Laminate

Abstract

To provide a laminate which has flexibility, water resistance and transparency, and a layer composed of an acrylic resin composition.SOLUTION: A laminate includes a layer composed of an acrylic resin composition (I) containing an acrylic resin and a hindered amine-based compound, and a layer composed of a thermoplastic resin composition (II) having a composition different from that of the acrylic resin composition (I), wherein the molecular weight of the hindered amine-based compound is 1,000 or more, an amount of an acrylate monomer unit which is contained in the acrylic resin composition (I) and has an alkyl group having two or more carbon atoms is 45 mass% or less with respect to the total amount of the acrylic resin composition (I), and the thermoplastic resin composition (II) contains 40 mass% or less of a plasticizer with respect to the total amount of the thermoplastic resin composition (II).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a laminate. [Background technology]

[0002] Acrylic resin films are widely used in various fields, such as building materials such as roofing materials and siding materials, interior and exterior materials for automobiles, and surface materials for furniture, etc. These acrylic resin films contain an elastic polymer made of a copolymer mainly composed of an acrylic acid ester, and a graft polymer having a hard polymer made of a copolymer mainly composed of a methacrylic acid ester, and flexibility and water resistance are imparted by appropriately setting the content of the elastic polymer (for example, see Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2010-131782 A [Patent Document 2] International Publication No. 2019 / 244791 Summary of the Invention [Problem to be solved by the invention]

[0004] However, these acrylic resin film laminates have room for improvement in terms of compatibility between flexibility and water resistance. For example, the film of Patent Document 1 has a sufficient amount of elastic polymer and has good flexibility, but insufficient water resistance. Also, the film of Patent Document 2 has a relatively small amount of elastic polymer and has relatively good water resistance, but has room for improvement in flexibility.

[0005] Therefore, an object of the present invention is to provide a laminate having a layer made of an acrylic resin composition, which has high flexibility, water resistance, and transparency. [Means for solving the problem]

[0006] The present invention has the following aspects. [1] A laminate comprising a layer made of an acrylic resin composition (I) containing an acrylic resin and a hindered amine compound, and a layer made of a thermoplastic resin composition (II) having a composition different from that of the acrylic resin composition (I), wherein the molecular weight of the hindered amine compound is 1,000 or more, the amount of acrylic ester monomer units having an alkyl group having two or more carbon atoms contained in the acrylic resin composition (I) is 45% by mass or less based on the total amount of the acrylic resin composition (I), and the thermoplastic resin composition (II) contains 40% by mass or less of a plasticizer based on the total amount of the thermoplastic resin composition (II). [2] The laminate according to [1], wherein the acrylic resin is a core-shell rubber (A). [3] The laminate according to [1] or [2], wherein the thermoplastic resin composition (II) contains a polyvinyl chloride resin. [4] The laminate according to any one of [1] to [3], wherein the layer made of the acrylic resin composition (I) has a tensile modulus of elasticity of 900 MPa or more and 1,900 MPa or less. [5] The laminate according to any one of [1] to [4], wherein the hindered amine compound has a structure represented by the following formula (1): [ka] [ka] [ka] [6] The laminate according to any one of [1] to [5], wherein the acrylic resin composition (I) contains a hydroxyl group-containing polymer (C1). [7] The laminate according to any one of [1] to [6], wherein the amount of monomer units having a hydroxyl group contained in the acrylic resin composition (I) is 5 mass % or less based on the total amount of the acrylic resin composition (I). [8] The laminate according to any one of [1] to [7], wherein the acrylic resin composition (I) has a glass transition temperature of 80° C. or higher. [9] The laminate according to any one of [1] to [8], wherein the gloss of at least one surface measured at an incident angle of 60° is 110% or less. Effect of the Invention

[0007] According to the present invention, it is possible to provide a laminate of an acrylic resin composition having high flexibility, water resistance, and transparency. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] The present invention will be described in more detail below based on the embodiments of the present invention, but the present invention is not limited to these embodiments. In the present invention, the term "monomer" means a compound having a polymerizable carbon-carbon double bond. The term "monomer unit" refers to a monomer-based structural unit formed by polymerization of one monomer molecule. "(Meth)acrylic acid" refers to acrylic acid or methacrylic acid. "X~Y" means greater than or equal to X and less than or equal to Y.

[0009] <Laminate> The laminate of the present invention has at least a layer made of an acrylic resin composition (I) and a layer made of a thermoplastic resin composition (II) having a composition different from that of the acrylic resin composition (I). In addition, the laminate of the present invention preferably has a layer made of the acrylic resin composition (I) adjacent to at least one surface of the layer made of the thermoplastic resin composition (II). Furthermore, the layer made of the acrylic resin composition (I) is preferably located as the outermost layer of the laminate. In this specification, the layer made of the thermoplastic resin composition (II) is also referred to as a substrate.

[0010] The laminate of the present invention preferably has a whiteness change after the hot water test of 0 to 20. When the whiteness change is within the above range, the laminate tends to have excellent water resistance. The upper limit of the whiteness change is more preferably 17 or less, particularly preferably 13 or less. The whiteness change refers to the difference between the whiteness after the hot water test and the whiteness before the hot water test (also called the initial whiteness). The hot water test can be performed by the method described in the Examples, and the whiteness can be measured according to JIS Z 8722:2009.

[0011] The thickness of the laminate of the present invention is preferably 10 μm or more, more preferably 40 μm or more, and even more preferably 100 μm or more. On the other hand, it is preferably 10 mm or less, more preferably 2 mm or less, and even more preferably 600 μm or less. If the thickness of the laminate is equal to or greater than the lower limit, the laminate is given appropriate rigidity, has good handleability, and tends to have excellent durability. If the thickness of the laminate is equal to or less than the upper limit, the laminate has appropriate flexibility, and tends to be easily bent. In addition, it tends to be economically advantageous in terms of mass per unit area.

[0012] The thickness of the layer (film) made of the acrylic resin composition (I) is preferably 5 μm or more, more preferably 10 μm or more, and even more preferably 25 μm or more, while it is preferably 200 μm or less, more preferably 100 μm or less, even more preferably 75 μm or less, and particularly preferably 70 μm or less. If the thickness of the layer made of the acrylic resin composition (I) is the lower limit or more, the weather resistance of the film tends to be good. If the thickness of the layer made of the acrylic resin composition (I) is the upper limit or less, the film has moderate flexibility, so that the bending processability tends to be good. In addition, it tends to be economically advantageous in terms of mass per unit area.

[0013] The thickness of the layer (film, sheet) made of the thermoplastic resin composition (II) is preferably 5 μm or more, more preferably 30 μm or more, and even more preferably 75 μm or more, while it is preferably 10 mm or less, more preferably 1 mm or less, and even more preferably 300 μm or less. If the thickness of the layer of the thermoplastic resin (II) is the above-mentioned lower limit or more, the concealment property of the laminate tends to be good, and excellent designability tends to be imparted when used as a decorative sheet. In addition, the tear resistance of the laminate tends to be good, and processing tends to be easy. If the thickness of the layer made of the thermoplastic resin composition (II) is the above-mentioned upper limit or less, moderate flexibility tends to be imparted, and handling tends to be good. In addition, it tends to be economically advantageous in terms of mass per unit area. In addition, when there are multiple layers made of the thermoplastic resin composition (II), the thickness of one layer may be within the above-mentioned range.

[0014] The ratio of the thickness of the layer made of the acrylic resin composition (I) to the thickness of the layer made of the thermoplastic resin composition (II) [(I) / (II)] is usually 50:50 to 5:95, and preferably 40:60 to 15:85. When there are multiple layers made of the thermoplastic resin composition (II), the above thickness is the total thickness of all the layers made of the thermoplastic resin composition (II).

[0015] The appearance of the laminate of the present invention can be appropriately adjusted depending on the purpose of use, for example by imparting an uneven surface. For applications requiring a matte appearance, the surface can be unevenly imparted by embossing or by adding a matting agent to achieve a matte appearance. When a matte appearance is required, the glossiness of at least one surface of the laminate measured at an incidence angle of 60° is preferably 110% or less, more preferably 60% or less, and even more preferably 40% or less. The lower the glossiness, the more luxurious the appearance can be imparted depending on the application. In addition, it is preferable that the layer made of the acrylic resin composition (I) has the above glossiness. The glossiness can be measured in accordance with JIS Z8741:1997.

[0016] Each of the resin compositions constituting the laminate of the present invention will now be described.

[0017] [Acrylic resin composition (I)] The acrylic resin composition (I) contains at least an acrylic resin and a hindered amine compound having a specific molecular weight.

[0018] [Acrylic resin] The acrylic resin used in the present invention is not particularly limited as long as it is a rubber-containing acrylic resin, and examples thereof include core-shell rubber, acrylic rubber, ethylene acrylate rubber, etc. These may be used alone or in combination of two or more. Among them, the core-shell rubber (A) is preferred because it can more effectively exert the effects of the present invention.

[0019] The content of the acrylic resin in the acrylic resin composition (I) is preferably 70% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, while it is preferably 99.999% by mass or less, more preferably 99.9% by mass or less, and even more preferably 99.8% by mass or less. If the content of the acrylic resin is equal to or more than the lower limit, the flexibility of the film is improved, and whitening during bending tends to be easily suppressed. Also, if the content of the acrylic resin is equal to or less than the upper limit, the thermal decomposition resistance of the film tends to be good.

[0020] (Core-shell rubber (A)) The core-shell rubber (A), which is the most preferred acrylic resin, will be described in detail below. The core-shell rubber (A) is a multilayer rubber containing a core portion (hereinafter also referred to as "core portion (A1)") having a glass transition temperature (hereinafter also referred to as "Tg") of 0°C or lower and a shell portion (hereinafter also referred to as "shell portion (A2)") having a Tg of higher than 20°C. The Tg of the core part (A1) is preferably -60° C. or higher, and preferably -10° C. or lower. The Tg of the shell part (A2) is preferably 40° C. or higher, and preferably 120° C. or lower. The Tg can be measured by the method described in the Examples below.

[0021] An example of the core portion (A1) is a polymer obtained by polymerizing a monomer composition (α1) containing an alkyl (meth)acrylate and a graft crossing agent.

