JP2008231304A - Acrylic resin composition for coating and plastic molded body using the same - Google Patents

Abstract

An acrylic resin composition for coating having excellent weather resistance and a plastic molded body using the same are provided.
(A) Acrylic ester having 1 to 60 mol% of methyl ester repeating unit ((A-1) unit), exceeding 35 mol% and 85 mol% of cycloalkyl group Repeating unit ((A-2) unit), acrylic acid ester repeating unit ((A-3) unit) having an ultraviolet absorbing group of 0.1 to 15 mol%, hydroxy group of 1 to 15 mol%, alkoxysilyl An acrylic copolymer containing an acrylate ester ((A-4) unit) having at least one selected from the group consisting of a group, a glycidyloxy group, and an isocyanate group, wherein all of the acrylic copolymers are repeated Acrylic resin composition for coating containing an acrylic copolymer in which the total of units (A-1) to (A-4) is at least 70 mol% in 100 mol% units
[Selection figure] None

Description

  The present invention relates to an acrylic resin composition for coating having excellent weather resistance and a plastic molded article using the same. More specifically, by introducing an ultraviolet-absorbing group with a specific structure into the side chain of the acrylic resin, it gives the plastic substrate excellent weather resistance and durability, and less contamination of the UV absorber during heat curing causes process contamination. A coating acrylic resin composition with excellent recoatability and storage stability, and a thermosetting coating layer of the resin composition laminated on a plastic substrate, and then thermosetting the organosiloxane resin composition of a specific composition The present invention relates to a plastic molded board having a coating layer laminated thereon.

  Plastic materials are used in a variety of applications, taking advantage of their impact resistance, light weight, and workability. In particular, transparent plastics such as acrylic resin, polycarbonate resin, and styrene resin are widely used as an alternative to glass. However, these resins are not sufficient in weather resistance and are known to be deteriorated in physical properties and appearance because they are decomposed and deteriorated in long-term outdoor use. Further, these resins have drawbacks such as poor abrasion resistance, easily scratched surfaces, and being easily attacked by solvents.

  In recent years, there has been a movement to apply organic glass based on transparent plastic to window glass, particularly automobile window glass, taking advantage of its light weight and safety. When applying a transparent plastic for such a use, the high weather resistance like a glass is requested | required. Further, it is necessary to prevent the occurrence of scratches when the wiper is operated on the front glass, and it is necessary to prevent the occurrence of scratches when the window is raised and lowered on the side window. In such applications, a high level of wear resistance is required. Furthermore, the sunroof is expected to be considerably hot under the hot summer heat, and the plastic molded body used for this application is required to have a higher durability under the changing environment and the high temperature environment.

For the purpose of improving these defects, the weather resistance, durability, and wear resistance have been improved by providing a thermosetting acrylic resin layer on the surface of a plastic substrate and then coating it with a cured siloxane film. Many proposals have been made.
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. However, in a high temperature environment, the heat of the layer formed by thermosetting the substrate and the organosiloxane resin is obtained. Depending on the difference in expansion coefficient, a layer formed by thermosetting an organosiloxane resin may be pulled to cause cracks in the coating layer, and a layer having higher durability is required.

  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.

  For the purpose of imparting weather resistance, for example, Patent Document 6 and Patent Document 7 propose to add a benzophenone ultraviolet absorber or a benzotriazole ultraviolet absorber to the thermosetting acrylic resin layer. The stability of the agent itself against ultraviolet rays is poor and sufficient weather resistance cannot be obtained. Further, when the acrylic resin layer is laminated by heat curing, there is a problem that the process is contaminated by volatilization / scattering of the ultraviolet absorber. Furthermore, when applying an organosiloxane resin composition that forms an organosiloxane resin layer on an acrylic resin, the UV absorber dissolves from the acrylic resin layer and enters the organosiloxane resin layer, impairing wear resistance and appearance. It also has problems.

For the purpose of improving this point, Patent Document 8 discloses a benzophenone-based UV absorber having a copolymerizable vinyl group and a polymer UV-absorber copolymerized with a benzotriazole-based UV absorber, and a coating agent composition using the same. However, as described above, the ultraviolet absorber has poor stability against ultraviolet rays and its weather resistance is insufficient.
In addition, triazine-based UV absorbers are known as UV absorbers with a low photodegradation rate. However, when the triazine-based UV absorber is added to a thermosetting acrylic resin layer, it can be subjected to a weather resistance test or outdoor exposure. The coating film tends to whiten, and has the disadvantages that the appearance of the plastic and the transparency of the transparent plastic are impaired.

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 Japanese Patent Laid-Open No. 11-058654 JP 11-217519 A JP 2001-139924 A

  The purpose of the present invention is to impart excellent weather resistance, abrasion resistance, adhesion, hot water resistance, etc. to the plastic substrate, and to suppress the volatilization of the UV absorber during the heat curing of the acrylic resin composition and to provide a second layer. Acrylic resin composition for coating excellent in suppression of elution of ultraviolet absorber from first layer to organosiloxane resin composition during formation, and excellent in recoatability and storage stability, and the resin composition on plastic substrate A plastic molded plate with excellent appearance, weather resistance, wear resistance, adhesion and hot water resistance is obtained by laminating a thermosetting coating layer of a product and then laminating a thermosetting coating layer of an organosiloxane resin composition of a specific composition. It is to provide.

  As a result of intensive studies to achieve this object, the inventors of the present invention contain a repeating unit composed of a cycloalkyl group-containing methacrylate in an amount of more than 35 mol% and 85 mol% or less, and a UV-absorbing group, particularly a light-absorbing group. By using an acrylic resin composition containing an acrylic copolymer having a highly stable triazine-based UV-absorbing group in the side chain, the coating film will not be whitened even in long-term weather resistance tests and outdoor exposure. I found out. In addition, an organosiloxane resin composition for imparting abrasion resistance with little volatilization of an ultraviolet absorber when a thermosetting acrylic resin coating layer is formed by applying and heat curing the acrylic resin composition to a plastic substrate. The inventors have invented an acrylic resin composition for coating that is less melted out of the UV absorber when applied and has excellent recoatability.

  Further, a thermosetting coating of an organosiloxane resin composition comprising a first layer on a plastic substrate using the acrylic resin composition for coating and further containing colloidal silica and an alkoxysilane hydrolyzed condensate as the second layer. By laminating the films, wear resistance was imparted, and a plastic molded body excellent in weather resistance, adhesion and hot water resistance was invented.

（式中Ｒ^１はメチル基またはエチル基である。）
３５モル％を超えて８５モル％以下の下記式（２）で表される繰返し単位（（Ａ−２）単位）、

（式中Ｒ^２はシクロアルキル基であり、Ｘ^１は水素原子またはメチル基である。）
０．１〜１５モル％の下記式（３）で表される繰返し単位（（Ａ−３）単位）、および

（式中Ｘ^２は水素原子またはメチル基であり、Ｗは紫外線吸収性基である。）
１〜１５モル％の下記式（４）で表される繰り返し単位（（Ａ−４）単位）

（式中Ｒ^３は炭素数２〜５のアルキレン基であり、Ｘ³は水素原子またはメチル基であり、Ｚはヒドロキシ基、アルコキシシリル基、グリシジルオキシ基、イソシアネート基からなる群から選ばれる少なくとも１種の置換基である。）
を含有するアクリル共重合体（Ａ成分）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）〜（Ａ−４）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を含有するコーティング用アクリル樹脂組成物、 That is, according to the present invention,
1. (A) 1 to 60 mol% of a repeating unit ((A-1) unit) represented by the following formula (1),

(In the formula, R ¹ is a methyl group or an ethyl group.)
A repeating unit ((A-2) unit) represented by the following formula (2) in an amount of more than 35 mol% and not more than 85 mol%,

(Wherein R ² is a cycloalkyl group, and X ¹ is a hydrogen atom or a methyl group.)
0.1 to 15 mol% of a repeating unit ((A-3) unit) represented by the following formula (3), and

(In the formula, X ² is a hydrogen atom or a methyl group, and W is an ultraviolet absorbing group.)
1 to 15 mol% of a repeating unit represented by the following formula (4) (unit (A-4))

(Wherein R ³ is an alkylene group having 2 to 5 carbon atoms, X ³ is a hydrogen atom or a methyl group, and Z is at least selected from the group consisting of a hydroxy group, an alkoxysilyl group, a glycidyloxy group, and an isocyanate group. 1 type of substituent.)
In which the total of (A-1) to (A-4) units is at least 70 mol% in 100 mol% of all repeating units of the acrylic copolymer. An acrylic resin composition for coating containing an acrylic copolymer,

  2. The acrylic resin composition for coating according to the above item 1, wherein W in the unit (A-3) is a triazine-based ultraviolet absorbing group;

（式中Ｒ^４は炭素数２〜６のアルキレン基であり、Ｒ^５は水素原子、炭素数１〜１８のアルキル基または炭素数１〜１８のアルコキシ基を表し、Ｒ^６、Ｒ^７は同一または互いに独立して水素原子、ハロゲン原子、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、または炭素数１〜１８のアルキル基もしくはハロゲン原子で置換されていてもよいフェニル基を表し、Ｒ^８は炭素数１〜１８のアルキル基を表し、Ｘ^４は水素原子またはメチル基であり、Ｙ^１は水素原子、ＯＨ基または炭素数１〜１２のアルキル基を表す。）

（式中Ｒ^９は水素原子、炭素数１〜１８のアルキル基または炭素数１〜１８のアルコキシ基を表し、Ｒ^１０、Ｒ^１１は同一または互いに独立して水素原子、ハロゲン原子、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、または炭素数１〜１８のアルキル基もしくはハロゲン原子で置換されていてもよいフェニル基を表し、Ｒ^１２は炭素数１〜１８のアルキル基を表し、Ｘ^５は水素原子またはメチル基であり、Ｙ^２は水素原子、ＯＨ基または炭素数１〜１２のアルキル基を表す。） 3. 2. The acrylic resin for coating according to item 1, wherein the unit (A-3) is a repeating unit derived from an acrylic monomer containing an ultraviolet absorbing group represented by the following formula (5) and / or the following formula (6): Composition,

(Wherein R ⁴ represents an alkylene group having 2 to 6 carbon atoms, R ⁵ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, and R ⁶ and R ⁷ are the same) Or independently of each other, a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a phenyl group optionally substituted by an alkyl group having 1 to 18 carbon atoms or a halogen atom R ⁸ represents an alkyl group having 1 to 18 carbon atoms, X ⁴ represents a hydrogen atom or a methyl group, and Y ¹ represents a hydrogen atom, an OH group, or an alkyl group having 1 to 12 carbon atoms.)

