JP2005097351A - Acrylic resin composition, acrylic resin film using the same, acrylic resin laminated film, and acrylic resin laminate molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an acrylic resin composition excellent in resistance to an aromatizing agent, a hair-conditioning agent, and thermal aging and to provide an acrylic resin film, an acrylic resin laminate film, and an acrylic resin laminate molding each using the same. <P>SOLUTION: The acrylic resin comprises an acrylic resin and a combination of a hindered amine light stabilizer and an ultraviolet absorber having a melting point of 180°C or lower. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to an acrylic resin composition excellent in solvent resistance and heat aging resistance, an acrylic resin film using the same, and an acrylic resin laminated molded article using the acrylic resin film.

  An acrylic resin film made of an acrylic resin containing a rubber-like material is excellent in transparency, weather resistance, flexibility, and workability. Therefore, it is bonded to the surface of resin molded products, woodwork products, metal molded products, vehicles, It is used as a covering material for building materials such as furniture, door materials, window frames, baseboards, and bathroom interiors, marking films, and films for coating high-intensity reflectors. Further, by laminating a printed acrylic resin film on various members, it is possible to impart high design properties to the members.

  Conventionally, various films are known as acrylic resin films. For example, an acrylic resin film excellent in stress whitening resistance such as weather resistance, transparency, and bending whitening resistance (see, for example, Patent Document 1, Patent Document 2, and Patent Document 3), weather resistance, transparency, flexibility Excellent acrylic resin film (see, for example, Patent Document 4), acrylic resin film having low temperature dependency of total light transmittance and haze, and excellent in impact resistance and solvent resistance (see, for example, Patent Document 5) Etc. are disclosed.

  In particular, there is an in-mold molding method as a method suitable for imparting a high degree of design to a molded product having a complicated three-dimensional shape at low cost. In this method, a printed thermoplastic resin film (hereinafter referred to as a sheet) is formed into a three-dimensional shape by vacuum forming, pressure forming or the like in advance or without being formed in an injection mold. This is a method of inserting and molding a resin to be a base material. In in-mold molding, there are a case where the thermoplastic resin film and the base resin are integrated, and a case where only the printing layer is transferred.

  In the in-mold molding in which the thermoplastic resin film and the base resin are integrated, an acrylic resin film is often applied particularly for applications that require a high degree of transparency.

  As an acrylic resin film that can be used for in-mold molding, an acrylic resin film rich in processability and flexibility made of a multilayered polymer containing rubber is known (for example, see Patent Document 6).

  Acrylic resin films excellent in surface hardness and heat resistance are known (see, for example, Patent Document 7, Patent Document 8, Patent Document 9, Patent Document 10, etc.), and also excellent in surface hardness, heat resistance, and transparency. An acrylic resin film (for example, see Patent Document 11) and a decorative acrylic resin film having a metallic feeling (for example, see Patent Document 12) are also known. Such an acrylic resin film is simply used as an alternative material for coating without printing.

  When plastic products are exposed to chemicals or heat in their respective usage environments, the surface is often damaged, and the decorative properties often deteriorate significantly. In the case of a plastic product in which an acrylic resin film is laminated on the outermost surface, the chemical resistance and heat aging resistance of the acrylic resin itself greatly influence the chemical resistance and heat aging resistance of the plastic product surface appearance.

  For example, in vehicles, cosmetics such as on-vehicle air fresheners and hair styling used by passengers may come into contact with vehicle interior parts due to accidental falls or indirect contact with interior parts via hands, etc. There is a great potential to do.

  In addition, it is known that the inside of a vehicle is exposed to sunlight through the glass, and the surface of the interior parts becomes hot. Due to the high temperature, the surface of the interior part is subject to heat aging, the appearance is remarkably deteriorated, and the decorativeness may be significantly reduced. Furthermore, when exposed to heat, the degradation by the solvent is further accelerated.

Japanese Examined Patent Publication No. 62-19309 Japanese Patent Laid-Open No. 10-45854 JP 2002-307519 A JP-A 63-77963 JP-A-7-149994 JP-A-8-267500 JP-A-8-323934 JP-A-10-279766 Japanese Patent Laid-Open No. 11-147237 JP 2002-80679 A JP 2002-80678 A JP 2002-146054 A

  The acrylic resin films disclosed in Patent Document 1 and Patent Documents 4 to 11 have a surface smoothness that is significantly deteriorated when heat is applied after the hairdressing material or the like is attached, and fabrics such as clothes are in contact therewith. When doing so, there was a problem that adhesion marks remained.

  The acrylic resin films disclosed in Patent Document 3 and Patent Document 12 have a problem of whitening due to chemicals containing alcohols such as vehicle fragrances. Moreover, when it was left under high temperature for a long time, there was a problem of whitening similarly.

  That is, an object of the present invention is to provide an acrylic resin composition having excellent fragrance resistance, hairstyling resistance, and heat aging resistance, and an acrylic resin film, an acrylic resin laminated film, and an acrylic resin laminated molded product using the same. There is to do.

  As a result of intensive studies to solve the above problems, the present inventors have found that an acrylic resin composition containing a hindered amine light stabilizer and an ultraviolet absorber having a specific melting point has very excellent performance. As a result, the present invention has been completed.

  That is, the present invention is an acrylic resin composition containing a hindered amine light stabilizer and an ultraviolet absorber having a melting point of 180 ° C. or lower.

  The acrylic resin used here comprises (A) 50 to 100% by weight of methacrylic acid alkyl ester, 50 to 0% by weight of acrylic acid alkyl ester and 0 to 49% by weight of monomer copolymerizable with these esters, 0.9-94.5 parts by mass of a thermoplastic polymer (I) having a reduced viscosity (0.1 g of polymer dissolved in 100 ml of chloroform and measured at 25 ° C.) of 0.5 l / g or less, at least acrylic acid 1 to 99 parts by mass of a multilayer structure polymer (II) composed of a polymer layer mainly comprising an alkyl ester and an outermost polymer layer mainly comprising an alkyl methacrylate, and 50 to 100% by mass of methyl methacrylate and methacryl It consists of 50 to 0% by mass of a monomer copolymerizable with methyl acid, and has a reduced viscosity (0.1 g of polymer is dissolved in 100 ml of chloroform, 2 Thermoplastic polymer (III) having a measurement value of 0.5 liter / g or more, and (B) an inner polymer layer mainly composed of at least an alkyl acrylate ester and methacrylic acid Monolayer structure polymer (II) comprising 90 to 100 parts by mass of an outermost polymer layer mainly composed of an alkyl ester and 50 to 100% by mass of methyl methacrylate and a monomer 50 to 0 copolymerizable with methyl methacrylate It consists of 0-10 parts by mass of a thermoplastic polymer (III) having a reduced viscosity (0.1 g of polymer dissolved in 100 ml of chloroform and measured at 25 ° C.) exceeding 0.5 liter / g. Those in which the total of the polymers (I) to (III) is 100 parts by mass) are preferred. The preferred range of the blending ratio is appropriately determined by the multilayer structure polymer (II).

  Furthermore, this invention is an acrylic resin film, an acrylic resin laminated film, and an acrylic resin laminated molded product using said acrylic resin composition.

  ADVANTAGE OF THE INVENTION According to this invention, the acrylic resin composition excellent in fragrance-resistant property, hair-styling-proof property, and heat aging resistance, an acrylic resin film using this, an acrylic laminated film, and an acrylic resin laminated molded product can be obtained.

  The acrylic laminated molded article including an acrylic resin film excellent in fragrance resistance, hair styling resistance, and heat aging resistance of the present invention is particularly highly industrially useful as a vehicle interior part.

  The acrylic resin composition of the present invention is characterized in that the acrylic resin contains both a hindered amine light stabilizer and an ultraviolet absorber having a melting point of 180 ° C. or less at the same time.

  While using an ultraviolet absorber with a melting point of 180 ° C. or less, if a hindered amine light stabilizer is not used, a fragrance resistance test, a heat aging resistance test, and a hair styling resistance property applied to vehicle interior parts. When the test is carried out, the eluted and bleed ultraviolet absorber does not crystallize, but the surface smoothness cannot be maintained in the hair-styling resistance test, and the appearance deteriorates.

  Using a UV absorber with a melting point exceeding 180 ° C while using a hindered amine light stabilizer, the surface smoothness can be maintained in the hair-styling resistance test, but the fragrance resistance test and hair-styling resistance test In the heat aging resistance test, the eluted and bleed ultraviolet absorber is crystallized and the appearance is deteriorated.

  As the hindered amine light stabilizer to be contained in the acrylic resin composition of the present invention, known ones can be used. From the viewpoint of hair-styling resistance, 0.1 part by mass or more is preferably added per 100 parts by mass of the acrylic resin, more preferably 0.2 part by mass or more, and further preferably 0.5 part by mass or more. When 0.1 mass part or more is added, the improvement effect is recognized by the surface smoothness deterioration at the time of implementing a hair-styling-proof property test to the lamination molded product which has this acrylic resin composition in the outermost layer.

  Various conventionally known hindered amine light stabilizers can be used, for example, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxyl. Rate, some of the 2,2,6,6-tetramethyl-4-piperidyl moieties of tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate In which is a tridecyl group, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like can be used.

  From the viewpoint of volatility during melt processing and retention after processing, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis (2, 2,6,6-tetramethyl-4-piperidyl) 2,2,6,6-tetramethyl-4-piperidyl moiety of 1,2,3,4-butanetetracarboxylate becomes tridecyl group It is preferable to use those that are present.

  Examples of commercially available hindered amine light stabilizers include ADK STAB LA-57 (Asahi Denka Kogyo Co., Ltd., trade name), ADK STAB LA-67 (Asahi Denka Kogyo Co., Ltd. trade name), and Tinuvin 770 (Ciba Special). T Chemicals, trade name), Sanol LS-770 (Sankyo, trade name), and the like.

  The ultraviolet absorber contained in the acrylic resin composition of the present invention must have a melting point of 180 ° C. or lower.

  When the ultraviolet absorber has a melting point of 180 ° C. or lower, when a laminated molded product having the acrylic resin composition of the present invention in the outermost layer is subjected to an fragrance resistance test, a hair styling resistance test, and a heat aging resistance test The eluted and bleed-out UV absorber is difficult to crystallize and the appearance is not deteriorated. The thing of 150 degrees C or less is more preferable.

  Furthermore, when the melting point of the ultraviolet absorber is 180 ° C. or less, the ultraviolet absorber bleeds out for a relatively short period of time from several days to several months after the acrylic resin composition of the present invention is formed into a film. Less likely to occur. A relatively short bleed-out property is likely to occur as the softness of the acrylic resin as the base material increases. In this case, however, such a bleed-out property is less likely to occur if an ultraviolet absorber having a low melting point is used.

  The molecular weight of the ultraviolet absorber is preferably 300 or more, and more preferably 400 or more. When an ultraviolet absorbent having a molecular weight of 300 or more is used, mold contamination due to volatilization of the ultraviolet absorbent during vacuum molding or pressure molding in an injection mold can be prevented. In general, the higher the molecular weight of the UV absorber, the longer the long-term bleed-out after the acrylic resin composition of the present invention is formed into a film, and the longer the UV absorption performance than the lower the molecular weight. Lasts for a long time.

  Furthermore, when the molecular weight of the ultraviolet absorber is 300 or more, the amount of the ultraviolet absorber that volatilizes before the acrylic resin composition of the present invention is extruded from the T die and cooled by the cooling roll is small. Therefore, since the amount of the remaining ultraviolet absorber is sufficient, good performance is exhibited. In addition, the volatilized UV absorber recrystallizes on the chain that suspends the T die at the top of the T die and the exhaust hood and grows over time. This eventually falls on the film and becomes a defect in appearance. This also reduces the problem.

As such an ultraviolet absorber, various conventionally known ones can be used as long as the melting point is 180 ° C. or lower. In addition, it is preferable to add so that it may become 0.2 g / m < ² > or more when an acrylic resin composition is made into a film form or a layer form. When it is 0.2 g / m ² or more, it is possible to exhibit a good ultraviolet cut-off property at 300 to 380 nm. Moreover, it is preferable to add 10 mass parts or less per 100 mass parts of acrylic resins. Addition of 10 parts by mass or less tends to improve the film forming property, appearance, and the like.

  Specifically, as a benzotriazole ultraviolet absorber having a melting point of 180 ° C. or lower, for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-) Butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl] benzotriazole, 2- (2′-hydroxy) -3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2 ′ -Hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t -Bu Butylphenyl) can be used benzotriazole.

  Commercially available benzotriazole ultraviolet absorbers having a melting point of 180 ° C. or less include, for example, Tinuvin 234 (trade name, manufactured by Ciba Specialty Chemicals), Tinuvin 328 (trade name, manufactured by Ciba Specialty Chemicals), Tinuvin 329, and the like. (Ciba Specialty Chemicals, trade name), Tinuvin P (Ciba Specialty Chemicals, trade name), Adekastab LA-32 (Asahi Denka Kogyo, trade name) and the like.

  Examples of the triazine ultraviolet absorber having a melting point of 180 ° C. or lower include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] phenol, 2- [4, 6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol and the like can be used.

  Examples of commercially available triazine ultraviolet absorbers having a melting point of 180 ° C. or lower include Tinuvin 1577 (trade name, manufactured by Ciba Specialty Chemicals), Siasolv UV-1164 (trade name, manufactured by Cytec), and the like.

  Among these, TINUVIN 234, TINUVIN 328, TINUVIN 329, and TINUVIN 1577 (all of which are trade names), which are ultraviolet absorbers having a molecular weight of 300 or more and a melting point of 180 ° C. or less, are fragrance-resistant and hair-resistant. It is particularly preferable since it is excellent in material properties, heat aging resistance, durability of UV-grade yield, volatilization resistance during film formation, and bleed-out resistance for a relatively short period of time.

  As the acrylic resin used in the acrylic resin composition of the present invention, known resins can be used, but weather resistance, stain resistance, chemical resistance, and film forming properties when the acrylic resin composition is formed into a film shape. From this viewpoint, an acrylic resin (A) or an acrylic resin (B) in which an acrylic polymer described later is appropriately mixed is preferable.

