JP2024007545A - laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: 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

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present invention relates to a laminate.

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

Japanese Patent Application Publication No. 2010-131782 International Publication No. 2019/244791

However, these acrylic resin film laminates have room for improvement in terms of both flexibility and water resistance. For example, the film of Patent Document 1 has a sufficient amount of elastic polymer and has good flexibility, but has insufficient water resistance. Further, the film of Patent Document 2 has a relatively small amount of elastic polymer and has relatively good water resistance, but there is room for improvement in flexibility.

Therefore, an object of the present invention is to provide a laminate including a layer made of an acrylic resin composition, which has high flexibility, water resistance, and transparency.

［６］ 前記アクリル樹脂組成物（Ｉ）が水酸基含有重合体（Ｃ１）を含有する、［１］～［５］のいずれかに記載の積層体。
［７］ 前記アクリル樹脂組成物（Ｉ）に含まれる水酸基を有する単量体単位量が、アクリル樹脂組成物（Ｉ）全量に対して５質量％以下である、［１］～［６］のいずれかに記載の積層体。
［８］ 前記アクリル樹脂組成物（Ｉ）のガラス転移温度が８０℃以上である、［１］～［７］のいずれかに記載の積層体。
［９］ 入射角６０°にて測定した少なくとも片面の光沢度が１１０％以下である、［１］～［８］のいずれかに記載の積層体。 The present invention has the following aspects.
[1] 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 the acrylic resin composition (I). A laminate, wherein the hindered amine compound has a molecular weight of 1,000 or more, and the acrylic acid ester monomer unit amount having an alkyl group having 2 or more carbon atoms contained in the acrylic resin composition (I) is The amount of the plasticizer 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 the plasticizer based on the total amount of the thermoplastic resin composition (II). , laminate.
[2] The laminate according to [1], wherein the acrylic resin is 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 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).

[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 acrylic resin composition (I) contains hydroxyl group-containing monomer units of 5% by mass or less based on the total amount of the acrylic resin composition (I), [1] to [6]. The laminate according to any one of the above.
[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 glossiness of at least one side measured at an incident angle of 60° is 110% or less.

According to the present invention, it is possible to provide a laminate of an acrylic resin composition that has high flexibility, water resistance, and transparency.

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

<Laminated body>
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 different composition from the acrylic resin composition (I). Moreover, in the laminate of the present invention, it is preferable that the layer made of the acrylic resin composition (I) is adjacent to at least one surface of the layer made of the thermoplastic resin composition (II). Furthermore, the layer made of acrylic resin composition (I) is preferably located at the outermost layer of the laminate. In addition, in this specification, the layer made of thermoplastic resin composition (II) is also referred to as a base material.

The laminate of the present invention preferably has a whiteness change of 0 to 20 after a hot water test. When the whiteness change is within the above range, water resistance tends to be excellent. The upper limit value of 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 referred to as initial whiteness). Here, the hot water test can be performed by the method described in Examples, and the whiteness can be measured according to JIS Z 8722:2009.

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, the thickness 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 will have appropriate rigidity, will have good handling properties, and will tend to have excellent durability. If the thickness of the laminate is less than or equal to the upper limit, the laminate has appropriate flexibility and tends to be easily bent. Moreover, it tends to be economically advantageous in terms of mass per unit area.

The thickness of the layer (film) made of acrylic resin composition (I) is preferably 5 μm or more, more preferably 10 μm or more, even more preferably 25 μm or more, while preferably 200 μm or less, more preferably 100 μm or less, and 75 μm or less. is more preferable, and particularly preferably 70 μm or less. If the thickness of the layer made of acrylic resin composition (I) is at least the above lower limit, the weather resistance of the film tends to be good. If the thickness of the layer made of acrylic resin composition (I) is at most the above upper limit, the film will have appropriate flexibility and will tend to have good bending workability. Moreover, it tends to be economically advantageous in terms of mass per unit area.

