Acrylic resin composition, film, multilayer film, protective film for decorative melamine board surface, and decorative melamine board

Abstract

The purpose of the present invention is to provide: an acrylic resin composition that excels in adhesiveness to a decorative melamine board, water-whitening resistance, and appearance; a film; a multilayer film; a protective film for a decorative melamine board surface; and a decorative melamine board. Provided is an acrylic resin composition including a reactive-group-containing acrylic polymer (B-1) having a Tg of 0°C or higher, wherein the acid value of an acetone-soluble portion of the acrylic resin composition is 35-180 mgKOH / g, and the acid value of an acetone-insoluble portion of the acrylic resin composition is no higher than 20 mgKOH / g. Further provided are a film, a multilayer film, a protective film for a decorative melamine board surface, and a decorative melamine board using the acrylic resin composition.

Description

Acrylic resin composition, film, laminated film, surface protective film for melamine decorative laminates, and melamine decorative laminates 【0001】 The present invention relates to an acrylic resin composition, a film, a laminated film, a film for protecting the surface of a melamine decorative laminate, and a melamine decorative laminate. 【0002】 Acrylic resin films are favored for their excellent transparency, weather resistance, and high surface hardness, and are therefore often used as protective films for various molded products for indoor or outdoor use, such as optical components in electrical products, interior parts for automobiles, signs, and building materials. Furthermore, by applying surface treatments such as anti-reflective or anti-fouling treatments to the surface of the acrylic resin film and then laminating it to the molded product, surface functions such as anti-reflective and anti-fouling properties can be imparted to the molded product. 【0003】 When laminating these acrylic resin films to substrates with poor adhesion to acrylic resin, using adhesives, primers, etc., is time-consuming and labor-intensive, making it costly. Therefore, acrylic resin films with improved adhesion have been developed by introducing reactive groups into the acrylic resin film. 【0004】 For example, Patent Documents 1 and 2 disclose a film containing a polymer that includes structural units derived from monomers having reactive groups, which exhibits excellent adhesion to melamine decorative laminates. Furthermore, Patent Document 3 discloses a film containing a polymer that includes structural units derived from monomers having reactive groups, which exhibits excellent adhesion to metals. 【0005】 International Publication No. 2014 / 192708, International Publication No. 2016 / 084740, Japanese Patent Publication No. 2013-103385 【0006】However, in Patent Documents 1 and 2, the adhesion and water resistance to whitening when the film was laminated to the melamine decorative laminate were insufficient. Furthermore, in Patent Document 3, it was difficult to achieve both adhesion, water resistance to whitening, and appearance when the film was laminated to the melamine decorative laminate. Therefore, the object of the present invention is to provide an acrylic resin composition that can produce a film with excellent adhesion to the melamine decorative laminate, water resistance to whitening, and appearance, as well as a film obtained thereby, a laminated film, a film for protecting the surface of the melamine decorative laminate, and a melamine decorative laminate. 【0007】 The inventors have conducted diligent research and have found that the above objective can be achieved, thus completing the present invention. That is, the present invention has the following embodiments: [1] An acrylic resin composition comprising a reactive group-containing acrylic polymer (B-1) with a Tg of 0°C or higher, wherein the acid value of the acetone-soluble portion of the acrylic resin composition is 35 to 180 mgKOH / g, and the acid value of the acetone-insoluble portion of the acrylic resin composition is 20 mgKOH / g or less. [2] The acrylic resin composition according to [1], wherein the hydroxyl value of the acrylic resin composition is 10 mgKOH / g or less. [3] The acrylic resin composition according to [1] or [2], wherein the reactive group of the reactive group-containing acrylic polymer (B-1) is a carboxyl group. [4] The acrylic resin composition according to any one of [1] to [3], wherein the content of a carboxylic acid anhydride structure in 100% by mass of the acrylic resin composition is 0.01% by mass or more. [5] The acrylic resin composition according to any one of [1] to [4], wherein the reactive group-containing acrylic polymer (B-1) contains structural units derived from aromatic vinyl monomers, and the content of structural units derived from aromatic vinyl monomers in the reactive group-containing acrylic polymer (B-1) is 2% by mass or less. [6] The acrylic resin composition according to any one of [1] to [5], wherein the Tg of the reactive group-containing acrylic polymer (B-1) is 120°C or less. [7] The SP value of the reactive group-containing acrylic polymer (B-1) is 25.0 (J / cm²). ３ ) １／２The following are acrylic resin compositions according to any one of [1] to [6]: [8] The acrylic resin composition according to any one of [1] to [7], further comprising core-shell rubber (B-2). [9] The acrylic resin composition according to [8], wherein the core-shell rubber (B-2) substantially does not contain constituent units derived from the monomer represented by the following formula (1). CH ２ = C(R １ ) COO-R ２ ...Formula (1) In formula (1), R １ is a hydrogen atom or a methyl group, R ２

[10] The acrylic resin composition according to any one of [1] to [9], further comprising an acrylic resin that is substantially free of reactive groups as a thermoplastic polymer (B-3).

[11] The acrylic resin composition according to any one of [1] to

[10] , wherein the MFR retention rate at a temperature of 230°C and a load of 49N is greater than 90%.

[12] The acrylic resin composition according to

[10] , wherein the acrylic resin that is substantially free of reactive groups is an acrylic polymer with a mass-average molecular weight of 500,000 or more, and the content of the acrylic polymer in the acrylic resin composition is greater than 2% by mass.

[13] A film made of the acrylic resin composition according to any one of [1] to

[12] .

[14] A laminated film comprising a resin layer (I) made of a resin composition (A) having an acid value of acetone-soluble portion less than 35 mg KOH / g, and a resin layer (II) made of the acrylic resin composition according to any one of [1] to

[12] .

[15] The laminated film according to

[14] , wherein the thickness of the resin layer (II) is 10 μm or less.

[16] The laminated film according to

[14] or

[15] , wherein the resin layer (II) is used as a bonding layer facing the substrate side and the resin layer (I) is used as a surface layer facing the opposite side of the substrate.

[17] A film for protecting the surface of a melamine decorative laminate, comprising the laminated film according to any one of

[14] to

[16] .

[18] A melamine decorative laminate in which the laminated film according to any one of