  That is, the acrylic resin (A) is composed of a polymer having a methacrylic acid alkyl ester as a main component (simply referred to as “thermoplastic polymer (I)”) and an acrylic polymer having a multilayer structure (simply referred to as “multilayer structure weight”). And a thermoplastic polymer having methyl methacrylate as a main component (simply referred to as “thermoplastic polymer (III)”).

  The acrylic resin (B) is mainly composed of the multilayer structure polymer (II), and may contain a thermoplastic polymer (III) as necessary.

  From the viewpoint of heat resistance and surface hardness, it is preferable to use an acrylic resin (A). When the acrylic resin (A) is used, the heat resistance and hardness can be easily adjusted by changing the ratio of the thermoplastic polymer (I) and the multilayer structure polymer (II). For example, sufficient heat resistance can be exhibited when applied to a laminated molded article having an acrylic resin composition as the outermost layer, such as a vehicle member, which is easily exposed to high temperatures and easily touched by hands and objects.

  The acrylic resin composition of the present invention preferably has a heat distortion temperature (measured based on ASTM D648) of 80 ° C. or higher. When the heat distortion temperature is 80 ° C. or higher, when the laminated molded product having the acrylic resin composition as the outermost layer is exposed at a high temperature for a long time, the acrylic resin composition surface is not whitened or clouded, so that the industrial use Value is high. In addition, in vehicle applications, a laminated molded product having the acrylic resin composition of the present invention as the outermost layer can also be used for parts that receive direct sunlight in the vehicle, such as a front control panel, from the viewpoint of further expanding the applications. The heat distortion temperature is more preferably 90 ° C. or higher.

  The acrylic resin composition of the present invention preferably has a pencil hardness (measurement based on JIS K5400) of 2B or more. Furthermore, HB or more is more preferable, and F or more is most preferable. When the pencil hardness is 2B or more, when the acrylic resin composition is formed into a film and subjected to insert molding or in-mold molding, it is difficult to be damaged during the process, and the laminate has the acrylic resin composition as the outermost layer. The scratch resistance of the molded product is also good. Further, when used for a vehicle, if the pencil hardness of the acrylic resin composition is HB or more, a laminated molded product having the acrylic resin composition on the outermost layer also at a site having a high possibility of scratches such as a front control panel. From the viewpoint of expanding applications, it is very useful industrially. When the pencil hardness is F or more, the scratches are not noticeable even when scratched with a rough cloth such as gauze, and the industrial utility value is very high.

<< Thermoplastic polymer (I) >>
The thermoplastic polymer (I) is composed of 50 to 100% by mass of methacrylic acid alkyl ester and 0 to 50% by mass of acrylic acid alkyl ester, and 0 to 49% by mass of monomer having a double bond copolymerizable therewith. A thermoplastic polymer having a reduced viscosity (measured at 25 ° C. by dissolving 0.1 g of the polymer in 100 ml of chloroform) of 0.5 liter / g or less.

  When the reduced viscosity of the thermoplastic polymer (I) is 0.5 liter / g or less, moderate elongation occurs at the time of melting when the acrylic resin composition is processed into a film shape, and the film forming property is improved. . More preferably, it is 0.1 liter / g or less. The lower limit of the reduced viscosity is preferably 0.05 liter / g or more. If it is 0.05 liter / g or more, the problem of film breakage at the time of film-formation of the acrylic resin composition resulting from brittleness and at the time of printing on the film is less likely to occur.

  Examples of the alkyl methacrylate used for the thermoplastic polymer (I) include methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like. Of these, methyl methacrylate is most preferred. The alkyl methacrylate is used in the range of 50 to 100% by mass. More preferably, it is the range of 85-100 mass%, More preferably, it is the range of 92-100 mass%. For example, a vehicle member or the like is a member that is easily exposed to high temperatures and is easily touched by hands and objects, but has a high heat resistance necessary when a laminated molded article having an acrylic resin composition as the outermost layer is applied to the vehicle member. Hardness can be demonstrated.

  Examples of the alkyl acrylate used as necessary for the thermoplastic polymer (I) include methyl acrylate, ethyl acrylate, and butyl acrylate. The acrylic acid alkyl ester is used in the range of 0 to 50% by mass, preferably in the range of 0.1 to 40% by mass. More preferably, it is the range of 0.1-15 mass%, More preferably, it is the range of 0.1-8 mass%. For example, a vehicle member or the like is a member that is easily exposed to high temperatures and is easily touched by hands and objects, but has a high heat resistance necessary when a laminated molded article having an acrylic resin composition as the outermost layer is applied to the vehicle member. Hardness can be demonstrated.

  As the monomer having a copolymerizable double bond used as necessary in the thermoplastic polymer (I), various conventionally known monomers can be used, and the range is from 0 to 49% by mass. Use within.

  The thermoplastic polymer (I) is obtained by polymerizing these monomers. The polymerization method is not particularly limited, and can be performed by suspension polymerization, emulsion polymerization, bulk polymerization, or the like. A chain transfer agent may be used to bring the reduced viscosity of the polymer into a predetermined range. As the chain transfer agent, various conventionally known ones can be used, and mercaptans are particularly preferable. The amount of chain transfer agent to be used must be appropriately determined depending on the type and composition of the monomer.

<< Multilayer structure polymer (II) >>
The multilayer structure polymer (II) is important for transparency, heat resistance, hardness, impact resistance, acrylic resin film obtained by molding the acrylic resin composition, and whitening resistance of the acrylic laminated film. A graft copolymer having a multilayer structure containing an alkyl acrylate ester as a main component of rubber is preferable.

  From the viewpoint of transparency of the acrylic resin composition, the average particle size of the multilayer structure polymer (II) is preferably 0.4 μm or less, more preferably less than 0.2 μm, and still more preferably 0.18 μm or less. For example, when a layer made of the acrylic resin composition of the present invention is applied in place of the clear coating applied to vehicle parts, good transparency can be obtained by setting it to less than 0.2 μm, and 0.18 μm or less. Thus, a good jet black feeling can be obtained when the acrylic resin composition is formed into a film and then printed with black ink and viewed through the film. In addition, from the viewpoint of film forming properties when the acrylic resin composition is formed into a film shape, the average particle diameter is preferably 0.05 μm or more. Such a multilayer structure polymer (II) is obtained, for example, by ordinary emulsion polymerization.

  As the multilayer structure polymer (II), for example, the following multilayer structure polymer (IIa) and multilayer structure polymer (IIb) can be used.

<< Multilayer structure polymer (IIa) >>
In the presence of the inner layer polymer (IIa-A) having a structure of one layer or two or more layers, which is an inner layer obtained by polymerizing a monomer containing an acrylic acid alkyl ester, the multilayer structure polymer (IIa) Two or more multilayers formed by graft polymerization of a monomer mainly composed of methacrylic acid alkyl ester to form an outermost layer polymer (IIa-B) having a structure of one layer or two or more layers as an outer layer A multilayer structure polymer having a structure.

  Below, the structure of the above-mentioned multilayer structure polymer (IIa) is demonstrated concretely.

[Inner layer polymer (IIa-A)]
As the acrylic acid alkyl ester (IIa-A1) used for the inner layer polymer (IIa-A), various conventionally known ones are used. In particular, butyl acrylate, 2-ethylhexyl acrylate, and the like are preferable. The amount of the acrylic acid alkyl ester (IIa-A1) used is preferably 35 to 100% by mass in monomers other than the crosslinkable monomer (IIa-A3) used for the inner layer polymer (IIa-A). Preferably it is 50-100 mass%. The lower limit of these ranges is significant in terms of the whitening resistance of the acrylic resin film obtained by molding the acrylic resin composition and the acrylic resin laminated film.

  In obtaining the inner layer polymer (IIa-A), another monomer (IIa-A2) having a double bond copolymerizable with the alkyl acrylate (IIa-A1) is copolymerized. As the other monomer (IIa-A2) having a copolymerizable double bond, alkyl methacrylate such as methyl methacrylate, butyl methacrylate and cyclohexyl methacrylate, styrene, acrylonitrile and the like are preferable. These can be used alone or in combination of two or more. The amount of the other monomer having a copolymerizable double bond is preferably 65% by mass in the monomers other than the crosslinkable monomer (IIa-A3) used for the inner layer polymer (IIa-A). % Or less.

  In order to obtain the inner layer polymer (IIa-A), usually a crosslinkable monomer (IIa-A3) is further used. The crosslinkable monomer (IIa-A3) is not particularly limited, but ethylene glycol dimethacrylate, butanediol dimethacrylate, allyl acrylate, allyl methacrylate, diallyl phthalate, triallyl cyanurate, triallyl isocyania. Examples include nurate, divinylbenzene, diallyl maleate, trimethylolpropane triacrylate, and allyl cinnamate. These can be used alone or in combination of two or more.

  The amount of the crosslinkable monomer (IIa-A3) used is preferably 0 with respect to 100% by mass of the monomer other than the crosslinkable monomer (IIa-A3) used for the inner layer polymer (IIa-A). 0.1 to 10% by mass. In view of the molding whitening resistance of the acrylic resin film and the acrylic resin laminated film obtained by molding the acrylic resin composition, 0.3% by mass or more is more preferable. Even if the amount used exceeds 10% by mass, there is no particular problem in terms of physical properties, but since the improvement in the effect accompanying the increase in the amount used is small, 10% by mass or less is preferable from the viewpoint of the addition efficiency.

  The inner layer polymer (IIa-A) can have a structure of one layer or two or more layers. When it is set as the structure of 2 layers or more, 35 mass% or more is preferable and, as for the quantity of the acrylic acid alkylester (IIa-A1) as the whole inner layer polymer (IIa-A), 50 mass% or more is more preferable.

  When making it a hard core structure, content of the acrylic acid alkyl ester (IIa-A1) of the 1st layer can also be 35 mass% or less. For example, although it is not described that it is used for paint replacement, a hard core structure multilayer structure polymer having an average particle diameter of less than 0.2 μm as described in Patent Document 5 can be used.

[Outermost layer polymer (IIa-B)]
The outermost layer polymer (IIa-B) is formed by graft polymerization of a monomer containing a methacrylic acid alkyl ester (IIa-B1) in the presence of the inner layer polymer (IIa-A). The outermost layer polymer (IIa-B) can be obtained by polymerization in at least one stage, and can have a structure of one layer or two or more layers.

  The amount of the methacrylic acid alkyl ester (IIa-B1) used is preferably 50% by mass or more in the monomer used for the outermost layer polymer (IIa-B). Examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate and the like.

  In obtaining the outermost layer polymer (IIa-B), another monomer (IIa-B2) having a double bond copolymerizable with the methacrylic acid alkyl ester (IIa-B1) can be used in combination. Examples of the other monomer (IIa-B2) having a copolymerizable double bond include alkyl acrylates such as methyl acrylate, butyl acrylate and cyclohexyl acrylate, styrene, acrylonitrile and the like. These can be used alone or in combination of two or more. The amount of the other monomer (IIa-B2) having a copolymerizable double bond is preferably 50% by mass or less in the monomer used for the outermost layer polymer (IIa-B).

  The outermost layer polymer (IIa-B) is preferably 10 to 400% by mass and more preferably 20 to 200% by mass with respect to the inner layer polymer (IIa-A). The lower limit of these ranges is significant in terms of preventing deterioration of transparency due to aggregation of the inner layer polymer.

<< Multilayer structure polymer (IIb) >>
The multilayer structure polymer (IIb) has a multilayer structure having the innermost layer polymer (IIb-A), the intermediate layer polymer (IIb-B), and the outermost layer polymer (IIb-C) as basic structures in order from the inside. Have.

  Below, the structure of the above-mentioned multilayer structure polymer is demonstrated concretely.

[Innermost layer polymer (IIb-A)]
The innermost layer polymer (IIb-A) constitutes the central portion of the polymer having the multilayer structure, and includes an acrylic acid alkyl ester (IIb-A1), a methacrylic acid alkyl ester (IIb-A2), these Another monomer (IIb-A3) having a double bond copolymerizable with the components (IIb-A1) and (IIb-A2), a polyfunctional monomer (IIb-A4) and a graft crossing agent ( It is a polymer obtained by polymerizing a monomer composition having IIb-A5) as a constituent component.

  The acrylic acid alkyl ester of the component (IIb-A1) constituting the innermost layer polymer (IIb-A) may be either linear or branched. Specific examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. These can be used individually or in mixture of 2 or more types. Of these, n-butyl acrylate is preferred.

  The alkyl methacrylate of component (IIb-A2) constituting the innermost layer polymer (IIb-A) may be either linear or branched. Specific examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and n-butyl methacrylate. These can be used alone or in admixture of two or more. Of these, methyl methacrylate is preferred.

  Other monomers having a copolymerizable double bond of the component (IIb-A3) constituting the innermost layer polymer (IIb-A) are lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid, methacrylic acid, etc. Acrylic monomers, styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile and the like can be used.

  The polyfunctional monomer of the component (IIb-A4) constituting the innermost layer polymer (IIb-A) can be used as necessary. A polyfunctional monomer is defined as a monomer 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. In addition, polyvinylbenzene such as divinylbenzene and trivinylbenzene can be used. Of these, 1,3-butylene glycol dimethacrylate is preferred.

  Also, even when the polyfunctional monomer does not act at all, as long as the grafting agent is present, a fairly stable multilayer structure polymer is obtained. For example, when the hot strength or the like is strictly required, it may be arbitrarily performed depending on the purpose of addition.

  The graft crossing agent (IIb-A5) constituting the innermost layer polymer (IIb-A) is defined as a monomer having two or more different copolymerizable double bonds in one molecule. Specific examples thereof include allyl, methallyl or crotyl ester of copolymerizable α, β-unsaturated carboxylic acid or dicarboxylic acid. Particularly preferred are allyl esters of acrylic acid, methacrylic acid, maleic acid or fumaric acid. Of these, allyl methacrylate is preferable because of its excellent effect. In addition, triallyl cyanurate, triallyl isocyanurate and the like are also effective. The graft crossing agent (IIb-A5) is polymerized mainly because the conjugated unsaturated bond of the ester reacts much faster than the allyl group, methallyl group or crotyl group. During this time, a substantial portion of the allyl, methallyl, or crotyl group works effectively during the polymerization of the next layer of polymer, providing a graft bond between adjacent two layers.

