin composition used in the present invention preferably further contains a curing catalyst. Examples of the curing catalyst include lithium salts of aliphatic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, tartaric acid, and succinic acid, alkali metal salts such as sodium salt and potassium salt, benzyltrimethylammonium salt, choline salt, Quaternary ammonium salts such as tetramethylammonium salt and tetraethylammonium salt can be mentioned. Specifically, sodium acetate, potassium acetate, choline acetate and benzyltrimethylammonium acetate are preferably used. The curing catalyst is preferably used in an amount of 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total of the component (E) and the component (F).

  The weather resistance can be further enhanced by adding the above-described ultraviolet absorber to the organosiloxane resin composition used in the present invention. The ultraviolet absorber is preferably used in an amount of 0.1 to 6.0 parts by weight, more preferably 0.2 to 5.0 parts by weight, based on 100 parts by weight of the total of the components (E) and (F).

(About the formation method of the thermosetting coating film layer of organosiloxane resin composition)
As a method for forming the thermosetting coating film layer (second layer) of the organosiloxane resin composition, an organosiloxane resin composition containing the component (E) and the component (F) is dissolved in a solvent, and this coating is performed. It is formed by applying the organosiloxane resin paint for coating on the first layer formed on the polycarbonate substrate and then heat-curing.

  As such a solvent, it is necessary that the organosiloxane resin composition is stably dissolved. For this purpose, it is desirable to use a solvent in which at least 20% by weight, preferably 50% by weight or more is alcohol.

  Specific examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-ethoxyethanol, and 4-methyl-2-pentanol. 2-butoxyethanol and the like. Among them, a low-boiling alcohol having 1 to 4 carbon atoms is preferable, and 2-propanol is particularly preferable in terms of solubility, stability, and coatability.

  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 coating material for coating 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 usable solvents must be miscible with water / alcohol, such as ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and ethers such as tetrahydrofuran, 1,4-dioxane, and 1,2-dimethoxyethane. , Esters such as ethyl acetate, n-butyl acetate, isobutyl acetate and ethoxyethyl acetate.

  The amount of the solvent used is preferably 50 to 900 parts by weight, more preferably 150 to 700 parts by weight with respect to 100 parts by weight as the total of the component (E) and the component (F).

  The coating organosiloxane resin coating is preferably adjusted to a pH of 3.0 to 6.0, more preferably 4.0 to 5.5 by adjusting the contents of the acid and the curing catalyst. By adjusting the pH within this range, gelation of the organosiloxane resin coating at room temperature can be prevented, and storage stability can be increased. The organosiloxane resin paint usually becomes a stable paint by further aging for several hours to several days.

  The formation of the thermosetting coating layer (second layer) of the organosiloxane resin composition is preferably performed continuously following the formation of the first layer.

  As a coating method for applying the coating organosiloxane resin paint, 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, the shape of the substrate to be coated It can be appropriately selected depending on the situation. The substrate coated with such an organosiloxane resin composition is usually cured by heating after drying and removing the solvent at a temperature from room temperature to a temperature lower than the heat distortion temperature of the substrate. The 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. At normal temperature, thermosetting does not proceed and a cured film cannot be obtained. This means that the organosiloxane resin composition in the coating organosiloxane resin coating is partially condensed. In the process of thermosetting, the remaining Si—OH undergoes a condensation reaction to form a Si—O—Si bond, resulting in a coat layer with excellent wear resistance.

  The thermosetting is preferably in the range of 50 ° C. to 200 ° C., more preferably in the range of 80 ° C. to 160 ° C., further preferably in the range of 100 ° C. to 140 ° C., preferably 10 minutes to 4 hours, more preferably 20 minutes to Heat curing for 3 hours, more preferably 30 minutes to 2 hours.

(About film thickness of thermosetting coating layer of organosiloxane resin composition)
The thickness of the thermosetting coating film layer (second layer) of the organosiloxane resin composition is preferably 2 to 10 μm, more preferably 3 to 8 μm. If the thickness of the coating layer is within such a range, cracks may occur in the coating layer due to the stress generated during thermosetting, or the adhesion between the coating layer and the acrylic resin layer (first layer) may be reduced. Thus, a coating layer having sufficient wear resistance as an object of the present invention can be obtained.

