JP2006022262A - Acrylic resin film, decorated acrylic resin film and laminate-molded product including the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an acrylic resin film having excellent moldability without causing appearance defects such as flow of decoration at in-mold decorating; to provide a decorating acrylic resin film; and to provide a laminate molded product having the film on the surface. <P>SOLUTION: The acrylic resin film comprises an acrylic resin composition having ≥7×10<SP>3</SP>Pa storage modulus (G') at 250°C and ≥80°C heat distortion temperature (measured based on ASTM D648). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an acrylic resin film, a decorative acrylic resin film, and a molded product in which these are laminated.

  Acrylic resin films made of acrylic resin containing rubber are laminated on the surface of various resin molded products, woodwork products, and metal molded products, taking advantage of excellent properties in transparency, weather resistance, flexibility, and workability. Used as interior and exterior, skin materials for building materials such as furniture, door materials, window frames, baseboards, and bathroom interiors, marking films, and high-intensity reflector coating films.

  Conventionally, various resin compositions have been proposed and put to practical use as acrylic resin film raw materials used for the above-mentioned applications. Of these, alkyl acrylates, methacrylate esters, and graft crossing agents are used as raw materials to provide acrylic resin films that are particularly excellent in weather resistance, transparency, and stress whitening resistance such as bending whitening resistance. A multilayer structure polymer having a specific structure as a constituent component of the coalescence is known (see, for example, Patent Documents 1 and 2). Moreover, the multilayer structure polymer as a raw material of the acrylic resin film which has the same characteristic is disclosed (for example, refer patent documents 3-5).

  On the other hand, there is an in-mold molding method as a method for imparting design properties to a molded product at low cost. The in-mold molding method is a method in which a polyester resin, polycarbonate resin, acrylic resin sheet or film that has been decorated for printing or the like is placed in an injection mold, vacuum molded, and then in the same mold. An integrated molded product is obtained by injection molding a resin as a base material. 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.

  As an acrylic resin film excellent in surface hardness and heat resistance that can be used for in-mold molding, a rubber-containing polymer having a specific composition and a thermoplastic polymer having a specific composition are mixed at a specific ratio. An acrylic resin film is disclosed (see, for example, Patent Documents 6 to 9). Such an acrylic resin film not only imparts decorativeness to the molded product, but also has a function as an alternative material for clear coating.

  By the way, in the in-mold molding method, as described above, after mounting the decorated sheet or film inside the molding die, the molten high-temperature substrate resin is injected at a high pressure. Depending on the injection molding conditions and the shape of the mold, the decoration applied to the sheet or film flows particularly near the gate. In severe cases, the decorative layer disappears (hereinafter referred to as “decoration flow”). May occur), or the decorative flow may cause insufficient adhesion strength between the sheet or film and the base resin. In particular, in the case of a high-intensity decorative layer such as a metallic tone, not only the defects in the decorative flow are conspicuous in the vicinity of the gate, but also an appearance defect that appears as if the decorative layer is recessed may occur. In addition, there is a problem that the sheet or film is deformed, the quality of the product is inferior, and the product cannot be used as a product.

Therefore, in order to solve such problems, a method using a printing ink with high heat resistance (for example, see Patent Document 10) or a method using an ink containing metal fine particles subjected to a specific surface coating treatment (for example, a patent) Reference 11), a mold having a specific mold gate diameter, a method of forming a molded product and a decorative sheet with a specific thickness (see, for example, Patent Document 12), heat conduction in the decorative layer of the decorative sheet A method of laminating a suppression layer (for example, see Patent Document 13), a method using a decorative sheet having a specific thickness (for example, see Patent Document 14), and the like have been proposed.
Japanese Examined Patent Publication No. 62-19309 Japanese Patent Publication No. 63-8983 Japanese Patent Laid-Open No. 11-60876 JP 11-335511 A JP 2001-81266 A Japanese Patent No. 3142774 Japanese Patent No. 3287315 JP 2002-80678 A Japanese Patent No. 3479645 Japanese Patent No. 2997636 Japanese Patent No. 3422966 Japanese Patent No. 3396654 Japanese Patent Application Laid-Open No. 2002-113738 Japanese Patent No. 2725735

  In Patent Documents 1 to 5, there is no description regarding in-mold molding of the obtained acrylic resin film, and further there is no description regarding surface hardness and heat resistance. For this reason, when the present inventors made the acrylic resin film described in the publication example, and decorated it after in-mold molding, the film was deformed and wrinkles were generated in the molded product. . Further, the surface hardness (abrasion resistance) and heat resistance of the film did not reach the levels required for vehicle use.

  In addition, the acrylic resin films described in Patent Documents 6 to 9 are not described in detail with respect to the appearance of the molded product when in-mold molding is performed after applying the decorative layer, and the inventors described in this publication. When an acrylic resin film was actually created and decorated, in-mold molding was performed. As a result, a decorative layer near the gate flowed, and an appearance defect in which the color tone of the resin for the substrate appeared.

  In addition, various problems that occur when in-mold molding is performed by the method described in Patent Documents 10 to 13 using acrylic resin films described in Patent Documents 6 to 9 (decoration flow, film and base due to decoration flow) In order to reduce the adhesiveness with the resin for the material and the deformation of the film, etc., these gazettes are methods for improving the in-mold formability from the surface of the decorative sheet or film of acrylic resin etc. It is not described. In addition, these improved methods restrict the material of the ink layer used for the decorative layer, restrict the design of the mold, restrict the injection molding conditions, and provide a heat insulating layer to decorate the decorative film. It is intended to narrow the degree of design freedom for obtaining a laminated molded product such as restricting the structure, and an improvement from an acrylic resin film has been desired.

  Moreover, although the description regarding the polymethyl methacrylate film is made | formed in the Example of patent document 14, description of the composition of this film, the brand name of a polymethyl methacrylate film, etc. is not made at all. For this reason, when applying in-mold molding after giving a decoration layer using what adjusted the thickness of the acrylic resin film of patent documents 6-9 to 100 micrometers, a decoration flow is observed in all. It was.

  That is, an object of the present invention is to provide an acrylic resin film having excellent moldability, a decorative acrylic resin film, and these films that do not cause appearance defects such as decorative flow when used for in-mold molding. An object of the present invention is to provide a laminated molded article having a surface thereof.

The above object of the present invention can be solved by the following present invention.
An acrylic resin film comprising an acrylic resin composition having a storage elastic modulus (G ′) at 250 ° C. of 7 × 10 ³ Pa or higher and a heat distortion temperature (measured based on ASTM D648) of 80 ° C. or higher.
-Said acrylic resin film which has a decoration layer at least on one side.
-A laminated molded product obtained by laminating the above acrylic resin film on a substrate.

According to the present invention, an acrylic resin comprising an acrylic resin composition having a storage elastic modulus (G ′) at 250 ° C. of 7 × 10 ³ Pa or more and a heat distortion temperature (measured based on ASTM D648) of 80 ° C. or more. By adopting a resin film, when performing in-mold molding after applying a decorative layer to the film, the occurrence of appearance defects due to the decoration flow particularly near the gate, and the accompanying film and substrate It is possible to provide a laminated molded product without causing problems during in-mold molding, such as a decrease in adhesive strength with the resin for use, and generation of wrinkles on the surface of the molded product due to deformation of the film.

  In addition, by using the acrylic resin film of the present invention, restrictions on the material of the ink layer used for the decorative layer, restrictions on the mold design, restrictions on the injection molding conditions, restrictions on the decorative film configuration such as the arrangement of the heat insulating layer, etc. The problem of narrowing the degree of freedom of design for obtaining a laminated molded product can be solved. The acrylic resin film of the present invention has a very high industrial utility value, and can greatly expand the conventional usage.

The acrylic resin composition constituting the acrylic resin film of the present invention has a storage elastic modulus (G ′) at 250 ° C. of 7 × 10 ³ Pa or more. The decoration flow that occurs during in-mold molding is caused by the flow near the acrylic resin film interface on the side in contact with the decoration layer at the moment when the base resin is injected into the mold cavity at high temperature and high pressure. To do. Therefore, when an acrylic resin film made of an acrylic resin composition having a storage elastic modulus (G ′) at 250 ° C. of 7 × 10 ³ Pa or more is used as in the present invention, a large amount of the resin for the base material is used during injection molding. Even if the amount of heat is transmitted, it is possible to prevent flow and the like from occurring in the decorated film (hereinafter, sometimes referred to as “decorated acrylic resin film” in particular). Since a laminated molded product can be obtained without causing appearance defects and a decrease in the adhesive strength between the film and the resin for the substrate accompanying this, the industrial utility value is increased.