[14] to

[16] and a melamine substrate are laminated in the order of the resin layer (I), the resin layer (II), and the melamine substrate. 【0008】According to the present invention, it is possible to provide an acrylic resin composition that can produce a film with excellent adhesion to melamine decorative laminates, water resistance to whitening, and appearance, as well as a film obtained thereby, a laminated film, a film for protecting the surface of melamine decorative laminates, and a melamine decorative laminate. 【0009】 The following describes in detail one aspect of the present invention, but the present invention is not limited to the following aspects without departing from its purpose. In this specification, "~" includes both a lower limit and an upper limit. Furthermore, for each preferred range, the upper limit and lower limit can be used in any combination. "Constituent unit" means a constituent unit derived from a monomer, that is, a constituent unit formed by the polymerization of monomers, or a constituent unit in which a part of the constituent unit is converted to a different structure by processing the polymer. The general term for acrylate and methacrylate is "(meth)acrylate". The general term for acrylic and methacrylic is "(meth)acrylic". The general term for acryloyl and methacryloyl is "(meth)acryloyl". 【0010】 The present inventors have found that by using an acrylic resin composition containing a reactive group-containing acrylic polymer (B-1) with a Tg of 0°C or higher, wherein the acid value of the acetone-soluble component of the acrylic resin composition is 35 to 180 mgKOH / g, and the acid value of the acetone-insoluble component of the acrylic resin composition is 20 mgKOH / g or less, a film with excellent adhesion to melamine decorative laminates, water resistance to whitening, and appearance can be provided. Although the mechanism is not clear, it is thought that when the Tg and the acid value of the acetone-soluble component are within the range of this application, the chemical and physical interaction with the melamine decorative laminate improves, and adhesion improves. Furthermore, when immersed in hot water, water is less likely to enter the interface between the film and the melamine decorative laminate, preventing the formation of voids and water absorption of the film, thus providing excellent water resistance to whitening. In addition, by adjusting the acid values ​​of the acetone-soluble and acetone-insoluble components, gelation and tarnishing of the resin composition can be suppressed, resulting in an excellent appearance. 【0011】[Acrylic Resin Composition] The acrylic resin composition of the present invention (hereinafter also referred to as "acrylic resin composition (B)") is an acrylic resin composition comprising a reactive group-containing acrylic polymer (B-1) with a Tg of 0°C or higher, wherein the acid value of the acetone-soluble portion of the acrylic resin composition is 35 to 180 mgKOH / g, and the acid value of the acetone-insoluble portion of the acrylic resin composition is 20 mgKOH / g or less. The acrylic resin composition (B) of the present invention can be molded to obtain a film, and the film may comprise at least a resin layer (II) made of the acrylic resin composition (B). The film of the present invention may also be a laminated film in which a resin layer (I) made of a resin composition (A) having an acid value of less than 35 mgKOH / g for its acetone-soluble portion is laminated on the resin layer (II). 【0012】 [Resin layer (I)] The resin layer (I) is a layer made of a resin composition (A) having an acid value of acetone-soluble components of less than 35 mg KOH / g. The resin composition (A) is preferably an acrylic resin composition (A1) or a fluorine-based resin composition (C). The acid value of the acetone-soluble components of resin composition (A) is preferably 20 mg KOH / g or less, more preferably 10 mg KOH / g or less, and even more preferably 5 mg KOH / g or less. There is no particular lower limit to the acid value of the acetone-soluble components of resin composition (A), but it may be 0 mg KOH / g. 【0013】 The maximum height Rz of the resin layer (I) is preferably 0.11 μm or more, more preferably 0.15 μm or more, and even more preferably 0.18 μm or more. When the maximum height Rz of the resin layer (I) is equal to or greater than the lower limit, blocking of the films can be prevented when storing the films in single sheets for melamine decorative laminates, resulting in excellent handling performance. 【0014】The storage modulus of the resin layer (I) at 100°C is preferably 1 to 1500 MPa, more preferably 1 to 1000 MPa, even more preferably 100 to 950 MPa, and still more preferably 500 to 900 MPa. If the storage modulus of the resin layer (I) at 100°C is above the lower limit, the heat resistance and surface hardness of the melamine decorative laminate will be better. If the storage modulus of the resin layer (I) at 100°C is below the upper limit, the transferability of the embossed shape will be good when transferring the embossed shape by heat pressing, and a melamine decorative laminate with a good appearance can be obtained. Melamine decorative laminates are usually made by heat pressing at a temperature of 140 to 160°C, but when many large-area laminated films are laminated and pressed simultaneously, the temperature may be uneven depending on the area, resulting in low-temperature areas around 100°C. Even in such cases, if the storage modulus at 100°C is 1000 MPa or less, a melamine decorative laminate with a good appearance can be obtained. The storage modulus can be measured by the method described in the examples. 【0015】 [Acrylic Resin Composition (A1)] The acrylic resin composition (A1) of the present invention preferably contains core-shell rubber (A-1) from the viewpoint of film productivity and handling, and may contain, for example, core-shell rubber (A-1), thermoplastic polymer (A-2), and additive (A-3). In particular, the acrylic resin composition (A1) contains 5.5 to 95% by mass of core-shell rubber (A-1) and 5 to 94.5% by mass of thermoplastic polymer (A-2) based on 100% by mass of the total of core-shell rubber (A-1) and thermoplastic polymer (A-2), and further preferably contains 0.01 to 20 parts by mass of additive (A-3) based on 100 parts by mass of the total of (A-1) and thermoplastic polymer (A-2). If the content of core-shell rubber (A-1) is 5.5% by mass or more, the resin layer (I) is given greater toughness, film tearing is less likely to occur during film production, and productivity is better. In addition, the handling when using the film is good. If the content of thermoplastic polymer (A-2) is 5% by mass or more, the surface hardness of the resin layer (I) will be better. 【0016】The acrylic resin composition (A1) more preferably contains 10 to 90% by mass of core-shell rubber (A-1) and 10 to 90% by mass of thermoplastic polymer (A-2) based on a total of 100% by mass of core-shell rubber (A-1) and thermoplastic polymer (A-2), and even more preferably contains 15 to 85% by mass of core-shell rubber (A-1) and 15 to 85% by mass of thermoplastic polymer (A-2). Furthermore, the acrylic resin composition (A1) more preferably contains 0.1 to 10 parts by mass of additive (A-3) based on a total of 100 parts by mass of core-shell rubber (A-1) and thermoplastic polymer (A-2), and even more preferably contains 1 to 8 parts by mass. 【0017】 [Core-shell rubber (A-1)] The core-shell rubber (A-1) can be any multilayered particle, and is preferably a rubber particle having a multilayered structure of two or more layers, in which a layer containing a rigid polymer (a-2) as an outer layer is formed on top of a layer containing an elastic copolymer (a-1) as an inner layer. Examples of materials for the core-shell rubber (A-1) include acrylic rubber, silicone rubber, and butadiene rubber, but acrylic rubber is preferred in terms of transparency and weather resistance. Examples of acrylic rubber include those described in Patent Document 1. 【0018】 The particle size of the core-shell rubber (A-1) is preferably 100 to 400 nm, more preferably 150 to 350 nm, and even more preferably 200 to 300 nm. If the particle size of the core-shell rubber (A-1) is above the lower limit, the surface hardness is better, from the viewpoint of being able to reduce the amount of rubber added per unit area. If the particle size of the core-shell rubber (A-1) is below the upper limit, the transparency of the film is even better. 【0019】[Thermoplastic Polymer (A-2)] The thermoplastic polymer (A-2) is a thermoplastic polymer other than the core-shell rubber (A-1), and is preferably a polymer obtained by polymerizing monomers mainly composed of alkyl methacrylate. However, "mainly composed of alkyl methacrylate" means that the proportion of constituent units derived from alkyl methacrylate to the total constituent units of the thermoplastic polymer (A-2) is 50% by mass or more. Examples of thermoplastic polymers (A-2) include the thermoplastic polymers and polymer-based processing aids described in Patent Document 1. 【0020】 [Additives (A-3)] Additives (A-3) are compounds other than core-shell rubber (A-1) and thermoplastic polymer (A-2), and include, for example, antiblocking agents, stabilizers, lubricants, plasticizers, foaming agents, fillers, colorants, and ultraviolet absorbers. 【0021】 For example, it is preferable that the additive (A-3) contains an ultraviolet absorber in order to provide weather resistance in order to protect the substrate. The molecular weight of the ultraviolet absorber is preferably 300 or more, and more preferably 400 or more. If the molecular weight is above the lower limit, the ultraviolet absorber is less likely to volatilize when vacuum forming or pressure forming is performed in the injection molding die, and mold contamination is less likely to occur. Furthermore, the bleed-out of the ultraviolet absorber after molding is reduced. As the ultraviolet absorber, benzotriazole-based ultraviolet absorbers and triazine-based ultraviolet absorbers with a molecular weight of 400 or more are preferred. Triazine-based ultraviolet absorbers with a molecular weight of 400 or more are more preferred in order to maintain long-term ultraviolet shielding ability. 【0022】 Examples of commercially available benzotriazole-based UV absorbers with a molecular weight of 400 or more include "Chinubin 234" (trade name, manufactured by BASF) and "Adekastab LA-31" (trade name, manufactured by ADEKA). Examples of commercially available triazine-based UV absorbers with a molecular weight of 400 or more include "Chinubin 1577" (trade name, manufactured by BASF), "Chinubin 1600" (trade name, manufactured by BASF), and "Adekastab LAF-70" (trade name, manufactured by ADEKA). These may be used individually or in combination of two or more. 【0023】 From the viewpoint of weather resistance, the amount of UV absorber added is preferably 0 to 20 parts by mass per 100 parts by mass of the total of the core-shell rubber (A-1) and the thermoplastic polymer (A-2). Furthermore, from the viewpoint of preventing mold contamination or bleed-out during molding, the amount of UV absorber added is more preferably 1 to 5 parts by mass. 【0024】 Furthermore, to further improve weather resistance, it is preferable to use radical scavengers such as hindered amine-based light stabilizers in combination with ultraviolet absorbers. Examples of commercially available radical scavengers include "ADEKA LA-57", "ADEKA LA-62", "ADEKA LA-67", "ADEKA LA-63", and "ADEKA LA-68" (all trade names, manufactured by ADEKA Corporation); "SANOL LS-770", "SANOL LS-765", "SANOL LS-292", "SANOL LS-2626", "SANOL LS-1114", "SANOL LS-744", "CHIMASSORB2020FDL", "CHIMASSORB944FDL", "CHINUVIN 622", "CHINUVIN PA144", "CHINUVIN 765", "CHINUVIN 770DF", and "CHINUVIN XT55FB" (all trade names, manufactured by BASF Corporation). These may be used individually or in combination of two or more. 【0025】 From the viewpoint of resistance to bleed-out, the amount of radical scavenger added is preferably 0 to 10 parts by mass, and more preferably 0.2 to 5 parts by mass, per 100 parts by mass of the total of the core-shell rubber (A-1) and the thermoplastic polymer (A-2). 【0026】 Furthermore, from the standpoint of providing an anti-blocking effect, it is preferable that the additive (A-3) contains an anti-blocking agent. Examples of commercially available anti-blocking agents include "AEROSIL R976" (manufactured by Nippon Aerosil Co., Ltd.), "Epostor MA1002", "Epostor MA1004", "Epostor MA1006", "Epostor MA1010", "Epostor MA1013EX-F", and "Epostor MA2003" (all are trade names, manufactured by Nippon Shokubai Co., Ltd.). 【0027】The addition amount of the anti-blocking agent is preferably 0.01 to 2 parts by mass, more preferably 0.05 to 1.5 parts by mass, and even more preferably 0.1 to 1.0 parts by mass with respect to 100 parts by mass of the acrylic resin composition (A1). When the content rate of the anti-blocking agent is at least the lower limit value, blocking between the films can be prevented when storing the film in sheets for melamine decorative boards, and the handling property is excellent. When the content rate of the anti-blocking agent is at most the upper limit value, a decrease in the transparency of the obtained film can be suppressed, and the generation of fish eyes can be reduced. 【0028】 Also, from the viewpoint of preventing adhesion to the press plate when producing a melamine decorative board by pressing, it is preferable that the additive (A-3) contains a release agent. Examples of the release agent include silicone compounds, fluorine compounds, alkyl alcohols, and alkyl carboxylic acids. Among them, alkyl carboxylic acids are preferable from the viewpoints of easy availability and economy. Examples of the alkyl carboxylic acid include linoleic acid, vaccenic acid, stearic acid, oleic acid, margaric acid, palmitoleic acid, palmitic acid, and pentadecylic acid. These may be used alone or in combination of two or more. 【0029】 The addition amount of the release agent is preferably 0.01 to 2 parts by mass, more preferably 0.1 to 0.5 parts by mass with respect to 100 parts by mass in total of the core-shell rubber (A-1) and (A-2) from the viewpoint of preventing adhesion to the press plate. 【0030】 [Fluorine-based resin composition (C)] The fluorine-based resin composition (C) of the present invention can contain a fluorine-based resin (C-1), a thermoplastic polymer (C-2), and an additive (C-3). The fluorine-based resin composition (C) contains 60 to 100% by mass of the fluorine-based resin (C-1) and 0 to 40% by mass of the thermoplastic polymer (C-2) with respect to 100% by mass in total of the fluorine-based resin (C-1) and the thermoplastic polymer (C-2), and further preferably contains 0 to 20 parts by mass of the additive (C-3) with respect to 100 parts by mass in total of the fluorine-based resin (C-1) and the thermoplastic polymer (C-2). 【0031】If the content of fluororesin (C-1) is 60% by mass or more, the resin layer (I) is provided with chemical resistance and high water resistance, resulting in good chemical resistance and water resistance for the laminated film and the molded product made by laminating the laminated film. If the content of thermoplastic polymer (C-2) is 40% by mass or less, the resin layer (I) is provided with chemical resistance and high water resistance, resulting in good chemical resistance and water resistance for the laminated film and the molded product made by laminating the laminated film. 【0032】 From the standpoint of chemical resistance and water resistance, a higher content of fluororesin (C-1) is preferable. On the other hand, when a crystalline polymer such as polyvinylidene fluoride is used for the fluororesin (C-1), curling may occur in the laminated film due to crystallization shrinkage or the difference in thermal shrinkage rate with the resin layer (II), potentially causing handling problems. Adding a thermoplastic polymer (C-2) can suppress curling and improve the handling properties of the laminated film. From the standpoint of suppressing curling, a higher content of thermoplastic polymer (C-2) is preferable. 【0033】 Furthermore, when a relatively soft resin such as polyvinylidene fluoride is used for the fluoropolymer (C-1) and a relatively hard resin such as polymethyl methacrylate is used for the thermoplastic polymer (C-2), the addition of the thermoplastic polymer (C-2) increases the surface hardness and improves scratch resistance. From the standpoint of scratch resistance, a higher content of the thermoplastic polymer (C-2) is preferable. 【0034】 Furthermore, when crystalline polymers such as polyvinylidene fluoride are used in the fluororesin (C-1), there is a possibility of deterioration in optical properties, such as a decrease in film transparency, an increase in haze value, and an increase in yellowness. In such cases, the optical properties can be further improved by adding a thermoplastic polymer (C-2) to lower the degree of crystallinity or to refine the crystal size. 