(In the formula, R ⁹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, and R ¹⁰ and R ¹¹ are the same or independently of each other, a hydrogen atom, a halogen atom, and a carbon number 1 Represents an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or an alkyl group having 1 to 18 carbon atoms or a phenyl group optionally substituted with a halogen atom, and R ¹² represents an alkyl group having 1 to 18 carbon atoms. X ⁵ represents a hydrogen atom or a methyl group, and Y ² represents a hydrogen atom, an OH group, or an alkyl group having 1 to 12 carbon atoms.)

（式中Ｒ^１３は炭素数２〜５のアルキレン基であり、Ｘ^６は水素原子またはメチル基である。） 4). The acrylic resin composition for coating according to item 1, wherein the unit (A-4) is a repeating unit represented by the following formula (7):

(Wherein R ¹³ is an alkylene group having 2 to 5 carbon atoms, and X ⁶ is a hydrogen atom or a methyl group.)

5. (A) The acrylic copolymer (component A) according to item 1 above, (B) having a converted isocyanate group ratio of 5.5 to 50% by weight, and (A-3) based on 1 equivalent of hydroxy group in the unit Blocked polyisocyanate compound (B component) having an isocyanate group in an amount of 0.8 to 1.5 equivalents, and 0 to 100 parts by weight of the total of (C) (A) component and (B) component The acrylic resin composition for coating according to the preceding item 1, comprising 0.001 to 0.4 parts by weight of a curing catalyst (component C),

（式中Ｒ^１４は、水素原子または炭素数１〜１４のアルキル基またはアルコキシ基である。） 6). (A) component is 1-59.9 mol% of said (A-1) unit, exceeds 35 mol% of said (A-2) unit, and is 85 mol% or less, said 0.1 unit of (A-3). An acrylic copolymer containing 15 mol%, 1 to 15 mol% of (A-4) units and 0.1 to 20 mol% of repeating units ((A-5) units) represented by the following formula (8): The acrylic resin composition for coating according to item 1, wherein the total number of (A-1) to (A-5) units is at least 70 mol% in 100 mol% of all repeating units of the acrylic copolymer,

(In the formula, R ¹⁴ represents a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an alkoxy group.)

  7. It contains 0.1 to 10 parts by weight of the silane coupling agent and / or the hydrolysis condensate of the silane coupling agent as the component (D) with respect to 100 parts by weight of the total of the component (A) and the component (B). The acrylic resin composition for coating according to the preceding item 1,

  8). Acrylic resin paint for coating having an acrylic resin composition concentration of 1 to 50% by weight obtained by dissolving the acrylic resin composition according to any one of items 1 to 7 in a solvent,

（式中Ｒ^１はメチル基またはエチル基である。）
３５モル％を超えて８５モル％以下の前記式（２）で表される繰返し単位（（Ａ−２）単位）、

（式中Ｒ^２はシクロアルキル基であり、Ｘ¹は水素原子またはメチル基である。）
０．１〜１５モル％の前記式（３）で表される繰返し単位（（Ａ−３）単位）、および

（式中Ｘ^２は水素原子またはメチル基であり、Ｗは紫外線吸収性基である。）
１〜１５モル％の前記式（４）で表される繰り返し単位（（Ａ−４）単位）

（式中Ｒ^３は炭素数２〜５のアルキレン基であり、Ｘ³は水素原子またはメチル基であり、Ｚはヒドロキシ基、アルコキシシリル基、グリシジルオキシ基、イソシアネート基からなる群から選ばれる少なくとも１種の置換基である。）
を含有するアクリル共重合体（Ａ成分）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）〜（Ａ−４）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を含有するアクリル樹脂組成物を熱硬化させてなるアクリル樹脂層が積層され、その第１層上に第２層として、
（Ｅ）コロイダルシリカ（ｅ成分）および
（Ｆ）下記式（９）で表わされるアルコキシシランの加水分解縮合物（ｆ成分）、

（但し、式中Ｒ^１５、Ｒ^１６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のアルキル基またはビニル基であり、Ｒ^１７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。）
を含有し、ｅ成分が１０〜６０重量％、ｆ成分がＲ^１５ _ｍＲ^１６ _ｎＳｉＯ_{（４−ｍ−ｎ）／２}に換算して４０〜９０重量％であるオルガノシロキサン樹脂組成物の熱硬化塗膜層が積層されたプラスチック成形体、 9. As a first layer on at least one surface of the plastic substrate surface,
(A) 1 to 60 mol% of the repeating unit represented by the formula (1) ((A-1) unit),

(In the formula, R ¹ is a methyl group or an ethyl group.)
The repeating unit ((A-2) unit) represented by the formula (2) above 35 mol% and below 85 mol%,

(In the formula, R ² is a cycloalkyl group, and X ¹ is a hydrogen atom or a methyl group.)
0.1 to 15 mol% of the repeating unit represented by the formula (3) ((A-3) unit), and

(In the formula, X ² is a hydrogen atom or a methyl group, and W is an ultraviolet absorbing group.)
1 to 15 mol% of the repeating unit represented by the formula (4) (unit (A-4))

(Wherein R ³ is an alkylene group having 2 to 5 carbon atoms, X ³ is a hydrogen atom or a methyl group, and Z is at least selected from the group consisting of a hydroxy group, an alkoxysilyl group, a glycidyloxy group, and an isocyanate group. 1 type of substituent.)
In which the total of (A-1) to (A-4) units is at least 70 mol% in 100 mol% of all repeating units of the acrylic copolymer. An acrylic resin layer obtained by thermally curing an acrylic resin composition containing an acrylic copolymer is laminated, and as a second layer on the first layer,
(E) colloidal silica (component e) and (F) a hydrolytic condensate (component f) of an alkoxysilane represented by the following formula (9):

(In the formula, each of R ¹⁵ and R ¹⁶ is 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 or a vinyl group substituted with a group, R ¹⁷ is an alkyl group having 1 to 4 carbon atoms, and m and n are each an integer of 0, 1, or 2, respectively. M + n is an integer of 0, 1, or 2.)
Of an organosiloxane resin composition containing 10 to 60% by weight of the e component and 40 to 90% by weight of the f component in terms of R ¹⁵ _m R ¹⁶ _n SiO _{(4-mn) / 2} A plastic molded body on which a cured coating layer is laminated,

  10. The plastic molded article according to 9 above, wherein W in the unit (A-3) of the component (A) is a triazine-based ultraviolet absorbing group.

（式中Ｒ^４は炭素数２〜６のアルキレン基であり、Ｒ^５は水素原子、炭素数１〜１８のアルキル基または炭素数１〜１８のアルコキシ基を表し、Ｒ^６、Ｒ^７は同一または互いに独立して水素原子、ハロゲン原子、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、または炭素数１〜１８のアルキル基もしくはハロゲン原子で置換されていてもよいフェニル基を表し、Ｒ^８は炭素数１〜１８のアルキル基を表し、Ｘ^４は水素原子またはメチル基であり、Ｙ^１は水素原子、ＯＨ基または炭素数１〜１２のアルキル基を表す。）

（式中Ｒ^９は水素原子、炭素数１〜１８のアルキル基または炭素数１〜１８のアルコキシ基を表し、Ｒ^１０、Ｒ^１１は同一または互いに独立して水素原子、ハロゲン原子、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、または炭素数１〜１８のアルキル基もしくはハロゲン原子で置換されていてもよいフェニル基を表し、Ｒ^１２は炭素数１〜１８のアルキル基を表し、Ｘ^５は水素原子またはメチル基であり、Ｙ^２は水素原子、ＯＨ基または炭素数１〜１２のアルキル基を表す。） 11. 8. The item 7 above, wherein the unit (A-3) of the component (A) is a repeating unit derived from an acrylic monomer containing an ultraviolet absorbing group represented by the following formula (5) and / or the following formula (6). Plastic molded body,

(Wherein R ⁴ represents an alkylene group having 2 to 6 carbon atoms, R ⁵ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, and R ⁶ and R ⁷ are the same) Or independently of each other, a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a phenyl group optionally substituted by an alkyl group having 1 to 18 carbon atoms or a halogen atom R ⁸ represents an alkyl group having 1 to 18 carbon atoms, X ⁴ represents a hydrogen atom or a methyl group, and Y ¹ represents a hydrogen atom, an OH group, or an alkyl group having 1 to 12 carbon atoms.)

(In the formula, R ⁹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, and R ¹⁰ and R ¹¹ are the same or independently of each other, a hydrogen atom, a halogen atom, or a carbon atom having 1 carbon atom. Represents an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or an alkyl group having 1 to 18 carbon atoms or a phenyl group optionally substituted with a halogen atom, and R ¹² represents an alkyl group having 1 to 18 carbon atoms. X ⁵ represents a hydrogen atom or a methyl group, and Y ² represents a hydrogen atom, an OH group, or an alkyl group having 1 to 12 carbon atoms.)

（式中Ｒ^１３は炭素数２〜５のアルキレン基であり、Ｘ^６は水素原子またはメチル基である。） 12 The plastic molded article according to item 9, wherein the unit (A-4) of the first layer is a repeating unit represented by the following formula (7):

(Wherein R ¹³ is an alkylene group having 2 to 5 carbon atoms, and X ⁶ is a hydrogen atom or a methyl group.)

13. The acrylic resin composition according to item 9 above has (A) an acrylic copolymer (component A), (B) a converted isocyanate group ratio of 5.5 to 50% by weight, and (A-3) hydroxy in the unit. Blocked polyisocyanate compound (B component) having an isocyanate group in an amount of 0.8 to 1.5 equivalents per 1 equivalent of the group, and (C) (A) component and (B) component total 100 10. The plastic molded article according to 9 above, which is an acrylic resin composition for coating containing 0.001 to 0.4 parts by weight of a curing catalyst (component C) with respect to parts by weight.