(About components that can be added to the first layer and the second layer)
In the present invention, a known leveling agent can be blended in the coating composition for the first layer and the second layer for the purpose of improving the coatability and the smoothness of the resulting coating film.

  Such leveling agents include silicone compounds SH200-100cs, SH28PA, SH29PA, SH30PA, Toray Dow Corning Silicone Co., Ltd., ST83PA, ST80PA, ST97PA, ST86PA, SH21PA, Shin-Etsu Chemical Co., Ltd. silicone compounds KP321, KP322. , KP323, KP324, KP326, KP340, KP341, fluorinated surfactants F-179, F-812A, F-815 from Dainippon Ink & Chemicals, Inc., and the like. These leveling agents may be used alone or in combination of two or more, and are preferably 0.0001 to 2.0 parts by weight, more preferably 0.0005 to 1.0 parts by weight with respect to 100 parts by weight of the coating resin. Used part.

  A dye, pigment, filler, or the like may be added to the coating composition for the first layer and the second layer as long as the object of the present invention is not impaired. An acrylic resin can be added for the purpose of improving flexibility.

(About colored layer)
As the resin component for forming the colored layer used in the present invention, it is sufficient that adhesion with the silicone hard coat layer is obtained, and urethane resin, epoxy resin, silicone-modified acrylic resin, polyester resin, and the like can be used. In order to obtain a high degree of adhesion with a silicone hard coat, an epoxy resin is preferable. For example, MAB series manufactured by Teikoku Ink Manufacturing Co., Ltd. as an ink of urethane resin, for example, PS series manufactured by Teikoku Ink Manufacturing Co., Ltd. as an ink of epoxy resin, for example, Silicone Wide manufactured by Toupe Co., Ltd. as a silicone-modified acrylic resin ink Examples of polyester resin ink include IPX series manufactured by Teikoku Ink Mfg. Co., Ltd.

There is no restriction | limiting in particular about the method of forming a colored layer in this invention, Various methods, such as screen printing, gravure printing, offset printing, roller printing, spray coating, and brush coating, are applicable. The curing conditions are not particularly limited and may be either room temperature drying or heat drying. However, in order to accelerate the progress of the curing reaction, it is preferable to perform heat drying at 80 to 120 ° C. for 30 minutes to 1 hour.
The coating thickness of the colored layer is preferably in the range of 5 to 100 μm, more preferably in the range of 10 to 80 μm.

(About adhesive)
The adhesive used in the present invention is an adhesive generally used when joining a metal frame body of a vehicle window material and a transparent resin plate, and is made of an adhesive made of urethane resin or a polysulfide resin. An adhesive or the like can also be applied, and an adhesive made of a urethane resin is preferable from the viewpoint of adhesion. It is preferable that a primer layer of a silane resin or a urethane resin is interposed between the coloring layer and the adhesive. Examples of the adhesive made of urethane resin include Sunrise MSI SR Seal U90 and Sunstar Penguin Seal # 560. As a primer for each adhesive, there are Primer # 35 manufactured by Sunrise MSI and GP-402 manufactured by Sunstar.

  The thickness of the adhesive layer is preferably in the range of 3 to 8 mm, more preferably in the range of 4 to 6 mm. When the thickness of the adhesive layer is in the range of 3 to 8 mm, practically sufficient adhesive strength can be obtained, which is economically advantageous.

(About metal frame)
In the present invention, the metal frame joined to the transparent resin laminate means, for example, a metal frame formed on a window glass or sunroof of an automobile window, a window glass (skylight) of a construction machine, or other vehicle window glass. Therefore, it joins via the adhesive agent between the part in which the colored layer of the said transparent resin laminated body was formed, and a metal frame. In addition, you may use the metal frame painted with the melamine resin etc.

(About polycarbonate substrate)
The polycarbonate substrate used in the present invention is a polycarbonate resin substrate having a haze value of 10% or less.