[0022] The (meth)acrylic acid alkyl ester is preferably an acrylic acid alkyl ester having an alkyl group with 1 to 8 carbon atoms (hereinafter also referred to as "monomer (a11)"), or a methacrylic acid alkyl ester having an alkyl group with 1 to 4 carbon atoms (hereinafter also referred to as "monomer (a12)"). The alkyl group in the (meth)acrylic acid alkyl ester may be linear or branched.

[0023] Examples of the monomer (a11) include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. Among them, acrylic acid alkyl esters having low Tg are preferred, and n-butyl acrylate is more preferred, from the viewpoint of excellent impact resistance of the core part (A1) and easy molding. The monomer (a11) used for the core part (A1) may be one type or two or more types.

[0024] Examples of the monomer (a12) include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, etc. The monomer (a12) used in the core portion (A1) may be one type or two or more types. In addition, either one of the monomer (a11) or the monomer (a12) may be used, or both of them may be used.

[0025] The graft crosslinking agent imparts rubber elasticity to the core part (A1) through a crosslinking reaction, and also crosslinks the core part (A1) and the shell part (A2) through a graft crosslinking reaction. Specifically, the graft crosslinking agent mainly reacts with the conjugated unsaturated bond of the ester faster than the allyl group, methallyl group, or crotyl group to form a chemical bond. Meanwhile, most of the allyl group, methallyl group, or crotyl group in the graft crosslinking agent remains unreacted and reacts during polymerization to form the shell part (A2), providing a graft bond between the core part (A1) and the shell part (A2).

[0026] Examples of the graft crossing agent include allyl esters, methallyl esters, or crotyl esters of copolymerizable α,β-unsaturated carboxylic acids, and allyl esters, methallyl esters, or crotyl esters of dicarboxylic acids. In addition, triallyl cyanurate and triallyl isocyanurate can also be used as the graft crossing agent. Among them, acrylic acid allyl ester, methacrylic acid allyl ester, maleic acid allyl ester, and fumaric acid allyl ester are preferred, and methacrylic acid allyl ester is more preferred. These may be used alone or in combination of two or more kinds.

[0027] The monomer composition (α1) may contain, in addition to the monomer (a11), the monomer (a12) and the graft crosslinking agent, a monomer having one polymerizable carbon-carbon double bond (hereinafter also referred to as "monomer (a13)") and a crosslinking monomer other than the graft crosslinking agent (hereinafter also referred to as "crosslinking monomer (a14)").

[0028] Examples of the monomer (a13) include higher alkyl acrylates having an alkyl group with 9 or more carbon atoms, lower alkoxyalkyl acrylates having an alkoxyalkyl group with 8 or less carbon atoms, alkyl acrylates such as cyanoethyl acrylate, acrylamide, acrylic acid, methacrylic acid, styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile, etc. The monomer (a13) used in the core part (A1) may be one type or two or more types.

[0029] Examples of the crosslinkable monomer (a14) include alkylene glycol dimethacrylates such as ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and propylene glycol dimethacrylate, and polyvinylbenzenes such as divinylbenzene and trivinylbenzene. The crosslinkable monomer (a14) may be one type or two or more types. By using the crosslinkable monomer (a14), further rubber elasticity can be imparted to the core portion (A1).

[0030] The content of the monomer (a1) relative to the total mass of the monomer (a11) and the monomer (a12) contained in the monomer composition (α1) is preferably 50 mass% or more, more preferably 80 mass% or more. The upper limit of the proportion of the monomer (a11) is not particularly limited, and may be 100 mass%.

[0031] Furthermore, the total content of the monomer (a11) and the monomer (a12) in the monomer composition (α1) is preferably 80 mass% or more, more preferably 95 mass% or more, while it is preferably 98.7 mass% or less, more preferably 98.4 mass% or less.

[0032] The content of the graft crosslinking agent relative to the monomer composition (α1) is preferably 0.5% by mass or more, more preferably 0.9% by mass or more, while it is preferably 6.0% by mass or less, more preferably 2.0% by mass or less. If the content of the graft crosslinking agent is equal to or more than the lower limit, the crosslinking between the core portion (A1) and the shell portion (A2) becomes stable, and sufficient transparency is easily exhibited. In addition, the rubber elasticity is improved, and the impact resistance of the obtained film tends to be improved. If the content of the graft crosslinking agent is equal to or less than the upper limit, the core portion (A1) has appropriate flexibility, and the film handling property is improved. In addition, the fluidity of the acrylic resin composition is increased, and the moldability tends to be improved.

[0033] When the monomer composition (α1) contains the monomer (a13), the content thereof is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 1% by mass or less, based on the monomer composition (α1). The lower limit of the amount of the monomer (a13) used is not particularly limited, and may be 0% by mass.

[0034] When the monomer composition (α1) contains the crosslinkable monomer (a14), the content thereof is preferably 10% by mass or less, more preferably 5% by mass or less, based on the monomer composition (α1). The lower limit of the amount of the crosslinkable monomer (a14) used is not particularly limited, and may be 0% by mass.

[0035] An example of the shell portion (A2) is a polymer obtained by polymerizing a monomer composition (α2) containing an alkyl methacrylate ester.

[0036] The alkyl methacrylate ester is preferably an alkyl methacrylate ester having an alkyl group having 1 to 4 carbon atoms (hereinafter, also referred to as "monomer (a21)"). Examples of the monomer (a21) include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. The monomer (a21) used in the shell portion (A2) may be one type or two or more types.

[0037] The monomer composition (α2) may further contain a monomer (hereinafter also referred to as "monomer (a22)") other than the monomer (a21). Examples of the monomer (a22) include the same monomers as the monomer (a11) and the monomer (a13) of the core portion (A1). The monomer (a22) used in the shell portion (A2) may be one type or two or more types.

[0038] The content of the monomer (a21) in the monomer composition (α2) is preferably 70% by mass or more, more preferably 85% by mass or more. If the content of the monomer (a21) is equal to or more than the lower limit, the Tg of the shell part (A2) tends to be high, and the heat resistance and durability tend to be good. The upper limit of the content of the monomer (a21) is not particularly limited, and may be 100% by mass.

[0039] When the monomer composition (α2) contains the monomer (a22), the content thereof is preferably 30% by mass or less, more preferably 15% by mass or less, and particularly preferably 8% by mass or less, based on the monomer composition (α2). The lower limit of the content of the monomer (a22) is not particularly limited, and may be 0% by mass.

[0040] The core-shell rubber (A) may contain an intermediate portion (A3) having a Tg of more than 0° C. and not more than 20° C. between the core portion (A1) and the shell portion (A2). An example of the intermediate portion (A3) is a polymer obtained by polymerizing a monomer composition (α3) containing an alkyl (meth)acrylate.

[0041] Examples of the (meth)acrylic acid alkyl ester include an acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms (hereinafter also referred to as "monomer (a31)") and a methacrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms (hereinafter also referred to as "monomer (a32)").

[0042] In addition to the monomer (a31) and the monomer (a32), the monomer composition (α3) may contain a monomer having one polymerizable carbon-carbon double bond (hereinafter also referred to as "monomer (a33)") and a crosslinkable monomer (a34).

[0043] Examples of the monomers (a31) to (a34) include the same monomers as the monomers (a11) to (a14), respectively.

[0044] The content of each monomer in the monomer composition (α3) is preferably 10 to 90 mass% for monomer (a31), 10 to 90 mass% for monomer (a32), 0 to 20 mass% for monomer (a33), and 0 to 10 mass% for crosslinkable monomer (a34).

[0045] The core-shell rubber (A) may contain, inside the core portion (A1), an innermost portion (A4) having a Tg exceeding 0° C. The Tg of the innermost portion (A4) is lower than that of the shell portion (A2). An example of the innermost part (A4) is a polymer obtained by polymerizing a monomer composition (α4) containing an alkyl (meth)acrylate.

[0046] Examples of the (meth)acrylic acid alkyl ester used in the monomer composition (α4) include an acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms (hereinafter also referred to as "monomer (a41)") and a methacrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms (hereinafter also referred to as "monomer (a42)").

[0047] In addition to the monomer (a41) and the monomer (a42), the monomer composition (α4) may contain a monomer having one polymerizable carbon-carbon double bond (hereinafter also referred to as "monomer (a43)") and a crosslinkable monomer (a44).

[0048] Examples of the monomers (a41) to (a44) include the same monomers as the monomers (a11) to (a14), respectively. The content of each monomer in the monomer composition (α4) is preferably 10 to 50 mass% for monomer (a41), 20 to 70 mass% for monomer (a42), 0 to 10 mass% for monomer (a43), and 0.1 to 10 mass% for crosslinkable monomer (a44).

[0049] The core-shell rubber (A) is obtained by polymerizing these monomer compositions in order from the inside. The polymerization for forming the core part (A1) may be one stage or may be divided into two or more stages. The polymerization for forming the shell part (A2), the intermediate part (A3), and the innermost part (A4) may also be one stage or may be divided into two or more stages.

[0050] The polymerization method is not particularly limited, and examples thereof include emulsion polymerization and suspension polymerization. In the case of emulsion polymerization, it is preferable to use an emulsifier, a radical polymerization initiator, and a chain transfer agent.

[0051] Examples of emulsifiers include anionic surfactants, cationic surfactants, and nonionic surfactants, with anionic surfactants being preferred. Examples of anionic surfactants include, but are not limited to, carboxylates (rosin acid soap, potassium oleate, sodium stearate, etc.), sulfates (sodium lauryl sulfate, etc.), sulfonates (sodium dioctyl sulfosuccinate, etc.), and phosphates (sodium polyoxyethylene alkylphenyl ether phosphate, etc.). The emulsifiers used may be one type or two or more types.

[0052] The radical polymerization initiator is not particularly limited, and examples thereof include persulfates (potassium persulfate, sodium persulfate, etc.), organic peroxides (t-butyl hydroperoxide, etc.), azo compounds (azobisisobutyronitrile, etc.), and redox initiators in which persulfates or organic peroxides are combined with a reducing agent. Among these, redox initiators are preferred. The radical polymerization initiator used may be one type or two or more types.