The thickness of the layer (film, sheet) made of thermoplastic resin composition (II) is preferably 5 μm or more, more preferably 30 μm or more, even more preferably 75 μm or more, on the other hand, preferably 10 mm or less, more preferably 1 mm or less. , more preferably 300 μm or less. When the thickness of the thermoplastic resin (II) layer is equal to or greater than the lower limit, the laminate tends to have good hiding properties and can provide excellent design when used as a decorative sheet. In addition, the tear resistance of the laminate tends to be good and processing tends to be easier. If the thickness of the layer made of thermoplastic resin composition (II) is less than or equal to the above-mentioned upper limit, appropriate flexibility will be imparted and handling properties will tend to be good. Moreover, it tends to be economically advantageous in terms of mass per unit area. In addition, when a plurality of layers made of thermoplastic resin composition (II) are present, the thickness of each layer may be within the above range.

Further, 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, preferably 40:60 to 15:85. In addition, when a plurality of layers made of thermoplastic resin composition (II) are present, the above-mentioned thickness is the sum of the thicknesses of all the layers made of thermoplastic resin composition (II).

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

Each resin composition constituting the laminate of the present invention will be explained below.

[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.

[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, and the like. These may be used alone or in combination of two or more. Among these, core-shell rubber (A) is preferable because it can more effectively exhibit the effects of the present invention.

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, even more preferably 95% by mass or more, while preferably 99.999% by mass or less, 99% by mass or more. The content is more preferably .9% by mass or less, and even more preferably 99.8% by mass or less. When the content of the acrylic resin is equal to or higher than the lower limit, the flexibility of the film improves, and whitening during bending tends to be easily suppressed. Moreover, if the content of the acrylic resin is below the above-mentioned upper limit, the heat decomposition resistance of the film tends to be good.

(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) has a core part (hereinafter also referred to as "core part (A1)") having a glass transition temperature (hereinafter also referred to as "Tg") of 0°C or lower, and a core part (hereinafter also referred to as "core part (A1)") having a Tg higher than 20°C. The rubber has a multilayer structure and includes a shell part (hereinafter also referred to as "shell part (A2)").
The Tg of the core portion (A1) is preferably -60°C or higher, and on the other hand, preferably -10°C or lower. The Tg of the shell portion (A2) is preferably 40°C or higher, and preferably 120°C or lower. In addition, Tg can be measured by the method of the Example mentioned later.

As the core part (A1), a polymer obtained by polymerizing a monomer composition (α1) containing an alkyl (meth)acrylate and a grafting agent can be exemplified.

The (meth)acrylic acid alkyl esters include acrylic acid alkyl esters having an alkyl group having 1 to 8 carbon atoms (hereinafter also referred to as "monomer (a11)"), and alkyl esters having an alkyl group having 1 to 4 carbon atoms. A methacrylic acid alkyl ester (hereinafter also referred to as "monomer (a12)") is preferred. Moreover, the alkyl group that the (meth)acrylic acid alkyl ester has may be linear or branched.

Examples of the monomer (a11) include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. Among these, acrylic acid alkyl esters having a low Tg are preferred, and n-butyl acrylate is more preferred, since the core portion (A1) has excellent impact resistance and can be easily molded. The number of monomers (a11) used in the core part (A1) may be one or two or more.

Examples of the monomer (a12) include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. The number of monomers (a12) used in the core part (A1) may be one or two or more.
Further, monomer (a11) and monomer (a12) may be used alone or both.

The graft cross-agent imparts rubber elasticity to the core portion (A1) through a cross-linking reaction, and also cross-links the core portion (A1) and the shell portion (A2) through a graft cross-reaction. Specifically, the conjugated unsaturated bonds of the ester of the grafting cross-agent react faster than the allyl group, methallyl group, or crotyl group, and are chemically bonded. During this time, most of the allyl group, methallyl group, or crotyl group in the graft cross agent remains unreacted and reacts during the polymerization to form the shell part (A2), and the core part (A1) and the shell part ( Provide a graft bond between A2).

Examples of the grafting agent include copolymerizable allyl esters, methallyl esters, or crotyl esters of α,β-unsaturated carboxylic acids, and allyl esters, methallyl esters, or crotyl esters of dicarboxylic acids. Moreover, triallyl cyanurate and triallyl isocyanurate can also be used as the graft cross-agent. Among these, as the graft cross-over agent, allyl acrylate, allyl methacrylate, allyl maleate, and allyl fumarate are preferable, and allyl methacrylate is more preferable. These may be used alone or in combination of two or more.

