JP2010240969A - Heating molding method of decorative molding sheet made of acrylic resin and method of producing laminated molding article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heating molding method of a decorative molding sheet made of acrylic resin which is excellent in transparency and anti-molding whitening property, and is excellent in suppression of the occurrence of pattern defect of surface roughness even when performing the heating molding, and to provide a method of producing laminated molding article according to an insert molding method or an in-mold molding method using the decorative molding sheet. <P>SOLUTION: In the heating molding method of the decorative molding sheet made of acrylic resin, the decorative molding sheet made of acrylic resin is prepared by laminating a patterning layer (B) and a base material sheet (C) on the side of a thermoplastic resin layer (A-a) of an acrylic resin-based lamination film (A) comprising: the thermoplastic resin layer (A-a); and an acrylic resin layer (A-b) which has an acrylic resin composition (X) containing an acrylic rubber-containing polymer (A-b-1) or the acrylic rubber-containing polymer (A-b-1) and a thermoplastic polymer (A-b-2) as a constitutional component and has a thermal deformation temperature lower than that temperature (T<SB>A-a</SB>) of the thermoplastic resin layer (A-a) by at least 5°C, and hot-molding the laminate at a specified temperature. The method of producing laminated molding article is also disclosed. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for heat forming an acrylic resin decorative molding sheet and a method for producing a laminated molded product.

  As a method for imparting design properties to a molded product at a low cost, there are an insert molding method and an in-mold molding method.

  In the insert molding method, a decorative film or sheet such as polyester resin, polycarbonate resin, or acrylic resin that has been decorated by printing or the like is previously molded into a three-dimensional shape by vacuum molding or the like, and unnecessary portions are removed. This is a method for obtaining a molded product in which a decorative film or sheet and a base material are integrated by transferring the resin into an injection mold and injection molding a resin to be the base material.

  On the other hand, the in-mold molding method is to place a decorative film or sheet in an injection mold, perform vacuum molding in the mold, and then injection mold a resin as a base material in the same mold. Is a method for obtaining a molded product in which a decorative film or sheet and a substrate are integrated.

As an acrylic resin film excellent in surface hardness and heat resistance that can be used for insert molding or in-mold molding, and excellent in resistance to molding whitening, for example, Patent Document 1 discloses a rubber-containing polymer having a specific composition and a specific composition. An acrylic resin film obtained by mixing a thermoplastic polymer having a composition at a specific ratio is disclosed. This acrylic resin film not only gives decorativeness to the molded product, but also has a function as an alternative material for clear coating, and the following (1) to (3) as compared with the conventional acrylic resin film Since it is unlikely to cause a decrease in designability due to molding whitening, it has a high industrial utility value.
(1) In insert molding, an acrylic resin film or a laminated sheet laminated with an acrylic resin film is removed after vacuum forming, and in in-mold molding, a punching process is performed to remove an acrylic resin film protruding from the base resin. And whitening occurs at the end of the molded product.
(2) Whitening occurs when a molded product having an undercut design is removed from the mold.
(3) When using a concave or convex mold to obtain a molded article having a convex or concave design such as letters, an acrylic resin film is still in the concave or convex part of the mold even after vacuum or pressure forming. Since the base resin must be injection molded at a temperature below the glass transition temperature (hereinafter referred to as “Tg”) of the acrylic resin film without following the mold, whitening occurs when the film is stretched by the resin pressure. It is likely to occur and cracks may occur in some cases.

  As described above, although the acrylic resin film of Patent Document 1 is excellent in whitening resistance, when performing insert molding or the like, it is punched to remove unnecessary portions of the acrylic resin film or a laminated sheet including the same after vacuum forming In the processing (trimming) process, cracks and cracks may occur in the acrylic resin film, and there is room for improvement in trimming processability during molding.

  As an acrylic resin film excellent in trimming processability, for example, Patent Document 2 discloses an acrylic resin film containing a specific rubber-containing polymer and having a specific rubber content and a specific gel content. .

  However, when the acrylic resin film of Patent Document 2 is used, it is excellent in trimming processability at the time of forming, but when heat forming is performed in the steps before and after that, the appearance of a rough pattern on the film surface is exhibited. In some cases, there was room for improvement in terms of suppressing the occurrence of surface roughness pattern defects (surface rust skin pattern defects) during the heat molding.

  Patent Document 3 discloses a layer containing acrylic rubber particles and an acrylic resin as an acrylic resin film that has good flexibility and does not whiten when being colored. An acrylic resin laminate comprising an acrylic resin layer not containing an impact material is disclosed.

  Furthermore, Patent Document 4 contains rubber particles as an acrylic resin film that is not easily whitened even during bending and tensioning while maintaining flexibility, and has a flexural modulus of 1,500 MPa or less. An acrylic resin laminated film including a soft layer made of an acrylic resin and a hard layer made of an acrylic resin having a flexural modulus of 1,600 MPa or more is disclosed.

  Further, in Patent Document 5, as an acrylic resin film excellent in bonding property, surface hardness and film forming property, a layer made of an acrylic resin containing 50% by mass or more of a methacrylic resin, and a Vicat softening temperature is at least 5 than that. An acrylic resin laminated film including a layer made of an acrylic resin having a low temperature is disclosed.

  However, in Patent Documents 3 to 5, there is no description regarding the trimming process at the time of insert molding or in-mold molding of an acrylic resin decorative film having a pattern layer such as printing, and a pattern layer such as printing is applied. There is no description regarding the appearance of rough surface defects due to heating during molding of the acrylic resin decorative film.

Patent Document 1: JP-A-2005-163,003 Patent Document 2: JP-A-2008-106,252 Patent Document 3: JP-A-2001-260,288 Patent Document 4: JP-A-2002-292,808 Patent Document 5: Japanese Patent Laid-Open No. 2006-110,744

  The subject of the present invention is a method for thermoforming an acrylic resin decorative molding sheet that is excellent in transparency and molding whitening resistance, and that is excellent in suppressing the appearance of surface roughness pattern defects even when thermoforming, and for molding the same. It is providing the manufacturing method of the laminated molded article by the insert molding or in-mold molding method using a sheet | seat.

The gist of the present invention is that the thermoplastic resin layer (Aa), the acrylic rubber-containing polymer (Ab-1) or the acrylic rubber-containing polymer (Ab-1) and the thermoplastic polymer. The acrylic resin composition (X) containing (A-b-2) is used as a constituent component, and the thermal deformation temperature (T _A-a ) of the thermoplastic resin layer ( _A-a ) (measurement based on ASTM D648). A pattern layer (B) on the thermoplastic resin layer (Aa) side of the acrylic resin-based laminated film (A) having an acrylic resin layer (Ab) having a heat distortion temperature (measured based on ASTM D648) that is at least 5 ° C lower. ) And the acrylic resin decorative molding sheet laminated with the base sheet (C) at a temperature (T _s ) satisfying the following formula (1): Is the first invention.

T _s (° C.) ≦ 5 × (TA _A− 55) (1)
The gist of the present invention is that the thermoplastic resin layer (A-a), the acrylic rubber-containing polymer (A-b-1) or the acrylic rubber-containing polymer (A-b-1) and the thermoplastic are used. The acrylic resin composition (X) containing the polymer (A-b-2) is used as a constituent component, and the heat distortion temperature (T _A-a ) of the thermoplastic resin layer ( _A-a ) (measurement based on ASTM D648) A pattern layer on the thermoplastic resin layer (Aa) side of the acrylic resin-based laminated film (A) having an acrylic resin layer (Ab) having a heat distortion temperature (measured based on ASTM D648) lower than 5 ° C. The acrylic resin decorative molding sheet in which (B) and the base sheet (C) are laminated is injected so that the acrylic resin-based laminated film (A) side of the acrylic resin decorative molding sheet is on the cavity side. Above in the mold Vacuum molding or pressure molding at a temperature (T _s ) satisfying the formula (1), and then injection molding a resin constituting the molded product (D) in an injection mold to form an acrylic resin decorative molding sheet and molding The manufacturing method of the laminated molded product in which the product (D) is integrated is a second invention.

Thermoplastic resin layer (AA)

The thermoplastic resin layer (Aa) used in the present invention is a constituent component for forming an acrylic resin-based laminated film (A) by laminating with an acrylic resin layer (Ab) described later.

  The thermal deformation temperature (measured based on ASTM D648) of the thermoplastic resin layer (A-a) (hereinafter referred to as “HDT”) suppresses the occurrence of surface roughness pattern defects during the heat molding of a decorative molding sheet made of acrylic resin. In this respect, 90 ° C. or higher is preferable, and 93 ° C. or higher is more preferable.

  Examples of the thermoplastic resin component constituting the thermoplastic resin layer (Aa) include acrylic resin; ABS resin (acrylonitrile-butadiene-styrene copolymer); AS resin (acrylonitrile-styrene copolymer); vinyl chloride. Resin; Polyolefin resin such as polyethylene, polypropylene, polybutene, and polymethylpentene; Polyolefin copolymer such as ethylene-vinyl acetate copolymer or saponified product thereof, ethylene- (meth) acrylate copolymer; polyethylene terephthalate Polyester resins such as polybutylene terephthalate, polyethylene naphthalate, polyarylate and polycarbonate; Polyamide resins such as 6-nylon, 6,6-nylon, 6,10-nylon and 12-nylon; Polystyrene resin; Cellulose Fiber derivatives such as cetate and nitrocellulose; fluorine-based resins such as polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, and ethylene-tetrafluoroethylene copolymer; and two or more kinds of copolymers selected from these; These mixtures, composites and laminates can be mentioned.

  In these, as a thermoplastic resin component which comprises a thermoplastic resin layer (Aa), an acrylic resin and a polycarbonate resin are preferable at the point of heat-fusibility with an acrylic resin layer (Ab).

  Moreover, an acrylic resin is preferable as a thermoplastic resin component which comprises a thermoplastic resin layer (Aa) at the point of the transparency (beauty) of the acrylic resin decorative molding sheet | seat mentioned later.

Furthermore, as the thermoplastic resin layer (Aa), an acrylic resin composition (Y) containing an acrylic rubber-containing polymer (Aa-1) and a thermoplastic polymer (Aa-2) described later. An acrylic resin layer (Aa-α) having a component as a component is more preferable.

Acrylic rubber-containing polymer (A-a-1)

Examples of the acrylic rubber-containing polymer (Aa-1) used in the present invention include, for example, JP-A-8-323,934, JP-A-11-147,237, and JP2002-80,678. Acrylic rubber-containing polymers described in JP-A Nos. 2002-80,679, 2005-97,351, 2005-163,003 and 2005-139,416. Is mentioned. Among these, as the acrylic rubber-containing polymer (Aa-1) in terms of resistance to molding whitening when insert molding or in-mold molding is performed, JP 2005-163003 A and JP The acrylic rubber-containing polymer described in Kaikai 2005-139,416 is preferable.

Although it does not specifically limit as a compounding quantity of the acrylic rubber containing polymer (Aa-1) in an acrylic resin composition (Y), Usually, it is 0-50 mass%.

Thermoplastic polymer (AA-2)

As the thermoplastic polymer (A-a-2) used in the present invention, for example, a methacrylic acid alkyl ester (A1) unit or a methacrylic acid alkyl ester (A1) as a main component is a monomer unit. The polymer which has is mentioned.

  Specific examples of the polymer include 50 to 100% by mass of methacrylic acid alkyl ester (A1) units, 0 to 50% by mass of acrylic acid alkyl ester (I) units and other copolymerizable double bonds. Examples thereof include a polymer containing 0 to 50% by mass of monomer (x1) unit. The reduced viscosity of this polymer is preferably 0.15 L / g or less, and more preferably 0.1 L / g or less. Further, the reduced viscosity of this polymer is preferably 0.01 L / g or more, and more preferably 0.03 L / g or more. Further, the Tg calculated from the FOX formula of this polymer is preferably 80 ° C. or higher, more preferably 90 ° C. or higher.

  Examples of the methacrylic acid alkyl ester (A1) that is a constituent material of the methacrylic acid alkyl ester (A1) unit include those having a linear or branched alkyl group. Specific examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate and n-butyl methacrylate. These can be used alone or in combination of two or more. Of these, methyl methacrylate is preferred.

  The acrylic acid alkyl ester (I 1), which is a constituent raw material of the acrylic acid alkyl ester (I 1) unit, may have either a linear or branched alkyl group. Specific examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. These can be used alone or in combination of two or more. Of these, methyl acrylate is preferred.

  Examples of other monomer (1) having a copolymerizable double bond that is a constituent material of another monomer (1) unit having a copolymerizable double bond include, for example, lower alkoxy acrylate Acrylic monomers such as cyanoethyl acrylate, acrylamide, acrylic acid, methacrylic acid; unsaturated dicarboxylic acids such as styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile, maleic anhydride, itaconic anhydride or anhydrides thereof; and And maleimide monomers such as N-phenylmaleimide and N-cyclohexylmaleimide. These can be used alone or in combination of two or more.

  As the content of alkyl methacrylate (A1), surface hardness of acrylic resin decorative molding sheet, heat resistance, and suppression of surface roughness pattern defects in synchronism with printed pattern when thermoformed In this respect, the amount of the monomer used as the constituent material of the thermoplastic polymer (A-a-2) is preferably 50 to 100% by mass, more preferably 80% by mass or more, and more preferably 99.9% by mass or less. .

  The content of the acrylic acid alkyl ester (1) includes the film-formability of the acrylic resin-based laminated film (A) described later, and the toughness required for insert molding or in-mold molding of the acrylic resin decorative molding sheet, heating From the viewpoint of suppressing the appearance of rough surface pattern defects in synchronization with the printed pattern at the time of molding, 0 to 50% by mass is preferable in the monomer as a constituent material of the thermoplastic polymer (Aa-2). 0.1 mass% or more is more preferable, and 20 mass% or less is more preferable.

