JP2006299038A - Acrylic resin film and laminated molded product obtained by laminating the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acrylic resin film having surface hardness, scratch resistance and heat resistance that can be used for insert molding and in-mold molding, and has good printability and good design properties. To do.
SOLUTION: An acrylic resin composition (A) comprising a rubber-containing polymer (I) and a thermoplastic polymer (II) having a reduced viscosity of 0.15 L / g or less of a polymer mainly composed of alkyl methacrylate. ) The refractive index of the thermoplastic polymer (II) at 20 ° C. with the acrylic resin composition (B) added with 0.5 to 50 parts by mass of the core-shell polymer (III) to 100 parts by mass An acrylic resin film in which the refractive index (n ′) of the core layer polymer (III-A) of n) and the core-shell polymer (III) satisfies the formula (i).
Formula (i): 0 ≦ | n−n ′ | ≦ 0.003
[Selection figure] None

Description

  The present invention relates to an acrylic resin film and a laminated molded product obtained by laminating the acrylic resin film. In particular, the present invention relates to an acrylic resin film suitable for imparting design properties to a molded article by in-mold molding after performing decoration such as printing, and a laminated molded article obtained by laminating the acrylic resin film.

  There are an insert molding method and an in-mold molding method as methods for imparting design properties to a molded product at low cost. In the insert molding method, a film or sheet of polyester resin, polycarbonate resin, acrylic resin or the like that has been decorated for printing or the like is previously formed into a three-dimensional shape by vacuum forming or the like, and unnecessary film or sheet portions are removed. Thereafter, the molded product is transferred into an injection molding die, and an integrated molded product is obtained by injection molding a resin as a base material. On the other hand, the in-mold molding method uses a polyester resin, polycarbonate resin, acrylic resin sheet or film that has been decorated for printing, etc., placed in an injection mold, vacuum molded, and the same mold A molded product integrated by injection molding of a resin as a base material is obtained.

  In particular, according to this in-mold molding method, the sheet or film and the base material can be integrated with high productivity, or only the printing part can be transferred. The member having an acrylic resin film on the surface layer thus obtained is used as a component for vehicle use.

  In recent years, it has been required to add a design and decoration such as a high-class feeling and a deep feeling by making the surface of an acrylic resin film subjected to high-luminance printing such as metallic to a matte state. Such a request can be realized by printing on a matte acrylic resin film.

  Conventional matting methods for thermoplastic resins can be broadly divided into (1) a patterning process and a matting process, and (2) a method of adding an inorganic or organic matting material. Although the method (1) generally has the advantage that the physical properties are hardly lowered, the productivity is poor, the processing cost is increased, and the matting effect is insufficient. In many cases, the film is heated by secondary processing. However, there is a problem that the gloss is lost and the matting effect disappears, which is not suitable for the application. On the other hand, the method (2) can control the degree of matting without reducing the productivity so much, and can be applied to the application of secondary processing. Contains a problem.

  Therefore, in order to solve such problems, resin compositions containing a matting material having a sufficient matting effect are disclosed (for example, see Patent Documents 1 to 4).

On the other hand, unlike the matte effect, acrylic resin compositions containing organic particles are known in order to improve the scattered light scattering property (see, for example, Patent Documents 5 and 6).
JP 2000-53841 A JP 11-335511 A JP 2001-81266 A JP 2002-254495 A Japanese Patent Publication No. 7-37579 Japanese Patent Laid-Open No. 2001-294631

  These Patent Documents 1 to 6 disclose a resin composition, a film-like or sheet-like resin composition or a molded product containing a core-shell polymer as a matting agent or scattering particles.

  Among these, Patent Documents 5 and 6 disclose light-scattering resin compositions, and there is a clear difference between the refractive index of the core layer polymer of the core-shell polymer and the refractive index of the thermoplastic polymer serving as the matrix resin. The light scattering property is expressed by the presence of. Patent Document 5 is characterized in that the refractive index difference is within ± 0.05 unit and is not closer than ± 0.003. In Patent Document 6, the absolute value of the difference is 0.01 or more and 0.1 or less. It is described that it is preferable. However, these publications do not assume that the molded product is printed. As defined in these publications, the core layer polymer of the core-shell polymer and the thermoplastic polymer that becomes the matrix resin. When there is a clear difference in refractive index between the two, the internal haze when formed into a film or sheet is prominent. After printing on one side of the film or sheet resin composition, in-mold When molding or the like is performed, the design of the printed layer is impaired, and the industrial utility value is lowered.

  On the other hand, Patent Documents 1 to 4 do not describe the difference between the refractive index of the core layer polymer of the core-shell polymer and the refractive index of the thermoplastic polymer serving as the matrix resin. When the film-like or sheet-like resin composition described in the examples of this publication was actually prepared, the internal haze was high. In addition, when it calculates with the refractive index calculation method mentioned later, the resin composition described in any Example will also exceed 0.003.

  Further, these publications do not describe in-mold molding of the obtained film, and do not describe surface hardness, scratch resistance, and heat resistance. For this reason, when the present inventors performed in-mold molding using the film or sheet-shaped resin composition described in the examples of these publications, scratches occurred during the molding process. Appearance defect due to. Further, the surface hardness, scratch resistance, and heat resistance of the laminated molded product obtained by laminating these films or sheets did not reach the level required for vehicle use.

  In addition, Patent Documents 1 and 2 do not describe that the obtained film-like or sheet-like resin composition or molded product is subjected to printing.

  Accordingly, an object of the present invention is to have surface hardness, scratch resistance and heat resistance that can be used for insert molding and in-mold molding, and has good printability and good design properties. An object of the present invention is to provide an acrylic resin film and a laminated molded product obtained by laminating this film.

  The above object of the present invention can be solved by the following present invention.

[1] An acrylic resin composition comprising a rubber-containing polymer (I) shown below and a thermoplastic polymer (II) having a reduced viscosity of 0.15 L / g or less of a polymer mainly composed of alkyl methacrylate. (A) The acrylic resin composition (B) formed by adding 0.5 to 50 parts by mass of the core-shell polymer (III) shown below with respect to 100 parts by mass is a constituent component, and a thermoplastic polymer at 20 ° C. ( An acrylic resin film in which the refractive index (n) of II) and the refractive index (n ′) of the core layer polymer (III-A) of the core-shell polymer (III) satisfy the following formula (i).
Rubber-containing polymer (I):
In the presence of an elastic polymer (IA) as an innermost layer having a structure of one layer or two or more layers obtained by using an alkyl acrylate ester as a main component, at least a single component having an alkyl methacrylate ester as a main component A multilayer structure of two or more layers having a mass average particle diameter of 0.01 to 0.5 μm, which is obtained by molding the outermost layer polymer (IC) having a structure of one layer or two or more layers by graft polymerization of the body Rubber-containing polymer having a core-shell polymer (III):
The core layer polymer (III-A) and the shell layer polymer (III-B) are laminated in this order, and each polymer layer is composed of the monomer components shown below. (1) Monomer component for constituting the core layer polymer (III-A) (III-A1) alkyl acrylate ester 10 to 90% by mass
(III-A2) Methacrylic acid alkyl ester 10 to 90% by mass
(III-A3) Other monomer having copolymerizable double bond 0 to 50% by mass
(III-A4) Polyfunctional monomer 0 to 20% by mass
(III-A5) Graft crossing agent 0.1-20% by mass
Content of core layer polymer (III-A) in core-shell polymer (III) 25-85 mass%
(2) Monomer component for constituting shell layer polymer (III-B) (III-B1) Methacrylic acid alkyl ester 60-100% by mass
(III-B2) Acrylic acid alkyl ester 0 to 40% by mass
(III-B3) Other monomer having copolymerizable double bond 0 to 40% by mass
Content of shell layer polymer (III-B) in core-shell polymer (III) 15 to 75% by mass
Formula (i):
0 ≦ | n−n ′ | ≦ 0.003

[2] The acrylic resin film according to [1], which is produced by melt-extruding the resin composition and then forming a film by sandwiching the film with a mirror roll and a rubber roll or a textured roll.
[3] The acrylic resin film according to [2], wherein printing is performed on one side of the acrylic resin film.
[4] An acrylic resin laminated molded product obtained by laminating the acrylic resin film according to any one of [1] to [3] on a base material.

  According to the present invention, a specific rubber-containing polymer (I) and 100 parts by mass of an acrylic resin composition (A) composed of a thermoplastic polymer (II) mainly composed of a methacrylic acid alkyl ester are 20 ° C. The core-shell weight satisfying that the refractive index (n) of the thermoplastic polymer (II) and the refractive index (n ′) of the core-layer polymer (III-A) of the core-shell polymer (III) are within a specific range. Surface hardness that can be used for insert molding and in-mold molding by adopting an acrylic resin film comprising the acrylic resin composition (B) formed by adding 0.5 to 50 parts by mass of coalescence (III) Further, it is possible to provide an acrylic resin film having scratch resistance, heat resistance, good printability, and good design properties, and a laminated molded product obtained by laminating this film.

  The acrylic resin film of the present invention is composed of a rubber-containing polymer (I) and a thermoplastic polymer (II) (hereinafter, also simply referred to as “thermoplastic polymer (II)”) mainly composed of alkyl methacrylate. It is comprised from the alkyl resin composition (B) formed by adding 0.5-50 mass parts of core-shell polymers (III) with respect to 100 mass parts of acrylic resin compositions (A).

  The rubber-containing polymer (I) used in the present invention is in the presence of the elastic polymer (IA) as an innermost layer having a structure of one layer or two or more layers obtained mainly from an acrylic acid alkyl ester. , A multilayer structure of two or more layers formed by graft polymerization of a monomer having at least an alkyl methacrylate ester as a main component to form an outermost layer polymer (IC) having a structure of one layer or two or more layers It is a rubber-containing polymer having

  Specifically, it is a rubber-containing polymer (I) [(I ′) or (I ″)] shown below. In the present invention, “rubber” indicates rubber elasticity at room temperature (25 ° C.). It means a polymer, specifically a polymer having a glass transition temperature (Tg) of less than 25 ° C, more preferably 10 ° C or less, and most preferably 0 ° C or less. Tg can be calculated from the FOX equation using the values described in Polymer HandBook (Polymer HandBook (J. Brandrup, Interscience, 1989)).

<< Rubber-containing polymer (I ') >>
Examples of the alkyl acrylate used in the innermost layer polymer (I′-A) include various conventionally known alkyl acrylates. Specific examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. Of these, n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferable. This alkyl acrylate is used as a main component of the monomers constituting the innermost layer polymer (I′-A). Specifically, the usage amount of the acrylic acid alkyl ester is preferably 35 to 99.9% by mass in all monomers. When the amount used is 35% by mass or more, the obtained resin becomes an elastic body, and the moldability of the film becomes good. Furthermore, the preferable usage-amount is 50 mass% or more. When the innermost layer polymer (I′-A) has a structure of two or more layers, the ranges of these usage amounts are the use of the acrylic acid alkyl ester as a whole of the innermost layer polymer (I′-A). It shows the amount. Further, the innermost layer polymer (I′-A) can also have a hard core structure, and in this case, even if the amount of the first layer (core) alkyl acrylate is less than 35% by mass, Good. At this time, for example, the Tg of the first layer (core part) is preferably 105 ° C. or lower, and more preferably 25 ° C. or lower. The Tg of the second layer is less than 25 ° C., more preferably 10 ° C. or less, most preferably 0 ° C. or less, and particularly preferably less than −30 ° C.

  As a monomer constituting the innermost layer polymer (I′-A), an acrylic acid alkyl ester and another vinyl monomer copolymerizable therewith can be used. When other vinyl monomers are used, the amount used is preferably 64.9% by mass or less based on the total monomers. Other vinyl monomers include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, methacrylic acid alkyl esters such as cyclohexyl methacrylate, lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, and acrylic acid. Acrylic monomers such as methacrylic acid, styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile and the like are preferable. These can be used individually by 1 type or in combination of 2 or more types.

  A polyfunctional monomer is preferably used as a part of the monomer constituting the innermost layer polymer (I′-A). As the polyfunctional monomer, for example, alkylene glycol dimethacrylate such as ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and propylene glycol dimethacrylate is preferably used. In addition, polyvinyl benzene such as divinylbenzene and trivinylbenzene, triallyl cyanurate, triallyl isocyanurate, and the like can also be used. These can be used individually by 1 type or in combination of 2 or more types. The amount of the polyfunctional monomer used is preferably 0.1 to 10% by mass in the total monomers.

  In the presence of the innermost layer polymer (I′-A) described above, the rubber-containing polymer (I ′) is graft-polymerized with a monomer having a methacrylic acid alkyl ester as a main component to form an outermost layer polymer ( I′-C) is a rubber-containing polymer having a multilayer structure of two or more layers. That is, the innermost layer polymer (I′-A) constitutes the inner layer, and the outermost layer polymer (I′-C) constitutes the outer layer.

  Although not particularly limited, it is preferable that the polymer having only the monomer component for constituting the outermost layer polymer (I′-C) has a Tg of 60 ° C. or higher. A Tg of 60 ° C. or higher is preferable because a film having surface hardness and heat resistance suitable for vehicle use can be obtained. More preferably, it is 80 degreeC or more, Most preferably, it is 90 degreeC or more. Further, from the viewpoint of coagulability and handleability of the resulting rubber-containing polymer (I ′), 105 ° C. or lower is preferable.