It is more preferable to use an acrylic resin film made of an acrylic resin composition having a storage elastic modulus (G ′) at 250 ° C. of 9 × 10 ³ Pa or more. In this case, even in a metallic printed pattern containing metal particles such as aluminum particles in which appearance defects are conspicuous, a laminated molded product can be obtained without causing the above-described problems, and thus the industrial utility value is extremely high. Furthermore, an acrylic resin film made of an acrylic resin composition having a storage elastic modulus (G ′) of 13 × 10 ³ Pa or higher at 250 ° C. is preferable.

Moreover, it is preferable to use the acrylic resin film which consists of an acrylic resin composition whose storage elastic modulus (G ') in 250 degreeC is 150 * 10 < ³ > Pa or less. In this case, the acrylic resin film has good vacuum formability or pressure formability in the injection mold. Moreover, when manufacturing this acrylic resin film by a melt extrusion method, it has favorable film forming property. Furthermore, the acrylic resin film which consists of an acrylic resin composition which has the storage elastic modulus (G ') of 130 * 10 < ³ > Pa or less in 250 degreeC is preferable.

  The storage elastic modulus (G ′) is measured by forming raw material pellets made of an acrylic resin composition constituting the acrylic resin film into a plate shape having a thickness of 2 mm by injection molding, and from this molded product to a disk shape. It can measure by using what was cut out for a test piece. For the measurement, RDA-700 (trade name) manufactured by Rheometrics is used, and the measurement conditions are a measurement temperature: 150 to 270 ° C. (temperature increase rate: 2 ° C./min), and a measurement angular frequency: 10 rad / sec.

  In addition, the acrylic resin composition constituting the acrylic resin film of the present invention has a heat distortion temperature (measured based on ASTM D648) of 80 ° C. or higher. When an acrylic resin film made of an acrylic resin composition having a heat distortion temperature of 80 ° C. or higher is used, the substrate resin is injected into the mold cavity at a high temperature and high pressure, but it becomes a molded product. As a result, it is possible to obtain a laminated molded article having a good appearance without causing a large deformation to remain. Furthermore, when exposed to a high temperature for a long time, the acrylic resin film surface is not whitened or clouded, and thus has high industrial utility value. Thereby, 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. The measurement of the heat distortion temperature is carried out using a heat deformation temperature measurement specimen obtained by molding raw material pellets made of an acrylic resin composition constituting an acrylic resin film by injection molding and annealing at 60 ° C. for 4 hours. The measured heat deformation temperature is usually the same as the heat deformation temperature of the acrylic resin film.

  Although it does not specifically limit, 130 degreeC or less is preferable for the heat deformation temperature of the acrylic resin composition which comprises the acrylic resin film of this invention. In this case, the acrylic resin film has good vacuum formability or pressure formability in the injection mold. Moreover, it has good productivity during vacuum forming. Furthermore, the heat distortion temperature is preferably 120 ° C. or lower.

  The resin used as a base material during in-mold molding is not particularly limited, but acrylonitrile-butadiene-styrene copolymer resin (ABS resin), polypropylene resin, polycarbonate resin, polystyrene resin, polyethylene resin, acrylonitrile-styrene resin (AS resin), Polymethyl methacrylate resin and the like are common. The temperature at the time of injection of the resin for the base material is set according to the resin at a temperature that can be sufficiently melted and kneaded in the cylinder and filled to every corner of the cavity when injected into the mold. Strictly speaking, the temperature of the molten resin for the base material entering the mold is lower than the set temperature of the nozzle part, and is 200 to 260 ° C. in most cases.

Accordingly, the acrylic resin composition constituting the acrylic resin film of the present invention preferably has a storage elastic modulus (G ′) of 7 × 10 ³ Pa or more in the range of 200 ° C. to 260 ° C. When an acrylic resin film having a storage elastic modulus (G ′) of 7 × 10 ³ Pa or more is used in the range of 200 ° C. to 260 ° C., the base resin is injected within the temperature range, and a large amount of heat is transmitted. However, it is possible to prevent flow and the like from occurring in the decorated film, and as a result, appearance defects due to the decoration flow and a decrease in the adhesive strength between the film and the resin for the substrate are caused. Since the laminated molded product can be obtained without increasing the industrial utility value. In addition, this effect can be applied to typical base resin used for in-mold molding, and the acrylic resin film can be used in most cases of obtaining laminated molded products by in-mold molding. The value is very high. Moreover, when the acrylic resin film which consists of an acrylic resin composition whose storage elastic modulus (G ') in the range of 200-260 degreeC is 9x10 < ³ > Pa or more was used, it contained metal particles, such as an aluminum particle with which an external appearance defect is conspicuous. Even in a metallic print pattern, a laminated molded product can be obtained without causing the above-described problems, so that the industrial utility value is extremely high. Even in the case of a resin for a substrate injected at a temperature higher than 260 ° C., the acrylic resin film of the present invention has a higher storage elastic modulus than conventionally known acrylic resin films. The effect of preventing the flow or the like of the decorated film is high, it is difficult to cause a decorative flow, and it is difficult to cause poor adhesion between the film and the substrate resin. Moreover, it is preferable to use the acrylic resin film which consists of an acrylic resin composition whose storage elastic modulus (G ') in the range of 200-260 degreeC is 150x10 < ³ > Pa or less. In this case, the acrylic resin film has good vacuum formability or pressure formability in the injection mold. Moreover, when manufacturing this acrylic resin film by a melt extrusion method, it has favorable film forming property. Furthermore, the acrylic resin film which consists of an acrylic resin composition whose storage elastic modulus (G ') in the range of 200-260 degreeC is 130 * 10 < ³ > Pa or less is preferable.

  The acrylic resin composition having the above characteristics preferably includes, for example, an acrylic polymer having a multilayer structure (hereinafter also simply referred to as “multilayer structure polymer (I)”).

  The acrylic resin composition used in the present invention may be only the above-mentioned multilayer structure polymer (I), but further, a polymer having a methacrylic acid alkyl ester unit as a main component (hereinafter simply referred to as “thermoplastic polymer (II)”. It is also preferable to use a resin composition (III) that is also used in combination. In this case, the heat resistance and hardness can be easily adjusted by changing the ratio of the multilayer structure polymer (I) to the thermoplastic polymer (II). 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.

<< Multilayer structure polymer (I) >>
The multilayer structure polymer (I) has a multilayer structure having the innermost layer polymer (IA), the intermediate layer polymer (IB), and the outermost layer polymer (IC) as basic structures in order from the inside. Have.

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

[Innermost layer polymer (IA)]
The innermost layer polymer (IA) constitutes the central portion of the polymer having the multilayer structure, and includes an acrylic acid alkyl ester (I-A1), a methacrylic acid alkyl ester (I-A2), and these Component comprising as a constituent other monomer (I-A3) having a double bond copolymerizable with polyfunctional monomer (I-A4) and graft crossing agent (I-A5) Is a polymer obtained by polymerizing 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) are optional. It is an ingredient.

  The alkyl acrylate ester of the component (IA1) contained in the monomer component for constituting the innermost layer polymer (IA) may be either linear or branched alkyl group. Specific examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. These can be used 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 as necessary in the monomer component for constituting the innermost layer polymer (IA), has a linear or branched alkyl group. Either is fine. 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 in the monomer component for constituting the innermost layer polymer (IA) 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 polyfunctional monomer of the component (I-A4) contained as necessary in the monomer component for constituting the innermost layer polymer (IA) is the same copolymerizable duplex. 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. Further, polyvinylbenzene 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 considerably stable multilayer structure 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 (IA5) contained in the monomer component for constituting the innermost layer polymer (IA) 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. In addition, triallyl cyanurate, triallyl isocyanurate and the like of the above polyfunctional monomer (I-A4) are also effective as the graft crossing agent (I-A5). The graft crossing agent (I-A5) is polymerized mainly because the conjugated unsaturated bond of the ester reacts much faster than the allyl group, methallyl group or crotyl group. During this time, a substantial portion of the allyl, methallyl, or crotyl group works effectively during the polymerization of the next layer of polymer, providing a graft bond between adjacent two layers.

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

  The total content of the acrylic acid alkyl ester (I-A1) and the methacrylic acid alkyl ester (I-A2) in the monomer component for constituting the innermost layer polymer (IA) is 80 to 99. .9% by mass is preferred.

  The content of the acrylic acid alkyl ester (I-A1) in the monomer component for constituting the innermost layer polymer (IA) 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 (IA) 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 (IA) is 0 to 20% by mass. preferable. More preferably, it is 15 mass% or less.