  The content of the other monomer (1) having a copolymerizable double bond is 0 to 50% by mass in the monomer as a constituent material of the thermoplastic polymer (Aa-2). Is preferred.

It does not specifically limit as a manufacturing method of a thermoplastic polymer (Aa-2), A normal suspension polymerization method, an emulsion polymerization method, a block polymerization method etc. are mentioned.

Acrylic resin composition (Y)

The acrylic resin composition (Y) used in the present invention contains an acrylic rubber-containing polymer (A-a-1) and a thermoplastic polymer (A-a-2). Agents such as stabilizers, lubricants, processing aids, plasticizers, impact aids, foaming agents, fillers, colorants and UV absorbers can be included.

Acrylic resin layer (A-a-α)

The acrylic resin layer (Aa-α) used in the present invention comprises the above-mentioned acrylic resin composition (Y) as a constituent component.

  In the present invention, in the acrylic resin layer (Aa), if necessary, a general compounding agent such as a stabilizer, a lubricant, a processing aid, a plasticizer, an impact resistance aid, a foaming agent, a filler, Coloring agents, ultraviolet absorbers and the like can be included.

  In this invention, it is preferable to add a ultraviolet absorber in order to provide a weather resistance to an acrylic resin layer (Aa) from the point of protection of the base material (C) mentioned later.

  Examples of the ultraviolet absorber include known ones, but a benzotriazole ultraviolet absorber having a molecular weight of 400 or more and a triazine ultraviolet absorber having a molecular weight of 400 or more are preferable.

  Examples of commercially available benzotriazole ultraviolet absorbers having a molecular weight of 400 or more include Tinuvin 234 (trade name) manufactured by Ciba Specialty Chemicals Co., Ltd. and Adeka Stub LA-31 (trade name) manufactured by ADEKA Corporation. . Moreover, as a commercial item of the triazine type | system | group ultraviolet absorber with a molecular weight of 400 or more, Ciba Specialty Chemicals Co., Ltd. Tinuvin 1577 (brand name) and ADEKA Co., Ltd. ADEKA STAB LA-46 (brand name) are mentioned, for example. It is done.

  As addition amount of a ultraviolet absorber, 0.1-10 mass parts is preferable with respect to 100 mass parts of components which comprise a thermoplastic resin layer (Aa), 0.5 mass part is more preferable, 1 mass part The above is particularly preferable. Further, the addition amount of the ultraviolet absorber is preferably 5 parts by mass or less, more preferably 3 parts by mass or less from the viewpoint of process contamination, chemical resistance and transparency during the production of the acrylic resin-based laminated film (A). .

  In the present invention, a light stabilizer is preferably added.

  Examples of the light stabilizer include known ones, but a hindered amine light stabilizer that is a radical scavenger is preferable from the viewpoint of light resistance and chemical resistance of the acrylic resin decorative molding sheet of the present invention.

  Examples of commercially available hindered amine light stabilizers include ADK STAB LA-57, ADK STAB LA-67, SANOL LS-770, etc. (trade name) manufactured by ADEKA Corporation.

  The addition amount of the hindered amine light stabilizer is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the component constituting the thermoplastic resin layer (Aa). The addition amount of the hindered amine light stabilizer is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more in terms of light resistance and chemical resistance of the acrylic resin decorative molding sheet of the present invention. Particularly preferred. Further, the amount of the hindered amine light stabilizer added is more preferably 2 parts by mass or less, and particularly preferably 1 part by mass or less, from the viewpoint of process contamination during the production of the acrylic resin-based laminated film (A).

As a method for adding these compounding agents, for example, a method of supplying the compounding agent together with the components constituting the thermoplastic resin layer (Aa) to an extruder for forming the acrylic resin-based laminated film (A) and heat The method of kneading and mixing the mixture which added the compounding agent previously to the component which comprises a plastic resin layer (Aa) with various kneaders is mentioned. Examples of the kneader used in the latter method include a normal single screw extruder, a twin screw extruder, a Banbury mixer, and a roll kneader.

Acrylic rubber-containing polymer (Ab-1)

The acrylic rubber-containing polymer (Ab-1) used in the present invention is for forming an acrylic resin composition (X) that is a constituent component of an acrylic resin layer (Ab) described later.

Examples of the acrylic rubber-containing polymer (Ab-1) include the same polymers as the acrylic rubber-containing polymer (A-a-1), but the surface hardness of the acrylic resin decorative molding sheet, Rubber-containing polymer (Ab-1-1) and rubber-containing polymer shown below from the viewpoint of heat resistance, transparency, molding whitening resistance when subjected to insert molding or in-mold molding, and trimming processability Those containing (A-b-1-2) are preferred.

Rubber-containing polymer (Ab-1-1)

The rubber-containing polymer (Ab-1-1) is obtained by using the following monomer mixture (1-A), monomer mixture (1-B), and monomer mixture (1-C). First, the monomer mixture (1-A) is polymerized, then the monomer mixture (1-B) is polymerized in the presence of the polymer of the monomer mixture (1-A), and the monomer mixture ( It is a rubber-containing polymer by multistage polymerization obtained by polymerizing the monomer mixture (1-C) in the presence of the polymer of 1-B).
<Monomer mixture (1-A)>
(1-A1) Acrylic acid alkyl ester 50-99.9% by mass
(1-A2) Methacrylic acid alkyl ester 0 to 49.9% by mass
(1-A3) Other monomer having copolymerizable double bond 0 to 20% by mass
(1-A4) Polyfunctional monomer 0 to 10% by mass
(1-A5) Graft crossing agent 0.1 to 10% by mass
In addition, Tg calculated | required by the formula of FOX of the polymer obtained from component (1-A1)-(1-A3) is less than 25 degreeC.
<Monomer mixture (1-B)>
(1-B1) Acrylic acid alkyl ester 9.9 to 90% by mass
(1-B2) Methacrylic acid alkyl ester 9.9 to 90% by mass
(1-B3) Other monomer having copolymerizable double bond 0 to 20% by mass
(1-B4) Polyfunctional monomer 0 to 10% by mass
(1-B5) Graft crossing agent 0.1 to 10% by mass
In addition, Tg calculated | required by the formula of FOX of the polymer obtained from component (1-B1)-(1-B3) is 25-100 degreeC.
<Monomer mixture (1-C)>
(1-C1) Methacrylic acid alkyl ester 80 to 100% by mass
(1-C2) Acrylic acid alkyl ester 0-20% by mass
(1-C3) Other monomer having copolymerizable double bond 0 to 20% by mass
As the acrylic acid alkyl ester (1-A1), (1-B1) or (1-C2), the acrylic acid alkyl ester (I-1) used as a raw material for the thermoplastic polymer (A-a-2) and The same thing is mentioned. These can be used alone or in combination of two or more. Of these, n-butyl acrylate is preferred.

  Examples of the methacrylic acid alkyl ester (1-A2), (1-B2) or (1-C1) include those having a linear or branched alkyl group. Specific examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate and n-butyl methacrylate. These can be used alone or in combination of two or more. Of these, methyl methacrylate is preferred.

  As other monomer (1-A3), (1-B3) or (1-C3) having a copolymerizable double bond, acrylic acid alkyl ester (1-A1), (1-B1) or Monomers other than (1-C2) and methacrylic acid alkyl ester (1-A2), (1-B2) or (1-C1), and having a double bond copolymerizable therewith in one molecule One monomer is included. Specific examples thereof include acrylic monomers such as lower alkoxy acrylate having 1 to 8 carbon atoms alkoxy group, cyanoethyl acrylate, acrylamide, acrylic acid, methacrylic acid, styrene, alkyl-substituted styrene, acrylonitrile and methacrylonitrile. Is mentioned. These can be used alone or in combination of two or more.

  Examples of the polyfunctional monomer (1-A4) or (1-B4) include monomers having two or more copolymerizable double bonds in one molecule. Specific examples thereof include alkylene glycol dimethacrylates such as ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and propylene glycol dimethacrylate, and polyvinylbenzene such as divinylbenzene and trivinylbenzene. , Triallyl cyanurate and triallyl isocyanurate. These can be used alone or in combination of two or more. Of these, 1,3-butylene glycol dimethacrylate is preferred.

  The use of the polyfunctional monomer (1-A4) or (1-B4) is particularly effective when, for example, the hot strength is strictly required.

  In addition, even if the polyfunctional monomer (1-A4) or (1-B4) is not present, if the following graft crossing agent (1-A5) or (1-B5) is present, it is quite stable. The rubber-containing polymer (Ab-1-1) tends to be obtained.

  Examples of the graft crossing agent (1-A5) or (1-B5) include monomers having two or more different copolymerizable double bonds in one molecule. Specific examples thereof include allyl, methallyl or crotyl esters of copolymerizable α, β-unsaturated carboxylic acid or dicarboxylic acid. Among them, acrylic acid, methacrylic acid, maleic acid or fumaric acid allyl ester, triallyl cyanurate and triallyl isocyanurate are preferable, and methacrylic acid allyl ester is more preferable. These can be used alone or in combination of two or more. Graft-crossing agents (1-A5) or (1-B5) are primarily chemically conjugated unsaturated bonds of their esters that react much faster than allyl, methallyl or crotyl groups.

  In the monomer mixture (1-A), (1-B) or (1-C), the components (1-A1) to (1-A5), (1-B1) to (1- In addition to B5) or (1-C1) to (1-C3), a chain transfer agent can be further added.

  Known chain transfer agents may be used. Specific examples thereof include alkyl mercaptan having 2 to 20 carbon atoms, mercapto acids, thiophenol and carbon tetrachloride.

  Content of the acrylic acid alkyl ester (1-A1) in the monomer mixture (1-A) is 50 to 99.9% by mass. The content of the acrylic acid alkyl ester (1-A1) in the monomer mixture (1-A) is preferably 55% by mass or more from the viewpoint of molding whitening resistance of the acrylic resin decorative molding sheet, 60% or more is more preferable. In addition, the content of the acrylic acid alkyl ester (1-A1) in the monomer mixture (1-A) is 79.9 masses in terms of surface hardness and heat resistance of the acrylic resin decorative molding sheet. % Or less is preferable, and 69.9 mass% or less is more preferable.

  Content of the alkyl methacrylate (1-A2) in a monomer mixture (1-A) is 0-49.9 mass%. The content of the alkyl methacrylate (1-A2) in the monomer mixture (1-A) is preferably 20% by mass or more, and more preferably 30% by mass or more. Moreover, as content of the methacrylic acid alkylester (1-A2) in a monomer mixture (1-A), 44.9 mass% or less is preferable, and 39.9 mass% or less is more preferable.

  The content of the other monomer (1-A3) having a copolymerizable double bond in the monomer mixture (1-A) is 0 to 20% by mass, and preferably 0 to 15% by mass or less. .

  Content of the polyfunctional monomer (1-A4) in a monomer mixture (1-A) is 0-10 mass%. The content of the polyfunctional monomer (1-A4) in 100% by mass of the monomer mixture (1-A) is, from the viewpoint of molding whitening resistance of the acrylic resin decorative molding sheet, 0. 1 mass% or more is preferable and 3 mass% or more is more preferable. In addition, as the content of the polyfunctional monomer (1-A4) in 100% by mass of the monomer mixture (1-A), sufficient flexibility and toughness for the acrylic resin decorative molding sheet are provided. In terms of imparting, 6% by mass or less is preferable, and 5% by mass or less is more preferable.

  The content of the graft crossing agent (1-A5) in the monomer mixture (1-A) is 0.1 to 10% by mass. As content of the graft crossing agent (1-A5) in the monomer mixture (1-A), the whitening resistance of the acrylic resin decorative molding sheet is good and the optical properties such as transparency are good. 0.5 mass% or more is preferable at the point which can shape | mold without reducing. Moreover, as content of the graft crossing agent (1-A5) in a monomer mixture (1-A), it is 5 at the point which provides sufficient softness | flexibility and toughness to the acrylic resin decorative molding sheet. % By mass or less is preferable, and 2% by mass or less is more preferable.

  As Tg calculated | required by the formula of FOX of the polymer obtained from component (1-A1)-(1-A3), it is less than 25 degreeC at the point of impact resistance of an acrylic resin-type laminated | multilayer film (A), 10 degrees C or less is preferable and 0 degrees C or less is more preferable.

  In the present invention, the Tg determined by the FOX formula of the polymer is the polymer handbook [Polymer Handbook, J. Chem. It is calculated from the formula of FOX using the value of Tg when it is made into the homopolymer about each of the monomer used described in Brandrup, Interscience, 1989].

  As a usage-amount of a monomer mixture (1-A), the sum total of a monomer mixture (1-A), a monomer mixture (1-B), and a monomer mixture (1-C) is 100 mass parts. When it is, it is possible to impart molding whitening resistance to the acrylic resin decorative molding sheet, and at least 15 parts by mass in terms of achieving both film forming properties and toughness suitable for insert molding or in-mold molding. preferable. Moreover, as the usage-amount of a monomer mixture (1-A), the sum total of a monomer mixture (1-A), a monomer mixture (1-B), and a monomer mixture (1-C) is 100. In the case of mass parts, 50 parts by mass or less is preferable and 35 parts by mass or less is more preferable in terms of obtaining a film having surface hardness and heat resistance suitable for a laminate such as a vehicle member.

  When the monomer mixture (1-A) is polymerized, the monomer mixture (1-A) can be polymerized in a lump, but it is preferable to polymerize in two or more stages. When polymerizing in two or more stages, it is preferable that the monomer composition ratio of the monomer mixture in each polymerization stage is different.

