JP2005219299A - Laminate made of synthetic resin and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent laminate made of a synthetic resin excellent in scratch resistance, abrasion resistance and weatherability, and its manufacturing method. <P>SOLUTION: The laminate made of the synthetic resin is manufacture by bonding at least one side of a transparent synthetic resin layer (A) formed by injection molding and the surface of the transparent resin base material (b-1) of a laminated substrate (B), which is obtained by providing an acrylic resin layer (b-2) containing an ultraviolet absorber to one side of the transparent resin base material (b-1), and has a cured film layer (b-3) formed by coating the acrylic resin layer (b-2) of the laminated substrate (B) with a thermosetting polyorganosiloxane composition which substantially contains no monomer-dimer components and comprises 0.01-3% of a trimer component, 1-15% of a tetramer component, 1-13% of a pentamer and 69-97% of a hexamer and has a number average polymerization degree of 8-100. This laminate is excellent in transparency, surface hardness, scratch resistance, abrasion resistance and weatherability and has excellent appearance and a hue. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a synthetic resin laminate and a method for producing a synthetic resin laminate, and more specifically, a transparent synthetic resin having a cured film layer on the surface and excellent in transparency, scratch resistance, abrasion resistance, and weather resistance. The present invention relates to a laminate and a method for producing the synthetic resin laminate.

  Transparent synthetic resin base materials have been widely used as structural materials to replace glass because of their excellent processing freedom and lightness. For example, automotive covers such as instrument covers, glazings, and lamp lenses, mobile phones, OA / electrical / electronic applications such as mobile terminal housings, display boards, etc., greenhouse materials, arcades, building materials such as daylighting roofing materials, sidewalk lumbar boards, road materials such as highway fences, nameplates, etc. Widely used for materials.

  However, since the surface properties such as scratch resistance, abrasion resistance, weather resistance and the like are insufficient, the use thereof is limited, and there is a strong demand for improving the surface properties of the synthetic resin base material. As a method for improving the surface characteristics, there is a method of coating the surface of a synthetic resin molded article with a surface treatment agent, for example, a polyfunctional acrylic photo-curing resin, a melamine-based or polyorganosiloxane-based thermosetting resin. There has been proposed a method of forming a cured film layer made of the above material on the surface of a synthetic resin substrate.

  Among these, products coated with polyorganosiloxane are excellent in wear resistance and chemical resistance, and coating with polyorganosiloxane is considered useful. However, the coating with polyorganosiloxane has a problem in adhesion to the synthetic resin, and particularly when used outdoors for a long time, there is a problem that the coating layer is peeled off from the synthetic resin layer.

As a method for improving the adhesion, for example, Patent Document 1 describes a method of blending various polymers having good adhesion to the paint, but the surface hardness is lowered, and in some cases, the weather resistance of the paint is remarkably lowered. . In order to improve the weather resistance, there is a method of adding a high concentration UV absorber, but there is a problem that the wear resistance is remarkably lowered. Therefore, in applications requiring surface hardness and weather resistance, a two-coat method using an acrylic primer is generally used, but the work process becomes long and the productivity tends to decrease.
Further, as a synthetic resin laminate having improved surface hardness, weather resistance, abrasion resistance, etc., for example, an ultraviolet resistant transparent synthetic resin layer (b) and a cured coating layer are formed on at least one surface of the transparent synthetic resin layer (a). The synthetic resin laminate in which (c) is sequentially laminated is disclosed in Patent Document 2 or on at least one surface of the transparent synthetic resin layer (a) via the transparent synthetic resin intermediate layer (b). Patent Document 3 discloses a synthetic resin laminate in which a resin layer (c) and a cured film layer (d) are laminated. In addition, a plastic laminate in which polyorganosiloxane is applied and cured on an acrylic resin layer of a laminate provided with an acrylic resin layer containing an ultraviolet absorber on at least one surface of a plastic substrate is manufactured by a continuous polymerization method. Patent Document 4 describes a plastic laminate using an acrylic resin.

JP-A-7-90224 JP 2001-334610 A JP 2001-315271 A JP 2003-11293 A

  An object of the present invention is to solve the above-mentioned problems in the prior art, and to provide a transparent synthetic resin laminate having excellent scratch resistance, abrasion resistance and weather resistance, and a method for producing the synthetic resin laminate. It is in.

  The present invention has been made to solve the above-mentioned problems, and the gist thereof is that at least one surface of the transparent synthetic resin layer (A) formed by injection molding and a transparent resin substrate (b-1). ) Is coated with a specific thermosetting polyorganosiloxane composition on the acrylic resin coating layer of the laminated substrate provided with an acrylic resin layer (b-2) containing an ultraviolet absorber on one side and cured. The present invention relates to a synthetic resin laminate obtained by bonding a transparent resin substrate (b-1) surface of a resin laminate (B) having a coating layer (b-3) and a method for producing the same.

Furthermore, the linear expansion coefficients of the transparent synthetic resin layer (A), the transparent resin substrate (b-1), the acrylic resin layer (b-2), and the coating layer (b-3) formed by injection molding were variously changed. When the performance was evaluated by forming a coating film, a laminate made of a synthetic resin having a difference in linear expansion coefficient between each layer of 10 × 10 ⁻⁵ / ° C. or less is scratch resistant even after a severe weather resistance test. As a result, the present invention was completed.

  That is, the present invention provides an acrylic resin layer (b-) containing an ultraviolet absorber on at least one surface of the transparent synthetic resin layer (A) formed by injection molding and one surface of the transparent resin substrate (b-1). 1) The dimer component is not substantially present in the acrylic resin coating layer of the laminated substrate provided with 2), the trimer component is 0.01 to 3%, and the tetramer component is 1 to 15%. A thermosetting polyorganosiloxane composition having a pentamer component of 1 to 13%, a hexamer of 69 to 97% and a number average degree of polymerization of 8 to 100 is applied and cured. It is related with the synthetic resin laminated body formed by joining the transparent resin base material (b-1) surface of the resin laminated board (B) which has a cured film layer (b-3) which becomes.

  Further, the resin laminate (B) is disposed so that the cured coating layer (b-3) in the resin laminate (B) is in contact with at least one surface of the inner surface of the mold, and then injected into the mold by injection molding. A transparent synthetic resin layer (A) to be formed is injected and injected with a transparent synthetic resin layer (B), and a transparent synthetic resin layer (B-1) surface and a transparent synthetic resin layer (B) formed by injection molding ( The present invention relates to a method for producing a synthetic resin laminate, wherein A) is joined and laminated and integrated.