[0053] The chain transfer agent is not particularly limited, and examples thereof include alkyl mercaptans having 2 to 20 carbon atoms, mercapto acids, thiophenol, and carbon tetrachloride. The chain transfer agent used may be one type or two or more types. The amount of the chain transfer agent used is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the total amount of the monomers, while it is preferably 1.5 parts by mass or less, more preferably 1.0 parts by mass or less, and even more preferably 0.5 parts by mass or less. If the amount of the chain transfer agent used is the lower limit or more, the flexibility of the film tends to improve. If the amount of the chain transfer agent used is the upper limit or less, the mechanical strength of the film tends to improve.

[0054] The polymerization temperature varies depending on the type and amount of the polymerization initiator, but is preferably 40° C. or higher, more preferably 60° C. or higher, while it is preferably 120° C. or lower, more preferably 95° C. or lower.

[0055] The content (core ratio) of the core part (A1) in the core-shell rubber (A) thus obtained is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total mass of the core-shell rubber (A). On the other hand, it is preferably 70% by mass or less, more preferably 50% by mass or less. If the content of the core part (A1) is equal to or more than the lower limit, the mechanical strength and flexibility of the film tend to be improved, and breakage, cracking, and whitening during molding and bending tend to be easily suppressed. In addition, void generation when exposed to water tends to be suppressed, and water whitening resistance tends to be good. In addition, if the content of the core part (A1) is equal to or less than the upper limit, the film is given appropriate rigidity, and the handleability tends to be good. In addition, the sticking of the films to each other tends to be suppressed, and the handleability and productivity tend to be good.

[0056] The content of the shell portion (A2) in the core-shell rubber (A) is preferably 30 mass% or more, and more preferably 50 mass% or more, based on the total mass of the core-shell rubber (A), and is preferably 70 mass% or less, and more preferably 80 mass% or less.

[0057] When the core-shell rubber (A) has the intermediate portion (A3), the content of the intermediate portion (A3) may be 0 mass% relative to the total mass of the core-shell rubber (A), and is preferably 5 mass% or more, and is preferably 20 mass% or less, and more preferably 15 mass% or less. In addition, when the core-shell rubber (A) has the innermost part (A4), the content of the innermost part (A4) is preferably 10 mass% or less based on the total mass of the core-shell rubber (A). The lower limit of the content of the innermost part (A4) is not particularly limited, and may be 0 mass%.

[0058] The core-shell rubber (A) is preferably a rubber consisting of a core portion (A1) and a shell portion (A2), or a rubber consisting of a core portion (A1), an intermediate portion (A3) and a shell portion (A2). The core-shell rubber (A) consisting of a core portion (A1) and a shell portion (A2) is preferably a rubber having 40 to 80 mass % of the core portion (A1) and 20 to 60 mass % of the shell portion (A2) (total of 100 mass %). The core-shell rubber (A) consisting of a core portion (A1), an intermediate portion (A3) and a shell portion (A2) is preferably a rubber having a core portion (A1) of 40 to 75 mass%, an intermediate portion (A3) of 5 to 15 mass%, and a shell portion (A2) of 20 to 55 mass% (total of 100 mass%).

[0059] Also, the amount of acrylic acid ester monomer units having an alkyl group having 2 or more carbon atoms contained in the core-shell rubber (A) is usually 20% by mass or more and 50% by mass or less. The amount of the monomer units is more preferably 25% by mass or more, and even more preferably 30% by mass or more, while it is more preferably 45% by mass or less, and even more preferably 40% by mass or less. If the amount of the monomer units is equal to or more than the lower limit, the flexibility of the layer and laminate made of the acrylic resin composition (I) is improved, and the handling property and cutting processability tend to be better. On the other hand, if the amount of the monomer units is equal to or less than the upper limit, the layer and laminate made of the acrylic resin composition (I) tend to have an appropriate rigidity, and the handling property and scratch resistance tend to be better, and the hot water discoloration resistance and weather resistance tend to be better. The amount of the acrylic acid ester monomer unit having an alkyl group having 2 or more carbon atoms can be calculated from the charged amount of the acrylic acid ester monomer having an alkyl group having 2 or more carbon atoms contained in the core-shell rubber (A). The amount of the monomer unit can also be actually measured by subjecting the core-shell rubber (A) to pyrolysis GC / MS.

[0060] The mass average molecular weight of the acetone soluble portion of the core-shell rubber (A) is preferably 25,000 or more, more preferably 30,000 or more, while it is preferably 70,000 or less, more preferably 50,000 or less. If the mass average molecular weight of the acetone soluble portion of the core-shell rubber (A) is the lower limit or more, the mechanical strength of the film is improved and cracking is easily suppressed. In addition, there is a tendency that breakage and whitening during molding and bending processing are easily suppressed. If the mass average molecular weight of the acetone soluble portion of the core-shell rubber (A) is the upper limit or less, the fluidity of the obtained resin composition is improved and the processability during melt molding tends to be excellent. In addition, the surface smoothness of the film obtained by melt molding is improved, and the appearance tends to be good.

[0061] The mass average molecular weight of the acetone soluble portion of the core-shell rubber (A) is a value measured by gel permeation chromatography (GPC) for the acetone soluble portion obtained by dissolving 1 g of the core-shell rubber (A) in 50 g of acetone and refluxing the resultant for 4 hours at 70° C. The mass average molecular weight of the acetone soluble portion of the core-shell rubber (A) can be adjusted by appropriately changing the amount of the chain transfer agent during polymerization.

[0062] The average particle size of the core-shell rubber (A) is preferably 0.01 μm or more, more preferably 0.08 μm or more, and is preferably 0.5 μm or less, more preferably 0.3 μm or less. If the average particle size of the core-shell rubber (A) is the lower limit or more, flexibility and film-forming properties are good, and if it is the upper limit or less, transparency and surface smoothness tend to be good. The average particle size can be measured by a dynamic light scattering method using a light scattering photometer (for example, trade name: "DLS-700", manufactured by Otsuka Electronics Co., Ltd.).

[0063] [Hindered amine compounds (B)] The acrylic resin composition (I) contains a hindered amine-based compound (B) having a molecular weight of 1,000 or more. In general, an antioxidant is used to prevent oxidation of a resin composition. Among antioxidants, phosphorus-based antioxidants are sometimes used due to their high thermal stability, but since phosphorus-based antioxidants are easily hydrolyzed, when phosphorus-based antioxidants are used, water resistance and whitening resistance (transparency) are poor. On the other hand, in the present invention, it has been found that high water resistance and transparency can be obtained by using a hindered amine-based compound having a specific molecular weight among hindered amine-based compounds. Therefore, in the present invention, it is preferable that the acrylic resin composition (I) does not contain a phosphorus-based antioxidant.

[0064] The molecular weight of the hindered amine compound (B) is preferably 1,200 or more, more preferably 1,500 or more, and even more preferably 2,000 or more, while it is preferably 10,000 or less, more preferably 7,000 or less, even more preferably 5,000 or less, and particularly preferably 3,000 or less. When the molecular weight is the lower limit or more, the water whitening resistance of the laminate is good. In addition, adhesion to the production equipment during the production of the film and laminate is suppressed, and the productivity is good. On the other hand, when the molecular weight is the upper limit or less, it is easy to mix with the acrylic resin, and the transparency of the acrylic resin composition (I) is good. In addition, when the hindered amine compound (B) has a molecular weight distribution, the molecular weight refers to the mass average molecular weight.

[0065] The hindered amine compound (B) preferably has a structure represented by the following formula (1).

[0066] [ka] In formula (1), n=1 to 13, A is a hydrogen atom or a structure of formula (2) below, and B is preferably a t-octylamino group, an n-butyl group, or a structure of formula (3) below. In addition, when n in formula (1) is within the above range, compatibility with acrylic resins tends to be better. n is more preferably 1.5 or more, and particularly preferably 2 or more. On the other hand, n is more preferably 10 or less, and particularly preferably 5 or less. In addition, when B in formula (1) has the above structure, the compatibility with the acrylic resin is improved, and the transparency of the acrylic resin composition (I) tends to be good.

[0067] [ka]

[0068] [ka]

[0069] From the viewpoint of weather resistance and water resistance, the amount of the hindered amine compound (B) added is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.2 parts by mass or more, relative to 100 parts by mass of the acrylic resin, while it is preferably 10 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 1 part by mass or less. If the amount of the hindered amine compound (B) added is the lower limit or more, the weather resistance and water resistance tend to be good. On the other hand, if the amount of the hindered amine compound (B) added is the upper limit or less, the transparency and film formability of the film tend to be better.

[0070] Examples of commercially available hindered amine compounds (B) include "Chimassrob2020", "Chimassrob944", "Tinuvin622", "Tinuvin111" (all trade names, manufactured by BASF Japan Ltd.), "Adeka STAB LA-63P", and "Adeka STAB LA-68" (all trade names, manufactured by ADEKA Corporation). Among these, "Chimassrob2020" and "Chimassrob944" (all trade names, manufactured by BASF Japan Ltd.) are more preferred. These may be used alone or in combination of two or more kinds.

[0071] The acrylic resin composition (I) may contain other components. In the present invention, the acrylic resin composition means a mixture of all compounds constituting the layer made of the acrylic resin composition (I).

[0072] [Matte agent (C)] The acrylic resin composition (I) preferably contains a matting agent (C). By containing the matting agent (C), the light reflection on the surface is suppressed, and the design tends to be good when used as a decorative sheet. Examples of the matting agent (C) include a hydroxyl group-containing polymer (C1) and a crosslinked fine particle (C2), and from the viewpoint of film-forming property and moldability, the hydroxyl group-containing polymer (C1) is more preferable.

[0073] (Hydroxyl Group-Containing Polymer (C1)) The hydroxyl-containing polymer (C1) is a polymer having a hydroxyl group as a substituent therein, and is obtained by copolymerizing a total of 100 parts by mass of monomer components consisting of 1 to 80 parts by mass of a (meth)acrylic acid hydroxyalkyl ester having an alkyl group of 1 to 8 carbon atoms, 10 to 99 parts by mass of a methacrylic acid alkyl ester having an alkyl group of 1 to 13 carbon atoms, and 0 to 79 parts by mass of an acrylic acid alkyl ester having an alkyl group of 1 to 8 carbon atoms. The hydroxyl-containing polymer (C1) is different from the acrylic resin in that it does not have rubber properties.