（式中Ｒ^１４は、水素原子または炭素数１〜１４のアルキル基またはアルコキシ基である。） 14 The component (A) is 1 to 59.9 mol% of the (A-1) unit, more than 35 mol% of the (A-2) unit and 85 mol% or less, and 0.1 of the (A-3) unit. Acrylic copolymer containing -15 mol%, (A-4) 1-15 mol% units and 0.1-20 mol% of repeating units ((A-5) units) represented by the following formula (8) The plastic according to item 9, which is an acrylic copolymer in which the total of (A-1) to (A-5) units is at least 70 mol% in 100 mol% of all the repeating units of the acrylic copolymer. Molded body,

(In the formula, R ¹⁴ represents a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an alkoxy group.)

  15. In the first layer, 0.1 to 10 parts by weight of silane coupling agent and / or silane coupling agent as component (D) is added to 100 parts by weight of component (A) and component (B). 10. The plastic molded article according to 9 above, which is a coating layer formed by thermally curing an acrylic resin composition for coating containing a decomposition condensate.

  16. The organosiloxane resin composition in which the second layer contains 0.5 to 5 parts by weight of a metal oxide (g component) as the (G) component with respect to 100 parts by weight of the total of the (E) component and the (F) component. The plastic molded article according to the preceding item 9, which is a thermosetting coating layer of a product,

  17. (G) The plastic molded article according to 16 above, wherein the component is at least one metal oxide fine particle selected from the group consisting of titanium oxide, zinc oxide, cerium oxide, tin oxide, and tungsten oxide;

18. The plastic molded article according to 9 above, wherein the plastic substrate is a polycarbonate resin substrate,
Is provided.

Hereinafter, the present invention will be described in detail.
((A) Component Acrylic Copolymer)
The acrylic copolymer of the component (A) is a copolymer comprising at least 70 mol%, preferably at least 80 mol%, more preferably at least 90 mol% consisting of repeating units represented by the following formulas (1) to (4). An alkyl methacrylate monomer corresponding to the formula (1), an acrylate and / or methacrylate monomer containing a cycloalkyl group corresponding to the formula (2), and an ultraviolet absorbing group corresponding to the formula (3). An acrylic copolymer having an ultraviolet absorbing group obtained by copolymerizing an acrylate and / or methacrylate monomer and an acrylate and / or methacrylate monomer having a functional group corresponding to the formula (4).

（式中Ｒ^１はメチル基またはエチル基である。）

(In the formula, R ¹ is a methyl group or an ethyl group.)

（式中Ｒ^２はシクロアルキル基であり、Ｘ^１は水素原子またはメチル基である。）

(Wherein R ² is a cycloalkyl group, and X ¹ is a hydrogen atom or a methyl group.)

（式中Ｘ^２は水素原子またはメチル基であり、Ｗは紫外線吸収性基である。）

(In the formula, X ² is a hydrogen atom or a methyl group, and W is an ultraviolet absorbing group.)

（式中Ｒ^３は炭素数２〜５のアルキレン基であり、Ｘ³は水素原子またはメチル基であり、Ｚはヒドロキシ基、アルコキシシリル基、グリシジルオキシ基、イソシアネート基からなる群から選ばれる少なくとも１種の置換基である。）

(Wherein R ³ is an alkylene group having 2 to 5 carbon atoms, X ³ is a hydrogen atom or a methyl group, and Z is at least selected from the group consisting of a hydroxy group, an alkoxysilyl group, a glycidyloxy group, and an isocyanate group. 1 type of substituent.)

Examples of the alkyl methacrylate corresponding to the formula (1) include methyl methacrylate and ethyl methacrylate, which can be used alone or in combination.
The acrylate or methacrylate monomer having a cycloalkyl group corresponding to the formula (2) is not particularly limited as long as it is an acrylate or methacrylate having at least one cycloalkyl group in the molecule. The cycloalkyl group preferably has 5 to 12 carbon atoms.

  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.

  As the monomer corresponding to the formula (3), an acrylic monomer having a triazine ultraviolet absorbing group is preferable. The triazine-based ultraviolet absorbing group is a residue of a triazine-based ultraviolet absorber and has ultraviolet absorbing performance. Among these, an acrylic monomer represented by the following formula (5) or formula (6) is preferably used.

（式中Ｒ^４は炭素数２〜６のアルキレン基であり、Ｒ^５は水素原子、炭素数１〜１８のアルキル基または炭素数１〜１８のアルコキシ基を表し、Ｒ^６、Ｒ^７は同一または互いに独立して水素原子、ハロゲン原子、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、または炭素数１〜１８のアルキル基もしくはハロゲン原子で置換されていてもよいフェニル基を表し、Ｒ^８は炭素数１〜１８のアルキル基を表し、Ｘ^４は水素原子またはメチル基であり、Ｙ^１は水素原子、ＯＨ基または炭素数１〜１２のアルキル基を表す。）

(Wherein R ⁴ represents an alkylene group having 2 to 6 carbon atoms, R ⁵ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, and R ⁶ and R ⁷ are the same) Or independently of each other, a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a phenyl group optionally substituted by an alkyl group having 1 to 18 carbon atoms or a halogen atom R ⁸ represents an alkyl group having 1 to 18 carbon atoms, X ⁴ represents a hydrogen atom or a methyl group, and Y ¹ represents a hydrogen atom, an OH group, or an alkyl group having 1 to 12 carbon atoms.)

（式中Ｒ^９は水素原子、炭素数１〜１８のアルキル基または炭素数１〜１８のアルコキシ基を表し、Ｒ^１０、Ｒ^１１は同一または互いに独立して水素原子、ハロゲン原子、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、または炭素数１〜１８のアルキル基もしくはハロゲン原子で置換されていてもよいフェニル基を表し、Ｒ^１２は炭素数１〜１８のアルキル基を表し、Ｘ^５は水素原子またはメチル基であり、Ｙ^２は水素原子、ＯＨ基または炭素数１〜１２のアルキル基を表す。）

(In the formula, R ⁹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, and R ¹⁰ and R ¹¹ are the same or independently of each other, a hydrogen atom, a halogen atom, and a carbon number 1 Represents an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or an alkyl group having 1 to 18 carbon atoms or a phenyl group optionally substituted with a halogen atom, and R ¹² represents an alkyl group having 1 to 18 carbon atoms. X ⁵ represents a hydrogen atom or a methyl group, and Y ² represents a hydrogen atom, an OH group, or an alkyl group having 1 to 12 carbon atoms.)

  Specifically, 2-acryloxyethylcarbamic acid 1- [3-hydroxy-4- {4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl} phenyloxy ] -3- (2-ethylhexyloxy) -2-propyl, 2-methacryloxyethylcarbamic acid 1- [3-hydroxy-4- {4,6-bis (2,4-dimethylphenyl) -1,3 5-Triazin-2-yl} phenyloxy] -3- (2-ethylhexyloxy) -2-propyl, 2-acryloxy-1- [3-hydroxy-4- {4,6-bis (2,4-dimethyl) Phenyl) -1,3,5-triazin-2-yl} phenyloxy] -3- (2-ethylhexyloxy) -2-propane, 2-methacryloxy-1- [3-hydroxy-4- {4,6- Scan (2,4-dimethylphenyl) -1,3,5-triazin-2-yl} phenyl oxy] -3- (2-ethylhexyl) -2-propane.

  Specific examples of the acrylate or methacrylate monomer having a functional group corresponding to the formula (4) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3- Hydroxy groups such as hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate Monomers having, alkoxysilyl such as 3-trimethoxysilylpropyl acrylate, 3-trimethoxysilylpropyl methacrylate Monomers having a 3-glycidoxypropyl acrylate, include monomers having a glycidyl group such as 3-glycidoxy propyl methacrylate, it may be used alone or in combination of two or more. Of these, a monomer having a hydroxy group is preferable, and 2-hydroxyethyl methacrylate is particularly preferable.

  The ratio of the repeating units represented by the formulas (1) to (4) is such that the molar ratio of the repeating units ((A-1) units) represented by the formula (1) is 1 to 60 mol%, preferably 1 It is -50 mol%, More preferably, it is 5-40 mol%. The molar ratio of the repeating unit represented by formula (2) (unit (A-2)) is more than 35 mol% and 85 mol% or less, preferably more than 35 mol% and 75 mol% or less. The molar ratio of the repeating unit ((A-3) unit) represented by the formula (3) is 0.1 to 15 mol%, preferably 0.1 to 10 mol%. The molar ratio of the repeating unit represented by the formula (4) ((A-4) unit) is 1 to 15 mol%, preferably 5 to 15 mol%.

  When the proportion of the repeating unit represented by the formula (1) is less than 1 mol%, the flexibility of the first layer is lowered, and the cured organosiloxane resin layer is likely to crack, or the substrate and the second layer Adhesion decreases. Furthermore, since the solubility with respect to the solvent which dissolves the acrylic copolymer mentioned later falls, it is unpreferable. When the proportion of the repeating unit represented by the formula (2) is 35 mol% or less, the dispersibility of the triazine-based ultraviolet absorber is lowered and the coating film is liable to be whitened. This is not preferable because the adhesion to the layer is lowered and the solubility of the acrylic copolymer is lowered. When the proportion of the repeating unit represented by the formula (3) is less than 0.1 mol%, sufficient weather resistance cannot be obtained, and when it exceeds 15 mol%, cracks are likely to occur in the coating layer, And the adhesion to the second layer is unfavorable. Further, if the proportion of the repeating unit represented by the formula (4) is less than 1 mol%, the crosslinking density is insufficient and the durability becomes poor, and if it exceeds 15 mol%, the adhesion to the substrate or the second layer is lowered. Therefore, it is not preferable.

  The acrylic copolymer (component A) in the present invention preferably further contains a repeating unit represented by the following formula (A-5). (A-5) Weather resistance improves by containing a unit.

式中、Ｒ^１４は、水素原子、炭素数１〜１４のアルキル基またはアルコキシ基を表す。
Ｒ^１４は、好ましくは炭素数１〜８のアルキル基またはアルコキシ基である。具体的には、メチル基、エチル基、プロピル基、ブチル基、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等が挙げられる。

^{Wherein, R 14} represents a hydrogen atom, an alkyl group or an alkoxy group having 1 to 14 carbon atoms.
R ¹⁴ is preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

  The proportion of (A-5) units is preferably from 0.1 to 20 mol%, more preferably from 1 to 20 mol%, in 100 mol% of all repeating units of the acrylic copolymer. If it exceeds 20 mol%, the adhesion to the substrate and the second layer tends to be lowered.