Furthermore, the synthetic resin laminate of the present invention comprises a transparent synthetic resin layer (A) formed by injection molding, a transparent resin substrate (b-1), an acrylic resin layer (b-2), and a coating layer (b- 3) The difference in linear expansion coefficient between the respective layers is 10 × 10 ⁻⁵ / ° C. or less.
In the present specification, hereinafter, a transparent synthetic resin laminate may be simply referred to as a “laminate”.

  The laminate of the present invention is excellent in transparency, surface hardness, scratch resistance, abrasion resistance, weather resistance, and also in appearance and color tone, instrument cover, glazing, lamp lens , Automotive applications such as glass for roof windows, mobile phone, mobile terminal housings, OA / electrical / electronic applications such as display boards, greenhouse coating materials, arcades, building materials such as daylighting roofing materials, sidewalk lumbars, It is useful in various applications such as road materials such as highway fences and industrial materials such as nameplates.

  As the transparent synthetic resin of the transparent synthetic resin layer (A) formed by injection molding constituting the laminate of the present invention and the transparent synthetic resin of the transparent resin substrate (b-1), respectively, polycarbonate resin (PC), Polyester polycarbonate resin, methacrylic resin (PMMA), MS resin (MMA-SM copolymer resin), amorphous polyolefin resin (APO), transparent ABS resin, transparent polystyrene resin (transparent PS), special acrylic resin, acrylonitrile-styrene Resin (AS), polyarylate resin (PAR), polysulfone resin (PSF), polyethersulfone resin (PES), transparent epoxy resin, TPX resin (poly-4-methylpentene-1), fluorinated polyimide resin, transparent Fluorine resin, transparent phenoxy resin, sulfur-containing urethane resin, norvol Such as down resin. Particularly preferred examples include a polycarbonate resin (PC) is.

  The thickness of the transparent synthetic resin layer (A) formed by injection molding in the laminate of the present invention is preferably 0.8 to 30 mm. If it is 0.8 mm or less, filling of the resin tends to be difficult, and if it is 30 mm or more, product shaping becomes difficult. The thickness of the transparent synthetic resin layer formed by injection molding is more preferably 1 to 20 mm, and most preferably 1.2 to 10 mm.

  The haze of the transparent synthetic resin in the transparent synthetic resin layer (A) formed by the injection molding is preferably 10% or less as measured with a molded product having a thickness of 1 mm. When the haze is 10% or more, the transparency in the laminate tends to be insufficient. The haze of the transparent synthetic resin formed by injection molding is more preferably 8% or less, and most preferably 5% or less, as measured with a molded product having a thickness of 1 mm.

  The haze of the transparent synthetic resin forming the transparent resin substrate (b-1) in the laminate of the present invention is preferably 10% or less as measured with a molded product having a thickness of 1 mm. When the haze is 10% or more, the transparency in the laminate tends to be insufficient. The haze of the transparent synthetic resin forming the transparent resin substrate (b-1) is more preferably 8% or less, and most preferably 5% or less, as measured with a molded product having a thickness of 1 mm.

  The transparent synthetic resin of the transparent synthetic resin layer (A) formed by injection molding constituting the laminate according to the present invention and the haze of the transparent synthetic resin forming the transparent resin substrate (b-1) are the same or approximate. It is important from the viewpoint of ensuring the transparency of the molded product. If the hazes of the two are greatly different, the transparency of the molded product is lowered, which is not preferable. Therefore, the transparent synthetic resin forming the transparent synthetic resin layer (A) and the transparent synthetic resin forming the transparent resin substrate (b-1) are selected in consideration of these points.

  The transparent synthetic resin of the transparent synthetic resin layer (A) formed by the injection molding of the present invention and the transparent synthetic resin forming the transparent resin substrate (b-1) are benzotriazole-based to the extent that transparency is not impaired. It may contain organic UV absorbers such as compounds, benzophenone compounds, benzoate compounds, salicylate compounds, triaryltriazine compounds, and inorganic UV shielding agents such as titanium oxide, zinc oxide, and cerium oxide. Other light stabilizers, antioxidants, heat stabilizers, antistatic agents, heat ray reflectors, heat ray absorbers, flame retardants, lubricants, pigments, fillers, and the like may be included.

  When the transparent synthetic resin forming the transparent resin substrate (b-1) contains an ultraviolet absorber, the ultraviolet absorber content of the transparent synthetic resin depends on the ultraviolet absorbing ability of the ultraviolet absorber used and the transparent resin substrate. Although it depends on the thickness of (b-1), it is preferably less than 0.5% by weight with respect to the transparent synthetic resin. In the laminate of the present invention, an ultraviolet absorber is contained in the acrylic resin forming the acrylic resin layer (b-2), and the transparent resin base material is obtained by sufficiently maintaining the ultraviolet resistance of the acrylic resin layer. Even if the content of the ultraviolet absorbent in the transparent synthetic resin in (b-1) is 0.5% by weight or more, no significant effect is observed in the weather resistance of the laminate of the present invention.

Acrylic resin layer (b-2) located in the middle of the transparent resin substrate (b-1) and the cured film layer (b-3) obtained by curing the thermosetting polyorganosiloxane composition in the laminate of the present invention. The acrylic resin that forms the film will be specifically described. The acrylic resin is a copolymer of methyl methacrylate and methyl acrylate or ethyl acrylate, and the copolymer composition and molecular weight may be appropriately selected depending on the co-extrusion conditions and the appearance of the produced film, sheet, board, etc. As the polymerization composition ratio, methyl methacrylate 80 to 99%, methyl or ethyl acrylate 1 to 20% is appropriate, and the molecular weight is about 5 to 300,000, but is not limited thereto. The load deflection temperature of the acrylic resin is preferably 90 ° C. or higher, preferably 95 ° C. or higher, more preferably 100 ° C. or higher.
The method of producing the acrylic resin for forming the acrylic resin layer (b-2) is generally roughly divided into an emulsion polymerization method, a suspension polymerization method, and a continuous polymerization method. The acrylic resin used in the present invention is An acrylic resin produced by a continuous polymerization method is preferably used. Further, the continuous polymerization method can be divided into a continuous bulk polymerization method and a continuous solution polymerization method. In the invention, an acrylic resin obtained by either method can be used. Some are manufactured by the method described in JP-A-7-133303.