The monomer composition (α1) contains, in addition to the monomer (a11), the monomer (a12), and the grafting agent, a monomer having one polymerizable carbon-carbon double bond (hereinafter referred to as Also referred to as "monomer (a13)". ) or a crosslinking monomer (hereinafter also referred to as "crosslinking monomer (a14)") other than the graft cross-agent may be included.

Examples of the monomer (a13) include acrylic acid higher alkyl esters having an alkyl group having 9 or more carbon atoms, acrylic acid lower alkoxyalkyl esters having an alkoxyalkyl group having 8 or less carbon atoms, and acrylic acids such as cyanoethyl acrylate. Examples include acid alkyl esters, acrylamide, acrylic acid, methacrylic acid, styrene, alkyl-substituted styrene, acrylonitrile, and methacrylonitrile. The number of monomers (a13) used in the core part (A1) may be one or two or more.

Examples of the crosslinkable monomer (a14) include dimethacrylic acids such as ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and propylene glycol dimethacrylate. Examples include alkylene glycol, polyvinylbenzene such as divinylbenzene and trivinylbenzene. The crosslinking 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).

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

Further, the total content of the monomer (a11) and the monomer (a12) with respect to the monomer composition (α1) is preferably 80% by mass or more, more preferably 95% by mass or more, and on the other hand, 98% by mass or more. The content is preferably .7% by mass or less, more preferably 98.4% by mass or less.

The content of the graft cross-agent relative to the monomer composition (α1) is preferably 0.5% by mass or more, more preferably 0.9% by mass or more, and on the other hand, preferably 6.0% by mass or less, 2. More preferably, it is 0% by mass or less. If the content of the graft cross-agent is equal to or higher than the lower limit, the crosslinking between the core part (A1) and the shell part (A2) becomes stable, and sufficient transparency is likely to be exhibited. Furthermore, the rubber elasticity tends to be improved, and the impact resistance of the obtained film tends to be improved. If the content of the graft cross-agent is below the upper limit, the core portion (A1) will have appropriate flexibility and the film handling properties will improve. Moreover, the fluidity of the acrylic resin composition tends to be high, and the moldability tends to be improved.

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

When the monomer composition (α1) contains a crosslinkable monomer (a14), its content is preferably 10% by mass or less, and 5% by mass or less with respect to the monomer composition (α1). More preferred. The lower limit of the amount of the crosslinkable monomer (a14) to be used is not particularly limited, and may be 0% by mass.

As the shell portion (A2), a polymer obtained by polymerizing a monomer composition (α2) containing an alkyl methacrylate ester can be exemplified.

The methacrylic acid alkyl ester is preferably a methacrylic acid alkyl 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 number of monomers (a21) used in the shell portion (A2) may be one or two or more.

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

The content of the monomer (a21) with respect to the monomer composition (α2) is preferably 70% by mass or more, more preferably 85% by mass or more. When the content of the monomer (a21) is equal to or higher than the lower limit, the Tg of the shell portion (A2) tends to be increased, 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.

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

Note that the core-shell rubber (A) may include an intermediate portion (A3) having a Tg of more than 0° C. and 20° C. or less between the core portion (A1) and the shell portion (A2).
As the intermediate portion (A3), a polymer obtained by polymerizing a monomer composition (α3) containing an alkyl (meth)acrylate ester can be exemplified.

The (meth)acrylic acid alkyl ester includes an acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms (hereinafter also referred to as "monomer (a31)") and an alkyl group having 1 to 4 carbon atoms. An example is a methacrylic acid alkyl ester (hereinafter also referred to as "monomer (a32)") having the following.

In addition to the monomer (a31) and the monomer (a32), the monomer composition (α3) also contains a monomer having one polymerizable carbon-carbon double bond (hereinafter referred to as “monomer It is also called "body (a33))". ) or a crosslinkable monomer (a34) may be included.

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

The content of each monomer in the monomer composition (α3) is 10 to 90% by mass of monomer (a31), 10 to 90% by mass of monomer (a32), and 10 to 90% by mass of monomer (a33). ) is preferably 0 to 20% by mass, and the crosslinking monomer (a34) is preferably 0 to 10% by mass.

The core-shell rubber (A) may contain an innermost portion (A4) having a Tg of more than 0° C. inside the core portion (A1). Note that the Tg of the innermost portion (A4) is lower than that of the shell portion (A2).
As the innermost part (A4), a polymer obtained by polymerizing a monomer composition (α4) containing an alkyl (meth)acrylate ester can be exemplified.