  The content of the polyfunctional monomer (IA4) in the monomer component for constituting the innermost layer polymer (IA) 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 (IA-5) in the monomer component for constituting the innermost layer polymer (IA) is preferably 0.1 to 10% by mass. When the content is 0.1% by mass or more, the resulting multilayer structure polymer (I) can be molded without reducing optical properties such as transparency. A content of 10% by mass or less is preferable because sufficient flexibility and toughness can be imparted to the multilayer structure polymer (I). 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 (IA) alone is an intermediate layer described later from the viewpoint of impact resistance and molding whitening resistance of the resulting acrylic resin film, decorative acrylic resin film, and laminate. It is preferable that it is less than Tg of a polymer (IB) single. More preferably, it is less than 25 degreeC, More preferably, it is 10 degreeC or less, Most preferably, it is 0 degreeC or less. Tg can be calculated from the FOX equation using values described in Polymer Handbook (Polymer HandBook (J. Brandrup, Interscience, 1989)).

  Although it does not specifically limit, 15-50 mass% is preferable for content of innermost layer polymer (IA) in multilayer structure polymer (I). In the case of 15% by mass or more, the resulting acrylic resin film, decorative acrylic resin film and laminate can be imparted with resistance to molding whitening, decorative flow resistance at the time of in-mold molding, and the like. Can be made compatible with the toughness that can be obtained by insert molding and in-mold molding of the resulting acrylic resin film and decorative acrylic resin film. 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 (IA) may be a single layer or multiple layers, but more preferably is two layers. Although not particularly limited, it is preferable that the monomer constitution ratio of the two layers in the innermost layer polymer (IA) is different.

If the innermost layer polymer (I-A) is composed of two layers, the Tg of the inner layer (I-A ₁₎ Tg and the outer layer of (I-A _2), but may be the same, resulting acrylic resin film From the viewpoint of molding whitening resistance, impact resistance, and surface hardness of the decorative acrylic resin film and laminate, the Tg of the inner layer (IA- ₁ ) is lower than the Tg of the outer layer (IA- ₂ ). Is preferred. Specifically, the resulting acrylic resin film, in view of the decorative acrylic resin film and耐成type whitening resistance and impact resistance of the laminate, the Tg of the inner layer (I-A ₁₎ is preferably less than -30 ° C., The Tg of the outer layer (I-A ₂ ) is preferably 10 ° C. or less. In particular, from the viewpoint of surface hardness, the outer layer (IA ₂ ) preferably has a Tg of −15 ° C. or higher. At this time, in view of the surface obtained hardness, the content of the innermost layer polymer (I-A) the inner layer in (I-A ₁₎ is 1 mass% or more, preferably 20 wt% or less, the outer layer (I -A ₂ content) of 80 mass% or more, preferably 99 mass% or less.

[Intermediate layer polymer (IB)]
The intermediate layer polymer (IB) is copolymerized with alkyl acrylate (I-B1), alkyl methacrylate (I-B2), and these in the presence of the innermost layer polymer (IA). A monomer component comprising other monomer (I-B3) having a possible double bond, multifunctional monomer (I-B4) and graft crossing agent (I-B5) as a constituent component is polymerized. Preferably, it is a polymer in which the polymer Tg of the monomer component here is higher than the Tg of the innermost layer polymer. In this monomer component, component (I-B1), component (I-B2), and component (I-B5) are essential components, and component (I-B3) and component (I-B4) are optional. It is an ingredient.

  The alkyl acrylate ester of the component (I-B1) contained in the monomer component for constituting the intermediate layer polymer (IB) may be either a linear or branched alkyl group. Specific examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. These can be used alone or in admixture of two or more. Of these, preferred are methyl acrylate and n-butyl acrylate.

  The methacrylic acid alkyl ester of the component (IB2) contained in the monomer component for constituting the intermediate layer polymer (IB) may be either a linear or branched alkyl group. Specific examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and n-butyl methacrylate. These can be used alone or in 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 as necessary in the monomer component for constituting the intermediate layer polymer (IB) 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 polyfunctional monomer of the component (I-B4) contained as necessary in the monomer component for constituting the intermediate layer polymer (IB) is ethylene glycol dimethacrylate, 1,3-butylene. It is preferable to use alkylene glycol dimethacrylates such as glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and propylene glycol dimethacrylate. Further, polyvinylbenzene 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 multilayer structure 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.

  As the graft crossing agent (I-B5) contained in the monomer component for constituting the intermediate layer polymer (IB), allyl of copolymerizable α, β-unsaturated carboxylic acid or dicarboxylic acid, Examples include 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. In addition, triallyl cyanurate, triallyl isocyanurate and the like of the above polyfunctional monomer (I-B4) are also effective as the graft crossing agent (I-B5). Graft-crossing agent (I-B5) is chemically bonded mainly because the conjugated unsaturated bond of its ester reacts much faster than 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 polymer to provide a graft bond between adjacent two layers.

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

  The total content of alkyl acrylate (I-B1) and alkyl methacrylate (I-B2) in the monomer component for constituting the intermediate layer polymer (IB) is 19.8. -90 mass% is preferable.

  The content of the acrylic acid alkyl ester (I-B1) in the monomer component for constituting the intermediate layer polymer (IB) is preferably 9.9 to 90% by mass. From the viewpoint of molding whitening resistance, surface hardness, heat resistance, and decorative flow resistance when in-mold molding of the resulting acrylic resin film, decorative acrylic resin film and laminate, more preferably 19.9 masses. % Or more, most preferably 29.9% by mass or more. Further, it is more preferably 60% by mass or less, and most preferably 50% by mass or less.

  The content of the methacrylic acid alkyl ester (I-B2) in the monomer component for constituting the intermediate layer polymer (IB) is preferably 9.9 to 90% by mass. From the viewpoint of molding whitening resistance, surface hardness, heat resistance, and decorative flow resistance when in-mold molding of the obtained acrylic resin film, decorative acrylic resin film and laminate, more preferably 39.9 masses. % Or more, most preferably 49.9% by mass or more. Further, it is more preferably 80% by mass or less, and most preferably 70% by mass or less.

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

  The content of the polyfunctional monomer (IB-4) in the monomer component for constituting the intermediate layer polymer (IB) 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 (IB) is preferably 0.1 to 10% by mass. When the content is 0.1% by mass or more, the obtained multilayer structure polymer (I) can be molded without deteriorating the optical properties. A content of 5% by mass or less is preferable because sufficient flexibility and toughness can be imparted to the multilayer structure polymer (I). More preferably, it is 0.5 mass% or more and 2 mass% or less.

  Here, the composition of the intermediate layer polymer (IB) is preferably different from the composition of the innermost layer polymer (IA). 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 (IB) is 25 to 100 ° C. When Tg is 25 ° C. or higher, the decorative flow resistance when in-mold molding is good, and the surface hardness and heat resistance are at levels required for vehicle use. More preferably, it is 40 degreeC or more, Most preferably, it is 50 degreeC or more. Moreover, when Tg is 100 degrees C or less, the shaping | molding property at the time of shape | molding an acrylic resin to a film form becomes favorable with the shaping | molding whitening resistance good of the acrylic resin film obtained, a decorative acrylic resin film, and a laminated body. More preferably, it is 80 degrees C or less, Most preferably, it is 70 degrees C or less.

  Thus, by providing the intermediate layer polymer (IB) having a specific composition and Tg, the multilayer structure polymer (I) or resin suitable for satisfying the required physical properties has not been designed so far. It is difficult to realize the above, and it is possible to achieve both the whitening resistance, surface hardness, heat resistance, and anti-decorative flow resistance when in-mold molding of the resulting acrylic resin film, decorative acrylic resin film and laminate. Can do.

  Although not particularly limited, the content of the intermediate layer polymer (IB) in the preferred multilayer structure polymer (I) is preferably 5 to 35% by mass. If it is within this range, the molding resin whitening resistance of the resulting acrylic resin film, decorative acrylic resin film and laminate, surface hardness, heat resistance, and anti-decoration flow resistance when in-mold molding are compatible. Therefore, the function of the intermediate layer polymer (IB) important for the purpose can be expressed, and other physical properties of the obtained film, for example, the film forming property when an acrylic resin is formed into a film, the resulting acrylic It is preferable because the toughness possible for insert molding and in-mold molding of the resin film and the decorative acrylic resin film can be imparted. More preferably, it is 20 mass% or less.

[Outermost layer polymer (IC)]
The outermost layer polymer (IC) is copolymerized with methacrylic acid alkyl ester (I-C1), acrylic acid alkyl ester (I-C2), and these in the presence of the polymer formed up to the intermediate layer. It is formed by graft polymerization of a monomer component containing another monomer (I-C3) having a possible double bond as a constituent component. The outermost layer polymer (IC) 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 (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 (IC) may be either a linear or branched alkyl group. Specific examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and n-butyl methacrylate. These can be used alone or in admixture of two or more. Of these, methyl methacrylate is preferred.

  The acrylic acid alkyl ester of the component (I-C2), which is included as necessary in the monomer component for constituting the outermost layer polymer (I-C), 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 component (I-C3) included as necessary in the monomer component for constituting the outermost layer polymer (IC) is Acrylic monomers such as 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 methacrylic acid alkyl ester (I-C1) in the monomer component for constituting the outermost layer polymer (IC) is preferably 51 to 100% by mass. From the viewpoints of surface hardness, heat resistance, and decorative flow resistance when in-molded, the acrylic resin film is more preferably 80% by mass or more, more preferably 90% by mass or more, and most preferably 93% by mass. % Or more. Moreover, it is 99 mass% or less more preferably.