  The polymerization may be performed in the presence of a chain transfer agent.

  The content of the acrylic acid alkyl ester (IIb-A1) and / or the methacrylic acid alkyl ester (IIb-A2) in the innermost layer polymer (IIb-A) is preferably 80 to 100% by mass.

  In particular, the content of the acrylic acid alkyl ester (IIb-A1) in the innermost layer polymer (IIb-A) is preferably 50 to 99.9% by mass. From the viewpoint of resistance to molding whitening of an acrylic resin film and an acrylic resin laminated film obtained by molding the acrylic resin composition, it is more preferably 55% by mass or more, and most preferably 60% by mass or more. Moreover, from a viewpoint of the surface hardness of the acrylic resin film and acrylic resin laminated film obtained by shape | molding an acrylic resin composition, More preferably, it is 79.9 mass% or less, Most preferably, it is 69.9 mass% or less.

  The content of the methacrylic acid alkyl ester (IIb-A2) in the innermost layer polymer (IIb-A) is preferably 0 to 49.9% by mass. From the viewpoint of the surface hardness of an acrylic resin film or an acrylic resin laminated film obtained by molding the acrylic resin composition, it is more preferably 20% by mass or more, and most preferably 30% by mass or more. Further, from the viewpoint of resistance to whitening of the acrylic resin film obtained by molding the acrylic resin composition and the acrylic resin laminated film, it is more preferably 44.9% by mass or less, most preferably 39.9% by mass or less. .

  The other monomer (IIb-A3) having a copolymerizable double bond in the innermost layer polymer (IIb-A) is preferably 0 to 20% by mass. More preferably, it is 15 mass% or less.

  The content of the polyfunctional monomer (IIb-A4) in the innermost layer polymer (IIb-A) is preferably 0 to 10% by mass. More preferably, it is 0.1 mass% or more and 6 mass% or less.

  The content of the graft crossing agent (IIb-A5) in the innermost layer polymer (IIb-A) is preferably 0.1 to 10% by mass. When the content is 0.1% by mass or more, the resulting multilayer structure polymer can be molded without deteriorating optical properties such as transparency. A content of 10% by mass or less is preferable because sufficient flexibility and toughness can be imparted to the multilayer structure polymer. More preferably, it is 0.5 mass% or more and 2 mass% or less.

  Although not particularly limited, the Tg of the innermost layer polymer (IIb-A) alone is an acrylic resin film obtained by molding the acrylic resin composition, from the viewpoint of impact resistance and molding whitening resistance of the acrylic resin laminated film, It is preferably less than the Tg of the below-described intermediate layer polymer (IIb-B) alone. More preferably, it is less than 25 degreeC, More preferably, it is 10 degreeC or less, Most preferably, it is 0 degreeC or less.

  Although not particularly limited, the content of the innermost layer polymer (IIb-A) in the multilayer structure polymer is preferably 15 to 50% by mass. In the case of 15% by mass or more, it is possible to impart molding whitening resistance to an acrylic resin film and an acrylic resin laminated film obtained by molding the acrylic resin composition, and the production when the acrylic resin composition is molded into a film shape. It is possible to achieve both film properties and toughness capable of insert molding and in-mold molding of an acrylic resin film and an acrylic resin laminated film obtained by molding an acrylic resin composition. More preferably, it is 20 mass% or more. Moreover, when it is 50 mass% or less, since surface hardness and heat resistance required for a vehicle use are obtained, it is preferable. More preferably, it is 35 mass% or less.

  The innermost layer polymer (IIb-A) may be a single layer, but more preferably forms two layers. Although not particularly limited, it is preferable that the monomer constitution ratio of the two layers in the innermost layer polymer (IIb-A) is different.

The Tg of the inner layer (IIb-A ₁ ) and the Tg of the outer layer (IIb-A ₂ ) may be the same, but the acrylic resin film obtained by molding the acrylic resin composition, and the molding resistance of the acrylic resin laminated film From the viewpoint of whitening property, impact resistance, and surface hardness, when the innermost layer polymer (IIb-A) is composed of two layers, the Tg of the inner layer (IIb-A ₁ ) is that of the outer layer (IIb-A ₂ ). Lower than Tg is preferable. Specifically, the Tg of the inner layer (IIb-A ₁ ) is −30 ° C. from the viewpoint of molding resin whitening resistance and impact resistance of the acrylic resin film obtained by molding the acrylic resin composition and the acrylic resin laminated film. The Tg of the outer layer (IIb-A ₂ ) is preferably 10 ° C. or less. In particular, from the viewpoint of surface hardness, the outer layer (IIb-A ₂ ) preferably has a Tg of −15 ° C. or higher. At this time, from the viewpoint of the surface hardness to be obtained, the content of the inner layer (IIb-A ₁ ) in the innermost layer polymer (IIb-A) is preferably 1% by mass or more and 20% by mass or less, and the outer layer (IIb -A ₂ content) of 80 mass% or more, preferably 99 mass% or less.

[Interlayer polymer (IIb-B)]
In the presence of the innermost layer polymer (IIb-A), the intermediate layer polymer (IIb-B) is an acrylic acid alkyl ester (IIb-B1), a methacrylic acid alkyl ester (IIb-B2), (IIb-B1). ) And (IIb-B2), another monomer having a double bond copolymerizable with the component (IIb-B3), polyfunctional monomer (IIb-B4) and graft crossing agent (IIb-B5) Is a polymer having a polymer Tg higher than the tg of the innermost layer polymer, preferably higher than the tg of the innermost layer polymer.

  The acrylic acid alkyl ester of the component (IIb-B1) constituting the intermediate layer polymer (IIb-B) may be either linear or branched. 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 admixture of two or more. Of these, preferred are methyl acrylate and n-butyl acrylate.

  The alkyl methacrylate of component (IIb-B2) constituting the intermediate layer polymer (IIb-B) may be either linear or branched. Specific examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and n-butyl methacrylate. These can be used alone or in admixture of two or more. Of these, methyl methacrylate is preferred.

  Other monomers having a copolymerizable double bond of the component (IIb-B3) constituting the intermediate layer polymer (IIb-B) are lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid, methacrylic acid, etc. Acrylic monomers, styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile and the like can be used.

  The polyfunctional monomer of the component (IIb-B4) constituting the intermediate layer polymer (IIb-B) may be used as necessary. 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. In addition, polyvinylbenzene such as divinylbenzene and trivinylbenzene can be used. Of these, 1,3-butylene glycol dimethacrylate is preferred.

  Even when the polyfunctional monomer does not act at all, as long as the grafting agent is present, a fairly stable multilayer structure polymer is obtained. For example, when the hot strength or the like is strictly required, it may be arbitrarily performed depending on the purpose of addition.

  Examples of the graft crossing agent (IIb-B5) constituting the intermediate layer polymer (IIb-B) include allyl, methallyl, or crotyl ester of copolymerizable α, β-unsaturated carboxylic acid or dicarboxylic acid. . Particularly preferred are allyl esters of acrylic acid, methacrylic acid, maleic acid, or fumaric acid. Of these, allyl methacrylate is preferable because of its excellent effect. In addition, triallyl cyanurate, triallyl isocyanurate and the like are also effective. Graft-crossing agent (IIb-B5) reacts much faster than the allyl group, methallyl group, or crotyl group, and chemically bonds mainly with the conjugated unsaturated bond of the ester. During this time, a substantial portion of the allyl, methallyl, or crotyl group works effectively during the polymerization of the next layer polymer to provide a graft bond between adjacent two layers.

  In addition, you may perform superposition | polymerization here in presence of a chain transfer agent.

  The content of the acrylic acid alkyl ester (IIb-B1) and / or the methacrylic acid alkyl ester (IIb-B2) in the intermediate layer polymer (IIb-B) is preferably 9.9 to 90% by mass.

  In particular, the content of the acrylic acid alkyl ester (IIb-B1) in the intermediate layer polymer (IIb-B) is preferably 9.9 to 90% by mass. From the viewpoint of molding whitening resistance, surface hardness and heat resistance of the acrylic resin film obtained by molding the acrylic resin composition and the acrylic resin laminated film, more preferably 19.9% by mass or more, and most preferably 29.9% by mass. % Or more. Further, it is more preferably 60% by mass or less, and most preferably 50% by mass or less.

  In particular, the content of the methacrylic acid alkyl ester (IIb-B2) in the intermediate layer polymer (IIb-B) is preferably 9.9 to 90% by mass. From the viewpoint of molding whitening resistance, surface hardness and heat resistance of the acrylic resin film obtained by molding the acrylic resin composition and the acrylic resin laminated film, it is more preferably 39.9% by mass or more, most preferably 49.9% by mass. % Or more. Further, it is more preferably 80% by mass or less, and most preferably 70% by mass or less.

  The content of the other monomer (IIb-B3) having a copolymerizable double bond in the intermediate layer polymer (IIb-B) is preferably 0 to 20% by mass. More preferably, it is 15 mass% or less.

  The content of the polyfunctional monomer (IIb-B4) in the intermediate layer polymer (IIb-B) is preferably 0 to 10% by mass. More preferably, it is 6 mass% or less.

  The content of the graft crossing agent (IIb-B5) in the intermediate layer polymer (IIb-B) is preferably 0.1 to 10% by mass. When the content is 0.1% by mass or more, the resulting multilayer structure polymer can be molded without deteriorating optical properties such as transparency. A content of 5% by mass or less is preferable because sufficient flexibility and toughness can be imparted to the multilayer structure polymer. More preferably, it is 0.5 mass% or more and 2 mass% or less.

  The composition of the intermediate layer polymer (IIb-B) needs to be different from the composition of the innermost layer polymer (IIb-A). When the compositions of these polymers are different, the impact resistance and the molding whitening resistance of the acrylic resin film obtained by molding the acrylic resin composition and the acrylic resin laminated film can be satisfied at the same time.

  The definition of “different composition” as used in the present invention refers to alkyl acrylates, methacrylic acid alkyl esters, other monomers having a copolymerizable double bond, and multifunctional monomers. The type and / or amount of the monomer and the graft crossing agent are different.

  Although not particularly limited, it is preferable that the Tg of the polymer alone obtained when polymerizing only the monomer composition constituting the intermediate layer polymer (IIb-B) is 25 to 100 ° C. When Tg is 25 ° C. or higher, the surface hardness and heat resistance are at levels required for vehicle applications, and a good film can be obtained from the viewpoint of anti-glare resistance in building material exterior applications. More preferably, it is 40 degreeC or more, Most preferably, it is 50 degreeC or more. Moreover, when Tg is 100 ° C. or lower, the acrylic resin film obtained by molding the acrylic resin composition, the whitening resistance of the acrylic laminated film is good, and the film-forming property when the acrylic resin composition is molded into a film is good. A good film is obtained. More preferably, it is 80 degrees C or less, Most preferably, it is 70 degrees C or less.

  Thus, by providing an intermediate layer polymer (IIb-B) having a specific composition and Tg, no multilayer structure polymer or resin composition suitable for satisfying the required physical properties has been designed so far. An acrylic resin film that is difficult to realize and can be obtained by molding an acrylic resin composition and an acrylic resin film that achieves both molding whitening resistance, surface hardness, and heat resistance of an acrylic resin laminated film can be obtained.

  Although not limited in particular, the content of the intermediate layer polymer (IIb-B) in the preferred multilayer structure polymer is preferably 5 to 35% by mass. Within this range, it is important to achieve both the whitening resistance of the acrylic resin film obtained by molding the acrylic resin composition and the acrylic resin laminated film, the surface hardness, the heat resistance, and the anti-glare resistance. The function of the intermediate layer polymer (IIb-B) can be expressed, and other physical properties of the resulting film, for example, film forming properties when the acrylic resin composition is formed into a film, an acrylic resin composition It is preferable because the toughness possible for insert molding and in-mold molding of an acrylic resin film and an acrylic resin laminated film obtained by molding can be provided. More preferably, it is 20 mass% or less.

[Outermost layer polymer (IIb-C)]
In the presence of the polymer of the inner layer, the outermost layer polymer (IIb-C) is a methacrylic acid alkyl ester (IIb-C1), an acrylic acid alkyl ester (IIb-C2), (IIb-C1) and (IIb- It is formed by graft polymerization of a monomer composition containing as a constituent component another monomer (IIb-C3) having a double bond copolymerizable with the component C2). The outermost layer polymer (IIb-C) can be obtained by polymerization in at least one stage, and can have a structure of one layer or two or more layers.

  The alkyl methacrylate of component (IIb-C1) constituting the outermost layer polymer (IIb-C) may be either linear or branched. Specific examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and n-butyl methacrylate. These can be used alone or in admixture of two or more. Of these, methyl methacrylate is preferred.

  The acrylic acid alkyl ester of the component (IIb-C2) constituting the outermost layer polymer (IIb-C) may be either linear or branched. 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 admixture of two or more. Of these, preferred are methyl acrylate and n-butyl acrylate.

  Other monomers having a copolymerizable double bond of the component (IIb-C3) constituting the outermost layer polymer (IIb-C) are lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid, methacrylic acid, etc. Acrylic monomers, styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile and the like can be used.

  The content of the methacrylic acid alkyl ester (IIb-C1) in the outermost layer polymer (IIb-C) is preferably 51 to 100% by mass. From the viewpoint of the surface hardness and heat resistance of the resulting acrylic resin film, it is more preferably 80% by mass or more, further preferably 90% by mass or more, and most preferably 93% by mass or more. Moreover, it is 99 mass% or less more preferably.

  As for content of acrylic acid alkylester (IIb-C2) in outermost layer polymer (IIb-C), 0-20 mass% is preferable. More preferably, it is 1 mass% or more. Further, it is more preferably 10% by mass or less, and most preferably 7% by mass or less.

  The content of the monomer (IIb-C3) having a copolymerizable double bond in the outermost layer polymer (IIb-C) is preferably 0 to 49% by mass. More preferably, it is 20 mass% or less, More preferably, it is 15 mass% or less.