The (meth)acrylic acid alkyl ester used in the monomer composition (α4) is an acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms (hereinafter also referred to as "monomer (a41)"). Examples include methacrylic acid alkyl esters having an alkyl group having 1 to 4 carbon atoms (hereinafter also referred to as "monomer (a42)").

In addition to monomer (a41) and monomer (a42), the monomer composition (α4) also contains a monomer having one polymerizable carbon-carbon double bond (hereinafter referred to as "monomer It is also called "body (a43))". ) or a crosslinkable monomer (a44) may be included.

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

The core-shell rubber (A) is obtained by sequentially polymerizing these monomer compositions from the inside. Further, the polymerization for forming the core portion (A1) may be performed in 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 be carried out in one stage, or may be carried out in two or more stages.

The polymerization method is not particularly limited, and examples 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.

Examples of the emulsifier include anionic surfactants, cationic surfactants, and nonionic surfactants, with anionic surfactants being preferred. Anionic surfactants are not particularly limited, and include, for example, carboxylates (rosin acid soap, potassium oleate, sodium stearate, etc.), sulfate ester salts (sodium lauryl sulfate, etc.), sulfonates (sodium dioctyl sulfosuccinate, etc.) etc.), and phosphate ester salts (polyoxyethylene alkylphenyl ether sodium phosphate, etc.). The number of emulsifiers used may be one or two or more.

The radical polymerization initiator is not particularly limited, and includes, for example, persulfates (potassium persulfate, sodium persulfate, etc.), organic peroxides (t-butyl hydroperoxide, etc.), azo compounds (azobisisobutyrobutylene, etc.). (nitrile, etc.), persulfate, or a redox initiator in which an organic peroxide is combined with a reducing agent. Among these, redox initiators are preferred. The number of radical polymerization initiators used may be one or two or more.

The chain transfer agent is not particularly limited, and examples include alkyl mercaptans having 2 to 20 carbon atoms, mercapto acids, thiophenol, and carbon tetrachloride. The number of chain transfer agents used may be one or two or more.
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, even more preferably 0.1 parts by mass or more, based on 100 parts by mass of the total amount of monomers. , 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 at least the above lower limit, the flexibility of the film tends to improve. If the amount of the chain transfer agent used is below the above upper limit, the mechanical strength of the film tends to improve.

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 preferably 120°C or lower, and more preferably 95°C or lower.

The content (core ratio) of the core part (A1) in the core-shell rubber (A) obtained in this way is preferably 20% by mass or more, and 30% by mass or more with respect to the total mass of the core-shell rubber (A). is more preferable. 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 portion (A1) is at least the lower limit value, the mechanical strength and flexibility of the film will improve, and there will be a tendency to easily suppress breakage, cracks, and whitening during molding and bending. In addition, void formation when exposed to water is suppressed, and water whitening resistance tends to be improved. Moreover, if the content of the core part (A1) is below the above-mentioned upper limit value, appropriate rigidity will be imparted to the film, and the handling property will tend to be good. Moreover, sticking of the films to each other is suppressed, and handling properties and productivity tend to be improved.

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

When the core-shell rubber (A) has an intermediate part (A3), the content of the intermediate part (A3) may be 0% by mass, and preferably 5% by mass or more, based on the total mass of the core-shell rubber (A). On the other hand, it is preferably 20% by mass or less, more preferably 15% by mass or less.
Moreover, when the core-shell rubber (A) has an innermost part (A4), the content of the innermost part (A4) is preferably 10% by mass or less with respect to the total mass of the core-shell rubber (A). The lower limit of the content of the innermost portion (A4) is not particularly limited, and may be 0% by mass.

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

Further, 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 monomer unit amount is more preferably 25% by mass or more, 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. When the monomer unit amount is at least the lower limit, the flexibility of the layer and laminate made of the acrylic resin composition (I) tends to improve, and the handleability and cutting processability tend to improve. On the other hand, if the monomer unit amount is below the upper limit, the layer and laminate made of the acrylic resin composition (I) will have appropriate rigidity, and will have better handling properties and scratch resistance. Warm water colorability and weather resistance tend to be good.
The unit amount of the acrylic ester monomer having an alkyl group having 2 or more carbon atoms is calculated from the charged amount of the acrylic ester monomer having an alkyl group having 2 or more carbon atoms contained in the core shell rubber (A). I can do it. Moreover, the monomer unit amount can also be actually measured using pyrolysis GC/MS of the core shell rubber (A).