[0074] Examples of the (meth)acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,3-dihydroxypropyl methacrylate, 2-hydroxyethyl acrylate, and 4-hydroxybutyl acrylate. These can be used alone or in combination of two or more. Among them, 2-hydroxyethyl methacrylate is particularly preferred.

[0075] The content of the (meth)acrylic hydroxyalkyl ester having an alkyl group with 1 to 8 carbon atoms in the monomer component is usually in the range of 1 to 80% by mass. By making the content of the (meth)acrylic hydroxyalkyl ester having an alkyl group with 1 to 8 carbon atoms 1% by mass or more, the matte effect tends to be enhanced. In addition, by making the content of the (meth)acrylic hydroxyalkyl ester having an alkyl group with 1 to 8 carbon atoms 80% by mass or less, the dispersibility of the particles becomes better, and the film formability tends to be better.

[0076] From the viewpoint of matte properties, the content of the (meth)acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms in the monomer component is preferably 5% by mass or more, and more preferably 20% by mass or more. Furthermore, from the viewpoint of film-forming properties, the content of the (meth)acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms in the monomer component is preferably 50 mass % or less.

[0077] In terms of fully exhibiting resistance in applications requiring chemical resistance, the content of the (meth)acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms relative to the monomer component is preferably 5 mass% or more and 25 mass% or less. From the viewpoint of achieving both matte finish and chemical resistance, the content of the (meth)acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms in the monomer component is preferably 10% by mass or more and 20% by mass or less.

[0078] Examples of the methacrylic acid alkyl ester having an alkyl group having 1 to 13 carbon atoms include lower methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate. Among these, methyl methacrylate is particularly preferred. These can be used alone or in combination of two or more.

[0079] The content of the methacrylic acid alkyl ester having an alkyl group having 1 to 13 carbon atoms in the monomer component is usually 10 to 99% by mass. From the viewpoint of film-forming properties, the content of the methacrylic acid alkyl ester having an alkyl group having 1 to 13 carbon atoms in the monomer component is preferably 30% by mass or more. Furthermore, from the viewpoint of matte properties, the content of the methacrylic acid alkyl ester having an alkyl group having 1 to 13 carbon atoms in the monomer component is preferably 90% by mass or less.

[0080] Examples of the alkyl acrylate ester having an alkyl group having 1 to 8 carbon atoms include lower alkyl acrylate esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc. These may be used alone or in combination of two or more.

[0081] The content of the acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms in the monomer component is usually 0 to 79% by mass. From the viewpoints of film-forming properties and matte properties, the content of the acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms in the monomer component is preferably 0.5% by mass or more, and more preferably 5% by mass or more. Furthermore, from the viewpoint of the heat resistance of the resulting film, the content of the acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms in the monomer component is preferably 40% by mass or less, and more preferably 25% by mass or less.

[0082] The hydroxyl-containing polymer (C1) can be obtained by copolymerizing monomer components according to a known polymerization method.

[0083] The glass transition temperature of the hydroxyl group-containing polymer (C1) thus obtained is preferably 80° C. or higher, more preferably 90° C. or higher, from the viewpoint of chemical resistance.

[0084] From the viewpoint of the expression of the matte effect and the appearance, the intrinsic viscosity of the hydroxyl-containing polymer (C1) is preferably within the range of 0.05 to 0.3 L / g. The intrinsic viscosity of the hydroxyl-containing polymer (C1) is more preferably 0.06 L / g or more. The intrinsic viscosity of the hydroxyl-containing polymer (C1) is more preferably 0.15 L / g or less.

[0085] In order to adjust the intrinsic viscosity (molecular weight) to within the above range, it is preferable to use a polymerization regulator such as mercaptan during copolymerization. Examples of mercaptan include n-octyl mercaptan, n-dodecyl mercaptan, and t-dodecyl mercaptan, but the mercaptan is not limited to these, and various conventionally known mercaptans can be used.

[0086] (Crosslinked fine particles (C2)) The crosslinked fine particles (C2) are not particularly limited, and examples thereof include organic crosslinked fine particles, inorganic crosslinked fine particles, and organic-inorganic composite fine particles. As the crosslinked fine particles, one type may be used alone, or two or more types may be used in combination.

[0087] Examples of organic crosslinked fine particles include crosslinked styrene resin particles, crosslinked acrylic resin particles, crosslinked urethane resin particles, crosslinked melamine resin particles, and crosslinked phenol resin particles. Crosslinked styrene resin particles are obtained by polymerizing, for example, a styrene monomer (styrene, methylstyrene, ethylstyrene, etc.) with a crosslinkable monomer. (Meth)acrylic acid alkyl esters (methyl methacrylate, n-butyl methacrylate, methyl acrylate, n-butyl acrylate, etc.) with a crosslinkable monomer.

[0088] Examples of the inorganic crosslinked fine particles include particles of silicon dioxide, aluminosilicate, magnesium silicate such as talc, aluminum silicate such as kaolin, alumina, titania, aluminum borate, calcium carbonate, and silicone resin.

[0089] As the crosslinked fine particles (C2), organic crosslinked fine particles are preferred, and crosslinked acrylic resin particles are more preferred.

[0090] An example of a commercially available crosslinked acrylic resin particle is "Eposter (registered trademark) MV1004" manufactured by Nippon Shokubai Co., Ltd., having an average particle size of 4 μm and a refractive index of 1.51.

[0091] When the acrylic resin composition (I) contains the matting agent (C), the content thereof is usually 0.1 to 50 mass%, preferably 0.5 to 40 mass%, and more preferably 1 to 30 mass% based on the acrylic resin composition (I). By containing the matting agent (C), light reflection on the surface is suppressed, and the design tends to be good when used as a decorative sheet.

[0092] [Thermoplastic polymer (D)] The acrylic resin composition (I) may contain, in addition to the acrylic resin, a thermoplastic polymer (D) other than the acrylic resin. The thermoplastic polymer (D) contained in the acrylic resin composition (I) may be one type or two or more types.

[0093] The thermoplastic polymer (D) is preferably a polymer obtained by polymerizing a monomer composition mainly composed of an alkyl methacrylate ester, and more preferably a polymer obtained by polymerizing a monomer other than an alkyl methacrylate ester, an alkyl acrylate ester, and an alkyl (meth)acrylate ester. The polymer obtained by polymerizing a monomer composition mainly composed of an alkyl methacrylate ester is different from the acrylic resin in that it does not have rubber properties.

[0094] Examples of the methacrylic acid alkyl ester include methyl methacrylate, ethyl methacrylate, and butyl methacrylate. Examples of the acrylic acid alkyl ester include methyl acrylate, ethyl acrylate, and butyl acrylate. Examples of the other monomer include aromatic vinyl monomers such as styrene, cyanide vinyl monomers such as acrylonitrile, unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride, N-phenylmaleimide, and N-cyclohexylmaleimide. These monomers used in the thermoplastic polymer (D) may be one type or two or more types may be used in combination.

[0095] The method for producing the thermoplastic polymer (D) is not particularly limited, and various polymerization methods such as suspension polymerization, emulsion polymerization, and bulk polymerization can be used. During polymerization, a chain transfer agent, other polymerization aids, etc. may be used. The chain transfer agent is not particularly limited, but mercaptans are preferred.

[0096] The thermoplastic polymer (D) is preferably a polymer containing 50 to 99.9 mass% of alkyl methacrylate units having an alkyl group having 1 to 4 carbon atoms, 0.1 to 50 mass% of alkyl acrylate units, and 0 to 49.9 mass% of other monomer units (total 100 mass%).

[0097] The mass average molecular weight of the thermoplastic polymer (D) is preferably 10,000 or more, and is preferably 150,000 or less. If the mass average molecular weight is the lower limit or more, the layer made of the acrylic resin composition (I) tends to have better handleability. If the mass average molecular weight is the upper limit or less, the film-forming property tends to be better.

[0098] When the acrylic resin composition (I) contains a thermoplastic polymer (D), the content thereof is usually 0 to 50 mass%, preferably 0 to 30 mass%, and more preferably 0 to 10 mass% relative to the acrylic resin composition (I). By containing the thermoplastic polymer (D), the film thickness precision is improved when the layer made of the acrylic resin composition (I) is melt-formed into a film, improving film formability, and the surface appearance is also improved.

[0099] [Ultraviolet absorber (E)] The acrylic resin composition (I) used in the present invention may contain an ultraviolet absorber (E) from the viewpoint of imparting weather resistance to protect the substrate. Examples of the ultraviolet absorber (E) include benzotriazole-based compounds, triazine-based compounds, benzophenone-based compounds, and cyanoacrylate-based compounds. Among them, benzotriazole-based compounds or triazine-based compounds are preferred from the viewpoint of imparting high weather resistance over a long period of time, and benzotriazole-based compounds are particularly preferred. These may be used alone or in combination of two or more.

[0100] The molecular weight of the ultraviolet absorber (E) is preferably 300 or more, more preferably 400 or more, and is preferably 100,000 or less, more preferably 10,000 or less. When the molecular weight is 300 or more, the ultraviolet absorber is less likely to volatilize during heat molding, and the molding machine such as a mold is less likely to become dirty. On the other hand, when the molecular weight is 100,000 or less, mixing with the core-shell rubber (A) becomes easy, and the transparency of the acrylic resin composition (I) tends to be better.

[0101] Examples of commercially available benzotriazole compounds include "Tinuvin 231", "Tinuvin 234", "Tinuvin 326", "Tinuvin 329", "Tinuvin 571" (all trade names, manufactured by BASF), and "Adeka STAB LA-31" (all trade names, manufactured by ADEKA). Examples of commercially available triazine compounds include "Tinuvin 1577", "Tinuvin 1600", "Tinuvin 460", "Tinuvin 477", "Tinosorb S" (all trade names, manufactured by BASF), "Adeka STAB LA-46", and "Adeka STAB LA-F70" (all trade names, manufactured by ADEKA). These may be used alone or in combination of two or more.

[0102] From the viewpoint of weather resistance, the amount of the ultraviolet absorber (E) added is preferably 0.01 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 1.7 parts by mass or more, relative to 100 parts by mass of the acrylic resin, and is preferably 20 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less.