  In the graft polymerization for obtaining the outermost layer polymer (I′-C), methacrylic acid alkyl ester is used as a main component. Specifically, the amount of methacrylic acid alkyl ester used is preferably 50% by mass or more based on the total amount of monomers used for graft polymerization. Examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate and the like. Of these, methyl methacrylate is preferred.

  As the monomer used for the graft polymerization for obtaining the outermost layer polymer (I'-C), together with the alkyl methacrylate, other vinyl monomers copolymerizable therewith can also be used. When other vinyl monomers are used, the amount used is preferably 50% by mass or less based on the total monomers. Examples of other vinyl monomers include acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, and cyclohexyl acrylate. Preferred are acrylic monomers such as lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid and methacrylic acid, styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile and the like. These 1 type can be used individually or in combination of 2 or more types.

  By graft-polymerizing each of these monomers in one or more stages in the presence of the innermost layer polymer (I′-A), the outermost layer polymer (I′-C) as the outer layer is formed, A rubber-containing polymer (I ′) is obtained. The amount of the outermost layer polymer (I′-C) in the rubber-containing polymer (I ′) is preferably 10 to 400 parts by mass with respect to 100 parts by mass of the innermost layer polymer (I′-A). Preferably it is 20-200 mass parts.

  The rubber-containing polymer (I ′) has a mass average particle diameter of 0.01 to 0.5 μm. 0.08 to 0.3 μm is more preferable. In particular, from the viewpoint of film formability, the particle diameter is preferably 0.08 μm or more. The mass average particle diameter can be measured by a dynamic light scattering method using a light scattering photometer “DLS-700” (trade name) manufactured by Otsuka Electronics Co., Ltd.

  Next, a method for producing the rubber-containing polymer (I ′) will be described.

  As the method for producing the rubber-containing polymer (I ′), 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 It can also be carried out by an emulsion suspension polymerization method in which the polymer (I′-C) is converted to a suspension polymerization system at the time of polymerization.

  As the emulsifier used in the emulsion polymerization, 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 dodecylbenzene sulfonate, sodium alkyldiphenyl ether disulfonate, etc., polyoxyethylene alkylphenyl ether sodium phosphate phosphate, etc., polyoxyethylene alkyl ether phosphate Examples thereof include sodium phosphate-based aliphatic ester salts. Of these, in particular, polyoxyethylene alkyl ether sodium phosphate phosphates and the like are preferable.

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

  On the other hand, the polymerization initiator used for forming the innermost layer polymer (I′-A) and the outermost layer polymer (I′-C) constituting the preferred rubber-containing polymer (I ′) of the present invention is known. As the addition method, 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, ethylenediaminetetraacetic acid disodium salt, longalite, and hydroperoxide is particularly preferable.

  A monomer component that gives the innermost layer polymer (I′-A) described above mixed with a surfactant is supplied to the reactor and polymerized, and then the outermost layer polymer (I′-C). In the method of polymerizing by supplying the monomer component to give a reactor, the aqueous solution containing ferrous sulfate, ethylenediaminetetraacetic acid disodium salt and Rongalite is heated to the polymerization temperature, and then the prepared emulsion is reacted. A method of supplying a monomer component to give an outermost layer polymer (I′-C) containing a polymerization initiator such as a peroxide to the reactor and polymerizing the monomer component is provided in the present invention. The most preferable method for obtaining the rubber-containing polymer (I ′).

  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 preferred rubber-containing polymer (I ′) obtained by the above method can be treated using a filtration apparatus provided with a filter medium, if necessary. This filtration treatment is for removing scales generated during the polymerization from the latex, or for removing contaminants from the polymerization raw material and from the outside during the polymerization. The rubber-containing polymer (I ′) is removed. This is a more preferred method to obtain.

  The rubber-containing polymer (I ′) can be produced by recovering from the polymer latex produced by the above-described method. The method for recovering the rubber-containing polymer (I ′) 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. The

  Among these, when salting out using a metal salt, the residual metal content in the finally obtained rubber-containing polymer (I ′) 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, the final rubber-containing polymer (I ′ When an acrylic resin film having a raw material as a raw material 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.

<< Rubber-containing polymer (I ") >>
The rubber-containing polymer (I ″) has an innermost layer polymer (I ″ -A), an intermediate layer polymer (I ″ -B), and an outermost layer polymer (I ″ -C) in the order from the inner side. It has a multilayer structure.

  Below, the structure of the above-mentioned rubber-containing polymer (I ″) will be specifically described.

[Innermost layer polymer (I "-A)]
The innermost layer polymer (I ″ -A) constitutes the central portion of the polymer having the multilayer structure, and includes an alkyl acrylate ester (I ″ -A1) and an alkyl methacrylate ester (I ″ -A2). ), Other monomers having a double bond copolymerizable therewith (I ″ -A3), multifunctional monomer (I ″ -A4) and graft crossing agent (I ″ -A5) Is a polymer obtained by polymerizing the monomer component. In this monomer component, component (I ″ -A1) and component (I ″ -A5) are essential components, and component (I ″ -A2), component (I ″ -A3) and component (I ″) -A4) is an optional component.

  The alkyl acrylate ester of the component (I ″ -A1) contained in the monomer component for constituting the innermost layer polymer (I ″ -A) may be either linear or branched alkyl groups. good. 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 methacrylic acid alkyl ester of the component (I ″ -A2), which is included in the monomer component for constituting the innermost layer polymer (I ″ -A) as necessary, has a linear or branched alkyl group. Any of those. 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 other monomer having a copolymerizable double bond of the component (I ″ -A3) included as necessary in the monomer component for constituting the innermost layer polymer (I ″ -A), Acrylic monomers such as lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid and methacrylic acid, styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile and the like can be used. These can be used alone or in admixture of two or more.

  The polyfunctional monomer of the component (I ″ -A4) included as necessary in the monomer component for constituting the innermost layer polymer (I ″ -A) has the same degree of copolymerizability. A monomer having two or more double bonds in one molecule is defined. 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, polyvinyl benzene such as divinylbenzene and trivinylbenzene, triallyl cyanurate, triallyl isocyanurate, and the like can also be used. These can be used alone or in admixture of two or more. Of these, 1,3-butylene glycol dimethacrylate is preferred. Even when the polyfunctional monomer does not act at all, as long as the graft crossing agent (I ″ -A5) is present, a fairly stable rubber-containing polymer (I ″) 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 (I ″ -A5) contained in the monomer component for constituting the innermost layer polymer (I ″ -A) basically has a different copolymerizable double bond as one molecule. It is defined as a monomer having two or more. 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. Graft-crossing agent (I ″ -A5) is polymerized mainly because the conjugated unsaturated bond of its ester reacts much faster than allyl, methallyl or crotyl groups. During this time, allyl, methallyl or crotyl groups are polymerized. In addition, a substantial part of the polyfunctional monomer, which works effectively during the polymerization of the polymer of the next layer and gives a graft bond between adjacent two layers, is a triaryl cyanurate, a triallyl isocyanurate of the above-mentioned polyfunctional monomer. In the present invention, when the above-exemplified graft crossing agent (I ″ -A5) is not used and instead these cyanurate derivatives effectively act as graft crossing agents, these cyanurate derivatives Is regarded as a graft crossing agent (I ″ -A5).

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

  In the monomer component for constituting the innermost layer polymer (I ″ -A), the total content of the acrylic acid alkyl ester (I ″ -A1) and the methacrylic acid alkyl ester (I ″ -A2) is: 80-99.9 mass% is preferable.

  The content of the acrylic acid alkyl ester (I ″ -A1) in the monomer component for constituting the innermost layer polymer (I ″ -A) is preferably 50 to 99.9% by mass. From the viewpoint of resistance to molding whitening of the resulting acrylic resin film, decorated acrylic resin film and laminate, 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 obtained acrylic resin film, a decorative acrylic resin film, and a laminated body, 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 (I ″ -A2) in the monomer component for constituting the innermost layer polymer (I ″ -A) is preferably 0 to 49.9% by mass. From the viewpoint of the surface hardness of the obtained acrylic resin film, decorated acrylic resin film and laminate, it is more preferably 20% by mass or more, and most preferably 30% by mass or more. Moreover, from a viewpoint of the shaping | molding whitening resistance of the obtained acrylic resin film, a decorative acrylic resin film, and a laminated body, More preferably, it is 44.9 mass% or less, Most preferably, it is 39.9 mass% or less.

  The content of the other monomer (I ″ -A3) having a copolymerizable double bond in the monomer component for constituting the innermost layer polymer (I ″ -A) is 0 to 20 mass. % Is preferred. More preferably, it is 15 mass% or less.

  The content of the polyfunctional monomer (I ″ -A4) in the monomer component for constituting the innermost layer polymer (I ″ -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 (I ″ -A5) in the monomer component for constituting the innermost layer polymer (I ″ -A) is preferably 0.1 to 10% by mass. When the content is 0.1% by mass or more, the resulting rubber-containing polymer (I ″) can be molded without deteriorating optical properties such as transparency. The content is 10% by mass or less. Then, since sufficient softness | flexibility and toughness can be provided to rubber-containing polymer (I ''), it is preferable. 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 (I ″ -A) alone is an intermediate described later from the viewpoint of impact resistance and molding whitening resistance of the resulting acrylic resin film, decorative acrylic resin film, and laminate. The layer polymer (I ″ -B) is preferably less than Tg 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 (I ″ -A) in the rubber-containing polymer (I ″) is preferably 15 to 50% by mass. When the content is 15% by mass or more, the resulting acrylic resin film, the decorative acrylic resin film and the laminate can be imparted with resistance to molding whitening, and further, the film-forming property obtained when the acrylic resin is formed into a film shape can be obtained. The toughness that can be used for insert molding and in-mold molding of the acrylic resin film and the decorated acrylic resin film can be made compatible. 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 (I ″ -A) may be a single layer or multiple layers, but is preferably two layers. Although not particularly limited, the innermost layer polymer (I ″ -A) is not limited to two layers. It is preferable that the monomer composition ratios are different.

When the innermost layer polymer (I ″ -A) is composed of two layers, the Tg of the inner layer (I ″ -A ₁ ) and the Tg of the outer layer (I ″ -A ₂ ) may be the same, but are obtained. From the viewpoint of molding whitening resistance, impact resistance, and surface hardness of the acrylic resin film, decorative acrylic resin film and laminate, the Tg of the inner layer (I ″ -A ₁ ) is the outer layer (I ″ -A ₂ ). In particular, from the viewpoint of molding whitening resistance and impact resistance of the resulting acrylic resin film, decorative acrylic resin film, and laminate, the inner layer (I ″ -A ₁ ) Tg is preferably less than −30 ° C., and Tg of the outer layer (I ″ -A ₂ ) is preferably 10 ° C. or less. In particular, from the viewpoint of surface hardness, Tg of the outer layer (I ″ -A ₂ ) is −15. C. or higher is preferable. At this time, from the viewpoint of the surface hardness to be obtained, the content of the inner layer (I ″ -A ₁ ) in the innermost layer polymer (I ″ -A) is preferably 1% by mass or more and 20% by mass or less. The content of (I ″ -A ₂ ) is preferably 80% by mass or more and 99% by mass or less.

[Interlayer polymer (I "-B)]
In the presence of the innermost layer polymer (I ″ -A), the intermediate layer polymer (I ″ -B) is an acrylic acid alkyl ester (I ″ -B1), a methacrylic acid alkyl ester (I ″ -B2), Other monomer (I ″ -B3) having a double bond copolymerizable with these, polyfunctional monomer (I ″ -B4) and graft crossing agent (I ″ -B5) A polymer obtained by polymerizing a monomer component, preferably a polymer in which the Tg of the polymer in the monomer component here is higher than the Tg of the innermost layer polymer. In the monomer component, the component (I ″ -B1), the component (I ″ -B2), and the component (I ″ -B5) are essential components, and the component (I ″ -B3) and the component (I ″ -B4) are It is an optional component.

  The alkyl acrylate ester of the component (I ″ -B1) contained in the monomer component for constituting the intermediate layer polymer (I ″ -B) may be either linear or branched alkyl groups. good. 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 methacrylic acid alkyl ester of the component (I ″ -B2) contained in the monomer component for constituting the intermediate layer polymer (I ″ -B) may be either linear or branched alkyl groups. good. 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 other monomer having a copolymerizable double bond of the component (I ″ -B3) included in the monomer component for constituting the intermediate layer polymer (I ″ -B) as necessary, Acrylic monomers such as lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid and methacrylic acid, styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile and the like can be used. These can be used alone or in admixture of two or more.

  The polyfunctional monomer of the component (I ″ -B4) included as necessary in the monomer component for constituting the intermediate layer polymer (I ″ -B) is ethylene glycol dimethacrylate, 1, 3 -It is preferable to use alkylene glycol dimethacrylates such as butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and propylene glycol dimethacrylate. In addition, polyvinyl benzene such as divinylbenzene and trivinylbenzene, triallyl cyanurate, triallyl isocyanurate, and the like can also be used. Of these, 1,3-butylene glycol dimethacrylate is preferred. These can be used alone or in admixture of two or more.

  Even when the polyfunctional monomer does not act at all, as long as the graft crossing agent is present, a fairly stable rubber-containing polymer (I ″) is obtained. For example, when the hot strength or the like is strictly required, What is necessary is just to carry out arbitrarily according to the addition purpose.