  The content of the ultraviolet absorbent in the acrylic resin forming the acrylic resin layer (b-2) is preferably 0 with respect to the acrylic resin, although it depends on the ultraviolet absorbing ability of the ultraviolet absorbent used and the thickness of the acrylic resin layer. 0.01 to 5% by weight. When the content is less than 0.01% by weight, the UV resistance is insufficient, and when it exceeds 5% by weight, the UV-resistant transparent synthetic resin layer is likely to be colored peculiar to the UV absorber, and further during sheet molding. The cooling roll and the working environment are contaminated by the volatilization of the UV absorber, and the sheet appearance tends to be damaged. The ultraviolet absorber content in the acrylic resin forming the acrylic resin layer (b-2) is more preferably 0.02 to 3.5% by weight, and particularly preferably 0.03 to 3.5% by weight with respect to the acrylic resin. 3.2% by weight.

  Examples of the ultraviolet absorber contained in the acrylic resin include organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, benzoate compounds, salicylate compounds, triaryltriazine compounds, and preferably triaryls. A triazine type compound and a benzotriazole type compound are mentioned. The triaryltriazine-based compound has a high ultraviolet absorptivity around 280 to 300 nm and a low volatility, and remarkably improves the ultraviolet resistance in the synthetic resin laminate. As the triaryltriazine-based compound, a compound represented by the following chemical formula is preferable.

(Chemical formula 1)

In the formula, R ¹ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a halogen atom, an alkyl group having 2 to 6 carbon atoms substituted with an alkoxy group having 1 to 15 carbon atoms, or a benzyl group, and R ² to R ⁵ are each a hydrogen atom or a methyl group.

  The acrylic resin that forms the acrylic resin layer (b-2) may contain an inorganic ultraviolet shielding agent such as titanium oxide, zinc oxide, cerium oxide or the like as long as the transparency is not impaired. An agent, an antioxidant, a heat stabilizer, an antistatic agent, a heat ray reflective agent, a heat ray absorbent, a flame retardant, a lubricant, a pigment, a filler, and the like may be included.

  The transparent synthetic resin forming the transparent synthetic resin and the transparent resin base material (b-1) of the transparent synthetic resin layer (A) formed by the above injection molding is also used as the haze of the acrylic resin forming the acrylic resin layer (b-2). It is necessary from the viewpoint of ensuring the transparency of the molded product to be the same as or similar to the haze of the molded product. Therefore, the haze of the acrylic resin forming the acrylic resin layer (b-2) is preferably 10% or less as measured by a molded product having a thickness of 1 mm. When the haze is 10% or more, the transparency of the laminate tends to be insufficient. The haze of the acrylic resin forming the acrylic resin layer (b-2) is more preferably 8% or less, and most preferably 5% or less, as measured by a molded product having a thickness of 1 mm.

  The thickness of the acrylic resin layer (b-2) may be a thickness having required ultraviolet resistance, and is preferably 1 to 200 μm. If it is less than 1 μm, the ultraviolet absorption effect is insufficient, and if it exceeds 200 μm, the ultraviolet resistance is not significantly improved, and the impact strength may be significantly reduced. The thickness of the acrylic resin layer (b-2) is more preferably 3 to 150 μm, and most preferably 5 to 100 μm.

The total thickness of the transparent resin substrate (b-1) and the acrylic resin layer (b-2) is preferably 0.2 to 3 mm, more preferably 0.3 to 2.5 mm.
If the total thickness of the transparent resin base material (b-1) and the acrylic resin layer (b-2) is too small or too large, it is difficult to handle as a sheet or film, and workability during molding and the like is improved. Inferior. The thickness of the transparent resin substrate (b-1) is preferably larger than the thickness of the acrylic resin layer (b-2), and the transparent resin substrate (b-1) is thickened to absorb ultraviolet rays. The thickness of the UV-resistant acrylic resin layer (b-2) having excellent properties can be made relatively small.

  The ratio between the thickness of the acrylic resin layer (b-2) and the thickness of the transparent resin substrate (b-1) is preferably 1/250 to 1/2. If the thickness ratio is less than 1/250, the UV resistance effect of the UV resistant acrylic resin layer (b-2) tends to be insufficient, and if it exceeds 1/2, the UV resistance effect becomes excessive and costly. In addition to being disadvantageous, transparency tends to be hindered by coloring. The ratio of the thickness of the ultraviolet resistant acrylic resin layer (b-2) to the thickness of the transparent resin substrate (b-1) is more preferably 1/200 to 1/3, most preferably 1/150 to 1/4.

  The total of the thickness of the acrylic resin layer (b-2) and the thickness of the transparent resin substrate (b-1) is preferably 3/100 to 50/100 of the thickness of the laminate. If the total thickness of the UV-resistant acrylic resin layer (b-2) and the transparent resin substrate (b-1) is less than 3/100 of the thickness of the laminate, the UV resistance of the laminate is insufficient. If it exceeds 50/100, the thickness of the transparent synthetic resin layer (A) formed by injection molding may be insufficient and injection molding may be difficult. The total of the thickness of the ultraviolet resistant acrylic resin layer (b-2) and the thickness of the transparent resin substrate (b-1) is more preferably 5/100 to 40/100 of the thickness of the laminate.

  In the cured film layer (b-3) constituting the laminate of the present invention, the 1-dimer component is substantially absent, the trimer component is 0.01-3%, and the tetramer component is 1 A thermosetting polyorganosiloxane composition having a number average polymerization degree of 8 to 100 and an acrylic resin layer (1 to 15%, a pentamer component of 1 to 13%, a hexamer or more of 69 to 97%, and a number average polymerization degree of 8 to 100). It is applied to b-2) and cured.

The thermosetting polyorganosiloxane used in the present invention is a hydrolyzate obtained by hydrolyzing and condensing a normal organosilane represented by the general formula R _1n Si (OR ₂ ) _4-n and / or It is a partial condensate. Particularly preferred organosilanes are tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, and dimethyldiethoxysilane. These organosilanes can be used alone or in combination of two or more. These organosilanes are hydrolyzed / condensed using a predetermined amount of water to be oligomerized, and the monomers are almost consumed and do not exist in the reaction system. Thereafter, the dimer component is substantially absent, the trimer component is 0.01 to 3%, the tetramer component is 1 to 15%, the pentamer component is 1 to 13%, and 6 amount. The reaction is further advanced so as to obtain a polyorganosiloxane composition having a body content of 69 to 97% and a number average degree of polymerization of 8 to 100. The reaction temperature is usually 25 ° C. to 70 ° C., preferably 30 ° C. to 60 ° C., more preferably 30 to 50 ° C., and the subsequent reaction is gradually advanced. However, if it is less than 25 ° C., it takes a long time to obtain a desired oligomer composition, which is not preferable. If it exceeds 70 ° C., a crosslinking reaction may occur, which is not preferable.