  In the acrylic copolymer (component A), the (A-1) unit 1 to 59.9 mol%, the (A-2) unit 35 mol% to 85 mol% or less, the (A-3) unit 0.1 to 15 mol%, 1 to 15 mol% of the (A-4) unit and 0.1 to 20 mol% of the repeating unit ((A-5) unit) represented by the formula (8) The total of (A-1) to (A-5) units is preferably at least 70 mol% in 100 mol% of all repeating units of the acrylic copolymer.

  By including the unit (A-5), radical scavenging ability can be imparted, and weather resistance can be further improved. The total of (A-1) units to (A-5) units is at least 70 mol%, more preferably at least 80 mol%, and even more preferably at least 90 mol% in 100 mol% of all repeating units of the acrylic copolymer. is there.

  The (A-5) unit can be introduced by copolymerizing a corresponding acrylate and / or methacrylate monomer. Corresponding monomers include 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- -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-tetramethyl-4- Piperidyl methacrylate, 1-octoxy-2,2,6,6-tetramethyl-4-piperidyl methacrylate, -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 and the like, and these may be used alone or in admixture of two or more.

  The acrylic copolymer (component (A)) having a functional group composed of the repeating units containing the above units (A-1) to (A-4), and optionally (A-5) units, further provides functionality and the like. Therefore, other repeating units may be included. The other repeating unit is in a range of 30 mol% or less, preferably in a range of 20 mol% or less, particularly preferably in a range of 10 mol% or less with respect to 100 mol% of the acrylic copolymer of component (A).

  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 (A) is preferably 20,000 or more, more preferably 50,000 or more in terms of weight average molecular weight. Further, those having a weight average molecular weight of 10 million or less are preferably used. Therefore, the weight average molecular weight of the acrylic copolymer is preferably 50,000 to 10,000,000, more preferably 50,000 to 1,000,000, and even more preferably 50,000 to 500,000. An 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))
The blocked polyisocyanate compound of the component (B) is made by reacting an isocyanate group with a blocking agent so that the free isocyanate group is almost eliminated, and the blocking agent is separated by heating. Means a compound that becomes an isocyanate group and has reactivity.

  (B) As an isocyanate group of a polyisocyanate compound, an oxime such as acetoxime and methyl ethyl ketoxime, an active methylene compound such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate and acetylacetone, methanol, ethanol Block isocyanate obtained by adding a blocking agent represented by alcohols such as 2-propanol, n-butanol, sec-butanol and 2-ethyl-1-hexanol, and phenols such as phenol, cresol and ethylphenol Compounds.

  Examples of the polyisocyanate compound to which the blocking agent is added include polyisocyanates, adducts of polyisocyanates and polyhydric alcohols, cyclized polymers of polyisocyanates, isocyanate burettes, and the like. 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.

  In component (B), an isocyanate group is generated for the first time during the thermosetting reaction, so that the coating composition is excellent in storage stability, and the isocyanate group is used in moisture in the coating composition, air, and solvent coating composition. A cured film having a stable physical property which is hardly consumed by the side reaction with the alcohol solvent and hardly affected by the coating environment can be formed. 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 obtained by reacting (i) a hydroxy compound having 2 to 4 hydroxy groups with an aliphatic and / or alicyclic diisocyanate compound. An adduct polyisocyanate compound obtained by blocking an adduct polyisocyanate compound with a blocking agent, and (ii) an isocyanurate obtained by blocking an isocyanurate type polyisocyanate compound derived from an aliphatic and / or alicyclic diisocyanate compound with a blocking agent. Type polyisocyanate compounds are preferred. 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.
The converted isocyanate group ratio is a value that represents the weight of the isocyanate group to be produced as a percentage of the weight of the component (B) when the component (B) is heated to separate the blocking agent.

  The component (B) has a converted isocyanate group ratio of 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 ratio is less than 5.5% by weight, the blended amount of the blocked polyisocyanate compound with respect to the acrylic resin increases, and the adhesion to the substrate becomes poor. On the other hand, if the isocyanate group ratio is more than 50% by weight, the flexibility of the coating layer is lowered, and the coating layer is cracked when the second layer is thermally cured, thereby impairing durability against environmental changes. The isocyanate group ratio (% by weight) is determined by a method in which an isocyanate group is ureated with a known amount of amine and excess amine is titrated with an acid.

  The content of the component (B) is 0.8 to 1.5 equivalents, preferably 0.8 to 1.3 equivalents, most preferably an isocyanate group with respect to 1 equivalent of a hydroxy group in the acrylic copolymer (A). Is an amount of 0.9 to 1.2 equivalents.

  When the hydroxy group in component (A) and the isocyanate group in component (B) form a crosslink by a urethane bond, the first layer can maintain good adhesion to the substrate and the second layer. it can. Further, the crosslink density is hardly lowered by ultraviolet rays, water, oxygen, etc., and the adhesion can be maintained for a long time. In addition, durability under a high temperature environment can be maintained. It also has excellent weather resistance.

  When the isocyanate group is less than 0.8 equivalent, the crosslinking becomes insufficient, resulting in insufficient durability in a high temperature environment, and the unreacted hydroxy group absorbs moisture to show high affinity with water molecules, Weather resistance and hot water resistance also deteriorate. If there are more than 1.5 equivalents of isocyanate groups, the first layer will have a very high crosslink density with allophanate bonds, will be a hard and brittle layer, will be less responsive to environmental changes, and will be more adhesive to environmental changes. Inferior.

(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), The (C) component curing catalyst is used.
Examples of the curing catalyst include an organic tin compound, a quaternary ammonium salt compound, a tertiary amine compound, an organic titanium compound, and an organic zirconium compound. These compounds are used alone or in combination of two or more. Of these curing catalysts, organotin compounds are preferably used.

  Typical examples of such organotin compounds include monobutyltin tris (2-ethylhexanoate), dimethyltin dineodecanoate, dibutyltin bis (2-ethylhexanoate), monobutyltin tris ( n-butylpropionate), dibutyltin dilaurate, monohexyltin trioctate, 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 are used individually or in mixture of 2 or more types.

Representative examples of the quaternary ammonium salt compounds include 2-hydroxyethyl trin-butylammonium 2,2-dimethylpropionate, 2-hydroxyethyl trin-butylammonium 2,2-dimethylbutano. And 2-hydroxypropyl / tri-n-butylammonium / 2,2-dimethylpropionate, 2-hydroxypropyl / tri-n-butylammonium / 2,2-dimethylbutanoate, and the like. These are used individually or in mixture of 2 or more types.
Examples of tertiary amines include dimethylethanolamine and triethylenediamine. These are used individually or in mixture of 2 or more types.

  Typical examples of organic titanium compounds include alkoxy titanium compounds such as tetraisopropoxy titanium, tetrabutoxy titanium, and tetraoctoxy titanium, titanium chelate compounds such as titanium acetylacetonate and titanium ethyl acetoacetate. . These are used individually or in mixture of 2 or more types.

Typical examples of organic zirconium compounds include alkoxyzirconium compounds such as tetraisopropoxyzirconium, tetrabutoxyzirconium and tetraoctoxyzirconium, zirconium such as zirconium tetraacetylacetonate, zirconium tetraethylacetoacetate and zirconium tributoxyacetylacetonate. Examples include chelate compounds. These are used individually or in mixture of 2 or more types.
These quaternary ammonium salt compounds, tertiary amine compounds, organic titanium compounds, and organic zirconium compounds are preferably used alone or in combination of two or more in combination with the above organic tin 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 silane coupling agent and / or hydrolysis condensate of silane coupling agent)
The acrylic resin composition of the present invention may further contain a silane coupling agent and / or a hydrolytic condensate of the silane coupling agent as component (D). By including such a silane coupling agent and / or a hydrolysis condensate of the silane coupling agent, the adhesion between the transparent plastic substrate and the first layer and the first layer and the second layer is further improved, and the long-term It is preferably used because its adhesiveness is sustained over time.

  Examples of such silane coupling agents include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxy. Silane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, N -Β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltriethoxysilane hydrochloride, γ-glycol Sidoxypropyltrimethoxysilane, γ-g Sidoxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, vinyltriacetoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, vinyltrimethoxysilane , Vinyltriethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, octadecyldimethyl [3- (triethoxysilyl) propyl] ammonium chloride, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxy Examples thereof include silane, 3-isocyanatopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.

  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. The content is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 8 parts by weight with respect to 100 parts by weight as a total of the component (A) and the component (B).

(About other components that can be used in the acrylic resin composition)
An ultraviolet absorber may be added to the acrylic resin composition of the present invention. Examples of the ultraviolet absorber include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3 , 5-triazine, 2- [4-[(2-hydroxy-3- (2′-ethyl) hexyl) oxypropyl] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl)- 1,3,5-triazine, 2,4-bis (2-hydroxy-4-butyoxyphenyl) -6- (2,4-bis-butyloxyphenyl) -1,3,5-triazine, 2- (2-Hydro Triazines such as xyl-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, 2,4-dihydroxybenzophenone, 2-hydroxy- Benzophenones such as 4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2- (5'-methyl-2'-hydroxyphenyl) benzotriazole 2- (3'-t-butyl-5'-methyl-2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-di-t-butyl-2'-hydroxyphenyl) -5-chloro Benzotriazoles such as benzotriazole, ethyl-2-cyano-3,3-diphenyl acrylate, 2 Cyanoacrylates such as ethylhexyl-2-cyano-3,3-diphenylacrylate, salicylates such as phenyl salicylate, p-octylphenyl salicylate, diethyl-p-methoxybenzylidene malonate, bis (2-ethylhexyl) benzylidene malonate, etc. Benzylidene malonates, 2- (2′-hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole, a copolymer of vinyl monomer copolymerizable with the monomer, 2- (2′-hydroxy Copolymer of -5-acryloxyethylphenyl) -2H-benzotriazole and vinyl monomer copolymerizable with the monomer, titanium cerium oxide, zinc oxide, tin oxide, tungsten oxide, zinc sulfide, cadmium sulfide, etc. Metal oxide fine particles Kind. Such an ultraviolet absorber is preferably used in an amount of 0.1 to 30 parts by weight, more preferably 0.2 to 20 parts by weight with respect to 100 parts by weight as a total of the components (A) and (B).