  Examples of the graft crossing agent (I ″ -B5) contained in the monomer component for constituting the intermediate layer polymer (I ″ -B) include copolymerizable α, β-unsaturated carboxylic acid or dicarboxylic acid. Examples include allyl, methallyl, or crotyl ester. 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. Graft-crossing agent (I ″ -B5) mainly reacts and bonds chemically with the conjugated unsaturated bond of its ester much faster than allyl group, methallyl group, or crotyl group. During this time, allyl group, methallyl group, Alternatively, a substantial portion of the crotyl group works effectively during the polymerization of the next layer polymer to provide a graft bond between the adjacent two layers, and other polyfunctional monomers such as triallyl cyanurate and triallyl. Isocyanurate and the like are also effective as a graft crossing agent. In the present invention, when the above-exemplified graft crossing agent (I ″ -B5) is not used and these cyanurate derivatives effectively act as a graft crossing agent instead, Cyanurate derivatives are considered as grafting agents (I ″ -B5).

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

  The total content of the acrylic acid alkyl ester (I ″ -B1) and the methacrylic acid alkyl ester (I ″ -B2) in the monomer component for constituting the intermediate layer polymer (I ″ -B) is: 19.8-99.9 mass% is preferable.

  The content of the acrylic acid alkyl ester (I ″ -B1) in the monomer component for constituting the intermediate layer polymer (I ″ -B) is preferably 9.9 to 90 mass%. From the viewpoints of molding whitening resistance, surface hardness, heat resistance, etc. of the obtained acrylic resin film, decorative acrylic resin film and laminate, more preferably 19.9% by mass or more, most preferably 29.9% by mass or more. is there. Further, it is more preferably 60% by mass or less, and most preferably 50% by mass or less.

  The content of the alkyl methacrylate (I ″ -B2) in the monomer component for constituting the intermediate layer polymer (I ″ -B) is preferably 9.9 to 90 mass%. From the viewpoint of molding whitening resistance, surface hardness, heat resistance, etc. of the obtained acrylic resin film, decorative acrylic resin film and laminate, more preferably 39.9% by mass or more, most preferably 49.9% by mass or more. is there. Further, it is more preferably 80% by mass or less, and most preferably 70% by mass or less.

  The content of the other monomer (I ″ -B3) having a copolymerizable double bond in the monomer component for constituting the intermediate layer polymer (I ″ -B) is 0 to 20 mass. % Is preferred. More preferably, it is 15 mass% or less.

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

  The content of the graft crossing agent (I ″ -B5) in the monomer component for constituting the intermediate layer polymer (I ″ -B) is preferably 0.1 to 10% by mass. When the content is 0.1% by mass or more, the obtained rubber-containing polymer (I ″) can be molded without deteriorating the optical properties. When the content is 5% by mass or less, the rubber-containing polymer is contained. It is preferable because sufficient flexibility and toughness can be imparted to the polymer (I ″). More preferably, it is 0.5 mass% or more and 2 mass% or less.

  Here, the composition of the intermediate layer polymer (I ″ -B) is preferably different from the composition of the innermost layer polymer (I ″ -A). By different compositions of these polymers, the impact resistance and molding whitening resistance of the resulting acrylic resin film, decorated acrylic resin film and laminate 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 component constituting the intermediate layer polymer (I ″ -B) is 25 to 100 ° C. The Tg is 25. When the temperature is higher than or equal to ° C., the surface hardness and heat resistance are at the level required for vehicle use, more preferably higher than or equal to 40 ° C., and most preferably higher than or equal to 50 ° C. When the Tg is lower than or equal to 100 ° C. Further, the whitening resistance of the decorative acrylic resin film and the laminate is good, and the film-forming property when the acrylic resin is formed into a film is good, more preferably 80 ° C. or less, most preferably 70 ° C. or less. .

  Thus, by providing an intermediate layer polymer (I ″ -B) having a specific composition and Tg, a rubber-containing polymer (I ″) or resin suitable for satisfying the required physical properties has been designed. It was difficult to realize because of the absence, and it was possible to achieve both the whitening resistance, surface hardness, heat resistance, and the like of the resulting acrylic resin film, decorative acrylic resin film, and laminate.

  Although not particularly limited, the content of the intermediate layer polymer (I ″ -B) in the preferred rubber-containing polymer (I ″) is preferably 5 to 35% by mass. If it is within this range, an intermediate layer polymer (I ″ -B) important for achieving both molding whitening resistance, surface hardness, heat resistance and the like of the resulting acrylic resin film, decorative acrylic resin film and laminate. ) And other physical properties of the resulting film, for example, film forming properties when an acrylic resin is formed into a film, insert molding of the resulting acrylic resin film and decorative acrylic resin film, and It is preferable because the toughness possible for in-mold molding can be imparted, and more preferably 20% by mass or less.

[Outermost layer polymer (I "-C)]
In the presence of the polymer formed up to the intermediate layer, the outermost layer polymer (I ″ -C) is a methacrylic acid alkyl ester (I ″ -C1), an acrylic acid alkyl ester (I ″ -C2), and these It is formed by graft polymerization of a monomer component having as a constituent component another monomer (I ″ -C3) having a double bond copolymerizable with the monomer. The outermost layer polymer (I ″ -C) can be obtained by polymerization in at least one stage and can have a structure of one layer or two or more layers. In this monomer component, the component ( I ″ -C1) is an essential component, and component (I ″ -C2) and component (I ″ -C3) are optional components.

  The methacrylic acid alkyl ester of the component (I ″ -C1) contained in the monomer component for constituting the outermost layer polymer (I ″ -C) may be either linear or branched in the alkyl group. good. 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 alkyl acrylate ester of the component (I ″ -C2) contained as necessary in the monomer component for constituting the outermost layer polymer (I ″ -C) has a linear or branched alkyl group. Any of those. 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 other monomer having a copolymerizable double bond of the component (I ″ -C3) included as necessary in the monomer component for constituting the outermost layer polymer (I ″ -C), Acrylic monomers such as lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid and methacrylic acid, styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile and the like can be used. These can be used alone or in admixture of two or more.

  The content of the alkyl methacrylate (I ″ -C1) in the monomer component for constituting the outermost layer polymer (I ″ -C) is preferably 51 to 100% by mass. From the viewpoint of surface hardness, heat resistance, and the like of the obtained 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.

  The content of the acrylic acid alkyl ester (I ″ -C2) in the monomer component for constituting the outermost layer polymer (I ″ -C) is preferably 0 to 20% by mass. 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.

  In the monomer component for constituting the outermost layer polymer (I ″ -C), the content of the monomer (I ″ -C3) having a copolymerizable double bond is 0 to 49% by mass. preferable. More preferably, it is 20 mass% or less, More preferably, it is 15 mass% or less.

  Although not particularly limited, a chain transfer agent may be used during the polymerization of the outermost layer polymer (I ″ -C) to adjust the molecular weight of the outermost layer polymer (I ″ -C). 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 100% by mass of the monomers ((I ″ -C1) to (I ″ -C3)) included in the monomer component for constituting the polymer (I ″ -C). On the other hand, the content is preferably 0.01 to 5% by mass, more preferably 0.2% by mass or more, and most preferably 0.4% by mass or more.

  Although not particularly limited, it is preferable that the polymer having only the monomer component for constituting the outermost layer polymer (I ″ -C) has a Tg of 60 ° C. or higher. It is preferable because a film having a surface hardness suitable for the application and heat resistance can be obtained, more preferably 80 ° C. or higher, and most preferably 90 ° C. or higher. ) Is preferably 105 ° C. or lower.

  Although not particularly limited, the content of the outermost layer polymer (I ″ -C) in the rubber-containing polymer (I ″) 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. In addition, when the content is 80% by mass or less, the resulting acrylic resin film, the decorated acrylic resin film and the laminate can be molded whitening-resistant, and the resulting acrylic resin film and the decorated acrylic resin film can be molded in-mold. Toughness can be imparted, more preferably 70% by mass or less.

The rubber-containing polymer (I ″) of the present invention is composed of the polymer layers (I ″ -A), (I ″ -B) and (I ″ -C) described above. In the acrylic resin film, decorative acrylic resin film, and laminate, the rubber-containing polymer (I ″) preferably has a gel content of 50% or more in order to obtain excellent molding whitening resistance. More preferably, the gel content (%) in this case is a predetermined amount (mass before extraction: W ₀ (g)) of the rubber-containing polymer (I ″) under reflux in an acetone solvent. After extraction treatment, the acetone-soluble component is removed by centrifugation, and the remaining acetone-insoluble component is dried, and then the mass (mass after extraction: W ₁ (g)) is measured and calculated by the following formula. .

Gel content ratio = mass after extraction W ₁ / mass before extraction W ₀ × 100

  In terms of the molding whitening resistance of the resulting acrylic resin film, decorative acrylic resin film and laminate, the greater the gel content, the more advantageous, but from the viewpoint of easy moldability, a certain amount of free polymer or more. The gel content is preferably 80% or less.

  The rubber-containing polymer (I ″) has a mass average particle diameter of 0.01 to 0.5 μm. Preferably, it is in the range of 0.05 to 0.3 μm. From the viewpoint of mechanical properties, it is more preferably 0.07 μm or more, most preferably 0.09 μm or more, and from the viewpoint of molding whitening resistance of the resulting acrylic resin film, decorative acrylic resin film and laminate, More preferably, the average particle diameter is 0.15 μm or less, most preferably 0.13 μm or less, and the mass average particle diameter is measured using a light scattering photometer “DLS-700” (trade name) manufactured by Otsuka Electronics Co., Ltd. It can be measured by an automatic light scattering method.

  Next, a method for producing the rubber-containing polymer (I ″) will be described.

  As the method for producing the rubber-containing polymer (I ″), 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 It can also be carried out by an emulsion suspension polymerization method in which the polymer (I ″ -C) is converted to a suspension polymerization system at the time of polymerization.

  Although not particularly limited, when the rubber-containing polymer (I ″) is produced by emulsion polymerization, the innermost layer polymer (I ″ -A) in the rubber-containing polymer (I ″) is obtained. An emulsion prepared by mixing the monomer component with water and a surfactant in advance is supplied to the reactor for polymerization, and then the intermediate layer polymer (I ″ -B) and the outermost layer polymer (I ″ -C). A method of polymerizing the monomer components that give) is preferably supplied to the reactor in order.

  An emulsion prepared by mixing the monomer component that gives the innermost layer polymer (I ″ -A) with water and a surfactant in advance is supplied to the reactor and polymerized to be dispersed particularly in acetone. The rubber-containing polymer (I ″) 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 rubber-containing polymer (I ″) can be easily obtained. A film using the rubber-containing polymer (I ″) thus obtained as a raw material has a characteristic that the number of fish eyes in the film is small, and in particular, a light-colored wood grain pattern with low printing pressure in which printing omission is likely to occur. Even when solid gravure printing such as metallic tone, jet black tone or the like is performed, it is preferable because there are few printing omissions and high level printability.

  As the surfactant used in preparing the emulsion, anionic, cationic, and surfactant similar to the surfactant used in preparing the rubber-containing polymer (I ′) emulsion. Nonionic surfactants can be used, but anionic surfactants are particularly preferable. In addition, examples of the anionic surfactant and preferable examples of commercially available products include the same surfactants used in preparing the emulsion of the rubber-containing polymer (I ′).

  In addition, as a method for preparing an emulsion, a method in which a monomer component is charged in water and then a surfactant is added, a method in which a surfactant is charged in water and then a monomer component is charged, For example, a method in which water is added after a surfactant is charged into the monomer component. Among these, the method of charging the surfactant after charging the monomer component into water and the method of charging the monomer component after charging the surfactant into water include the rubber-containing polymer (I ″). It is preferable as a method of obtaining.

  As a mixing device for preparing an emulsion prepared by mixing the monomer component giving the innermost layer polymer (I ″ -A) with water and a surfactant, a stirrer and a homogenizer equipped with a stirring blade, Various forced emulsifiers such as mixers, membrane emulsifiers and the like can be mentioned.

  The emulsion to be prepared may be used in any of the dispersion structures of W / O type in which water droplets are dispersed in oil of monomer components and O / W type in which oil droplets of monomer components are dispersed in water. However, it is particularly preferable that the diameter of the oil droplets in the dispersed phase is 100 μm or less in the O / W type in which the oil droplets of the monomer component are dispersed in water.

  On the other hand, the innermost layer polymer (I ″ -A), the intermediate layer polymer (I ″ -B) and the outermost layer polymer (I ″ -C) constituting the preferred rubber-containing polymer (I ″) of the present invention. A known polymerization initiator can be used for the formation, and the addition method can be a method of adding to one or both of the aqueous phase and the monomer phase. 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, ethylenediaminetetraacetic acid disodium salt, longalite, and hydroperoxide is particularly preferable.

  An emulsion prepared by mixing the monomer component giving the innermost layer polymer (I ″ -A) with water and a surfactant is supplied to the reactor and polymerized, and then the intermediate layer polymer (I ″) -B) and the monomer component that gives the outermost layer polymer (I "-C) are sequentially fed to the reactor, and the method of polymerization includes ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, Rongalite After raising the temperature of the aqueous solution to the polymerization temperature, the prepared emulsion is supplied to the reactor for polymerization, and then the intermediate layer polymer (I ″ -B) and the outermost layer polymer containing a polymerization initiator such as peroxide. A method in which the monomer component giving (I ″ -C) is sequentially fed to the reactor and polymerized is the most preferable method for obtaining the rubber-containing polymer (I ″) 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 preferred rubber-containing polymer (I ″) obtained by the above method can be treated using a filtration apparatus provided with a filter medium as necessary. This filtration treatment is a scale generated during the polymerization. This is a method for removing the polymer from the latex, or for removing impurities mixed in from the polymerization raw material or from the outside during the polymerization, and is a more preferable method for obtaining the rubber-containing polymer (I ″).