The mass average molecular weight of the acetone soluble component of the core shell rubber (A) is preferably 25,000 or more, more preferably 30,000 or more, while 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 at least the lower limit, the mechanical strength of the film will improve and cracking will be easily suppressed. Furthermore, there is a tendency to easily suppress breakage and whitening during molding and bending. If the mass average molecular weight of the acetone soluble portion of the core shell rubber (A) is below the upper limit, the resulting resin composition tends to have improved fluidity and excellent processability during melt molding. Furthermore, the surface smoothness of the film obtained by melt molding tends to be improved and the appearance to be good.

The mass average molecular weight of the acetone-soluble component of the core-shell rubber (A) is determined by gel permeation chromatography ( This is a value measured by GPC). 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 chain transfer agent during polymerization.

The average particle diameter of the core-shell rubber (A) is preferably 0.01 μm or more, more preferably 0.08 μm or more, while preferably 0.5 μm or less, more preferably 0.3 μm or less. When the average particle diameter of the core-shell rubber (A) is at least the lower limit, flexibility and film formability tend to be good, and when it is at most the upper limit, transparency and surface smoothness tend to be good. Note that this average particle diameter can be measured by a dynamic light scattering method using a light scattering photometer (eg, trade name: "DLS-700", manufactured by Otsuka Electronics Co., Ltd.).

[Hindered amine compound (B)]
The acrylic resin composition (I) contains a hindered amine compound (B) having a molecular weight of 1,000 or more. Antioxidants are generally used to prevent oxidation of resin compositions. 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, This results in poor water resistance and whitening resistance (transparency). On the other hand, in the present invention, it has been discovered that high water resistance and transparency can be obtained by using a hindered amine compound having a specific molecular weight among hindered amine compounds. Therefore, in the present invention, it is preferable that the acrylic resin composition (I) does not contain a phosphorus antioxidant.

The molecular weight of the hindered amine compound (B) is preferably 1,200 or more, more preferably 1,500 or more, even more preferably 2,000 or more, while preferably 10,000 or less, more preferably 7,000 or less, It is more preferably 5,000 or less, particularly preferably 3,000 or less. When the molecular weight is at least the lower limit, the laminate will have good water whitening resistance. In addition, sticking to manufacturing equipment is suppressed during the production of films and laminates, improving productivity. On the other hand, when the molecular weight is below the upper limit, mixing with the acrylic resin becomes easy, and the transparency of the acrylic resin composition (I) becomes good. Note that when the hindered amine compound (B) has a molecular weight distribution, the molecular weight refers to the mass average molecular weight.

The hindered amine compound (B) preferably has a structure of the following formula (1).

式（１）中、ｎ＝１～１３、Ａは水素原子、または下記式（２）の構造であり、Ｂはｔ－オクチルアミノ基、ｎ－ブチル基、または下記式（３）の構造であることが好ましい。 また、式（１）中のｎが上記範囲内であればアクリル樹脂との相溶性がより良好となる傾向がある。ｎは、１．５以上がより好ましく、２以上が特に好ましい。一方、１０以下がより好ましく、５以下が特に好ましい。
また、式（１）中のＢが前記構造であれば、アクリル樹脂との相溶性が向上し、アクリル樹脂組成物（Ｉ）の透明性が良好となる傾向がある。

In formula (1), n = 1 to 13, A is a hydrogen atom or the structure of the following formula (2), and B is a t-octylamino group, n-butyl group, or the structure of the following formula (3). It is preferable that there be. Furthermore, if n in formula (1) is within the above range, the compatibility with the acrylic resin tends to be better. n is more preferably 1.5 or more, particularly preferably 2 or more. On the other hand, it is more preferably 10 or less, particularly preferably 5 or less.
Further, when B in formula (1) has the above structure, the compatibility with the acrylic resin tends to improve, and the transparency of the acrylic resin composition (I) tends to improve.