  When the monomer mixture (1-A) is polymerized in two stages, the first stage in terms of whitening resistance, impact resistance, heat resistance and surface hardness of the acrylic resin decorative molding sheet. Tg calculated | required by the formula of FOX of the polymer obtained from the monomer mixture (1-A-i) to be used is a polymer obtained from the monomer mixture (1-A-b) used in the second stage It is preferable that it is lower than Tg calculated | required by the formula of FOX. Specifically, Tg calculated | required by the formula of FOX of the polymer obtained from the monomer mixture (1-A-i) used for the 1st step is the molding whitening resistance of the acrylic resin decorative molding sheet In terms of impact resistance, it is preferably less than −30 ° C., and Tg determined by the FOX formula of the polymer obtained from the monomer mixture (1-A-ro) used in the second stage is an acrylic resin. In terms of surface hardness and heat resistance of the decorative molding sheet, −15 ° C. to 10 ° C. is preferable.

  As a usage-amount of the monomer mixture (1-A-i) used for the 1st step, 1-20 mass% is preferable in a monomer mixture (1-A), and the single amount used for a 2nd step As the usage-amount of a body mixture (1-A-ro), 80-99 mass% is preferable in a monomer mixture (1-A).

  Content of the acrylic acid alkyl ester (1-B1) in the monomer mixture (1-B) is 9.9 to 90% by mass. The content of the acrylic acid alkyl ester (1-B1) in the monomer mixture (1-B) is 19.9% by mass or more in terms of molding whitening resistance of the acrylic resin decorative molding sheet. Preferably, 29.9 mass% or more is more preferable. Further, the content of the acrylic acid alkyl ester (1-B1) in the monomer mixture (1-B) is 60% by mass or less in terms of the surface hardness and heat resistance of the acrylic resin decorative molding sheet. Is preferable, and 50 mass% or less is more preferable.

  Content of the methacrylic acid alkylester (1-B2) in a monomer mixture (1-B) is 9.9-90 mass%. The content of the alkyl methacrylate (1-B2) in the monomer mixture (1-B) is 39.9% by mass or more in terms of surface hardness and heat resistance of the acrylic resin decorative molding sheet. Is preferable, and 49.9 mass% or more is more preferable. Moreover, as content of the alkyl methacrylate (1-B2) in a monomer mixture (1-B), 80 mass% or less is the point of the shaping | molding whitening resistance of the acrylic resin decorative molding sheet. Preferably, 70 mass% or less is more preferable.

  The content of the other monomer (1-B3) having a copolymerizable double bond in the monomer mixture (1-B) is 0 to 20% by mass. The content of the other monomer (1-B3) having a copolymerizable double bond in the monomer mixture (1-B) is preferably 15% by mass or less.

  Content of the polyfunctional monomer (1-B4) in a monomer mixture (1-B) is 0-10 mass%. As content of the polyfunctional monomer (1-B4) in the monomer mixture (1-B), in terms of imparting sufficient flexibility and toughness to the acrylic resin decorative molding sheet, 6 mass% or less is preferable and 3 mass% or less is more preferable.

  The content of the graft crossing agent (1-B5) in the monomer mixture (1-B) is 0.1 to 10% by mass. As the content of the graft crossing agent (1-B5) in the monomer mixture (1-B), the whitening resistance of the acrylic resin decorative molding sheet is good and the optical properties such as transparency are good. 0.5 mass% or more is preferable at the point which can shape | mold without reducing. Moreover, as content of the graft crossing agent (1-B5) in a monomer mixture (1-B), it is 5 at the point which provides sufficient softness | flexibility and toughness to the acrylic resin decorative molding sheet. % By mass or less is preferable, and 2% by mass or less is more preferable.

  Tg calculated | required by the formula of FOX of the polymer obtained from component (1-B1)-(1-B3) is 25-100 degreeC. As Tg calculated | required by the formula of FOX of the polymer obtained from component (1-B1)-(1-B3), the surface hardness and heat resistance of the acrylic resin decorative molding sheet | seat are used for uses, such as a member for vehicles. 40 degreeC or more is preferable and 50 degreeC or more is more preferable at the point made into the suitable level. Moreover, as Tg calculated | required by the formula of FOX of the polymer obtained from component (1-B1)-(1-B3), the shaping | molding whitening resistance of an acrylic resin decorative molding sheet, and an acrylic resin-type laminated film ( In view of the film-forming property of A), 80 ° C. or lower is preferable, and 70 ° C. or lower is more preferable.

  As a usage-amount of a monomer mixture (1-B), the sum total of a monomer mixture (1-A), a monomer mixture (1-B), and a monomer mixture (1-C) is 100 mass parts. When it is, 5 to 35 mass in terms of imparting toughness required for molding whitening resistance, surface hardness, heat resistance, film forming property and insert molding or in-mold molding of the acrylic resin decorative molding sheet Part is preferable, and 5 to 20 parts by mass is more preferable.

  When polymerizing the monomer mixture (1-B), the monomer mixture (1-B) can be polymerized in a lump or can be polymerized in two or more stages.

  Content of the methacrylic acid alkylester (1-C1) in a monomer mixture (1-C) is 80-100 mass%. The content of the alkyl methacrylate (1-C1) in the monomer mixture (1-C) is preferably 90% by mass or more in terms of surface hardness and heat resistance of the acrylic resin decorative molding sheet. 93 mass% or more is more preferable. Moreover, as content of the methacrylic acid alkylester (1-C1) in a monomer mixture (1-C), 99 mass% or less is preferable.

  Content of the acrylic acid alkyl ester (1-C2) in the monomer mixture (1-C) is 0 to 20% by mass. The content of the alkyl acrylate ester (1-C2) in the monomer mixture (1-C) is preferably 1% by mass or more. Further, the content of the acrylic acid alkyl ester (1-C2) in the monomer mixture (1-C) is preferably 10% by mass or less, and more preferably 7% by mass or less.

  The content of the other monomer (1-C3) having a copolymerizable double bond in the monomer mixture (1-C) is 0 to 20% by mass, and preferably 0 to 15% by mass.

  When a chain transfer agent is added to the monomer mixture (1-C), the addition amount of the chain transfer agent is 0.01 to 5 parts by mass with respect to 100 parts by mass of the monomer mixture (1-C). preferable. Moreover, as an addition amount of a chain transfer agent, 0.2 mass part or more is more preferable, and 0.4 mass part or more is especially preferable.

  As Tg calculated | required by the formula of FOX of the polymer obtained from component (1-C1)-(1-C3), the surface hardness and heat resistance of the acrylic resin decorative molding sheet | seat are used for applications, such as a member for vehicles. 60 degreeC or more is preferable at the point made into the suitable level, 80 degreeC or more is more preferable, and 90 degreeC or more is especially preferable.

  As a usage-amount of a monomer mixture (1-C), the sum total of a monomer mixture (1-A), a monomer mixture (1-B), and a monomer mixture (1-C) is 100 mass parts. In terms of surface hardness and heat resistance of the acrylic resin decorative molding sheet, 15 parts by mass or more is preferable, and 45 parts by mass or more is more preferable. Moreover, as the usage-amount of a monomer mixture (1-C), the sum total of a monomer mixture (1-A), a monomer mixture (1-B), and a monomer mixture (1-C) is 100. When it is made into a mass part, 80 mass parts or less are preferable at the point which gives the toughness suitable for insert molding or in-mold shaping | molding while making the shaping | molding whitening resistance of the acrylic resin decorative molding sheet favorable.

  When polymerizing the monomer mixture (1-C), the monomer mixture (1-C) can be polymerized in a lump or can be polymerized in two or more stages.

  The gel content of the rubber-containing polymer (A-b-1-1) is preferably 50% by mass or more, more preferably 60% by mass or more in terms of resistance to molding whitening of the acrylic resin decorative molding sheet. preferable. Moreover, from the viewpoint of the molding whitening resistance of the acrylic resin decorative molding sheet, the larger the gel content of the rubber-containing polymer (Ab-1-1), the more advantageous, but the acrylic resin decoration. From the viewpoint of moldability of the molding sheet, the presence of a certain amount or more of free polymer (non-gelling polymer) is necessary, and therefore the gel content of the rubber-containing polymer (Ab-1-1) is 80. The mass% or less is preferable.

  The mass average particle diameter of the rubber-containing polymer (Ab-1-1) is preferably 0.03 to 0.3 μm. The mass average particle diameter of the rubber-containing polymer (Ab-1-1) is preferably 0.07 μm or more, more preferably 0.09 μm or more in terms of mechanical properties of the acrylic resin decorative molding sheet. Particularly preferred. The mass average particle diameter of the rubber-containing polymer (A-b-1-1) is as follows: molding whitening resistance of the acrylic resin decorative molding sheet, transparency, heat molding in insert molding or in-mold molding In view of maintaining transparency, the thickness is more preferably 0.15 μm or less, and particularly preferably 0.13 μm or less.

  In the present invention, the mass average particle diameter is a value measured by a dynamic light scattering method. As a commercially available measuring instrument of mass average particle diameter, for example, a light scattering photometer DLS-700 (trade name) manufactured by Otsuka Electronics Co., Ltd. may be mentioned.

  As a polymerization method for obtaining the rubber-containing polymer (A-b-1-1), first, the monomer mixture (1-A) is polymerized, and then the monomer mixture (1-A) is polymerized. It can be obtained by polymerizing the monomer mixture (1-B) in the presence, and further polymerizing the monomer mixture (1-C) in the presence of the polymer of the monomer mixture (1-B). it can. As this polymerization method, a sequential multistage polymerization method by emulsion polymerization is preferred. Another polymerization method is, for example, an emulsion suspension in which the monomer mixture (1-A) and (1-B) are emulsion-polymerized and then the monomer mixture (1-C) is polymerized in a suspension polymerization system. A turbid polymerization method is mentioned.

  When the rubber-containing polymer (Ab-1-1) is produced by emulsion polymerization, an emulsion prepared by previously mixing the monomer mixture (1-A) with water and a surfactant is used as a reactor. A method is preferred in which the polymerization is carried out by supplying the monomer mixture (1-B) and the monomer mixture (1-C) to the reactor in this order.

  An emulsion prepared by previously mixing the monomer mixture (1-A) with water and a surfactant is supplied to the reactor and polymerized to be present in the dispersion when dispersed in acetone. It is possible to easily obtain a rubber-containing polymer (Ab-1-1) in which the number of particles having a diameter of 55 μm or more is 0 to 50 per 100 g of the rubber-containing polymer (Ab-1-1). . The acrylic resin-based laminated film (A) obtained by using such a rubber-containing polymer (Ab-1-1) as the rubber-containing polymer (Ab-1) has a number of fish eyes in the film. It has the characteristic that there is little. As a result, on the surface of the resulting acrylic resin-based laminated film (A), gravure printing with a light-colored wood pattern with low printing pressure, which tends to cause printing omission, or solid gravure printing with metallic tone or jet black tone (pattern) Even when the layer (B)) is applied, there are few print omissions and high level printability.

  Examples of the surfactant used when preparing an emulsion prepared by previously mixing the monomer mixture (1-A) with water and a surfactant include anionic, cationic and nonionic interfaces. Among them, an anionic surfactant is preferable.

  Examples of the anionic surfactant include rosin soap, potassium oleate, sodium stearate, sodium myristate, sodium N-lauroyl sarcinate, dipotassium alkenyl succinate, and sulfuric acid such as sodium lauryl sulfate. Ester salts, sodium dioctyl sulfosuccinate, sodium dodecylbenzenesulfonate, sulfonates such as sodium alkyldiphenyl ether disulfonate, phosphate esters such as polyoxyethylene alkylphenyl ether sodium phosphate, and polyoxyethylene alkyl ether phosphate Examples thereof include sodium phosphate salts. Among these, phosphate esters such as sodium polyoxyethylene alkyl ether phosphates are preferred.

  Examples of commercially available surfactants include NC-718 manufactured by Sanyo Chemical Industries, Ltd., Phosphanol LS-529, Phosphanol RS-610NA, and Phosphanol RS manufactured by Toho Chemical Industry Co., Ltd. -620NA, Phosphanol RS-630NA, Phosphanol RS-640NA, Phosphanol RS-650NA and Phosphanol RS-660NA and Latemu P-0404, Latemulu P-0405, Latemulu P-manufactured by Kao Corporation 0406 and Latemul P-0407 (all are trade names).

  As a method for preparing an emulsion prepared by previously mixing the monomer mixture (1-A) with water and a surfactant, the surfactant is added after the monomer mixture (1-A) is charged in water. A method for charging, a method for charging a monomer mixture (1-A) after charging a surfactant in water, and a method for charging water after charging a surfactant in the monomer mixture (1-A) Is mentioned. Among these, the method of charging the surfactant after charging the monomer mixture (1-A) into water and the method of charging the monomer mixture (1-A) after charging the surfactant into water Is preferred.

  Examples of the apparatus for preparing the emulsified liquid include various forced emulsification apparatuses and membrane emulsification apparatuses such as a homogenizer and a homomixer.

  The emulsion is either W / O type in which water droplets are dispersed in the oil of the monomer mixture (1-A) or O / W type in which oil droplets of the monomer mixture (1-A) are dispersed in water. However, the O / W type in which the oil droplets of the monomer mixture (1-A) are dispersed in water, and the diameter of the oil droplets in the dispersed phase is preferably 100 μm or less.

  Examples of the polymerization initiator used when polymerizing the monomer mixture (1-A), (1-B), and (1-C) include peroxides, azo initiators, and oxidation with these initiators. Redox initiators combined with an agent / reducing agent. Among these, a redox initiator is preferable, and a sulfoxylate initiator combined with ferrous sulfate, disodium ethylenediaminetetraacetate, Rongalite and hydroperoxide is more preferable.

  The addition amount of the polymerization initiator is appropriately determined according to the polymerization conditions and the like. Moreover, the addition method of a polymerization initiator may be any of a method of adding to an aqueous phase, a monomer phase (oil phase), or both of them.