Hydrolysis of the organosilane for obtaining the thermosetting polyorganosiloxane composition used in the present invention can be carried out by a generally known method, and is carried out in the presence of water containing an acidic hydrolyzable catalyst. Is preferred. The hydrolyzable catalyst can be selected from known catalysts exhibiting acidity of pH 2-5.
In addition, a combination of acid and basic compounds (acetic acid and sodium acetate, disodium hydrogen phosphate and citric acid, etc.) that serve as a buffer for adjusting the pH, organic solvents to impart excellent film performance. Resins, pigments, dyes, leveling agents, ultraviolet absorbers, storage stabilizers and the like can be appropriately added and used.

The storage temperature of the polyorganosiloxane composition obtained here is usually 25 ° C. or lower, preferably 15 ° C. or lower, more preferably 5 ° C. or lower. If the temperature exceeds 25 ° C., the hydrolysis / condensation reaction proceeds gradually if the storage period is long.
When forming a cured film using the thermosetting polyorganosiloxane composition in the present invention, in order to impart optical functionality such as improved hardness and scratch resistance of the cured film, or higher refractive index, A curing catalyst, metal oxide, and other additives may be added as appropriate.

Examples of the curing catalyst include known basic compounds, metal compounds, and acidic compounds. The addition amount of the curing catalyst is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the thermosetting polyorganosiloxane composition.
Examples of the metal oxide include silica, alumina, titanium oxide, cesium oxide, tin oxide, zirconium oxide, antimony oxide, and iron oxide. In particular, colloidal silica (silica sol) is suitable for a hard coating agent for the purpose of scratch resistance. When used as a hard coating agent, the amount of metal oxide added is preferably 5 to 500 parts by weight, more preferably 10 to 200 parts by weight, per 100 parts by weight of thermosetting polyorganosiloxane. The condensation reaction may be performed in the presence of these metal oxides, or may be added after the condensation reaction.

  Depending on the purpose, the thermosetting polyorganosiloxane composition can be applied by brush, roll, dipping, flow coating, spray, roll coater, flow coater, centrifugal coater, ultrasonic coater, screen process, electrodeposition coating, vapor deposition. There are paintings.

  The thickness of the cured film layer in the laminate of the present invention is preferably 1 to 15 μm. If the thickness of the cured film layer is less than 1 μm, the effect of the surface cured film tends to be insufficient, and if it exceeds 15 μm, the effect of the surface cured film is hardly further improved, which is disadvantageous in terms of cost. The thickness of the cured film layer is more preferably 2 to 12 μm.

  The structure of the resin laminated board (B) which comprises the laminated body of this invention is the laminated board which provided the acrylic resin layer (b-2) containing a ultraviolet absorber in the single side | surface of a transparent resin base material (b-1). The acrylic resin coating layer comprises a cured coating layer (b-3) obtained by applying a thermosetting polyorganosiloxane composition and curing it.

  The printed part is formed on the surface opposite to the surface provided with the cured film layer (b-3) in the resin laminate (B) constituting the laminate of the present invention, that is, on the surface of the transparent resin substrate (b-1). Can be provided. Examples of the printing unit include characters, marks, colors, patterns, and the like. Conventionally known methods can be used as a method for forming a beautifying surface such as characters, marks, colors, and patterns, and specific examples include silk screen printing and hot stamping. . The transparent resin base material (b-1) which is the surface opposite to the surface provided with the cured coating layer (b-3) in the resin laminate (B) constituting the laminate of the present invention is further desired. Accordingly, at least one functional film such as heat ray reflection performance, heat ray absorption performance, and conductive performance can be printed.

  The synthetic resin laminate of the present invention is an acrylic resin layer containing an ultraviolet absorber on one side of the transparent synthetic resin layer (A) formed by injection molding and one side of the transparent resin substrate (b-1). A resin laminate having a cured coating layer (b-3) formed by applying a thermosetting polyorganosiloxane composition to the acrylic resin coating layer of the laminate substrate provided with (b-2) and curing the composition. A transparent resin substrate (b) is formed on both surfaces of a synthetic resin laminate formed by bonding the transparent resin substrate (b-1) surface of (B) and the transparent synthetic resin layer (A) formed by injection molding. The thermosetting polyorganosiloxane composition is applied and cured on the acrylic resin coating layer of the laminated substrate provided with the acrylic resin layer (b-2) containing an ultraviolet absorber on one side of 1) Of the resin laminate (B) on which the cured film layer (b-3) is formed Akira resin substrate (b-1) composed by bonding a surface of synthetic resin laminate and the like.

  The manufacturing method of the synthetic resin laminate of the present invention is as follows. That is, the resin laminate (B) is arranged so that the cured coating layer (b-3) provided on the resin laminate (B) is in contact with one or both surfaces of the inner surface of the mold, and then injected into the mold. A transparent synthetic resin layer (A) formed by molding is injected and injected, and the transparent synthetic resin (B-1) surface of the resin laminate (B) and the transparent synthetic resin formed by injection molding By laminating and integrating the layer (A), a synthetic resin laminate in which the cured film layer (b-3) of the resin laminate (B) is disposed on one side or both sides can be produced. .

  When the laminated body made of the synthetic resin of the present invention is used as a window glass for automobiles, the outside of the vehicle has severer performances such as weather resistance, scratch resistance, and abrasion resistance than the inside of the vehicle, so that the surface corresponding to the outside of the vehicle is used. Arranges the cured film layer (b-3) of the resin laminate (B) and cures the resin laminate (B) or the resin laminate (B) with an acrylic or other type of paint on the surface corresponding to the vehicle interior. It is also possible to dispose the coated film layer.

  In addition, in order to obtain a synthetic resin laminate with a high degree of drawing of the quadratic curved surface or the cubic curved surface as the product shape, the resin laminated plate (B) is pre-shaped into the shape of the mold cavity and then placed in the mold. It is preferable to do. When the resin laminate (B) and the transparent synthetic resin layer (A) formed by injection molding are laminated and integrally molded, if the product curvature (H / D) exceeds 0.1, the resin laminate (B) There is a problem that wrinkles occur because the resin laminate (B) that is shaped into the product shape by the resin flowing through the resin cannot be fully squeezed with the resin. In such a case, it is preferable to preform the resin laminate (B) in advance by vacuum forming, pressure forming, press forming, straight forming, drape forming, plug assist forming, etc., and giving the shape by vacuum forming or the like. As a result, a synthetic resin laminate having excellent formability can be obtained.