  Although it does not specifically limit, a chain transfer agent is used at the time of superposition | polymerization of outermost layer polymer (IIb-C), and the molecular weight of outermost layer polymer (IIb-C) can be adjusted. This chain transfer agent is preferably selected from those usually used for radical polymerization, and specific examples thereof include alkyl mercaptans having 2 to 20 carbon atoms, mercapto acids, thiophenol, carbon tetrachloride, and the like. These can be used alone or in admixture of two or more. The content of the chain transfer agent is preferably 0.01 to 5% by mass with respect to 100% by mass of the monomer ((IIb-C1) to (IIb-C3)) of the polymer (IIb-C). More preferably, it is 0.2% by mass or more, and most preferably 0.4% by mass or more.

  Although it does not specifically limit, Tg of the polymer only of the monomer composition of outermost layer polymer (IIb-C) will be 60 degreeC or more. When the Tg is 60 ° C. or higher, a film having surface hardness suitable for vehicle use, heat resistance, and anti-glare resistance suitable for active building material exterior use is preferable. More preferably, it is 80 degreeC or more, Most preferably, it is 90 degreeC or more. Further, from the viewpoint of coagulation property and handleability of the obtained multilayer structure polymer, 105 ° C. or lower is preferable.

  Although not particularly limited, the content of the outermost layer polymer (IIb-C) in the multilayer structure polymer is preferably 10 to 80% by mass. From the viewpoint of surface hardness and heat resistance, it is preferably 15% by mass or more, more preferably 45% by mass or more. When the content is 80% by mass or less, an acrylic resin film obtained by molding an acrylic resin composition, an anti-molding whitening resistance to an acrylic resin laminated film, an acrylic resin film obtained by molding an acrylic resin composition, The toughness possible for insert molding and in-mold molding of the acrylic resin laminated film can be imparted, and more preferably 70% by mass or less.

  The multilayer structure polymer (IIb) of the present invention is composed of the polymer layers (IIb-A), (IIb-B) and (IIb-C) described above. In the acrylic resin film and the acrylic resin laminated film obtained by molding, in order to obtain further excellent molding whitening resistance, the multilayer structure polymer (IIb) preferably has a gel content of at least 50%. More preferably, it is 60% or more.

In this case, the gel content G (%) means that a predetermined amount of the multilayer structure polymer (IIb) (mass before extraction: W ₀ (g)) is extracted under reflux in an acetone solvent, and acetone can be obtained by centrifugation. After removing the soluble matter and drying the remaining acetone insoluble matter, the mass (mass after extraction: W ₁ (g)) was measured and calculated by the following formula.
Gel content rate G = (mass after extraction W ₁ / mass before extraction W ₀ ) × 100

  In terms of the resistance to whitening of the acrylic resin film obtained by molding the acrylic resin composition and the acrylic laminated film, the larger the gel content, the more advantageous, but from the viewpoint of easy moldability, it is more than a certain amount. The free polymer must be present and the gel content is preferably 80% or less.

  The multilayer structure polymer (IIb) is not particularly limited, but preferably has a weight average particle diameter in the range of 0.05 to 0.3 μm. From the viewpoint of mechanical properties of the obtained acrylic resin film, it is more preferably 0.07 μm or more, and most preferably 0.09 μm or more. Further, from the viewpoint of the resistance to whitening of the acrylic resin film obtained by molding the acrylic resin composition, the acrylic resin laminated film, and the transparency of the acrylic resin film, it is more preferably 0.15 μm or less, most preferably 0.00. 13 μm or less.

  Next, the manufacturing method of multilayer structure polymer (IIb) is demonstrated.

  As the method for producing the multilayer structure polymer, the sequential multi-stage polymerization method by the emulsion polymerization method is the most suitable polymerization method, but is not particularly limited thereto. For example, after the emulsion polymerization, the outermost layer polymer (IIb It can also be carried out by an emulsion suspension polymerization method in which a suspension polymerization system is converted during the polymerization of -C).

  Although not particularly limited, when the multilayer structure polymer is produced by emulsion polymerization, a monomer mixture that gives the innermost layer polymer (IIb-A) in the multilayer structure polymer is preliminarily mixed with water and A monomer or a monomer mixture that gives an intermediate layer polymer (IIb-B) and an outermost layer polymer (IIb-C) after feeding and polymerizing an emulsion prepared by mixing with a surfactant. Is preferably supplied to the reactor in order and polymerized.

  The monomer mixture that gives the innermost layer polymer (IIb-A) was dispersed in water, particularly in acetone, by supplying an emulsion prepared by mixing with water and a surfactant in advance to the reactor and polymerizing it. At that time, a multilayer structure polymer in which the number of particles having a diameter of 55 μm or more present in the dispersion is 0 to 50 per 100 g of the multilayer structure polymer can be easily obtained. Films using the multilayer polymer thus obtained as a raw material have the characteristic that the number of fish eyes in the film is small, and in particular, a light-colored wood grain pattern with a low printing pressure that tends to cause printing failure, metallic tone, jet black Even when solid gravure printing such as tones is performed, it is preferable because there are few printing omissions and printability at a high level.

  As the surfactant used for preparing the emulsion, anionic, cationic, and nonionic surfactants can be used, and anionic surfactants are particularly preferable.

  Examples of anionic surfactants include rosin soap, potassium oleate, sodium stearate, sodium myristate, N-lauroyl sarcosine sodium, alkenyl succinate dipotassium salt, sulfate ester salt such as sodium lauryl sulfate, etc. , Sodium dioctyl sulfosuccinate, sodium dodecylbenzenesulfonate, sulfonates such as sodium alkyldiphenyl ether disulfonate, phosphate esters such as sodium polyoxyethylene alkylphenyl ether phosphate, sodium polyoxyethylene alkyl ether phosphate And phosphoric acid ester salts. Of these, phosphate esters such as polyoxyethylene alkyl ether sodium phosphates are preferable from the viewpoint of ecological protection from endocrine disrupting chemicals, which have become a problem in recent years.

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

  In addition, as a method for preparing an emulsified liquid, a method in which a monomer mixture is charged in water and then a surfactant is added, a method in which a surfactant is charged in water and then a monomer mixture is charged, Examples thereof include a method of charging water after charging a surfactant into the monomer mixture. Among these, the method of charging the surfactant after charging the monomer into water and the method of charging the monomer mixture after charging the surfactant into water are preferred as methods for obtaining the multilayer structure polymer. .

  As a mixing apparatus for preparing an emulsion prepared by mixing a monomer mixture that gives the innermost layer polymer (IIb-A) with water and a surfactant, a stirrer, a homogenizer, and a homomixer equipped with a stirring blade And various forced emulsifiers, membrane emulsifiers and the like.

  As the emulsion to be prepared, any dispersion structure of W / O type or O / W type can be used, but in particular, the dispersion phase is an O / W type in which oil droplets of a monomer mixture are dispersed in water. The diameter of the oil droplet is preferably 100 μm or less.

  On the other hand, the polymerization used in forming the innermost layer polymer (IIb-A), the intermediate layer polymer (IIb-B) and the outermost layer polymer (IIb-C) constituting the preferred multilayer structure polymer of the present invention. As the initiator, a known one can be used, and as a method for adding the initiator, a method of adding to one or both of the aqueous phase and the monomer phase can be used.

  As a particularly preferred polymerization initiator, a peroxide, an azo initiator, or a redox initiator in which an oxidizing agent and a reducing agent are combined is used. A redox initiator is preferable, and a sulfoxylate initiator combined with ferrous sulfate, disodium ethylenediaminetetraacetate, longalite, and hydroperoxide is particularly preferable.

  An emulsion prepared by mixing the monomer mixture giving the innermost layer polymer (IIb-A) with water and a surfactant is supplied to the reactor and polymerized, and then the intermediate layer polymer (IIb-B) is prepared. ) And the monomer mixture that gives the outermost layer polymer (IIb-C) are sequentially fed to the reactor to polymerize an aqueous solution containing ferrous sulfate, disodium ethylenediaminetetraacetate and Rongalite. After raising the temperature to the temperature, the prepared emulsion is supplied to the reactor for polymerization, and then the intermediate layer polymer (IIb-B) and outermost layer polymer (IIb-C) containing a polymerization initiator such as peroxide. The method of successively supplying a monomer mixture that gives) to the reactor and polymerizing is the most preferred method for obtaining the multilayer structure polymer (IIb) of the present invention.

  The polymerization temperature varies depending on the type and amount of the polymerization initiator used, but is preferably 40 to 120 ° C, more preferably 60 to 95 ° C.

  The polymer latex containing the preferable multilayer structure polymer (IIb) obtained by the above method can be treated by using a filtration apparatus provided with a filter medium as necessary. This filtration treatment is to remove scales generated during polymerization from latex, or to remove impurities in the polymerization raw material and from the outside during the polymerization, and obtain a multilayer structure polymer (IIb). Therefore, it is a more preferable method.

  In addition, as a filtering device in which the filter medium used at that time is arranged, a GAF filter system of ISP Filters PTE Ltd. using a bag-shaped mesh filter or a cylindrical filter medium on the inner surface of a cylindrical filter chamber is used. It is preferable to use a centrifugal type filtration device in which a stirring blade is arranged in the filter medium, or 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 multilayer structure polymer (IIb) of the present invention can be produced by recovering from the polymer latex produced by the above-described method. The method for recovering the multilayer structure polymer (IIb) from the polymer latex is not particularly limited, and examples thereof include salting out or acid precipitation coagulation, spray drying, freeze drying, and the like, and the powder is recovered in powder form. .

  Among these, when salting out using a metal salt, the residual metal content in the finally obtained multilayered polymer is preferably 800 ppm or less. In particular, when using a metal salt having a strong affinity for water such as magnesium and sodium as a salting-out agent, unless the residual metal content is reduced as much as possible, the finally obtained multilayer structure polymer is used as a raw material. When the obtained acrylic resin film is immersed in boiling water, a whitening phenomenon occurs, which is a serious problem in practical use. In addition, when calcium-based and sulfuric acid-based coagulation is performed, a relatively good tendency is shown. In any case, in order to give excellent water whitening resistance, it is necessary to make the residual metal amount 800 ppm or less, The smaller the amount, the better.

<< Thermoplastic polymer (III) >>
The thermoplastic polymer (III) to be blended with the polymer as required is 50 to 100% by mass of methyl methacrylate and 0 to 50% by mass of other monomers having a double bond copolymerizable therewith. The reduced viscosity of the polymer is preferably a thermoplastic polymer exceeding 0.5 liter / g.

  When the thermoplastic polymer (III) is used, the film forming property when the acrylic resin composition is formed into a film is improved, so that it is particularly useful when a high level of thickness accuracy and film forming speed are required. In particular, when the reduced viscosity of the thermoplastic polymer (III) is in a range exceeding 0.5 liter / g, a film with good thickness accuracy can be obtained. This reduced viscosity is usually more than 0.5 liter / g and not more than 2 liter / g, preferably not more than 1.2 liter / g.

  Other monomers having a double bond that can be copolymerized with methyl methacrylate, used as necessary for the thermoplastic polymer (III), include alkyl acrylates, alkyl methacrylates, and aromatic vinyl compounds. And vinylcyan compounds.

  The thermoplastic polymer (III) is obtained by polymerizing these monomers. The polymerization method is preferably an emulsion polymerization method, and the polymer can be recovered in a powder form by a usual emulsion polymerization method and post-treatment method.

  As an acrylic resin, what blended suitably the above-mentioned thermoplastic polymer (I), multilayer structure polymer (II), and thermoplastic polymer (III) is used. In addition, as a mixture ratio, (A) thermoplastic polymer (I) 0.9-94.5 mass parts, multilayer structure polymer (II) 1-99 mass parts, and thermoplastic polymer (III) 0-10 One consisting of parts by mass, or (B) 90 to 100 parts by mass of the multilayer structure polymer (II) and 0 to 10 parts by mass of the thermoplastic polymer (III) (wherein the polymers (I) to (III) Is preferably 100 parts by mass). Hereinafter, preferred embodiments will be described.

  In the acrylic resin (A), when the multilayer structure polymer (IIa) is used as the multilayer structure polymer (II) and the thermoplastic polymer (III) is not used, the thermoplastic polymer (I) and the multilayer structure polymer ( Based on the total of 100 parts by mass of IIa), 20 to 94.5 parts by mass of the thermoplastic polymer (I) and 5.5 to 80 parts by mass of the multilayer structure polymer (IIa) are preferable.

  When the multilayer polymer (IIa) is used as the multilayer polymer (II) and the thermoplastic polymer (III) is used, the thermoplastic polymer (I), the multilayer polymer (IIa) and the thermoplastic polymer are used. Based on a total of 100 parts by mass of the polymer (III), 10 to 94.4 parts by mass of the thermoplastic polymer (I), 5.5 to 80 parts by mass of the multilayer structure polymer (IIa) and the thermoplastic polymer (III ) It is preferably 0.1 to 10 parts by mass.

  From the viewpoint of heat resistance and surface hardness, when the total of the thermoplastic polymer (I), the multilayer structure polymer (IIa) and the thermoplastic polymer (III) is 100 parts by mass, the thermoplastic polymer (I) is 60 mass parts or more are more preferable, and 80 mass parts or more are still more preferable. For example, a vehicle member or the like is a member that is easily exposed to high temperatures and is easily touched by hands and objects. However, when the acrylic resin laminate molded product of the present invention is applied to a vehicle member, it has heat resistance and high hardness that can withstand it. It can be demonstrated.

  From the viewpoint of heat resistance, surface hardness and transparency, when the total of the thermoplastic polymer (I), the multilayer structure polymer (IIa) and the thermoplastic polymer (III) is 100 parts by mass, the multilayer structure polymer ( IIa) is more preferably 40 parts by mass or less, and further preferably 20 parts by mass or less. For example, when the acrylic laminated molded product of the present invention is applied to a vehicle member, it can exhibit heat resistance and high hardness that can be withstood, and light scattering on the surface and inside can be reduced, resulting in clear coating. Instead, good transparency can be obtained.

  The amount of the thermoplastic polymer (III) used is 0.1 parts by mass when the total of the thermoplastic polymer (I), the multilayer structure polymer (IIa) and the thermoplastic polymer (III) is 100 parts by mass. By making it above, the film-forming property when the acrylic resin composition is formed into a film shape is improved. On the other hand, by setting it to 10 parts by mass or less, the viscosity of the acrylic resin composition is suppressed, and the acrylic resin composition is It is possible to prevent a decrease in film formability and a decrease in transparency when formed into a film. From the viewpoint of transparency, the thermoplastic polymer (III) is more preferably 5 parts by mass or less, and further preferably 2.5 parts by mass or less. For example, when the acrylic resin laminate molded product of the present invention is applied to a vehicle member, good transparency can be obtained instead of clear coating.