  Specific examples of the polymerization method for obtaining the rubber-containing polymer (Ab-1-1) include the following methods.

  First, the temperature of the aqueous solution containing ferrous sulfate, disodium ethylenediaminetetraacetate and Rongalite charged in the reactor is raised to the polymerization temperature. Next, the monomer mixture (1-A), a polymerization initiator such as a peroxide, water and a surfactant are mixed and the emulsion prepared is supplied into the reactor to carry out the polymerization. A polymer of the mixture (1-A) is obtained. Further, the monomer mixture (1-B) is supplied into the reactor together with a polymerization initiator such as peroxide to carry out the polymerization, thereby obtaining a polymer of the monomer mixture (1-B). Next, the monomer mixture (1-C) is supplied into the reactor together with a polymerization initiator such as a peroxide, and polymerization is carried out to obtain a polymer of the monomer mixture (1-C). .

  The polymerization temperature for obtaining the rubber-containing polymer (Ab-1-1) varies depending on the type or amount of the polymerization initiator, but is usually preferably 40 ° C or higher, more preferably 60 ° C or higher. 120 ° C. or lower is preferable, and 95 ° C. or lower is more preferable.

  The polymer latex containing the rubber-containing polymer (Ab-1-1) obtained by the emulsion polymerization method is preferably filtered using a filtration device. This filtration treatment is a treatment for removing scales generated during the polymerization from the latex, and for removing foreign substances mixed from the outside in the raw material or during the polymerization.

  As a filtration device, for example, a GAF filter system of ISP Filters PTE Ltd. using a bag-shaped mesh filter, a cylindrical filter medium is arranged on the inner surface of a cylindrical filter chamber, and a stirring blade is provided in the filter medium. Examples thereof include a centrifugal separation type filter device and a vibration type filter device in which the filter medium performs a horizontal circular motion and a vertical amplitude motion with respect to the filter medium surface.

  The polymer latex containing the rubber-containing polymer (Ab-1-1) obtained by the above method or the like is subjected to a recovery operation to obtain a powder of the rubber-containing polymer (Ab-1-1). Can do.

  Examples of the recovery operation include salting out, acid precipitation solidification, spray drying, freeze drying, and the like.

In the recovery operation, the residual metal content in the finally obtained rubber-containing polymer (A-b-1-1) is preferably 800 ppm or less. In particular, when metal salts with strong water affinity, such as magnesium salts and sodium salts, are used as salting-out agents, boil the acrylic resin decorative molding sheet by reducing the residual metal content as much as possible. The whitening phenomenon when immersed in water can be suppressed. Further, salting out using calcium salt or acid precipitation using sulfuric acid is preferable in that the whitening phenomenon when the acrylic resin decorative molding sheet is immersed in boiling water can be suppressed.

Rubber-containing polymer (Ab-1-2)

Specific examples of the rubber-containing polymer (Ab-1-2) include the rubber-containing polymer (2a) and the rubber-containing polymer (2b) shown below.

Rubber-containing polymer (2a)

The acrylic acid alkyl ester (2) used in the rubber-containing polymer (2a) is the same as the acrylic acid alkyl ester (1) used as a raw material for the thermoplastic polymer (A-a-2). Is mentioned. These can be used alone or in combination of two or more. Of these, n-butyl acrylate and 2-ethylhexyl acrylate are preferred.

  As a monomer other than the alkyl acrylate ester (I 2) used in the monomer mixture mainly composed of the alkyl acrylate ester (I 2), it can be copolymerized with the alkyl acrylate ester (I 2). And a monomer having one vinyl group (E2).

  Examples of the monomer (e2) having one vinyl group copolymerizable with the alkyl acrylate ester (2) include alkyl methacrylates such as methyl methacrylate, n-butyl methacrylate, cyclohexyl methacrylate, and the like. Examples include esters, styrene and acrylonitrile. These can be used alone or in combination of two or more.

  Acrylic resin decorative molding sheet is used as the amount of acrylic acid alkyl ester (ii 2) in the monomer mixture mainly composed of acrylic acid alkyl ester (ii 2) or acrylic acid alkyl ester (ii 2). 35-100 mass parts is preferable at points, such as molding whitening-proof property, and 50-100 mass parts is more preferable.

  In the present invention, the crosslinkable monomer (2) is added to the monomer mixture mainly composed of the acrylic acid alkyl ester (2) or the acrylic acid alkyl ester (2) as necessary. be able to.

  Examples of the crosslinkable monomer (2) include ethylene glycol dimethacrylate, butanediol dimethacrylate, allyl acrylate, allyl methacrylate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene. , Diallyl maleate, trimethylolpropane triacrylate, and allylcinnamate. These can be used alone or in combination of two or more.

  The amount of the crosslinkable monomer (2) used is 0.1 with respect to 100 parts by mass of the monomer mixture mainly composed of alkyl acrylate (I 2) or alkyl acrylate (I 2). -10 mass parts is preferable. As a usage-amount of a crosslinkable monomer (2), 0.3 mass part or more is more preferable at the point of the shaping | molding whitening resistance of the acrylic resin decorative molding sheet. Moreover, even if it exceeds 10 mass parts as a usage-amount of a crosslinking | crosslinked monomer (2), there is no problem in a physical property, but the improvement with the increase in usage-amount is small.

  In the polymerization of a monomer mixture mainly composed of an acrylic acid alkyl ester (I 2) or an acrylic acid alkyl ester (I 2), the acrylic acid alkyl ester (I 2) or the acrylic acid alkyl ester (I 2) is mainly used. The monomer mixture as a component can be polymerized in two or more stages.

  In the present invention, if necessary, before polymerizing the acrylic acid alkyl ester (ii 2) or the monomer mixture mainly composed of the acrylic acid alkyl ester (ii 2), the acrylic acid alkyl ester (ii 2). A monomer or monomer mixture containing an alkyl methacrylate as a part of the monomer (E2) having one vinyl group copolymerizable with the monomer can be polymerized.

  Examples of the alkyl methacrylate (2) used for the rubber-containing polymer (2a) include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate and cyclohexyl methacrylate.

  The amount of the methacrylic acid alkyl ester (A2) used in the monomer mixture mainly composed of the methacrylic acid alkyl ester (A2) or the methacrylic acid alkyl ester (A2) is preferably 50 to 100 parts by mass.

  In the present invention, when polymerizing a monomer mixture mainly composed of alkyl methacrylate (A2) or alkyl methacrylate (A2), the polymerization may be carried out in two or more stages as required. it can.

  The amount of the methacrylic acid alkyl ester (2) or the monomer mixture mainly composed of the methacrylic acid alkyl ester (2) in the polymerization of the rubber-containing polymer (2a) is an acrylic resin-based laminated film (A). Monomer mixture 100 mainly composed of acrylic acid alkyl ester (ii 2) or acrylic acid alkyl ester (ii 2) in terms of preventing deterioration of transparency due to aggregation of rubber-containing polymer (2a) therein. 10-400 mass parts is preferable with respect to mass parts, and 20-200 mass parts is more preferable.

The mass average particle diameter of the rubber-containing polymer (2a) is preferably 0.03 to 0.3 μm. The mass average particle diameter of the rubber-containing polymer (2a) is more preferably 0.07 μm or more, and particularly preferably 0.09 μm or more in terms of mechanical properties of the acrylic resin decorative molding sheet. Further, the mass average particle diameter of the rubber-containing polymer (2a) is more preferably 0.15 μm or less, particularly 0.13 μm or less in terms of molding whitening resistance and transparency of the acrylic resin decorative molding sheet. preferable.

Rubber-containing polymer (2b)

The rubber-containing polymer (2b) is prepared by using the following monomer mixture (2b-A), monomer mixture (2b-B), and monomer mixture (2b-C). 2b-A) and then the monomer mixture (2b-B) in the presence of the polymer of the monomer mixture (2b-A), and further the polymerization of the monomer mixture (2b-B). It is a rubber-containing polymer by multistage polymerization obtained by polymerizing the monomer mixture (2b-C) in the presence of the product.

The rubber-containing polymer (2b) is suitable in that it can provide a trimming processability and molding whitening resistance at the time of molding to the acrylic resin decorative molding sheet in a balanced manner.
<Monomer mixture (2b-A)>
(2b-A1) Acrylic acid alkyl ester 50-99.9% by mass
(2b-A2) Methacrylic acid alkyl ester 0 to 49.9% by mass
(2b-A3) Other monomer having a copolymerizable double bond 0 to 20% by mass
(2b-A4) Polyfunctional monomer 0 to 10% by mass
(2b-A5) Graft crossing agent 0.1 to 10% by mass
In addition, Tg calculated | required by the formula of FOX of the polymer obtained from component (2b-A1)-(2b-A3) is less than 25 degreeC.
<Monomer mixture (2b-B)>
(2b-B1) Acrylic acid alkyl ester 9.9 to 90% by mass
(2b-B2) Methacrylic acid alkyl ester 9.9 to 90% by mass
(2b-B3) Other monomer having a copolymerizable double bond 0 to 20% by mass
(2b-B4) Polyfunctional monomer 0 to 10% by mass
(2b-B5) Graft crossing agent 0.1 to 10% by mass
In addition, Tg calculated | required by the formula of FOX of the polymer obtained from component (2b-B1)-(2b-B3) exceeds 0 degreeC, and is less than 25 degreeC.
<Monomer mixture (2b-C)>
(2b-C1) Methacrylic acid alkyl ester 80 to 100% by mass
(2b-C2) Acrylic acid alkyl ester 0 to 20% by mass
(2b-C3) Other monomer having a double bond capable of copolymerization 0 to 20% by mass.

  In the above monomer mixture, acrylic acid alkyl ester (2b-A1), (2b-B1) or (2b-C2), methacrylic acid alkyl ester (2b-A2), (2b-B2) or (2b- C1), another monomer having a copolymerizable double bond (2b-A3), (2b-B3) or (2b-C3), a polyfunctional monomer (2b-A4) or (2b- B4) and the graft crossing agent (2b-A5) or (2b-B5) are alkyl acrylate esters in the monomer mixture (1-A) of the rubber-containing polymer (Ab-1-1), respectively. (2b-A1), methacrylic acid alkyl ester (2b-A2), other monomer having a copolymerizable double bond (2b-A3), polyfunctional monomer (2b-A4) or graft crossing The same as the agent (2b-A5) It is.

  In the monomer mixture (2b-A), (2b-B) or (2b-C), the above-mentioned components (2b-A1) to (2b-A5), (2b-B1) to (2b- In addition to B5) or (2b-C1) to (2b-C3), a chain transfer agent can be further added.

  Examples of the chain transfer agent include the same chain transfer agents that can be used in obtaining the rubber-containing polymer (Ab-1-1).

  Content of the acrylic acid alkyl ester (2b-A1) in the monomer mixture (2b-A) is 50 to 99.9% by mass. The content of the acrylic acid alkyl ester (2b-A1) in the monomer mixture (2b-A) is 60% by mass or more in terms of trimming workability during molding of the acrylic resin decorative molding sheet. Preferably, 80 mass% or more is more preferable. The content of the acrylic acid alkyl ester (2b-A1) in the monomer mixture (2b-A) is 97.9 masses in terms of surface hardness and heat resistance of the acrylic resin decorative molding sheet. % Or less is preferable, and 94.9 mass% or less is more preferable.

  The content of the methacrylic acid alkyl ester (2b-A2) in the monomer mixture (2b-A) is 0 to 49.9% by mass. The content of the methacrylic acid alkyl ester (2b-A2) in the monomer mixture (2b-A) is preferably 2% by mass or more, and more preferably 5% by mass or more. Moreover, as content of the methacrylic acid alkylester (2b-A2) in a monomer mixture (2b-A), 39.9 mass% or less is preferable, and 19.9 mass% or less is more preferable.

  The content of the other monomer (2b-A3) having a copolymerizable double bond in the monomer mixture (2b-A) is 0 to 20% by mass, and preferably 0 to 15% by mass.

  Content of the polyfunctional monomer (2b-A4) in a monomer mixture (2b-A) is 0-10 mass%. The content of the polyfunctional monomer (2b-A4) in the monomer mixture (2b-A) is 0.1% by mass in terms of resistance to whitening of the acrylic resin decorative molding sheet. The above is preferable, and 3% by mass or more is more preferable. Moreover, as content of the polyfunctional monomer (2b-A4) in a monomer mixture (2b-A), it is 6 masses at the point of the softness | flexibility and toughness of the acrylic resin decorative molding sheet. % Or less is preferable and 5 mass% or less is more preferable.

  The content of the graft crossing agent (2b-A5) in the monomer mixture (2b-A) is 0.1 to 10% by mass. As the content of the graft crossing agent (2b-A5) in the monomer mixture (2b-A), the whitening resistance of the acrylic resin decorative molding sheet and the optical properties such as transparency are lowered. 0.5 mass% or more is preferable at the point which can shape | mold without. Further, the content of the graft crossing agent (2b-A5) in the monomer mixture (2b-A) is 5% by mass or less in terms of flexibility and toughness of the acrylic resin decorative molding sheet. Preferably, 2 mass% or less is more preferable.

  As Tg calculated | required by the formula of FOX of the polymer obtained from component (2b-A1)-(2b-A3), it is less than 25 degreeC at the point of the trimming workability at the time of the shaping | molding of the acrylic resin decorative molding sheet | seat Yes, 0 ° C. or lower is preferable, and −30 ° C. or lower is more preferable.