  The polycarbonate resin used in the present invention is, for example, 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 referred to as bisphenol A), 2,2-bis (3-methyl-4-hydroxyphenyl) propane, Bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy) Phenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 9,9-bis {(4-hydroxy-3-methyl) phenyl} fluorene, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) 3,3,5-trimethylcyclohexane and α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, and the like. But bisphenol A is preferred. 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 of distilling alcohol or phenols to be produced by stirring while heating a predetermined proportion of a dihydric phenol component and diphenyl carbonate in an inert gas atmosphere. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 350 ° 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

  Such polycarbonate resins include stabilizers such as phosphites, phosphates, and phosphonates as necessary, tetrabromobisphenol A, low molecular weight polycarbonate of tetrabromobisphenol A, flame retardants such as decabromodiphenol, and colorants. A lubricant or the like can be added.

(About the adhesive body of transparent resin laminate and metal frame)
The adhesive body of the transparent resin laminate having a protected surface and a metal frame according to the present invention is an acrylic obtained by thermally curing an acrylic resin composition containing an acrylic copolymer mainly composed of repeating units composed of alkyl methacrylate. By having a coating layer (second layer) formed by thermosetting an organosiloxane resin composition containing a hydrolyzed condensate of colloidal silica and alkoxysilane on the resin layer (first layer) and the first layer Thus, the adhesive body has a high level of weather resistance, wear resistance, hot water resistance, durability against environmental changes, and sufficient durability in a high temperature environment. The acrylic resin layer (first layer) and the organosiloxane resin layer (second layer) are preferably laminated on both sides of the polycarbonate substrate. When the adhesive body of the transparent resin laminate and the metal frame is used as a window glass and the metal frame side is attached to the inside of the vehicle, it is preferable because it has excellent wear resistance and weather resistance on the outside of the vehicle.

  Adhesives of such transparent resin laminates and metal frames are used for aircraft, vehicle, automobile window glass, sunroof, construction machine window glass, building, house, greenhouse window glass, garage, arcade roof, sound insulation wall, It can be suitably used for a lens of a traffic light, a curve mirror, a windshield of a motorcycle, other various sheets, a film, and the like.

  The bonded body of the transparent resin laminate having the colored layer of the present invention and the metal frame has good appearance, hot water resistance, adhesion, and abrasion resistance, has a high level of weather resistance, changes in the environment and high temperature environment Adhesives that are excellent in durability and that are protected on both sides are particularly suitable for automotive windowpanes, sunroofs, windowpanes for construction machinery, etc., and their industrial effects are exceptional.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to this from the first. In addition, evaluation of the storage stability of the obtained acrylic resin paint and evaluation of the polycarbonate molded body were performed by the following methods. Moreover, the part and% in an Example mean a weight part and weight%.

(A) Performance Evaluation of Acrylic Resin Paint (A-1) Storage Stability of Acrylic Resin Paint; After the acrylic resin paint was stored at 23 ° C. for 3 months, the state of the paint was visually evaluated. In addition, the thing in which the gelatinization of a coating material is not seen was made favorable.

(B) Performance evaluation of hard coat layer (B-1) Appearance evaluation: The appearance (existence of foreign matter) of the double-sided coat layer of the test piece and the presence or absence of cracks (cracks) were visually confirmed.
(B-2) Adhesiveness: Nichiban adhesive tape (trade name “Serotape (registered trademark)”) was pressure-bonded to the coat layer of one side of the double-sided coat layer by making 100 grids at 1 mm intervals with a cutter knife, Evaluation was based on the number of grids that were strongly peeled off vertically and remained on the substrate.
(B-3) Abrasion resistance: In accordance with JIS K6735, on one side of the double-sided coating layer, a CS-10F wear wheel manufactured by Calibrase was used, and a Taber abrasion test was performed at 1000 rpm with a load of 500 g. The difference ΔH between the haze and the haze before the Taber abrasion test was measured and evaluated. However, the wear wheel was refaced at 25 revolutions using abrasive paper S-11 instead of abrasive paper AA-400.
(Haze = Td / Tt × 100, Td: scattered light transmittance, Tt: total light transmittance)
(B-4) Weather resistance: UV irradiation intensity 180 W / m ² , black panel temperature 63 ° C. using Suga Test Instruments Co., Ltd. Super Xenon Weather Meter SX-75 without changing the ultraviolet irradiation surface of the test piece. , After exposure test for 3000 hours under rainfall conditions for 18 minutes in 120 minutes, the test piece was taken out, and the surface was lightly rubbed and washed with a sponge soaked with a neutral detergent, then the yellowness change (ΔYI) and haze before and after the test The change (ΔH) was evaluated. During the exposure test, the test piece was taken out every 500 hours, and the surface was lightly rubbed and washed with a sponge soaked with a neutral detergent. The yellowness (YI) measurement was performed using a spectroscopic colorimeter SE-2000 manufactured by Nippon Denshoku Co., Ltd.