  The amount of the inner layer polymer (IIa-A) in the multilayer structure polymer (IIa) is 100 parts by mass of the total of the thermoplastic polymer (I) and the multilayer structure polymer (IIa), or It is 5-72 mass parts on the basis of a total of 100 mass parts of union (I), multilayer structure polymer (IIa), and thermoplastic polymer (III). By making this amount 5 parts by mass or more, the acrylic resin film obtained by molding the acrylic resin composition, the molding whitening resistance of the acrylic resin laminated film, and the film formation when the acrylic resin composition is molded into a film shape Improves. About this lower limit, 18 mass parts or more are further preferable, and 25 mass parts or more are especially preferable. Moreover, about an upper limit, transparency and the film forming property when shape | molding an acrylic resin composition in a film form improve by setting it as 72 mass parts or less.

  In the acrylic resin (A), when the multilayer structure polymer (IIb) is used as the multilayer structure polymer (II) and the thermoplastic polymer (III) is not used, the thermoplastic polymer (I) and the multilayer structure polymer are used. It is preferable to use 1 to 99 parts by mass of the thermoplastic polymer (I) and 1 to 99 parts by mass of the multilayer structure polymer (IIb) on the basis of a total of 100 parts by mass of (IIb).

  Further, when the multilayer polymer (IIb) is used as the multilayer polymer (II) and the thermoplastic polymer (III) is used, the thermoplastic polymer (I), the multilayer polymer (IIb) and the heat Based on a total of 100 parts by mass of the plastic polymer (III), 0.9 to 89 parts by mass of the thermoplastic polymer (I), 1 to 99 parts by mass of the multilayer structure polymer (IIb), and a thermoplastic polymer (III ) It is preferably 0.1 to 10 parts by mass.

  From the viewpoint of resistance to molding whitening of the acrylic resin film obtained by molding the acrylic resin composition and the acrylic laminated film, the thermoplastic polymer (I), the multilayer structure polymer (IIb) and the thermoplastic polymer (III) When the total is 100 parts by mass, the multilayer structure polymer (IIb) is more preferably 50 parts by mass or more, and further preferably 70 parts by mass or more.

  From the viewpoint of resistance to molding whitening of the acrylic resin film obtained by molding the acrylic resin composition and the acrylic resin laminated film, the thermoplastic polymer (I) is more preferably 50 parts by mass or less, and further preferably 30 parts by mass or less. . Moreover, 5 mass parts or more are preferable from a viewpoint of heat resistance and hardness, and 20 mass parts or more are preferable. By doing so, when the acrylic laminated molded product of the present invention is applied to a vehicle member, it can exhibit heat resistance and high hardness that can withstand it, and is obtained by molding an acrylic resin composition The molding whitening resistance of the film and the acrylic resin laminated film is not impaired.

  When the multilayer structure polymer (IIb) is used as the multilayer structure polymer (II), the gel content in the multilayer structure polymer (IIb) blended in the acrylic resin (A) or the acrylic resin (B) is: From the viewpoint of the molding resin whitening resistance of the acrylic resin film obtained by molding the acrylic resin composition, the acrylic resin laminated film, and the film forming property when the acrylic resin composition is molded into a film shape, it should be 10% by mass or more. Is preferable, 20 mass% or more is more preferable, and 40 mass% or more is more preferable. Moreover, 80 mass% or less is preferable, 75 mass% or less is more preferable, and 70 mass% or less is further more preferable.

  In the acrylic resin (B), it is preferable to use the multilayer structure polymer (IIb) as a main component. When the thermoplastic polymer (III) is contained, 10 parts by mass or less is preferable when the total of the multilayer structure polymer (IIb) and the thermoplastic polymer (III) is 100 parts by mass.

  By doing so, when the acrylic resin film and acrylic resin laminated film obtained by molding the acrylic resin composition are integrated with the base resin by insert molding or in-mold molding, the printed pattern disappears due to molding whitening caused by stretching. There is no fear that the design will be deteriorated by whitening itself.

  In addition to the hindered amine light stabilizer defined in the present invention and the ultraviolet absorber having a melting point of 180 ° C. or lower, the acrylic resin composition of the present invention may be a general compounding agent such as a stabilizer, a lubricant, Processing aids, plasticizers, impact aids, foaming agents, fillers, colorants, matting agents and the like can be included.

  The acrylic resin film of the present invention is a film forming method known in the art such as a melt casting method, a melt extrusion method such as a T-die method or an inflation method, a calendar method, etc., using the acrylic resin composition of the present invention as a raw material. Can be manufactured. From the economical point of view, the T-die method is particularly preferable.

  In the T-die method, it is preferable to form the acrylic resin film after being cooled with a cooling roll so as to come into contact with the cooling roll again. In this way, dirt generated on the cooling roll can be removed continuously, so that the cooling roll is always kept clean and the appearance of the acrylic resin film can be kept good. On the other hand, when an acrylic resin film is formed in a state where it is in contact with the cooling roll only once, dirt accumulates over time on the cooling roll, and at a certain point, it is transferred to the acrylic resin film to cause a large defect in appearance. It becomes.

  In addition, when the acrylic resin film is formed by the T-die method, the surface smoothness of the resulting acrylic resin film can be improved by using a method in which the film is formed by being sandwiched between a plurality of metal rolls, non-metal rolls and / or metal belts. It is possible to suppress printing omission when printing is performed on the acrylic resin film.

  In addition, as a metal roll, the roll used by the sleeve touch system which consists of a metal mirror surface touch roll, a metal sleeve (metal thin film pipe), and a molding roll (for example, patent 2808251 gazette, WO97 / 28950 gazette) For example). Moreover, examples of the non-metallic roll include a touch roll made of silicon rubber or the like. Furthermore, examples of the metal belt include a metal endless belt. A combination of a plurality of these metal rolls, non-metal rolls and metal belts can also be used (for example, JP 2002-301754 A, JP 2002-301755 A, JP 10-279766 A (Patents). Reference 8), Japanese Patent Laid-Open No. 2003-25412, and Japanese Translation of PCT International Publication No. 2001-525277).

  In the above-described method for forming a film by sandwiching a plurality of metal rolls, non-metal rolls and / or metal belts, the acrylic resin composition after melt extrusion is substantially free from banks (resin pools). It is preferable to form a film by holding the film and transferring the surface without substantially rolling.

  When the film is formed without forming a bank (resin pool), the acrylic resin composition in the cooling process is surface-transferred without rolling, so the heat shrinkage rate of the acrylic resin film formed by this method is It can also be reduced.

  In addition, when forming a film using a plurality of metal rolls, non-metal rolls and / or metal belts, the surface of at least one metal roll, non-metal roll or metal belt to be used is embossed, matted, etc. By applying shape processing, the shape can be transferred to one or both sides of the acrylic resin film.

  The thickness of the acrylic resin film is preferably 300 μm or less, and more preferably 100 to 300 μm. When the thickness is 100 μm or more, a sufficient depth can be obtained as the appearance of the molded product, and a sufficient thickness can be maintained even when the molded product is stretched particularly in a complicated shape. In addition, the upper limit of these ranges is that the rigidity is moderately suppressed to maintain good laminating properties and secondary processability, the mass per unit area is suppressed to maintain economic efficiency, and the acrylic resin composition is used as a film. This is significant in terms of improving the film-forming property when formed into a shape and stably producing an acrylic resin film.

  In order to form a sufficiently thick coating film on a molded product by painting, it is necessary to apply more than a dozen times, which is costly and extremely deteriorated in productivity. Since the acrylic resin film itself becomes a coating film as long as it is a laminated molded product in the surface layer, a very thick coating film can be easily formed, which is industrially advantageous.

  It is preferable that the acrylic resin film used for such a paint substitute application has, for example, a 60 ° surface glossiness of 200 μm in thickness of 120% or more and a haze value of 2% or less.

  A layer of a photocurable resin composition can also be laminated on the surface of the acrylic resin film of the present invention.

  For example, the method of laminating | stacking the layer of the photocurable resin composition currently disclosed by Unexamined-Japanese-Patent No. 2002-80550 and Unexamined-Japanese-Patent No. 2002-79621 is mention | raise | lifted.

  These photocurable resin compositions contain a thermoplastic resin having a radically polymerizable unsaturated group in the side chain and a photopolymerization initiator, and substantially contain a crosslinkable compound other than the thermoplastic resin having a radically polymerizable unsaturated group. Is not included. By laminating the layer of the photocurable resin composition on the acrylic resin film of the present invention, a photocurable acrylic resin film can be obtained. In the photocurable resin composition, since a structure having a radically polymerizable unsaturated group is introduced into the polymer side chain in this way, a crosslinking reaction proceeds between the polymer side chains, and thus extremely good resistance to resistance after photocuring. A photocurable acrylic that provides abrasion and scratch resistance and does not require the inclusion of a low molecular weight crosslinkable compound having a reactive vinyl group, and therefore has no surface tackiness before photocuring and excellent storage stability. It has the advantage that a resin film is obtained. These photocurable acrylic resin films can be handled and processed in the same manner as an acrylic resin film in which a layer of the photocurable resin composition is not laminated.

  When the acrylic resin film of the present invention is used for coating substitution, a film provided with a decorative layer as necessary is usually used to impart designability to a molded product.

  Although a well-known thing can be used as a decoration layer, a printing layer or a metal layer is preferable. The printing layer can be formed by a known printing method such as a gravure printing method, a flexographic printing method, or a silk screen printing method. Arbitrary patterns such as wood grain or metal can be formed. The metal layer can be formed by a known method such as a vacuum deposition method, a sputtering method, or a plating method. The thickness of the decorative layer may be appropriately determined as necessary, but is usually about 0.5 to 30 μm.

  In this case, the acrylic resin film is preferably subjected to one-side decorating treatment and used as a film in which a pattern or the like is decorated on one side.

  In addition, it is preferable to arrange the decorative surface on the non-surface side during lamination and molding from the viewpoint of protecting the printed surface and imparting a high-class feeling. Moreover, when using as a substitute for transparent coating, making use of the color tone of plastics or the like as a base material, it can be used as it is transparent. In particular, acrylic resin films are superior in terms of transparency, depth, luxury, and the like to vinyl chloride and polyester films for applications that make use of the color tone of the substrate.

  In the present invention, the acrylic resin film formed by further molding the acrylic resin composition can be a laminate obtained by laminating other resin molded products, for example, films, sheets, plates, etc., and further decorated, Alternatively, an undecorated acrylic resin film is disposed in a mold, and another resin is injection-molded there, so that a molded product can be formed by so-called insert molding. In addition, it can replace with laminating | stacking an acrylic resin film and can shape | mold a laminated body also by the coextrusion which uses the acrylic resin composition of this invention as a surface layer.

  In addition, the acrylic resin laminated film of the present invention comprises a thermoplastic resin layer for supporting the acrylic resin film of the present invention and a sufficient strength for handling against external forces such as impact and deformation by supporting the acrylic resin film. .

  By using a thermoplastic resin layer, for example, the film can be removed from the mold after vacuum forming the film by insert molding or the like, and the impact or deformation that occurs when the vacuum molded product is loaded into an injection mold. However, cracks and the like hardly occur, and the handleability is improved.

  It does not specifically limit as a thermoplastic resin layer used here, A well-known thermoplastic resin can be used. Examples thereof include acrylic resin, ABS resin (acrylonitrile-butadiene-styrene resin), AS resin (acrylonitrile-styrene resin), vinyl chloride resin, polystyrene, polycarbonate, polyester, polyolefin and the like. Among these, acrylic resin, ABS resin, vinyl chloride resin, and polyolefin are preferable in consideration of printability and secondary moldability of the laminated film.

  The thermoplastic resin layer may contain general compounding agents such as stabilizers, lubricants, plasticizers, impact resistance aids, colorants, ultraviolet absorbers and the like.

  As a method for adding the compounding agent, there are a method of feeding the thermoplastic resin layer together with the thermoplastic resin to the extruder for forming the thermoplastic resin layer of the present invention, and a mixture in which the compounding agent is previously added to the thermoplastic resin in various kneaders. There is a method of kneading and mixing. Examples of the kneader used in the latter method include ordinary single screw extruders, twin screw extruders, Banbury mixers, roll kneaders, and the like.

  By laminating the acrylic resin laminated film of the present invention on the surface of a substrate such as various resin molded products, woodwork products, and metal molded products, a laminate having the laminated film on the surface can be produced.

  As a method for forming a laminated film of the present invention, there are a method of laminating an acrylic resin film and a thermoplastic resin film previously formed into a film shape, and a method of simultaneously laminating a thermoplastic resin layer on an acrylic resin film while melt extrusion. .

  As a manufacturing method of a thermoplastic resin film, it can manufacture by a well-known method. From the viewpoint of economy, a melt extrusion method such as a T-die method or an inflation method, a calendar method, or the like is preferable. In the case where the thermoplastic resin layer is previously formed into a film shape, a decorative layer can be formed on the film.

  Examples of the method of laminating the acrylic resin film and the thermoplastic resin film include a laminating method such as a method of laminating the acrylic resin film and the thermoplastic resin film by dry lamination, wet lamination, hot melt lamination, or the like. If heat fusion is possible, lamination can be performed by a hot press laminating method.

  Examples of the method of laminating the thermoplastic resin layer with the acrylic resin film at the same time while melt-extruding the thermoplastic resin layer include extrusion lamination in which the thermoplastic resin is laminated on the acrylic resin film while being melt-extruded into a film shape with a T die or the like.

  The thickness of the thermoplastic resin layer of the present invention may be appropriately determined as necessary, but is usually about 20 to 500 μm.

  The acrylic resin laminate molded product of the present invention is characterized in that the acrylic resin film of the present invention and the acrylic resin laminate film are laminated on a base material by fusion bonding or the like so that the acrylic resin layer becomes the outermost surface. .