  As a usage-amount of a monomer mixture (2b-A), the sum total of a monomer mixture (2b-A), a monomer mixture (2b-B), and a monomer mixture (2b-C) is 100 mass parts. In this case, the acrylic resin decorative molding sheet can be provided with good molding whitening resistance and trimming processability at the time of molding, and the acrylic resin-based laminated film (A) can be formed with insert molding or insert molding. 15 mass parts or more are preferable at the point which can make compatible the toughness suitable for molding. Moreover, as the usage-amount of a monomer mixture (2b-A), the favorable shaping | molding whitening resistance and the trimming workability at the time of shaping | molding can be provided to the acrylic resin decorative molding sheet | seat, an acrylic resin-type lamination | stacking 50 mass parts or less are preferable and 35 mass parts or less are more preferable at the point which can make film forming property and toughness suitable for insert molding or in-mold molding compatible with a film (A).

  When polymerizing the monomer mixture (2b-A), the monomer mixture (2b-A) can be polymerized in a lump, but can also be polymerized in two or more stages.

  When the monomer mixture (2b-A) is polymerized in two stages, the amount of the monomer mixture (2b-A-i) used in the first stage is the monomer mixture (2b-A). 1) to 20% by mass is preferable, and the amount of the monomer mixture (2b-A-ro) used in the second stage is 80 to 99% by mass in the monomer mixture (2b-A). Is preferred.

  Content of the acrylic acid alkylester (2b-B1) in a monomer mixture (2b-B) is 9.9-90 mass%. As a content of the acrylic acid alkyl ester (2b-B1) in the monomer mixture (2b-B), in terms of trimming processability and molding whitening resistance during molding of the acrylic resin decorative molding sheet, 19.9 mass% or more is preferable and 29.9 mass% or more is more preferable. Moreover, as content of acrylic acid alkylester (2b-B1) in a monomer mixture (2b-B), it is 60 mass% or less in terms of the surface hardness and heat resistance of the acrylic resin decorative molding sheet. Is preferable, and 50 mass% or less is more preferable.

  Content of the methacrylic acid alkyl ester (2b-B2) in a monomer mixture (2b-B) is 9.9-90 mass%. The content of the alkyl methacrylate ester (2b-B2) in the monomer mixture (2b-B) is 39.9% by mass or more in terms of surface hardness and heat resistance of the acrylic resin decorative molding sheet. Is preferable, and 49.9 mass% or more is more preferable. Moreover, as content of the methacrylic acid alkyl ester (2b-B2) in a monomer mixture (2b-B), the point of the trimming workability at the time of shaping | molding of the acrylic resin decorative molding sheet | seat, and a molding whitening-proof point Is preferably 80% by mass or less, and more preferably 70% by mass or less.

  The content of the other monomer (2b-B3) having a copolymerizable double bond in the monomer mixture (2b-B) is 0 to 20% by mass. The content of the other monomer (2b-B3) having a copolymerizable double bond in the monomer mixture (2b-B) is preferably 15% by mass or less.

  Content of the polyfunctional monomer (2b-B4) in a monomer mixture (2b-B) is 0-10 mass%. As content of the polyfunctional monomer (2b-B4) in the monomer mixture (2b-B), in terms of imparting sufficient flexibility and toughness to the acrylic resin decorative molding sheet, 6 mass% or less is preferable and 3 mass% or less is more preferable.

  The content of the graft crossing agent (2b-B5) in the monomer mixture (2b-B) is 0.1 to 10% by mass. As the content of the graft crossing agent (2b-B5) in the monomer mixture (2b-B), the whitening resistance of the acrylic resin decorative molding sheet is good and the optical properties such as transparency are good. 0.5 mass% or more is preferable at the point which can shape | mold without reducing. Moreover, as content of the graft crossing agent (2b-B5) in a monomer mixture (2b-B), it is 5 at the point which provides sufficient softness | flexibility and toughness to the acrylic resin decorative molding sheet. % By mass or less is preferable, and 2% by mass or less is more preferable.

  Tg calculated | required by the formula of FOX of the polymer obtained from component (2b-B1)-(2b-B3) exceeds 0 degreeC, and is less than 25 degreeC. As Tg calculated | required by the formula of FOX of the polymer obtained from a component (2b-B1)-(2b-B3), the surface hardness and heat resistance of the acrylic resin decorative molding sheet | seat are used for uses, such as a member for vehicles. 10 degreeC or more is preferable and 15 degreeC or more is more preferable at the point which gives the trimming workability at the time of favorable insert molding, hold | maintaining at the suitable level.

  As a usage-amount of a monomer mixture (2b-B), the sum total of a monomer mixture (2b-A), a monomer mixture (2b-B), and a monomer mixture (2b-C) is 100 mass parts. 5 to 35 parts by mass is preferable, and 5 to 20 parts by mass is more preferable. The amount of the monomer mixture (2b-B) used in such a range is preferable in terms of molding whitening resistance, surface hardness, heat resistance, and trimming processability during insert molding of the acrylic resin decorative molding sheet. . Moreover, the usage-amount of the monomer mixture (2b-B) of such a range is required for the other physical property of an acrylic resin-type laminated | multilayer film (A), for example, film forming property, insert molding, or in-mold molding. This is preferable in terms of imparting toughness.

  When polymerizing the monomer mixture (2b-B), the monomer mixture (2b-B) can be polymerized in a lump, or can be polymerized in two or more stages.

  The content of the alkyl methacrylate (2b-C1) in the monomer mixture (2b-C) is 80 to 100% by mass. The content of the methacrylic acid alkyl ester (2b-C1) in the monomer mixture (2b-C) is preferably 90% by mass or more in terms of the surface hardness and heat resistance of the acrylic resin decorative molding sheet. .

  Content of the acrylic acid alkylester (2b-C2) in a monomer mixture (2b-C) is 0-20 mass%. The content of the acrylic acid alkyl ester (2b-C2) in the monomer mixture (2b-C) is preferably 10% by mass or less.

  Content of the other monomer (2b-C3) which has a copolymerizable double bond in a monomer mixture (2b-C) is 0-20 mass%. The content of the other monomer (2b-C3) having a copolymerizable double bond in the monomer mixture (2b-C) is preferably 15% by mass or less.

  When a chain transfer agent is added to the monomer mixture (2b-C), the addition amount of the chain transfer agent is 0.01 to 5 parts by mass with respect to 100 parts by mass of the monomer mixture (2b-C). preferable. As addition amount of a chain transfer agent, 0.2 mass part or more is more preferable with respect to 100 mass parts of monomer mixtures (2b-C).

  As Tg calculated | required by the formula of FOX of the polymer obtained from a component (2b-C1)-(2b-C3), the surface hardness and heat resistance of the acrylic resin decorative molding sheet | seat are used for applications, such as a member for vehicles. 60 degreeC or more is preferable and 80 degreeC or more is more preferable at the point used as the suitable level.

  As a usage-amount of a monomer mixture (2b-C), the sum total of a monomer mixture (2b-A), a monomer mixture (2b-B), and a monomer mixture (2b-C) is 100 mass parts. In terms of surface hardness and heat resistance of the acrylic resin decorative molding sheet, 15 parts by mass or more is preferable, and 45 parts by mass or more is more preferable. In addition, the amount of the monomer mixture (2b-C) used is that of the whitening resistance of the acrylic resin decorative molding sheet, the toughness suitable for insert molding or in-mold molding, and the trimming processability during insert molding. In this respect, when the total of the monomer mixture (2b-A), the monomer mixture (2b-B), and the monomer mixture (2b-C) is 100 parts by mass, 80 parts by mass or less is preferable.

  When polymerizing the monomer mixture (2b-C), the monomer mixture (2b-C) can be polymerized in a lump, or can be polymerized in two or more stages.

Regarding the gel content, mass average particle diameter and production method of the rubber-containing polymer (2b), the same as the rubber-containing polymer (A-b-1-1) is preferable.

Thermoplastic polymer (Ab-2)

The thermoplastic polymer (Ab-2) used in the present invention can be used to form an acrylic resin composition (X) which is a constituent component of an acrylic resin layer (Ab) described later. Is.

As a thermoplastic polymer (Ab-2), the thermoplastic polymer (Aa) contained in the acrylic resin composition (Y) which is a structural component of the above-mentioned acrylic resin layer (Aa-α). -2).

In the present invention, the rubber content of the acrylic resin composition (X) is preferably 26% by mass or more from the viewpoint of trimability during insert molding or in-mold molding of the acrylic resin decorative molding sheet. The rubber content of the acrylic resin composition (X) is less than 50% by mass in terms of surface hardness, heat resistance of the acrylic resin decorative molding sheet, and suppression of surface roughness pattern defects during heat molding. Preferably, it is less than 40% by mass.

  In the present invention, the “rubber” is obtained from a monomer composition used as a raw material in the acrylic rubber-containing polymer (A-a-1) or the acrylic rubber-containing polymer (A-b-1). The polymer whose Tg calculated | required by the formula of FOX of a polymer to be obtained is less than 25 degreeC. Therefore, the rubber content of the acrylic resin composition (X) refers to the proportion of the polymer having a Tg of less than 25 ° C. in the acrylic resin composition.

In the present invention, the gel content of the acrylic resin composition (X) is the film forming property of the acrylic resin-based laminated film (A) and the molding resistance during insert molding or in-mold molding of the acrylic resin decorative molding sheet. From the point of whitening property, 45 mass% or more is preferable, and 50 mass% or more is more preferable. The gel content of the acrylic resin composition (X) is determined by the film forming properties of the acrylic resin-based laminated film (A), trimming processability and heating during insert molding or in-mold molding of acrylic resin decorative molding sheets. Less than 70% by mass is preferable from the viewpoint of suppressing the appearance of surface roughness pattern defects during molding.
When this gel content rate is 45 mass% or more, it is excellent in the film forming property of an acrylic resin-type laminated | multilayer film (A), and the molding whitening resistance at the time of insert molding or in-mold molding of the acrylic resin decoration molding sheet. 50 mass% or more is more preferable.

In the present invention, the rubber content and the gel content of the acrylic rubber-containing polymer (Ab-1) blended in the acrylic resin composition (X) are not particularly limited, and the acrylic resin composition A method of adjusting the polymerization prescription of the acrylic rubber-containing polymer (Ab-1) or a thermoplastic polymer (Ab) so that the rubber content and the gel content of (X) are the target content. -2) can be adjusted by the method of adjusting the blending amount.
Acrylic resin layer (A-b)

The acrylic resin layer (Ab) used in the present invention comprises the acrylic resin composition (X) as a constituent component. Further, HDT is intended at least 5 ° C. lower than the HDT _{(T A-a)} of the thermoplastic resin layer (A-a) of the acrylic resin layer (A-b).

  When the HDT of the acrylic resin layer (Ab) satisfies the above conditions, the resulting acrylic resin decorative molding sheet has excellent trimming workability when insert molding or in-mold molding is performed. can do.

  Moreover, as HDT of an acrylic resin layer (Ab), 80 degreeC or more is preferable. By setting the HDT of the acrylic resin layer (Ab) to 80 ° C. or higher, even if the acrylic resin layer (Ab) constituting one surface of the laminate of the present invention described later is exposed at a high temperature for a long time. Whitening and fogging are not observed on the surface of the acrylic resin layer (A-b). In addition, by setting the HDT of the acrylic resin layer (A-b) to 80 ° C. or higher, the laminate obtained by the present invention can also be used for a part that receives direct sunlight in the vehicle, such as a front control panel in a vehicle application. This is preferable.

  Furthermore, 84 degreeC or more is more preferable as HDT of an acrylic resin layer (Ab). By setting the HDT of the acrylic resin layer (Ab) to 84 ° C. or higher, the pencil hardness of the acrylic resin layer (Ab) constituting one surface of the laminate obtained in the present invention is higher than HB, It is suitable for various vehicle members such as door waist garnish, front control panel, power window switch panel, and airbag cover.

  The HDT of the acrylic resin layer (Ab) is particularly preferably 85 ° C. or higher. By setting the HDT of the acrylic resin layer (Ab) to 85 ° C. or higher, the pencil hardness of the acrylic resin layer (Ab) constituting one surface of the laminate obtained in the present invention is set to F or higher. The scratches are hardly noticeable even when scratched with a rough cloth such as gauze.

In the present invention, in the acrylic resin layer (A-b), as in the case of the thermoplastic resin layer (A-a), general compounding agents such as stabilizers, lubricants, processing aids are used as necessary. , Plasticizers, impact aids, foaming agents, fillers, colorants and UV absorbers. Moreover, the kind and compounding quantity of compounding agents, such as a ultraviolet absorber and a light stabilizer, and the compounding method of a compounding agent can be made to be the same as that of the case of a thermoplastic resin layer (Aa).

Acrylic resin laminated film (A)

The acrylic resin-based laminated film (A) used in the present invention is a laminated film having a two-layer structure in which a thermoplastic resin layer (Aa) and an acrylic resin layer (Ab) are laminated.

  Although it does not specifically limit as thickness of an acrylic resin type laminated | multilayer film (A), 300 micrometers or less are preferable.

  When the acrylic resin-based laminated film (A) is used as a paint substitute film, the thickness of the acrylic resin-based laminated film (A) is preferably 50 to 300 μm. By setting the thickness to 50 μm or more, the appearance of a molded product having a sufficient depth tends to be obtained. Moreover, even if it extends | stretches when shape | molding in a complicated shape, the thickness of an acrylic resin type laminated | multilayer film (A) can be made sufficient. On the other hand, when the thickness of the acrylic resin-based laminated film (A) is 300 μm or less, the acrylic resin-based laminated film (A) has appropriate rigidity, so that the laminating property, the secondary workability, and the like are improved. The acrylic resin-based laminated film (A) is economically advantageous in terms of mass per unit area. Furthermore, the film forming property is stable and the production of the acrylic resin-based laminated film (A) is facilitated.