  In addition, as a filtration device in which the filter medium used at that time is arranged, a “GAF filter system” of ISP Filters PTE Ltd. using a bag-like mesh filter, or a cylindrical filter on the inner surface of a cylindrical filter chamber is used. A centrifugal filter device in which a filter medium is disposed and a stirring blade is disposed in the filter medium, or a vibration filter device in which the filter medium performs horizontal circular motion and vertical amplitude motion with respect to the filter medium surface is preferable.

  The rubber-containing polymer (I ″) can be produced by recovering from the polymer latex produced by the above-described method. As a method for recovering the rubber-containing polymer (I ″) from the polymer latex, particularly, Although not limited, methods such as salting out or acid precipitation coagulation, spray drying, freeze drying and the like can be mentioned, 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 rubber-containing polymer (I ″) is preferably 800 ppm or less. In particular, magnesium, sodium, etc. When using a metal salt having a strong affinity for water as a salting-out agent, it is necessary to reduce the residual metal content as much as possible, so that the final rubber-containing polymer (I ″) can be used as a raw material. When the resin film is immersed in boiling water, a whitening phenomenon occurs, which is a big 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 (II) >>
The thermoplastic polymer (II) has a methacrylic acid alkyl ester of 50 to 100% by mass, an acrylic acid alkyl ester of 0 to 50% by mass, and a monomer having a double bond copolymerizable therewith of 0 to 49% by mass. % Of a polymer having a reduced viscosity (0.1 g of polymer dissolved in 100 mL of chloroform and measured at 25 ° C.) of 0.15 L / g or less. It is a coalescence.

  When the reduced viscosity of the thermoplastic polymer (II) is 0.15 L / g or less, moderate elongation occurs at the time of melting when the acrylic resin is processed into a film, and the film-forming property is improved. More preferably, it is 0.1 L / g or less. Further, the lower limit of the reduced viscosity is preferably 0.05 L / g or more. If it is 0.05 L / g or more, the problem of film breakage at the time of film-formation of acrylic resin due to brittleness and at the time of printing on the film becomes difficult to occur.

  Examples of the alkyl methacrylate used for the monomer component for obtaining the thermoplastic polymer (II) include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and n-butyl methacrylate. Of these, methyl methacrylate is most preferred. In the monomer component for obtaining the thermoplastic polymer (II), the alkyl methacrylate is in the range of 50 to 100% by mass, preferably in the range of 85 to 99.9% by mass, more Preferably it is the range of 92-99.9 mass%. By setting this range, for example, vehicle members and the like are members that are easily exposed to high temperatures and are easily touched by hands and objects, but are necessary when a laminate having an acrylic resin as the outermost layer is applied to the vehicle members. It can exhibit heat resistance and high hardness.

  Examples of the alkyl acrylate used as necessary for the monomer component for obtaining the thermoplastic polymer (II) include methyl acrylate, ethyl acrylate, propyl acrylate, and n-butyl acrylate. . In the monomer component for obtaining the thermoplastic polymer (II), the alkyl acrylate is in the range of 0 to 50% by mass, preferably in the range of 0.1 to 40% by mass, and more preferably. Is in the range of 0.1 to 15% by mass, most preferably in the range of 0.1 to 8% by mass. By setting this range, for example, vehicle members and the like are members that are easily exposed to high temperatures and are easily touched by hands and objects, but are necessary when a laminate having an acrylic resin as the outermost layer is applied to the vehicle members. It can exhibit heat resistance and high hardness.

  As a monomer having a copolymerizable double bond used as necessary in the monomer component for obtaining the thermoplastic polymer (II), various conventionally known monomers can be used. Examples thereof include styrenes such as styrene and α-methylstyrene, maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide, maleic acid, maleic anhydride, and acrylonitrile.

  The thermoplastic polymer (II) is obtained by polymerizing these monomer components. 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. What is necessary is just to determine the usage-amount of a chain transfer agent suitably with the kind and composition of a monomer.

  By changing the ratio of the rubber-containing polymer (I) and the thermoplastic polymer (II) used in the acrylic resin film of the present invention, the heat resistance and hardness of the film can be easily adjusted. For example, sufficient heat resistance can be exhibited when applied to a laminate having an acrylic resin film as the outermost layer, such as a vehicle member, which is easily exposed to high temperatures and easily touched by hands and objects.

  The compounding ratio of the rubber-containing polymer (I) and the thermoplastic polymer (II) is based on 100 parts by mass of the rubber-containing polymer (I) and the thermoplastic polymer (II) as a reference. 1) to 99 parts by mass and 1 to 99 parts by mass of the thermoplastic polymer (II).

  From the viewpoint of heat resistance and surface hardness, when using the rubber-containing polymer (I ′), the total of the rubber-containing polymer (I ′) and the thermoplastic polymer (II) from the viewpoint of heat resistance and surface hardness. Is 100 parts by mass, the thermoplastic polymer (II) is preferably 60 parts by mass or more, and more preferably 70 parts by mass or more. On the other hand, the rubber-containing polymer (I ′) is more preferably 40 parts by mass or less, and further preferably 30 parts by mass or less.

On the other hand, when the rubber-containing polymer (I ″) is used, the rubber-containing polymer (I ″), the thermoplastic heavy polymer, the decorative acrylic resin film, and the laminate from the viewpoint of molding whitening resistance. When the total of the combined (II) is 100 parts by mass, the rubber-containing polymer (I ″) is more preferably 50 parts by mass or more, and further preferably 65 parts by mass or more.
The thermoplastic polymer (II) is more preferably at most 50 parts by mass, further preferably at most 35 parts by mass. Further, from the viewpoint of heat resistance and hardness, the thermoplastic polymer (II) is preferably 5 parts by mass or more, and more preferably 20 parts by mass or more. By doing so, when applying the laminated body which laminated | stacked the acrylic resin film of this invention on the base material to a vehicle member, it can exhibit the heat resistance and high hardness which can endure it, and the acrylic resin obtained The laminated molded product which does not impair the whitening resistance of the film, the decorative acrylic resin film and the laminate can be provided.

  The gel content of the acrylic resin composition (A) (rubber-containing polymer (I) and thermoplastic polymer (II)) constituting the acrylic resin film of the present invention is such that the acrylic resin composition (B) is in the form of a film. From the viewpoint of film forming properties when molding, and from the viewpoint of molding whitening resistance of the resulting acrylic resin film, decorative acrylic resin film and laminate, it is preferably 10% by mass or more, more preferably 20% by mass or more. Preferably, 40 mass% or more is more preferable. Moreover, from a viewpoint of the film forming property at the time of shape | molding an acrylic resin composition in a film form, 80 mass% or less is preferable, 75 mass% or less is more preferable, and 70 mass% or less is further more preferable.

  The surface gloss of the acrylic resin film of the present invention can be appropriately selected depending on the design effect. The content of the core-shell polymer (III) to be used can be appropriately selected within the above range depending on the target film surface gloss. When the amount is 0.5 parts by mass or more with respect to 100 parts by mass of the acrylic resin composition (A), an excellent matting effect is exhibited. The content of the core-shell polymer (III) in the acrylic resin film is more preferably 2 parts by mass or more with respect to 100 parts by mass of the acrylic resin composition (A), from the viewpoint of obtaining better matting properties. 5 parts by mass or more is most preferable. Moreover, when it is 50 mass parts or less, favorable film forming property is obtained, and it is further preferable from the viewpoint of good film mechanical properties that enable insert molding and in-mold moldability. More preferably, it is 15 parts by mass or less. In addition, the surface glossiness of a film is obtained by using a gloss meter (manufactured by Murakami Color Research Laboratory, GM-26D type) and forming a film by sandwiching it between a mirror roll and a rubber roll or a wrinkled roll. On the other hand, when the film that is in contact with the rubber roll or wrinkled roll is sandwiched between the mirror roll and the silicone mirror rubber roll, the surface that is in contact with the mirror roll of the obtained film is measured at an angle of 60 °. Obtained.

<Core-shell polymer (III)>
The core-shell polymer (III) has a multilayer structure in which the core layer polymer (III-A) and the shell layer polymer (III-B) are basic structures in order from the inside.

  Below, the structure of the above-mentioned core shell polymer (III) is demonstrated concretely.

[Core layer polymer (III-A)]
The core layer polymer (III-A) constitutes the central part of the polymer having the multilayer structure, and includes an acrylic acid alkyl ester (III-A1), a methacrylic acid alkyl ester (III-A2), Component comprising other monomer (III-A3), polyfunctional monomer (III-A4) and graft crossing agent (III-A5) having a double bond copolymerizable with styrene Is a polymer obtained by polymerizing In this monomer component, components (III-A1), (III-A2) and (III-A5) are essential components, and components (III-A3) and (III-A4) are optional components. is there.

  The alkyl acrylate ester of the component (III-A1) contained in the monomer component for constituting the core layer polymer (III-A) may be either linear or branched in the alkyl group. Specific examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. These can be used individually or in mixture of 2 or more types.

  The methacrylic acid alkyl ester of the component (III-A2) contained in the monomer component for constituting the core layer polymer (III-A) has either an ester group of a linear alkyl group or a branched alkyl group. But it ’s okay. Specific examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, cyclohexyl methacrylate and the like. These can be used alone or in admixture of two or more.

  The other monomer having a copolymerizable double bond of the component (III-A3) included as necessary in the monomer component for constituting the core layer polymer (III-A) is (meta ) Acrylic esters such as (meth) acrylic esters other than (III-A1) and (III-A2) such as benzyl acrylate and phenyl (meth) acrylate, lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid, methacrylic acid, etc. Monomer, styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile and the like can be used. These can be used alone or in admixture of two or more.

  The polyfunctional monomer of the component (III-A4) included as necessary in the monomer component for constituting the core layer polymer (III-A) is a copolymerizable duplex of the same degree. A monomer having two or more bonds in one molecule is defined. 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, polyvinyl benzene such as divinylbenzene and trivinylbenzene, triallyl cyanurate, triallyl isocyanurate, and the like can also be used. These can be used alone or in admixture of two or more. Of these, 1,3-butylene glycol dimethacrylate is preferred. Even when the polyfunctional monomer does not act at all, as long as the graft crossing agent (III-A5) is present, a fairly stable core-shell polymer (III) 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 (III-A5) contained in the monomer component for constituting the core layer polymer (III-A) is a single copolymer having two or more different copolymerizable double bonds in one molecule. Defined as a mer. 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. The graft crossing agent (III-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. In addition, the above polyfunctional monomers such as triallyl cyanurate and triallyl isocyanurate are also effective as grafting agents. In the present invention, when the above-exemplified graft crossing agent (III-A5) is not used and instead these cyanurate derivatives effectively act as graft crossing agents, these cyanurate derivatives are regarded as graft crossing agents (III-A5). .

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

  The content of the acrylic acid alkyl ester (III-A1) in the monomer component for constituting the core layer polymer (III-A) is 10 to 90% by mass. From the viewpoint of molding whitening resistance and film forming property of the obtained acrylic resin film, decorative acrylic resin film and laminate, it is more preferably 30% by mass or more. Moreover, from a viewpoint of the surface hardness of the acrylic resin film obtained, a decorative acrylic resin film, and a laminated body, More preferably, it is 85 mass% or less.

  The content of the methacrylic acid alkyl ester (III-A2) in the monomer component for constituting the core layer polymer (III-A) is 10 to 90% by mass. From the viewpoint of the surface hardness of the obtained acrylic resin film, decorated acrylic resin film and laminate, it is more preferably 15% by mass or more. Moreover, from the viewpoint of the molding whitening resistance of the obtained acrylic resin film, decorative acrylic resin film and laminate, and film forming property, it is more preferably 70% by mass or less.

  The content of the other monomer (III-A3) having a copolymerizable double bond in the monomer component for constituting the core layer polymer (III-A) is 0 to 50% by mass. is there.

  The content of the polyfunctional monomer (III-A4) in the monomer component for constituting the core layer polymer (III-A) is 0 to 20% by mass.

  The content of the graft crossing agent (III-A5) in the monomer component for constituting the core layer polymer (III-A) is 0.1 to 20% by mass.

  The content of the core layer polymer (III-A) in the core-shell polymer (III) is 25 to 85% by mass. In the case of 25% by mass or more, the obtained acrylic resin film, decorative acrylic resin film and laminate whitening resistance of the laminate can be imparted, and further, the film forming property and obtained when the acrylic resin is formed into a film shape. The toughness that can be used for insert molding and in-mold molding of the acrylic resin film and the decorated acrylic resin film can be made compatible. More preferably, it is 45 mass% or more. Moreover, when it is 85 mass% or less, since surface hardness and heat resistance required for a vehicle use are obtained, it is preferable. More preferably, it is 75 mass% or less.

  The core layer polymer (III-A) may be a single layer or a multilayer.

  In the present invention, the refractive index (n ′) of the core layer polymer (III-A) and the refractive index (n) of the thermoplastic polymer (II) at 20 ° C. are 0 ≦ | n−n ′ | ≦ 0. It is important to satisfy the relational expression of .003.

  The refractive index at 20 ° C. was the value described in “PROPERTIES OF POLYMERS 3rd Edition” (ELSEVIER, 1990). Further, the refractive index of the copolymer can be calculated from its volume ratio.