【0035】From the viewpoint of chemical resistance and water resistance, it is more preferable that the fluororesin composition (C) contains 70 to 95% by mass of fluororesin (C-1) and 5 to 30% by mass of thermoplastic polymer (C-2) based on a total of 100% by mass of fluororesin (C-1) and thermoplastic polymer (C-2). From the viewpoint of curling, it is more preferable that the fluororesin composition (C) contains 60 to 95% by mass of fluororesin (C-1) and 5 to 40% by mass of thermoplastic polymer (C-2) based on a total of 100% by mass of fluororesin (C-1) and thermoplastic polymer (C-2), and even more preferable that it contains 60 to 85% by mass of fluororesin (C-1) and 15 to 40% by mass of thermoplastic polymer (C-2). If the content of thermoplastic polymer (C-2) is 5% by mass or more, curling is suppressed and the handling properties of the laminated film are improved. 【0036】 From the viewpoint of scratch resistance, the fluororesin composition (C) more preferably contains 50 to 90% by mass of fluororesin (C-1) and 10 to 50% by mass of thermoplastic polymer (C-2) based on a total of 100% by mass of fluororesin (C-1) and thermoplastic polymer (C-2), and even more preferably contains 50 to 75% by mass of fluororesin (C-1) and 25 to 50% by mass of thermoplastic polymer (C-2). 【0037】 Furthermore, the fluororesin composition (C) more preferably contains 0 to 10 parts by mass of the additive (C-3) per 100 parts by mass of the total of the fluororesin (C-1) and the thermoplastic polymer (C-2), and even more preferably contains 0 to 3 parts by mass of the additive (C-3). However, the fluororesin composition (C) does not necessarily have to contain the thermoplastic polymer (C-2) and the additive (C-3). 【0038】[Fluorine-based resin (C-1)] The fluorine-based resin (C-1) may be any homopolymer or copolymer of monomers having a fluorine substituent, and may also contain non-fluoropolymers such as ethylene. Examples of monomers having a fluorine substituent include vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ethers such as perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether), and perfluoro(propyl vinyl ether), fluoroalkyl methacrylates such as perfluoro(1,3-dioxole), perfluoro(2,2-dimethyl-1,3-dioxole), perfluorobutylethylene, 3,3,3-trifluoropropene, and trifluoroethyl methacrylate, and fluoroalkyl acrylates such as trifluoroethyl acrylate. 【0039】 As the fluororesin (C-1), a homopolymer or copolymer of vinylidene fluoride is preferred due to its chemical resistance and availability, and a homopolymer of vinylidene fluoride is more preferred. Examples of commercially available products include "KYNAR720" and "KYNAR740" (both trade names, manufactured by Arkema); and "KF Polymer T#850," "KF Polymer T#1000," and "KF Polymer T#1100" (all trade names, manufactured by Kureha Corporation). All of the aforementioned commercially available products are homopolymers of vinylidene fluoride. 【0040】 The melt viscosity of the fluoropolymer (C-1) is preferably 5 to 50 g / 10 min, and more preferably 10 to 30 g / 10 min, as measured by MFR at 230°C and 5 kg in accordance with ASTM D1238, because it facilitates melt molding. Specifically, "KYNAR720" and "KF Polymer T#850" are examples. 【0041】 The mass-average molecular weight (Mw) of the fluororesin (C-1) is preferably between 100,000 and 500,000. Note that Mw is the value measured using a dimethylformamide solution by the method described later. 【0042】[Thermoplastic polymer (C-2)] The thermoplastic polymer (C-2) is a resin other than the fluororesin (C-1), and includes the same as the core-shell rubber (A-1) or the thermoplastic polymer (A-2), or mixtures thereof. 【0043】 [Additive (C-3)] Additive (C-3) is a compound other than the fluororesin (C-1) and the thermoplastic polymer (C-2), and the same additive (A-3) used in the preparation of the acrylic resin composition (A1) can be used. However, fluororesins may have poor compatibility with various additives, which may worsen the appearance, so the amount added may be zero. In particular, hindered amine radical scavengers may react with the fluororesin (C-1) and cause discoloration, so the amount added may be zero. 【0044】 [Resin layer (II)] The resin layer (II) is a layer made of the acrylic resin composition (B) described above. 【0045】 [Acrylic resin composition (B)] The acrylic resin composition (B) of the present invention is an acrylic resin composition comprising a reactive group-containing acrylic polymer (B-1) with a Tg of 0°C or higher, wherein the acid value of the acetone-soluble portion of the acrylic resin composition (B) is 35 to 180 mg KOH / g, and the acid value of the acetone-insoluble portion of the acrylic resin composition (B) is 20 mg KOH / g or less. 【0046】In this invention, the "acid value" is a value obtained by general neutralization titration, specifically by the method described in the examples below. If there are any anhydrides in the resin, they are ring-opened to become acids, and the total amount of these acids is taken as the acid value. This is because the proportion of acids that become anhydrides varies greatly depending on the extrusion conditions. The method of ring-opening is not particularly limited, but for example, the method described in Japanese Patent Application Publication No. 2006-161003, which involves ring-opening under conditions of 50 to 99% RH humidity and 50 to 100°C, can be used. Furthermore, since it is difficult to measure the acid value of the acetone-insoluble portion, a value calculated by the method described below is used. The acid value of the acetone-insoluble portion of an unknown sample can be determined by analyzing the monomer composition and then calculating it by the method described below. The acid value of the acetone-soluble portion of acrylic resin composition (B) is 35 mg KOH / g or more, preferably 38 mg KOH / g or more, more preferably 40 mg KOH / g or more, and even more preferably 50 mg KOH / g or more. When the acid value is above the lower limit, adhesion to melamine decorative laminate and water-resistant whitening are improved. On the other hand, the acid value of the acetone-soluble component of acrylic resin composition (B) is preferably 180 mg KOH / g or less, more preferably 170 mg KOH / g or less, even more preferably 160 mg KOH / g or less, and particularly preferably 150 mg KOH / g or less. When the acid value is below the upper limit, the buildup of mold residue near the die during melt molding can be suppressed, and productivity is further improved. The acid value is calculated by the method described later. The acid value of the acetone-soluble component of acrylic resin composition (B) can be adjusted by the amount of acid groups contained in the resin that dissolves in acetone, more specifically, by the amount of acid group-containing acrylic polymer. 【0047】The acid value of the acetone-insoluble portion of acrylic resin composition (B) is 20 mg KOH / g or less, preferably 15 mg KOH / g or less, more preferably 10 mg KOH / g or less, and even more preferably 5 mg KOH / g or less. The film appearance is improved when the acid value is below the upper limit. On the other hand, there is no particular limit on the lower limit, and it may be 0 mg KOH / g. The acid value is calculated by the method described later. The acid value of the acetone-insoluble portion of acrylic resin composition (B) can be adjusted by the amount of acid groups contained in the resin that does not dissolve in acetone, more specifically, by the amount of core-shell rubber containing acid groups. 【0048】 The hydroxyl value of the acrylic resin composition (B) of the present invention is preferably 10 mg KOH / g or less. The "hydroxyl value" in the present invention is a value that can be determined by general neutralization titration, and specifically by the method described in the examples below. When the hydroxyl value of the acrylic resin composition (B) is 10 mg KOH / g or less, thermal degradation during melt molding, specifically the formation of gels due to hydroxyl groups and acid, is suppressed, foreign matter is reduced, and the film appearance is improved. The hydroxyl value of the acrylic resin composition (B) is preferably 7.5 mg KOH / g or less, more preferably 5 mg KOH / g or less, and even more preferably 2.5 mg KOH / g or less. On the other hand, there is no particular lower limit to the hydroxyl value of the acrylic resin composition (B), and it may be 0 mg KOH / g. The hydroxyl value of the acrylic resin composition (B) can be adjusted by the content of polymers containing hydroxyl groups contained in the acrylic resin composition (B). 【0049】The Tg of the acetone-soluble portion of the acrylic resin composition (B) of the present invention is preferably 120°C or lower, more preferably 110°C or lower, and even more preferably 100°C or lower. Furthermore, the Tg of the acetone-soluble portion of the acrylic resin composition (B) is 0°C or higher, preferably 30°C or higher, and more preferably 50°C or higher. If the Tg of the acetone-soluble portion of the acrylic resin composition (B) is above the lower limit, the heat resistance and water-resistant whitening properties of the melamine decorative laminate using the film of the present invention will be good. In addition, the blocking properties of the film and the raw resin will be reduced, making it easy to unwind from the film roll and providing excellent handling, and reducing the likelihood of appearance defects due to blocking marks, resulting in a film with excellent appearance quality. If the Tg of the acetone-soluble portion of the acrylic resin composition (B) is below the upper limit, when creating a melamine decorative laminate by laminating the film of the present invention, the adhesion between the melamine substrate and the film will be better even when press processing is performed at a lower temperature. That is, the processing conditions when creating a melamine decorative laminate by laminating the film will be relaxed. Furthermore, the Tg of the acetone-soluble portion of acrylic resin composition (B) is determined by calculating the Tg of each component that is acetone-soluble in acrylic resin composition (B) using the Fox formula described later, and then calculating the weight average of each component. 【0050】 The acrylic resin composition (B) of the present invention preferably has a carboxylic acid anhydride structure content of 0.01% by mass or more per 100% by mass of the acrylic resin composition. The "carboxylic acid anhydride structure content" in the present invention is determined by the method described in the examples below. A carboxylic acid anhydride structure content of 0.01% by mass or more in the acrylic resin composition (B) suppresses the formation of foam due to chemical reactions during melt molding, resulting in a good film appearance. The carboxylic acid anhydride structure content is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.4% by mass or more. On the other hand, there is no particular upper limit to the carboxylic acid anhydride structure content, but it is preferably, for example, 20% by mass or less. 【0051】The acrylic resin composition (B) of the present invention preferably has an MFR retention rate of more than 90% at a temperature of 230°C and a load of 49N. The "MFR retention rate" in the present invention is determined by the method described in the examples below. When the MFR retention rate of the acrylic resin composition (B) is more than 90%, the formation of gelled products due to thermal degradation during melt molding is suppressed, foreign matter is reduced, and the film appearance is improved. The MFR retention rate is preferably 95% or more, more preferably 98% or more, and even more preferably 100% or more. On the other hand, there is no particular upper limit to the MFR retention rate, but from the viewpoint of suppressing the formation of decomposition products due to thermal degradation during melt molding, it is preferably 300% or less, more preferably 200% or less, and even more preferably 150% or less. 【0052】 In addition to the reactive group-containing acrylic polymer (B-1) that constitutes the acrylic resin composition (B), one or more components selected from core-shell rubber (B-2), thermoplastic polymer (B-3), and additives (B-4) may be included. 【0053】 The acrylic resin composition (B) preferably contains 1 to 100% by mass of the reactive group-containing acrylic polymer (B-1), 0 to 99% by mass of the core-shell rubber (B-2), and 0 to 99% by mass of the thermoplastic polymer (B-3) based on a total of 100% by mass of the reactive group-containing acrylic polymer (B-1), core-shell rubber (B-2), and thermoplastic polymer (B-3). Furthermore, it preferably contains 0 to 50 parts by mass of additive (B-4) based on a total of 100 parts by mass of the reactive group-containing acrylic polymer (B-1), core-shell rubber (B-2), and thermoplastic polymer (B-3). 【0054】The acrylic resin composition (B) preferably contains 5 to 95% by mass of reactive group-containing acrylic polymer (B-1), 5 to 95% by mass of core-shell rubber (B-2), and 0 to 95% by mass of thermoplastic polymer (B-3) based on 100% by mass of the total of reactive group-containing acrylic polymer (B-1), core-shell rubber (B-2), and thermoplastic polymer (B-3). It is more preferably composed of 10 to 90% by mass of reactive group-containing acrylic polymer (B-1), 10 to 90% by mass of core-shell rubber (B-2), and 1 to 90% by mass of thermoplastic polymer (B-3). It is even more preferably composed of 12 to 88% by mass of reactive group-containing acrylic polymer (B-1), 12 to 88% by mass of core-shell rubber (B-2), and more than 2% by mass and 85% by mass or less of thermoplastic polymer (B-3). Furthermore, it is preferable to contain 0.1 to 10 parts by mass of additive (B-4) per 100 parts by mass of the total of the reactive group-containing acrylic polymer (B-1), core-shell rubber (B-2), and thermoplastic polymer (B-3), more preferably 1 to 5 parts by mass, and even more preferably 2 to 4 parts by mass. 【0055】 From the viewpoint of melamine adhesion, it is preferable to contain both a reactive group-containing acrylic polymer (B-1) and a core-shell rubber (B-2). If the reactive group-containing acrylic polymer (B-1) is 5% by mass or more, the content of reactive groups in the acrylic resin composition (B) increases, improving adhesion. If the reactive group-containing acrylic polymer (B-1) is 95% by mass or less, the amount of die residue adhering near the die during melt molding is reduced, further improving film productivity. Furthermore, if the core-shell rubber (B-2) is 5% by mass or more, cohesive failure within the resin layer (II) rather than at the interface between the film and the melamine decorative laminate is suppressed, thus improving adhesion. In addition, if the core-shell rubber (B-2) is 5% by mass or more, the toughness of the resin layer (II) is improved, resulting in better handling of the laminated film. If the core-shell rubber (B-2) is 95% by mass or less, the pencil hardness of the resin layer (II) increases, further improving scratch resistance. Furthermore, if the core-shell rubber (B-2) is 95% by mass or less, the formation of gelled material due to thermal degradation during melt molding is suppressed, foreign matter is reduced, and the film appearance is improved. 【0056】 The gel fraction of the acrylic resin composition (B) is preferably 5 to 80%. When the gel fraction is 80% or less, the toughness of the film is improved, and the handling and film-forming properties of the film are good. Furthermore, when the gel fraction is 5% or more, the generation of thermal degradation foreign matter in the resin is suppressed, and the appearance of the film is good. In other words, if the gel fraction is between 5% and 80%, both film toughness and film appearance can be achieved. The gel fraction of the acrylic resin composition (B) is more preferably 7 to 75%, and even more preferably 10 to 70%. The gel fraction of the acrylic resin composition (B) can be adjusted by the content of the core-shell rubber (B-2). 【0057】 [Reactive Group-Containing Acrylic Polymer (B-1)] Reactive group-containing acrylic polymer (B-1) is a polymer that contains structural units derived from monomers having reactive groups. In addition to structural units derived from monomers having reactive groups, reactive group-containing acrylic polymer (B-1) may contain structural units derived from aromatic vinyl monomers and structural units derived from other monomers. Specifically, it is preferable that reactive group-containing acrylic polymer (B-1) contains 1 to 100% by mass of structural units derived from monomers having reactive groups, 0 to 2% by mass of structural units derived from aromatic vinyl monomers, and 0 to 97% by mass of structural units derived from other monomer units per 100% by mass of reactive group-containing acrylic polymer (B-1). 