[0103] (Additives) The acrylic resin composition (I) may contain additives such as stabilizers (excluding the hindered amine compound (B)), lubricants, processing aids, plasticizers, impact resistance improvers, foaming agents, fillers, colorants, etc., as necessary, within the range that does not impair the effects of the present invention. The additives contained in the acrylic resin composition (I) may be one type or two or more types.

[0104] The acrylic resin composition (I) can be obtained by blending these components in predetermined amounts and mixing them by a known mixing method (for example, dry blending, melt kneading, etc.).

[0105] The amount of acrylic acid ester monomer units having an alkyl group having 2 or more carbon atoms contained in the acrylic resin composition (I) is 45% by mass or less based on the total amount of the acrylic resin composition (I). The amount of the monomer units is preferably 20% by mass or more, more preferably 25% by mass or more, and even more preferably 30% by mass or more, while it is more preferably 40% by mass or less, and even more preferably 35% by mass or less. If the amount of the monomer units is equal to or more than the lower limit, the flexibility of the acrylic resin composition (I) and the laminate is improved, and the handling property and cutting processability are improved. On the other hand, if the amount of the monomer units is equal to or less than the upper limit, the acrylic resin composition (I) and the laminate have appropriate rigidity, and the handling property and scratch resistance are improved. In addition, the hot water discoloration resistance and weather resistance are improved. The amount of the acrylic ester monomer units having an alkyl group having two or more carbon atoms contained in the acrylic resin composition (I) is the total amount of the acrylic ester monomer units having an alkyl group having two or more carbon atoms contained in the polymers contained in the acrylic resin composition (I), such as the acrylic resin, the matting agent (C), the thermoplastic polymer (D) and the additives, expressed as a ratio to the acrylic resin composition (I). The amount of the acrylic acid ester monomer unit having an alkyl group having 2 or more carbon atoms can be calculated from the charged amount of the acrylic acid ester monomer having an alkyl group having 2 or more carbon atoms contained in the polymer constituting the acrylic resin composition (I). The amount of the monomer unit can also be actually measured by subjecting the acrylic resin composition (I) to pyrolysis GC / MS.

[0106] In addition, the amount of monomer units having a hydroxyl group contained in the acrylic resin composition (I) is preferably 5% by mass or less, more preferably 4% by mass or less, based on the total amount of the acrylic resin composition (I). If the amount of the monomer units is equal to or less than the upper limit, the generation of foreign matter due to the crosslinking reaction of the hydroxyl groups is suppressed, and the film appearance tends to be better. In addition, the water resistance tends to be improved. On the other hand, the amount of monomer units having a hydroxyl group is preferably 0.1% by mass or more, more preferably 1.5% by mass or more, and particularly preferably 2.0% by mass or more. If the amount of the monomer units is equal to or more than the lower limit, the film is given a matte appearance, and the matte property tends to be better. The amount of monomer units having a hydroxyl group contained in the acrylic resin composition (I) is the total amount of monomer units having a hydroxyl group contained in polymers contained in the acrylic resin composition (I), such as the acrylic resin, the matting agent (C), the thermoplastic polymer (D) and the additives, expressed as a ratio to the acrylic resin composition (I). The amount of the hydroxyl group-containing monomer unit can be calculated from the charged amount of the hydroxyl group-containing monomer of the above polymer constituting the acrylic resin composition (I).

[0107] The glass transition temperature of the acrylic resin composition (I) is preferably 80°C or higher, more preferably 85°C or higher, and is preferably 110°C or lower, more preferably 95°C or lower. If the glass transition temperature is equal to or higher than the lower limit, the laminate tends to have good water resistance, weather resistance, and heat resistance. On the other hand, if the glass transition temperature is equal to or lower than the upper limit, the laminate tends to have improved toughness, and better bending processability and handling properties. The glass transition temperature can be measured by the method described in the examples below.

[0108] The gel fraction of the acrylic resin composition (I) is preferably 5% or more, and more preferably 90% or less, more preferably 80% or less. When the gel fraction is 5% or more, the toughness of the film is improved, and the handling property and film-forming property of the film tend to be improved. In addition, when the gel fraction is 90% by mass or less, the generation of thermally deteriorated foreign matter of the resin is suppressed, and the film appearance tends to be better. From the viewpoint of film toughness, the gel fraction of the acrylic resin composition (I) is more preferably 45% or more, particularly preferably 50% or more, and further preferably 80% or less. Furthermore, from the viewpoint of the appearance of the film, the gel fraction of the acrylic resin composition (I) is preferably 5% or more, more preferably 30% or less, and particularly preferably 25% or less. The gel fraction means a value calculated by the following formula, which is obtained by subjecting a predetermined amount (mass before extraction) of the acrylic resin composition (I) to extraction treatment under reflux in an acetone solvent, separating the treated liquid by centrifugation, drying the acetone-insoluble matter, and then measuring the mass (mass after extraction). Gel fraction (%) = mass after extraction (g) / mass before extraction (g) × 100

[0109] The melt flow rate (MFR) of the acrylic resin composition (I) at 230°C and a load of 49N is preferably 0.1 g / 10 min or more, more preferably 1 g / 10 min or more, and even more preferably 3 g / 10 min or more, while it is preferably 100 g / 10 min or less, more preferably 50 g / 10 min or less, and even more preferably 20 g / 10 min or less. If the MFR of the acrylic resin composition (I) is the lower limit or more, the moldability during melt molding is good, and the surface smoothness of the melt-molded film tends to be improved, resulting in a better appearance. If the MFR of the acrylic resin composition (I) is the upper limit or less, the moldability during melt molding tends to be better. The MFR can be measured by the method described in the examples described below.

[0110] In the present invention, a layer is formed from the acrylic resin composition (I) and then laminated with a layer made of the thermoplastic resin composition (II) described below. The layer may be formed from the acrylic resin composition (I) by a known method (e.g., coating, melt extrusion, etc.).

[0111] The tensile modulus of the layer made of the acrylic resin composition (I) is preferably 900 MPa or more, more preferably 1,200 MPa or more, and particularly preferably 1,300 MPa or more. On the other hand, it is preferably 1,900 MPa or less, more preferably 1,850 MPa or less, and particularly preferably 1,800 MPa or less. When the tensile modulus is equal to or more than the lower limit, appropriate rigidity is imparted and the handling property tends to be improved. On the other hand, when the tensile modulus is equal to or less than the upper limit, flexibility is imparted and the processability and handling property tend to be improved. The tensile modulus of the layer made of the acrylic resin composition (I) can be measured by the method described in the examples described later.

[0112] [Thermoplastic resin composition (II)] The layer made of the thermoplastic resin composition (II) is a film or sheet made of the thermoplastic resin composition (II) having a composition different from that of the acrylic resin composition (I). The thermoplastic resin is not particularly limited, and examples thereof include polyvinyl chloride resins, polyvinylidene chloride resins, polyolefin resins, thermoplastic polyurethane resins, acrylic resins, polyvinylidene fluoride resins, polystyrene resins, ABS resins, AS resins, MS resins, polycarbonate resins, polylactic acid resins, thermoplastic polyester resins, and polyimide resins. These may be used alone or in combination of two or more. Among them, polyvinyl chloride resins, polyvinylidene fluoride resins, acrylic resins, ABS resins, AS resins, MS resins, and polycarbonate resins are preferred from the viewpoint of good adhesion to the acrylic resin composition (I), polyvinyl chloride resins and polyvinylidene fluoride resins are more preferred, and polyvinyl chloride resins are particularly preferred from the viewpoint of design. The acrylic resin is preferably different from the acrylic resin used in the acrylic resin composition (I) in that it does not have rubber properties.

[0113] The content of the thermoplastic resin in the thermoplastic resin composition (II) is preferably 50% by mass or more, more preferably 65% ​​by mass or more, and on the other hand, is preferably 95% by mass or less, more preferably 90% by mass or less.

[0114] The polyvinyl chloride resin is a polymer containing vinyl chloride as a main monomer component, and examples thereof include a homopolymer of vinyl chloride monomer and a copolymer of vinyl chloride monomer and other monomers. These may be used alone or in combination of two or more kinds. Examples of copolymers of vinyl chloride monomer and other monomers include vinyl chloride copolymers such as urethane-vinyl chloride copolymer, ethylene-vinyl chloride copolymer, vinyl acetate-vinyl chloride copolymer, and ethylene-vinyl acetate-vinyl chloride copolymer.

[0115] The average degree of polymerization of the polyvinyl chloride resin is not particularly limited, but from the viewpoint of processability and moldability, the average degree of polymerization based on JIS K6720-2:1999 is preferably 700 to 1,700, more preferably 800 to 1,500, and even more preferably 900 to 1,300.

[0116] The polyvinylidene fluoride resin may, for example, be polyvinylidene fluoride, which is a homopolymer of vinylidene fluoride. Examples of commercially available polyvinylidene fluoride products include Kynar 720 (vinylidene fluoride content: 100% by mass, crystalline melting point: 169°C) and Kynar 710 (vinylidene fluoride content: 100% by mass, crystalline melting point: 169°C) manufactured by Arkema; ​​KFT#850 (vinylidene fluoride content: 100% by mass, crystalline melting point: 173°C) manufactured by Kureha Corporation; and Solef 1006 (vinylidene fluoride content: 100% by mass, crystalline melting point: 174°C) and Solef 1008 (vinylidene fluoride content: 100% by mass, crystalline melting point: 174°C) manufactured by Solvay Specialty Polymers.

[0117] When the thermoplastic resin contained in the thermoplastic resin composition (II) having a composition different from that of the acrylic resin composition (I) is a polyvinyl chloride resin, the thermoplastic resin composition (II) preferably contains a plasticizer. Examples of the plasticizer include phthalate-based plasticizers such as di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisodecyl phthalate, dibutyl phthalate, and dihexyl phthalate; adipic acid-based plasticizers such as adipic acid esters and adipic acid polyesters, such as dioctyl adipate, diisononyl adipate, diisodecyl adipate, dibutoxyethyl adipate, and bis(butyl triglycol) adipate; epoxy-based plasticizers such as epoxidized linseed oil and liquid epoxy resin; phosphoric acid ester-based plasticizers such as triphenyl phosphate, trixylyl phosphate, and tricresyl phosphate; and other plasticizers such as dioctyl sebacate, trimellitic acid esters, citric acid esters, and benzoic acid esters. Among them, the adipic acid plasticizers are preferred, and dioctyl adipate is more preferred, from the viewpoint of good weather resistance. These may be used alone or in combination of two or more kinds.