  When the absolute value of the difference between the refractive index (n ′) of the core layer polymer (III-A) and the refractive index (n) of the thermoplastic polymer (II) at 20 ° C. is 0.003 or less, Acrylic resin film containing coalesce has low internal haze, excellent transparency, and after printing on one side, in-mold molding can be used to obtain a molded product without impairing the design of the printed layer. Because it is possible, the industrial utility value is extremely high.

  The internal haze is JIS K7136 (fogging measurement method) after the obtained acrylic resin film is heated to 130 ° C. and subjected to hot pressing under a condition of 3 MPa to make the surface mirror-finished. It can be measured according to the test method.

[Shell layer polymer (III-B)]
The shell layer polymer (III-B) is prepared from the methacrylic acid alkyl ester (III-B1), the acrylic acid alkyl ester (III-B2) in the presence of the polymer forming the core layer polymer (III-A). ) And other monomer components having a double bond copolymerizable therewith (III-B3) as a constituent component. The shell layer polymer (III-B) can be obtained by polymerization in at least one stage, and can have a structure of one layer or two or more layers. In this monomer component, component (III-B1) is an essential component, and component (III-B2) and component (III-B3) are optional components.

  The alkyl methacrylate of the component (III-B1) contained in the monomer component for constituting the shell layer polymer (III-B) may be either linear or branched alkyl group. Specific examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and n-butyl methacrylate. These can be used alone or in admixture of two or more. Of these, methyl methacrylate is preferred.

  The acrylic acid alkyl ester of the component (III-B2), which is included as necessary in the monomer component for constituting the shell layer polymer (III-B), has a linear or branched alkyl group. Either is fine. 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 other monomer having a copolymerizable double bond of the component (III-B3) included in the monomer component for constituting the shell layer polymer (III-B) as required is a lower alkoxy Acrylic monomers such as acrylate, cyanoethyl acrylate, acrylamide, acrylic acid, methacrylic acid, styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile, and the like can be used. These can be used alone or in admixture of two or more.

  The content of the methacrylic acid alkyl ester (III-B1) in the monomer component for constituting the shell layer polymer (III-B) is 60 to 100% by mass. 70-100 mass% is more preferable.

  Content of the acrylic acid alkyl ester (III-B2) in the monomer component for constituting the shell layer polymer (III-B) is 0 to 40% by mass. 0-30 mass% is more preferable.

  The content of the monomer (III-B3) having a copolymerizable double bond in the monomer component for constituting the shell layer polymer (III-B) is 0 to (40% by mass). is there.

  Although it does not specifically limit, a chain transfer agent can be used at the time of superposition | polymerization of shell layer polymer (III-B), and the molecular weight of shell layer polymer (III-B) 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 100% by mass of the monomers ((III-B1) to (III-B3)) contained in the monomer component for constituting the polymer (III-B). 0-5 mass% is preferable.

  The content of the shell layer polymer (III-B) in the core-shell polymer (III) is 15 to 75% by mass. From the viewpoint of surface hardness and heat resistance, it is preferably 25% by mass or more. In addition, when the content is 75% by mass or less, the resulting acrylic resin film, the decorated acrylic resin film and the laminate are resistant to molding whitening, and can be molded in-mold into the resulting acrylic resin film and decorative acrylic resin film. Toughness can be imparted, and more preferably 55% by mass or less.

  The mass average particle diameter of the core-shell polymer (III) is 0.5 to 20 μm. From the viewpoint of expressing good matting properties of the obtained acrylic resin film, it is more preferably 1 μm or more. Further, from the viewpoint of mechanical properties such as impact resistance and molding whitening resistance of the resulting acrylic resin film, decorative acrylic resin film and laminate, it is more preferably 10 μm or less, and most preferably 8 μm or less. The mass average particle diameter can be measured using a laser diffraction / scattering particle size distribution measuring apparatus (LA-910, manufactured by Horiba, Ltd.). Moreover, when the core-shell polymer (III) used in the present invention and the mass average particle diameter of the polymer particles are Dw, it is preferable not to include particles having a particle diameter of 10 × Dw μm or more. When the core-shell polymer (III) to be used does not contain coarse particles having a particle diameter of 10 × Dw μm or more, the film surface is free from defects and a film having a very good surface appearance can be obtained. In particular, even when high brightness printing such as a silver metallic tone in which the surface defects are very conspicuous, a decorative film having a good surface appearance can be obtained, which is preferable. In addition, in the case of a film obtained by sandwiching between a mirror roll and a rubber roll during film production, it is good without developing concave surface defects when the film is heated in a secondary processing step such as in-mold molding. A laminated molded product can be obtained while maintaining a good surface appearance. From these viewpoints, the acrylic resin film of the present invention has a very high industrial utility value. In addition, the presence or absence of coarse particles in the core-shell polymer is observed with a scanning electron microscope for the mass of the matte material blended in the predetermined film area. In other words, when only a small amount of coarse particles are present in the organic crosslinked particles or inorganic particles blended in the predetermined film area, the specific mass average particle size region (10 × Dw μm) is converted into mass by the laser light scattering method. In such a case, when the film is formed into a film, defects with a concave surface are not generated, and the film has a poor industrial appearance value with a poor surface appearance. This is because by observing with a scanning electron microscope, it is not necessary to miss a very small amount of coarse molecules.

  Next, the manufacturing method of core-shell polymer (III) is demonstrated.

  As a method for producing the core-shell polymer (III), a known production method can be used. Among these, a polymerization method by suspension polymerization is preferable. As the concentration of the polymerizable monomer in the suspension and the method for preparing the suspension, a known method can be adopted. In order to obtain the core-shell polymer (III) of the present invention, first, the dispersion is performed. Desired by mixing water in which a stabilizer is dissolved or suspended and a polymerizable monomer forming a core layer polymer (III-A) containing a polymerization initiator, and applying mechanical shear to the mixture. It is preferable to prepare an O / W type emulsion having a droplet diameter of 5 and then polymerize.

  In order to stabilize the suspension, it is preferable to add a dispersion stabilizer to the suspension as necessary. Specifically, water-soluble polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, methylcellulose, anionic surfactants such as sodium oleate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium dialkylsulfosuccinate, laurylamine acetate, Known ones such as cationic surfactants such as lauryltrimethylammonium chloride and nonionic surfactants such as polyoxyethylene alkyl ether and polyoxyethylene alkylphenyl ether can be used.

  As the polymerization initiator, oil-soluble peroxide-based or azo-based initiators usually used for suspension polymerization can be used. Specifically, peroxides such as benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, 2,2′-azobisisobutyronitrile, 2,2 Examples include azo initiators such as' -azobis (2,4-dimethylvaleronitrile).

  The polymerization temperature varies depending on the type and amount of the polymerization initiator used, but is preferably 50 to 95 ° C.

  The core layer polymer (III-A) is reacted, and a monomer mixture that becomes the shell layer polymer (III-B) is added to the obtained core layer polymer particle suspension. As an addition method, a method of preparing a suspension together with the above-mentioned dispersion stabilizer and supplying it all at once or over a predetermined time is preferable.

  The method for taking out the core-shell polymer particles from the suspension is not particularly limited, although a method for separating by filtration, a method using a separator such as a centrifugal separator, or spray drying is simple. The core-shell polymer particles taken out from the suspension may be washed and dried as necessary, but the drying temperature and the drying method are not particularly limited.

  It is preferable to remove specific coarse particles by classifying the core-shell polymer particles obtained by drying. The classification method is not particularly limited, but an air classifier is preferred from the balance of the classification ability and the processing amount.

  Of the rubber-containing polymer (I), thermoplastic polymer (II), and core-shell polymer (III), which are the main raw materials for the acrylic resin film of the present invention, the rubber-containing polymer (I) and the core-shell polymer (III) The shape of is powdery. On the other hand, when the thermoplastic polymer (II) to be used is melt-extruded in advance and shaped into a pellet shape, the raw materials for the film are mixed and then put into the extruder hopper, Classification is caused by the difference in shape, and there arises a problem that a difference in film quality such as matte property becomes extremely large during production. For this reason, the shape of the thermoplastic polymer (II) is preferably a bead or powder. That is, the rubber-containing polymer (I), thermoplastic polymer (II), and core-shell polymer (III) used as the main raw material for the acrylic resin film of the present invention are all in the form of powder or beads. Is preferred. When the main raw materials for film are all in the form of powder or beads, after mixing the raw materials for film, it is possible to stabilize film quality such as matte properties without causing classification in the extruder hopper. It becomes.

  In the acrylic resin composition (B) constituting the acrylic resin film of the present invention, the reduced viscosity of the polymer (0.1 g of the polymer dissolved in 100 mL of chloroform) as an additive separately from the thermoplastic polymer (II) described above. And measured at 25 ° C.) a thermoplastic polymer (IV) exceeding 0.15 L / g can be used.

<Thermoplastic resin (IV)>
The thermoplastic polymer (IV) to be blended with the above polymer as required contains 50 to 100% by mass of methyl methacrylate and 0 to 50 other monomers having a double bond copolymerizable therewith. It is a polymer obtained by polymerizing a monomer component of mass%, and is a thermoplastic polymer in which the reduced viscosity of the polymer exceeds 0.15 L / g.

  Use of the thermoplastic polymer (IV) improves the film-forming property when the acrylic resin composition (B) is formed into a film, which is particularly useful when high levels of thickness accuracy and film-forming speed are required. It is. In particular, when the reduced viscosity of the thermoplastic polymer (IV) is in a range exceeding 0.15 L / g, a film with good thickness accuracy can be obtained. This reduced viscosity usually exceeds 0.15 L / g and is 2 L / g or less, preferably 1.2 L / g or less.

  Other monomers having a double bond copolymerizable with methyl methacrylate used as necessary for the monomer component for obtaining the thermoplastic polymer (IV) include alkyl acrylates, methacrylates. Examples include acid alkyl esters, aromatic vinyl compounds, and vinyl cyanide compounds.

  The thermoplastic polymer (IV) is obtained by polymerizing these monomer components. 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.

  It is preferable that the usage-amount of thermoplastic polymer (IV) is 0-10 mass parts with respect to 100 mass parts of acrylic resin compositions (A). By using the thermoplastic polymer (IV), the film-forming property when the acrylic resin is formed into a film is improved. On the other hand, by making it 10 parts by mass or less, the increase in the viscosity of the acrylic resin is suppressed, It is possible to prevent the film formability from being lowered when the acrylic resin is formed into a film.

  In addition, the acrylic resin composition (B) constituting the acrylic resin film of the present invention may be prepared by adding a general compounding agent such as a stabilizer, a lubricant, a processing aid, and the core-shell polymer (III) of the present invention as necessary. Other known matting agents, light diffusing agents, plasticizers, impact resistance aids, foaming agents, fillers, colorants, antibacterial agents, fungicides, mold release agents, antistatic agents, light stabilizers, UV absorbers Agents and the like.

  From the viewpoint of protecting the substrate, it is preferable to add an ultraviolet absorber to the acrylic resin composition (B) constituting the acrylic resin film of the present invention in order to impart weather resistance. The molecular weight of the ultraviolet absorber is preferably 300 or more, and more preferably 400 or more. If this molecular weight is 300 or more, it is difficult to volatilize when vacuum forming or pressure forming is performed in an injection mold, and mold contamination is difficult to occur. The type of the UV absorber is not particularly limited, but a benzotriazole UV absorber having a molecular weight of 400 or more and a triazine UV absorber having a molecular weight of 400 or more are particularly preferable. As the former commercial product, for example, trade name “Tinubin 234” of Ciba Specialty Chemicals Co., Ltd., the trade name “Adeka Stub LA-31” of Asahi Denka Kogyo Co., Ltd. The name “Tinubin 1577” and the like can be mentioned.

  From the viewpoint of stabilizing production, it is preferable to add silica particles having a mass average particle diameter of 100 nm or less to the acrylic resin composition (B) which is a constituent component of the acrylic resin film of the present invention.

  When silica particles having a mass average particle diameter of 100 nm or less were added to the acrylic resin composition (B), the main raw materials for the acrylic resin film were all made into powder or beads for the purpose of stabilizing the film quality described above. This is preferable because it can prevent the solidification of the raw material powder, which is likely to occur in some cases, improves the fluidity in the extruder hopper, and realizes good supply to the extruder. Preferably, it is 0.2 mass part or more with respect to 100 mass parts of acrylic resin compositions (B). Further, when 1 part by mass or less of the silica particles is added, it is preferable because optical films such as transparency of the obtained film and mechanical properties such as elongation at break are small. More preferably, it is 0.8 mass part or less, More preferably, it is 0.5 mass part or less.

  Examples of the method for producing the acrylic resin film of the present invention include known methods such as a melt casting method, a melt extrusion method such as a T-die method and an inflation method, and a calendar method. Is preferred.

  A method is preferred in which the resin composition, which is the raw material for the acrylic resin film of the present invention, is formed into a film shape by a melt extrusion method such as a T-die method, and is then sandwiched between a mirror surface roll and a rubber roll or a textured roll. By sandwiching between a mirror roll and a rubber roll or a wrinkled roll, surface protrusions due to foreign matters that cause printing omission can be remarkably reduced, and printing omission is significantly reduced when printing is performed on the obtained film. be able to. In particular, the method of sandwiching between a mirror roll and a rubber roll is more preferable in that a film having a relatively thin film thickness of about 50 μm can be produced as compared with a method of sandwiching between a mirror roll and a textured roll. In the calendering method, the film can be formed by replacing one side of two mirror-finished rolls between which the film is finally sandwiched with a rubber roll or a roll with grain. Or after forming into a film shape once by a well-known method, an acrylic resin film can be heated again more than a glass transition temperature, and it can also manufacture by inserting | pinching with a mirror surface roll, a rubber roll, or a wrinkled roll. Various conventionally known rolls can be used as the mirror roll. In particular, a roll having a surface roughness of 0.5 S or less subjected to chrome plating is preferable. Various conventionally known rolls can be used as the rubber roll. From the viewpoint of heat resistance, the rubber roll is preferably made of silicone rubber.