【0058】 The reactive group-containing acrylic polymer (B-1) preferably contains constituent units derived from monomers having reactive groups for amino groups or methylol groups. This is because heating the polymer in contact with a material containing methylolmelamine and its derivatives, specifically the melamine resin of a melamine decorative laminate or its precursor, makes it easier to achieve close adhesion with the melamine decorative laminate. 【0059】Examples of reactive groups for the amino group or methylol group include hydroxyl group, carboxyl group, amino group, amide group, acid anhydride group, imide group, and epoxy group. The reactive group-containing acrylic polymer (B-1) may have one of these reactive groups, or two or more. Among these, carboxyl groups and acid anhydride groups are preferred as reactive groups from the viewpoint of adhesion to melamine decorative laminates and prevention of crosslinking during melt molding. 【0060】 Examples of monomers having a carboxyl group as a reactive group include methacrylic acid, acrylic acid, (meth)acrylic acid, (meth)acryloyloxyalkyl carboxylic acid, (meth)acryloyloxy aromatic carboxylic acid, and mono-2-(methacryloyloxy)ethyl succinic acid. Examples of monomers having an acid anhydride group as a reactive group include maleic anhydride and glutaric anhydride. Maleic anhydride and glutaric anhydride are preferred in that they prevent the film appearance from becoming poor due to crosslinking reactions during melt molding. Among these, methacrylic acid and acrylic acid are preferred as monomers having a carboxyl group in that they prevent yellowing due to UV degradation. These may be used individually or in combination of two or more. 【0061】 The content of constituent units derived from monomers having reactive groups is preferably 3 to 95% by mass per 100% by mass of the reactive group-containing acrylic polymer (B-1). More preferably, the content is 5 to 90% by mass, and even more preferably 7 to 85% by mass. If the content is 95% by mass or less, side reactions due to the reactive groups can be suppressed, and the generation of die residue that adheres to the die area during melt molding can be suppressed. On the other hand, if the content is 3% by mass or more, good melamine adhesion is achieved. Furthermore, if the monomer having reactive groups is water-soluble, dissolution in water can be suppressed by using a water-insoluble monomer in combination, and the reactive group-containing acrylic polymer (B-1) can be efficiently produced in water-based polymerization such as emulsion polymerization and suspension polymerization. 【0062】Examples of aromatic vinyl monomers include, but are not limited to, styrene, bromostyrene, divinylbenzene, and α-methylstyrene. 【0063】 The content of constituent units derived from aromatic vinyl monomers is preferably 2% by mass or less per 100% by mass of the reactive group-containing acrylic polymer (B-1). If the content is 2% by mass or less, the weather resistance of the resulting film and melamine decorative laminate will be better. The content is more preferably 0 to 1% by mass, and even more preferably 0 to 0.1% by mass. It is preferable to use a small amount of aromatic vinyl monomer, and it may even be 0% by mass. 【0064】 Other monomers can be the same monomers used in the polymerization of the thermoplastic polymer (A-2). However, acrylic monomers, particularly methyl methacrylate, are preferred in terms of compatibility with the core-shell rubber (B-2) and thermoplastic polymer (B-3), and adhesion to the resin layer (I). The content of constituent units derived from other monomers is preferably 0 to 97% by mass, and more preferably 0 to 95% by mass, relative to 100% by mass of the reactive group-containing acrylic polymer (B-1), in order to suppress reactions such as crosslinking by reactive groups. 【0065】 Various polymerization methods such as suspension polymerization, emulsion polymerization, bulk polymerization, and solution polymerization can be used to produce reactive group-containing acrylic polymers (B-1). However, when monomers having acid anhydride groups or imide groups are used as the monomers containing reactive groups, hydrolysis occurs during polymerization, and therefore, they cannot be produced by aqueous polymerization methods such as suspension polymerization or emulsion polymerization. Chain transfer agents and other polymerization aids may be used during polymerization. Mercaptans are preferred as chain transfer agents. 【0066】The Tg of the reactive group-containing acrylic polymer (B-1) is preferably 0 °C or higher, more preferably 30 °C or higher, and even more preferably 50 °C or higher. On the other hand, the Tg of the reactive group-containing acrylic polymer (B-1) is preferably 120 °C or lower, more preferably 110 °C or lower, and even more preferably 100 °C or lower. When the Tg of the reactive group-containing acrylic polymer (B-1) is at or above the lower limit value, the heat resistance and water whitening resistance of the melamine decorative board using the film of the present invention are good. In addition, since the blocking property of the film and the raw material resin is reduced, the film can be easily unwound from the film roll, and it has excellent handling properties. Moreover, it is less likely to cause appearance defects due to blocking marks, and a film with excellent appearance quality can be obtained. When the Tg of the reactive group-containing acrylic polymer (B-1) is at or below the upper limit value, when producing a melamine decorative board laminated with the film of the present invention, even if the press processing is performed at a lower temperature, the adhesion between the melamine base material and the film becomes better. That is, the processing conditions for producing a melamine decorative board laminated with the film are relaxed. 【0067】 The Tg of the reactive group-containing acrylic polymer (B-1) can be determined by the Fox formula using the Tg values of the homopolymers of the components constituting the reactive group-containing acrylic polymer (B-1). The Fox formula is shown below. 1 / (273 + Tg) = Σ(wi / (273 + Tgi)) In the formula, Tg is the Tg (°C) of the copolymer (or its mixture), wi is the mass fraction of monomer i, and Tgi is the Tg (°C) of the homopolymer obtained by polymerizing monomer i. 【0068】 Here, as the Tg value of the homopolymer, the values described in POLYMER HANDBOOK THIRD EDITION (WILEY INTERSCIENCE) or the catalog values of the monomer manufacturer are used. When the monomer contains a crosslinkable monomer, the Tg is determined for the monomer excluding the crosslinkable monomer. 【0069】 The SP value of the reactive group-containing acrylic polymer (B-1) is preferably ３ ) １／２ or less, and more preferably ３ )１／２ It is more preferable that the following conditions apply: 21.9 (J / cm²). ３ ) １／２ It is even more preferable that the following conditions are met. On the other hand, the SP value of the reactive group-containing acrylic polymer (B-1) is 18.0 (J / cm²). ３ ) １／２ Preferably, it should be 18.5 (J / cm²). ３ ) １／２ It is more preferable that the value be greater than or equal to 19.0 (J / cm²). ３ ) １／２ It is even more preferable that the above conditions are met. When the SP value is within the above range, the affinity with the melamine substrate is excellent, and the adhesion between the melamine substrate and the laminated film is better. Also, when the SP value is within the above range, the affinity with water is low, and the melamine adhesion and water-resistant whitening after immersion in 100°C hot water for 2 hours are good. 【0070】 The SP value (Solubility Parameter) is a measure of solubility. A higher SP value indicates higher polarity, while a lower SP value indicates lower polarity. In this invention, the SP value is calculated using the method proposed by Fedors et al. Specifically, it can be calculated by referring to "Polymer Engineering and Science, February, 1974, Vol. 14, No. 2, Robert F. Fedors (147-154)". 【0071】 The mass-average molecular weight (Mw) of the reactive group-containing acrylic polymer (B-1) is preferably 10,000 to 500,000. More preferably 20,000 to 300,000, even more preferably 30,000 to 150,000, and particularly preferably 50,000 to 100,000. When the Mw is below the upper limit, the conformability to the melamine substrate is excellent, and the adhesion between the melamine substrate and the film is better. When the Mw is above the lower limit, the film toughness is good. The Mw values ​​are measured by the method described later. 【0072】[Core-shell rubber (B-2)] The core-shell rubber (B-2) preferably contains substantially no constituent units derived from the monomer shown in the following formula (1), but is otherwise not particularly limited. CH ２ = C(R １ ) COO-R ２ ...Equation (1) Here, R １ is a hydrogen atom or a methyl group, R ２ This group is selected from a hydrogen atom or a tertiary hydrocarbon group, an aromatic hydrocarbon group, and an alicyclic hydrocarbon group. 【0073】 Furthermore, the acid value of the acetone-soluble portion of the core-shell rubber (B-2) is preferably 35 mg KOH / g or less, and the acid value of the acetone-insoluble portion is preferably 20 mg KOH / g or less. There are no particular lower limits on the acid values ​​of the acetone-soluble and acetone-insoluble portions of the core-shell rubber (B-2), but they may be 0 mg KOH / g. By keeping the acid value of the core-shell rubber (B-2) within the above range, gelation during film manufacturing can be suppressed, and a film with a good appearance can be obtained. 【0074】Furthermore, the core-shell rubber (B-2) preferably has a multilayer structure of two or more layers, in which a layer containing a rigid polymer (b-2) as an outer layer is formed on a layer containing an elastic copolymer (b-1) as an inner layer. Examples of materials for the core-shell rubber (B-2) include acrylic rubber, silicone rubber, butadiene rubber, etc., and acrylic rubber is preferred in terms of transparency and weather resistance. More specifically, it is preferable that the acrylic rubber has a multilayer structure of two or more layers, in which a layer containing a rigid polymer (b-2) as an outer layer, in which a layer containing an elastic copolymer (b-1) as an inner layer having a structure of one or more layers obtained mainly from alkyl methacrylate is formed on a layer containing an elastic copolymer (b-1) having a structure of one or more layers obtained mainly from alkyl methacrylate is formed on a layer containing an elastic copolymer (b-1) having a structure of one or more layers. However, in the case of the elastic copolymer (b-1), "mainly composed of alkyl (meth)acrylate" means that the ratio of alkyl (meth)acrylate to the total mass of the elastic copolymer (b-1) is 50% by mass or more. In rigid polymer (b-2), "mainly composed of alkyl methacrylate" means that the proportion of alkyl methacrylate to the total mass of rigid polymer (b-2) is 50% by mass or more. In particular, it is preferable that rigid polymer (b-2) contains core-shell rubber (B-2) that substantially does not contain constituent units derived from the monomer shown in the following formula (1). CH ２ = C(R １ ) COO-R ２ ...Equation (1) Here, R １ is a hydrogen atom or a methyl group, R ２ This group is selected from a hydrogen atom or a tertiary hydrocarbon group, an aromatic hydrocarbon group, and an alicyclic hydrocarbon group. Specific examples of monomers represented by formula (1) include tributyl (meth)acrylate, phenyl (meth)acrylate, and isobornyl (meth)acrylate. 【0075】Furthermore, the core-shell rubber (B-2) may have one or more layers containing an intermediate polymer (b-3) between the layer containing the elastic copolymer (b-1) and the layer containing the rigid polymer (b-2). The content of the elastic copolymer (b-1) in the core-shell rubber (B-2) is preferably 10 to 90% by mass, and more preferably 20 to 70% by mass. The content of the rigid polymer (b-2) in the core-shell rubber (B-2) is preferably 10 to 90% by mass, and more preferably 30 to 70% by mass. The content of the intermediate polymer (b-3) in the core-shell rubber (B-2) is preferably 0 to 35% by mass, and more preferably 0 to 20% by mass. Also, when the content of the intermediate polymer (b-3) is 35% by mass or less, the balance of the core-shell rubber (B-2) is good. 【0076】 The elastic copolymer (b-1) is preferably a polymer obtained by polymerizing a monomer composition containing an alkyl acrylate (meth)acrylate. Note that (meth)acrylic acid refers to acrylic acid or methacrylic acid. The elastic copolymer (b-1) is more preferably a polymer obtained by polymerizing a monomer composition containing an alkyl acrylate (meth)acrylate. The monomer composition may further contain monomers other than alkyl acrylate (meth)acrylate and crosslinkable monomers. For example, the elastic copolymer (b-1) may contain 80 to 100% by mass of one or more selected from alkyl acrylates having an alkyl group having 1 to 8 carbon atoms and alkyl methacrylates having an alkyl group having 1 to 4 carbon atoms, 0 to 20% by mass of monomers other than alkyl acrylate (meth)acrylate, and 0 to 10% by mass of crosslinkable monomers (total 100% by mass). 【0077】 Preferred alkyl acrylates having an alkyl group with 1 to 8 carbon atoms include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate, with alkyl acrylates having a lower Tg being more preferred. These may be used individually or in combination of two or more. 【0078】The alkyl acrylate is used as the main component of the monomer constituting the elastic copolymer (b-1). Specifically, the amount of alkyl acrylate used is preferably 30 to 99.9% by mass relative to the total monomers constituting the elastic copolymer (b-1). When the amount used is 30% by mass or more, the moldability of the film is better. The amount used is more preferably 50 to 95% by mass. Note that the range of the amount used refers to the total amount of alkyl acrylate used in the elastic copolymer (b-1) when the elastic copolymer (b-1) has a structure of two or more layers. For example, when the elastic copolymer (b-1) has a hard core structure, the amount of alkyl acrylate used in the first layer (core) can be less than 30% by mass. 【0079】 Examples of alkyl methacrylate esters having an alkyl group with 1 to 4 carbon atoms include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. These may be used individually or in combination of two or more. The amount of alkyl methacrylate ester used is preferably 0 to 69.9% by mass, and more preferably 0 to 40% by mass, relative to the total monomers constituting the elastic copolymer (b-1). 【0080】 Other monomers besides alkyl (meth)acrylate include other vinyl monomers copolymerizable with the alkyl (meth)acrylate. Examples of monomers other than alkyl (meth)acrylate include styrene and acrylonitrile. These may be used individually or in combination of two or more. When monomers other than alkyl (meth)acrylate are used, the amount used is preferably 0 to 69.9% by mass, and more preferably 0 to 20% by mass, relative to the total monomers constituting the elastic copolymer (b-1). 【0081】Examples of the crosslinkable monomers include ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, propylene glycol dimethacrylate, and graft crossing agents. These may be used individually or in combination of two or more. The amount of crosslinkable monomer used is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass, relative to the total monomers constituting the elastic copolymer (b-1). In terms of the stability of the core-shell rubber (B-2), it is preferable to use a graft crossing agent as the crosslinkable monomer. 【0082】 Examples of the graft crossing agents include allyl esters, metharyl esters, or clotyl esters of α,β-unsaturated carboxylic acids or unsaturated dicarboxylic acids; triallyl cyanurate, triallyl isocyanurate. Among these, allyl esters of acrylic acid, methacrylic acid, maleic acid, fumaric acid, etc. are preferred, and allyl methacrylate is more preferred due to its excellent effect. In such graft crossing agents, the conjugated unsaturated bonds of the ester react and chemically bond much faster than the allyl, metharyl, or clotyl groups. The majority of the slower-reacting allyl, metharyl, or clotyl groups then work effectively during the polymerization of the sublayer polymer, providing graft bonds between adjacent layers. 【0083】The rigid polymer (b-2) is preferably a polymer obtained by polymerizing alkyl methacrylate, alkyl acrylate, and monomers other than alkyl (meth)acrylate. The rigid polymer (b-2) preferably contains 80 to 99% by mass of linear alkyl (meth)acrylate, and more preferably 85 to 99% by mass, in the presence of the elastic copolymer (b-1). The linear alkyl (meth)acrylate used in the rigid polymer (b-2) is not particularly limited, but from the viewpoint of polymerization reactivity and cost, those with 1 to 12 carbon atoms in the alkyl group are preferred. Specific examples include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, methyl acrylate, n-butyl acrylate, etc., and these monomers may be used individually or in combination of two or more. Monomers other than alkyl (meth)acrylate used in the rigid polymer (b-2) are the same as those used in the elastic copolymer (b-1). 