(C) Performance evaluation of colored layer (C-1) Appearance evaluation: The appearance of the colored layer of the test piece (existence of foreign matters) and the presence or absence of cracks (cracks) were visually confirmed.
(C-2) Adhesiveness: 100 colored grids with a 1 mm interval were made on the colored layer with a cutter knife, Nichiban adhesive tape (trade name “Sero Tape (registered trademark)”) was pressure-bonded, and peeled strongly and vertically. Evaluation was based on the number of grids remaining on the wood.
(C-3) 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.
(C-4) High temperature environmental durability: The test piece was left under a 100 ° C. environment for 1000 hours, and the test piece was taken out to evaluate the appearance and adhesion.
(C-5) 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% at 50 ° C. A cycle that was allowed to stand in an RH environment for 1 hour was defined as 1 cycle. After repeating such a cycle 30 times, a test piece was taken out to evaluate the appearance and adhesion.

(D) Performance Evaluation of Adhesive Layer (D-1) Adhesive Strength: An adhesive body (test piece) having a configuration shown in FIG. 2 was prepared, and the center of the polycarbonate substrate was 70 mm / min. The load at the time when peeling was generated by applying a load at a speed of was measured.

(Synthesis of acrylic copolymer solutions (A) to (E))
[Reference Example 1]
A flask equipped with a reflux condenser and a stirring device, and 102.7 parts of ethyl methacrylate (hereinafter abbreviated as EMA), 13.0 parts of 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA), methyl isobutyl ketone ( 115.7 parts (hereinafter abbreviated as MIBK) and 57.9 parts of 2-butanol (hereinafter abbreviated as 2-BuOH) were added and mixed. The mixture was deoxygenated by bubbling nitrogen gas for 15 minutes, then heated to 70 ° C. under a nitrogen gas stream, 0.33 parts of azobisisobutyronitrile (hereinafter abbreviated as AIBN) was added, and nitrogen gas was added. The reaction was conducted with stirring at 70 ° C. for 5 hours in an air stream. Further, 0.08 part of AIBN was added, the temperature was raised to 80 ° C., and the mixture was reacted for 3 hours to obtain an acrylic copolymer solution (A) having a nonvolatile content concentration of 39.6%. The weight average molecular weight of the acrylic copolymer was 115000 in terms of polystyrene from the measurement of GPC (column: Shodex GPCA-804, eluent: THF).

[Reference Example 2]
In a flask equipped with a reflux condenser and a stirrer and purged with nitrogen, 79.9 parts of EMA, 33.6 parts of cyclohexyl methacrylate (hereinafter abbreviated as CHMA), 13.0 parts of HEMA, 126.6 parts of MIBK, and 2-BuOH 63.3 parts was added and mixed. The mixture was deoxygenated by bubbling nitrogen gas for 15 minutes, then heated to 70 ° C. under a nitrogen gas stream, added with 0.33 parts of AIBN, and reacted in the nitrogen gas stream at 70 ° C. with stirring for 5 hours. I let you. Further, 0.08 part of AIBN was added, the temperature was raised to 80 ° C., and the mixture was reacted for 3 hours to obtain an acrylic copolymer solution (B) having a nonvolatile content concentration of 39.6%. The weight average molecular weight of the acrylic copolymer was 125000 in terms of polystyrene from the measurement of GPC (column; Shodex GPCA-804, eluent: THF).