  When using a general rubber roll or wrinkled roll for film production, if the mirror roll temperature is high, the followability to the rubber roll or wrinkled roll is good, and the film surface in contact with the rubber roll or wrinkled roll is good. In the same manner, the mirror surface transfer to the acrylic resin film of the mirror surface roll is improved, the smoothness of the surface in contact with the mirror surface roll is increased, and the printing omission is reduced. However, if the temperature is too high, the peelability of the acrylic resin film from the mirror roll may be poor, or the acrylic resin film may wrap around the mirror roll. Moreover, when the temperature of the mirror surface roll is too low, the mirror surface transferability of the mirror surface roll to the acrylic resin film becomes poor, and the effect of reducing printing omission becomes insufficient, or wrinkles easily occur on the film. Although it does not specifically limit by the glass transition temperature of an acrylic resin film, It is preferable to temperature-control a mirror surface roll within the range of 20-140 degreeC. The temperature range is preferably 50 to 120 ° C, more preferably 60 to 100 ° C.

  In order to obtain good matting properties, the rubber roll is preferably sand or silicon rubber containing alumina. In the acrylic resin film, the preferred matte appearance varies depending on the use, and therefore the particle size / shape and addition amount of sand or alumina added to the silicone rubber can be changed according to the use. Specifically, for example, a silicone rubber roll to which 50% by mass of alumina having an average particle size of 40 μm is added can be used. In addition, a textured roll can be used instead of the rubber roll. As the textured roll, various conventionally known rolls can be used. In this case, the surface of the manufactured film that is in contact with the mirror surface roll is the surface on which the printing process is performed.

In addition, when using a silicone rubber roll whose surface is mirror-finished by polishing or the like (hereinafter also simply referred to as “silicone mirror rubber roll”) during film production, one surface is a mirror surface roll and the other surface is a silicone mirror surface rubber roll. Can be used as a smooth surface for the silicone mirror surface rubber roll contact surface and a matte surface for the mirror surface roll contact surface. Especially, the maximum height of the film surface, such as the film of the present invention, is 5 μm or less. It becomes possible to manufacture while maintaining the original surface roughness of the film material having a fine uneven shape, that is, the matte degree. Specific examples of the silicone mirror rubber roll include “IT68S silicone mirror roll” (trade name, hardness = A87, surface roughness R _MAX = 2 μm, manufactured by Mochida Corporation). Moreover, although it does not specifically limit, it is preferable to temperature-control a mirror surface roll within the range of 20-140 degreeC. The temperature range is preferably 50 to 120 ° C, more preferably 60 to 100 ° C. When the mirror roll is in this temperature range, the mirror roll contact surface is matte and the silicone mirror rubber roll contact surface is smooth while maintaining good film-forming properties such as good release of the acrylic resin film from the mirror roll. A good-looking film can be obtained. In this case, the surface of the manufactured film that has been in contact with the silicone mirror rubber roll is the surface on which printing is performed.

  Moreover, when melt-extruding a resin composition, it is preferable to extrude while filtering the resin composition in a molten state with a screen mesh of 80 mesh or more.

  The acrylic resin film of the present invention is not particularly limited, but preferably has a pencil hardness (measured based on JIS K5400) of 2B or higher (higher hardness including 2B). Further, HB or more is preferable, and F or more is most preferable. When an acrylic resin film having a pencil hardness of 2B or more is used, the acrylic resin film and the decorative acrylic resin film are not easily scratched during the process of insert molding or in-mold molding. Good scratch resistance.

  For example, when used for a vehicle, the pencil hardness of the acrylic resin film of the present invention is preferably HB or higher. Acrylic resin films with pencil hardness of HB or higher, decorative acrylic resin films, and laminated molded products with these layers are suitable for various vehicle members such as door waist garnish, front control panel, power window switch panel, airbag cover, etc. Can be used for It is very useful industrially from the viewpoint of expanding applications. Furthermore, if the pencil hardness is F or more, the scratches are not noticeable even when scratched with a cloth with a rough surface such as gauze, and have practical scratch resistance equivalent to a molded product using an acrylic resin film with a pencil hardness of 2H. Since it can be imparted, the industrial utility value is extremely high.

  The acrylic resin film of the present invention preferably has a heat distortion temperature (measured based on ASTM D648) of 80 ° C. or higher. In the case of an acrylic resin film having a heat distortion temperature (hereinafter also simply referred to as HDT) of 80 ° C. or higher, the melt viscosity of the resin composition for the film becomes moderately high when the film is formed, and the film is peeled off from the mirror roll. It becomes possible to prevent problems such as winding around a mirror surface roll. In addition, for example, in a vehicle application, the acrylic resin film, the decorative acrylic resin film of the present invention, and the laminated molded product including these can be used for a part that receives direct sunlight in the vehicle, such as a front control panel. From the viewpoint of further expanding the application, the heat distortion temperature is preferably 90 ° C. or higher. Moreover, it is preferable that the heat distortion temperature of the acrylic resin film of this invention is 130 degrees C or less. The measurement of the heat distortion temperature is carried out using a heat deformation temperature measurement specimen obtained by molding raw material pellets of an acrylic resin film by injection molding and annealing at 60 ° C. for 4 hours. Usually, it is the same as the thermal deformation temperature of the acrylic resin film.

  It is particularly useful to use the acrylic resin film of the present invention after printing by an appropriate printing method as necessary in order to impart design properties to various substrates. In this case, it is preferable that the acrylic resin film is subjected to a one-side printing process and used as a film having a printing layer (pattern layer) on one side. In the case of the acrylic resin film of the present invention, it is preferable to produce while maintaining the fine irregular shape of the original surface of the film. As the production method, the resin composition melt-extruded from the T-die as described above is used as a mirror roll. And a rubber roll or a textured roll. Among the obtained acrylic resin films, the preferred surface for arranging the printing layer is as described above. Moreover, at the time of shaping | molding, it is preferable from a viewpoint of protection of the surface (printing layer surface) which gave decorating, and provision of a high-class feeling to arrange a printing layer surface on the adhesive surface with base-material resin. Examples of the printing method include a method of applying ink by a conventionally known printing method and coating method. Specifically, gravure printing method, flexographic printing method, silk screen printing method, offset printing method, roll coating method, gravure coating method, comma coating method and the like.

  As the ink used in the printing layer, a known thermoplastic resin such as an acrylic resin, a polyvinyl resin, a polyester resin, a polyurethane resin, or a polyamide resin can be used as a binder. The acrylic resin composition (A) comprising the rubber-containing polymer (I) and the thermoplastic polymer (II) of the present invention can also be used as a thermoplastic resin binder. In particular, when the acrylic resin composition (A ″) comprising the rubber-containing polymer (I ″) and the thermoplastic polymer (II) of the present invention is used as a thermoplastic resin binder, printing is performed near the gate at the time of in-mold molding described later. Since the printing layer which suppresses loss | disappearance of a layer can be provided, it is preferable.

  In the case of metallic tone printing, the ink contains a high brightness pigment as an essential component. For example, a known high brightness pigment such as an aluminum pigment such as non-leafing aluminum paste (manufactured by Showa Aluminum Powder) or a pearl pigment such as “Iriodin” (registered trademark of Merck) is used. Moreover, a pigment or dye of an appropriate color can be contained as a colorant.

  Further, as a method other than the printing method and the coating method, a metallic print layer can be formed by a known method such as a vacuum deposition method, a sputtering method, an ion plating method, or a plating method. Although a known metal can be used as the printing layer, it is preferable from the viewpoint of in-mold moldability to use aluminum, indium, or an alloy containing these with excellent malleability.

The number of missing prints on the surface on which the acrylic resin film is printed is preferably 10 pieces / m ² or less from the viewpoints of design properties and decorating properties. By setting the number of printing omissions to 10 pieces / m ² or less, the appearance of the laminated product of this film becomes better. The number of missing prints on the printed surface is more preferably 5 pieces / m ² or less.

When the number of missing prints is 10 pieces / m ² or less, even in the case of a metallic printed pattern in which the missing prints are obvious as defects, the design properties and the surface appearance are not deteriorated. It is preferable because it does not decrease, and the industrial utility value is extremely high.

  Moreover, what colored the acrylic resin film of this invention can be used.

  Further, in addition to the printing layer, it is preferable to provide an adhesive layer in order to enhance the adhesiveness with the resin as the base material. The adhesive layer may be provided on the printing layer, or may be provided on the film surface opposite to the printing layer. It is also possible to provide an adhesive layer on the surface of an acrylic resin film having no printed layer.

  As for the thickness of the acrylic resin film of this invention, 10-500 micrometers is preferable. By setting the thickness of the acrylic resin film to 500 μm or less, rigidity suitable for insert molding and in-mold molding can be obtained, and the film can be manufactured more stably. Moreover, by making the thickness of the acrylic resin film 10 μm or more, the sense of depth can be more sufficiently imparted to the obtained molded product together with the protection of the base material. As for the thickness of an acrylic resin film, 30 micrometers or more are more preferable. The thickness of the acrylic resin film is more preferably 200 μm or less.

  Usually, in order to form a coating film having a sufficient thickness on a molded product by coating, it may be necessary to apply several tens of times, and in this case, the cost is high and the productivity is not so good. On the other hand, since the acrylic resin film itself becomes a coating film, the laminated molded product of the present invention can easily form a very thick coating film and has high industrial utility value.

  The laminated molded product of the present invention is characterized in that the acrylic resin film or the decorated acrylic resin film of the present invention is laminated on a substrate. In particular, it is obtained by an in-mold molding method in which the acrylic resin film is subjected to vacuum molding or pressure molding in an injection mold, and then the resin as the base material is injection molded in the injection mold. It is preferable to use a laminated molded product. Also, a laminate obtained by an insert molding method in which a preform such as vacuum molding or pressure forming is applied, the preform is inserted into another mold, and then a resin as a base material is injection molded to obtain a laminate molded product. It can also be a molded product. In the case of this insert molding method, it is preferable to use a laminated sheet or film obtained by laminating the acrylic resin film or the decorated acrylic resin film of the present invention on a thermoplastic resin layer. As the thermoplastic resin layer used for the laminated sheet or film, a known thermoplastic resin film or sheet can be used. For example, acrylic resin, ABS resin, AS resin, vinyl chloride resin, polystyrene resin, polycarbonate resin, polyester resin, polyolefin resin, and the like can be given. Among these, acrylic resin, ABS resin, vinyl chloride resin, and polyolefin resin are preferable from the viewpoints of printability and secondary moldability of the laminated film or sheet. The position of the printing layer in the laminated sheet or film in which the decorative acrylic resin film is laminated on the thermoplastic resin layer is not particularly limited, but from the viewpoint of imparting the desired design to the laminated molded product, the thermoplastic resin layer and It is preferable to arrange between acrylic resin layers. Thereby, a decoration layer can be protected and the design property with the depth can be implement | achieved.

  Furthermore, it is preferable to provide an adhesive layer in order to enhance the adhesiveness with the resin as the base material. The adhesive layer may be provided on the thermoplastic resin layer, or may be provided on the surface facing the thermoplastic resin layer of the resin serving as the base material.

  It is preferable that resin used as the base material in the laminated molded product of the present invention is a resin that can be melt bonded to an acrylic resin film or a decorative acrylic resin film. For example, ABS resin, AS resin, polystyrene resin, polycarbonate resin, vinyl chloride resin, acrylic resin, polyester resin, or resin containing these as main components can be given. 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 adhere an acrylic resin film or a decorative acrylic resin film and a base material at the time of molding by using an adhesive layer even with a base material resin such as polyolefin resin that is not thermally fused.

  When the laminated molded product of the present invention is molded into a two-dimensional shape, 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. Moreover, when shape | molding in three-dimensional shape, well-known methods, such as an insert molding method and an in-mold shaping | molding method, can be used, and the in-mold shaping | molding method is preferable from the point of productivity. In the in-mold molding method, after heating an acrylic resin film or a decorative acrylic resin film, vacuum molding is performed in a mold having a vacuuming function. This method is preferable from the viewpoints of workability and economy because the film can be molded and injection molded in one step.

  When in-mold molding is performed using an acrylic resin film having a printing layer, the printing layer near the gate may disappear depending on the mold shape and injection molding conditions. The gate is roughly classified into an unrestricted gate in which the resin path cannot be narrowed in the gate portion and a restricted gate in which the resin path is narrowed. Typical examples of the latter include pinpoint gates, side gates, and submarine gates. Although these gate shapes reduce the residual stress near the gate, the temperature of the resin passing through the gate increases, or the injection resin pressure per unit area on the acrylic resin film surface near the gate increases. The printed layer on the acrylic resin film surface tends to disappear.

  Among the acrylic resin films of the present invention, in particular, by using an acrylic resin film comprising an acrylic resin composition (A ″) composed of a rubber-containing polymer (I ″) and a thermoplastic polymer (II), Compared with the case where a conventional acrylic resin film is used, the disappearance of the pattern can be reduced. In addition, it is preferable to perform insert molding using a laminated sheet or a film from the point which can suppress the loss | disappearance of a printing layer more by suppressing transmission of a calorie | heat amount by presence of a thermoplastic resin layer.