  In the present invention, a light stabilizer can be further added to the acrylic resin composition. Examples of the light stabilizer include 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, didecanoic acid bis (2,2,6,6-tetramethyl-1-octyloxy-4-piperidinyl) ester, Bis (1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, 2,4- Bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-2-yl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine, Bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis (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-tetra Methyl-4-piperidyl) diphenylmethane-p, p'-dicabamate, bis (2,2,6,6-tetramethyl-4-piperidyl) benzene-1,3-disulfonate, bis (2,2,6 , 6-tetramethyl-4-piperidyl) phenyl phosphite, hindered amines, nickel bis (octylphenyl sulfide, nickel complex-3,5-di Examples thereof include nickel complexes such as t-butyl-4-hydroxybenzyl phosphate monoethylate, nickel dibutyldithiocarbamate, etc. These light stabilizers may be used alone or in combination of two or more. ) Component and (B) component, the total amount is preferably 0.01 to 50 parts by weight, more preferably 0.05 to 10 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 a coating of this invention, 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 increases, and the crosslinking reaction does not proceed sufficiently at the time of thermosetting, so that the coating layer has poor durability. In addition, the solvent used for dissolving the acrylic resin composition for coating becomes insufficiently volatilized, and the solvent remains in the coating film, which impairs hot water resistance and weather resistance.

(About the method of forming the acrylic resin layer)
In the present invention, as a method of forming the acrylic resin layer (first layer), the acrylic resin composition of the present invention is dissolved in a volatile solvent that does not react with and dissolves the plastic as a base material. An acrylic resin paint for coating is applied to the surface of a plastic substrate, then the solvent is removed by heating or the like, and further heated to react and crosslink the hydroxyl group and the isocyanate group produced by heating to form a crosslink.

  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) is preferably 1 to 50% by weight, and 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.

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. By heating, a crosslinkable group is cross-linked, and a transparent plastic substrate having the acrylic resin layer laminated as a first layer is obtained. When the heat curing time is shorter than 10 minutes, 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 transparent plastic substrate is improved, and the transparency is excellent in wear resistance and weather resistance. A plastic molded body can be obtained.

(Second layer; thermosetting coating layer of organosiloxane resin composition)
In the present invention, the second layer laminated on the first layer is obtained by thermosetting an organosiloxane resin composition containing colloidal silica (component e) and a hydrolysis condensate (component f) of alkoxysilane. It is the coating layer which becomes.
The second layer is preferably formed by using a coating material for coating comprising an organosiloxane resin solid content comprising the colloidal silica and a hydrolysis condensate of alkoxysilane, an acid, a curing catalyst, and a solvent.

(About colloidal silica of e component)
As the e-component colloidal silica, silica fine particles having an average particle size of 5 to 200 nm, more preferably an average particle size of 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 SN30 of Catalyst Chemical Industry Co., Ltd., a product dispersed in a basic aqueous solution. Snow Chemicals Corporation's 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 hydrolysis condensate of alkoxysilane of component f)
The hydrolysis-condensation product of alkoxysilane which is the f component of the present invention is obtained by subjecting alkoxysilane of the following formula (9) to hydrolysis-condensation reaction.

式中Ｒ^１５、Ｒ^１６は各々独立に、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のアルキル基である。Ｒ^１５、Ｒ^１６は各々独立に、炭素数１〜４のアルキル基が好ましく、特にメチル基が好ましい。
Ｒ^１７は炭素数１〜４のアルキル基、またはビニル基である。Ｒ^１７は炭素数１〜３のアルキル基が好ましく、特にメチル基またはエチル基が好ましい。ｍ、ｎは各々独立に、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。ｍ、ｎはそれぞれ０または１が好ましい。また、ｍ＋ｎは１が好ましい。

In the formula, R ¹⁵ and R ¹⁶ are each independently 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. It is a C1-C3 alkyl group substituted with a group. R ¹⁵ and R ¹⁶ are each independently preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group.
R ¹⁷ is an alkyl group having 1 to 4 carbon atoms or a vinyl group. R ¹⁷ is preferably an alkyl group having 1 to 3 carbon atoms, particularly preferably a methyl group or an ethyl group. m and n are each independently an integer of 0, 1 or 2, and m + n is an integer of 0, 1 or 2. m and n are each preferably 0 or 1. Further, m + n is preferably 1.

  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 70-100 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, and these are obtained by subjecting to a sol-gel reaction. It is.

(Regarding organosiloxane resin composition containing component e and component f)
The organosiloxane resin composition containing the e component and the f component is preferably employed through the following process, because it produces a coating layer that is free from precipitation and is more excellent in abrasion resistance.
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 hydrolytic condensation reaction are not unambiguous because the conditions vary depending on the type of alkoxysilane used, the type and amount of colloidal silica coexisting in the system, but usually the system temperature is 20 to 70 ° C., and 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, the adhesion and the occurrence of cracks. When the total of the e component and the f component is 100% by weight, the preferable mixing ratio of the two components is 10 to 60% by weight for the e component and R ¹⁵ _m R ¹⁶ _{n for the} f component. It is 40 to 90% by weight in terms of SiO 2 _{(4-mn) / 2} , more preferably 10 to 40% by weight of the e component and R ¹⁵ _m R ¹⁶ _n SiO _{(4-mn). ) / 2} to 60 to 90% by weight.

  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 used in an amount of preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the total of the e component and the f component.

  The organosiloxane resin composition preferably contains a metal oxide as the component (G). The weather resistance can be increased by the component (G). As the component (G), at least one metal oxide selected from the group consisting of titanium oxide, zinc oxide, cerium oxide, tin oxide and tungsten oxide is preferably used since it is less decomposed by light. In particular, titanium oxide is preferably used. The content of the component (G) is preferably 0.1 to 15 parts by weight, more preferably 0.2 to 5.0 parts by weight, based on 100 parts by weight of the total of the E component and the F component.

(About the formation method of the thermosetting coating film layer of organosiloxane resin composition)
As a method of forming a thermosetting coating film layer (second layer) of the organosiloxane resin composition, an organosiloxane resin composition containing an e component, an f component and optionally a g component is dissolved in a solvent, The coating is formed by applying an organosiloxane resin coating material on the first layer formed on the transparent plastic substrate and then heat-curing the coating.
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 1900 parts by weight, more preferably 150 to 900 parts by weight with respect to 100 parts by weight of the total of the e component and the f component. The concentration of the solid content is preferably 5 to 70% by weight, more preferably 7 to 40% by weight.

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 selected as appropriate according to the conditions. 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 temperature is preferably 50 to 200 ° C, more preferably 80 to 160 ° C, and still more preferably 100 to 140 ° C. The heat curing time is preferably 10 minutes to 4 hours, more preferably 20 minutes to 3 hours, and further 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, ST83PA, ST80PA, ST97PA, ST86PA, SH21PA from Toray Dow Corning Co., Ltd., silicone compounds KP321, KP322, KP323 from Shin-Etsu Chemical Co., Ltd. , KP324, KP326, KP340, KP341, fluorinated surfactants F-179, F-812A, F-815, etc., manufactured by Dainippon Ink & Chemicals, Inc. 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 plastic substrate)
Specific examples of the substrate used in the present invention include polycarbonate resins, acrylic resins such as polymethyl methacrylate, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and poly (ethylene-2,6-naphthalate), polystyrene, and polypropylene. , Polyarylate, polyethersulfone and the like. These resins can be used alone or in admixture of two or more.
A polycarbonate resin and an acrylic resin are preferable, and a polycarbonate resin is particularly preferable because of its usefulness as a base material having adhesion to the first layer and excellent wear resistance.

  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, etc. 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. Further, other resins such as a lubricant, the above-described polyester resin and ABS can be added.

(About plastic moldings)
The plastic molded body having a protected surface according to the present invention includes an acrylic resin layer (first layer) obtained by thermally curing an acrylic resin composition in which an ultraviolet absorbing group having a specific structure is introduced into an acrylic resin side chain, and a first layer. 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 top, the plastic substrate has excellent weather resistance and durability. The molded article can be provided with wear resistance and hot water resistance and can be used outdoors for a long time.

  Such plastic moldings are used for aircraft, vehicle, automobile window glass, sunroofs, pillars, window glass for construction machinery, windows for buildings, houses, greenhouses, garages, arcade roofs, headlamp lenses, optical It can be suitably used for lenses, mirrors, glasses, goggles, sound barriers, traffic light lenses, curve mirrors, motorcycle windshields, nameplates, other various sheets, films, and the like.

  The acrylic resin composition for coating according to the present invention imparts excellent weather resistance, abrasion resistance, adhesion, hot water resistance, etc. to a plastic substrate, and suppresses volatilization of an ultraviolet absorber during heat curing of the acrylic resin composition. In addition, it is excellent in suppressing elution of the UV absorber from the first layer to the organosiloxane resin composition when forming the second layer, and can prevent process contamination, and is excellent in recoatability and storage stability. In addition, a plastic molded plate obtained by laminating a thermosetting coating layer of the resin composition and then laminating a thermosetting coating layer of an organosiloxane resin composition having a specific composition has appearance, wear resistance, adhesion, and hot water resistance. Good, high level of weather resistance, excellent durability, especially plastic moldings with both sides protected are used suitably for automotive window glass and sunroof, and the industrial effects that they exhibit 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 elution property of the obtained ultraviolet absorber from the acrylic resin layer and the evaluation of the plastic molded body (laminate) was performed by the following methods. Moreover, the part and% in an Example mean a weight part and weight%.

  (1) Dissolvability of UV absorber: Acrylic resin composition was applied to a 5 mm thick, 10 cm square polycarbonate resin (hereinafter abbreviated as PC resin) sheet so that the dry film thickness was 4 μm. What was heat-cured for a long time was taken out after being immersed for 1 minute in 350 g of a mixed solution of methanol: 2-propanol: 1-butanol = 16: 50: 34 (weight ratio). After repeating this operation 30 times, the absorption spectrum of the mixed solution was measured and evaluated by determining the absorbance at the maximum wavelength near 300 nm. The measurement used Hitachi Ltd. spectrophotometer U-3100, and used the mixed solution before sheet | seat immersion as a blank.