  Ratio of the thickness of the thermoplastic resin layer (Aa) and the acrylic resin layer (Ab) constituting the acrylic resin-based laminated film (A) (the thickness of the thermoplastic resin layer (Aa) / acrylic resin) The thickness of the layer (Ab) is not particularly limited, but is preferably 1/99 to 99/1.

  Moreover, as a ratio of the thickness of the thermoplastic resin layer (Aa) and the acrylic resin layer (Ab), the trimming processability at the time of insert molding or in-mold molding of the acrylic resin decorative molding sheet is used. In this respect, 50/50 or less is more preferable, 30/70 or less is particularly preferable, and 20/80 or less is most preferable.

  On the other hand, as a ratio of the thicknesses of the thermoplastic resin layer (Aa) and the acrylic resin layer (Ab), it is possible to suppress the appearance of rough surface pattern defects during the heat molding of the acrylic resin decorative molding sheet. In this respect, 5/95 or more is more preferable, and 10/90 or more is particularly preferable.

  In this invention, an acrylic resin-type laminated | multilayer film (A) forms other layers other than two layers of a thermoplastic resin layer (Aa) and an acrylic resin layer (Ab) as needed. Can do. Other layers are formed on the surface of the thermoplastic resin layer (Aa) on the side different from the pattern layer (B), between the thermoplastic resin layer (Aa) and the acrylic resin layer (Ab). Any location of

  Examples of the method for producing the acrylic resin-based laminated film (A) used in the present invention include a thermoplastic resin layer (Aa) and an acrylic resin layer by a coextrusion molding method using a feed block die or a multi-manifold die. (Ab) and a method of forming a laminated structure of other layers as necessary, and a thermoplastic resin layer (Aa), an acrylic resin layer (Ab) and other layers as necessary, Examples thereof include a method of forming a film by a melt extrusion method using a T die, and laminating films for forming each layer by a heat laminating method.

  Moreover, as a manufacturing method of an acrylic resin-type laminated | multilayer film (A), one resin layer of a thermoplastic resin layer (Aa) or an acrylic resin layer (Ab) is made into a film form, and the other resin layer is melted after that. The extrusion lamination method which laminates | stacks by the extrusion method is mentioned.

  Among these production methods, the above-described coextrusion method is preferable from the viewpoint of economy and process simplification.

  In the present invention, when the acrylic resin-based laminated film (A) is formed by the T-die method, a method of forming a film by sandwiching it between a plurality of rolls or belts selected from a metal roll, a non-metal roll and a metal belt is adopted. Thereby, the surface smoothness of an acrylic resin-type laminated | multilayer film (A) can be improved, and the printing omission at the time of printing-processing to an acrylic resin-type laminated | multilayer film (A) can be suppressed. As the metal roll, a metal mirror surface touch roll, a sleeve comprising a metal sleeve (metal thin film pipe) described in Japanese Patent No. 2,808,251 or WO97 / 28,950, and a molding roll. Examples of the roll used in the touch method can be given. Moreover, as a non-metallic roll, touch rolls made of silicone rubber can be exemplified. Further, as the metal belt, a metal endless belt can be exemplified. In the T-die method, a plurality of these metal rolls, non-metal rolls and metal belts can be used in combination.

  In the method of forming a film by sandwiching a plurality of rolls or belts selected from the above metal rolls, non-metal rolls and metal belts, the raw material for forming each resin layer after melt extrusion is substantially banked ( It is preferable to hold the film in a state where there is no resin reservoir and to transfer the film without substantial rolling to form a film. When a film is formed without forming a bank (resin pool), each resin layer forming the acrylic resin-based laminated film (A) in the cooling process is surface-transferred without being rolled. It exists in the tendency which can reduce the heat shrinkage rate of the acrylic resin-type laminated | multilayer film (A) which formed the film.

Moreover, when adopting the melt extrusion method, in order to remove nuclei and foreign matters that cause printing omission, each of the acrylic resin-based laminated films (A) for forming a molten state with a screen mesh of 200 mesh or more is used. It is preferable to carry out extrusion while filtering the raw material for the resin layer.

Pattern layer (B)

The pattern layer (B) used in the present invention is for imparting design properties to the laminate described later.

The pattern layer (B) can be formed of at least one layer selected from a printing layer formed by a printing method and a vapor deposition layer formed by a vapor deposition method.

Print layer

The printed layer forms a pattern, characters, etc. on the surface of the laminate obtained in the present invention.

  Examples of the print pattern in the print layer include a pattern made of wood grain, stone grain, cloth grain, sand grain, geometric pattern, characters, full face, and the like.

  Examples of the binder for the printing layer include polyvinyl resins such as vinyl chloride / vinyl acetate copolymers, polyamide resins, polyester resins, polyacrylic resins, polyurethane resins, polyvinyl acetal resins, polyester urethane resins. , Cellulose ester resins, alkyd resins, and chlorinated polyolefin resins.

  For the formation of the printing layer, for example, a colored ink in which a pigment or dye having an appropriate color as a colorant is contained in a binder can be used.

  Examples of the pigment include the following. Examples of yellow pigments include azo pigments such as polyazo, organic pigments such as isoindolinone, and inorganic pigments such as yellow lead. Examples of red pigments include azo pigments such as polyazo, organic pigments such as quinacridone, and inorganic pigments such as petals. Examples of the blue pigment include organic pigments such as phthalocyanine blue and inorganic pigments such as cobalt blue. Examples of the black pigment include organic pigments such as aniline black. Examples of white pigments include inorganic pigments such as titanium dioxide.

  Examples of the dye include known dyes.

  Examples of the method for forming the printing layer include printing methods such as offset printing, gravure rotary printing, and screen printing; coating methods such as roll coating and spray coating; and flexographic printing.

  Although the thickness of a printing layer is not specifically limited, Usually, it is about 0.5-30 micrometers.

The number of printing omissions in the printed layer is preferably 10 pieces / m ² or less, more preferably 5 pieces / m ² or less, more preferably 1 piece / m ^{2 in} terms of the design and decoration properties of the acrylic resin decorative molding sheet. m ² or less is particularly preferable. By setting the number of printing omissions to 10 pieces / m ² or less, the appearance of the laminate using the acrylic resin decorative molding sheet becomes better.

In the present invention, when a laminate is obtained by insert molding or in-mold molding, the thickness of the printed layer is appropriately selected according to the degree of extension during insert or in-mold molding so as to obtain a desired surface appearance. can do.

Deposition layer

As a material for forming the vapor deposition layer, at least one metal selected from the group consisting of aluminum, nickel, gold, platinum, chromium, iron, copper, indium, tin, silver, titanium, lead, zinc, etc., an alloy thereof, or A metal compound is mentioned.

  Examples of the method for forming the vapor deposition layer include a vacuum vapor deposition method, a sputtering method, an ion plating method, and a plating method.

In the present invention, when a laminate is obtained by insert molding or in-mold molding, the thickness of the vapor deposition layer is appropriately selected according to the degree of extension during insert or in-mold molding so that a desired surface appearance can be obtained. can do.

Base sheet (C)

As a base material sheet (C), a thermoplastic resin and a curable resin are mentioned, for example, It can select according to the objective.

  Specific examples of the thermoplastic resin include acrylic resin; ABS resin (acrylonitrile-butadiene-styrene copolymer); AS resin (acrylonitrile-styrene copolymer); vinyl chloride resin; polyethylene, polypropylene, polybutene, polymethylpentene, etc. Polyolefin resins such as ethylene-vinyl acetate copolymer or a saponified product thereof, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid ester copolymer, and the like; polyethylene terephthalate, polybutylene terephthalate, polyethylene Polyester resins such as naphthalate, polyarylate and polycarbonate; Polyamide resins such as 6-nylon, 6,6-nylon, 6,10-nylon and 12-nylon; Polystyrene resin; Cellulose acetate Fibrin derivatives such as nitrocellulose, fluorine resins such as polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, and ethylene-tetrafluoroethylene copolymer; and two or more copolymers selected from these , Mixtures, composites or laminates.

For the base sheet (C), a stabilizer, an antioxidant, a lubricant, a processing aid, a plasticizer, an impact-resistant agent, a foaming agent, a filler, an antibacterial agent, an antifungal agent, and a mold release agent, as necessary. In addition, compounding agents such as an antistatic agent, a colorant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, and a flame retardant can be blended.

Acrylic resin decorative molding sheet

The decorative sheet made of acrylic resin used in the present invention has a pattern layer (B) and a base sheet (C) laminated on the thermoplastic resin layer (Aa) side of the acrylic resin-based laminated film (A). It is what.

  In the acrylic resin decorative molding sheet, the pattern layer (B) is laminated so as to be in contact with the acrylic resin-based laminated film (A) and the base sheet (C). It is protected and can impart a high-class feeling to the molding sheet.

  Examples of the method for producing the acrylic resin decorative molding sheet include a thermal lamination method.

The acrylic resin decorative molding sheet uses an acrylic resin-based laminated film (A) in which a thermoplastic resin layer (Aa) and a thermoplastic resin layer (Ab) are laminated. It is excellent in molding whitening property, and the crease in the bending test is not whitened at all or only slightly whitened, and molding whitening that occurs in the process of insert molding or in-mold molding is hardly noticeable. Moreover, the molded product excellent in design property can be obtained without the printed pattern of the acrylic resin decorative molding sheet subjected to the printed pattern even after the insert molding or in-mold molding.

Thermoforming

In the present invention, examples of the heat forming include vacuum forming and pressure forming.

  In the present invention, when the acrylic resin decorative molding sheet is thermoformed, the acrylic resin decorative molding sheet is thermoformed at a molding temperature satisfying the above-described formula (1). By performing heat molding under these conditions, surface roughness pattern defects can be suppressed in the acrylic resin decorative molding sheet. Further, during insert molding or in-mold molding, the resin decorative molding sheet is vacuum molded or pressure molded at a molding temperature satisfying the above-described formula (1) in an injection mold, thereby providing a laminate with a good surface appearance. A molded product is obtained.

In the present invention, it can be appropriately set by a molding temperature (T _s) of the shape of the thermal properties or the laminated molded article at the time of heat-molding the acrylic resin decorative molding sheet, the acrylic resin decorative molding It is preferably at or above the temperature at which the sheet is softened, and is usually at least 100 ° C.

Molded product (D)
The molded product (D) used in the present invention is used to obtain a laminated molded product by laminating acrylic resin decorative molding sheets.

  As resin which comprises a molded article (D), the thing similar to the said base material sheet (C) is mentioned.

  For the molded product (D), if necessary, stabilizers, antioxidants, lubricants, processing aids, plasticizers, impact agents, foaming agents, fillers, antibacterial agents, antifungal agents, mold release agents, Compounding agents such as an antistatic agent, a colorant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, and a flame retardant can be blended.

The method for producing the molded product (D) is not particularly limited, and the molded product (D) can be obtained by various molding methods such as an injection molding method.

Laminated molded product

The laminated molded product obtained by the present invention is a product laminated on the molded product (D) through the surface of the base sheet (C) of the acrylic resin decorative molding sheet. Accordingly, in the laminated molded product, the base sheet (C), the pattern layer (B), the thermoplastic resin layer (Aa), and the acrylic resin layer (Ab) are sequentially laminated on the surface of the molded product (D). The acrylic resin layer (Ab) is formed on the surface of the laminated molded product.

  In the laminated molded article obtained in the present invention, the decorative layer (B) is laminated so that the pattern layer (B) of the acrylic resin decorative molding sheet is in contact with the base sheet (C). It is protected and can give a high-class feeling to the laminated molded product.

  Examples of the method for producing a laminated molded product include an insert molding method and an in-mold molding method, and the in-mold molding method is preferable in terms of productivity.

  In the in-mold molding method, after the acrylic resin decorative molding sheet is heated, vacuum molding is performed in a mold having a vacuum drawing function, and then the resin constituting the molded product (D) is molded in the same mold. This is a method of obtaining a laminated molded product in which an acrylic resin decorative molding sheet and a molded product (D) are integrated by injection molding. The in-mold molding method is preferable from the viewpoints of workability and economy because the film molding and injection molding can be performed in one step.

  In the method for producing a laminated molded product of the present invention, when the laminated molded product is obtained, the acrylic resin layer (Ab) surface of the acrylic resin decorative molding sheet is produced so as to be the surface of the laminated molded product. Therefore, the surface of the acrylic resin decorative molding sheet at the time of heat molding without impairing the whitening resistance and trimming processability of the acrylic resin decorative molding sheet at the time of insert molding or in-mold molding. Since it can satisfy the contradictory performance of being excellent in suppressing the appearance of rough pattern defects and having excellent surface hardness and heat resistance of the surface of the laminated molded product, the industrial utility value is extremely high.

  In the present invention, when a laminated molded product is obtained by in-mold molding or insert molding, the shrinkage rate after injection molding of the resin constituting the molded product (D) is set to the shrinkage rate of the acrylic resin decorative molding sheet. Approximation is preferable in terms of suppression of warpage of the laminated molded product or peeling of the acrylic resin decorative molding sheet.

  Examples of a method for adjusting the shrinkage rate after injection molding of the resin constituting the molded product (D) include a method of blending a filler and an elastomer component with the resin constituting the molded product (D).

  Specific examples of the filler include talc, calcium carbonate, silica, mica, glass fiber, and carbon fiber.

  Examples of the use of the laminated molded article obtained in the present invention include automotive interior members such as instrument panels, console boxes, meter covers, door lock pezels, steering wheels, power window switch bases, center clusters, and dashboards; weather strips, Bumpers, bumper guards, side mudguards, body panels, spoilers, front grills, strut mounts, wheel caps, center pillars, door mirrors, center ornaments, side moldings, door moldings, wind moldings, windows, head lamp covers, tail lamp covers, windshield parts, etc. Automotive exterior parts; AV equipment and other front panels; Buttons, emblems and other surface decorative materials; Cellular phone housings, display windows, buttons and other parts ; Exterior materials for furniture; interior materials for buildings such as walls, ceilings, floors; exterior walls for siding, etc .; exterior materials for buildings such as fences, roofs, gates, windbreak boards; window frames, doors, railings, sills, duck Furniture surface decoration materials; Optical members such as various displays, lenses, mirrors, goggles, and window glass; Interior and exterior members of various vehicles other than automobiles such as trains, aircraft, and ships; and bottles, cosmetic containers, accessory cases, etc. Other various uses such as various packaging containers, packaging materials, giveaways, and other sundries are included.

  Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, “part” represents “part by mass”, and “%” represents “% by mass”. Abbreviations in the examples are as shown in Table 1.

また、本発明において、重合体、フィルム、成形用シート及び積層成形品に関する各種評価は以下の方法により実施した。
（１）質量平均粒子径
乳化重合にて得られた重合体ラテックスの重合体の粒子の質量平均粒子径を、大塚電子（株）製の光散乱光度計ＤＬＳ−７００（商品名）を用い、動的光散乱法で測定した。
（２）Ｔｇ
重合体用原料として使用する単量体の組成から、ポリマーハンドブック〔Ｐｏｌｙｍｅｒ ＨａｎｄＢｏｏｋ（Ｊ．Ｂｒａｎｄｒｕｐ，Ｉｎｔｅｒｓｃｉｅｎｃｅ，１９８９）〕に記載されている値を用いてＦＯＸの式から得られる重合体のＴｇを算出した。
（３）還元粘度
重合体０．１ｇをクロロホルム１００ｍＬに溶解し、２５℃で熱可塑性重合体の還元粘度を測定した。
（４）ゲル含有率
所定量（抽出前質量）のゴム含有重合体を含有するアクリル樹脂組成物の粉体を押出成形してペレット状物を得た。このペレット状物の全量をアセトン溶媒中、還流下で抽出処理し、得られた処理液を遠心分離により分別し、乾燥後、アセトン不溶分の質量（抽出後質量）を測定した。ゲル含有率は下式にて算出した。

Moreover, in this invention, various evaluation regarding a polymer, a film, a sheet | seat for shaping | molding, and a laminated molded product was implemented with the following method.
(1) Mass average particle diameter The mass average particle diameter of the polymer latex polymer particles obtained by emulsion polymerization was measured using a light scattering photometer DLS-700 (trade name) manufactured by Otsuka Electronics Co., Ltd. It was measured by a dynamic light scattering method.
(2) Tg
Calculate the Tg of the polymer obtained from the formula of FOX from the composition of the monomer used as the raw material for the polymer, using the values described in the polymer handbook [Polymer HandBook (J. Brandrup, Interscience, 1989)]. did.
(3) Reduced viscosity 0.1 g of the polymer was dissolved in 100 mL of chloroform, and the reduced viscosity of the thermoplastic polymer was measured at 25 ° C.
(4) Gel content rate A powder of an acrylic resin composition containing a predetermined amount (mass before extraction) of a rubber-containing polymer was extruded to obtain a pellet. The total amount of the pellets was extracted in an acetone solvent under reflux, and the resulting treatment solution was separated by centrifugation, dried, and then the mass of acetone-insoluble matter (mass after extraction) was measured. The gel content was calculated by the following formula.

Gel content (%) = (mass after extraction (g) / mass before extraction (g)) × 100
(5) HDT
The pellet of the resin composition used for manufacture of an acrylic resin-type laminated | multilayer film (A) was used, the heat-deformation temperature measurement test piece based on ASTM D648 was produced by injection molding, and it annealed at about 80 degreeC for 4 hours. Next, the HDT of the resin composition was measured according to ASTM D648 at a low load of 0.45 MPa, unless otherwise specified.
(6) Thickness of thermoplastic resin layer (Aa) and acrylic resin layer (Ab) A sample obtained by cutting the acrylic resin-based laminated film (A) in the cross-sectional direction so that the thickness of the section becomes 70 nm. Observation with a transmission electron microscope (manufactured by JEOL Ltd., J100S), measuring the thickness at five locations, and averaging them, the thermoplastic resin layer (Aa) and the acrylic resin layer (A The thickness of -b) was determined.

A decorative film made of acrylic resin (using the acrylic resin-based laminated film (A) with a pattern layer (B)) prepared using a 90 μm-thick acrylic resin-based laminated film (A), Under the atmosphere, the whitening state when bent 180 degrees at a relatively high speed was evaluated with naked eyes, and the molding whitening resistance of the acrylic resin decorative film was evaluated according to the following criteria.
(8) Surface state of acrylic resin-made decorative molding sheet The same acrylic resin-made decorative film as in the evaluation of the above-described molding whitening resistance and the base material sheet (C), an adhesive layer (vinyl chloride-acetic acid). 1 mm thick ABS sheet having a vinyl copolymer system (obtained by melt extrusion of UMGGABS (registered trademark) EX215 (trade name) manufactured by UMG ABS Co., Ltd.)) and a decorative film made of acrylic resin It laminated | stacked by the heat lamination so that a layer (B) and an contact bonding layer might contact | connect, and the acrylic resin-made decorative molding sheet was obtained.

The obtained acrylic resin decorative molding sheet is placed in a mold having a vacuuming function so that the acrylic resin laminated film (A) side is the cavity side, and the acrylic resin decorative molding sheet is After heating with a heater until reaching the heat forming temperature (T _s ) shown in Table 3, vacuum forming was performed to obtain a preformed product for acrylic resin decorative molding. The appearance state of the rough surface pattern defect of the obtained preform was visually evaluated, and the surface state of the acrylic resin decorative molding sheet was evaluated according to the following criteria.
(9) Trimming processability of acrylic resin decorative molding sheet End of preform of acrylic resin decorative molding sheet obtained by vacuum forming acrylic resin decorative molding sheet in (8) above After trimming an unnecessary sheet part remaining in the part (a part of the laminated molded product that does not adhere to the molded product) from the acrylic resin-based laminated film (A) side using a Thomson punching die, The state was visually observed, and the trimming processability of the acrylic resin decorative molding sheet was evaluated according to the following criteria.
(10) Insert moldability The preform of the acrylic resin decorative molding sheet after trimming unnecessary portions in (9) above is 3 cm laterally from the bottom of the mold on the cavity side and the central gate. The acrylic resin-based laminated film (A) side was placed on the cavity side at the bottom of a mold having a square dent with an area of 1 cm ² and a depth of 1 mm at the position.

  Next, the ABS resin (made by UMG ABS, Diapet ABS Bulk Sum TM25 (trade name)) constituting the molded product (D) is injection-molded on the ABS sheet side of the acrylic resin decorative molding sheet, and the insert A laminated molded product was obtained by molding.

  The shape of the laminated molded product was a box shape having a length of 150 mm, a width of 120 mm, a thickness of 2 mm, and a depth of 10 mm. In addition, the mold used has gates in three places, one at the center of the mold and one above each at a position 40 mm above and below the center gate (vertical direction in the laminated molded product). Used is a pinpoint gate having a diameter of 1 mm. Furthermore, the corner corner R connecting the bottom surface and the side surface on the cavity side of the mold is about 3. That is, the corner R of the edge portion of the laminated molded product on the side where the acrylic resin film is laminated is about 3. The corner R was measured with a RADIUS GAGE (trade name) manufactured by Fuji Tool Co., Ltd.

  Injection molding was performed using a J85EL11 type injection molding machine (trade name) manufactured by Nippon Steel Works, Ltd. under the conditions of a cylinder temperature of 250 ° C., an injection speed of 30%, an injection pressure of 43%, and a mold temperature of 60 ° C.

The resulting state of the corner of the convex portion or laminated molded article edge portion of the laminated formed in the molded article was an area 1 cm ² and a height of 1mm macroscopically observed and evaluated the insert molding of the laminated molded product according to the following criteria.
(11) Pencil hardness The pencil hardness of the surfaces of the acrylic resin decorative molding sheet and the laminated molded product was measured according to J1S K5600.
[Production Example 1] Production of rubber-containing polymer (Ab-1-1) (1) After charging 10.8 parts of deionized water in a container equipped with a stirrer, the following monomer mixture (1- A) The monomer mixture (1-A-i) (1) for the first stage polymerization in (1) was added and stirred and mixed at room temperature. Next, 1.3 parts of the emulsifier (1) was charged into the container while stirring, and stirring was continued for 20 minutes to prepare an emulsion.

  Next, 139.2 parts of deionized water was put into a polymerization vessel equipped with a cooler, and the temperature was raised to 75 ° C. Thereafter, a mixture prepared by adding 0.20 part of SFS, 0.0001 part of ferrous sulfate and 0.0003 part of EDTA to 5 parts of ion-exchanged water was put into the polymerization vessel at once. Next, the emulsion prepared above was added dropwise into the polymerization vessel over 8 minutes while stirring under nitrogen, and then the reaction was continued for 15 minutes, whereby the first stage of the monomer mixture (1-A) (1) The eye polymerization was completed. Subsequently, the monomer mixture (1-A-ro) (1) for the second stage polymerization of the following monomer mixture (1-A) (1) was dropped into the polymerization vessel over 90 minutes. The reaction was continued for 60 minutes to complete the second stage polymerization of the monomer mixture (1-A) (1) to obtain a polymer. The Tg determined from the FOX equation of the polymer obtained in the first stage polymerization is −48 ° C., and the Tg obtained from the FOX equation of the polymer obtained in the second stage polymerization is −10. ° C.

  Subsequently, the following monomer mixture (1-B) (1) was dropped into the polymerization vessel over 45 minutes, and then the reaction was continued for 60 minutes to polymerize the monomer mixture (1-B) (1). Completed. Tg calculated | required from the formula of FOX of the polymer obtained by superposition | polymerization of monomer mixture (1-B) (1) was 60 degreeC.

  Thereafter, the following monomer mixture (1-C) (1) was dropped into the polymerization vessel over 140 minutes, and then the reaction was continued for 60 minutes to obtain a rubber-containing polymer (Ab-1-1) (1 ) Polymer latex was obtained. The Tg determined from the FOX formula of the polymer obtained by polymerization of the monomer mixture (1-C) was 99 ° C.

  The mass average particle diameter of the rubber-containing polymer (Ab-1-1) (1) particles in the obtained polymer latex was 0.11 μm.

  The obtained rubber-containing polymer (Ab-1-1) (1) polymer latex was filtered using a vibration type filtration apparatus equipped with a SUS mesh (average opening: 62 μm) as a filter medium. Then, it was salted out in an aqueous solution containing 3.5 parts of calcium acetate, washed with water to recover a solid content, and then dried to form a powdery rubber-containing polymer (Ab-1-1) (1) Got. The gel content of the rubber-containing polymer (Ab-1-1) (1) was 70%, and the rubber content was 30%.

The powdery rubber-containing polymer (Ab-1-1) 214.3 g was charged into 1500 mL of acetone filtered through a nylon mesh having an opening of 25 μm, and stirred for 3 hours to give a rubber-containing polymer (Ab). An acetone dispersion of 1-1-1) was prepared. Subsequently, this dispersion was filtered through a nylon mesh having a mesh size of 32 μm, and then the nylon mesh was ultrasonically washed in chloroform for 15 minutes to wash the captured matter on the mesh with chloroform. After that, the captured matter on the mesh after ultrasonic cleaning is put together with the nylon mesh into 150 mL of acetone filtered through a nylon mesh having a mesh size of 25 μm, and this liquid is subjected to ultrasonic treatment for 15 minutes, and then the nylon mesh is removed. Thus, 150 mL of an acetone dispersion of the trapped material on the mesh was prepared. Subsequently, 70 mL of this dispersion was measured at 25 ° C. with an automatic liquid particle counter (model: KL-01) manufactured by Rion Co., Ltd., and the number of particles having a diameter of 55 μm or more was determined. It was a piece.
<Monomer mixture (1-A-i) (1)>
MMA 0.3 part n-BA 4.5 part 1,3-BD 0.2 part AMA 0.05 part CHP 0.025 part <monomer mixture (1-A-ro) (1)>
MMA 9.6 parts n-BA 14.4 parts 1,3-BD 1.0 part AMA 0.25 parts CHP 0.016 parts <Monomer mixture (1-B) (1)>
MMA 6.0 parts MA 4.0 parts AMA 0.075 parts CHP 0.0125 parts <Monomer mixture (1-C) (1)>
MMA 57.0 parts MA 3.0 parts n-OM 0.264 parts t-BH 0.075 parts [Production Example 2] Production of rubber-containing polymer (2a) (1) Desorbed in a polymerization vessel equipped with a reflux condenser. Aqueous solution of 310 parts ionic water, 0.5 part emulsifier (2), 0.1 part sodium carbonate, 0.5 part SFS, 0.00024 part ferrous sulfate and 0.00072 part EDTA is stirred and stirred in a nitrogen atmosphere. Then, the following first-stage monomer mixture was added dropwise at 80 ° C. over 200 minutes, followed by further polymerization for 120 minutes to obtain a polymer latex. The Tg determined from the FOX formula of the polymer obtained by the polymerization of the monomer mixture in the first stage was -29 ° C.

  Subsequently, an aqueous solution of 10 parts of deionized water and 0.15 part of SFS was added to the latex of this polymer, and the second stage of the rubber-containing polymer (2a) (1) described below was stirred under a nitrogen atmosphere. The monomer mixture was added dropwise at 80 ° C. over 100 minutes, and then polymerization was further performed at 80 ° C. for 60 minutes to obtain a latex of the rubber-containing polymer (2a) (1). The Tg determined from the FOX equation of the polymer obtained by the polymerization of the second stage monomer mixture was 99 ° C.

  The mass average particle diameter of the rubber-containing polymer (2a) (1) in the obtained polymer latex was 0.12 μm.