【0084】 As the intermediate polymer (b-3), a polymer obtained by polymerizing a monomer composition containing alkyl acrylates, alkyl methacrylates, monomers other than alkyl (meth)acrylates, and crosslinkable monomers is preferred. As the intermediate polymer (b-3), a polymer obtained by polymerizing a monomer composition containing alkyl acrylates having C1 to C8 alkyl groups, alkyl methacrylates having C1 to C4 alkyl groups, monomers other than alkyl (meth)acrylates, and crosslinkable monomers is more preferred. For example, the intermediate polymer (b-3) may contain 10 to 90% by mass of alkyl acrylates having C1 to C8 alkyl groups, 90 to 10% by mass of alkyl methacrylates having C1 to C4 alkyl groups, 0 to 20% by mass of monomers other than alkyl (meth)acrylates, and 0 to 10% by mass of crosslinkable monomers (total 100% by mass). 【0085】Each monomer used in the intermediate polymer (b-3) can be the same monomer used in the polymerization of the elastic copolymer (b-1). Furthermore, it is preferable that the content of alkyl acrylate in the intermediate polymer (b-3) (monomer composition ratio) is lower than the content of alkyl acrylate in the elastic copolymer (b-1) and higher than the content of alkyl acrylate in the rigid polymer (b-2). 【0086】 The average particle size of the core-shell rubber (B-2) is preferably 50 to 300 nm, more preferably 50 to 200 nm, and even more preferably 60 to 100 nm. From the viewpoint of film transparency and film-forming properties, an average particle size of 50 nm or more is preferred. The average particle size can be measured by the method described later. 【0087】 The method for producing the core-shell rubber (B-2) is not particularly limited. For example, emulsion polymerization can be used to produce the elastic copolymer (b-1) and the rigid polymer (b-2). Alternatively, it can be produced by emulsion-suspension polymerization, in which the polymerization of the polymer constituting the outermost layer is converted to a suspension polymerization system after emulsion polymerization. The polymerization temperature is appropriately selected depending on the type and amount of polymerization initiator used, but is preferably 40 to 120°C, and more preferably 60 to 95°C. Known polymerization initiators can be used as polymerization initiators. The polymerization initiator can be added to either the aqueous phase or the monomer phase, or both. 【0088】Examples of emulsifiers that can be used in emulsion polymerization include anionic, cationic, and nonionic surfactants, but anionic surfactants are preferred. Examples of anionic surfactants include carboxylate-based surfactants such as potassium oleate, sodium stearate, sodium myristate, sodium N-lauroyl sarcosinate, and dipotassium alkenylsuccinate; sulfate-based surfactants such as sodium lauryl sulfate; sulfonate-based surfactants such as sodium dioctyl sulfosuccinate, sodium dodecylbenzenesulfonate, and sodium alkyldiphenyl ether disulfonate; and phosphate-based surfactants such as sodium polyoxyethylene alkylphenyl ether phosphate. These may be used individually or in combination of two or more. 【0089】 The polymer latex obtained by emulsion polymerization can be filtered, for example, through a filter with a mesh size of 100 μm or less, and then separated and recovered by methods such as acid coagulation, salt coagulation, freeze-coagulation, and spray drying. For acid coagulation, inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, and organic acids such as acetic acid can be used. For salt coagulation, inorganic salts such as sodium sulfate, magnesium sulfate, aluminum sulfate, and calcium chloride, and organic salts such as calcium acetate and magnesium acetate can be used. From the viewpoint of the flow characteristics of the obtained powder, calcium chloride is preferred. On the other hand, from the viewpoint of metal corrosivity, calcium acetate is preferred. These may be used individually or in combination of two or more. The separated and recovered polymer can be further washed, dehydrated, dried, etc., to obtain core-shell rubber (B-2). 【0090】[Thermoplastic Polymer (B-3)] The thermoplastic polymer (B-3) can be any resin other than the reactive group-containing acrylic polymer (B-1) and core-shell rubber (B-2), and it is preferable that it is an acrylic resin that substantially does not contain reactive groups. More specifically, it can be the same as the thermoplastic polymer (A-2) described above, and one type may be used alone, or two or more types may be used in combination. The thermoplastic polymer (B-3) preferably contains an acrylic polymer with a mass-average molecular weight of 500,000 or more. The mass-average molecular weight is more preferably 1,000,000 or more, and even more preferably 2,000,000 or more. The upper limit of the mass-average molecular weight is not particularly limited, but for example it is 5,000,000 or less. The content of the acrylic polymer with a mass-average molecular weight of 500,000 or more in 100% by mass of the acrylic resin composition (B) is preferably more than 2% by mass from the viewpoint of suppressing die buildup near the die during melt molding. Also, from the viewpoint of suppressing melt viscosity, the content of the acrylic polymer is preferably 10% by mass or less. The content of the acrylic polymer is more preferably 2.5% by mass or more and 9% by mass or less, and even more preferably 3% by mass or more and 8% by mass or less. If the content of the acrylic polymer is more than 2% by mass and 10% by mass or less, the molecular weight distribution of the acrylic resin composition (B) will be 4 to 7. The molecular weight distribution can be determined by the method described in the examples below. 【0091】 [Additive (B-4)] Additive (B-4) is a compound other than the reactive group-containing acrylic polymer (B-1), core-shell rubber (B-2), and thermoplastic polymer (B-3), and the same additive as that used in the acrylic resin composition (A) (A-3) can be used. 【0092】 [Film, Laminated Film] The acid values ​​of the acetone-soluble and acetone-insoluble components of the resin layer (I) and resin layer (II) in the film and laminated film of the present invention are equivalent to the acid values ​​of the acetone-soluble and acetone-insoluble components of the resin composition (A) constituting the resin layer (I) and the resin composition (B) constituting the resin layer (II), respectively. 【0093】The thickness of the film and laminated film of the present invention is preferably 10 to 200 μm, more preferably 20 to 100 μm, and even more preferably 25 to 80 μm. If the thickness is above the lower limit, the film and laminated film can be easily manufactured, and sufficient weather resistance can be imparted to the resulting melamine decorative laminate. If the thickness is below the upper limit, the film and laminated film have appropriate flexibility, so peeling can be prevented when cutting the resulting melamine decorative laminate. Furthermore, it is economically advantageous in terms of mass per unit area. In addition, the film-forming properties are stable, making it easier to manufacture the laminated film. Furthermore, when laminated to a melamine decorative laminate, the pencil hardness of the decorative laminate increases, and scratch resistance is further improved. When the film of the present invention is a laminated film of resin layer (I) and resin layer (II), when laminating with a melamine substrate, it is preferable to have the resin layer (II) made of acrylic resin composition (B) facing the substrate side as the laminating layer, and the resin layer (I) made of resin composition (A) facing the opposite side from the substrate as the surface layer. 【0094】 When the resin layer (I) is made of an acrylic resin composition (A1), the thickness of the resin layer (I) is preferably 1 to 199 μm, more preferably 5 to 99 μm, and even more preferably 20 to 79 μm. If the thickness of the resin layer (I) is equal to or greater than the lower limit, the weather resistance and water whitening resistance of the resulting melamine decorative laminate will be good. Furthermore, if the thickness of the resin layer (I) is equal to or less than the upper limit, it will be economically advantageous in terms of mass per unit area. 【0095】 When the resin layer (I) is made of an acrylic resin composition (A1), the thickness of the resin layer (II) is preferably 199 μm or less, preferably 10 μm or less, and more preferably 7 μm or less. On the other hand, the thickness of the resin layer (II) is preferably 0.5 μm or more, more preferably 2 μm or more, and even more preferably 3 μm or more. If the thickness of the resin layer (II) is above the lower limit, the melamine adhesion is improved. If the thickness of the resin layer (II) is below the upper limit, it is economically advantageous in terms of mass per unit area. 【0096】When the resin layer (I) is made of a fluororesin composition (C), the thickness of the resin layer (I) is preferably 99 μm or less, more preferably 10 μm or less, and more preferably 7 μm or less. On the other hand, the thickness of the resin layer (I) is preferably 0.5 μm or more, more preferably 2 μm or more, and even more preferably 3 μm or more. If the thickness of the resin layer (I) is above the lower limit, the weather resistance and water whitening resistance of the resulting melamine decorative laminate will be good. Furthermore, if the thickness of the resin layer (I) is below the upper limit, it is economically advantageous in terms of mass per unit area. 【0097】 When the resin layer (I) is made of a fluororesin composition (C), the thickness of the resin layer (II) is preferably 199 μm or less, more preferably 100 μm or less, and more preferably 79 μm or less. On the other hand, the thickness of the resin layer (II) is preferably 1 μm or more, more preferably 5 μm or more, and even more preferably 20 μm or more. If the thickness of the resin layer (II) is above the lower limit, the melamine adhesion is improved. If the thickness of the resin layer (II) is below the upper limit, it is economically advantageous in terms of mass per unit area. 【0098】 The laminated film of the present invention may have layers other than resin layer (I) and resin layer (II) (hereinafter referred to as intermediate layers), and known resins may be used as intermediate layers. Examples of such compositions include polyvinyl chloride resins, polycarbonate resins, ABS resins, AS resins, MBS resins, MS resins, styrene resins, methacrylic resins, polyglutarimide, glutaric acid anhydride polymers, lactone cyclized methacrylic resins, polyvinylidene fluoride, fluororesins, polyethylene terephthalate resins, polybutylene terephthalate resins, TPO resins, polyethylene resins, and polypropylene resins. From the viewpoint of compatibility with resin layer (I) and resin layer (II), acrylic resins and fluororesins are more preferred. 【0099】 The intermediate layer is preferably three layers or less, and preferably two layers or less. If there are more than three layers, film formation may be difficult. 【0100】The cloudiness value of the film and laminated film of the present invention is preferably 20% or less, and more preferably 10% or less. If the cloudiness value is 20% or less, for example, when used for the protection of decorative panels, the pattern of the underlying decorative layer will not become cloudy, and a decorative panel with excellent design can be obtained. 【0101】 [Method for Manufacturing Film and Laminated Film] Methods for manufacturing the film of the present invention include the T-die method and the inflation method by melt extrusion, and among these, the T-die method is preferred in terms of economy. As for the method for manufacturing the laminated film of the present invention, a method of forming a laminated structure of resin layer (I) and resin layer (II) by co-extrusion via a feed block die or a multi-manifold die is preferred in terms of productivity. Alternatively, resin layer (I) and resin layer (II) can be formed into films by melt extrusion using a T-die, and the two films can be laminated by a thermal lamination method. Furthermore, an extrusion lamination method can be used in which one resin layer is formed into a film, and then the other resin layer is laminated by melt extrusion. When performing melt extrusion, the molten resin composition can be filtered through a screen mesh of 200 mesh or more to remove nuclei and impurities that cause surface defects while extruding. 【0102】 The extruder used for pellet production is preferably equipped with one or more vents. This is because heating the acrylic resin composition (B) causes the acid to anhydride, generating water, methanol, decomposition products, etc. Removing these through the vents prevents defects in appearance caused by foaming during film production. Single-screw or multi-screw extruders may be used. Similarly, for film production, it is preferable to use an extruder equipped with vents. 【0103】Furthermore, in order to prevent foaming and thermal degradation of the acrylic resin composition (B), it is preferable to use a coating method in which a solution containing the acrylic resin composition (B) is applied to a film-shaped resin layer (I) to laminate a resin layer (II). For example, a solution obtained by dissolving the acrylic resin composition (B) in a solvent such as an organic solvent is applied to the resin layer (I) by a printing method such as gravure printing, screen printing, or offset printing, or a coating method such as blade coating or rod coating, and then heated and dried to remove the solvent. Alternatively, a solution containing the acrylic resin composition (A) may be applied to a film-shaped resin layer (II) to laminate a resin layer (I). 【0104】 Examples of the aforementioned solvents include alcoholic solvents such as methanol and ethanol; aromatic solvents such as xylene and toluene; aliphatic hydrocarbon solvents such as hexane and pentane; halogenated hydrocarbon solvents such as chloroform and carbon tetrachloride; phenolic solvents such as phenol and cresol; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; etheric solvents such as diethyl ether and methoxytoluene; fatty acid solvents such as formic acid and acetic acid; acid anhydride solvents such as acetic anhydride; esteric solvents such as ethyl acetate and n-propyl acetate; nitrogen-containing solvents such as dimethylformamide and dimethylacetamide; sulfur-containing solvents such as thiophene and dimethyl sulfoxide; solvents having two or more functional groups such as diacetone alcohol and 2-methoxyethanol (methyl cellosolve); and water. Among these, dimethylformamide and dimethylacetamide are preferred from the viewpoint of solubility. These may be used individually or in combination of two or more. 【0105】 Depending on the printability or coating suitability as a paint, additives to improve the solution properties, such as anti-skinning agents, thickeners, anti-settling agents, anti-sagging agents, defoaming agents, and leveling agents, may be added to the resin composition. Furthermore, additives to improve the coating film performance, such as extender pigments, light stabilizers, UV absorbers, antioxidants, antibacterial agents, antifungal agents, and flame retardants, may be added to the resin composition. 【0106】[Protective film, film for protecting the surface of melamine decorative laminates, melamine decorative laminates] The film and laminated film of the present invention have excellent adhesion and can be bonded to various substrates (melamine resin, phenolic resin, polyamide resin, polyurethane resin, epoxy resin, metal), making them suitable for use as protective films. In particular, the laminated film of the present invention exhibits excellent adhesion to melamine resin (melamine adhesion), making it suitable for use as a film for protecting the surface of melamine decorative laminates. Furthermore, it also has excellent water resistance and whitening resistance, making it suitable for outdoor use. 【0107】 Melamine decorative laminates are used on horizontal surfaces such as desks and countertops, and vertical surfaces such as walls. Their composition and manufacturing methods are described in detail in publications such as the Decorative Laminate Handbook (Shinkenzai Kenkyujo, published in 1973). These melamine decorative laminates are obtained, for example, by impregnating decorative paper for decorative laminates with melamine resin, laminating the dried melamine resin-impregnated paper with a resin-impregnated core paper which serves as the core material layer, and, if necessary, impregnating overlay paper with melamine resin to protect the pattern of the decorative paper, laminating the dried melamine resin-impregnated overlay paper with a balance paper as the bottom layer to suppress warping, and then hot-pressing the laminate. 