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

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

  Although it does not specifically limit, a chain transfer agent is used at the time of superposition | polymerization of outermost layer polymer (IC), and the molecular weight of outermost layer polymer (IC) 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 ((I-C1) to (I-C3)) contained in the monomer component for constituting the polymer (IC), 0.01-5 mass% is preferable. More preferably, it is 0.2% by mass or more, and most preferably 0.4% by mass or more.

  Although it does not specifically limit, Tg of the polymer of only the monomer component for comprising outermost layer polymer (IC) becomes what becomes 60 degreeC or more. A Tg of 60 ° C. or higher is preferable because the decorative flow resistance at the time of in-mold molding is good and 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. Moreover, from a viewpoint of the coagulation property and the handleability of the obtained multilayer structure polymer (I), 105 ° C. or lower is preferable.

  Although it does not specifically limit, 10-80 mass% is preferable for content of outermost layer polymer (IC) in multilayer structure polymer (I). 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. High toughness, decorative flow resistance at the time of in-mold molding, and the like, more preferably 70% by mass or less.

The multilayer structure polymer (I) of the present invention is composed of the polymer layers (IA), (IB), and (IC) described above, but the resulting acrylic resin film In order to obtain further excellent molding whitening resistance, decorative flow resistance when in-mold molding, etc. in the decorative acrylic resin film and laminate, the multilayer structure polymer (I) has a gel content of 50. % Or more is preferable. More preferably, it is 60% or more. In this case, the gel content (%) means that a predetermined amount of the multilayer structure polymer (I) (mass before extraction: W ₀ (g)) is extracted under reflux in an acetone solvent, and acetone-soluble by centrifugation. After removing the portion and drying the remaining acetone-insoluble matter, the mass (mass after extraction: W ₁ (g)) was measured and calculated by the following formula.

Gel content ratio = mass after extraction W ₁ / mass before extraction W ₀ × 100
In terms of the whitening resistance of the resulting acrylic resin film, decorative acrylic resin film and laminate, and the decorative flow resistance when in-mold molding, the greater the gel content, the more advantageous, From the viewpoint of easy moldability, the presence of a certain amount or more of free polymer is necessary, and the gel content is preferably 80% or less.

  The multilayer polymer (I) is not particularly limited, but those having a weight average particle diameter in the range of 0.05 to 0.3 μm are preferable. From the viewpoint of mechanical properties of the obtained acrylic resin film, it is more preferably 0.07 μm or more, and most preferably 0.09 μm or more. Moreover, from the viewpoints of molding whitening resistance of the resulting acrylic resin film, decorative acrylic resin film and laminate, and anti-decorative flow resistance when in-mold molding, more preferably 0.15 μm or less, most preferably 0.13 μm or less. The weight 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, the manufacturing method of multilayer structure polymer (I) is demonstrated.

  As the production method of the multilayer structure polymer (I), the sequential multi-stage polymerization method by the emulsion polymerization method is the most suitable polymerization method, but is not particularly limited to this, for example, after the emulsion polymerization, It can also be carried out by an emulsion suspension polymerization method in which the polymer (IC) is converted to a suspension polymerization system at the time of polymerization.

  In addition, although not particularly limited, when the multilayer structure polymer (I) is produced by emulsion polymerization, the monomer that gives the innermost layer polymer (IA) in the multilayer structure polymer (I) A single amount which gives an intermediate layer polymer (IB) and an outermost layer polymer (IC) after supplying an emulsion prepared by mixing the components with water and a surfactant in advance to the reactor and polymerizing the emulsion. A method in which the body components are sequentially supplied to the reactor and polymerized is preferable.

  The monomer component that gives the innermost layer polymer (IA) was mixed with water and a surfactant in advance and supplied to the reactor to be polymerized and dispersed, particularly in acetone. In this case, the multilayer structure 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 multilayer structure polymer (I) can be easily obtained. The film using the multilayer structure 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 or metallic with a low printing pressure that tends to cause printing omission. Even when solid gravure printing such as tone and jet black tone is applied, it is preferable because printing loss is small and printability is high.

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

  Examples of anionic surfactants include rosin soap, potassium oleate, sodium stearate, sodium myristate, N-lauroyl sarcosine sodium, alkenyl succinate dipotassium salt, sulfate ester salt such as sodium lauryl sulfate, etc. , Sodium dioctyl sulfosuccinate, sodium dodecylbenzenesulfonate, sulfonates such as sodium alkyldiphenyl ether disulfonate, phosphate esters such as sodium polyoxyethylene alkylphenyl ether phosphate, sodium polyoxyethylene alkyl ether phosphate And phosphoric acid ester salts. Among these, phosphate ester salts such as sodium polyoxyethylene alkyl ether sodium phosphate are particularly preferable.

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

  In addition, as a method for preparing an 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 them, 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 yield the multilayer structure polymer (I). It is preferable as a method.

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

  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, when forming the innermost layer polymer (IA), the intermediate layer polymer (IB) and the outermost layer polymer (IC) constituting the preferred multilayer structure polymer (I) of the present invention. As the polymerization initiator to be used, known ones can be used, 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, disodium ethylenediaminetetraacetate, longalite, and hydroperoxide is particularly preferable.

  An emulsion prepared by mixing the monomer component giving the innermost layer polymer (IA) with water and a surfactant is supplied to the reactor and polymerized, and then the intermediate layer polymer (IB). ) And the monomer component that gives the outermost layer polymer (IC) are sequentially fed to the reactor, and in the polymerization method, an aqueous solution containing ferrous sulfate, disodium ethylenediaminetetraacetate, Rongalite is polymerized. After raising the temperature to the temperature, the prepared emulsion is supplied to the reactor for polymerization, and then the intermediate layer polymer (IB) and outermost layer polymer (IC) containing a polymerization initiator such as peroxide. The method in which the monomer component that provides (1) is sequentially fed to the reactor and polymerized is the most preferred method for obtaining the multilayer structure 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 multilayer structure polymer (I) obtained by the above method can be treated using a filtration device provided with a filter medium as necessary. This filtration treatment is for removing scales generated during the polymerization from the latex, or for removing impurities mixed in from the polymerization raw material and from the outside during the polymerization, and the multilayer structure polymer (I) is obtained. Therefore, it is a more preferable method.

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

  The multilayer structure polymer (I) can be produced by recovering from the polymer latex produced by the above-described method. The method of recovering the multilayer structure 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, and the powder is recovered in a powder form. .

  Among these, when salting out using a metal salt, the residual metal content in the finally obtained multilayer structure polymer (I) is preferably 800 ppm or less. In particular, when a metal salt having strong affinity with water such as magnesium or sodium is used as a salting-out agent, the final multilayer structure polymer (I) must be obtained unless the residual metal content is reduced as much as possible. When an acrylic resin film made from 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.

<< 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 preferably 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 decorative flow resistance at the time of in-mold molding will be good, and the film breakage at the time of film formation of acrylic resin due to brittleness and printing on the film The problem is less likely to occur.

  Examples of the alkyl methacrylate used for the monomer component for obtaining the thermoplastic polymer (II) include methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like. Of these, methyl methacrylate is most preferred. In the monomer component for obtaining the thermoplastic polymer (II), the methacrylic acid alkyl ester is preferably in the range of 50 to 100% by mass. More preferably, it is the range of 85-99.9 mass%, More preferably, it is the range of 92-99.9 mass%. By setting it as this range, the decoration flow resistance etc. at the time of in-mold shaping | molding become favorable. In addition, for example, vehicle members and the like are members that are easily exposed to high temperatures and are easily touched by hands and objects. However, heat resistance and high hardness required when a laminate having an acrylic resin as the outermost layer is applied to a vehicle member. Can be demonstrated.

  Examples of the alkyl acrylate used as necessary for the monomer component for obtaining the thermoplastic polymer (II) include methyl acrylate, ethyl acrylate, and butyl acrylate. In the monomer component for obtaining the thermoplastic polymer (II), the acrylic acid alkyl ester is preferably in the range of 0 to 50% by mass. More preferably, it is the range of 0.1-40 mass%, More preferably, it is the range of 0.1-15 mass%, Most preferably, it is the range of 0.1-8 mass%. By setting it as this range, the decoration flow resistance etc. at the time of in-mold shaping | molding become favorable. In addition, for example, vehicle members and the like are members that are easily exposed to high temperatures and are easily touched by hands and objects. However, heat resistance and high hardness required when a laminate having an acrylic resin as the outermost layer is applied to a vehicle member. Can be demonstrated.