The polymer latex of the obtained rubber-containing polymer (2a) (1) was filtered using a vibration type filter attached with a SUS mesh (average opening: 62 μm) as a filter medium, and then calcium acetate 3. Salting out was carried out in an aqueous solution containing 5 parts, and the solid content was recovered by washing with water, followed by drying to obtain a powdery rubber-containing polymer (2a) (1). The gel content of the rubber-containing polymer (2a) (1) was 84%, and the rubber content was 62.5%.
<First-stage monomer mixture>
n-BA 81.0 parts AMA 1.0 part tBH 0.25 part <second stage monomer mixture>
MMA 57.0 parts MA 3.0 parts n-OM 0.2 part t-BH 0.1 part [Production Example 3] Production of rubber-containing polymer (2a) (2) SFS 0.6 was added to the latex of this polymer. Part was added and held for 15 minutes. Next, while stirring at 80 ° C. in a nitrogen atmosphere, the second-stage monomer mixture of the monomer mixture mainly composed of the following acrylate is used as the second-stage monomer mixture for water. Was added dropwise at an increase rate of 4% / hour, and then held for 120 minutes to obtain a polymer latex. In addition, Tg calculated | required from the formula of FOX of the polymer obtained from the monomer mixture of the 2nd step | paragraph of the monomer mixture which has acrylic acid ester as a main component was -38 degreeC.

  Moreover, Tg calculated | required from the formula of FOX of the polymer obtained from the monomer mixture which has as a main component the acrylic ester obtained by said 2 step polymerization was -23 degreeC.

  0.4 parts of SFS was added to this polymer latex and held for 15 minutes. Next, while stirring at 80 ° C. in a nitrogen atmosphere, the monomer mixture containing the following methacrylic acid ester as a main component was increased by 10% / After dripping so that time may be reached, the polymer was held for 60 minutes to obtain a polymer latex of the rubber-containing polymers (2a) and (2). In addition, Tg calculated | required from the formula of FOX of the polymer obtained from the monomer mixture which has methacrylic acid ester as a main component was 99 degreeC.

The obtained polymer latex of the rubber-containing polymer (2a) (2) is salted out in an aqueous solution containing 3.5 parts of calcium acetate, washed with water to recover a solid content, dried, and then powdered. The rubber-containing polymer (2a) (2) was obtained. The rubber-containing polymer (2a) (2) had a gel content of 90% and a rubber content of 62.5%.
<First monomer mixture of monomer mixture mainly composed of acrylic acid ester>
MMA 18.0 parts n-BA 20.0 parts St 2.0 parts 1,3-BD 0.14 parts t-BH 0.18 parts <Second stage of monomer mixture mainly composed of acrylate ester Eye monomer mixture>
n-BA 50.0 parts St 10.0 parts AMA 0.4 parts 1,3-BD 0.14 parts t-HH 0.2 parts Emulsifier (2) 1.0 part <Methacrylate is the main component Monomer mixture>
MMA 57.0 parts MA 3.0 parts t-BH 0.06 parts Thereafter, the following monomer mixture (2b-C) was added dropwise to the polymerization vessel over 140 minutes, and then the reaction was continued for 60 minutes. A polymer latex of the containing polymer (2b) was obtained. Tg calculated | required from the formula of FOX of the polymer obtained from a monomer mixture (2b-C) was 84 degreeC.
<Monomer mixture (2b-A-i)>
MMA 0.3 part n-BA 4.5 part 1,3-BD 0.2 part AMA 0.05 part CHP 0.025 part <monomer mixture (2b-A-ro)>
MMA 1.5 parts n-BA 22.5 parts 1,3-BD 1.0 part AMA 0.25 parts CHP 0.016 parts <Monomer mixture (2b-B)>
n-BA 4.0 parts AMA 0.075 parts CHP 0.0125 parts <Monomer mixture (2b-C)>
MMA 55.2 parts MA 4.8 parts n-OM 0.19 parts t-BH 0.08 parts [Production Example 5] Production of acrylic resin composition constituting thermoplastic resin layer (Aa) Acrylic rubber containing As polymer (A-a-1), 45 parts of rubber-containing polymer (Ab-1-1) of Production Example 1 and MMA / MA copolymer as thermoplastic polymer (A-a-2) (MMA / MA = 99/1 (mass ratio), reduced viscosity ηsp / c = 0.06 L / g, HDT (load 1.8 MPa) = 101 ° C.) 55 parts, Ciba Specialty Chemicals Co., Ltd. ) Tinuvin 234 (trade name) 1.4 parts, Adeka ADEKA STAB AO-50 (trade name) 0.1 parts and ADEKA ADEKA STAB LA-67 (trade name) 0.3 parts added Then, it was mixed using a Henschel mixer. This mixture was supplied to a degassing extruder heated to 230 ° C. (PCM-30 (trade name), manufactured by Ikekai Tekko Co., Ltd.), kneaded, extruded while removing foreign matters with a 300 mesh screen mesh, The pellet of the acrylic resin composition which comprises a plastic resin layer (Aa) was obtained. The acrylic resin composition had an HDT of 94 ° C.
[Production Example 6] Production of acrylic resin composition constituting acrylic resin layer (A-b) As acrylic rubber-containing polymer (A-b-1), rubber-containing polymer (A-b-1-1) 75 Parts and rubber-containing polymer (2b) 15 parts and MMA / MA copolymer (MMA / MA = 99/1 (mass ratio) as thermoplastic polymer (Ab-2), reduced viscosity (ηsp / c ) = 0.06 L / g, HDT (load 1.8 MPa) = 101 ° C.) 10 parts, Ciba Specialty Chemicals Co., Ltd., Tinuvin 234 (trade name) 1.4 parts, Co., Ltd. After adding 0.1 part of ADEKA Adeka Stub AO-50 (trade name) and 0.3 part of ADEKA, Adeka Stub LA-67 (trade name), they were mixed using a Henschel mixer. This mixture was supplied to a degassing extruder heated to 230 ° C. (PCM-30 (trade name), manufactured by Ikekai Tekko Co., Ltd.), kneaded, extruded while removing foreign matters with a 300 mesh screen mesh, and acryl The pellet of the acrylic resin composition which comprises a resin layer (Ab) was obtained. The acrylic resin composition had an HDT of 86 ° C., a rubber content of 29%, and a gel content of 62%.
[Production Examples 7 to 12] Production of acrylic resin composition constituting acrylic resin layer (Ab) Rubber-containing polymer in the amount shown in Table 2 as a rubber-containing polymer (Ab-1-1) In addition, the types and amounts of the rubber-containing polymers (2a) (1), (2a) (2) or (2b) described in Table 2 were used as the rubber-containing polymer (A-b-1-2). Other than that was carried out similarly to manufacture example 6, and obtained the acrylic resin composition which comprises an acrylic resin layer (Ab). Table 2 shows the evaluation results of the obtained acrylic resin composition.

［実施例１］
製造例５で得た熱可塑性樹脂層（Ａ−ａ）を構成するアクリル樹脂組成物と、製造例６で得たアクリル樹脂層（Ａ−ｂ）を構成するアクリル樹脂組成物のペレットを、８０℃で一昼夜乾燥した。

[Example 1]
80 pellets of the acrylic resin composition constituting the thermoplastic resin layer (Aa) obtained in Production Example 5 and the acrylic resin composition constituting the acrylic resin layer (Ab) obtained in Production Example 6 Dried overnight at ℃.

  Next, using a non-vent screw type 30 mmφ extruder, the acrylic resin composition constituting the thermoplastic resin layer (A-a) was treated with a 500 mesh screen mesh under a cylinder temperature of 180 to 240 ° C. Plasticized while removing.

  Construct the acrylic resin layer (Ab) using a non-vent screw type 40 mmφ extruder in parallel with the plasticization of the acrylic resin composition constituting the thermoplastic resin layer (Aa). The acrylic resin composition was plasticized while removing foreign matter with a 500 mesh screen mesh at a cylinder temperature of 180 to 240 ° C.

  A melted film-like material obtained by extruding these depopulated ones with a multi-manifold die for two types and two layers set at 240 ° C. is passed between two metal cooling rolls to form a bank (resin pool). A surface transfer was carried out without rolling while sandwiching the resin in the absence of the film, and this was wound around a paper tube with a winder to prepare an acrylic resin-based laminated film (A) having a total thickness of 90 μm.

  When the cross section of the acrylic resin-based laminated film (A) was observed, the thickness of the thermoplastic resin layer (Aa) was 9 μm, and the thickness of the acrylic resin layer (Ab) was 81 μm.

  Next, a wood grain pattern was provided by gravure printing as a pattern layer (B) on the thermoplastic resin layer (Aa) side of the acrylic resin-based laminated film (A) to obtain an acrylic resin decorative film. The bending whitening resistance of the acrylic resin decorative film was evaluated. The obtained results are shown in Table 3.

［実施例２〜６］
熱可塑性樹脂層（Ａ−ａ）を構成する構成成分及び熱可塑性樹脂層（Ａ−ｂ）を構成する構成成分として表３に示すアクリル樹脂組成物を使用した。それ以外は実施例１と同様にしてアクリル樹脂製加飾成形用シート及び積層成形品を得た。アクリル樹脂製加飾成形用シート及び積層成形品の評価結果を表３に示す。
［実施例７］
熱可塑性樹脂層（Ａ−ａ）及びアクリル樹脂層（Ａ−ｂ）の厚さを表３に示す各厚さに変更した以外は実施例１と同様にアクリル樹脂製加飾成形用シート及び積層成形品を得た。アクリル樹脂製加飾成形用シート及び積層成形品の評価結果を表３に示す。
［実施例８及び９］
前記の（８）の評価方法に開示されているアクリル樹脂製加飾成形用シートの加熱成形温度Ｔ_ｓを表３に示す温度に変更した以外は実施例１と同様にアクリル樹脂製加飾成形用シート及び積層成形品を得た。アクリル樹脂製加飾成形シート及び積層成形品の評価結果を表３に示す。 The acrylic resin decorative film is laminated with the base sheet (C) by the method disclosed in the evaluation methods (8) to (10) above, and the acrylic resin decorative molding sheet and the laminated molded product are laminated. Obtained. The trimming processability, surface state and pencil hardness of the acrylic resin decorative molding sheet, and the insert moldability and pencil hardness of the laminated molded product were evaluated. The obtained results are shown in Table 3.

[Examples 2 to 6]
The acrylic resin composition shown in Table 3 was used as a constituent component constituting the thermoplastic resin layer (Aa) and a constituent component constituting the thermoplastic resin layer (Ab). Other than that was carried out similarly to Example 1, and obtained the acrylic resin-made decorative molding sheet | seat and laminated molding. Table 3 shows the evaluation results of the acrylic resin decorative molding sheet and the laminated molded product.
[Example 7]
Acrylic resin decorative molding sheet and laminate as in Example 1 except that the thicknesses of the thermoplastic resin layer (Aa) and the acrylic resin layer (Ab) were changed to the thicknesses shown in Table 3. A molded product was obtained. Table 3 shows the evaluation results of the acrylic resin decorative molding sheet and the laminated molded product.
[Examples 8 and 9]
Similarly acrylic resin decorative molded except that said heating forming temperature T _s of the sheet made of an acrylic resin decorative molding disclosed in evaluation method (8) was changed to the temperature shown in Table 3 as Example 1 Sheet and laminated molded product were obtained. Table 3 shows the evaluation results of the acrylic resin decorative molded sheet and the laminated molded product.

Claims (3)

Contains a thermoplastic resin layer (Aa) and an acrylic rubber-containing polymer (Ab-1) or an acrylic rubber-containing polymer (Ab-1) and a thermoplastic polymer (Ab-2) The thermal deformation temperature (ASTM) is at least 5 ° C. lower than the thermal deformation temperature (T _A-a ) (measured based on ASTM D648) of the thermoplastic resin layer (Aa). The pattern layer (B) and the substrate sheet (C) are on the thermoplastic resin layer (Aa) side of the acrylic resin-based laminated film (A) having the acrylic resin layer (Ab) having the measurement based on D648. A method for thermoforming an acrylic resin decorative molding sheet, wherein the laminated acrylic resin decorative molding sheet is thermoformed at a temperature (T _s ) satisfying the following formula (1).
T _s (° C.) ≦ 5 × (TA _A− 55) (1) A method for thermoforming an acrylic resin decorative molding sheet, wherein the thermoplastic resin layer (Aa) according to claim 1 has a heat distortion temperature (measured based on ASTM D648) of 90 ° C or higher.
Contains a thermoplastic resin layer (Aa) and an acrylic rubber-containing polymer (Ab-1) or an acrylic rubber-containing polymer (Ab-1) and a thermoplastic polymer (Ab-2) The thermal deformation temperature (ASTM) is at least 5 ° C. lower than the thermal deformation temperature (T _A-a ) (measured based on ASTM D648) of the thermoplastic resin layer (Aa). The pattern layer (B) and the substrate sheet (C) are on the thermoplastic resin layer (Aa) side of the acrylic resin-based laminated film (A) having the acrylic resin layer (Ab) having the measurement based on D648. The laminated acrylic resin decorative molding sheet is expressed by the following formula (1) in the injection mold so that the acrylic resin laminated film (A) side of the acrylic resin decorative molding sheet is the cavity side. true at a temperature _{(T s)} that meet Manufacturing of laminated molded product by molding or pressure forming, and then injection molding the resin constituting the molded product (D) in an injection mold to integrate the acrylic resin decorative molding sheet and the molded product (D) Method.
T _s (° C.) ≦ 5 × (TA _A− 55) (1)   The manufacturing method of the laminated molded product whose heat distortion temperature (measurement based on ASTM D648) of the thermoplastic resin layer (Aa) of Claim 3 is 90 degreeC or more.