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 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, based on 100 parts by mass of the acrylic resin. It is more preferably 2 parts by mass or more, on the other hand, preferably 10 parts by mass or less, more preferably 3 parts by mass or less, even more preferably 1 part by mass or less. When the amount of the hindered amine compound (B) added is at least the lower limit, weather resistance and water resistance tend to be good. On the other hand, if the amount of the hindered amine compound (B) added is below the upper limit, the transparency and film formability of the film tend to be better.

Commercially available products of the hindered amine compound (B) include, for example, "Chimassrob2020", "Chimassrob944", "Tinuvin622", "Tinuvin111" (all product names, manufactured by BASF Japan), "ADKASTAB LA-63P", " ADEKA STAB LA-68'' (all of the above are trade names, manufactured by ADEKA). Among them, "Chimassrob2020" and "Chimassrob944" (both trade names, manufactured by BASF Japan) are more preferable. These may be used alone or in combination of two or more.

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

[Flatting agent (C)]
It is preferable that the acrylic resin composition (I) contains a matting agent (C). 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. Examples of the matting agent (C) include a hydroxyl group-containing polymer (C1) and crosslinked fine particles (C2), and the hydroxyl group-containing polymer (C1) is more preferable from the viewpoint of film formability and moldability.

(Hydroxy group-containing polymer (C1))
The hydroxyl group-containing polymer (C1) is a polymer having a hydroxyl group as a substituent in the polymer, and is a (meth)acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms. 10 to 99 parts by weight of an alkyl methacrylate having an alkyl group having 1 to 13 carbon atoms, and 0 to 79 parts by weight of an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms, a total of 100 parts by weight. It is obtained by copolymerizing polymeric components. The hydroxyl group-containing polymer (C1) is different from the acrylic resin in that it does not have rubber properties.

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, and 2-hydroxypropyl acrylate. -hydroxyethyl, 4-hydroxybutyl acrylate, etc. These can be used alone or in combination of two or more. Among them, 2-hydroxyethyl methacrylate is particularly preferred.

The content of the (meth)acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms based on the monomer components is usually in the range of 1 to 80% by mass. By setting the content of the (meth)acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms to 1% by mass or more, the matting effect tends to become higher. In addition, by controlling the content of (meth)acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms to 80% by mass or less, the dispersibility of particles becomes better and the film formability becomes better. There is a tendency to

In addition, from the viewpoint of matting properties, the content of (meth)acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms is preferably 5% by mass or more, and 20% by mass or more based on the monomer component. is more preferable.
Furthermore, from the viewpoint of film formability, the content of the (meth)acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms is preferably 50% by mass or less based on the monomer components.

In applications where chemical resistance is required, from the viewpoint of sufficiently developing resistance, the content of (meth)acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms relative to the monomer component should be 5% by mass. % or more, and preferably 25% by mass or less.
In addition, from the viewpoint of achieving both matting properties and chemical resistance, the content of (meth)acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms should be 10% by mass or more based on the monomer component. is preferable, and 20% by mass or less is preferable.

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 them, methyl methacrylate is particularly preferred. These can be used alone or in combination of two or more.

The content of the methacrylic acid alkyl ester having an alkyl group having 1 to 13 carbon atoms based on the monomer components is usually 10 to 99% by mass.
Furthermore, 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 is preferably 30% by mass or more based on the monomer components.
Furthermore, from the viewpoint of matting properties, the content of the methacrylic acid alkyl ester having an alkyl group having 1 to 13 carbon atoms is preferably 90% by mass or less based on the monomer components.

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

The content of the acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms based on the monomer components is usually 0 to 79% by mass.
In addition, from the viewpoint 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 is preferably 0.5% by mass or more, and 5% by mass based on the monomer component. % or more is more preferable.
Furthermore, from the viewpoint of heat resistance of the obtained film, the content of the acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms is preferably 40% by mass or less, and 25% by mass or less based on the monomer components. More preferred.

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

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.

The intrinsic viscosity of the hydroxyl group-containing polymer (C1) is preferably within the range of 0.05 to 0.3 L/g from the viewpoint of developing a matte effect and appearance. The intrinsic viscosity of the hydroxyl group-containing polymer (C1) is more preferably 0.06 L/g or more. Moreover, the intrinsic viscosity of the hydroxyl group-containing polymer (C1) is more preferably 0.15 L/g or less.