  The heating temperature during in-mold molding is preferably equal to or higher than the temperature at which the acrylic resin film or the decorative acrylic resin film is softened. Specifically, although it depends on the thermal properties of the 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 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, a 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, high-cycle vacuum forming is possible, and the industrial utility value is high.

  As a method for suppressing the problem of disappearance of the printed layer generated when performing in-mold molding from the molding conditions, the preheating temperature during vacuum molding may be increased. The purpose of this is to use a printing layer having a heat-crosslinking reactive component and apply heat more than usual during molding to firmly fix the printing layer on the acrylic resin film and then mold it. This method naturally reduces the molding cycle. Among the acrylic resin films of the present invention, in particular, when an acrylic resin film comprising an acrylic resin composition (A ″) composed of a rubber-containing polymer (I ″) and a thermoplastic polymer (II) is used, Without adopting such a method, a laminated molded article having a good appearance can be obtained, so that a high cycle of molding is possible, and the industrial utility value is very high.

  Thus, when a three-dimensional shape is imparted to the film by vacuum forming, the acrylic resin film or the decorative acrylic resin film is rich in elongation at high temperatures, which is very advantageous.

  The laminated molded product obtained by laminating the acrylic resin film or the decorated acrylic resin film of the present invention on a base material can be subjected to surface treatment for imparting various functions as needed. For example, printing processes such as silk printing and ink jet printing, metal deposition / sputtering / wet plating process for imparting metal tone or preventing reflection, surface hardening process for improving surface hardness, water repellency process for preventing dirt, or Examples include photocatalyst layer forming treatment, dust adhesion prevention or antistatic treatment for the purpose of cutting electromagnetic waves, and antiglare treatment.

  Laminated molded products in which the acrylic resin film or decorative acrylic resin film of the present invention is laminated on a base material are instrument panels, console boxes, meter covers, door lock pezels, steering wheels, power window switch bases, center clusters, dashboards, etc. Automotive interior applications, weather strip, bumper, bumper guard, side mud guard, body panel, spoiler, front grill, strut mount, wheel cap, center pillar, door mirror, center ornament, side molding, door molding, wind molding, window, head Automotive exterior applications such as lamp covers, tail lamp covers, windshield parts, front panels for AV equipment and furniture products, buttons, emblems, surface cosmetics, Applications such as housings for mobile phones, display windows, buttons, etc., furniture exterior materials, wall interiors, ceilings, floors, etc., exterior walls such as siding, fences, roofs, gates, windbreak boards, etc. Applications for exterior building materials, window frames, doors, handrails, sills, duck, furniture, surface decoration materials for architectural interior materials, various displays, lenses, mirrors, goggles, optical materials such as window glass, and trains It can be suitably used for interior and exterior applications of various vehicles other than automobiles such as airplanes and ships, 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. it can.

  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 BzMA: benzyl methacrylate PhMA: phenyl methacrylate MA: methyl acrylate n-BA: n-butyl acrylate St: styrene ED: ethylene glycol dimethacrylate 1,3-BD: 1,3-butylene glycol dimethacrylate AMA: allyl Methacrylate CHP: Cumene hydroperoxide LPO: Lauryl peroxide t-BH: t-butyl hydroperoxide n-OM: n-octyl mercaptan EDTA: Disodium ethylenediaminetetraacetate

  Rubber-containing polymer (I) [(I ′) and (I ″)], thermoplastic polymer (II), thermoplastic polymer (IV), core-shell polymer (III) [(III-1) to (III −22)], acrylic resin film, and laminated molded product were measured for various physical properties by the following test methods.

The glass transition temperature of each polymer layer of the rubber-containing polymer (I) was calculated from the FOX equation using values described in Polymer Handbook (J. Brandrup, Interscience, 1989).

Gel content G (%) of rubber-containing polymer (I)
A predetermined amount of rubber-containing polymer (I) (mass before extraction: W ₀ (g)) is extracted under reflux in an acetone solvent, 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

Mass average particle diameter of rubber-containing polymer (I) The mass average particle diameter of the polymer latex of rubber-containing polymer (I) obtained by emulsion polymerization was measured by a light scattering photometer (Otsuka Electronics Co., Ltd., “DLS- 700 "(trade name)) and measured by a dynamic light scattering method.

Mass average particle diameter of core-shell polymer (III) [(III-1) to (III-22)] Using a laser diffraction / scattering type particle size distribution measuring device (“LA-910” (trade name) manufactured by Horiba, Ltd.) Measured.

Refractive index at 20 ° C. of core layer polymer (III-A) and thermoplastic polymer (II)
Values described in “PROPERTIES OF POLYMERS 3rd Edition” (ELSEVIER, 1990) were used. The refractive index of the copolymer was calculated from the volume ratio.

Reduced viscosity of thermoplastic polymer (II) and thermoplastic polymer (IV) Measured at 25 ° C. using “AVL-2C” (trade name) automatic viscometer manufactured by San Denki Kogyo, using chloroform as the solvent. did. In the measurement of the reduced viscosity, a sample prepared by dissolving 0.1 g of a sample in 100 mL of chloroform was used.

Surface glossiness of film Using a gloss meter (manufactured by Murakami Color Research Laboratory, GM-26D type), the surface in contact with the mirror surface roll of the film obtained by sandwiching the film between the mirror surface roll and the silicone mirror surface roll is 60. Measured at an angle of °.

Internal haze of the film Acrylic resin film is sandwiched between two mirror-finished SUS plates with a thickness of 3 mm and a surface roughness of 0.5 S, held for 3 minutes under conditions of 130 ° C. and 3 MPa, and then cooled to room temperature or below. The film thus prepared was measured according to JIS K7164.

Film HDT
The pellets of the resin composition were formed into heat deformation temperature measurement specimens based on ASTM D648 by injection molding and annealed at 60 ° C. for 4 hours. And this test piece was used and measured according to ASTM D648 with a low load (0.45 MPa).

Pencil hardness of film Measured according to JIS K5400.

Number of missing prints A gravure pattern was printed on one side of the acrylic resin film, a 5 m ² visual inspection was performed, and the number of missing prints was measured and converted to 1 m ² .

Designability of laminated molded product The surface appearance of the in-mold molded product was visually observed and evaluated as follows.
○: The printed layer looks clear.
X: The printed layer looks dull.

<1. Production of rubber-containing polymer (I ′)>
Under a nitrogen atmosphere, 244 parts of deionized water was placed in a reaction vessel equipped with a reflux condenser, and the temperature was raised to 80 ° C. Then, (15) shown below was added, and while stirring, 1/15 of the raw material (b) for the polymer (I′-A ₁ ) shown below was charged and held for 15 minutes. Next, the remaining raw material (b) was continuously added at an increase rate of 8% / hour of the monomer mixture [raw material (b)] with respect to water, and then held for 60 minutes to obtain a polymer (I′-A ₁ ) Latex was obtained. The Tg of the polymer (I′-A ₁ ) alone was 24 ° C.

Subsequently, 0.6 parts of sodium formaldehyde sulfoxylate was added to the latex and held for 15 minutes. Then, while stirring at 80 ° C. in a nitrogen atmosphere, the raw material (c) for the polymer (I′-A ₂ ) shown below was increased by 4% in the monomer mixture [raw material (c)] with respect to water. / Hour, continuously added, then held for 120 minutes to polymerize the polymer (I′-A ₂ ), and the innermost layer polymer (I′-A) [(I′-A ₁ ) + (I′-A ₂ )] latex was obtained. The Tg of the polymer (I′-A ₂ ) alone was −38 ° C.

  Subsequently, 0.4 parts of sodium formaldehyde sulfoxylate was added to the latex and held for 15 minutes. Then, while stirring at 80 ° C. in a nitrogen atmosphere, the raw material (d) for the outermost layer polymer (I′-C) shown below was increased by a monomer mixture [raw material (d)] with respect to water at an increase rate of 10 After continuously adding at% / hour, the mixture was held for 60 minutes, and the outermost layer polymer (I′-C) was polymerized to obtain a polymer latex of the rubber-containing polymer (I ′). The Tg of the outermost layer polymer (I′-C) alone was 99 ° C.

  The polymer latex of the obtained rubber-containing polymer (I ′) is subjected to coagulation, aggregation and solidification using calcium acetate, filtered, washed with water, and dried to obtain the rubber-containing polymer (I ′). Obtained. The rubber-containing polymer (I ′) obtained had a mass average particle diameter of 0.28 μm. Further, the gel content of the rubber-containing polymer (I ′) was 90%.

(I) sodium formaldehyde sulfoxylate 0.6 part,
0.00012 parts of ferrous sulfate,
0.0003 parts EDTA.

(B) MMA 22.0 parts,
n-BA 15.0 parts,
3.0 parts of St,
0.4 part AMA,
1,3-BD 0.14 parts,
0.18 parts t-BH,
40% mono (polyoxyethylene nonylphenyl ether) phosphoric acid
Di (polyoxyethylene nonylphenyl ether) phosphoric acid 60%
1.0 part of a partially neutralized mixture of sodium hydroxide.

(C) 50.0 parts of n-BA,
10.0 parts of St,
0.4 part AMA,
1,3-BD 0.14 parts,
0.2 part of t-BH,
40% mono (polyoxyethylene nonylphenyl ether) phosphoric acid
Di (polyoxyethylene nonylphenyl ether) phosphoric acid 60%
1.0 part of a partially neutralized mixture of sodium hydroxide.

(D) 57.0 parts of MMA,
3.0 parts of MA,
n-OM 0.3 part,
0.06 parts t-BH.

<2. Production of rubber-containing polymer (I ")>
After charging 10.8 parts of deionized water into a vessel equipped with a stirrer, it consists of 0.3 part of MMA, 4.5 parts of n-BA, 0.2 part of 1,3-BD, 0.05 part of AMA and 0.025 part of CHP. The monomer mixture was added and stirred and mixed at room temperature. Next, 1.3 parts of an emulsifier (manufactured by Toho Chemical Industry Co., Ltd., trade name “phosphanol RS610NA”) was charged into the container while stirring, and stirring was continued for 20 minutes to prepare an emulsion.

Next, 139.2 parts of deionized water was put into a polymerization vessel equipped with a cooler, and the temperature was raised to 75 ° C. Further, a mixture prepared by adding 0.20 part of sodium formaldehyde sulfoxylate, 0.0001 part of ferrous sulfate and 0.0003 part of EDTA to 5 parts of ion-exchanged water was put into the polymerization vessel at once. Next, the prepared emulsion was added dropwise to 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 polymer (I ″ -A ₁ ).

Subsequently, a monomer mixture consisting of 9.6 parts of MMA, 14.4 parts of n-BA, 1.0 part of 1,3-BD and 0.25 part of AMA is dropped into the polymerization vessel over 90 minutes together with 0.016 part of CHP. Then, the reaction was continued for 60 minutes to complete the polymerization of the polymer (I ″ -A ₂ ) to obtain the innermost layer polymer (I ″ -A).

The Tg of the polymer (I ″ -A ₁ ) alone was −48 ° C., and the Tg of the polymer (I ″ -A ₂ ) alone was −10 ° C.

  Subsequently, a monomer mixture consisting of 6 parts of MMA, 4 parts of MA and 0.075 part of AMA was added dropwise to 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 ( I ″ -B) was formed. The Tg of the intermediate layer polymer (I ″ -B) alone was 60 ° C.

  Subsequently, a monomer mixture consisting of 57 parts of MMA, 3 parts of MA, 0.264 part of n-OM and 0.075 part of t-BH was dropped into the polymerization vessel over 140 minutes, and then the reaction was continued for 60 minutes. The polymer (I ″ -C) was formed to obtain a polymer latex of the rubber-containing polymer (I ″). The Tg of the outermost layer polymer (I ″ -C) alone was 99 ° C.

  The mass average particle diameter of the rubber-containing polymer (I ″) measured after the polymerization was 0.11 μm.

  The polymer latex of the rubber-containing polymer (I ″) thus obtained was filtered using a vibration type filtration device in which a SUS mesh (average opening: 62 μm) was attached to the filter medium, and then 3.5 parts of calcium acetate. It was salted out in an aqueous solution containing water, washed with water, collected, and dried to obtain a powdery rubber-containing polymer (I ″). The gel content of the rubber-containing polymer (I ″) was 70%.

  Further, 214.3 g of the obtained rubber-containing polymer (I ″) was added to 1500 mL of acetone filtered through a nylon mesh having an opening of 25 μm, and stirred for 3 hours to obtain an acetone dispersion of the rubber-containing polymer (I ″). Was prepared. Next, this dispersion was filtered through a nylon mesh having a mesh size of 32 μm, and then the nylon mesh was washed in chloroform for 15 minutes to wash the captured matter on the mesh with chloroform. Next, the captured substance after ultrasonic cleaning is put into 150 mL of acetone filtered through a nylon mesh having an opening of 25 μm together with the nylon mesh, and this liquid is subjected to ultrasonic treatment for 15 minutes, after which the nylon mesh is removed, A 150 mL acetone dispersion of the trapped material was prepared. Next, 70 mL of this dispersion was measured at 25 ° C. with an automatic liquid particle counter (model: KL-01) manufactured by Rion Co., Ltd., and the number of particles having a diameter of 55 μm or more was determined. there were.