  As the 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 monomer component for obtaining the thermoplastic polymer (II) is preferably in the range of 0 to 49% by mass.

  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.

  The acrylic resin composition used in the present invention preferably includes a resin composition (III) composed of the multilayer polymer (I) and the thermoplastic polymer (II). These compounding ratios are based on a total of 100 parts by mass of the multilayer structure polymer (I) and the thermoplastic polymer (II), and 1 to 99 parts by mass of the multilayer structure polymer (I) and the thermoplastic polymer (II). It is preferable to set it as 1-99 mass parts.

  From the viewpoint of the molding resin whitening resistance of the resulting acrylic resin film, decorative acrylic resin film and laminate, and the decorative flow resistance when in-mold molding is performed, the multilayer structure polymer (I), the thermoplastic polymer ( When the total of II) is 100 parts by mass, the multilayer structure polymer (I) is more preferably 50 parts by mass or more, and further preferably 70 parts by mass or more.

  In addition, from the viewpoint of the whitening resistance of the resulting acrylic resin film, decorative acrylic resin film and laminate, and the decorative flow resistance during in-mold molding, the thermoplastic polymer (II) is 50 parts by mass or less. Is more preferable, and 30 parts by mass or less is more preferable. Moreover, 5 mass parts or more are preferable from a viewpoint of heat resistance and hardness, and 20 mass parts or more are preferable. By doing so, when 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 molding whitening resistance of the film, the decorative acrylic resin film and the laminate is not impaired, and there is no problem of the decoration flow that occurs during in-mold molding, and the adhesion strength between the film and the substrate resin by the decoration flow Therefore, there is no problem that the film is insufficient, and there is no problem of deformation of the film, and a laminated molded product can be provided.

  The gel content of the resin composition (III) constituting the acrylic resin film of the present invention is such that the resulting acrylic resin film, the decorative acrylic resin film and the laminate are molded white and resistant to decoration during in-mold molding. From the viewpoint of flowability, it is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 40% by mass or more. 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 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 damaged during the process of in-mold molding, and the scratch resistance of the laminated molded product obtained by laminating these films. Is also good.

  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 composition constituting the acrylic resin film of the present invention can be prepared by adding a general compounding agent such as a stabilizer, a lubricant, a processing aid, a matting agent, a light diffusing agent, a plasticizer, and an impact resistance aid, as necessary. Agents, foaming agents, fillers, colorants, antibacterial agents, fungicides, mold release agents, antistatic agents, light stabilizers, ultraviolet absorbers and the like.

  From the viewpoint of imparting design properties, the acrylic resin composition constituting the acrylic resin film of the present invention may contain a matting agent. Examples of the matting agent to be contained include conventionally known matting agents regardless of whether they are organic or inorganic. Matting agents can be used alone or in admixture of two or more. As the matting agent, for example, spherical fine particles having a weight average particle diameter of about 2 to 20 μm made of a crosslinked resin mainly composed of polymethyl methacrylate are preferable from the viewpoint of transparency. Moreover, the polymer containing a hydroxyl group is preferable from the viewpoints of transparency, matting property, film-forming property, and moldability. Moreover, you may provide a matte design property by embossing.

  Viewpoint of reducing appearance defects that appear as if the decorative layer is dented near the gate when in-mold molding is performed using a decorative acrylic resin film that has been given designability and decorated with high brightness in a metallic tone Therefore, the acrylic resin composition constituting the acrylic resin film of the present invention may contain a light diffusing agent. Although not particularly limited, an acrylic resin film containing a light diffusing agent is a film obtained by sandwiching the film between a mirror surface SUS plate heated to 130 ° C., subjecting the film to hot press molding under a condition of 3 MPa, and making the surface mirror surface The internal haze (JIS K7136; measurement based on “how to obtain haze of plastic-transparent material”) is in the range of 2 to 75%, and the whiteness (JIS L1015; white as described in “Chemical fiber staple test method”) The measurement based on the degree measurement method C (hunter method) is preferably 30% or less.

  As a light diffusing agent to be used, conventionally known various light diffusing agents can be mentioned regardless of organic or inorganic. A light-diffusion agent can be used individually or in mixture of 2 or more types. The light diffusing agent to be used is preferably about 2 to 30 μm from the viewpoint of not making the decorative part of the laminate excessively clouded and the film forming property of the acrylic resin film, for example, a silicone resin or a styrene resin. Styrene-acrylic resin, acrylic resin, benzoguanamine-formaldehyde condensate, benzoguanamine-melamine-formaldehyde condensate, melamine-formaldehyde condensate, mica, talc, calcium carbonate, silica and the like.

  From the viewpoint of protecting the substrate, it is preferable to add an ultraviolet absorber to the acrylic resin composition 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. Examples of the former commercial product include Ciba Geigy's trade name Tinuvin 234, Asahi Denka Kogyo Co., Ltd., trade name Adeka Stub LA-31. Examples of the latter commercial product include Ciba Geigy's trade name Tinuvin 1577.

In order to realize the acrylic resin composition as described above, as a resin component excluding the compounding agent used as necessary, the storage elastic modulus (G ′) at 250 ° C. is 7 × 10 ³ Pa or more, and A heat distortion temperature (measurement based on ASTM D648) of 80 ° C. or more can be used. The storage elastic modulus (G ′) at 250 ° C. of the resin component is preferably 9 × 10 ³ Pa or more, more preferably 13 × 10 ³ Pa or more, and preferably 150 × 10 ³ Pa or less. 130 × 10 ³ Pa or less is more preferable. Moreover, it is preferable that the heat deformation temperature of a resin component is 90 degreeC or more. An acrylic resin having excellent formability that does not cause appearance defects such as decorative flow during in-mold molding by forming an acrylic resin film comprising an acrylic resin composition containing such a resin component. Become a film.

Moreover, it is preferable that the storage elastic modulus (G ') in the range of 200 degreeC-260 degreeC of a resin component is 7 * 10 < ³ > Pa or more. In this case, even if the resin for the base material is injected in the temperature range and a large amount of heat is transmitted, it is possible to prevent flow and the like from occurring in the decorated film, and as a result, depending on the decoration flow Since a laminated molded product can be obtained without causing appearance defects and a decrease in the adhesive strength between the film and the resin for the substrate accompanying this, the industrial utility value is increased. In addition, this effect can be applied to typical base resin used for in-mold molding, and the acrylic resin film can be used in most cases of obtaining laminated molded products by in-mold molding. The value is very high. In addition, in the metallic printed pattern containing metal particles such as aluminum particles in which appearance defects are conspicuous when the storage elastic modulus (G ′) in the range of 200 ° C. to 260 ° C. of the resin component is 9 × 10 ³ Pa or more, Since a laminated molded product can be obtained without causing the above problems, the industrial utility value becomes extremely high. Even in the case of a resin for a substrate injected at a temperature higher than 260 ° C., the acrylic resin film of the present invention has a higher storage elastic modulus than conventionally known acrylic resin films. The effect of preventing the flow or the like of the decorated film is high, it is difficult to cause a decorative flow, and it is difficult to cause poor adhesion between the film and the substrate resin. Moreover, it is preferable that the storage elastic modulus (G ') in the range of 200-260 degreeC of a resin component is 150 * 10 < ³ > Pa or less. In this case, the acrylic resin film has good vacuum formability or pressure formability in the injection mold. Moreover, when manufacturing this acrylic resin film by a melt extrusion method, it has favorable film forming property. Furthermore, it is preferable that the storage elastic modulus (G ′) in the range of 200 to 260 ° C. of the resin component is 130 × 10 ³ Pa or less.

  As the resin component having the above characteristics, for example, it is preferable to include the above-mentioned multilayer structure polymer (I). Moreover, this resin component may be only the multilayer structure polymer (I), but it is also preferable to use the resin composition (III) in combination with the above-mentioned thermoplastic polymer (II). In this case, the heat resistance and hardness can be easily adjusted by changing the ratio of the multilayer structure polymer (I) to the thermoplastic polymer (II). 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.

  Examples of the method for producing the acrylic resin film used in 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. The die method is preferred.

  When melt extrusion is performed by a T-die method or the like, it is preferable to extrude while filtering an acrylic resin in a molten state with a screen mesh of 200 mesh or more. More preferably, it is 300 mesh or more, Most preferably, it is 500 mesh or more.

  In addition, when an acrylic resin film is formed by the T-die method, an acrylic resin obtained by using a method in which a film is formed by being sandwiched between a plurality of rolls or belts selected from a plurality of metal rolls, non-metal rolls, and metal belts. It is possible to improve the surface smoothness of the film and suppress printing omission when the acrylic resin film is printed. As the metal roll, a metal mirror surface touch roll; a roll used in a sleeve touch system composed of a metal sleeve (metal thin-film pipe) and a molding roll described in Japanese Patent No. 2808251 or WO97 / 28950, etc. It can be illustrated. Moreover, examples of the non-metallic roll include a touch roll made of silicon rubber or the like. Furthermore, examples of the metal belt include a metal endless belt. A plurality of these metal rolls, non-metal rolls and metal belts can be used in combination.