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

(Crosslinked fine particles (C2))
The crosslinked fine particles (C2) are not particularly limited, and include, for example, 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.

Examples of the 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, for example, by polymerizing a styrene monomer (styrene, methylstyrene, ethylstyrene, etc.) and a crosslinkable monomer. It is obtained by polymerizing a (meth)acrylic acid alkyl ester (methyl methacrylate, n-butyl methacrylate, methyl acrylate, n-butyl acrylate, etc.) and a crosslinkable monomer.

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.

As the crosslinked fine particles (C2), organic crosslinked fine particles are preferable, and crosslinked acrylic resin particles are more preferable.

Examples of commercially available crosslinked acrylic resin particles include "Epostor (registered trademark) MV1004" manufactured by Nippon Shokubai Co., Ltd., average particle diameter: 4 μm, refractive index: 1.51, and the like.

When the acrylic resin composition (I) contains a matting agent (C), its content is usually 0.1 to 50% by mass, preferably 0.5% by mass, based on the acrylic resin composition (I). ~40% by weight, more preferably 1~30% by weight. 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.

[Thermoplastic polymer (D)]
In addition to the acrylic resin, the acrylic resin composition (I) may contain a thermoplastic polymer (D) other than the acrylic resin. Furthermore, the number of thermoplastic polymers (D) contained in the acrylic resin composition (I) may be one or two or more.

The thermoplastic polymer (D) is preferably a polymer obtained by polymerizing a monomer composition containing an alkyl methacrylate as a main component; ) A polymer obtained by polymerizing a monomer other than the acrylic acid alkyl ester is more preferable. Note that the polymer obtained by polymerizing the monomer composition containing the methacrylic acid alkyl ester as a main component differs from the acrylic resin in that it does not have rubber properties.

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 other monomers include aromatic vinyl monomers such as styrene, vinyl cyanide monomers such as acrylonitrile, unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride, and N-phenylmaleimide. , N-cyclohexylmaleimide. These monomers used in the thermoplastic polymer (D) may be used alone or in combination of two or more.

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 employed. 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.

The thermoplastic polymer (D) contains 50 to 99.9% by mass of methacrylic acid alkyl ester units having an alkyl group having 1 to 4 carbon atoms, 0.1 to 50% by mass of acrylic acid alkyl ester units, and It is preferable that the polymer contains 0 to 49.9% by mass of other monomer units (total 100% by mass).

The mass average molecular weight of the thermoplastic polymer (D) is preferably 10,000 or more, and on the other hand, preferably 150,000 or less. If the mass average molecular weight is at least the lower limit, the layer made of acrylic resin composition (I) tends to have better handling properties. If the mass average molecular weight is below the upper limit, film formability tends to be better.

When the acrylic resin composition (I) contains a thermoplastic polymer (D), its content is usually 0 to 50% by mass, preferably 0 to 30% by mass, based on the acrylic resin composition (I). %, more preferably 0 to 10% by mass. By containing the thermoplastic polymer (D), when melt-forming the layer made of the acrylic resin composition (I), the film thickness accuracy improves, film formability is improved, and the surface appearance is good. becomes.

[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 base material. Examples of the ultraviolet absorber (E) include benzotriazole compounds, triazine compounds, benzophenone compounds, cyanoacrylate compounds, etc. Among them, benzotriazole compounds are preferred because they can provide high weather resistance over a long period of time. Alternatively, triazine compounds are preferred, and benzotriazole compounds are particularly preferred. These may be used alone or in combination of two or more.

The molecular weight of the ultraviolet absorber (E) is preferably 300 or more, more preferably 400 or more, while 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 molding machines such as molds are less likely to be contaminated. On the other hand, when the molecular weight is 100,000 or less, mixing with the core-shell rubber (A) becomes easier, and the transparency of the acrylic resin composition (I) tends to be better.

Commercially available benzotriazole compounds include, for example, "Tinuvin 231", "Tinuvin 234", "Tinuvin 326", "Tinuvin 329", "Tinuvin 571" (all trade names, manufactured by BASF), "Adekastab" LA-31'' (all of the above are product names, manufactured by ADEKA). Commercially available triazine compounds include, for example, "Tinuvin 1577", "Tinuvin 1600", "Tinuvin 460", "Tinuvin 477", "Tinosorb S" (all trade names, manufactured by BASF), and "ADK 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.