<3. Production of core-shell polymer particles>
A container equipped with a stirrer was charged with 200 parts of deionized water in which 30 parts of a 5% polyvinyl alcohol aqueous solution was dissolved as a dispersion stabilizer, and the core layer polymer (III- A) Raw material was added. Thereafter, this mixed solution was treated with T.W. A uniform suspension having a predetermined droplet diameter was prepared using a K homomixer (manufactured by Tokushu Kika Kogyo Co.). Next, the temperature was raised to 70 ° C., and a polymerization reaction was carried out with stirring for 2 hours under a nitrogen atmosphere to obtain a core layer polymer (III-A) particle suspension. Next, this core layer polymer (III-A) particle suspension is cooled to 60 ° C., and the raw material for the shell layer polymer (III-B) shown in Table 1 is increased by a monomer mixture with respect to water. After continuous addition at 10% / hour, the temperature was raised to 80 ° C. when polymerization started and an exothermic peak was observed, and the reaction was terminated with stirring for 3 hours. The suspension was cooled, filtered and dried to obtain polymer particles. The obtained polymer particles are classified by an air classifier (manufactured by Nissin Engineering Co., Ltd .; trade name “TC-15N”), and the mass average particle diameter Dw of the core-shell polymer particles is 10 × Dw μm or more. Coarse particles were removed to obtain core-shell polymer particles. In addition, about 1.78 g of the core-shell structure polymer (the mass when assuming that the resin amount per 0.125 m ^{2 of the} 125 μm film is 17.8 g and the core-shell structure polymer is added by 10% by mass), It observed using the electron microscope (The Hitachi Ltd. make; brand name "S570"), and confirmed that the coarse particle of 10xDwmicrometer or more did not exist.

<4. Production of thermoplastic polymer (IV)>
The reaction vessel was charged with 200 parts of ion-exchanged water substituted with nitrogen, 1 part of “Latemul ASK” (trade name; manufactured by Kao Corporation) and 0.15 part of potassium persulfate as an emulsifier. Subsequently, 40 parts of MMA, 2 parts of n-BA, and 0.004 part of n-OM were charged and stirred at 65 ° C. for 3 hours in a nitrogen atmosphere to complete the polymerization. Subsequently, a monomer mixture consisting of 44 parts of MMA and 14 parts of n-BA was added dropwise over 2 hours, and then maintained for 2 hours to complete the polymerization. The obtained latex was added to a 0.25% aqueous sulfuric acid solution, the polymer was acidified, dehydrated, washed with water, and dried to recover the polymer in powder form. The reduced viscosity of the obtained copolymer was 0.38 L / g.

Example 1
23 parts of the rubber-containing polymer (I ′) obtained above, thermoplastic polymer (II) (MMA / MA copolymer, MMA / MA = 99/1 (mass ratio), reduced viscosity 0.06 L / g, Refractive index (20 ° C.) 1.4897, bead shape) 67 parts, core-shell polymer (III-1) 10 parts, Ciba Specialty Chemicals Co., Ltd. as a compounding agent; trade name “Tinubin 234” 1.4 parts, Asahi Denka Kogyo Product name: “Adeka Stub AO-60” 0.1 part, Asahi Denka Kogyo Co., Ltd. “LA-67” 0.3 part, Johoku Chemical Industry Co., Ltd. product name “JP333E” 0.3 part, Nippon Aerosil Co., Ltd. Manufactured; 0.3 part of a trade name “Aerosil R972” and 6 parts of a thermoplastic polymer (IV) were mixed in a Henschel mixer. This mixture was supplied to a degassing extruder (manufactured by Ikekai Tekko Co., Ltd .; trade name “PCM-30”) heated to 230 ° C. and kneaded to obtain pellets. The obtained pellet had an HDT of 90 ° C.

  The pellets were dried at 80 ° C. for a whole day and night, and a cylinder temperature of 180 to 240 ° C. and a T die temperature of 240 ° C. were used using a 40 mmφ non-vent screw type extruder (L / D = 26) equipped with a 300 mm wide T die. Under the conditions, melt extrusion was performed through a 100-mesh metal filter and a T-die. The extruded resin was sandwiched between a mirror mirror roll for cooling adjusted to 75 ° C. (a chrome-plated roll having a surface roughness of 0.2S) and a silicone mirror rubber roll to form an acrylic resin film having a thickness of 125 μm. . The film had a pencil hardness of H.

  On the silicone mirror surface rubber roll contact surface side of the obtained acrylic resin film, scaly aluminum is added to 10 parts of gravure ink in which acrylic resin is dissolved in MEK and toluene (= 1/1 vol / vol) at a solid content of 25%. Using an ink containing 2 parts of pigment, printing in silver metallic tone was performed by gravure printing. The thickness of the printing layer was 5 μm. No print loss occurred.

  Next, using a heat-resistant ABS resin “Bulksum TM25B” (trade name; manufactured by UMGABS) and a printed acrylic resin film as a base resin, it has a vacuum drawing function, and a mold (molded product shape: Box shape: 150 mm long × 120 mm wide × 2 mm thick, 10 mm deep, gate position: 1 location in the center of the molded product, and 1 location each at 40 mm above and below the central gate (vertical direction of the molded product), gate Shape: 1mm diameter pinpoint gate) and in-mold molding equipment combined with J85ELII type injection molding machine (trade name; manufactured by Nippon Steel Co., Ltd.) and hot pack system (produced by Nissha Printing Co., Ltd.) Molding (film vacuum molding conditions: heater temperature 260 ° C., heating time 15 seconds, heater-film distance 15 mm, injection molding conditions: cylinder to nose A temperature of 250 ° C., an injection speed of 30%, an injection pressure of 43%, a mold temperature of 60 ° C., vacuum-molded so that the non-decorated surface is in contact with the mold, and a base resin was injected from the decorated surface side) A laminated molded product was obtained.

(Example 2)
Example 1 except that the blending ratio of the rubber-containing polymer (I ′), the thermoplastic polymer (II), and the core-shell polymer (III-1) is 23/62/15 (part / part / part). It carried out similarly. The obtained pellet had an HDT of 89 ° C. Further, the pencil hardness of the obtained film was H.

(Example 3)
The same as Example 1 except that the blending ratio of the rubber-containing polymer (I), the thermoplastic polymer (II), and the core-shell polymer (III-1) was 23/72/5 (part / part / part). Implemented. The obtained pellet had an HDT of 91 ° C. Further, the pencil hardness of the obtained film was H.

(Examples 4 to 21)
In Example 1, it implemented like Example 1 except having changed the composition of the core-shell polymer as shown in Table 1, respectively (core-shell polymer (III-2)-(III-19)). The HDT of the obtained pellets was 90 ° C., and the pencil hardness of the obtained film was H.

(Example 22)
65 parts of rubber-containing polymer (I ″), thermoplastic polymer (II) (MMA / MA copolymer, MMA / MA = 99/1 (mass ratio), reduced viscosity 0.06 L / g, refractive index (20 ° C) 1.4897, bead shape) 25 parts, 10 parts of core-shell polymer (III-1), manufactured by Ciba Specialty Chemicals Co., Ltd .; 1.4 parts of “Tinuvin 234”, manufactured by Asahi Denka Kogyo Co., Ltd .; Name “Adeka Stub AO-60” 0.1 part, Asahi Denka Kogyo Co., Ltd. LA-67 0.3 part, Johoku Chemical Industry Co., Ltd. trade name “JP333E” 0.3 part, Nippon Aerosil Co., Ltd. product name “ Aerosil R972 "0.3 part and thermoplastic polymer (IV) 3 part were mixed in a Henschel mixer. This mixture was supplied to a degassing extruder (manufactured by Ikekai Tekko Co., Ltd .; trade name “PCM-30”) heated to 230 ° C. and kneaded to obtain pellets. The same procedure as in Example 1 was performed except that pellets of this resin composition were used. The obtained pellet had an HDT of 88 ° C. Further, the pencil hardness of the obtained film was H.

(Example 23)
Example 22 except that the blending ratio of the rubber-containing polymer (I ″), the thermoplastic polymer (II), and the core-shell polymer (III-1) is 65/20/15 (part / part / part). The HDT of the obtained pellet was 88 ° C. The pencil hardness of the obtained film was H.

(Example 24)
Example 22 except that the blending ratio of the rubber-containing polymer (I ″), the thermoplastic polymer (II), and the core-shell polymer (III-1) is 65/30/5 (part / part / part). The HDT of the obtained pellet was 89 ° C. The pencil hardness of the obtained film was H.

(Comparative Examples 1-3)
In Example 1, it implemented like Example 1 except having changed the composition of the core-shell polymer as shown in Table 1, respectively (core-shell polymer (III-20)-(III-22)). The HDT of the obtained pellets was 90 ° C., and the pencil hardness of the obtained film was H.

  Table 2 summarizes the evaluation results of the acrylic resin film, the decorative film, and the laminated molded product obtained as described above.

  The difference (absolute value) between the refractive index (n) of the thermoplastic polymer (II) at 20 ° C. and the refractive index (n ′) at 20 ° C. of the core layer polymer (III-A) of the core-shell polymer (III) is Using the acrylic resin films of Examples 1 to 24 that are 0.003 or less, a laminated molded product obtained by performing in-mold molding after printing on one side of the film has an appearance of the printed layer. It became clear and excellent in design.

  On the other hand, the absolute difference between the refractive index (n) of the thermoplastic polymer (II) at 20 ° C. and the refractive index (n ′) of the core layer polymer (III-A) of the core-shell polymer (III) at 20 ° C. When the acrylic resin films of Comparative Examples 1 to 3 having a value exceeding 0.003 were used, the printed layer looked dull and inferior in design, and the industrial utility value was low.

  The acrylic resin film of the present invention has surface hardness, scratch resistance, and heat resistance that can be used for insert molding and in-mold molding, has good printability, and has good design properties. Is.

  Laminated molded products laminated with acrylic resin films of the present invention include instrument panels, console boxes, meter covers, door lock pezels, steering wheels, power window switch bases, center clusters, dashboards and other automotive interior applications, weather strips, bumpers, Bumper guard, side mud guard, body panel, spoiler, front grill, strut mount, wheel cap, center pillar, door mirror, center ornament, side molding, door molding, wind molding, window, head lamp cover, tail lamp cover, windshield parts, etc. Automotive exterior applications, front panels for AV equipment and furniture products, buttons, emblems, surface cosmetics, housings for mobile phones, display windows, buttons Applications, furniture exterior materials, wall interiors, ceilings, floors and other architectural interior materials, siding exterior walls, roofs, roofs, gates, windbreak boards, and other architectural exterior materials, window frames, doors, Use for surface decoration of architectural interior materials such as handrails, sills, duck, furniture, etc., various displays, lenses, mirrors, goggles, optical materials such as window glass, or various vehicles other than automobiles such as trains, airplanes, ships, etc. It can be suitably used for interior / exterior use, various packaging containers and materials such as bottles, cosmetic containers and accessory cases, and other various uses such as miscellaneous goods such as prizes and accessories.

Claims (4)

Acrylic resin composition (A) comprising a rubber-containing polymer (I) shown below and a thermoplastic polymer (II) having a reduced viscosity of 0.15 L / g or less of a polymer mainly composed of alkyl methacrylate. The acrylic resin composition (B) formed by adding 0.5 to 50 parts by mass of the core-shell polymer (III) shown below with respect to 100 parts by mass is a constituent component, and the thermoplastic polymer (II) at 20 ° C. An acrylic resin film in which the refractive index (n) and the refractive index (n ′) of the core layer polymer (III-A) of the core-shell polymer (III) satisfy the following formula (i).
Rubber-containing polymer (I):
In the presence of an elastic polymer (IA) as an innermost layer having a structure of one layer or two or more layers obtained by using an alkyl acrylate ester as a main component, at least a single component having an alkyl methacrylate ester as a main component A multilayer structure of two or more layers having a mass average particle diameter of 0.01 to 0.5 μm, which is obtained by molding the outermost layer polymer (IC) having a structure of one layer or two or more layers by graft polymerization of the body Rubber-containing polymer having a core-shell polymer (III):
The core layer polymer (III-A) and the shell layer polymer (III-B) are laminated in this order, and each polymer layer is composed of the monomer components shown below. (1) Monomer component for constituting the core layer polymer (III-A) (III-A1) alkyl acrylate ester 10 to 90% by mass
(III-A2) Methacrylic acid alkyl ester 10 to 90% by mass
(III-A3) Other monomer having copolymerizable double bond 0 to 50% by mass
(III-A4) Polyfunctional monomer 0 to 20% by mass
(III-A5) Graft crossing agent 0.1-20% by mass
Content of core layer polymer (III-A) in core-shell polymer (III) 25-85 mass%
(2) Monomer component for constituting shell layer polymer (III-B) (III-B1) Methacrylic acid alkyl ester 60-100% by mass
(III-B2) Acrylic acid alkyl ester 0 to 40% by mass
(III-B3) Other monomer having copolymerizable double bond 0 to 40% by mass
Content of shell layer polymer (III-B) in core-shell polymer (III) 15 to 75% by mass
Formula (i):
0 ≦ | n−n ′ | ≦ 0.003   The acrylic resin film according to claim 1, wherein the resin composition is produced by melt-extrusion and then forming a film by sandwiching between a mirror roll and a rubber roll or a textured roll.   The acrylic resin film of Claim 2 which printed on the single side | surface of the acrylic resin film.   An acrylic resin laminated molded product obtained by laminating the acrylic resin film according to any one of claims 1 to 3 on a base material.