  In the above-described method for forming a film by sandwiching a plurality of rolls or belts selected from a plurality of metal rolls, non-metal rolls and metal belts, the acrylic resin composition after melt extrusion is substantially banked ( It is preferable to hold the film in a state where there is no resin reservoir and to transfer the film without substantial rolling to form a film. When the film is formed without forming a bank (resin pool), the acrylic resin composition in the cooling process is surface-transferred without rolling, so the heat shrinkage rate of the acrylic resin film formed by this method is It can also be reduced.

  When forming a film using a plurality of rolls or belts selected from a plurality of metal rolls, non-metal rolls and metal belts, embossing is performed on the surface of at least one metal roll, non-metal roll or metal belt to be used. By performing shape processing such as processing or mat processing, the shape can be transferred to one or both sides of the acrylic resin film.

  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.

  In order to form a coating film having a sufficient thickness on a molded product by coating, it may be necessary to apply ten or more times of recoating. In this case, the cost is high and the productivity is not so good. On the other hand, the laminate in which the acrylic resin film or the decorative acrylic resin film of the present invention is laminated on the base material can easily form a very thick coating film because the acrylic resin film itself becomes a coating film. Yes, and industrial use value is high.

  The decorated acrylic resin film of the present invention can be obtained by forming a decorative layer such as a woodgrain or metallic tone on one surface of the acrylic resin film described above. Examples of the method for forming the decorative layer include a method of applying ink by a known printing method or coating method. Specifically, various conventionally known methods such as a gravure printing method, a flexographic printing method, a silk screen printing method, an offset printing method, a roll coating method, a gravure coating method, and a comma coating method can be used.

  As the ink used for forming the woodgrain decorative 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.

  As the ink used for forming the metallic decorative 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. In the case of a metallic decorative layer, the ink contains a high-intensity pigment as an essential component. For example, aluminum pigments such as non-leafing aluminum paste (trade name manufactured by Showa Aluminum Powder Co., Ltd.), iridium (trade name manufactured by Merck Co., Ltd.) A known high-luminance pigment such as a pearl pigment is used. As an example of the preferable commercial item of the said aluminum pigment, the pigment or dye of a suitable color can also be contained as a coloring agent.

  Further, as a method other than the printing method and the coating method, the metallic decorative 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. A known metal can be used as the decorative layer, but it is preferable to use aluminum, indium, or an alloy containing these with excellent malleability from the viewpoint of in-mold moldability.

  In addition, the acrylic resin film and the decorative acrylic resin film of the present invention do not cause various problems such as a decoration flow when performing in-mold molding. That is, in the in-mold molding process, the resin serving as a base material is injected. Even when a large amount of heat is transmitted during molding, the film does not flow or the like.

  Taking advantage of this feature, it is also possible to form a decorative layer that does not cause a decorative flow by using the acrylic resin composition that is a constituent of the acrylic resin film of the present invention as a thermoplastic resin binder of the decorative layer. It is.

The number of printing omissions of the decorative acrylic resin film 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, and particularly preferably 1 piece / m ² or less.

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

  Further, in addition to the decorative 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 decorative layer, or may be provided on the film surface opposite to the decorative layer. It is also possible to provide an adhesive layer on the surface of an acrylic resin film that does not have a decorative layer.

  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. Laminated molded product obtained by insert molding method that performs preforming such as vacuum molding or compressed air molding, inserts preformed product into another mold, and then injection molding resin as base material to obtain laminated molded product It can also be.

  In addition, the laminated molded product of this invention can also be made into a laminated molded product using the laminated sheet or film which laminated | stacked the acrylic resin film or decorative acrylic resin film of this invention on the 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 decorative 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 between the 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 film surface opposite to the thermoplastic resin layer.

  In the case of an insert molding method in which a preformed product such as vacuum forming or pressure forming is applied, the preformed product is inserted into another mold, and then a resin as a base material is injection molded to obtain a laminate molded product, a laminated sheet Or it is preferable to use a film. At this time, since the thermoplastic resin layer is present in the laminated sheet or film, the amount of heat transferred to the acrylic resin film is reduced compared to the in-mold molding method described above, and the decorative flow is less likely to occur. Accordingly, it is difficult to cause poor adhesion between the film and the substrate resin, and the film is less likely to be deformed. However, depending on the molding conditions, the thermoplastic resin layer disappears, and the same problems as in in-mold molding (decoration flow, reduced adhesion between the resin for the film and the substrate, deformation of the film, etc.) May occur. For this reason, the acrylic resin film of this invention is useful also as an acrylic resin layer of such a laminated sheet or film.

  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.

  As described above, when in-mold molding is performed using an acrylic resin film with a decorative layer such as woodgrain or metallic tone, the decorative layer near the gate flows depending on the shape of the mold and injection molding conditions. Or disappear. Moreover, when the decorative layer flows, there may be a case where the adhesive strength between the decorative acrylic resin film and the base resin is insufficient. In addition, the decorative acrylic resin film may be deformed. Gates are roughly divided into a non-restricted gate in which the resin flow path is not narrowed at the gate portion and a restricted gate in which the flow 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, and the injection resin pressure per unit area on the decorative acrylic resin film surface near the gate increases. The decorative layer on the surface of the decorative acrylic resin film tends to disappear, and in the case of a metallic decorative layer, the appearance defect that the decorative layer appears to be recessed near the gate is likely to occur, and the decorative acrylic resin film Is easy to deform.

  When the decorative acrylic resin film of the present invention is used, the decorative layer flows in the vicinity of the gate, the decorative layer disappears, or the decoration is compared with the case where a conventionally known acrylic resin film is used. In-mold molding can be performed without deformation of the acrylic resin film. In addition, in the case of a high-luminance decorative acrylic resin film such as a metallic tone, it is possible to reduce appearance defects that appear to be recessed near the gate.

  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 various problems such as decoration flow from the molding conditions, the preheating temperature at the time of vacuum molding may be increased. The purpose of this is to use a decorative layer having a heat-crosslinking reactive component and apply heat more than in normal molding, so that the decorative layer is firmly fixed to an acrylic resin film and then molded. This method naturally reduces the molding cycle. When the acrylic resin film of the present invention is used, a laminated molded product having a good appearance can be obtained without adopting such a method, so that a high cycle of molding is possible, and the industrial utility value is extremely high. Very expensive.

  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 mobile phone housings, display windows, buttons, etc., furniture exterior materials, wall interiors, ceilings, floors, etc., exterior walls such as siding, fences, roofs, gates, windbreak boards, etc. Use for exterior materials for buildings, use for surface decorations for furniture such as window frames, doors, handrails, sills, duck, various displays, lenses, mirrors, goggles, use for optical members such as window glass, trains, aircraft, ships, etc. It can be suitably used for interior / exterior applications of various vehicles other than automobiles, various packaging containers and materials such as bottles, cosmetic containers, and accessories, and other various applications such as miscellaneous goods such as prizes and accessories.

  Since the acrylic resin film and the decorative acrylic resin film of the present invention are excellent in surface hardness, heat resistance, and moldability, it is possible to dramatically expand conventional usage applications. In particular, the decorative acrylic resin film of the present invention is excellent in the appearance of a molded product when in-mold molding is performed, and the use of the acrylic resin film of the present invention limits the design of the mold in the in-mold molding method. The industrial utility value is extremely high because problems such as occurrence, restrictions on injection molding conditions, and the configuration of the decorative film must be devised.

  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.

Methyl methacrylate MMA,
Methyl acrylate MA,
n-butyl acrylate n-BA,
Styrene St,
1,3-butylene glycol dimethacrylate 1,3-BD,
Allyl methacrylate AMA,
Cumene hydroperoxide CHP,
t-butyl hydroperoxide t-BH,
n-octyl mercaptan n-OM,
Ethylenediaminetetraacetic acid disodium EDTA.

  Regarding the multilayer structure polymer (I), the thermoplastic polymer (II), the acrylic resin film, and the in-mold molded product (laminated molded product), various physical properties were measured by the following test methods.

(1) Glass transition temperature of each polymer layer of multilayer structure polymer (I) [(I-1) to (I-3)] Polymer Handbook (Polymer Handbook (J. Brandrup, Interscience, 1989)) Calculated from the formula of FOX.

(2) Gel content G (%) of multilayer structure polymer (I) [(I-1) to (I-3)]
A predetermined amount (mass before extraction: W ₀ (g)) of the multilayer structure polymer (I) is extracted under reflux in an acetone solvent, and acetone-soluble components are removed by centrifugation, and the remaining acetone-insoluble components are dried. Then, the mass (mass after extraction: W ₁ (g)) was measured and calculated by the following formula.