[Reference Example 3]
In a flask equipped with a reflux condenser and a stirrer and purged with nitrogen, 74.2 parts of EMA, 33.6 parts of CHMA, 13.0 parts of HEMA, LA-82 (a hindered amine light-stabilizing group manufactured by Asahi Denka Kogyo Co., Ltd.) Containing methacrylate; 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, a compound in which R ⁷ is a methyl group in the formula (5)) 12.0 parts, MIBK 132.8 parts and 2-BuOH 66 4 parts were added and mixed. The mixture was deoxygenated by bubbling nitrogen gas for 15 minutes, then heated to 70 ° C. under a nitrogen gas stream, 0.33 parts of AIBN was added, and the mixture was reacted in the nitrogen gas stream at 70 ° C. with stirring for 5 hours. It was. Further, 0.08 part of AIBN was added, the temperature was raised to 80 ° C., and the mixture was reacted for 3 hours to obtain an acrylic copolymer solution (C) having a nonvolatile content concentration of 39.7%. The weight average molecular weight of the acrylic copolymer was 115000 in terms of polystyrene from the measurement of GPC (column: Shodex GPCA-804, eluent: THF).

[Reference Example 4]
In a flask equipped with a reflux condenser and a stirrer and purged with nitrogen, 51.4 parts of EMA, 75.7 parts of CHMA, 13.0 parts of HEMA, 140.1 parts of MIBK, and 70.0 parts of 2-BuOH were added and mixed. . The mixture was deoxygenated by bubbling nitrogen gas for 15 minutes, then heated to 70 ° C. under a nitrogen gas stream, 0.33 parts of AIBN was added, and the mixture was reacted in the nitrogen gas stream at 70 ° C. with stirring for 5 hours. It was. Further, 0.08 part of AIBN was added, the temperature was raised to 80 ° C., and the mixture was reacted for 3 hours to obtain an acrylic copolymer solution (D) having a nonvolatile content concentration of 39.7%. The weight average molecular weight of the acrylic copolymer was 135000 in terms of polystyrene from the measurement of GPC (column; Shodex GPCA-804, eluent: THF).

[Reference Example 5]
EMA 91.3 parts, HEMA 26.0 parts, MIBK 117.3 parts and 2-BuOH 58.7 parts were added and mixed in a flask equipped with a reflux condenser and a stirrer and purged with nitrogen. The mixture was deoxygenated by bubbling nitrogen gas for 15 minutes, then heated to 70 ° C. under a nitrogen gas stream, 0.33 parts of AIBN was added, and the mixture was reacted in the nitrogen gas stream at 70 ° C. with stirring for 5 hours. It was. Further, 0.08 part of AIBN was added, the temperature was raised to 80 ° C., and the mixture was reacted for 3 hours to obtain an acrylic copolymer solution (E) having a nonvolatile content concentration of 39.7%. The weight average molecular weight of the acrylic copolymer was 115000 in terms of polystyrene from the measurement of GPC (column: Shodex GPCA-804, eluent: THF).

In Table 1, each symbol indicates the following.
EMA; ethyl methacrylate CHMA; cyclohexyl methacrylate HEMA; 2-hydroxyethyl methacrylate LA-82; 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, R ^{7 as} a raw material of the repeating unit of the formula (5) Is a methyl group monomer (Adekastab LA-82 manufactured by Asahi Denka Kogyo Co., Ltd .; hindered amine light-stable group-containing methacrylate)
MIBK; methyl isobutyl ketone 2-BuOH; 2-butanol AIBN; azobisisobutyronitrile

(Preparation of acrylic resin paint)
[Reference Example 6]
To 100 parts of the acrylic copolymer solution (A), 65.1 parts of MIBK, 32.5 parts of 2-BuOH, and 105.4 parts of 1-methoxy-2-propanol were added and mixed, and 20.7 parts of Chemisorb 79, acrylic 11.6 parts of VESTANAT B1358 / 100 was added so that the isocyanate group was 1.0 equivalent with respect to 1 equivalent of hydroxy group of the acrylic copolymer in the copolymer solution (A), and monobutyltin tris ( 2-ethylhexanoate) 0.051 part, APZ-6633 (Nihon Unicar Co., Ltd. silane coupling agent hydrolysis condensate solution; solid content 5 wt%) 9.7 parts were added at 25 ° C. The mixture was stirred for 1 hour to obtain an acrylic resin paint (i-1).