  There is no restriction | limiting in particular about the method of manufacturing the laminated substrate which provided the acrylic resin layer (b-2) containing a ultraviolet absorber on the single side | surface of a transparent resin base material (b-1), For example, a transparent resin base material ( b-1) and a co-extrusion method in which the raw material resin of the acrylic resin layer (b-2) containing the ultraviolet absorber is melt-extruded at the same time, and the transparent resin of the transparent resin substrate (b-1) is formed into a sheet A method in which an acrylic resin layer containing an ultraviolet absorber is melt extruded and laminated at the same time as extrusion molding, and an acrylic resin layer (b-2) previously formed into a film is extruded into a transparent resin substrate (b-1). A method of continuously laminating at the time of molding, a method of thermocompression bonding the transparent resin base material (b-1) and the acrylic resin layer (b-2) formed into a sheet shape or a film shape with a press machine, etc. are used. But cheap and mass production If that coextrusion method is preferred.

  As an extrusion apparatus used in the coextrusion method, a main extruder for extruding a thermoplastic resin constituting the transparent resin base material (b-1) and an acrylic resin constituting an acrylic resin layer (b-2) serving as a coating layer The sub-extruder is usually smaller than the main extruder. The temperature condition of the main extruder is usually 230 ° C to 290 ° C, preferably 240 ° C to 280 ° C, and the temperature condition of the sub-extruder is usually 220 ° C to 270 ° C, preferably 230 ° C to 260 ° C. As a method for coating two or more kinds of molten resins, a known method such as a feed block method or a multi-manifold method can be used. In this case, the molten resin laminated in the feed block is guided to a sheet forming die such as a T die, and after being formed into a sheet shape, the molten resin flows into a forming roll (polishing roll) whose surface is mirror-finished. Form. This sheet-like molded product is mirror-finished and cooled while passing through the molding roll, thereby forming a laminate. In the case of a multi-manifold die, the molten resin laminated in the die is similarly formed into a sheet inside the die, and then mirror finished and cooled by a forming roll to form a laminated plate. The temperature of the die is usually 220 ° C. to 280 ° C., preferably 230 ° C. to 270 ° C., and the molding roll temperature is usually 100 to 190 ° C., preferably 110 to 180 ° C. As the roll, a vertical roll or a horizontal roll can be used as appropriate.

The synthetic resin laminate of the present invention has many features, but one of the major features is that by limiting the difference in linear expansion coefficient between the materials forming each layer to a certain value or less, Even when used under severe conditions, there is no delamination and excellent adhesion. That is, the transparent synthetic resin layer (A) and the transparent resin base material (b-1) formed by injection molding, the transparent resin base material (b-1), the acrylic resin layer (b-2), and the acrylic resin layer (b -2) and the difference between the linear expansion coefficients of the cured film layer (b-3) comprising the polyorganosiloxane composition are 10 × 10 ⁻⁵ / ° C. or less, preferably 8 × 10 ⁻⁵ / ° C. or less, respectively. Yes, and more preferably 7 × 10 ⁻⁵ / ° C. or less. Transparent synthetic resin layer (A) and transparent resin substrate (b-1), transparent resin substrate (b-1), acrylic resin layer (b-2), and acrylic resin layer (b-) formed by injection molding The difference in coefficient of linear expansion between 2) and the cured film layer (b-3) comprising the polyorganosiloxane composition should be as small as possible, and if it exceeds 10 × 10 ⁻⁵ / ° C., the desired weather resistance is obtained. It may be difficult to manufacture a synthetic resin laminate.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary is exceeded. In addition, what obtained by cut | disconnecting the obtained synthetic resin laminated body to a suitable magnitude | size was used for the sample for evaluation.
Evaluation methods in Examples and Comparative Examples are as follows.

(1) Linear expansion coefficient 3 g of the paint was weighed in an aluminum cup and allowed to stand on a hot plate at about 45 ° C. for 2 hours to remove volatile components. Subsequently, it was cured in a dryer at 125 ° C. for 2 hours, and this was used as a sample for measuring the linear expansion coefficient. The polycarbonate was used as a sheet, and the polymethyl methacrylate was used as a sample for measuring the linear expansion coefficient.
Measuring instrument: TMA100 (Seiko Electronics Co., Ltd.)
Temperature conditions: 30-190 ° C., 10 ° C./min, temperature rising load: −1 g
Atmosphere: N ₂ , 300 ml / min Measurement: Data at the second and subsequent temperature increases are adopted (the first time is for erasing the heat history).
The measurement was repeated 5 times, and the values in the temperature range of 60 to 90 ° C were averaged.

(2) GPC
Volatile components (mainly water and organic solvents; alcohols, acetylacetone, etc.) are removed under reduced pressure of 10 mmHg or less in 5 g of polyorganosiloxane composition solution. Next, the sample was dissolved in THF to make a 0.1% concentration solution, passed through a 0.1 μ membrane filter, and then subjected to GPC analysis.
Measuring equipment: Shodex system 21 (Showa Denko)
Column (for low molecular weight): KF-803L x 1 + KF-802.5 x 1 + KF-801 x 2 Molecular weight measurement range = 200 to 70,000
Sample concentration: 0.1% THF
Eluent: THF
Oven temperature: 40 ° C
Calibration curve reference material: polystyrene

(3) Weather resistance Using a super UV tester manufactured by Iwasaki Electric Co., Ltd., light irradiation for 5 hours (ultraviolet light intensity 50 mW / cm ² , black panel temperature 63 ° C., humidity 50%), dew condensation 1 hour (temperature 30 ° C. or higher, The test was performed with a cycle of 100% humidity, and a shower was performed every 10 minutes during light irradiation for 10 seconds. The appearance of the cured film such as cracks and natural peeling after 600 hours of treatment and the change in yellowing degree (ΔYI) were examined. In addition, the test was installed so that the cured film layer (b-3) of a sample might become an irradiation surface side.

(4) Taber wear resistance In accordance with ASTM-D1044, wear wheel CS-10F is mounted with a Taber wear tester, the haze after 500 rotations is measured under a load of 500 g, and the value obtained by subtracting the haze before the test is obtained. Indicated.