【0108】 As the melamine resin-impregnated paper, for example, decorative paper for decorative panels can be impregnated with melamine-formaldehyde resin and dried to produce resin-impregnated paper. As the resin-impregnated core paper, for example, kraft paper, nonwoven fabric, woven fabric, etc. can be impregnated with a slurry containing a resin liquid mainly composed of phenol-formaldehyde resin, melamine-formaldehyde resin, or a mixture thereof, and an inorganic filler such as aluminum hydroxide or calcium carbonate, and dried to produce core paper for decorative panels. Hot-press molding can be performed, for example, by laminating the resin-impregnated core paper and melamine resin-impregnated paper (melamine substrate) with the laminated film of the present invention, under conditions of a temperature of 110 to 170°C, a pressure of 5 to 10 MPa, and a time of 10 to 90 minutes. 【0109】When laminating the film and laminated film of the present invention to a melamine substrate, it is preferable to heat-seal them so that the resin layer (II) made of the acrylic resin composition (B) is in contact with the melamine substrate. This method allows lamination without the use of adhesives and tacks. Lamination can be performed continuously or discontinuously, for example, by a discontinuous lamination method using a hot press. In particular, when creating a melamine decorative laminate, if the melamine substrate and the laminated film of the present invention are laminated and then hot-pressed, the laminated film can be laminated simultaneously with the creation of the melamine decorative laminate, which is advantageous because it reduces the number of steps. Furthermore, using the laminated film of the present invention is industrially advantageous because it exhibits excellent adhesion after a hot water test even when the pressing conditions during lamination to the melamine decorative laminate are low temperature and short time. 【0110】 On the other hand, if a film consisting only of a resin layer (I), for example, is used instead of the film and laminated film of the present invention, the adhesion to the melamine substrate is poor, requiring the use of adhesives and primers, which increases costs and significantly reduces productivity. In contrast, when using the laminated film of the present invention, the use of adhesives and primers is unnecessary, thus reducing the number of steps and costs, which is industrially advantageous. 【0111】 The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples, "parts" refers to "parts by mass". The abbreviations used in the examples are as follows. 【0112】MMA: Methyl methacrylate MA: Methyl acrylate EA: Ethyl acrylate BMA: Butyl methacrylate BA: Butyl acrylate HPMA: 2-Hydroxypropyl methacrylate MAA: Methacrylic acid AA: Acrylic acid St: Styrene AMA: Allyl methacrylate BDMA: 1,3-Butylene glycol dimethacrylate CHP: Cumene hydroperoxide tBH: t-Butyl hydroperoxide LPO: Lauryl peroxide AMBN: 2,2'-Azobis(2-methylbutyronitrile) nOM: n-Octyl mercaptan RS610NA: Mono-n-dodecyloxytetraoxyethylene sodium phosphate (product name: "Phosphanol RS-610NA", manufactured by Toho Chemical Industry Co., Ltd.) Pellex OTP: Sodium dialkyl sulfosuccinate (product name: "Pellex OT-P", manufactured by Kao Corporation) LA31: ADEKA Corporation, "ADEKA Stab LA-31RG" (product name) Tv. 1577: BASF Corporation, "Chinubin 1577" (product name) 2020: BASF Corporation, "Chimassorb 2020" (product name) R976: Nippon Aerosil Corporation, "AEROSIL R976" (product name) 1076: BASF Corporation, "Irganox 1076" (product name) AO60: ADEKA Corporation, "ADEKA Stab AO-60" (product name) VH5: Methacrylic resin (PMMA), Mitsubishi Chemical Corporation, "Acrypet VH5001" (product name) VH: Mitsubishi Chemical Corporation, "Acrypet VH001" (product name) T850: Kureha Corporation, "KF Polymer T#850" (product name) 【0113】 The various physical properties in the examples were measured according to the following method. 【0114】(1) Acid Value of Reactive Group-Containing Acrylic Polymer (B-1) and Acrylic Resin Composition (A1) The acid value of the acetone-soluble portion of the reactive group-containing acrylic polymer (B-1) and acrylic resin composition (A1) was determined by the following method. First, 0.4 g of the sample was dissolved in 50 mL of propylene glycol monomethyl ether and stirred at 65°C for 3 hours. Then, 50 mL of a mixed solvent of acetone / ethanol was added and subjected to neutralization titration. Using phenolphthalein as an indicator, the sample was titrated with a 0.1 mol / L ethanolic potassium hydroxide solution. A blank test was also performed using the same procedure except that no sample was used, and the acid value was determined from the following formula: Acid value = (A - B) × f × 56.1 × 0.1 / S f: Titer of 0.1 mol / L ethanolic potassium hydroxide solution S: Amount of sample (g) A: Amount of ethanolic potassium hydroxide solution used for titration (mL) B: Amount of ethanolic potassium hydroxide solution used for blank test (mL). 【0115】 (2) Theoretical acid value (calculated value) of acetone-soluble and acetone-insoluble components of core-shell rubber (B-2) For samples with low solubility in organic solvents, such as core-shell rubber (B-2), the following theoretical acid value (calculated value) can be applied. Theoretical acid value (mgKOH / g) = Number of moles of acid-containing raw material charged × 56.1 (KOH molecular weight) / Weight of acetone-soluble or acetone-insoluble component of core-shell rubber (B-2) (g) × 1000 In addition, the acid value of the acetone-insoluble component of acrylic resin composition (B) can be directly applied to the acid value of the acetone-insoluble component of core-shell rubber (B-2). The acid value of fluororesin composition (C) was calculated using the same method. 【0116】(3) Acid value of the acetone-soluble component of acrylic resin composition (B) The acid value of the acetone-soluble component of acrylic resin composition (B) is calculated by dividing it into the following cases (I) to (IV). (I) When the reactive group-containing acrylic polymer (B-1) contains an acid-containing raw material: Acid value of acetone-soluble component = {Content of reactive group-containing acrylic polymer (B-1) in 100% by mass of acrylic resin composition (B) (%) / (100 - Gel fraction of acrylic resin composition (B) (%))} × Acid value of acetone-soluble component of reactive group-containing acrylic polymer (B-1) (II) When the core-shell rubber (B-2) contains an acid-containing raw material: Acid value of acetone-soluble component = {(Content of core-shell rubber (B-2) in 100% by mass of acrylic resin composition (B) (%) - Gel fraction of (B) (%) / (100 - Gel fraction of acrylic resin composition (B) (%))} × Acid value of acetone-soluble component of core-shell rubber (B-2) (III) When both the reactive group-containing acrylic polymer (B-1) and the core-shell rubber (B-2) contain an acid-containing raw material: The acid value of the acetone-soluble component is the sum of the acid values ​​obtained in (I) and (II) above. (IV) When the reactive group-containing acrylic polymer (B-1) and core-shell rubber (B-2) do not contain acid-containing raw materials: The acid value of the acetone-soluble component is 0. Note that acid-containing raw materials refer to acrylic polymers containing carboxyl groups or acid anhydride groups, for example. 【0117】 (4) Hydroxyl value After measuring the acid value in (1), the sample was dissolved in acetic anhydride and pyridine, acetylated, and then titrated with 0.5 mol / L ethanolic potassium hydroxide solution using phenolphthalein as an indicator. A blank test was also performed using the same procedure except that no sample was used, and the hydroxyl value was determined from the following formula. 【0118】 Hydroxyl value = (B - A) × f × 56.1 × 0.5 / S + Acid value f: Titer of 0.5 mol / L ethanol potassium hydroxide solution S: Sample volume (g) A: Volume of ethanol potassium hydroxide solution used for titration (mL) B: Volume of ethanol potassium hydroxide solution used for blank test (mL). 【0119】(5) Mass-average molecular weight (Mw) or number-average molecular weight (Mn), molecular weight distribution (PDI) The mass-average molecular weight (Mw) or number-average molecular weight (Mn) of the polymer was determined by the following method. Samples of the polymer dissolved in tetrahydrofuran were measured at a temperature of 40°C using gel permeation chromatography (model name: "HLC-8200", manufactured by Tosoh Corporation), columns (product name: "TSK-GEL SUPER MULTIIPORE HZ-H", manufactured by Tosoh Corporation, inner diameter 4.6 mm x length 15 cm x 2), and eluent (tetrahydrofuran). The mass-average molecular weight (Mw) and number-average molecular weight (Mn) were determined from a calibration curve using standard polystyrene. The molecular weight distribution (PDI) was calculated from the mass-average molecular weight (Mw) / number-average molecular weight (Mn). 【0120】 (6) Glass transition temperature (Tg) The glass transition temperature of the polymer was calculated using the Fox formula, using values ​​listed in the Polymer Handbook [J. Brandrup, Interscience, 1989] or catalog values ​​from monomer manufacturers. 【0121】 (7) Average particle diameter The average particle diameter of the core-shell rubber was measured using the dynamic light scattering method with a light scattering photometer (product name: "DLS-700", manufactured by Otsuka Electronics Co., Ltd.) to obtain the final particle diameter of the polymer latex of the polymer obtained by emulsion polymerization. 【0122】 (8) Gel fraction 50 mL of acetone was added to 0.5 g of acrylic resin composition (B) and stirred at 65°C for 4 hours. Then, it was centrifuged at 4°C and 14000 rpm for 30 minutes, the supernatant was removed, and another 50 mL of acetone was added, and it was centrifuged again under the same conditions. After removing the supernatant, the settled gel portion was vacuum dried for 8 hours and its mass was measured, and the gel fraction was calculated using the following formula: Gel fraction (%) = (Mass of gel portion (g) / 0.5) × 100 The gel fraction of the core shell rubber was calculated in the same way. 【0123】 (9) The thickness of the resin layers (I) and (II) was measured by cutting the film or laminated film to an appropriate size and using a reflectance spectrophotometer FE3000 (product name, manufactured by Otsuka Electronics Co., Ltd.). 【0124】 (10) Total light transmittance (TT), haze value (Haze), yellowness (YI), color difference (E), and whiteness (W (Lab)) The total light transmittance (TT) of the film or laminated film was evaluated in accordance with JIS K7361-1, haze value (Haze) in accordance with JIS K7136, yellowness (YI) in accordance with JIS K7373, color difference in accordance with JIS K5600-4-6, and whiteness (W (Lab)) in accordance with JIS Z8715. 【0125】 (11) Endothermic peak temperature of melamine substrate Using DSC6200 (product name, manufactured by SII Nanotechnology), the endothermic peak temperature was measured when the melamine substrate was heated from 25°C to 200°C at a rate of 10°C / min under a nitrogen atmosphere, and the first endothermic peak temperature was defined as the endothermic peak temperature of the melamine substrate. 【0126】 (12) Evaluation of water resistance and whitening properties Using the obtained melamine decorative laminate, a boiling test (water resistance test) was conducted at 100°C for 2 hours in accordance with the CEN (European Committee for Standardization) standard, EN438-2, and the change in whiteness (ΔW (Lab)) before and after the boiling test was measured. 【0127】 (13) Adhesion evaluation (adhesion) A grid of 100 squares was cut into a melamine decorative laminate at 1 mm intervals using a utility knife at room temperature, and peelability was checked using cellophane tape (manufactured by Nichiban Co., Ltd.). This test was performed on the melamine decorative laminate after the boiling test (water resistance test) and evaluated according to the following criteria: 0: No squares peel off at all 1: Less than 5% of the squares peel off 2: Less than 15% of the squares peel off 3: Less than 35% of the squares peel off 4: Less than 65% of the squares peel off 5: Classification 5 was used when 65% or more of the squares peeled off. 【0128】(14) MFR (Melt Flow Rate) and MFR Retention Rate The MFR (Melt Flow Rate) was measured using a melt indexer (product name "L243", manufactured by Techno Seven Co., Ltd.) in accordance with JIS K7210 (Method A) with a heating time of 4 minutes. The MFR (Melt Flow Rate) was also measured with a heating time of 20 minutes, and the MFR (Melt Flow Rate) retention rate was calculated using the following formula: MFR Retention Rate = {MFR (20 mins) / MFR (4 mins)} × 100 The measurement conditions for MFR were a temperature of 230°C, a load of 49N, and a sample cutting time interval of 60 seconds or 120 seconds depending on the MFR value of the sample. 【0129】 (15) Solubility parameter value (SP value) The solubility parameter value (SP value) was calculated by referring to "Polymer Engineering and Science, February, 1974, Vol. 14, No. 2, Robert F. Feders. (147-154)". 【0130】 (16) After preparing a single-layer film (thickness 45 μm) made of the storage modulus resin layer (I), test pieces cut to a width of 6 mm and a length of 20 mm were measured using an EXSTAR DMS6100 manufactured by Seiko Instruments Inc. in tensile mode under the conditions of a heating rate of 2 °C / min, a measurement frequency of 0.1 Hz, and a measurement temperature of 100 °C. 【0131】 (17) Weather resistance evaluation: Using a metal weather meter (model name: "KU-R4CI-A", manufactured by Daipla Wintes Co., Ltd.), irradiation intensity of 65 mW / cm² ２ Weather resistance tests were conducted using filters KF-1 (300-400 nm) and KF-1 (295-780 nm), with irradiation (53°C, 50% RH) for 20 hours, followed by irradiation + spraying (30°C, 98% RH) for 4 hours (including 30 seconds of spraying only), for a total of 24 hours per cycle. The color difference ΔE was measured at the initial stage and after 20 cycles (480 hours). In addition, the adhesion evaluation described in (13) above was performed on the melamine decorative laminate after the weather resistance test. 【0132】 (18) Film appearance Measurement area of ​​obtained film 0.2 m ２ 0.25 mm in the middle ２Visually count the number of fisheyes of the above size, 1 meter ２ The number of items per unit was converted and evaluated according to the following criteria: A: 1-10 items B: 10-100 items C: 100-200 items D: 200 or more items 【0133】 (19) Carboxylic acid anhydride structure content Acrylic resin composition (B) was measured using an FT-IR (model name: "Niclet iS10", manufactured by Thermo Fisher Scientific Co., Ltd.) with a single-reflection horizontal ATR Smart iTR diamond crystal accessory, under 32 cumulative conditions. 1724 cm⁻¹ －１ Nearby peak and 1801 cm －１ The height-intensity ratio of nearby peaks was calculated. The carboxylic acid anhydride structure content (wt%) relative to 100 wt% of acrylic resin composition (B) was calculated from a calibration curve prepared using samples with known carboxylic acid anhydride structure content. 【0134】 <Manufacturing Example 1: Manufacturing of Core-Shell Rubber (A-1A)> Under a nitrogen atmosphere, 206 parts of deionized water were placed in a reaction vessel with a reflux condenser and the temperature was raised to 80°C. Component (i) shown below was added, and while stirring, 1 / 10 of the raw material (ii) shown below (part of the raw material for elastic copolymer (a-1)) was charged and held for 15 minutes. Next, the remaining raw material (ii) was continuously added so that the rate of increase of the monomer mixture relative to water was 8% by mass / hour. Polymerization was then carried out by holding for 1 hour to obtain a polymer latex. Subsequently, 0.2 parts of sodium formaldehyde sulfoxylate were added to the polymer latex. After holding for 15 minutes, while stirring at 80°C under a nitrogen atmosphere, raw material (iii) shown below (part of the raw material for elastic copolymer (a-1)) was continuously added so that the rate of increase of the monomer mixture relative to water was 4% by mass / hour. Polymerization was then carried out by holding for 2 hours to obtain elastic copolymer (a-1) latex. 【0135】To the latex of this elastic copolymer (a-1), 0.2 parts by mass of sodium formaldehyde sulfoxylate was added. After holding for 15 minutes, the following raw material (iv) (raw material for rigid polymer (a-2)) was continuously added while stirring at 80°C under a nitrogen atmosphere, so that the increase rate of the monomer mixture relative to water was 10% by mass / hour. Polymerization was then carried out by holding for 1 hour to obtain the latex of core-shell rubber (A-1A). The average particle size of core-shell rubber (A-1A) was 280 nm. 【0136】 The latex of this core-shell rubber (A-1A) was filtered through a filter with a mesh size of 50 μm. Next, a coagulation, aggregation, and solidification reaction was carried out using calcium acetate, followed by filtration, washing with water, and drying to obtain core-shell rubber (A-1A). 