Gel content rate G = mass after extraction W ₁ / mass before extraction W ₀ × 100
(3) Weight average particle diameter of multilayer structure polymer (I) [(I-1) to (I-3)] Weight average particle diameter of polymer latex of multilayer structure polymer (I) obtained by emulsion polymerization Was measured by a dynamic light scattering method using a light scattering photometer (manufactured by Otsuka Electronics Co., Ltd., DLS-700 (trade name)).

(4) Reduced viscosity of thermoplastic polymer (II) Using an AVL-2C (trade name) automatic viscometer manufactured by San Denshi Kogyo, chloroform was used as a solvent, and the viscosity was measured at 25 ° C. 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.

(5) Storage elastic modulus G ′ (Pa) of acrylic resin film
A pellet-shaped acrylic resin composition, which is a raw material of the acrylic resin film, was molded into a plate shape having a thickness of 2 mm by injection molding. A disk cut out from this molded product was used as a test piece and measured with RDA-700 (trade name) manufactured by Rheometrics. Other measurement conditions are measurement temperature: 150 to 270 ° C. (temperature increase rate: 2 ° C./min), measurement angular frequency: 10 rad / sec.

(6) Acrylic resin film thermal deformation temperature (HDT)
A pellet-shaped acrylic resin composition, which is a raw material for the acrylic resin film, was molded by injection molding into a thermal deformation temperature measurement specimen based on ASTM D648, 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).

(7) Pencil hardness of acrylic resin film and laminated molded product Measured according to JIS K5400.

(8) Evaluation of in-mold moldability The appearance of the molded product in the vicinity of the gate of the laminate obtained by in-mold molding was evaluated according to the following criteria.
○: Appearance is good (decoration flow did not occur)
Δ: A slight decorative flow can be confirmed, but the color tone of the base resin is not clear. X: Deterioration of appearance (decoration flow generation: the decoration flows completely, and the color tone of the base resin becomes clear. Appearance defects, wrinkles occurred: wrinkles due to film deformation)
(9) Scratch resistance of laminated molded product The appearance of a laminated molded product when a load of 0.049 MPa is applied on a five-layer gauze and 200 strokes are scratched at a speed of 30 strokes / min. Evaluation was performed according to the criteria.
○: No scratch ×: Scratched and whitening is observed in the scratched part (10) Heat aging resistance of the laminated molded product The appearance of the laminated molded product when heated at 80 ° C. for 400 hours was evaluated according to the following criteria.
○: No change ×: Whitening and cloudiness <1. Production of Multilayer Structure Polymer (I-1)>
After charging 10.8 parts of deionized water in a container equipped with a stirrer, it consists of MMA 0.3 part, n-BA 4.5 part, 1,3-BD 0.2 part, AMA 0.05 part and CHP 0.025 part. Monomer components were 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, while stirring under nitrogen, the prepared emulsion was dropped into the polymerization vessel over 8 minutes, and then the reaction was continued for 15 minutes to complete the polymerization of the innermost polymer inner layer (I-1-A ₁ ). did. Subsequently, a monomer component 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 obtain the innermost layer polymer (I-1-A) including the innermost layer polymer outer layer (I-1-A ₂ ). The Tg of the innermost polymer inner layer (I-1-A ₁ ) alone was −48 ° C., and the Tg of the innermost polymer outer layer (I-1-A ₂ ) alone was −10 ° C.

  Subsequently, a monomer component consisting of 6 parts of MMA, 4 parts of MA and 0.075 part of AMA was dropped into the polymerization vessel over 45 minutes together with 0.0125 part of CHP, and then the reaction was continued for 60 minutes to obtain an intermediate layer polymer ( I-1-B) was formed. The Tg of the intermediate layer polymer (I-1-B) alone was 60 ° C.

  Subsequently, a monomer component 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. A coalescence (I-1-C) was formed to obtain a polymer latex of the multilayer structure polymer (I-1). The Tg of the outermost layer polymer (I-1-C) alone was 99 ° C.

  The weight average particle diameter of the multilayer structure polymer (I-1) measured after the polymerization was 0.11 μm.

  The polymer latex of the obtained multilayer structure polymer (I-1) 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 calcium acetate 3.5 It was salted out in an aqueous solution containing parts, washed with water, recovered, and dried to obtain a powdery multilayer structure polymer (I-1). The gel content of the multilayer structure polymer (I-1) was 70%.

  Further, 214.3 g of the obtained multilayer structure polymer (I-1) 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 acetone of the multilayer structure polymer (I-1). A dispersion 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.

<2. Production of multilayer structure polymer (I-2)>
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 innermost polymer inner layer (I-2-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 component [raw material (b)] with respect to water, and then held for 60 minutes, and the innermost polymer inner layer ( I-2-A ₁ ) latex was obtained. The Tg of the innermost polymer inner layer (I-2-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 innermost polymer outer layer (I-2-A ₂ ) shown below was converted into a monomer component [raw material (c)] for water. After the continuous addition at an increase rate of 4% / hour, the innermost layer polymer outer layer (I-2-A ₂ ) was polymerized by holding for 120 minutes to polymerize the innermost layer polymer (I-2- A latex of A) was obtained. The Tg of the innermost polymer outer layer (I-2-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-2-C) shown below is increased by the monomer component [raw material (d)] with respect to water. After continuously adding at 10% / hour, holding for 60 minutes, the outermost layer polymer (I-2-C) is polymerized to obtain a polymer latex of the multilayer structure polymer (I-2). It was. The Tg of the outermost layer polymer (I-2-C) alone was 99 ° C.

  The weight average particle diameter of the multilayer structure polymer (I-2) measured after polymerization was 0.28 μm.

  The polymer latex of the obtained multilayer structure polymer (I-2) is subjected to coagulation, aggregation, and solidification reaction using calcium acetate, filtered, washed with water, and dried to obtain a multilayer structure polymer (I-2). ) The resulting multilayer structure polymer (I-2) had a gel content of 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,
1.0 part of a partially neutralized product of a sodium hydroxide mixture of 40% mono (polyoxyethylene nonylphenyl ether) phosphoric acid and 60% di (polyoxyethylene nonylphenyl ether) phosphoric acid,
(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,
1.0 part of a partially neutralized product of a sodium hydroxide mixture of 40% mono (polyoxyethylene nonylphenyl ether) phosphoric acid and 60% di (polyoxyethylene nonylphenyl ether) phosphoric acid,
(D) 57.0 parts of MMA,
3.0 parts of MA,
n-OM 0.3 part,
0.06 parts t-BH.

<3. Production of multilayer structure polymer (I-3)>
After charging 8.5 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. Monomer components were 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, 186.5 parts of deionized water was put into a polymerization vessel equipped with a cooler, and the temperature was raised to 70 ° 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, while stirring under nitrogen, the prepared emulsion was dropped into the polymerization vessel over 8 minutes, and then the reaction was continued for 15 minutes to complete the polymerization of the innermost polymer inner layer (I-3-A ₁ ). did. Subsequently, a monomer component consisting of 1.5 parts of MMA, 22.5 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. After that, the reaction was continued for 60 minutes to obtain an innermost layer polymer (I-1-A) including an innermost layer polymer outer layer (I-3-A ₂ ). The Tg of the innermost polymer inner layer (I-3-A ₁ ) alone was −48 ° C., and the Tg of the innermost polymer outer layer (I-3-A ₂ ) alone was −48 ° C.

  Subsequently, a monomer component consisting of 6 parts of MMA, 4 parts of n-BA and 0.075 part of AMA was dropped into the polymerization vessel over 45 minutes together with 0.0125 part of CHP, and then the reaction was continued for 60 minutes. Combined (I-3-B) was formed.

  The Tg of the intermediate layer polymer (I-3-B) alone was 20 ° C.

  Subsequently, a monomer component consisting of 55.2 parts of MMA, 4.8 parts of n-BA, 0.19 part of n-OM and 0.08 part of t-BH was added dropwise to the polymerization vessel over 140 minutes, followed by reaction for 60 minutes. The outermost layer polymer (I-3-C) was formed to obtain a polymer latex of the multilayer structure polymer (I-3). The Tg of the outermost layer polymer (I-3-C) alone was 84 ° C.

  The weight average particle diameter of the multilayer structure polymer (I-3) measured after the polymerization was 0.12 μm.

  The polymer latex of the obtained multilayer structure polymer (I-3) 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 parts of calcium acetate was added. Salting out was carried out in an aqueous solution containing, recovered by washing with water, and then dried to obtain a powdery multilayer structure polymer (I-3). The gel content of the multilayer structure polymer (I-3) was 60%.

  Further, 214.3 g of the obtained multilayer structure polymer (I-3) 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 acetone of the multilayer structure polymer (I-3). A dispersion 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.