[0118] When the thermoplastic resin composition (II) contains a plasticizer, the content is 40% by mass or less, preferably 35% by mass or less, more preferably 30% by mass or less, and particularly preferably 25% by mass or less, based on the total amount of the thermoplastic resin composition (II). On the other hand, it is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass or more. When the plasticizer is 40% by mass or less, the handling property during molding of the polyvinyl chloride resin is improved, and the water resistance and interlayer adhesion of the laminate of the present invention are improved. In addition, when the plasticizer is 5% by mass or more, the flexibility and molding processability of the polyvinyl chloride resin tend to be improved, and the weather resistance of the laminate of the present invention tends to be improved.

[0119] Furthermore, the thermoplastic resin composition (II) may contain, as necessary, known additives such as antioxidants, matting agents, stabilizers, lubricants, antistatic agents, weather resistance aids, colorants, processing aids, ultraviolet absorbers, etc. These may be used alone or in combination of two or more kinds, within the range that does not impair the effects of the present invention.

[0120] The matting agent may be any of those described above in relation to the matting agent (C), and among these, the hydroxyl group-containing polymer (C1) is preferred. By including the matting agent, the glossiness of the film surface tends to decrease, resulting in good design properties.

[0121] The stabilizer is not particularly limited, and examples thereof include metal soaps such as zinc stearate, zinc palmitate, zinc laurate, zinc octanoate, zinc ricinoleate, zinc 2-ethylhexanoate, zinc naphthenate, tin stearate, lead stearate, dibasic lead stearate, and lead naphthenate; lead-based stabilizers such as white lead, basic lead silicate, tribasic lead sulfate, tribasic lead phosphite, tribasic lead maleate, dibasic lead phthalate, silica gel coprecipitated lead silicate, and normal lead salicylate; dibutyltin dilaurate, ... Examples of the stabilizers that can be used include organic tin stabilizers such as dibutyltin malate and dibutyltin mercaptide; barium-zinc complex stabilizer, calcium-zinc complex stabilizer, aluminum-magnesium-zinc complex stabilizer, cadmium-barium-zinc complex stabilizer, cadmium-barium-lead complex stabilizer, calcium-magnesium-zinc complex stabilizer, and epoxy compounds such as epoxidized vegetable oils, bisphenol-type epoxy compounds, and epoxy group-containing acrylic polymers. These can be used alone or in combination of two or more.

[0122] Examples of the lubricant include pure hydrocarbons such as liquid paraffin, natural paraffin, microwax, synthetic paraffin, and low molecular weight polyethylene; halogenated hydrocarbons; fatty acids such as higher fatty acids and oxyfatty acids; fatty acid amides such as fatty acid amides and bisfatty acid amides; esters such as lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids such as glycerides, polyglycol esters of fatty acids, and fatty alcohol esters of fatty acids (ester wax); metal soaps, fatty alcohols, polyhydric alcohols, polyglycols, polyglycerols, partial esters of fatty acids and polyhydric alcohols, partial esters of fatty acids and polyglycols and polyglycerols. Among these, lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids such as glycerides, and partial esters thereof, which have excellent high-temperature decomposition inhibition function, are particularly preferred. These can be used alone or in combination of two or more.

[0123] The weather resistance aid is preferably an organic copper carboxylate, a copper chelate complex compound, or an inorganic copper compound. Examples of the organic copper carboxylate include copper stearate, copper palmitate, copper laurate, copper octylate, copper acetate, copper benzoate, copper pt-butylbenzoate, copper 1,2-hydroxystearate, copper maleate, and copper naphthenate. Examples of the copper chelate complex include copper dialkylthiocarbamate, such as copper dimethylthiocarbamate and copper dibutylthiocarbamate, and copper dialkyldithiophosphate. Examples of the inorganic copper compound include copper chloride, copper sulfate, copper carbonate, copper oxide, and copper hydroxide.

[0124] The thermoplastic resin composition (II) can be obtained by blending these components to a predetermined content and mixing them by a known mixing method (e.g., dry blending, melt kneading, etc.). In addition, when forming a layer from the thermoplastic resin composition (II), a known method (e.g., melt extrusion, etc.) may be used to form a layer.

[0125] The laminate of the present invention is a laminate of a layer made of the acrylic resin composition (I) and a layer made of the thermoplastic resin composition (II), and the lamination method is not particularly limited, and may be a known method such as pressurization, heating and pressing, etc. The laminate may also be formed by applying the acrylic resin composition (I) onto the surface of the layer made of the thermoplastic resin composition (II).

[0126] The applications of the laminate of the present invention thus obtained are not particularly limited, and can be used, for example, as roofing materials, siding materials, gutters, flooring materials, skin materials for building materials such as bathrooms and kitchens, skin materials for the interior and exterior of automobiles, skin materials for furniture, and vinyl greenhouses for agriculture. EXAMPLES

[0127] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following descriptions. In the examples, "parts" means "parts by mass".

[0128] [Abbreviation] The abbreviations in the examples are as follows. [Monomer components] MMA: Methyl methacrylate ·BA: n-Butyl acrylate MA: Methyl acrylate HEMA: 2-hydroxyethyl methacrylate ·BDMA: 1,3-butylene glycol dimethacrylate [Grafting agent] ·AMA: Allyl methacrylate 〔emulsifier〕 RS610NA: mono-n-dodecyloxytetraoxyethylene sodium phosphate: "Phosphanol RS-610NA" (product name) manufactured by Toho Chemical Industry Co., Ltd. OTP: Kao Corporation's "Pelex OT-P" (product name) [Chain transfer agent] nOM: n-octyl mercaptan nDM: n-dodecyl mercaptan [Polymerization initiator] CHP: NOF Corp., "Perkmill H" (product name) tBH: NOF Corp., "Perbutyl H" (product name) LPO: NOF Corp.'s "Perloil L" (product name) [Hindered amine compounds] (Hindered amine compound (B) with molecular weight of 1,000 or more) C2020: BASF Japan, "Chimassorb2020" (product name) (molecular weight 2,600-3,400) C944: BASF Japan, "Chimassorb944" (trade name) (molecular weight 2,000-3,100) (Hindered amine compound (B') with molecular weight of less than 1,000) LA57: ADEKA Corporation, "LA-57" (trade name) (molecular weight 791) [Ultraviolet absorber (E)] LA31: ADEKA "LA-31" (product name) Tv1577: BASF Japan, "Tinuvin1577" (product name) [Additives] [Hindered phenol compounds] Irg1076: BASF Japan, "Irganox1076" (product name) [Polyvinyl chloride resin sheet] Semi-rigid polyvinyl chloride resin sheet: polyvinyl chloride resin, plasticizer (dioctyl adipate), stabilizer, and brown pigment are mixed and molded into a sheet. The amount of plasticizer is 19.7% by mass of the sheet, and the thickness is 100 μm. Soft polyvinyl chloride resin sheet: Polyvinyl chloride resin, plasticizer (dioctyl adipate), and stabilizer are mixed and molded into a sheet. The amount of plasticizer is 45% by mass, and the thickness is 100 μm. [Polyvinylidene fluoride resin] T850: KFT#850 (product name) manufactured by Kureha Corporation

[0129] The various test and measurement methods used in the examples are as follows.

[0130] [Tensile test] A test piece of 150 mm x 15 mm with the long side in the film formation direction was cut out from the layer (film) made of the acrylic resin composition, and a tensile test was carried out using an autograph tensile tester (manufactured by Shimadzu Corporation, product name: "AGS-X") with a chuck distance of 100 mm and a tensile speed of 100 mm / min to measure the tensile modulus and tensile elongation at break of the film.

[0131] [Average particle size] The core-shell rubber particles were dispersed in ion-exchanged water and diluted to a concentration sufficient for measurement. The median diameter calculated on a volume average basis was determined using a laser diffraction / scattering particle size distribution measuring device (manufactured by Shimadzu Corporation, product name: "SALD-7100"), and this median diameter was used as the average particle size.

[0132] [Hot water resistance test] The laminate and the layer (film) made of the acrylic resin composition were immersed in warm water at 80° C. for 48 hours, and after being taken out, were allowed to stand in an environment of 23° C. and a humidity of 50% for 24 hours. Thereafter, the whiteness of the laminate was measured before and after the test in accordance with JIS Z8715:1999. The film was visually evaluated for coloration before and after the test according to the following criteria. A: The film is not colored. △: The film is slightly discolored. ×: The film is discolored.

[0133] [Optical property evaluation] The total light transmittance, haze value, and 60° gloss of the layer (film) made of the acrylic resin composition were measured. The total light transmittance was measured in accordance with JIS K7361-1:1997, the haze value was measured in accordance with JIS K7136:2000, and the 60° gloss value was measured in accordance with JIS Z8741:1997.

[0134] [Melt flow rate] The melt flow rate (MFR) of the acrylic resin composition was measured at 230° C. and a load of 49 N in accordance with JIS K7210:1999.

[0135] [Cutting workability] The laminate was cut at 23° C. using a cutter knife (manufactured by NT Corporation, "SL10P" (product name)), and the cut surface was observed and visually evaluated according to the following criteria. ○: No cracks on the cut surface △: Cracks smaller than 1 mm have occurred on the cut surface. ×: Cracks of 1 mm or more occurred on the cut surface

[0136] [Film appearance] 0.1m 2 The layer (film) made of the acrylic resin composition was visually observed, the number of foreign matters was counted, and the appearance was judged according to the following criteria. 〇:0~3 pieces △:4~5 pieces ×:6 or more

[0137] [Glass transition temperature] The acrylic resin composition was melted and formed into a sheet, and a test piece with dimensions of 1 mm thickness, 6 mm width, and 65 mm length was cut out. Thereafter, using a dynamic viscoelasticity measuring device, the storage modulus (E') and loss modulus (E") of the test piece were measured in a tensile mode in accordance with ISO6721-4 under the conditions of an initial chuck distance of 2 cm, a measurement frequency of 0.1 Hz, a measurement temperature range of -90 to 150°C, a heating rate of 2°C / min, and a nitrogen gas flow of 200 mL / min, and tan δ (loss tangent) at each temperature was calculated from the formula tan δ = E" / E'. Next, when the value of tan δ is plotted against the temperature, two or more peaks appear. The temperature corresponding to the peak appearing on the highest temperature side among these was determined as the glass transition temperature of the composition.