  As a base material which laminates | stacks the acrylic resin film of this invention, and an acrylic resin laminated film, various resin molded products, woodwork products, and metal molded products are mentioned. Among the resin molded products, as the thermoplastic resin molded product that can be melt-bonded to the acrylic resin film and the acrylic laminated film of the present invention, ABS resin, AS resin, polystyrene resin, polycarbonate resin, vinyl chloride resin, acrylic resin, Examples thereof include polyester resins and resins containing these as main components. In terms of adhesiveness, an ABS resin, an AS resin, a polycarbonate resin, a vinyl chloride resin, or a resin containing these as a main component is preferable, and an ABS resin, a polycarbonate resin, or a resin containing these as a main component is more preferable. However, it is possible to bond an acrylic resin film and a base material, an acrylic laminated film and a base material at the time of molding by using an adhesive layer even with a base resin that is not heat-sealed, such as a polyolefin resin.

  When the acrylic resin laminate molded product of the present invention is molded into a two-dimensional laminate, a known method such as thermal lamination can be used for a base material that can be heat-sealed. It is possible to bond to a base material that is not heat-sealed through an adhesive. When molding into a three-dimensionally shaped laminate, a known method can be used, but an insert molding method or an in-mold molding method is preferably used.

  In the insert molding method, an acrylic resin film or an acrylic resin laminated film is subjected to vacuum molding or pressure molding in advance, then loaded into an injection mold, and a resin as a base material is injection-molded. The resin laminated film and the substrate are integrated.

  The in-mold molding method is a method in which an acrylic resin film or an acrylic resin laminated film is subjected to vacuum molding or pressure molding in an injection mold having a vacuuming function, and then a resin as a base material is injection molded to produce an acrylic resin film or The acrylic resin laminated film and the substrate are integrated. The heating temperature at the time of vacuum forming or pressure forming is preferably equal to or higher than the temperature at which the acrylic resin film or acrylic resin laminated film is softened. Specifically, although it depends on the thermal properties of the acrylic resin film or the acrylic resin laminated film or the shape of the molded product, it is usually 70 ° C. or higher. On the other hand, if the temperature is too high, the surface appearance tends to deteriorate or the releasability tends to deteriorate. Although this also depends on the thermal properties of the acrylic resin film or acrylic resin laminated film or the shape of the molded product, it is usually preferably 170 ° C. or lower.

  Furthermore, from the viewpoint of energy efficiency, it is preferable that the preheating temperature during vacuum forming is low. Specifically, 135 ° C. or lower is preferable. In addition, an acrylic resin film or an acrylic resin laminated film that can be molded even if the preheating temperature is low can shorten the preheating time instead of lowering the preheating temperature. In this case, it is possible to increase the cycle of vacuum forming, and the industrial utility value is high.

  An acrylic resin film using an acrylic resin composition having good molding whitening resistance, such as an acrylic resin (A) using the multilayer structure polymer (IIb) and an acrylic resin (B) using the multilayer structure polymer (IIb) In the case of an acrylic resin laminated film, if it is a molded product with a relatively shallow drawing, the preforming is omitted, and the acrylic resin film is directly loaded into the injection mold and only injected with the resin temperature and pressure of the molten resin to be injected. Alternatively, an acrylic resin laminated film can be molded and laminated.

  The acrylic resin film of the present invention, the acrylic resin laminated film, the acrylic resin laminated molded product obtained by laminating the acrylic resin film, and the acrylic resin laminated molded product obtained by laminating the acrylic resin laminated film are subjected to surface treatment for providing various functions as necessary. Can be applied to the surface. Surface treatments for imparting functions include printing processes such as silk printing and inkjet printing, metal tone imparting, metal deposition for antireflection, sputtering, wet plating treatment, surface hardening treatment for improving surface hardness, dirt Examples thereof include water repellency treatment for prevention, photocatalyst layer formation treatment, dust adhesion prevention, antistatic treatment for the purpose of cutting electromagnetic waves, antireflection layer formation, and antiglare treatment.

  Acrylic resin laminate molded product with laminated acrylic resin film of the present invention, acrylic resin laminated molded product with laminated acrylic resin laminated film, instrument panel, console box, meter cover, door lock pzel, steering wheel, power window switch base, center Automotive interior applications such as clusters and dashboards, weather strips, bumpers, bumper guards, side mud guards, 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 and other automotive exterior applications, AV equipment and furniture front panels, buttons, Applications such as emblems, surface decorative materials, mobile phone housings, display windows, buttons, etc., furniture exterior materials, walls, ceilings, floors and other building interior materials, siding outer walls, etc. , Architectural exterior materials such as roofs, gates, and windbreak boards, window frame, doors, handrails, sills, surface decoration materials for furniture such as duck, various displays, lenses, mirrors, goggles, optical members such as window glass Suitable for applications, interior / exterior applications of various vehicles other than automobiles such as trains, airplanes, ships, etc., various packaging containers and materials such as bottles, cosmetic containers, accessory cases, and other various applications such as miscellaneous goods such as prizes and accessories Can be used.

  The acrylic resin composition of the present invention has good chemical resistance.For example, when the acrylic resin composition of the present invention is provided on the outermost layer of a vehicle interior part, it is affected by a fragrance or hair styling agent during product use. Since it is difficult, the industrial value is remarkably high. In addition, the heat aging resistance is good. For example, when the acrylic resin composition of the present invention is provided on the outermost layer of a vehicle interior part, it is difficult to heat aging during use of the product, and thus the industrial value is remarkably high.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by an Example. In the examples, “part” represents “part by mass”, and “%” represents “% by mass”.

Abbreviations in the examples are as follows.
MMA methyl methacrylate BA butyl acrylate AMA allyl methacrylate St styrene MA methyl acrylate BD 1,3-butadiene tBH t-butyl hydroperoxide CHP cumene hydroperoxide nOM n-octyl mercaptan XP mono (polyoxyethylene nonylphenyl ether) phosphoric acid 40 % And di (polyoxyethylene nonylphenyl ether) phosphoric acid 60% sodium hydroxide partially neutralized product (trade name: Phosphanol RS610NA, manufactured by Toho Chemical Industry Co., Ltd.)
SFS sodium formaldehyde sulfoxylate (Longalite)
EDTA Disodium ethylenediaminetetraacetate

  For thermoplastic polymer (I), multilayer structure polymer (II), thermoplastic polymer (III), acrylic resin film, acrylic resin laminated film and acrylic resin laminated molded product, various physical properties are measured by the following test methods. did.

1) Reduced viscosity of thermoplastic polymers (I) and (III) 0.1 g of the polymer was dissolved in 100 ml of chloroform and measured at 25 ° C.

2) Gel content rate G (%) of multilayer structure polymer (II)
A predetermined amount (mass before extraction: W ₀ (g)) of the multilayer structure polymer (II) is extracted under reflux in an acetone solvent, and acetone-soluble components are removed by centrifugation, and the remaining acetone-insoluble components are dried. Then, the mass (mass after extraction: W ₁ (g)) was measured and calculated by the following formula.
Gel content rate G = mass after extraction W ₁ / mass before extraction W ₀ × 100

3) Glass transition temperature (Tg) of each polymer layer of the multilayer structure polymer (II)
Using the values described in Polymer Handbook (Polymer HandBook (J. Brandrup, Interscience, 1989)), it was calculated from the FOX equation.

4) Average particle diameter of multilayer structure polymer (II) The final particle diameter of the polymer latex of multilayer structure polymer (II) obtained by emulsion polymerization was measured with a light scattering photometer (DLS-700, manufactured by Otsuka Electronics Co., Ltd.). ) And measured by a dynamic light scattering method.

5) HDT (thermal deformation temperature) of acrylic resin film
According to ASTM D648, the pellet-shaped acrylic resin composition was molded into a heat distortion temperature measurement specimen by injection molding, and annealed at 60 ° C. for 4 hours, and then measured under a low load (0.45 MPa).

6) Total light transmittance and haze of acrylic resin film Evaluated according to JIS K6714.

7) Surface gloss of acrylic resin film The surface gloss at 60 ° was measured using a gloss meter (manufactured by Murakami Color Research Laboratory, model GM-26D).

8) Volatile resistance of ultraviolet absorbers When the film formation operation is performed for 5 hours, volatilized ultraviolet absorber crystals are generated in the exhaust hood installed at a position approximately 50 cm above the T-die. Observed, the case where there was no crystal precipitation was indicated as “◯”, and the case where it was present was indicated as “X”.

9) Film thickness of acrylic resin film Using a transmission electron microscope JEM100S (manufactured by JEOL Ltd.), the cross section of the acrylic resin film was observed, and the film thickness of the acrylic resin film was measured. Also when the layer of the photocurable resin composition was laminated on the acrylic resin film, the cross-sectional observation was performed in the same manner, and the film thicknesses of the photocurable resin composition layer and the acrylic resin film layer were measured.

10) Fragrance resistance of laminated molded product A polyethylene cylinder (inner diameter: 38 mm, height: 15 mm) is placed on the surface of the laminated molded product on the acrylic resin layer side, and is firmly attached to the test piece with a crimping device. 5 ml of Grace Mate Poppy Citrus (trade name; manufactured by Dia Chemical Co., Ltd.) is dropped as a fragrance, and the opening is covered with a glass plate and left in an oven at 55 ° C. After 4 hours, the crimper was removed, the test piece was washed with water and air-dried, and then the surface state of the fragrance contact portion was visually observed and evaluated as follows.
○: No change is observed ×: Whitening and roughening

11) Hair-styling property of laminated molded product Brabus hair liquid (trade name; manufactured by Shiseido Co., Ltd.) as a hair styling agent is evenly applied to the surface of the acrylic resin layer side of the laminated molded product with a finger so as to be ² g per 105 cm ^2. Then, a flannel slightly smaller than the test piece was placed and left in an oven at 80 ° C. One week later, after taking out, washing with water (or using a small amount of neutral detergent) and air-drying, the surface condition was visually observed, and the degree of occurrence of whitening and unevenness was evaluated as follows.
(Whitening)
○: No whitening is observed. △: Some whitening is observed. ×: Whitening is observed on one side.
◎: Unevenness is hardly seen ○: Unevenness is seen but not noticeable △: Unevenness is seen but mild ×: Remarkable unevenness is seen on one side

12) Heat aging resistance of laminated molded article The test piece was left in an oven at 100 ° C. After 400 hours, it was taken out and visually observed for the surface condition, and the following evaluation was performed.
○: No whitening is observed ×: Whitening is observed on one side

13) Pencil hardness of laminated molded product Measured according to JIS K5400.

14) Abrasion Resistance of Laminated Molded Article The haze value after a Taber abrasion test (the test was carried out at a rotation speed of 60 rpm, a test rotation speed of 100 times and 500 rotations using a 500 g load on one side and a CS10F wear wheel) was measured. And the value which subtracted the haze (%) before a test from the haze (%) after a test was shown as abrasion resistance (%).

(Example 1)
a) Production of Multilayer Structure Polymer (IIa-a) The following (A) is charged in a reaction vessel, and the following (B) (inner layer polymer (IIa -A) raw material) was continuously added, and then polymerization was further performed for 120 minutes to obtain a latex of the inner layer polymer (IIa-A). Subsequently, the following (c) is added, and the following (d) (raw material for the outermost layer polymer (IIa-B)) is continuously added over 100 minutes at 80 ° C. in a nitrogen atmosphere while stirring. Thereafter, the outermost layer polymer (IIa-B) was formed by continuously performing polymerization at 80 ° C. for 60 minutes to obtain a multilayer structure polymer (IIa-a) latex. The average particle size of the multilayer structure polymer (IIa-a) was 0.12 μm. The latex of this multilayer structure polymer (IIa-a) was subjected to coagulation, aggregation and solidification reaction using calcium acetate, filtered, washed with water and dried to obtain a multilayer structure polymer (IIa-a). .

(I)
Deionized water 310 parts XP 0.5 part Sodium carbonate 0.1 part SFS 0.5 part Ferrous sulfate 0.00024 part EDTA 0.00072 part

Raw material (b)
BA 81.0 parts St 19.0 parts AMA 1.0 parts tBH 0.25 parts XP 1.1 parts

(C)
Deionized water 10 parts SFS 0.15 parts

Raw material (d)
MMA 57.0 parts MA 3.0 parts nOM 0.2 parts tBH 0.1 part

b) Production of thermoplastic polymer (III) In a reaction vessel, 200 parts of ion-exchanged water substituted with nitrogen was charged, and 1 part of an emulsifier potassium oleate and 0.3 part of potassium persulfate were charged. Subsequently, 40 parts of MMA, 10 parts of BA, and 0.005 part of nOM were charged and stirred at 65 ° C. for 3 hours in a nitrogen atmosphere to complete the polymerization. Subsequently, a monomer mixture consisting of 48 parts of MMA and 2 parts of BA was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was held for 2 hours to complete the polymerization to obtain a latex of thermoplastic polymer (III). The latex was added to a 0.25% aqueous sulfuric acid solution to coagulate the polymer, and then dehydrated, washed with water and dried to recover the powdery thermoplastic polymer (III). The reduced viscosity of this thermoplastic polymer (III) was 0.38 liter / g.

c) Production of acrylic resin composition The multilayer polymer (IIa-a), the thermoplastic polymer (III), and the thermoplastic polymer (I) obtained as described above were used as the thermoplastic polymer (Ia) (for both MMA / MA). Polymer (MMA / MA = 98/2, reduced viscosity 0.06 liter / g)), tinuvin 234 (trade name, melting point 139 ° C.) as an ultraviolet absorber and ADK STAB LA67 (trade name) as a hindered amine light stabilizer Were mixed at a ratio shown in Table 2 using a Henschel mixer. Then, using a φ40 mm twin screw type extruder (L / D = 26), the mixture was melt-kneaded at a cylinder temperature of 200 to 260 ° C. and a die temperature of 250 ° C. and pelletized to obtain an acrylic resin composition pellet. .

d) Manufacture of acrylic resin film The pellet was dried at 80 ° C for a whole day and night, using a φ40 mm non-vent screw type extruder (L / D = 26) equipped with a 300 mmT die, a cylinder temperature of 200 to 240 ° C and a T die. A film having a thickness of 200 μm was formed at a temperature of 250 ° C. In addition, the volatility resistance of the ultraviolet absorber at the time of film formation was “◯”.

e) Manufacture of acrylic resin laminate molded product After the wood pattern is applied to the acrylic resin film obtained in d) by gravure printing method, after vacuum forming with an injection mold having a vacuum drawing function, the film is used as it is. In the state where it was arranged, ABS resin “Bulksum TM25B” (trade name, manufactured by UMG-ABS Co., Ltd.) was injection-molded on the printing surface side to obtain an acrylic laminated molded product.