[Reference Example 7]
To 100 parts of the acrylic copolymer solution (B), 67.3 parts of MIBK, 33.7 parts of 2-BuOH, and 107.6 parts of 1-methoxy-2-propanol are added and mixed, and 20.4 parts of Chemisorb 79, acrylic 10.6 parts of VESTANAT B1358 / 100 was added so that the isocyanate group was 1.0 equivalent with respect to 1 equivalent of the hydroxy group of the acrylic copolymer in the copolymer solution (B), and further dimethyltindineodecano. 0.015 parts of ate was added and stirred at 25 ° C. for 1 hour to obtain an acrylic resin paint (i-2).

[Reference Example 8]
To 100 parts of the acrylic copolymer solution (C), 63.1 parts of MIBK, 31.5 parts of 2-BuOH, and 103.3 parts of 1-methoxy-2-propanol were added and mixed. Chemisorb 79 20.3 parts, acrylic 10.1 parts of VESTANAT B1358 / 100 was added so that the isocyanate group was 1.0 equivalent with respect to 1 equivalent of the hydroxy group of the acrylic copolymer in the copolymer solution (C), and further dimethyltin dineodecano. 0.015 parts of ate, 9.5 parts of APZ-6633 (Nihon Unicar Co., Ltd. silane coupling agent hydrolysis condensate solution; solid content 5 wt%) were added and stirred at 25 ° C. for 1 hour, An acrylic resin paint (i-3) was obtained.

[Reference Example 9]
To 100 parts of the acrylic copolymer solution (B), 39.4 parts of MIBK, 19.7 parts of 2-BuOH, and 79.7 parts of 1-methoxy-2-propanol were added and mixed, and 5.3 parts of Tinuvin 400, acrylic 10.6 parts of VESTANAT B1358 / 100 was added so that the isocyanate group was 1.0 equivalent with respect to 1 equivalent of the hydroxy group of the acrylic copolymer in the copolymer solution (B), and further dimethyltindineodecano. 0.015 parts of ate, 9.5 parts of APZ-6633 (Nihon Unicar Co., Ltd. silane coupling agent hydrolysis condensate solution; solid content 5 wt%) were added and stirred at 25 ° C. for 1 hour, An acrylic resin paint (i-4) was obtained.

[Reference Example 10]
To 100 parts of the acrylic copolymer solution (D), 62.3 parts of MIBK, 31.1 parts of 2-BuOH, and 102.5 parts of 1-methoxy-2-propanol were added and mixed. Chemisorb 79 20.1 parts, acrylic 9.6 parts of VESTANAT B1358 / 100 was added so that the isocyanate group was 1.0 equivalent with respect to 1 equivalent of the hydroxy group of the acrylic copolymer in the copolymer solution (D), and monobutyltin tris ( 2-ethylhexanoate) 0.049 parts, APZ-6633 (Nihon Unicar Co., Ltd. silane coupling agent hydrolysis condensate solution; solid content 5 wt%) 9.4 parts was added and 25 ° C. Was stirred for 1 hour to obtain an acrylic resin paint (i-5).

[Reference Example 11]
To 100 parts of the acrylic copolymer solution (E), 71.0 parts of MIBK, 35.5 parts of 2-BuOH, and 111.2 parts of PMA were added and mixed, and 21.9 parts of Chemisorb 79, acrylic copolymer solution (E) 11.5 parts of VESTANAT B1358 / 100 is added so that the isocyanate group becomes 1.0 equivalent with respect to 1 equivalent of the hydroxy group of the acrylic copolymer, and 0.015 part of dimethyltindineodecanoate is further added. The mixture was stirred at 25 ° C. for 1 hour to obtain an acrylic resin paint (i-6).

In Table 2, each symbol indicates the following.
VEST: Blocked polyisocyanate compound (VESTANAT B1358 / 100, manufactured by Degussa Japan Co., Ltd., a compound obtained by blocking an adduct-type polyisocyanate compound obtained by reacting trimethylpropanol and diisocyanate with a blocking agent; content ratio of isocyanate group 12.4 % By weight, blocking agent methyl ethyl ketoxime)
DMDNT; dimethyltin dineodecanoate BTEHT; monobutyltin tris (2-ethylhexanoate)
UVA-1; 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole (Chemisorb 79 manufactured by Chemipro Kasei Co., Ltd.)
UVA-2; 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5- Triazine and 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine A mixture of about 85% of the mixture and 15% of 1-methoxy-2-propanol (Tinubin 400 manufactured by Ciba Specialty Chemicals Co., Ltd.)
APZ: solution containing 5% by weight of amino group-containing silane coupling agent hydrolysis condensate (Nihon Unicar Co., Ltd. APZ-6633)
MIBK; methyl isobutyl ketone 2-BuOH; 2-butanol PMA; 1-methoxy-2-propanol