  (2) Appearance evaluation: The appearance (foreign matter, presence / absence of whitening) and presence / absence of cracks (cracks) were visually confirmed.

  (3) Adhesiveness: Nichiban adhesive tape (trade name “Serotape” (registered trademark)) is pressure-bonded to the coat layer of one side of the double-sided coat layer with a cutter knife and made of 100 grids at intervals of 1 mm. The operation of strongly peeling off was repeated 3 times, and the evaluation was made by the number of grids remaining on the substrate.

  (4) Hot water resistance: The adhesion of the coating layer after the test piece was immersed in boiling water for 3 hours was evaluated.

  (5) Abrasion resistance: According to JIS K6735, a Taber abrasion test is performed on a surface of a double-sided coating layer using a CS-10F (TYPE IV) abrasion wheel manufactured by Calibrase Corporation at a load of 500 g for 500 revolutions. The difference ΔH between the later haze and the haze before the Taber abrasion test was measured and evaluated.

(6) Weather resistance: Using one surface of the test piece as an ultraviolet-irradiated surface and using Super Xenon Weather Meter SX-75 manufactured by Suga Test Instruments Co., Ltd., UV irradiation intensity 180 W / m ² , black panel temperature 63 ° C., 120 minutes An exposure test was conducted for 3000 hours under 18-minute rainfall conditions, and the test piece was taken out to evaluate the appearance and adhesion after the test.

(Synthesis of methacrylate having triazine UV absorber residue)
[Reference Example 1]
443.4 parts of methyl isobutyl ketone (hereinafter abbreviated as MIBK), 2- [4-[(2-hydroxy-3- (2′-ethyl) hexyl) oxy] in a flask equipped with a reflux condenser and a stirring device 2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine (Ciba Specialty Chemicals Co., Ltd., Tinuvin 405) 350.3 parts, 2-isocyanate 93.1 parts of natoethyl methacrylate was added and mixed and heated to 80 ° C. Next, 0.1 part of dibutyltin dilaurate was added and stirred at the same temperature for 30 minutes. After cooling to room temperature, the resulting solution was transferred into water, and after stirring, the reaction product was extracted with MIBK. The oily substance obtained by distilling MIBK was dropped into methanol and stirred to obtain a pale yellow powder. The powder was dried and 2-methacryloxyethylcarbamic acid 1- [3-hydroxy-4- {4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine- 2-yl} phenyloxy] -3- (2-ethylhexyloxy) -2-propyl (hereinafter abbreviated as MOI-405) was obtained.

(Synthesis of acrylic copolymer solutions (I) to (V))
[Reference Example 2]
In a flask equipped with a reflux condenser and a stirrer and purged with nitrogen, 37.2 parts of ethyl methacrylate (hereinafter abbreviated as EMA), 201.9 parts of cyclohexyl methacrylate (hereinafter abbreviated as CHMA), 2-hydroxyethyl methacrylate (hereinafter referred to as “MAH”) (Abbreviated as HEMA) 26.0 parts, MOI-T405 54.7 parts obtained in Reference Example 1, LA-82 (Asahi Denka Kogyo Co., Ltd. hindered amine light-stable group-containing methacrylate; 1, 2, 2 , 6,6-pentamethyl-4-piperidylmethacrylate) 47.9 parts and MIBK 551.5 parts. The mixture was deoxygenated by bubbling nitrogen gas for 15 minutes, then heated to 70 ° C. under a nitrogen gas stream, 0.66 parts of azobisisobutyronitrile (hereinafter abbreviated as AIBN) was added, and nitrogen gas was added. The reaction was carried out in an air stream at 70 ° C. with stirring for 5 hours. Further, 0.16 part of AIBN was added, the temperature was raised to 80 ° C., and the reaction was performed for 3 hours. % Acrylic copolymer solution (I) was obtained.

[Reference Example 3]
In a flask equipped with a reflux condenser and a stirrer and purged with nitrogen, 62.1 parts of EMA, 168.2 parts of CHMA, 26.0 parts of HEMA, 41.4 parts of MOI-T405 obtained in Reference Example 1, LA- 82 47.9 parts and MIBK 518.4 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, 0.66 parts of AIBN was added, and the reaction was continued in the nitrogen gas stream at 70 ° C. for 5 hours with stirring. I let you. Further, 0.16 part of AIBN was added, the temperature was raised to 80 ° C., the mixture was reacted for 3 hours, cooled to near room temperature, 259.2 parts of 2-BuOH was added, and an acrylic copolymer solution (II )

[Reference Example 4]
In a flask equipped with a reflux condenser and a stirrer and purged with nitrogen, 83.6 parts of EMA, 168.2 parts of CHMA, 26.0 parts of HEMA, 50.3 parts of MOI-T405 obtained in Reference Example 1, MIBK 492 1 part 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, 0.66 parts of AIBN was added, and the reaction was continued in the nitrogen gas stream at 70 ° C. for 5 hours with stirring. I let you. Further, 0.16 part of AIBN was added, the temperature was raised to 80 ° C. and reacted for 3 hours. After cooling to near room temperature, 246.1 parts of 2-BuOH was added, and an acrylic copolymer solution (III )

[Reference Example 5]
A flask equipped with a reflux condenser and a stirrer, 48.9 parts of EMA, 201.9 parts of CHMA, 26.0 parts of HEMA, 53.2 parts of MOI-T405 obtained in Reference Example 1, LA- 82 23.9 parts and MIBK 530.9 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, 0.66 parts of AIBN was added, and the reaction was continued in the nitrogen gas stream at 70 ° C. for 5 hours with stirring. I let you. Further, 0.16 part of AIBN was added, the temperature was raised to 80 ° C., and the reaction was performed for 3 hours. After cooling to near room temperature, 265.4 parts of 2-BuOH was added, and an acrylic copolymer solution (IV ) (D) was obtained.

[Reference Example 6]
A reflux condenser and a stirrer were provided, and 205.5 parts of EMA, 26.0 parts of HEMA, and 347.2 parts of MIBK were added and mixed in a flask purged with nitrogen. The mixture was deoxygenated by bubbling nitrogen gas for 15 minutes, then heated to 70 ° C. under a nitrogen gas stream, 0.66 parts of AIBN was added, and the reaction was continued in the nitrogen gas stream at 70 ° C. for 5 hours with stirring. I let you. Further, 0.16 part of AIBN was added, the temperature was raised to 80 ° C., and the reaction was performed for 3 hours. After cooling to near room temperature, 173.6 parts of 2-BuOH was added, and an acrylic copolymer solution (V )

In Table 1, each symbol indicates the following.
(A-1 unit) EMA; ethyl methacrylate (A-2 unit) CHMA; cyclohexyl methacrylate (A-3 unit) HEMA; 2-hydroxyethyl methacrylate (A-4 unit) MOI-T405; 2-methacryloxyethylcarbamic acid 1- [3-Hydroxy-4- {4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl} phenyloxy] -3- (2-ethylhexyloxy) -2 -Propyl (A-5 unit) LA-82; 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (Adekastab LA-82 manufactured by Asahi Denka Kogyo Co., Ltd .; hindered amine light-stable group-containing methacrylate)
(Others) MIBK: Methyl isobutyl ketone
2-BuOH; 2-butanol
AIBN1; azobisisobutyronitrile added for the first time
AIBN2; azobisisobutyronitrile added for the second time

(Preparation of acrylic resin compositions (i-1) to (i-4))
[Reference Example 7]
To 100 parts of the acrylic copolymer solution (I), 18.6 parts of MIBK, 9.3 parts of 2-BuOH, and 64.9 parts of 1-methoxy-2-propanol (hereinafter abbreviated as PMA) are added and mixed. VESTANAT B1358 / 100 (Degussa Japan Co., Ltd. blocked polyisocyanate compound) so that the isocyanate group becomes 1.0 equivalent with respect to 1 equivalent of the hydroxy group of the acrylic copolymer in the resin solution (I) 5 6.9 parts of APZ-6633 (ethanol solution of silane coupling agent hydrolysis condensate produced by Toray Dow Corning Co., Ltd .; solid content 5 wt%), 0.011 part of dibutyltin dilaurate In addition, the mixture was stirred at 25 ° C. for 1 hour to obtain an acrylic resin composition (i-1). When the obtained acrylic resin composition was stored at 23 ° C. for 3 months and then visually evaluated for appearance, gelation was not observed and the storage stability was good.

[Reference Example 8]
Into 100 parts of the acrylic copolymer solution (II), 18.8 parts of MIBK, 9.4 parts of 2-BuOH, and 65.2 parts of PMA are added and mixed, and the hydroxy of the acrylic copolymer in the acrylic resin solution (II) is mixed. 6.0 parts of VESTANAT B1358 / 100 was added so that the isocyanate group was 1.0 equivalent with respect to 1 equivalent of the group, and Tinuvin 479 (Ciba Specialty Chemicals Co., Ltd. triazine ultraviolet absorber) 0.53 part , APZ-6633 7.0 parts, 0.011 part of dimethyltin dineodecanoate (hereinafter abbreviated as DMDNT) was added and stirred at 25 ° C. for 1 hour to obtain an acrylic resin composition (i-2). . When the obtained acrylic resin composition was stored at 23 ° C. for 3 months and then visually evaluated for appearance, gelation was not observed and the storage stability was good.

[Reference Example 9]
Into 100 parts of the acrylic copolymer solution (III), 19.5 parts of MIBK, 9.7 parts of 2-BuOH, and 65.8 parts of PMA are added and mixed, and the hydroxy of the acrylic copolymer in the acrylic resin solution (III) is mixed. 6.3 parts of VESTANAT B1358 / 100 was added so that the isocyanate group would be 1.0 equivalent to 1 equivalent of the group, 7.0 parts of APZ-6633 and 0.018 part of DMDNT were added, and the mixture was stirred at 25 ° C. for 1 hour. And an acrylic resin composition (i-3) was obtained. When the obtained acrylic resin composition was stored at 23 ° C. for 3 months and then visually evaluated for appearance, gelation was not observed and the storage stability was good.