【0137】 (i) Sodium formaldehyde sulfoxylate 0.4 parts, Ferrous sulfate 0.00004 parts, Disodium ethylenediaminetetraacetate 0.00012 parts (ii) MMA 11.25 parts, BA 12.5 parts, St 1.25 parts, AMA 0.094 parts, BDMA 0.75 parts, tBH 0.044 parts, RS610NA 0.75 parts (iii) BA 30.9 parts, St 6.6 parts, AMA 0.66 parts, BDMA 0.09 parts, CHP 0.11 parts, RS610NA 0.6 parts (iv) MMA 35.6 parts, MA 1.9 parts, nOM 0.11 parts, tBH 0.06 parts 【0138】 <Manufacturing Example 2: Manufacturing of Core Shell Rubber (A-1B)> After charging 8.5 parts of deionized water into a container equipped with a stirrer, component (ii) listed below was added while stirring, and the mixture was stirred for 20 minutes to prepare an emulsion. Next, 191.5 parts of deionized water and component (i) listed below were added to a polymerization vessel with a condenser, and the temperature was raised to 70°C. Then, under nitrogen, the prepared emulsion was added dropwise to the polymerization vessel over 8 minutes while stirring, and the reaction was continued for 15 minutes. Subsequently, component (iii) listed below was added dropwise to the polymerization vessel over 90 minutes, and the reaction was continued for 60 minutes to obtain an elastic copolymer latex. The Tg of the elastic copolymer alone was -48°C. 【0139】 Next, component (iv) was added dropwise to the polymerization vessel over 45 minutes, and the reaction was continued for 60 minutes to form an intermediate polymer on top of the elastic copolymer. The Tg of the intermediate polymer alone was 20°C. Next, component (v) was added dropwise to the polymerization vessel over 140 minutes, and the reaction was continued for 60 minutes to form a rigid polymer on top of the intermediate polymer. Through the above steps, a latex containing 100 parts of core-shell rubber (A-1B) was obtained. The Tg of the rigid polymer alone was 84°C. The average particle size of the core-shell rubber (A-1B) measured after polymerization was 120 nm. This core-shell rubber (A-1B) latex was filtered through a filter with a mesh size of 50 μm. Then, it was coagulated using calcium acetate, filtered, washed with water, and dried to obtain core-shell rubber (A-1B). 【0140】 (i) Sodium formaldehyde sulfoxylate 0.2 parts, Ferrous sulfate 0.0001 parts, Disodium ethylenediaminetetraacetate 0.0003 parts (ii) MMA 0.3 parts, BA 4.5 parts, AMA 0.05 parts, BDMA 0.2 parts, CHP 0.025 parts, RS610NA 1.1 parts (iii) MMA 1.5 parts, BA 22.5 parts, AMA 0.25 parts, BDMA 1.0 parts, CHP 0.016 parts (iv) MMA 6.0 parts, BA 4.0 parts, AMA 0.075 parts, CHP 0.013 parts (v) MMA 55.2 parts, BA 4.8 parts, nOM 0.22 parts, tBH 0.075 parts 【0141】<Production Example 3: Production of Thermoplastic Polymer (A-2A)> 200 parts of nitrogen-purged ion-exchanged water were charged into a reaction vessel, and 1 part potassium oleate and 0.3 parts potassium persulfate were added as emulsifiers. Subsequently, 40 parts MMA, 10 parts BA, and 0.005 parts nOM were added, and the mixture was stirred at 65°C under a nitrogen atmosphere for 3 hours to complete the polymerization. Next, a monomer mixture consisting of 48 parts MMA and 2 parts BA was added dropwise over 2 hours, and the mixture was held for 2 hours after the end of the dropwise addition to complete the polymerization. The obtained latex was added to a 0.25% by mass aqueous sulfuric acid solution to coagulate, filtered, washed with water, and dried to obtain thermoplastic polymer (A-2A). The Mw of the obtained thermoplastic polymer (A-2A) was 1,000,000. 【0142】 <Manufacturing Example 4: Manufacturing of Acrylic Resin Composition (A1)> In Manufacturing Example 4, 24 parts of core-shell rubber (A-1A) were mixed with 76 parts of VH5 as a thermoplastic polymer (A-2) and 2 parts of thermoplastic polymer (A-2A). 2.36 parts of LA31, 0.45 parts of 2020, 0.3 parts of R976, and 0.1 parts of 1076 were added as additives (A-3) and mixed using a Henschel mixer. Next, this was melt-kneaded using a 35 mmφ screw-type twin-screw extruder (L / D = 26) under conditions of cylinder temperature 200-240°C and die temperature 240°C, and then pelletized to obtain acrylic resin composition (A1) for the resin layer (I). The gel fraction of acrylic resin composition (A1) was 21%, and the acid value of the acetone-soluble component was 1.6 mgKOH / g. Furthermore, the storage modulus of a single-layer film (thickness 45 μm) consisting of a resin layer (I) obtained using the acrylic resin composition (A1) was 728 MPa. 【0143】<Manufacturing Example 5: Manufacturing of Acrylic Resin Composition (A2)> In Manufacturing Example 5, 2.36 parts of LA31, 0.45 parts of 2020, 0.3 parts of R976, and 0.1 parts of 1076 were added to 100 parts of core-shell rubber (A-1B) as additives (A-3), and mixed using a Henschel mixer. Next, this was melt-kneaded using a 35 mmφ screw-type twin-screw extruder (L / D = 26) under conditions of cylinder temperature 200-240°C and die temperature 240°C, and pelletized to obtain acrylic resin composition (A2) for resin layer (I). The gel fraction of acrylic resin composition (A2) was 60%, and the acid value of the acetone-soluble portion was 1.5 mg KOH / g. Furthermore, the storage modulus of a single-layer film (thickness 45 μm) made of the resin layer (I) obtained using acrylic resin composition (A2) was 42 MPa. 【0144】 <Manufacturing Example 6: Manufacturing of Reactive Group-Containing Acrylic Polymer (B-1a)> A mixture of the following components was charged into a reaction vessel equipped with a stirrer, reflux condenser, and nitrogen gas inlet: MMA 34 parts BMA 20 parts EA 25 parts MAA 21 parts nOM 0.25 parts AMBN 0.12 parts Methyl methacrylate / methacrylate / ethyl sulfonate methacrylate copolymer 0.02 parts Sodium sulfate 0.3 parts Ion-exchanged water 145 parts 【0145】 The container was thoroughly purged with nitrogen gas, and then heated to 75°C while stirring, allowing the polymerization reaction to proceed in a nitrogen gas stream. After 2 hours, the temperature was raised to 95°C and held for another 60 minutes to complete the polymerization. The resulting polymer beads were dehydrated and dried to obtain a reactive group-containing acrylic polymer (B-1a). 【0146】 <Production Examples 7-37: Production of Reactive Group-Containing Acrylic Polymers (B-1b) to (B-1F)> Reactive group-containing acrylic polymers (B-1b) to (B-1F) were obtained in the same manner as in Production Example 6, except that the raw materials used were changed as shown in Tables 1 and 2. 【0147】 The acid value, hydroxyl value, SP value, Mw, and Tg of the acetone-soluble components of the obtained reactive group-containing acrylic polymers (B-1a) to (B-1F) are shown in Tables 1 and 2. 【0148】 【0149】 【0150】 <Manufacturing Example 38: Manufacturing of Core Shell Rubber (B-2A)> The same core shell rubber (A-1B) used in Manufacturing Example 2 was used. 【0151】 <Manufacturing Example 39: Manufacturing of Core-Shell Rubber (B-2B)> Core-shell rubber (B-2B) was obtained in the same manner as in Manufacturing Example 1, except that the raw materials used were changed as shown in Table 3. 【0152】 <Manufacturing Example 40: Manufacturing of Core-Shell Rubber (B-2C)> After charging 8.5 parts of deionized water into a container equipped with a stirrer, component (ii) listed below was added while stirring, and the mixture was stirred for 20 minutes to prepare an emulsion. Next, 191.5 parts of deionized water were added to a polymerization vessel with a condenser, and the temperature was raised to 60°C under nitrogen. Then, while stirring, component (i) listed below was added dropwise into the polymerization vessel over 2 minutes, and the reaction was continued for 15 minutes. Subsequently, component (iii) listed below was added dropwise into the polymerization vessel over 100 minutes, and the reaction was continued for 60 minutes to obtain an elastic copolymer latex. The Tg of the elastic copolymer alone was -45°C. 【0153】 Next, component (iv) listed below was dropped into the polymerization vessel over a period of 150 minutes, and the reaction was continued for 30 minutes to form a rigid polymer on the elastic copolymer. Through the above steps, a latex containing 100 parts of core-shell rubber (B-2C) was obtained. The Tg of the rigid polymer alone was 75°C. The average particle size of the core-shell rubber (B-2C) measured after polymerization was 114 nm. This core-shell rubber (B-2C) latex was filtered through a filter with a mesh size of 50 μm. Then, it was coagulated using calcium acetate, filtered, washed with water, and dried to obtain core-shell rubber (B-2C). 【0154】(i) Sodium formaldehyde sulfoxylate 0.2 parts, Ferrous sulfate 0.0001 parts, Disodium ethylenediaminetetraacetate 0.0003 parts (ii) MMA 0.5 parts, BA 4.5 parts, AMA 0.085 parts, CHP 0.025 parts, Perex OTP 1.0 part (iii) MMA 4.0 parts, BA 36.0 parts, AMA 0.68 parts, CHP 0.04 parts (iv) MMA 52.3 parts, BA 2.8 parts, nOM 0.22 parts, tBH 0.069 parts 【0155】 <Manufacturing Examples 41 and 42: Manufacturing of Core-Shell Rubber (B-2D) and (B-2E)> Core-shell rubber (B-2D) and (B-2E) were obtained in the same manner as in Manufacturing Example 40, except that the raw materials used were changed as shown in Table 3. 【0156】 【0157】 <Manufacturing Example 43: Manufacturing of Thermoplastic Polymer (B-3A)> The thermoplastic polymer (B-3A) used was the same as that used for thermoplastic polymer (A-2A). 【0158】 <Production Example 44: Production of Thermoplastic Polymer (B-3B)> 200 parts of nitrogen-purged ion-exchanged water were charged into a reaction vessel, and 0.95 parts of dipotassium alkenylsuccinate and 0.15 parts of potassium persulfate were added as emulsifiers. Subsequently, 80 parts of MMA and 20 parts of BA were added, and the mixture was stirred at 65°C under a nitrogen atmosphere for 4 hours to complete the polymerization. The obtained latex was added to an aqueous solution containing 0.4% by mass sulfuric acid and 2.5% by mass aluminum sulfate to coagulate, and then filtered, washed with water, and dried to obtain thermoplastic polymer (B-3B). The Mw of the obtained thermoplastic polymer (B-3B) was 3,000,000. 【0159】<Production Example 45: Production of Thermoplastic Polymer (B-3C)> 280 parts of nitrogen-purged ion-exchanged water were charged into a reaction vessel, and 1.5 parts of dipotassium alkenylsuccinate, 0.03 parts of tBH, and 0.007 parts of nOM were added as emulsifiers. Subsequently, 30 parts of MMA, 0.0003 parts of ethylenediaminediacetic acid, 0.0001 parts of ferrous sulfate, and 0.5 parts of sodium formaldehyde sulfoxylate were charged, and the mixture was stirred at 65°C under a nitrogen atmosphere for 4 hours to complete the polymerization. Subsequently, a monomer mixture consisting of 20 parts of BMA, 30 parts of BA, and 0.75 parts of tBH was added dropwise over 1 hour, and the mixture was held for 2 hours after the end of the dropwise addition to complete the polymerization. Furthermore, a monomer mixture consisting of 20 parts of MMA, 30 parts of BA, 0.02 parts of tBH, and 0.01 parts of nOM was added dropwise over 1 hour, and the mixture was held for 2 hours after the end of the dropwise addition to complete the polymerization. The obtained latex was added to a 0.5% by mass aqueous sulfuric acid solution to induce coagulation, then filtered, washed with water, and dried to obtain a thermoplastic polymer (B-3C). The Mw of the obtained thermoplastic polymer (B-3C) was 290,000. 【0160】 <Production Examples 46-99: Production of Acrylic Resin Compositions (B1)-(B54)> Acrylic resin compositions (B1)-(B54) were obtained in the same manner as in Production Example 5, except that the raw materials used were changed as shown in Tables 4-6. For Production Examples 96 and 97, the mixture was used as acrylic resin composition (B51) and (B52) after dry blending, without melt kneading. The molecular weight distributions of acrylic resin compositions (B44), (B46), and (B47) were 4.3, 5.0, and 5.9, respectively. 【0161】 Tables 4 to 6 show whether or not the acrylic resin compositions (B1) to (B54) were pelletized, the acid value of the acetone-soluble portion, the acid value of the acetone-insoluble portion, the hydroxyl value, MFR, and the MFR retention rate. 【0162】 【0163】 【0164】 【0165】<Manufacturing Example 100: Manufacturing of Fluorine-based Resin Composition (C2)> 80 parts of T850 were used as the fluororesin (C-1), and 20 parts of VH were used as the thermoplastic polymer (C-2). To 100 parts of this mixture, 0.1 parts of 1076 were added as an additive (C-3), and the mixture was mixed using a Henschel mixer. Next, this mixture was melt-kneaded using a 35 mmφ screw-type twin-screw extruder (L / D = 26) under conditions of cylinder temperature 200-240°C and die temperature 240°C, and then pelletized to obtain the fluororesin composition (C2) for the resin layer (I). 【0166】 <Example 1: Preparation of Laminated Film and Melamine Decorative Panel> The acrylic resin composition (A1) for resin layer (I) obtained in Production Example 4 and the acrylic resin composition (B2) for resin layer (II) obtained in Production Example 47 were dried at 80°C overnight. Acrylic resin composition (B2) was plasticized in a 30 mmφ extruder set to a cylinder temperature of 230°C. Acrylic resin composition (A1) was also plasticized in a 40 mmφ extruder equipped with a 400 mesh screen mesh set to a cylinder temperature of 240°C. Next, a laminated film with a thickness of 50 μm was formed using a two-layer multi-manifold die set to 240°C. The thicknesses of resin layers (I) and (II) were 45 μm and 5 μm, respectively. The results for the total light transmittance (TT), haze value, degree of yellowing (YI), and film appearance of the obtained laminated film are shown in Table 7. 【0167】 Furthermore, a melamine substrate was laminated to the resin layer (II) side of this laminated film, sandwiched between mirror-finished stainless steel plates, and pressed at a temperature of 140°C, a pressure of 3 MPa, and a time of 10 minutes to create a melamine decorative laminate. The adhesion, whiteness, and weather resistance evaluation results after the water resistance test of the obtained melamine decorative laminate are shown in Table 7. The endothermic peak temperature of the melamine substrate used was 100°C. Note that "-" in the evaluation results means that it was not evaluated. 【0168】<Examples 2-58: Preparation of Films, Laminated Films, and Melamine Decorative Laminates> Laminated films and melamine decorative laminates were prepared in the same manner as in Example 1, except that the materials used were as shown in Tables 7-10, and the thicknesses of the resin layers (I) and (II) were as shown in Tables 7-10. The evaluation results of the obtained melamine decorative laminates are shown in Tables 7-10. Note that "-" in the evaluation results means that it was not evaluated. In addition, in Examples 38 and 58, the productivity was significantly reduced due to die residue adhering near the die during melt molding, and it was not possible to obtain films worthy of evaluation. Example 39 is a single-layer film consisting only of resin layer (II). 【0169】 <Comparative Examples 1-7: Preparation of Films, Laminated Films, and Melamine Decorative Laminates> Laminated films and melamine decorative laminates were prepared in the same manner as in Example 1, except that the materials used were as shown in Tables 9 and 10, and the thicknesses of the resin layers (I) and (II) were as shown in Tables 9 and 10. The evaluation results of the obtained melamine decorative laminates are shown in Tables 9 and 10. Note that "-" in the evaluation results means that it was not evaluated. Comparative Examples 4-6 are single-layer films consisting only of resin layer (II). 【0170】 【0171】 【0172】 【0173】 【0174】 From the above examples and manufacturing examples, the following became clear: The laminated films obtained in Examples 1 to 58 exhibit excellent adhesion to melamine substrates. Furthermore, melamine decorative laminates with good adhesion after boiling tests (water resistance tests), low increase in whiteness, and excellent water resistance to whitening can be obtained. In addition, they have excellent transparency and film appearance, and high industrial value. 【0175】On the other hand, the films obtained in Comparative Examples 1, 2, 4, and 7 had poor melamine adhesion because the acid value of the acetone-soluble portion of the acrylic resin composition (B) was less than 35 mg KOH / g. Furthermore, the film obtained in Comparative Example 3 had an acid value of more than 180 mg KOH / g for the acetone-soluble portion of the acrylic resin composition (B), resulting in significant deterioration of productivity due to die residue adhering near the die during melt molding, and thus it was not possible to obtain a film worthy of evaluation. In addition, the films obtained in Comparative Examples 5 and 6 had poor film appearance because the acid value of the acetone-insoluble portion of the acrylic resin composition (B) was more than 20 mg KOH / g.