Example 1
90 parts of multilayer structure polymer (I-1), 10 parts of MMA / MA copolymer (MMA / MA = 99/1 (mass ratio), reduced viscosity 0.06 L / g) as thermoplastic polymer (II), As a compounding agent, manufactured by Ciba Specialty Chemicals; trade name “Tinubin 234” 1.4 parts, manufactured by Asahi Denka Kogyo Co., Ltd .; trade name “Adeka Stub AO-60” 0.1 part, manufactured by Asahi Denka Kogyo Co., Ltd .; trade name “Adeka Stub LA” -67 "0.3 parts was mixed with 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 a pellet of an acrylic resin composition.

  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 500-mesh metal filter and a T die to form an acrylic resin film having a thickness of 125 μm. At this time, the molten acrylic resin composition extruded from a slit having a width of 0.5 mm is passed between two metal cooling rolls, the resin is sandwiched without any bank (resin pool), and the surface is not rolled. After the transfer, this was wound on a paper roll with a winder to obtain an acrylic resin film.

  On the mirror surface side of the obtained acrylic resin film, scaly aluminum pigment was applied to 10 parts of gravure ink in which acrylic resin was dissolved in MEK and toluene (= 1/1 (vol / vol)) at a solid content of 25%. Using the ink containing 2 parts, silver metallic printing was performed by gravure printing to obtain a decorative acrylic resin film (metallic decorative acrylic resin film). No print loss occurred.

  Separately, on the mirror side of the obtained acrylic resin film, woodgrain printing was performed by gravure printing to obtain a decorated acrylic resin film (woodgrain decorated acrylic resin film). In addition, all the decoration layers were 5 micrometers. No print loss occurred.

  Next, using the heat-resistant ABS resin bulk sum TM25B (trade name, manufactured by UMGABS) as the base resin and the above-mentioned two decorative acrylic resin films, it has a vacuum drawing function, and has a mold (molded product shape). : Vertical 150 mm × width 120 mm × thickness 2 mm, depth 10 mm box shape, gate position: one location in the center of the molded product, and 3 locations in total, one location each above and below the central gate (vertical direction of the molded product) 40 mm, Using a gate shape: a pinpoint gate with a diameter of 1 mm, an in-mold molding device combining a J85 ELII type injection molding machine (trade name, manufactured by Nippon Steel Works) and a hot pack system (produced by Nissha Printing Co., Ltd.) Molding (film vacuum forming conditions: heater temperature 260 ° C., heating time 15 seconds, heater-film distance 15 mm, injection molding conditions: cylinder to Slip temperature 250 ° C (estimated injection resin temperature 250 ° C), injection speed 30%, injection pressure 43%, mold temperature 60 ° C, vacuum-molded so that the non-decorated surface is in contact with the mold, and from the decorative surface side A base resin was injected) to obtain a laminated molded product (250 ° C. molded product).

  Further, in the above-described injection molding conditions at the time of in-mold molding, the cylinder-nozzle temperature is changed to 260 ° C. (estimated to be injection resin temperature 260 ° C.), and in-mold molding is performed in the same manner to obtain a laminated molded product (260 ° C. molded product )

(Example 2)
The same operation as in Example 1 was carried out except that the blending ratio of the multilayer structure polymer (I-1) and the thermoplastic polymer (II) was 75/25 (part / part).

Example 3
The same procedure as in Example 1 was conducted except that the blending ratio of the multilayer structure polymer (I-1) and the thermoplastic polymer (II) was 70/30 (part / part).

Example 4
The same procedure as in Example 1 was performed except that the blending ratio of the multilayer structure polymer (I-1) and the thermoplastic polymer (II) was 55/45 (parts / part).

(Comparative Example 1)
16 parts of multilayer structure polymer (I-2), 84 parts of MMA / MA copolymer (MMA / MA = 99/1 (mass ratio), reduced viscosity 0.06 L / g) as thermoplastic polymer (II), As a compounding agent, manufactured by Ciba Specialty Chemicals; trade name “Tinubin 234” 1.4 parts, manufactured by Asahi Denka Kogyo Co., Ltd .; trade name “Adeka Stub AO-60” 0.1 part, manufactured by Asahi Denka Kogyo Co., Ltd .; trade name “Adeka Stub LA” -67 "0.3 parts was mixed with 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 a pellet of an acrylic resin composition. And it implemented similarly to Example 1 except having used this pellet.

(Comparative Example 2)
100 parts of multilayer structure polymer (I-3), manufactured by Asahi Denka Kogyo Co., Ltd. as a compounding agent; 2.1 parts of trade name “Adeka Stub LA-31”, manufactured by Asahi Denka Kogyo Co., Ltd .; trade name “Adeka Stub AO-50” 1 part, manufactured by Asahi Denka Kogyo Co., Ltd .; 0.3 part of a trade name “ADK STAB LA-57” was mixed with 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 a pellet of an acrylic resin composition. And it implemented similarly to Example 1 except having used this pellet.

  Table 1 summarizes the evaluation results of the acrylic resin film obtained above and the laminated molded product.

Obtained in Examples 1 to 4 using the acrylic resin film of the present invention comprising an acrylic resin composition having a storage elastic modulus (G ′) at 250 ° C. of 7 × 10 ³ Pa or more and a heat distortion temperature of 80 ° C. or more. Appearance evaluation of the laminated molded product was confirmed in the case of using an acrylic resin film with a wood grain decoration, and all of the decorative flow, adhesiveness reduction between the film and the resin for the base material, and wrinkles due to film deformation were confirmed. It was not good. Furthermore, when the acrylic resin film of Examples 1-3 which consists of an acrylic resin composition whose storage elastic modulus (G ') in this temperature is 9x10 < ³ > Pa or more is used, the silver metallic tone with which defects, such as a decoration flow, are conspicuous. Even when the printing was performed, the decoration flow was not confirmed and it was good. Furthermore, when the acrylic resin films of Examples 1 to 3 made of an acrylic resin composition having a storage elastic modulus (G ′) at 260 ° C. of 7 × 10 ³ Pa or more are used, even when the injection resin temperature is 260 ° C., Appearance evaluation of the obtained laminated molded product is the case where an acrylic resin film with a woodgrain decoration is used, all of which are decorated flow, adhesiveness reduction between the film and the resin for the substrate, and wrinkles due to film deformation It was not confirmed and was good. Furthermore, when the acrylic resin film of Examples 1 and 2 consisting of an acrylic resin composition having a storage elastic modulus (G ′) at the temperature of 9 × 10 ³ Pa or more is used, a silver metallic tone in which defects such as decoration flow are conspicuous. Even when the printing was performed, the decoration flow was not confirmed and it was good.

On the other hand, in the acrylic resin film of Comparative Example 1 made of an acrylic resin composition having a storage elastic modulus (G ′) at 250 ° C. of less than 7 × 10 ³ Pa, the decorative flow was confirmed and the moldability was poor. It was. Moreover, when the acrylic resin film of Comparative Example 2 made of an acrylic resin composition having a heat distortion temperature of less than 80 ° C. is used, the film is deformed when in-mold molding is performed, and as a result, the molded product has wrinkles. As a result, the laminated molded product was poor in appearance. In addition, the heat-resistant aging performance of the obtained laminated molded product is low, for example, it does not reach the level necessary for vehicle use, and its value is low in view of industrial use. Furthermore, when the acrylic resin film of Comparative Example 2 having a pencil hardness of less than 2B (not including 2B and lower hardness) is used, the resulting laminated molded article has low scratch resistance and is used for in-mold molding. It is unsuitable and, for example, does not reach the level necessary for vehicle use, and its value is low when considering industrial use.

  Laminated molded products obtained by laminating and bonding the acrylic resin film or decorative acrylic resin film of the present invention to 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, etc., front panels, buttons, emblems, surface cosmetics, etc. for AV equipment and furniture products Applications such as mobile phone housings, display windows, buttons, etc., furniture exterior materials, wall interiors, ceilings, floors, and other building interior materials, siding exterior walls, fences, roofs, gates, windbreak boards, etc. Application for building exterior materials, application for surface decoration of furniture such as window frames, doors, handrails, sills, duck, various displays, lenses, mirrors, goggles, optical member applications such as window glass, or trains, aircraft, ships, etc. It can be suitably used for interior and exterior applications of various vehicles other than automobiles, various packaging containers and materials such as bottles, cosmetic containers, and accessories, and other various applications such as miscellaneous goods such as prizes and accessories.

Claims (3)

An acrylic resin film comprising an acrylic resin composition having a storage elastic modulus (G ′) at 250 ° C. of 7 × 10 ³ Pa or more and a heat distortion temperature (measured based on ASTM D648) of 80 ° C. or more.   The acrylic resin film according to claim 1, wherein the acrylic resin film has a decorative layer on at least one side.   A laminated molded product obtained by laminating the acrylic resin film according to claim 1 or 2 on a base material.