(Preparation of organosiloxane resin composition paint)
[Reference Example 12]
1.3 parts of 1M hydrochloric acid was added to 133 parts of water-dispersed colloidal silica dispersion (Cataloid SN-35, solid content concentration: 30% by weight, manufactured by Catalytic Chemical Industry Co., Ltd.) and stirred well. The dispersion was cooled to 10 ° C., and 162 parts of methyltrimethoxysilane was added dropwise with cooling in an ice-water bath. Immediately after the addition of methyltrimethoxysilane, the temperature of the mixture started to increase due to the reaction heat, and after 5 minutes from the start of the addition, the temperature rose to 60 ° C., and then the temperature of the mixture gradually decreased due to the cooling effect. The mixture was stirred at 30 ° C. for 10 hours so that the temperature of the mixed solution reached 30 ° C., and 0.8 parts of a methanol solution having a choline concentration of 45% by weight as a curing catalyst was added thereto. 5 parts of acetic acid and 200 parts of isopropyl alcohol as a diluting solvent were mixed to obtain an organosiloxane resin composition paint (ii-1).

(About coloring ink)
Ink (iii-1): 100 parts of PS911 ink (made by Teikoku Ink Manufacturing Co., Ltd.) containing epoxy resin, 30 parts of PSG curing agent (made by Teikoku Ink Manufacturing Co., Ltd.), 3 parts of PSG reinforcing agent (Empire Ink Manufacturing Co., Ltd.) and 15 parts of solvent (Teikoku Ink Manufacturing Co., Ltd.) were added to obtain printing ink (iii-1).
Ink (iii-2): 100 parts of MAB 911 (made by Teikoku Ink Manufacturing Co., Ltd.) containing urethane resin, 5 parts of 210 curing agent (made by Teikoku Ink Manufacturing Co., Ltd.), 0.5 part of glass reinforcing agent (Teikoku Ink Co., Ltd.) (Manufactured by Manufacturing Co., Ltd.) was added to obtain printing ink (iii-2).
Ink (iii-3); Silicon Wide # 500 (made by Tope Corporation) containing silicone-modified acrylic resin
Ink (iii-4): 100 parts of IPX971 ink (made by Teikoku Ink Manufacturing Co., Ltd.) containing polyester resin, 10 parts of 240 curing agent (made by Teikoku Ink Manufacturing Co., Ltd.), 10 parts of solvent (Teikoku Ink Manufacturing Co., Ltd.) Manufactured) to obtain printing ink (iii-4).

(About adhesive layer)
Primer (iv-1); Urethane primer 35 (manufactured by Sunrise MSI)
Primer (iv-2); Urethane primer # 435-98
Adhesive (v-1); Urethane adhesive SR seal U90 (manufactured by Sunrise MSI)
Adhesive (v-2); Urethane adhesive penguin seal # 560 (manufactured by Sunstar Giken)

[Examples 1-4 , Comparative Examples 1-2, AB]
Various test pieces were prepared with the constitution of acrylic resin layer / organosiloxane layer / colored layer / adhesive layer shown in Table 3. The test piece was prepared under the condition that the acrylic resin paint obtained in Reference Examples 6 to 11 was formed on a sheet made of polycarbonate resin (hereinafter abbreviated as PC resin) having a thickness of 8 mm so that the film thickness after thermosetting was 4.0 μm. Thus, both sides were coated by a dip coating method, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 130 ° C. for 1 hour. Next, the organosiloxane resin composition paint obtained in Reference Example 12 was applied on the surface of the sheet by a dip coating method so that the film thickness after thermal curing was 4.0 μm, and the coating was allowed to stand at 25 ° C. for 20 minutes. After placement, it was thermoset at 120 ° C. for 1 hour to obtain a PC resin molded body. Screen printing was performed with the pattern shown in FIG. 1 using a 250-mesh screen on the surface of the obtained PC resin molded body, followed by drying at 80 ° C. for 30 minutes to obtain a PC resin laminate having a colored layer with a thickness of 20 μm. . The PC resin laminate and the metal frame (melamine-coated iron frame) were bonded via a urethane primer and a urethane adhesive to prepare various test pieces (see FIG. 2). At that time, the adhesive layer had a thickness of 5 mm and a width of 15 mm. Table 4 shows the evaluation results for each test piece.