[0138] [Amount of acrylic acid ester monomer units having an alkyl group having 2 or more carbon atoms] The amount of acrylic ester monomer units having an alkyl group having two or more carbon atoms contained in the total amount of the acrylic resin composition was calculated from the amounts of the acrylic resins (core-shell rubbers (A-1), (A-2), hydroxyl group-containing polymers (C1-1), (C1-2), additive P, and additive Q) used in the production of the acrylic resin composition.

[0139] [Weather resistance test] The laminates of Examples 1 and 4 and Comparative Examples 3 and 4 were subjected to a metal weather test with an irradiation intensity of 65 mW / cm using a metal weather tester (manufactured by Daipla Wintes). 2 , temperature 53℃, humidity 50%RH, 20 hours, irradiation intensity 0mW / cm 2 The test was performed for a total of 24 hours, consisting of 4 hours at a temperature of 30°C and a humidity of 98% RH, for one cycle. The test was performed on the acrylic resin film side of each laminate. The color difference ΔE between before the test (0 hours) and after 144 hours (6 cycles) was measured in accordance with JIS Z8781-4:2013.

[0140] Prior to the examples, the core-shell rubbers (A-1) and (A-2), the hydroxyl-containing polymers (C1-1) and (C1-2), the additives P, Q and R were synthesized.

[0141] [Synthesis Example 1: Core-shell rubber (A-1)] A vessel equipped with a stirrer was charged with 8.5 parts of deionized water, and the monomer composition (α1-1(1)) shown below was added thereto while stirring, and the mixture was stirred for 20 minutes to prepare an emulsion. Next, 191.5 parts of deionized water and the component (i) shown below were added to a polymerization vessel equipped with a cooler, and the temperature was raised to 70°C. Next, while stirring under nitrogen, the prepared emulsion was dropped into the polymerization vessel over 8 minutes, and the reaction was continued for 15 minutes. Next, the monomer composition (α1-1(2)) shown below was dropped into the polymerization vessel over 90 minutes, and the reaction was continued for 60 minutes to obtain a latex of the core portion. The Tg of the core portion was -48°C. Next, the monomer composition (α3-1) shown below was dropped into the polymerization vessel over a period of 45 minutes, and the reaction was continued for 60 minutes to form an intermediate part on the core part. The Tg of the intermediate part alone was 20°C. Next, the monomer composition (α2-1) shown below was dropped into the polymerization vessel over 140 minutes, and the reaction was continued for 60 minutes to form a shell portion on the intermediate portion. Through the above steps, a latex containing 100 parts of core-shell rubber (A-1) was obtained. The Tg of the shell portion alone was 84°C. The average particle size of the core-shell rubber (A-1) measured after polymerization was 0.12 μm. This core-shell rubber (A-1) latex was subjected to coagulation, aggregation and solidification reactions using calcium acetate, filtered, washed with water and dried to obtain a core-shell rubber (A-1). The amount of acrylic acid ester monomer units having an alkyl group having two or more carbon atoms contained in the core-shell rubber (A-1), calculated from the production charge amount of the core-shell rubber (A-1), was 35.7 mass%.

[0142] [Component (i)] Sodium formaldehyde sulfoxylate: 0.2 parts Ferrous sulfate: 0.0001 parts Disodium ethylenediaminetetraacetate: 0.0003 parts [Monomer composition (α1-1(1))] MMA: 0.3 parts BA: 4.5 parts AMA: 0.05 parts ·BDMA: 0.2 parts ·CHP: 0.025 parts ·RS610NA: 1.1 part [Monomer composition (α1-1(2))] MMA: 1.5 division BA: 22.5 parts AMA: 0.25 parts ·BDMA: 1.0 copies ·CHP: 0.016 parts [Monomer composition (α3-1)] MMA: 6.0 BA: 4.0 parts AMA: 0.075 parts ·CHP: 0.013 parts [Monomer composition (α2-1)] MMA: 55.2 BA: 4.8 parts ·nOM: 0.22 parts tBH: 0.075 parts

[0143] [Synthesis Example 2: Core-shell rubber (A-2)] In a polymerization vessel equipped with a stirrer, a cooling tube, a thermocouple, and a nitrogen inlet tube, 195 parts of deionized water was added, followed by the monomer composition (α1-2(1)) shown below, and the temperature was raised to 60°C. After the temperature was raised, 5 parts of deionized water and the component (ii) shown below were added to initiate polymerization. After the peak temperature was confirmed, the reaction was continued for 15 minutes to complete the polymerization. Next, the monomer composition (α1-2(2)) shown below was dropped into the polymerization vessel over 120 minutes. The reaction was then continued for 60 minutes to complete the polymerization of the core portion. The Tg of the core portion was −49° C. Next, the monomer composition (α2-2) shown below was dropped into the polymerization vessel over 120 minutes, and the reaction was continued for 60 minutes to form a shell portion on the core portion. Through the above process, a latex-like core-shell rubber was obtained. The Tg of the shell portion alone was 79°C. The average particle size of the core-shell rubber (A-2) after polymerization was 0.12 μm. The latex-like core-shell rubber was dropped into 300 parts of hot water at 70°C containing 3.8 parts of calcium acetate to coagulate the latex. The temperature was then raised to 95°C and held for 5 minutes to solidify. The resulting coagulated material was separated, washed, and dried at 70°C for 24 hours to obtain a powdered core-shell rubber (A-2). The amount of acrylic acid ester monomer units having an alkyl group having two or more carbon atoms contained in the core-shell rubber (A-2), calculated from the production charge amount of the core-shell rubber (A-2), was 55.7% by mass.

[0144] [Component (ii)] Sodium formaldehyde sulfoxylate: 0.2 parts Ferrous sulfate: 0.0001 parts Disodium ethylenediaminetetraacetate: 0.0003 parts [Monomer composition (α1-2(1))] MMA: 0.3 parts BA: 4.7 parts AMA: 0.082 parts ·CHP: 0.025 parts ·OTP: 1.0 copies [Monomer composition (α1-2(2))] MMA: 3.0 BA: 47.0 parts AMA: 0.82 parts ·CHP: 0.05 part [Monomer composition (α2-2)] MMA: 40.5 BA: 4.5 parts tBH: 0.061 parts ·nOM: 0.3 parts

[0145] [Synthesis Example 3: Core-shell rubber (A-3)] A vessel equipped with a stirrer was charged with 8.5 parts of deionized water, and the monomer composition (α1-3(1)) shown below was added thereto while stirring, followed by stirring for 20 minutes to prepare an emulsion. Next, 191.5 parts of deionized water and the component (i) shown below were added to a polymerization vessel equipped with a cooler, and the temperature was raised to 70°C. Next, while stirring under nitrogen, the prepared emulsion was dropped into the polymerization vessel over 8 minutes, and the reaction was continued for 15 minutes. Next, the monomer composition (α1-3(2)) shown below was dropped into the polymerization vessel over 90 minutes, and the reaction was continued for 60 minutes to obtain a latex of the core portion. The Tg of the core portion was -48°C. Next, the monomer composition (α3-3) shown below was dropped into the polymerization vessel over a period of 45 minutes, and the reaction was continued for 60 minutes to form an intermediate part on the core part. The Tg of the intermediate part alone was 20°C. Next, the monomer composition (α2-3) shown below was dropped into the polymerization vessel over 140 minutes, and the reaction was continued for 60 minutes to form a shell portion on the middle portion. Through the above steps, a latex containing 100 parts of core-shell rubber (A-3) was obtained. The Tg of the shell portion alone was 84°C. The average particle size of the core-shell rubber (A-3) measured after polymerization was 0.12 μm. This core-shell rubber (A-3) latex was subjected to coagulation, aggregation and solidification reactions using calcium acetate, filtered, washed with water and dried to obtain a core-shell rubber (A-3). The amount of acrylic acid ester monomer units having an alkyl group having two or more carbon atoms contained in the core-shell rubber (A-3), calculated from the production charge amount of the core-shell rubber (A-3), was 35.5 mass%.

[0146] [Component (i)] Sodium formaldehyde sulfoxylate: 0.2 parts Ferrous sulfate: 0.0001 parts Disodium ethylenediaminetetraacetate: 0.0003 parts [Monomer composition (α1-3(1))] MMA: 0.2 parts BA: 4.5 parts AMA: 0.15 parts ·BDMA: 0.3 parts ·CHP: 0.025 parts ·RS610NA: 1.1 part [Monomer composition (α1-3(2))] MMA: 1.0 BA: 22.5 parts AMA: 0.75 parts ·BDMA: 1.5 copies ·CHP: 0.016 parts [Monomer composition (α3-3)] MMA: 6.0 BA: 4.0 parts AMA: 0.075 parts ·CHP: 0.013 parts [Monomer composition (α2-3)] MMA: 55.2 BA: 4.8 parts ·nOM: 0.24 parts tBH: 0.075 parts

[0147] [Synthesis Example 4: Hydroxyl-containing polymer (C1-1)] The following monomer component (1) was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet, etc. Next, after the inside of the vessel was sufficiently replaced with nitrogen gas, the monomer component (1) in the reaction vessel was heated to 75°C while stirring, and reacted in a nitrogen gas stream for 3 hours. After this, the temperature in the reaction vessel was raised to 90°C and maintained for an additional 45 minutes to complete the polymerization, and the hydroxyl-containing polymer (C1-1) was obtained by dehydration and drying. Since the hydroxyl-containing polymer (C1-1) does not contain an acrylic acid ester having an alkyl group having 2 or more carbon atoms, the amount of acrylic acid ester monomer units having an alkyl group having 2 or more carbon atoms contained in the hydroxyl-containing polymer (C1-1) calculated from the production charge amount was 0 mass%. In addition, the amount of monomer units having a hydroxyl group contained in the hydroxyl-containing polymer (C1-1) calculated from the production charge amount was 20.0 mass%.