Claims

1. An acrylic resin composition comprising a reactive group-containing acrylic polymer (B-1) with a Tg of 0°C or higher, wherein the acid value of the acetone-soluble portion of the acrylic resin composition is 35 to 180 mgKOH / g, and the acid value of the acetone-insoluble portion of the acrylic resin composition is 20 mgKOH / g or less.

2. The acrylic resin composition according to claim 1, wherein the hydroxyl value of the acrylic resin composition is 10 mg KOH / g or less.

3. The acrylic resin composition according to claim 1, wherein the reactive group of the reactive group-containing acrylic polymer (B-1) is a carboxyl group.

4. The acrylic resin composition according to claim 1, wherein the content of carboxylic acid anhydride structures in 100% by mass of the acrylic resin composition is 0.01% by mass or more.

5. The acrylic resin composition according to claim 1, wherein the reactive group-containing acrylic polymer (B-1) contains structural units derived from aromatic vinyl monomers, and the content of structural units derived from aromatic vinyl monomers in the reactive group-containing acrylic polymer (B-1) is 2% by mass or less.

6. The acrylic resin composition according to claim 1, wherein the Tg of the reactive group-containing acrylic polymer (B-1) is 120°C or lower.

7. The SP value of the reactive group-containing acrylic polymer (B-1) is 25.0 (J / cm²). ３ ) １／２ The acrylic resin composition according to claim 1, which is as follows:

8. The acrylic resin composition according to claim 1, further comprising core-shell rubber (B-2).

9. The acrylic resin composition according to claim 8, wherein the core-shell rubber (B-2) substantially does not contain any constituent units derived from the monomer represented by the following formula (1). ２ = C(R １ ) COO-R ２ ...Formula (1) In formula (1), R １ is a hydrogen atom or a methyl group, R ２ This group is selected from a hydrogen atom or a tertiary hydrocarbon group, an aromatic hydrocarbon group, and an alicyclic hydrocarbon group.

10. The acrylic resin composition according to claim 1, further comprising an acrylic resin substantially free of reactive groups as the thermoplastic polymer (B-3).

11. The acrylic resin composition according to claim 1, wherein the MFR retention rate at a temperature of 230°C and a load of 49N is greater than 90%.

12. The acrylic resin composition according to claim 10, wherein the acrylic resin substantially free of the reactive group is an acrylic polymer having a mass-average molecular weight of 500,000 or more, and the content of the acrylic polymer in the acrylic resin composition is more than 2% by mass.

13. A film comprising the acrylic resin composition according to any one of claims 1 to 12.

14. A laminated film comprising a resin layer (I) made of a resin composition (A) having an acid value of acetone-soluble components of less than 35 mg KOH / g, and a resin layer (II) made of an acrylic resin composition according to any one of claims 1 to 12.

15. The laminated film according to claim 14, wherein the thickness of the resin layer (II) is 10 μm or less.

16. The laminated film according to claim 14, wherein the resin layer (II) is used as a bonding layer facing the substrate, and the resin layer (I) is used as a surface layer facing the opposite side of the substrate.

17. A film for protecting the surface of a melamine decorative laminate, comprising the laminated film described in claim 14.

18. A melamine decorative laminate in which the laminated film according to claim 14 and a melamine substrate are laminated in the order of resin layer (I), resin layer (II), and melamine substrate.

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