FIG. 3 is a simplified plan view of a polycarbonate resin laminate having a colored layer of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a simplified plan view of a polycarbonate resin laminate having a colored layer and a metal frame and a simplified plan view and a simplified sectional view of an adhesive body of the polycarbonate resin laminate and a metal frame.

Explanation of symbols

1. 1. Colored layer Metal frame Adhesive layer

Claims (4)

A first layer made of an acrylic resin layer on at least one surface of a polycarbonate substrate, a second layer made of an organosiloxane resin layer on the first layer, and a colored layer are laminated in order on a part or all of the second layer. A transparent resin laminate having a colored layer, wherein the transparent resin laminate and the metal frame are bonded via an adhesive between the portion of the transparent resin laminate on which the colored layer is formed and the metal frame. And a metal frame,
The acrylic resin layer (first layer) is an acrylic resin layer obtained by thermally curing an acrylic resin composition containing the following components (A) to (D):
(A) component is 50 mol% or more of the repeating unit ((A-1) unit) represented by the following formula (1),

(In the formula, R ¹ is a methyl group or an ethyl group.)
1 to 15 mol% of a repeating unit represented by the following formula (2) (unit (A-2))

(Wherein R ² is an alkylene group having 2 to 5 carbon atoms, and Y is a hydrogen atom or a methyl group.)
And 1 to 35 mol% of a repeating unit represented by the following formula (4) (unit (A-3))

(Wherein R ⁶ is a cycloalkyl group, and X is a hydrogen atom or a methyl group.)
Acrylic copolymer having a total of (A-1) units to (A-3) units of at least 70 mol% in 100 mol% of all repeating units of the acrylic copolymer Coalescence,
The component (B) is a blocked polyisocyanate compound, the isocyanate group content of which is 5.5 to 50% by weight, and relative to 1 equivalent of the hydroxy group in the unit (A-2). A blocked polyisocyanate compound in an amount such that the isocyanate group is 0.8 to 1.5 equivalents,
(C) component is a 0.001-0.4 weight part curing catalyst with respect to a total of 100 weight part of (A) component and (B) component,
(D) component is 1-40 weight part ultraviolet absorber with respect to a total of 100 weight part of (A) component and (B) component,
The organosiloxane resin layer (second layer) is an organosiloxane resin layer obtained by thermally curing an organosiloxane resin composition containing the following components (E) and (F):
(E) component is colloidal silica,
Component (F) is a hydrolysis-condensation product of alkoxysilane represented by the following formula (3)

(In the formula, R ³ and R 4 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. R 5 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, It is an integer between 1 and 2.)
The component (E) is 10 to 60% by weight and the component (F) is 40 to 90% by weight in terms of R ³ _m R ⁴ _n SiO _{(4-mn) / 2.} An adhesive body of a transparent resin laminate having a colored layer and a metal frame. The component (A) is 50 mol% or more of the (A-1) unit, 1 to 15 mol% of the (A-2) unit, 1 to 35 mol% of the (A-3) unit, and the following formula (5). An acrylic copolymer containing 0.1 to 10 mol% of the repeating unit ((A-4) unit) represented by (A-1) in 100 mol% of all repeating units of the acrylic copolymer The bonded body of a transparent resin laminate and a metal frame according to claim 1, which is an acrylic copolymer having a total of units to (A-4) units of at least 70 mol%.

(Wherein R ⁷ is a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an alkoxy group having 1 to 14 carbon atoms.)   The bonded body of a transparent resin laminate and a metal frame according to claim 1, wherein the colored layer is a colored layer made of an epoxy resin.   The adhesive body of a transparent resin laminate and a metal frame according to claim 1, wherein the adhesive is an adhesive made of a urethane resin.

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