[Reference Example 10]
To 100 parts of the acrylic copolymer solution (IV), 7.8 parts of MIBK, 3.9 parts of 2-BuOH, and 81.3 parts of PMA are added and mixed, and the acrylic copolymer in the acrylic resin solution (IV) is mixed. 5.9 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 n-butyltris (2-ethylhexanoate) tin (hereinafter abbreviated as BTEHT). 0.036 part was added and it stirred at 25 degreeC for 1 hour, and obtained the acrylic resin composition (i-4). When the obtained acrylic resin composition was stored at 23 ° C. for 3 months and then visually evaluated for appearance, gelation was not observed and the storage stability was good.

[Reference Example 11]
To 100 parts of the acrylic copolymer solution (V), 23.2 parts of MIBK, 11.6 parts of 2-BuOH and 69.5 parts of PMA are added and mixed, and the acrylic copolymer in the acrylic resin solution (V) is mixed. VESTANAT B1358 / 100 9.0 parts was added so that an isocyanate group might be 1.0 equivalent with respect to 1 equivalent of the hydroxyl group of Tinuvin400 (Ciba Specialty Chemicals Co., Ltd. triazine type ultraviolet absorber). 1 part, 7.5 parts of APZ-6633 and 0.040 part of BTEHT were added, and it stirred at 25 degreeC for 1 hour, and obtained the acrylic resin composition (i-5). When the obtained acrylic resin composition was stored at 23 ° C. for 3 months and then visually evaluated for appearance, gelation was not observed and the storage stability was good.

In Table 2, each symbol indicates the following.
(B component)
VEST: Blocked polyisocyanate compound (VESTANAT B1358 / 100 manufactured by Degussa Japan Co., Ltd., content ratio of isocyanate group to be generated is 12.4% by weight)
(C component)
DBTDL: dimethyltin dilaurate DMDNT; dimethyltin dineodecanoate BTEHT; n-butyltris (2-ethylhexanoate) tin (component D)
APZ: ethanol solution containing 5% by weight of amino group-containing silane coupling agent hydrolysis condensate (APZ-6633 manufactured by Toray Dow Corning Co., Ltd.)
(Other)
UVA-1; 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl-4,6-bis (4-phenylphenyl) -1,3,5-triazine (Ciba Specialty Chemicals ( Tinuvin 479)
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.)
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-30, solid concentration 30% by weight, manufactured by Catalyst Chemical Industry Co., Ltd.) and stirred well. The dispersion was cooled to 10 ° C., and 216 parts of methyltrimethoxysilane was added dropwise with cooling in an ice-water bath. After completion of the addition of methyltrimethoxysilane, the mixture was stirred at 30 ° C. for 10 hours, and then mixed with 1.1 parts of choline methanol solution (containing 45% choline) as a curing catalyst, 6.7 parts of acetic acid, and 220 parts of isopropyl alcohol as a diluting solvent. Further, 3.4 parts of 710T (IPA dispersion type titanium oxide dispersion manufactured by Teika Co., Ltd.) was added to obtain an organosiloxane resin composition paint (ii-1).

[Reference Example 13]
1 part 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 a mixed reagent of 208.8 parts of methyltrimethoxysilane and 4.7 parts of dimethyldimethoxysilane was added dropwise while cooling in an ice water bath. After completion of the dropwise addition, the mixture was stirred at 30 ° C. for 10 hours, and then mixed with 1.1 parts of choline methanol solution (containing 45% choline) as a curing catalyst, 6.7 parts of acetic acid, and 210 parts of isopropyl alcohol as a diluting solvent. Further, 6.7 parts of 710T were added to obtain an organosiloxane resin composition paint (ii-2).

In Table 3, each symbol indicates the following.
(E component)
SN-30; Cataloid SN-30 (catalyst chemical industry Co., Ltd. water-dispersed colloidal silica dispersion, containing 30% by weight of solid content)
(F component)
MTMOS; Methyltrimethoxysilane DMDMOS; Dimethyldimethoxysilane (G component)
710T: IPA-dispersed titanium oxide dispersion manufactured by Teika Co., Ltd. (containing a solid content of 42.5% by weight)

(Evaluation of dissolution property of UV absorber in the first layer)
[Example 1]
Acrylic resin composition (i-1) was applied to a 5 mm thick, 10 cm square PC resin sheet so that the dry film thickness was 4 μm and thermally cured at 130 ° C. for 1 hour, then methanol: 2-propanol: 1 -Butanol = It was taken out after being immersed for 1 minute in 350 g of a mixed solution of 16:50:34 (weight ratio). When the absorption spectrum of the solution after repeating this operation 30 times was measured, the absorbance at 290 nm was 0.01.

[Example 2]
Acrylic resin composition (i-2) was applied to a 5 mm thick, 10 cm square PC resin sheet so that the dry film thickness was 4 μm and thermally cured at 130 ° C. for 1 hour, and then methanol: 2-propanol: 1 -Butanol = It was taken out after being immersed for 1 minute in 350 g of a mixed solution of 16:50:34 (weight ratio). When the absorption spectrum of the solution after repeating this operation 30 times was measured, the absorbance at 295 nm was 0.05.

[Example 3]
Acrylic resin composition (i-3) was applied to a 5 mm thick, 10 cm square PC resin sheet so that the dry film thickness was 4 μm and thermally cured at 130 ° C. for 1 hour, then methanol: 2-propanol: 1 -Butanol = 16:50:34 (weight ratio) It was taken out after being immersed for 1 minute in 350 g of a mixed solution. When the absorption spectrum of the solution after repeating this operation 30 times was measured, the absorbance at 295 nm was 0.01.

[Example 4]
An acrylic resin composition (i-4) was applied to a 5 mm thick, 10 cm square PC resin sheet so as to have a dry film thickness of 4 μm and thermally cured at 130 ° C. for 1 hour, and then methanol: 2-propanol: 1 -Butanol = It was taken out after being immersed for 1 minute in 350 g of a mixed solution of 16:50:34 (weight ratio). When the absorption spectrum of the solution after repeating this operation 30 times was measured, the absorbance at 295 nm was 0.01.

[Comparative Example 1]
An acrylic resin composition (i-5) was applied to a 5 mm thick, 10 cm square PC resin sheet so that the dry film thickness was 4 μm, and thermally cured at 130 ° C. for 1 hour, then methanol: 2-propanol: 1 -Butanol = It was taken out after being immersed for 1 minute in 350 g of a mixed solution of 16:50:34 (weight ratio). When the absorption spectrum of the solution after repeating this operation 30 times was measured, the absorbance at 295 nm was 1.12.

(Creation and evaluation of molded body (laminate))
[Example 5]
The acrylic resin composition (i-1) obtained in Reference Example 7 was coated on both sides by a dip coating method on a 5 mm thick PC resin sheet so that the film thickness after thermosetting was 8 μm, at 25 ° C. After standing for 20 minutes, it was thermoset at 130 ° C. for 1 hour. Next, the organosiloxane resin composition (ii-1) obtained in Reference Example 12 was applied on the coating surface of the sheet by a dip coating method so that the film thickness after thermosetting was 4 μm, and 20 ° C. at 25 ° C. After standing still, thermosetting was performed at 125 ° C. for 1 hour to obtain a PC resin molded body (laminate). Table 5 shows the configuration of the obtained PC resin laminate and the evaluation results.

[Example 6]
On both sides of the acrylic resin composition (i-2) obtained in Reference Example 8 on a 5 mm thick PC resin sheet by a dip coating method so that the film thickness after thermosetting is 8 μm, at 25 ° C. After standing for 20 minutes, it was thermoset at 130 ° C. for 1 hour. Next, the organosiloxane resin composition (ii-1) obtained in Reference Example 12 was applied on the coating surface of the sheet by a dip coating method so that the film thickness after thermosetting was 4 μm, and 20 ° C. at 25 ° C. After standing still, thermosetting was performed at 125 ° C. for 1 hour to obtain a PC resin molded body (laminate). Table 5 shows the configuration of the obtained PC resin laminate and the evaluation results.

[Example 7]
The acrylic resin composition (i-2) obtained in Reference Example 8 was coated on a 5 mm thick PC resin sheet on both sides by a dip coating method so that the film thickness after thermosetting was 10 μm, at 25 ° C. After standing for 20 minutes, it was thermoset at 130 ° C. for 1 hour. Next, the organosiloxane resin composition (ii-2) obtained in Reference Example 13 was applied on the surface of the sheet by a dip coating method so that the film thickness after thermosetting was 5 μm, and the coating was applied at 25 ° C. for 20 After standing still, thermosetting was performed at 125 ° C. for 1 hour to obtain a PC resin molded body (laminate). Table 5 shows the configuration of the obtained PC resin laminate and the evaluation results.

[Example 8]
The acrylic resin composition (i-3) obtained in Reference Example 9 was applied on both sides to a 5 mm thick PC resin sheet by a dip coating method so that the film thickness after thermosetting was 8 μm, at 25 ° C. After standing for 20 minutes, it was thermoset at 130 ° C. for 1 hour. Next, the organosiloxane resin composition (ii-2) obtained in Reference Example 13 was applied on the surface of the sheet by a dip coating method so that the film thickness after thermosetting was 5 μm, and the coating was applied at 25 ° C. for 20 After standing still, thermosetting was performed at 125 ° C. for 1 hour to obtain a PC resin molded body (laminate). The composition of the obtained PC resin laminate and the evaluation results are shown in Table 5.

[Example 9]
The acrylic resin composition (i-4) obtained in Reference Example 10 was applied to both sides by a dip coating method on a 5 mm thick PC resin sheet so that the film thickness after thermosetting was 8 μm, at 25 ° C. After standing for 20 minutes, it was thermoset at 130 ° C. for 1 hour. Next, the organosiloxane resin composition (ii-1) obtained in Reference Example 13 was applied on the surface of the sheet by a dip coating method so that the film thickness after thermosetting was 4 μm, and 20 ° C. at 25 ° C. After standing still, thermosetting was performed at 125 ° C. for 1 hour to obtain a PC resin molded body (laminate). The composition of the obtained PC resin laminate and the evaluation results are shown in Table 5.