  Table 3 shows the evaluation results of the obtained acrylic resin film and the acrylic resin laminated molded product.

(Examples 2 to 6)
In Example 1, except that the acrylic resin composition prepared by changing the blending amounts of the thermoplastic polymer (I) and the multilayer structure polymer (IIa-a) as shown in Table 2 was used. In the same manner as in Example 1, an acrylic resin film and an acrylic resin laminated molded product were obtained.

  Table 3 shows the evaluation results of the obtained acrylic resin film and the acrylic resin laminated molded product.

(Example 7)
a) Manufacture of Acrylic Resin Laminated Film ABS resin “Diapet ABS SW7” (trade name, manufactured by Mitsubishi Rayon Co., Ltd.) is used as the thermoplastic resin layer, and a screen mesh of φ40 mm provided with a 400 mesh screen mesh with a 300 mmT die attached. Using a non-vent screw type extruder (L / D = 26), the temperature of the resin melt-extruded through a T die was adjusted to 75 ° C. under conditions of a cylinder temperature of 180 to 220 ° C. and a T die temperature of 230 ° C. A film formed to a thickness of 125 μm through three polishing rolls was used.

  Next, after giving a wood grain pattern to the acrylic resin film obtained in the same manner as in Example 2 by a gravure printing method as a decorative layer, the decorative layer is in contact with the thermoplastic resin film via a heating roll. An acrylic resin laminated film was obtained by heat lamination.

b) Manufacture of acrylic resin laminated molded product The obtained acrylic resin laminated film is removed after vacuum forming with a mold having a vacuuming function, and the vacuum molded product is placed in an injection mold, and then ABS resin is used. “Bulksum TM25B” (trade name) was injection-molded on the thermoplastic resin layer side to obtain an acrylic resin laminated molded product.

  Table 3 shows the evaluation results of the obtained acrylic resin film and the acrylic resin laminated molded product.

(Example 8)
When forming the film, the molten acrylic resin composition extruded from the slit of the T-die is made of a metal cooling roll and a metal film made of an elastically deformable metal thin film as described in WO 97/28950. The elastic outer cylinder, a shaft portion that closes both ends of the metallic elastic outer cylinder, and a roll filled with a cooling fluid with internal pressure applied to the inside of the metallic elastic outer cylinder are subjected to surface transfer. After that, an acrylic resin film and an acrylic resin laminate molded product were obtained in the same manner as in Example 2 except that a 125 μm acrylic resin film was produced by winding it on a paper tube with a winder.

  Table 3 shows the evaluation results of the obtained acrylic resin film and the acrylic resin laminated molded product.

  In addition, when the wood pattern was given to the obtained acrylic resin film by the gravure printing method as a decoration layer, there were few printing omissions and it was favorable.

Example 9
a) Production of thermoplastic resin (a-1) having a radically polymerizable unsaturated group in the side chain 50 parts of methyl ethyl ketone was placed in a 1 liter four-necked flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer. The temperature was raised to 80 ° C. Under a nitrogen atmosphere, a mixture of 79.9 parts of methyl methacrylate, 20.1 parts of glycidyl methacrylate and 0.5 parts of azobisisobutyronitrile was added dropwise over 3 hours. Thereafter, a mixture of 80 parts of methyl ethyl ketone (boiling point 79.6 ° C.) and 0.2 part of azobisisobutyronitrile was added and polymerized. After 4 hours, 74.4 parts of methyl ethyl ketone, 0.5 part of hydroquinone monomethyl ether, 2.5 parts of triphenylphosphine and 10.1 parts of acrylic acid were added and stirred at 80 ° C. for 30 hours while blowing air. Then, after cooling, the reaction product was taken out from the flask, and a solution of a thermoplastic resin (a-1) having a radical polymerizable unsaturated group in the side chain was obtained.

  The polymerization rate of the monomer in the thermoplastic resin (a-1) having a radically polymerizable unsaturated group in the side chain is 99.5% or more, the polymer solid content is about 35%, and the number average molecular weight is about 30,000. The glass transition temperature was about 105 ° C., and the average double bond equivalent was 788 g / mol.

b) Production of colloidal silica (inorganic fine particles (a-3)) In a flask equipped with a stirrer, a condenser and a thermometer, IPA-ST (isopropanol-dispersed colloidal silica sol (Nissan Chemical Industries, Ltd.) ), Silica particle diameter = 15 nm) 1 part, KBM503 (γ-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), molecular weight = 248) 0.1 part, water 0.3 part are added and stirred. While raising the temperature of the hot water bath to 75 ° C. and reacting at that temperature for 2 hours, colloidal silica dispersed in isopropanol and treated with a silane compound was obtained. Subsequently, isopropanol was distilled off and toluene (boiling point 110.6 ° C.) was repeatedly added. By completely replacing isopropanol with toluene, the colloidal was dispersed in toluene and the surface was treated with a silane compound. Silica was obtained.

c) Production of photocurable resin solution 100 parts by weight of thermoplastic resin (a-1) having a radically polymerizable unsaturated group in the side chain in mass parts in terms of solid content, 1-hydroxycyclohexyl phenyl ketone (photopolymerization initiator) (A-2)) A photocurable resin solution consisting of 3 parts and 66 parts of colloidal silica (inorganic fine particles (a-3)) was prepared by stirring with a propeller mixer.

d) Production of photocurable acrylic resin film A photocurable resin solution was coated on the acrylic resin film obtained in Example 8 with a comma roll coater with a coating width of 250 mm. Subsequently, the tunnel-type drying furnace (width 800 mm, height 100 mm, length 8 m, divided into four drying zones (length of 2 m per zone)) set to the temperature conditions shown in Table 1 below is suitable for the movement of the sheet. The solvent was volatilized by passing it through a method in which hot air was fed so as to form a flow at a speed of 10 m / min to form a photocurable resin layer having a thickness of 8 μm. The table below shows the residence time of each drying zone.

  Subsequently, it was slit into a width of 200 mm and wound into a roll shape around an ABS core to a length of 20 m.

e) Production of Acrylic Resin Laminated Molded Article An acrylic resin laminated molded article was obtained in the same manner as in Example 2 except that the photocurable acrylic resin film obtained in d) was used as the acrylic resin film.

  Table 4 shows the evaluation results of the obtained photocurable acrylic resin film and the acrylic resin laminated molded product.

  In addition, when this photocurable acrylic resin film was given a wood grain pattern as a decorative layer by a gravure printing method, printing omission was small and good.

(Example 10)
In Example 2, an acrylic resin film and an acrylic laminate were used in the same manner as in Example 2 except that an acrylic resin composition prepared using 3 parts of Tinuvin 329 (trade name, melting point: 104 ° C.) was used as the ultraviolet absorber. A molded product was obtained. Table 3 shows the evaluation results of the obtained acrylic resin film and the acrylic resin laminated molded product. In addition, the volatility resistance of the ultraviolet absorber at the time of film formation was “◯”.

(Example 11)
In Example 2, an acrylic resin film and an acrylic resin were used in the same manner as in Example 2 except that an acrylic resin composition prepared using 3 parts of Tinuvin P (trade name, melting point 130 ° C.) was used as the ultraviolet absorber. A laminated molded product was obtained. Table 3 shows the evaluation results of the obtained acrylic resin film and the acrylic resin laminated molded product. In addition, the volatility resistance of the ultraviolet absorber at the time of film formation was “x”.

(Example 12)
In Example 2, an acrylic resin film and an acrylic resin were prepared in the same manner as in Example 2 except that an acrylic resin composition prepared using 3 parts of tinuvin 1577 (trade name, melting point 148 ° C.) was used as the ultraviolet absorber. A resin laminate molded product was obtained. Table 3 shows the evaluation results of the obtained acrylic resin film and the acrylic resin laminated molded product. In addition, the volatility resistance of the ultraviolet absorber at the time of film formation was “◯”.

(Example 13)
In Example 2, an acrylic resin film and an acrylic resin laminate molded product were obtained in the same manner as in Example 2 except that an acrylic resin composition in which the amount of ADK STAB LA67 (trade name) used was 0.1 part was used. It was. Table 3 shows the evaluation results of the obtained acrylic resin film and the acrylic resin laminated molded product.

(Example 14)
In Example 2, an acrylic resin film and an acrylic resin laminated molded product were obtained in the same manner as in Example 2 except that the acrylic resin composition in which the amount of ADK STAB LA67 (trade name) used was 1 part was used. Table 3 shows the evaluation results of the obtained acrylic resin film and the acrylic resin laminated molded product.

(Example 15)
In Example 2, an acrylic resin film and an acrylic resin laminate molding were performed in the same manner as in Example 2 except that an acrylic resin composition using 0.3 part of ADK STAB LA57 (trade name) was used as the hindered amine light stabilizer. I got a product. Table 3 shows the evaluation results of the obtained acrylic resin film and the acrylic resin laminated molded product.

(Example 16)
a) Production of multi-layer polymer (IIa-b) In a nitrogen atmosphere, 244 parts of deionized water was placed in a reaction vessel equipped with a reflux condenser, the temperature was raised to 80 ° C., and the following (A) was added and stirred 1/15 of the mixture of (b) (raw material of the first inner layer polymer (IIa-A ₁ )) shown below was charged and held for 15 minutes. Thereafter, the remaining raw material (b) was continuously added at an increase rate of 8% / hour of the monomer mixture with respect to water. Thereafter, it was kept for 1 hour to obtain a latex of the first inner layer polymer (IIa-A ₁ ).

Subsequently, 0.6 parts of SFS was added to this latex and held for 15 minutes, followed by stirring at 80 ° C. under a nitrogen atmosphere while (c) (raw material of the second inner layer polymer (IIa-A ₂ )) Was continuously added at a rate of 4% / hr increase in the monomer mixture with respect to water. After that, the latex of the inner layer polymer ((IIa-A ₁ ) + (IIa-A ₂ )) was obtained by polymerizing the second inner layer polymer (IIa-A ₂ ) while maintaining for 2 hours.

  Next, 0.4 parts of SFS was added to this latex, and the mixture was held for 15 minutes and stirred at 80 ° C. in a nitrogen atmosphere, and the following (d) (raw material of outermost layer polymer (IIa-B)) was added to water. The monomer mixture was continuously added at an increase rate of 10% / hour. After that, the outermost layer polymer (IIa-B) was polymerized by holding for 1 hour to obtain a latex of the multilayer structure polymer (IIa-b). The average particle size of the polymer (IIa-b) was 0.28 μm. The multilayer polymer (IIa-b) latex was subjected to coagulation, aggregation and solidification using calcium acetate, filtered, washed with water and dried to obtain a multilayer polymer (IIa-b). .

(I)
SFS 0.6 part Ferrous sulfate 0.00012 part EDTA 0.0003 part

Raw material (b)
MMA 18.0 parts BA 20.0 parts St 2.0 parts AMA 0.15 parts BD 1.2 parts tBH 0.18 parts XP 0.75 parts

Raw material (C)
BA 50.0 parts St 10.0 parts AMA 0.4 parts BD 0.14 parts tBH 0.2 parts XP 0.6 parts

Raw material (d)
MMA 57.0 parts MA 3.0 parts nOM 0.3 parts tBH 0.06 parts

b) Production of acrylic resin film and acrylic resin laminate molded product In Example 2, an acrylic resin composition using the multilayer structure polymer (IIa-b) produced above instead of the multilayer structure polymer (IIa-a) An acrylic resin film and an acrylic resin laminated molded product were obtained in the same manner as in Example 2 except that was used. Table 3 shows the evaluation results of the obtained acrylic resin film and the acrylic resin laminated molded product.

(Example 17)
In Example 16, acrylic polymer using thermoplastic polymer (Ib) (MMA / MA copolymer (MMA / MA = 90/10, reduced viscosity 0.06 liter / g)) as thermoplastic polymer (I). An acrylic resin film and an acrylic resin laminate molded product were obtained in the same manner as in Example 16 except that the resin composition was used. Table 3 shows the evaluation results of the obtained acrylic resin film and the acrylic resin laminated molded product.

(Example 18)
a) Production of multi-layer structure polymer (IIb-a) After charging 8.5 parts of ion-exchanged water into a vessel equipped with a stirrer, 0.3 part of MMA, 4.5 parts of BA, 0.2 part of BD, 0.05 part of AMA And a first monomer mixture comprising 0.025 part of CHP was added and stirred and mixed. Next, 1.1 parts of XP as an emulsifier was added to the vessel while stirring, and stirring was continued again for 20 minutes to prepare an emulsion. The average particle size of the dispersed phase in the obtained emulsion was 10 μm.

Into a reaction vessel with a condenser, 186.5 parts of ion-exchanged water is charged, and the temperature is raised to 70 ° C. Further, 0.25 parts of SFS, 0.0001 part of ferrous sulfate and EDTA0 are added to 5 parts of ion-exchanged water. The mixture prepared by adding .0003 parts was added all at once. The emulsion was dropped into the reaction vessel over 8 minutes while stirring under nitrogen, and then the reaction was continued for 15 minutes to obtain a first innermost layer polymer (IIb-A ₁ ). Incidentally, Tg of the first innermost layer polymer (IIb-A ₁₎ was -48 ° C..

Subsequently, a second monomer mixture consisting of 1.5 parts of MMA, 22.5 parts of BA, 1.0 part of BD and 0.25 part of AMA was added to the reaction vessel over 90 minutes together with 0.016 parts of CHP, and then 60 minutes. The reaction was continued to obtain a second innermost layer polymer (II-A ₂ ). Incidentally, were Tg also -48 ° C. The second outermost layer polymer (II-A _2).

  Subsequently, a third monomer mixture of 6 parts of MMA, 4 parts of BA, 0.075 part of AMA and 0.0125 part of CHP was dropped into the reaction vessel over 45 minutes, and then the reaction was continued for 60 minutes to obtain an intermediate layer polymer (IIb -B) was formed. The intermediate layer polymer (IIb-B) had a Tg of 20 ° C.