(5) Adhesiveness In accordance with JIS K5400, the sample was cut into 6 grids at intervals of 2 mm with a razor blade to make 25 grids, and a commercially available cello tape (registered trademark) was adhered closely, then 90 When the film was peeled off rapidly in the forward direction, the number of cells remaining without peeling off the coating film was indicated by X / 25.

(6) Transparency / Haze Haze (%) was measured with a haze meter manufactured by Nippon Denshoku Industries Co., Ltd.

(7) Color tone / yellowing degree Yellowing degree (YI) was measured with a haze meter manufactured by Nippon Denshoku Industries Co., Ltd.

(8) Boiling resistance The appearance change after immersion of the evaluation sample in boiling water at 100 ° C. for 2 hours and the adhesion of the cured film layer were evaluated.

(9) Heat resistance The evaluation sample was evaluated for the appearance change and the adhesion of the cured film layer after being left in a 100 ° C hot air circulating dryer for 100 hours.

(10) Drop weight impact strength In the test, a weight of 5 kg in a cylinder is lifted to a predetermined height with a wire, and then dropped onto a fixed 150 mm × 150 mm (thickness 3 mm) sample to be destroyed. The height was evaluated. The weight was dropped to the cured film layer (b-3) side of the evaluation sample.

Synthesis Example 1 Synthesis of Polyorganosiloxane To a reactor equipped with a stirrer and a reflux condenser, 272 parts by weight of methyltrimethoxysilane and 160 parts by weight of methanol were added, and ice-cooled to 10 ° C. or less in a nitrogen atmosphere. Next, 400 parts by weight of a 0.1% acetic acid solution was dropped over 40 minutes to hydrolyze the alkoxysilane. After completion of the dropwise addition, the reaction was continued for 1 hour under ice cooling and then stirred at room temperature for 3 hours to complete the hydrolysis.
200 parts by weight of methanol silica sol (particle size 15 μm, silica solid content 30%) and 600 parts by weight of isopropanol were added to the resulting silanol solution, and stripping was performed under a reduced pressure of 20 to 50 mmHg and an internal temperature of 35 ° C. or less. And methanol and residual water were removed. The finally obtained polyorganosiloxane solution (non-volatile substance (hereinafter referred to as NVM) 20%) was 650 parts by weight. Furthermore, this reaction solution was allowed to proceed gradually in the dark at 40 ° C. for 7 hours. As a result of GPC analysis of this polyorganosiloxane solution (H1), no 1-dimer was present, the trimer was 0.01%, the tetramer was 9.9%, and the pentamer was 11. 4%, hexamer or higher was 78.7%. The number average degree of polymerization was 10.8. During this oligomerization reaction, each molecule is considered to be linearly linked. And the linear expansion coefficient in 60-90 degreeC of the hardened | cured material which hardened this solution for 2 hours at 125 degreeC was 10.0 * 10 < ^-5 > / ^degreeC .

Synthesis Example 2 / Synthesis of Polyorganosiloxane To the silanol solution obtained in Synthesis Example 1, 200 parts by weight of methanol silica sol (particle size 15 μm, silica solid content 30%) and 600 parts by weight of isopropanol were added, and the pressure was reduced to 20 to 50 mmHg. Then, the internal temperature was stripped under a condition of 35 ° C. or less to remove methanol and remaining water. The final polyorganosiloxane solution (NVM 20%) was 650 parts by weight. As a result of GPC analysis of this polyorganosiloxane solution (H1), the dimer was 4.4%, the trimer was 7.2%, the tetramer was 19.7%, and the pentamer was 32. 4%, hexamer or higher was 36.3%. And the number average degree of polymerization was 5.3. During this oligomerization reaction, each molecule is considered to be linearly linked. And the linear expansion coefficient in 60-90 degreeC of the hardened | cured material which hardened this solution for 2 hours at 125 degreeC was 10.5 * 10 < ^-5 > / ^degreeC .

Synthesis Example 3 / Synthesis of acrylic primer 100 parts by weight of diacetone alcohol was added to a reactor equipped with a stirrer, a reflux condenser, a nitrogen gas introduction tube, and a dropping funnel, and the reactor was sufficiently filled with nitrogen gas Replace and heat to 80-90 ° C. On the other hand, 20 parts by weight of trimethoxypropyl methacrylate, 60 parts by weight of methyl methacrylate, 5 parts by weight of methyl acrylate, 5 parts by weight of vinyl acetate, 10 parts by weight of glycidyl methacrylate, 0.2 part by weight of ethylene glycol dimethacrylate and azobisiso as an initiator 3 parts by weight of butyronitrile (AIBN) was added to the dropping funnel, and gradually added to the reactor over 1 hour. During this period, stirring and introduction of nitrogen gas were continued. Thereafter, the reaction was continued at 90 ° C. for 3 hours, and the reaction was terminated. Then, 20 parts by weight of polymethyl methacrylate having a molecular weight (Mw) of 150,000, 150 parts by weight of methyl isobutyl ketone as a solvent, 150 parts by weight of cellosolve acetate, 110 parts by weight of propylene glycol monomethyl ether, 110 parts by weight of isopropanol, 50 parts by weight of diacetone alcohol NVM was made 15%. To this reaction solution, 2% of 2,2′-dihydroxybenzophenone as an ultraviolet absorber with respect to NVM was added to obtain a primer coating composition (P1). And the linear expansion coefficient in 60-90 degreeC of the hardened | cured material which hardened this solution for 2 hours at 125 degreeC was 24.0 * 10 < ^-5 > / degreeC.

Example of production of acrylic resin (method described in JP-A-7-133303)
88 parts by weight of methyl methacrylate, 4 parts by weight of methyl acrylate, 8 parts by weight of methanol, 0.032 parts by weight of di-t-butyl peroxide (2 × 10 ⁻³ mol / 1) and 0.21 parts by weight of n-dodecyl mercaptan ( After mixing 10 × 10 ⁻³ mol / 1), dissolved oxygen was removed by blowing nitrogen to prepare a raw material solution. 5 kg of the raw material liquid is added in advance to a 6 L internal polymerization tank equipped with a jacket that circulates the heat medium and a helical ribbon stirring blade, and the temperature is raised to 150 ° C. while sufficiently stirring and maintaining a uniform mixed state. Then, after polymerization was performed until the monomer conversion reached 75% and the polymer concentration reached 69%, this raw material liquid was continuously supplied to the polymerization tank at a rate of 1 kg / h.