[0148] [Monomer component (1)] MA: Part 1 MMA: 79th division HEMA: 20 copies ·nDM: 0.22 copies ·LPO: 0.53 copies Methyl methacrylate / potassium methacrylate / 2-sulfoethyl methacrylate sodium salt copolymer: 0.05 parts Deionized water: 250 parts

[0149] [Synthesis Example 5: Hydroxyl-containing polymer (C1-2)] A hydroxyl-containing polymer (C1-2) was obtained in the same manner as in Synthesis Example 4, except that the monomer component (1) was changed to the following monomer component (2). Since the hydroxyl-containing polymer (C1-2) does not contain an acrylate ester having an alkyl group having two or more carbon atoms, the amount of acrylate ester monomer units having an alkyl group having two or more carbon atoms contained in the hydroxyl-containing polymer (C1-2) calculated from the production charge amount was 0 mass%. In addition, the amount of monomer units having a hydroxyl group contained in the hydroxyl-containing polymer (C1-2) calculated from the production charge amount was 30.0 mass%.

[0150] [Monomer component (2)] MA: 10 parts MMA: 60 HEMA: 30 copies ·nDM: 0.25 copies ·LPO: 0.52 copies Methyl methacrylate / potassium methacrylate / 2-sulfoethyl methacrylate sodium salt copolymer: 0.05 parts Deionized water: 250 parts

[0151] [Synthesis Example 6: Additive P] Additive P was obtained according to the method for producing thermoplastic polymer IV in Preparation Example 4 of WO 2015 / 137309. The monomers constituting Additive P were MMA / BA=80 / 20, and the amount of acrylic acid ester monomer units having an alkyl group with 2 or more carbon atoms contained in Additive P calculated from the charged amount was 20.0 mass%.

[0152] [Synthesis Example 7: Additive Q] Additive Q was obtained according to the method for producing thermoplastic polymer III in Preparation Example 3 of WO 2015 / 137309. The monomers constituting Additive Q were MMA / BA=84 / 16, and the amount of acrylic acid ester monomer units having an alkyl group with 2 or more carbon atoms contained in Additive Q calculated from the charged amount was 16.0% by mass.

[0153] [Synthesis Example 8: Additive R] Additive R was obtained according to the method for producing copolymer composition (b-2) of Reference Example 2 of JP 2000-319516 A. The monomers constituting Additive R were MMA / BA / n-butyl methacrylate=50 / 30 / 20, and the amount of acrylic acid ester monomer units having an alkyl group with 2 or more carbon atoms contained in Additive R calculated from the charged amount was 30.0 mass%.

[0154] [Production Example 1] 100 parts of the core-shell rubber (A-1) obtained in Synthesis Example 1, 1.9 parts of LA31, 0.34 parts of C2020, 3 parts of additive P, 1 part of additive R, and 0.1 parts of Irg1076 were premixed, and melt-kneaded using a 35 mmφ screw-type twin-screw extruder (L / D=26) under conditions of a cylinder temperature of 200°C to 240°C and a die temperature of 240°C, and pelletized to obtain an acrylic resin composition. The glass transition temperature of the obtained resin composition was 99°C.

[0155] [Production Examples 2 to 16, Comparative Production Examples 1 to 3] Acrylic resin compositions were obtained in the same manner as in Production Example 1, except that the components of the acrylic resin composition were changed as shown in Table 1.

[0156] <Example 1> The pellets of the acrylic resin composition of Production Example 1 obtained were melt-extruded using a 40 mmφ (diameter) non-vent screw type extruder (L / D=33) equipped with a 400 mm wide T-die, and the extruded film was sandwiched between a pair of mirror-finished metal rolls and rubber rolls and cooled to form a film with a thickness of 50 μm. The extrusion conditions were a cylinder temperature of 240° C. and a T-die temperature of 240° C. The temperature of the mirror-finished metal roll was 85° C. The obtained acrylic resin film was laminated on a semi-rigid polyvinyl chloride resin sheet, and heated and pressed at 140° C. and a pressure of 2 MPa for 10 minutes to prepare a laminate.

[0157] <Examples 2 to 16> A laminate was obtained in the same manner as in Example 1, except that the pellets of the acrylic resin composition were changed as shown in Table 2.

[0158] <Example 17> T850 was plasticized using a 30 mmφ extruder with a cylinder temperature set to 240°C, and the pellets of the acrylic resin composition obtained in Production Example 14 were plasticized using a 40 mmφ extruder with a cylinder temperature set to 240°C. Next, a 50 μm thick acrylic resin film (laminated film) was produced using a two-kind two-layer multi-manifold die set to 240°C. The temperature of the mirror-finished metal roll was 85°C. The thickness of the T850 layer was 5 μm, and the thickness of the acrylic resin composition layer was 45 μm. The acrylic resin composition layer side of the obtained acrylic resin film was laminated to a semi-rigid polyvinyl chloride resin sheet, and heated and pressed at 140° C. and a pressure of 2 MPa for 10 minutes to prepare a laminate.

[0159] <Example 18> A laminate was obtained in the same manner as in Example 17, except that the pellets of the acrylic resin composition obtained in Production Example 15 were used.

[0160] <Comparative Examples 1 to 3> A laminate was obtained in the same manner as in Example 1, except that the pellets of the acrylic resin composition were changed as shown in Table 2.

[0161] <Comparative Example 4> A laminate was obtained in the same manner as in Example 1, except that a soft polyvinyl chloride resin sheet was used instead of the semi-rigid polyvinyl chloride resin sheet.

[0162] <Comparative Example 5> In Example 1, a laminate was obtained by using semi-cured melamine resin-impregnated paper, which is a thermosetting resin, instead of the semi-rigid polyvinyl chloride resin sheet, and heating and pressing at 140° C. and a pressure of 4 MPa for 20 minutes. The acrylic resin film and melamine resin-impregnated paper of the laminate were not sufficiently adhered to each other and were easily peeled off.

[0163] The evaluation results of the laminates of the examples and comparative examples are shown in Table 3 below.

[0164] [Table 1]

[0165] [Table 2]

[0166] [Table 3]

[0167] The above examples have revealed the following. That is, the laminates obtained in Examples 1 to 18 did not show any significant whitening or coloring after the hot water test, and had good water resistance. In addition, the cut processability was also good. In particular, the laminates obtained in Examples 2 to 12, 17, and 18 had a low gloss and achieved a good matte appearance, water resistance, and cut processability at the same time, and therefore have high industrial value.

[0168] On the other hand, the laminate obtained in Comparative Example 1 was inferior in water resistance and showed a large change in whiteness after the hot water test because an acrylic resin composition not containing a hindered amine compound having a molecular weight of 1,000 or more was used. The laminate obtained in Comparative Example 2 was inferior in water resistance and showed a large change in whiteness after the hot water test because an acrylic resin composition containing a hindered amine compound having a molecular weight of less than 1,000 or more was used. The laminate obtained in Comparative Example 3 was inferior in water resistance and showed a high haze value and poor design of the molded product because the amount of acrylic acid ester monomer units having an alkyl group having 2 or more carbon atoms contained in the acrylic resin composition exceeded 45% by mass. The laminate obtained in Comparative Example 4 was inferior in water resistance because the amount of plasticizer in the thermoplastic resin composition (II) exceeded 40% by mass. The laminate obtained in Comparative Example 5 was inferior in interlayer adhesion because a melamine resin, which is a thermosetting resin, was used instead of the thermoplastic resin composition (II). Furthermore, in comparison with Comparative Examples 3 and 4, Examples 1 and 4 had lower ΔE values ​​in a weather resistance test and were also excellent in weather resistance.

[0169] Although the present invention has been described above with reference to the embodiments and examples, the present invention is not limited to the above-mentioned embodiments and examples. Various modifications that can be understood by those skilled in the art can be made to the configuration and details of the present invention within the scope of the present invention. [Industrial Applicability]

[0170] The uses of the laminate of the present invention are not particularly limited, and can be used, for example, as roofing materials, siding materials, gutters, flooring materials, skin materials for building materials such as bathrooms and kitchens, skin materials for the interior and exterior of automobiles, skin materials for furniture, and vinyl greenhouses for agriculture.

Claims

1. A laminate comprising a layer made of an acrylic resin composition (I) containing an acrylic resin and a hindered amine-based compound, and a layer made of a thermoplastic resin composition (II) having a composition different from that of the acrylic resin composition (I), wherein the hindered amine-based compound has a molecular weight of 1,000 or more, the amount of acrylic ester monomer units having an alkyl group having two or more carbon atoms contained in the acrylic resin composition (I) is 45% by mass or less based on the total amount of the acrylic resin composition (I), and the thermoplastic resin composition (II) contains a plasticizer in an amount of 40% by mass or less based on the total amount of the thermoplastic resin composition (II).

2. The laminate according to claim 1 , wherein the acrylic resin is a core-shell rubber (A).

3. The laminate according to claim 1 or 2, wherein the thermoplastic resin composition (II) contains a polyvinyl chloride resin.

4. 3. The laminate according to claim 1, wherein the layer made of the acrylic resin composition (I) has a tensile modulus of elasticity of 900 MPa or more and 1,900 MPa or less.

5. The laminate according to claim 1 or 2, wherein the hindered amine compound has a structure represented by the following formula (1): 【Chemistry 1】 【Chemistry 2】 【Transformation 3】

6. The laminate according to claim 1 or 2, wherein the acrylic resin composition (I) contains a hydroxyl group-containing polymer (C1).

7. 3. The laminate according to claim 1, wherein the amount of the monomer unit having a hydroxyl group contained in the acrylic resin composition (I) is 5% by mass or less based on the total amount of the acrylic resin composition (I).

8. The laminate according to claim 1 or 2, wherein the acrylic resin composition (I) has a glass transition temperature of 80°C or higher.

9. 3. The laminate according to claim 1, wherein the gloss of at least one surface measured at an incident angle of 60° is 110% or less.

10. A film made of the acrylic resin composition (I) for use in forming the laminate described in claim 1 or 2.

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