[Comparative Example 2]
The acrylic resin composition (i-5) obtained in Reference Example 11 was applied to both sides by a dip coating method on a 5 mm thick PC resin sheet by a dip coating method so that the film thickness after thermosetting was 8 μm. After standing for 20 minutes, it was thermoset at 130 ° C. for 1 hour. Next, the organosiloxane resin composition (ii-1) obtained in Reference Example 13 was applied on the surface of the sheet by a dip coating method so that the film thickness after thermosetting was 4 μm, and 20 ° C. at 25 ° C. After standing still, thermosetting was performed at 125 ° C. for 1 hour to obtain a PC resin molded body (laminate). The composition of the obtained PC resin laminate and the evaluation results are shown in Table 5.

Claims (18)

(A) 1 to 60 mol% of a repeating unit ((A-1) unit) represented by the following formula (1),

(In the formula, R ¹ is a methyl group or an ethyl group.)
A repeating unit ((A-2) unit) represented by the following formula (2) in an amount of more than 35 mol% and not more than 85 mol%,

(Wherein R ² is a cycloalkyl group, and X ¹ is a hydrogen atom or a methyl group.)
0.1 to 15 mol% of a repeating unit ((A-3) unit) represented by the following formula (3), and

(In the formula, X ² is a hydrogen atom or a methyl group, and W is an ultraviolet absorbing group.)
1 to 15 mol% of a repeating unit represented by the following formula (4) (unit (A-4))

(Wherein R ³ is an alkylene group having 2 to 5 carbon atoms, X ³ is a hydrogen atom or a methyl group, and Z is at least selected from the group consisting of a hydroxy group, an alkoxysilyl group, a glycidyloxy group, and an isocyanate group. 1 type of substituent.)
In which the total of (A-1) to (A-4) units is at least 70 mol% in 100 mol% of all repeating units of the acrylic copolymer. An acrylic resin composition for coating containing an acrylic copolymer.   The acrylic resin composition for coating according to claim 1, wherein W in the unit (A-3) is a triazine-based ultraviolet absorbing group. The acrylic for coating according to claim 1, wherein the unit (A-3) is a repeating unit derived from an acrylic monomer containing an ultraviolet absorbing group represented by the following formula (5) and / or the following formula (6). Resin composition.

(Wherein R ⁴ represents an alkylene group having 2 to 6 carbon atoms, R ⁵ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, and R ⁶ and R ⁷ are the same) Or independently of each other, a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a phenyl group optionally substituted by an alkyl group having 1 to 18 carbon atoms or a halogen atom R ⁸ represents an alkyl group having 1 to 18 carbon atoms, X ⁴ represents a hydrogen atom or a methyl group, and Y ¹ represents a hydrogen atom, an OH group, or an alkyl group having 1 to 12 carbon atoms.)

(In the formula, R ⁹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, and R ¹⁰ and R ¹¹ are the same or independently of each other, a hydrogen atom, a halogen atom, or a carbon atom having 1 carbon atom. Represents an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or an alkyl group having 1 to 18 carbon atoms or a phenyl group optionally substituted with a halogen atom, and R ¹² represents an alkyl group having 1 to 18 carbon atoms. X ⁵ represents a hydrogen atom or a methyl group, and Y ² represents a hydrogen atom, an OH group, or an alkyl group having 1 to 12 carbon atoms.) The acrylic resin composition for coating according to claim 1, wherein the unit (A-4) is a repeating unit represented by the following formula (7).

(Wherein R ¹³ is an alkylene group having 2 to 5 carbon atoms, and X ⁶ is a hydrogen atom or a methyl group.) (A) The acrylic copolymer (component A) according to claim 1, (B) having a converted isocyanate group ratio of 5.5 to 50% by weight, and (A-3) based on 1 equivalent of hydroxy group in the unit To a blocked polyisocyanate compound (B component) having an isocyanate group in an amount of 0.8 to 1.5 equivalents, and (C) (A) component and (B) component in total 100 parts by weight The acrylic resin composition for coating according to claim 1, comprising 0.001 to 0.4 parts by weight of a curing catalyst (component C). (A) component is 1-59.9 mol% of said (A-1) unit, exceeds 35 mol% of said (A-2) unit, and is 85 mol% or less, said 0.1 unit of (A-3). An acrylic copolymer containing 15 mol%, 1 to 15 mol% of (A-4) units and 0.1 to 20 mol% of repeating units ((A-5) units) represented by the following formula (8): The acrylic resin composition for coating according to claim 1, wherein the total of (A-1) to (A-5) units is at least 70 mol% in 100 mol% of all repeating units of the acrylic copolymer.

(In the formula, R ¹⁴ is a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an alkoxy group.)   It contains 0.1 to 10 parts by weight of the silane coupling agent and / or the hydrolysis condensate of the silane coupling agent as the component (D) with respect to 100 parts by weight of the total of the component (A) and the component (B). The acrylic resin composition for coating according to claim 1.   The acrylic resin paint for coating whose acrylic resin composition density | concentration which melt | dissolved the acrylic resin composition of any one of Claims 1-7 in the solvent is 1 to 50 weight%. As a first layer on at least one surface of the plastic substrate surface,
(A) 1 to 60 mol% of a repeating unit ((A-1) unit) represented by the following formula (1),

(In the formula, R ¹ is a methyl group or an ethyl group.)
A repeating unit ((A-2) unit) represented by the following formula (2) in an amount of more than 35 mol% and not more than 85 mol%,

(Wherein R ² is a cycloalkyl group, and X ¹ is a hydrogen atom or a methyl group.)
0.1 to 15 mol% of a repeating unit ((A-3) unit) represented by the following formula (3), and

(In the formula, X ² is a hydrogen atom or a methyl group, and W is an ultraviolet absorbing group.)
1 to 15 mol% of a repeating unit represented by the following formula (4) (unit (A-4))

(Wherein R ³ is an alkylene group having 2 to 5 carbon atoms, X ³ is a hydrogen atom or a methyl group, and Z is at least selected from the group consisting of a hydroxy group, an alkoxysilyl group, a glycidyloxy group, and an isocyanate group. 1 type of substituent.)
In which the total of (A-1) to (A-4) units is at least 70 mol% in 100 mol% of all repeating units of the acrylic copolymer. An acrylic resin layer obtained by thermally curing an acrylic resin composition containing an acrylic copolymer is laminated, and as a second layer on the first layer,
(E) colloidal silica (component e) and (F) a hydrolytic condensate (component f) of an alkoxysilane represented by the following formula (9):

(In the formula, R ¹⁵ and R ¹⁶ 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 ¹⁷ is an alkyl group having 1 to 4 carbon atoms or a vinyl group, and m and n are each an integer of 0, 1, or 2, respectively. M + n is an integer of 0, 1, or 2.)
Of an organosiloxane resin composition containing 10 to 60% by weight of the e component and 40 to 90% by weight of the f component in terms of R ¹⁵ _m R ¹⁶ _n SiO _{(4-mn) / 2} A plastic molded body with a cured coating layer laminated.   The plastic molded body according to claim 9, wherein W in the unit (A-3) of the component (A) is a triazine-based ultraviolet absorbing group. The (A-3) unit of the component (A) is a repeating unit derived from an acrylic monomer containing an ultraviolet absorbing group represented by the following formula (5) and / or the following formula (6). The plastic molding as described.

(Wherein R ⁴ represents an alkylene group having 2 to 6 carbon atoms, R ⁵ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, and R ⁶ and R ⁷ are the same) Or independently of each other, a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a phenyl group optionally substituted by an alkyl group having 1 to 18 carbon atoms or a halogen atom R ⁸ represents an alkyl group having 1 to 18 carbon atoms, X ⁴ represents a hydrogen atom or a methyl group, and Y ¹ represents a hydrogen atom, an OH group, or an alkyl group having 1 to 12 carbon atoms.)

(In the formula, R ⁹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, and R ¹⁰ and R ¹¹ are the same or independently of each other, a hydrogen atom, a halogen atom, or a carbon atom having 1 carbon atom. Represents an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or an alkyl group having 1 to 18 carbon atoms or a phenyl group optionally substituted with a halogen atom, and R ¹² represents an alkyl group having 1 to 18 carbon atoms. X ⁵ represents a hydrogen atom or a methyl group, and Y ² represents a hydrogen atom, an OH group, or an alkyl group having 1 to 12 carbon atoms.) The plastic molded body according to claim 9, wherein the unit (A-4) of the first layer is a repeating unit represented by the following formula (7).

(In the formula, R ¹³ is an alkylene group having 2 to 5 carbon atoms, and X ⁶ is a hydrogen atom or a methyl group.) The acrylic resin composition according to claim 9 has (A) an acrylic copolymer (component A), (B) a converted isocyanate group ratio of 5.5 to 50% by weight, and (A-3) in units. Blocked polyisocyanate compound (B component) having an isocyanate group in an amount of 0.8 to 1.5 equivalents relative to 1 equivalent of hydroxy group, and the sum of (C) (A) component and (B) component The plastic molded article according to claim 9, which is an acrylic resin composition for coating containing 0.001 to 0.4 parts by weight of a curing catalyst (component C) with respect to 100 parts by weight. The component (A) is 1 to 59.9 mol% of the (A-1) unit, more than 35 mol% of the (A-2) unit and 85 mol% or less, and 0.1 of the (A-3) unit. Acrylic copolymer containing -15 mol%, (A-4) 1-15 mol% units and 0.1-20 mol% of repeating units ((A-5) units) represented by the following formula (8) 10. The acrylic copolymer according to claim 9, wherein a total of (A-1) to (A-5) units is at least 70 mol% in 100 mol% of all the repeating units of the acrylic copolymer. Plastic molded body.

(In the formula, R ¹⁴ is a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an alkoxy group.)   In the first layer, 0.1 to 10 parts by weight of silane coupling agent and / or silane coupling agent as component (D) is added to 100 parts by weight of component (A) and component (B). The plastic molded body according to claim 9, which is a coating layer formed by thermally curing an acrylic resin composition for coating containing a decomposition condensate.   The organosiloxane resin composition in which the second layer contains 0.5 to 5 parts by weight of a metal oxide (g component) as the (G) component with respect to 100 parts by weight of the total of the (E) component and the (F) component. The plastic molded body according to claim 9, which is a thermosetting coating layer of a product.   The plastic molded body according to claim 16, wherein the component (G) is at least one metal oxide fine particle selected from the group consisting of titanium oxide, zinc oxide, cerium oxide, tin oxide and tungsten oxide.   The plastic molded body according to claim 9, wherein the plastic substrate is a polycarbonate resin substrate.