When the polymerization temperature was maintained at 150 ° C. and the average residence time was maintained at about 5 hours, the viscosity of the polymerization solution was maintained at 45 Pa · sec, the monomer conversion was 75%, and the polymer concentration was 69%. This polymerization liquid was extracted at a flow rate of 1 kg / h, heated to 250 ° C., and flushed into a devolatilization tank under reduced pressure. The devolatilized polymer was extracted from the bottom of the devolatilization tank in a molten state, taken out into a strand by a die, pelletized by a pelletizer after water cooling. The obtained pellets were 0.27% methyl methacrylate and 0.01% methyl acrylate as residual volatile components, and n-dodecyl mercaptan as a polymerization initiator and a chain transfer agent was not detected by GC analysis. The appearance of the obtained pellets was clear and transparent. The weight average molecular weight (Mw) was 103,000 as measured by GPC, the load deflection temperature was 105 ° C., and the haze of the 1 mm thick molded product was 0.2%. The linear expansion coefficient at 60 to 90 ° C. was 8.0 × 10 ⁻⁵ / ° C.

The linear expansion coefficients of the polycarbonate according to the present invention, three types of polymethylmethacrylate pellets, the polyorganosiloxanes of Synthesis Examples 1 and 2 and the methacrylic primer of Synthesis Example 3 were measured, and the results are summarized in Table 1. From Table 1, it can be seen that the linear expansion coefficient between the resins other than the methacrylic primer is 2.5 × 10 ⁻⁵ / ° C. or less.

(Table 1)

Coextrusion plate production example 1
Polycarbonate (NF2000U, manufactured by Mitsubishi Gas Chemical Co., Ltd., 1 mm thick molded product has a haze of 0.3) is used as a substrate layer, and a polycarbonate extruder has a barrel diameter of 65 mm, a screw L / D = 35, and a cylinder temperature of 270 ° C. did. Moreover, the extruder of the acrylic resin which forms a coating layer was set to barrel diameter 32mm, screw L / D32, and cylinder temperature 250 ° C. Two types of resins were melt-extruded at the same time, and when they were laminated, a feed block (width 500 mm) was used, and an acrylic resin was laminated on one side of the polycarbonate. The temperature inside the die head is 260 ° C., and the resin laminated and integrated in the die is guided to three mirror-finished polishing rolls, the first roll temperature 110 ° C., the second roll temperature 180 ° C., and the third roll temperature. Set to 180 ° C.

After forming the bank at the first roll interval, the second and third rolls were passed. The take-up speed was 1.2 m / min, and the take-up pinch roll speed was 1.6 m / min. The obtained sheet thickness was 0.9 mm, the acrylic resin layer was 20 μm, and the appearance was excellent.
The acrylic resin used here is MGC-10 manufactured by Mitsubishi Gas Chemical Co., Ltd. manufactured by the continuous polymerization method according to the above production example, 2% Tinuvin 1577 (manufactured by Ciba Specialty Chemicals) as an ultraviolet absorber, and an antioxidant. As a resin, 0.1% of Sumilizer BHT (manufactured by Sumitomo Chemical Co., Ltd.) and 0.05% of Adeka Starve PEP-36 (manufactured by Asahi Denka Kogyo Co., Ltd.) were used (the haze of 1 mm thick molded product was 0.2%) .

Coextrusion plate production example 2
A sheet was molded using the same apparatus and production conditions as in Production Example 1 of the coextruded plate. Atfina Atglass V020 manufactured by a continuous solution (toluene) polymerization method was used as the acrylic resin used here (having a haze of 1 mm thick molded product is 0.2%). The manufactured sheet was free from irregularities, streaks, bubbles and the like and had an excellent appearance.

Coextrusion plate production example 3
Except for changing the acrylic resin from a continuous polymer (Atglass V020) to a suspension polymer (Parapet HR-L, manufactured by Kuraray Co., Ltd., haze of 1 mm thick molded product is 0.2%) The same operation as in Production Example 2 was performed. The manufactured sheet was not excellent in appearance because of noticeable spots, streaks, bubbles and the like.
Further, in order to improve these, the die head temperature was lowered to 250 ° C., but although the appearance of the obtained sheet tended to improve somewhat, it was not a sufficiently satisfactory appearance.

Example 1
The polyorganosiloxane solution (NVM 20%) prepared in Synthesis Example 1 was applied to the polycarbonate / acrylic resin sheet (0.9 mm thickness, acrylic resin layer 20 μm) of 500 mm × 1000 mm produced in Production Example 1 of the coextruded plate, and room temperature was applied. And then dried at 130 ° C. for 1 hour to obtain a resin laminate (B). Next, after screen printing was performed on the surface (b-1) of this resin laminate, it was cut into the shape of a sunroof model mold (600 mm × 400 mm), and the cured polyorganosiloxane film of the laminate was a sunroof model mold ( (Thickness 5 mm) was placed so as to be in contact with one surface of the inner surface, and then a transparent synthetic resin for injection molding was injected and injected into the mold to obtain a synthetic resin laminate. Table 2 shows the evaluation results of the obtained synthetic resin laminate.

Example 2
A synthetic resin laminate was obtained in the same manner as in Example 1, except that the polycarbonate / acrylic resin sheet (0.9 mm thickness, acrylic resin layer 30 μm) produced in Production Example 1 of the coextruded plate was used. Table 2 shows the evaluation results of the obtained synthetic resin laminate.

Example 3
The same resin laminate (B) as in Example 1 was cut into two sunroofs, and one sheet was placed so that the cured coating layer (b-3) was in contact with one side of the inner surface of the mold. A laminated resin plate (B) is placed so that the cured film layer (b-3) is in contact with the other surface, and then a transparent synthetic resin for injection molding is injected and injected into the mold. A laminate was obtained. Table 2 shows the evaluation results of the obtained synthetic resin laminate.

Example 4
A synthetic resin laminate was obtained in the same manner as in Example 1 using the polycarbonate / acrylic resin sheet (thickness 0.9 mm, acrylic resin layer 20 μm) produced in Production Example 2 of the coextruded plate. Table 2 shows the evaluation results of the obtained synthetic resin laminate.

Example 5
Using the polycarbonate / acrylic resin sheet (0.9 mm thickness, acrylic resin layer 40 μm) produced in Production Example 2 of the coextrusion plate, except for the film thickness of the cured film layer (b-3) being 7 μm, Example 1 and A synthetic resin laminate was obtained by the same method. Table 2 shows the evaluation results of the obtained synthetic resin laminate.