  Thereafter, a fourth monomer mixture consisting of 55.2 parts of MMA, 4.8 parts of BA, 0.19 part of nOM and 0.08 part of tBH was dropped into the reaction vessel over 140 minutes, and then the reaction was continued for 60 minutes. The outer layer polymer (IIb-C) was formed to obtain an acrylic resin latex containing the multilayer structure polymer (IIb-a). The scale amount measured after the polymerization was 0.001%, and the mass average particle diameter was 0.12 μm. In addition, Tg of this outermost layer polymer (IIb-C) was 84 degreeC.

  The acrylic resin latex containing the obtained multilayer structure polymer (IIb-a) is poured into an aqueous solution containing 3 parts of calcium acetate, salted out, washed with water, separated and recovered, dried, and powdered. A multilayer structure polymer (IIb-a) was obtained. The gel content of the multilayer structure polymer (IIb-a) was 60%.

b) Production of acrylic resin composition To the multilayer polymer (IIb-a) obtained as described above, an ultraviolet absorber tinuvin 234 (trade name) and a hindered amine light stabilizer Adekastab LA67 (trade name) The mixture shown in Table 2 was mixed using a Henschel mixer. Then, using a φ40 mm twin screw type extruder (L / D = 26), the mixture was melt-kneaded at a cylinder temperature of 200 to 260 ° C. and a die temperature of 250 ° C. and pelletized to obtain an acrylic resin composition pellet. .

c) Manufacture of acrylic resin film The pellet was dried at 80 ° C for a whole day and night, using a φ40 mm non-vent screw type extruder (L / D = 26) equipped with a 300 mmT die, a cylinder temperature of 200 to 240 ° C, and a T die. A film having a thickness of 200 μm was formed at a temperature of 250 ° C.

d) Manufacture of Acrylic Resin Laminate Molded Products The obtained acrylic resin film was subjected to a gravure printing method and subjected to vacuum forming with an injection mold having a vacuum drawing function, and then the film was placed in the same mold as it was In the state, ABS resin “Bulksum TM25B” (trade name) was injection-molded on the printing surface side to obtain an acrylic resin laminated molded product.

  Table 3 shows the evaluation results of the obtained acrylic resin film and the acrylic resin laminated molded product.

(Example 19)
a) Production of multi-layer polymer (IIb-b) After charging 10.8 parts of deionized water in a vessel equipped with a stirrer, 0.3 parts of MMA, 4.5 parts of BA, 0.2 parts of BD, 0.05 parts of AMA And a monomer mixture consisting of 0.025 parts of CHP was added and stirred at room temperature. Next, 1.3 parts of emulsifier XP was added to the vessel while stirring, and stirring was continued again for 20 minutes to prepare an emulsion.

Next, 139.2 parts of deionized water was charged into a polymerization vessel equipped with a condenser, the temperature was raised to 75 ° C., and 0.20 part of SFS, 0.0001 part of ferrous sulfate, A mixture prepared by adding 0.0003 part of EDTA was put into the polymerization vessel all at once. Next, the above emulsion was dropped into the polymerization vessel over 8 minutes while stirring under nitrogen, and then the reaction was continued for 15 minutes to complete the polymerization of the innermost layer polymer (IIb-A ₁ ). Subsequently, a monomer mixture consisting of 9.6 parts of MMA, 14.4 parts of BA, 1.0 part of BD and 0.25 part of AMA was dropped into the polymerization vessel over 90 minutes together with 0.016 part of CHP, and then the reaction was continued for 60 minutes. Thus, a crosslinked rubber elastic body containing a cross-linked elastic polymer (IIb-A ₂ ) was obtained. The Tg of the innermost layer polymer (IIb-A ₁ ) alone and the Tg of the crosslinked elastic polymer (IIb-A ₂ ) alone were −48 ° C. and −10 ° C., respectively.

  Subsequently, a monomer mixture consisting of 6 parts of MMA, 4 parts of MA and 0.075 part of AMA was dropped into the polymerization vessel over 45 minutes together with 0.0125 part of CHP, and then the reaction was continued for 60 minutes to obtain an intermediate layer polymer (IIb- B) was formed. The Tg of the intermediate layer polymer (IIb-B) alone was 60 ° C.

  Next, a monomer mixture consisting of 57 parts of MMA, 3 parts of MA, 0.264 part of nOM and 0.075 part of tBH was dropped into the polymerization vessel over 140 minutes, and then the reaction was continued for 60 minutes to obtain the outermost layer polymer (IIb-C ) To obtain a polymer latex of the multilayer structure polymer (IIb-b). The Tg of the outermost layer polymer (IIb-C) alone was 99 ° C. The average particle size measured after polymerization was 0.11 μm.

  After the coarse particles were removed by filtration using a vibration type filtration device in which the polymer latex of the obtained multilayer structure polymer (IIb-b) was attached to a filter medium with a SUS mesh filter (average opening 62 μm), calcium acetate Salting out was carried out in an aqueous solution containing 3.5 parts, and after washing with water and drying, a powdery multilayer structure polymer (IIb-b) was obtained. The gel content of the multilayer structure polymer (IIb-b) was 70%.

b) Production of acrylic resin composition 100 parts of the multilayer structure polymer (IIb-b) obtained as described above, 0.1 part of ADK STAB AO-60 (manufactured by Asahi Denka Kogyo Co., Ltd .; trade name), UV absorber 3 parts of Tinuvin 234 (trade name) and 0.3 part of a hindered amine light stabilizer Adekastab LA67 (trade name) were mixed using a Henschel mixer. Next, using a φ40 mm twin screw extruder (L / D = 26), the mixture is melt-kneaded at a cylinder temperature of 200 to 260 ° C. and a die temperature of 250 ° C., and pelletized to obtain a pellet made of an acrylic resin composition. It was.

c) Manufacture of acrylic resin film The pellet was dried at 80 ° C for a whole day and night, using a φ40 mm non-vent screw type extruder (L / D = 26) equipped with a 300 mmT die, a cylinder temperature of 200 to 240 ° C, and a T die. A film having a thickness of 200 μm was formed at a temperature of 250 ° C.

d) Manufacture of Acrylic Resin Laminate Molded Products The obtained acrylic resin film was subjected to a gravure printing method and subjected to vacuum forming with an injection mold having a vacuum drawing function, and then the film was placed in the same mold as it was In the state, ABS resin “Bulksum TM25B” (trade name) was injection-molded on the printing surface side to obtain an acrylic resin laminated molded product.

  Table 3 shows the evaluation results of the obtained acrylic resin film and the acrylic resin laminated molded product.

(Examples 20 and 21)
In Example 19, as the acrylic resin, the multilayer polymer (IIb-b) and the thermoplastic polymer (Ic) which is the thermoplastic polymer (I) (MMA / MA copolymer (MMA / MA = 99/1) The reduced viscosity 0.06 liter / g)) was used in the same manner as in Example 19 except that the acrylic resin composition prepared at the ratio shown in Table 2 was used. Obtained. Table 3 shows the evaluation results of the obtained acrylic resin film and the acrylic resin laminated molded product.

(Example 22)
An acrylic resin laminated film and an acrylic resin laminated molded product were obtained in the same manner as in Example 7 except that the acrylic resin film obtained in Example 21 was used. Table 3 shows the evaluation results of the obtained acrylic resin film and the acrylic resin laminated molded product.

(Example 23)
An acrylic resin film and an acrylic resin laminate molded product were obtained in the same manner as in Example 8, except that the acrylic resin film obtained in Example 21 was used. Table 3 shows the evaluation results of the obtained acrylic resin film and the acrylic resin laminated molded product.

  In addition, when the wood pattern was given to the obtained acrylic resin film by the gravure printing method as a decoration layer, there were few printing omissions and it was favorable.

(Example 24)
A photocurable acrylic resin film and an acrylic resin laminate molded product were obtained in the same manner as in Example 9, except that the acrylic resin film obtained in Example 23 was used. Table 4 shows the evaluation results of the obtained photocurable acrylic resin film and the acrylic resin laminated molded product.

  In addition, when this photocurable acrylic resin film was given a wood grain pattern as a decorative layer by a gravure printing method, printing omission was small and good.

(Comparative Example 1)
In Example 2, an acrylic resin film and an acrylic resin were used in the same manner as in Example 2 except that an acrylic resin composition prepared using 2 parts of Adeka Stub LA31 (trade name, melting point 195 ° C.) was used as the ultraviolet absorber. A laminated molded product was obtained. Table 3 shows the evaluation results of the obtained acrylic resin film and the acrylic resin laminated molded product.

  Even when a hindered amine light stabilizer is added, it is understood that the use of an ultraviolet absorber having a melting point exceeding 180 ° C. results in poor fragrance resistance.

(Comparative Example 2)
In Example 18, an acrylic resin film and an acrylic resin laminate molded article were prepared in the same manner as in Example 18 except that an acrylic resin composition prepared using 2 parts of Adeka Stub LA31 (trade name) was used as the ultraviolet absorber. Obtained. Table 3 shows the evaluation results of the obtained acrylic resin film and the acrylic resin laminated molded product.

  Even when a hindered amine light stabilizer is added, it can be seen that if an ultraviolet absorber having a melting point exceeding 180 ° C. is used, the fragrance resistance, the hairstyling resistance (whitening), and the heat aging resistance are poor.

(Comparative Example 3)
In Comparative Example 1, an acrylic resin film and an acrylic resin laminated molded article were obtained in the same manner as in Comparative Example 1, except that an acrylic resin composition prepared without adding a hindered amine light stabilizer was used. Table 3 shows the evaluation results of the obtained acrylic resin film and the acrylic resin laminated molded product.

  It can be seen that when an ultraviolet absorber having a melting point exceeding 180 ° C. is used without adding a hindered amine light stabilizer, the fragrance resistance and hair-styling resistance (unevenness) are poor.

(Comparative Example 4)
In Comparative Example 2, an acrylic resin film and an acrylic resin laminated molded article were obtained in the same manner as in Comparative Example 2, except that an acrylic resin composition prepared without adding a hindered amine light stabilizer was used. Table 3 shows the evaluation results of the obtained acrylic resin film and the acrylic resin laminated molded product.

  It can be seen that when an ultraviolet absorber having a melting point exceeding 180 ° C. is used without adding a hindered amine light stabilizer, the fragrance resistance, hair-styling resistance (whitening, unevenness), and heat aging resistance are all poor. .

(Comparative Example 5)
In Example 2, an acrylic resin film and an acrylic resin laminated molded product were obtained in the same manner as in Example 2 except that an acrylic resin composition prepared without adding a hindered amine light stabilizer was used. Table 3 shows the evaluation results of the obtained acrylic resin film and the acrylic resin laminated molded product.

  Even when an ultraviolet absorber having a melting point of 180 ° C. or lower is used, it can be seen that the hair-styling resistance (unevenness) is poor unless a hindered amine light stabilizer is added.

(Comparative Example 6)
In Example 18, an acrylic resin film and an acrylic resin laminated molded article were obtained in the same manner as in Example 18 except that an acrylic resin composition prepared without adding a hindered amine light stabilizer was used. Table 3 shows the evaluation results of the obtained acrylic resin film and the acrylic resin laminated molded product.

  Even when an ultraviolet absorber having a melting point of 180 ° C. or lower is used, it can be seen that the hair-styling resistance (unevenness) is poor unless a hindered amine light stabilizer is added.

Claims (8)

  Acrylic resin composition comprising a hindered amine light stabilizer and an ultraviolet absorber having a melting point of 180 ° C. or lower   The acrylic resin comprises (A) 50 to 100% by weight of methacrylic acid alkyl ester, 50 to 0% by weight of acrylic acid alkyl ester, and 0 to 49% by weight of monomer copolymerizable with these esters. 0.9 to 94.5 parts by mass of a thermoplastic polymer (I) in which 0.1 g of the compound is dissolved in 100 ml of chloroform and measured at 25 ° C. is 0.5 liter / g or less, and mainly contains at least alkyl acrylate. 1 to 99 parts by mass of a multilayer structure polymer (II) composed of a polymer layer as a component and an outermost polymer layer mainly composed of an alkyl methacrylate, and 50 to 100% by mass of methyl methacrylate and methyl methacrylate. It consists of 50 to 0% by mass of a polymerizable monomer, and has a reduced viscosity (measured at 25 ° C. by dissolving 0.1 g of a polymer in 100 ml of chloroform). 1 to 10 parts by weight of thermoplastic polymer (III) exceeding 1 liter / g, or (B) a polymer layer mainly comprising at least an alkyl acrylate ester and an outermost layer mainly comprising an alkyl methacrylate ester It is composed of 90 to 100 parts by mass of a multilayer structure polymer (II) comprising a polymer layer, 50 to 100% by mass of methyl methacrylate and 50 to 0% by mass of a monomer copolymerizable with methyl methacrylate, and reduced viscosity (heavy 0.1 g of the polymer is dissolved in 100 ml of chloroform and measured at 25 ° C., and consists of 0 to 10 parts by mass of the thermoplastic polymer (III) exceeding 0.5 l / g (however, the polymers (I) to (III)) The acrylic resin composition according to claim 1, wherein the total is 100 parts by mass.   An acrylic resin film comprising the acrylic resin composition according to claim 1.   The acrylic resin film which has a decoration layer on the single side | surface of the acrylic resin film of Claim 3.   The acrylic resin laminated film which has an acrylic resin film of Claim 3 or 4.   An acrylic resin laminated molded article, wherein the acrylic resin film according to claim 3 or 4 or the acrylic resin laminated film according to claim 5 is laminated on a substrate.   The acrylic resin film according to claim 3 or 4 or the acrylic resin laminated film according to claim 5 is subjected to vacuum molding or pressure molding in an injection mold, and then a resin serving as a base material in the same mold. The acrylic resin laminate molded article according to claim 6, which is obtained by injection molding and integrating the film and the substrate.   The acrylic resin film according to claim 3 or 4 or the acrylic resin laminated film according to claim 5 is subjected to vacuum forming or pressure forming, and then inserted into an injection mold to inject a resin as a base material. The acrylic resin laminate molded article according to claim 6, which is obtained by integrating the film and the substrate.