Comparative Example 1
The polyorganosiloxane (NVM 20%) prepared in Synthesis Example 2 was applied to the polycarbonate / acrylic resin sheet (0.9 mm thick, acrylic resin layer 20 μm) produced in Production Example 1 of the coextruded plate, and then naturally dried at room temperature for 20 minutes. Then, a synthetic resin laminate was obtained in the same manner as in Example 1 except that the resin laminate (B) was obtained by curing at 130 ° C. for 1 hour. Table 3 shows the evaluation results of the obtained synthetic resin laminate.

Comparative Example 2
A synthetic resin laminate was obtained in the same manner as in Example 1 except that the polycarbonate / acrylic resin sheet (0.9 mm thickness, acrylic resin layer 300 μm) produced in Production Example 1 of the coextruded plate was used. Table 3 shows the evaluation results of the obtained synthetic resin laminate.

Comparative Example 3
After the acrylic primer prepared in Synthesis Example 3 was applied to the polycarbonate / acrylic resin sheet (0.9 mm thickness, acrylic resin layer 7 μm) produced in Production Example 1 of the coextruded plate, and dried at room temperature for 20 minutes, It was cured and dried at 125 ° C. for 1 hour. Thereafter, the polyorganosiloxane solution (NVM 20%) obtained in Synthesis Example 1 was applied, naturally dried at room temperature for 20 minutes, and then cured at 130 ° C. for 1 hour to obtain a resin laminate (B). A synthetic resin laminate was obtained in the same manner as in Example 1. Table 3 shows the evaluation results of the obtained synthetic resin laminate.

(Table 2)

(Table 3)

The top view of the molded product of the sunroof for motor vehicles which laminated | stacked and integrated the resin laminated board (B) on both surfaces of the transparent synthetic resin layer (A) by injection molding is shown. The AA cross-section explanatory drawing of FIG. 1 is shown.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Hardened film layer 2 Acrylic resin layer 3 Transparent resin base material 4 Printing part 5 Transparent synthetic resin layer

Claims (18)

  Lamination provided with an acrylic resin layer (b-2) containing an ultraviolet absorber on at least one surface of the transparent synthetic resin layer (A) formed by injection molding and one surface of the transparent resin substrate (b-1) In the acrylic resin coating layer of the substrate, the 1-2 dimer component is substantially absent, the trimer component is 0.01-3%, the tetramer component is 1-15%, and the pentamer component is A cured film layer (b) formed by applying and curing a thermosetting polyorganosiloxane composition having 1 to 13%, hexamer or more of 69 to 97% and a number average degree of polymerization of 8 to 100 3) A synthetic resin laminate comprising a resin laminate (B) having a transparent resin base material (b-1) surface joined thereto.   The acrylic resin for forming the acrylic resin layer (b-2) containing an ultraviolet absorber is produced by a continuous polymerization method and is composed of an acrylic resin mainly composed of methyl methacrylate. Item 8. A synthetic resin laminate according to Item 1.   The synthetic resin laminate according to claim 1 or 2, wherein the amount of the ultraviolet absorbent in the acrylic resin layer (b-2) containing the ultraviolet absorbent is 0.01 to 5% by weight.   A transparent resin substrate (b-1) and an acrylic resin layer (b-2) containing an ultraviolet absorber are simultaneously molded by a coextrusion method, and the thickness of the transparent resin substrate (b-1) is 0.2. The synthetic resin laminate according to claim 1, wherein the acrylic resin layer (b-2) has a thickness of 1 to 200 μm.   The synthetic resin laminate according to any one of claims 1 to 4, wherein the polyorganosiloxane composition contains colloidal silica. Transparent synthetic resin layer (A) and transparent resin substrate (b-1), transparent resin substrate (b-1), acrylic resin layer (b-2), acrylic resin layer (b-2) formed by injection molding ) And a cured coating layer (b-3) obtained by curing the thermosetting polyorganosiloxane composition, each having a difference in linear expansion coefficient of 10 × 10 ⁻⁵ / ° C. or less. 5. A synthetic resin laminate according to any one of 5 above.   The haze of the transparent synthetic resin layer (A), the transparent resin substrate (b-1) and the acrylic resin layer (b-2) is 10% or less as measured by a molded product having a thickness of 1 mm. The synthetic resin laminate according to any one of claims 1 to 6.   8. The synthetic resin laminate according to claim 1, wherein the transparent synthetic resin layer (A) and the transparent resin substrate (b-1) are polycarbonate resins.   The synthetic resin laminate according to any one of claims 1 to 8, wherein the transparent synthetic resin layer (A) formed by injection molding has a thickness of 0.8 to 30 mm.   The synthetic resin laminate according to any one of claims 1 to 9, wherein the content of the ultraviolet absorber in the transparent resin of the transparent resin substrate (b-1) is less than 0.5 wt%. .   The composition according to any one of claims 1 to 10, wherein the thickness of the cured film layer (b-3) obtained by applying and curing the thermosetting polyorganosiloxane composition is 1 to 15 µm. Resin laminate.   It has a printing part in the transparent resin base material (b-1) which is a surface opposite to the surface which has a hardened film layer (b-3) in a resin laminated board (B). The synthetic resin laminate according to any one of the above.   The resin laminate (B) is bonded to both surfaces of the transparent synthetic resin layer (A) formed by injection molding so that the cured film layer (b-3) is the outermost layer. The synthetic resin laminate according to any one of 12 above.   The resin laminate (B) is disposed so that the cured coating layer (b-3) of the resin laminate (B) is in contact with at least one surface of the inner surface of the mold, and then formed by injection molding into the mold. The transparent synthetic resin layer (A) formed by injection injection of the transparent synthetic resin constituting the transparent synthetic resin layer (A) and injection molding of the transparent resin substrate (B-1) surface in the resin laminate (B) A method for producing a laminate made of a synthetic resin, characterized in that the two are joined together.   The method for producing a synthetic resin laminate according to claim 14, wherein the resin laminate (B) is preliminarily shaped into a mold cavity and then placed in the mold.   The method for producing a synthetic resin laminate according to claim 14, wherein the acrylic resin layer (b-2) has a thickness of 10 to 100 μm.   The composition according to any one of claims 14 to 16, wherein the content of the ultraviolet absorber in the acrylic resin layer (b-2) containing the ultraviolet absorber is 0.03 to 4.0 wt%. A method for producing a resin laminate. The synthetic resin laminate according to any one of claims 1 to 13, wherein the laminate comprising the transparent synthetic resin layer (A) and the resin laminate (B) is a vehicle window glass and a roof window glass.

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