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 1.7 parts by mass or more with respect to 100 parts by mass of the acrylic resin. More preferably, on the other hand, it is preferably 20 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less.

(Additive)
The acrylic resin composition (I) may contain a stabilizer (excluding the hindered amine compound (B)), a lubricant, a processing aid, a plasticizer, and an impact resistance improver, as necessary, within a range that does not impair the effects of the present invention. It may contain additives such as foaming agents, foaming agents, fillers, and coloring agents. The number of additives contained in the acrylic resin composition (I) may be one or two or more.

The acrylic resin composition (I) is obtained by blending these components in a predetermined content and mixing them using a known mixing method (for example, dry blending, melt kneading, etc.).

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 monomer unit amount 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 monomer unit amount is at least the lower limit, the flexibility of the acrylic resin composition (I) and the laminate will be improved, and the handleability and cutting processability will be better. On the other hand, if the monomer unit amount is below the upper limit, appropriate rigidity will be produced in the acrylic resin composition (I) and the laminate, and the handleability and scratch resistance will be better. In addition, hot water coloring resistance and weather resistance are improved.
The amount of acrylic ester monomer units having an alkyl group having 2 or more carbon atoms contained in the acrylic resin composition (I) refers to the amount of acrylic ester monomer units contained in the acrylic resin composition (I), such as acrylic resin, gloss, etc. Add up the amount of acrylic acid ester monomer units having an alkyl group having 2 or more carbon atoms contained in the erasing agent (C), thermoplastic polymer (D), and additives, and calculate the proportion to the acrylic resin composition (I). This is what I did.
In addition, the amount of acrylic ester monomer units having an alkyl group having 2 or more carbon atoms is the acrylic ester monomer unit having an alkyl group having 2 or more carbon atoms contained in the above polymer constituting the acrylic resin composition (I). It can be calculated from the amount of preparation. Moreover, the monomer unit amount can also be actually measured using pyrolysis GC/MS of the acrylic resin composition (I).

Further, the amount of monomer units having a hydroxyl group contained in the acrylic resin composition (I) is preferably 5% by mass or less, and preferably 4% by mass or less based on the total amount of the acrylic resin composition (I). It is more preferable. If the amount of the monomer unit is below the upper limit, the generation of foreign matter due to the crosslinking reaction of hydroxyl groups is suppressed, and the film tends to have a better appearance. Additionally, water resistance tends to improve. On the other hand, the amount of monomer units having hydroxyl groups 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 monomer unit amount is equal to or greater than the lower limit, the film tends to have a matte appearance and better matte properties.
The amount of hydroxyl group-containing monomer units contained in the acrylic resin composition (I) refers to the amount of monomer units contained in the acrylic resin composition (I), such as acrylic resin, matting agent (C), thermoplastic polymer, etc. The amount of hydroxyl group-containing monomer units contained in the aggregate (D) and the additive is summed and expressed as a proportion 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).

The glass transition temperature of the acrylic resin composition (I) is preferably 80°C or higher, more preferably 85°C or higher, while preferably 110°C or lower, and 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 below the upper limit, the laminate tends to have improved toughness and better bending workability and handleability. The glass transition temperature can be measured by the method described in Examples below.

The gel fraction of the acrylic resin composition (I) is preferably 5% or more, on the other hand, preferably 90% or less, and more preferably 80% or less. When the gel fraction is 5% or more, the toughness of the film tends to improve, and the handling properties and film forming properties of the film tend to improve. Further, when the gel fraction is 90% by mass or less, the generation of heat-degraded foreign substances in the resin is suppressed, and the film tends to have a better appearance.
In terms of film toughness, the gel fraction of the acrylic resin composition (I) is more preferably 45% or more, particularly preferably 50% or more, and even more preferably 80% or less.
Furthermore, from the viewpoint of film appearance, 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 is determined by extracting a predetermined amount (mass before extraction) of the acrylic resin composition (I) in an acetone solvent under reflux, fractionating this treated solution by centrifugation, and drying the acetone-insoluble content. After that, the mass is measured (mass after extraction), and the value is calculated using the following formula.
Gel fraction (%) = Mass after extraction (g) / Mass before extraction (g) x 100

The melt flow rate (MFR) of the acrylic resin composition (I) at 230° C. and a load of 49 N is preferably 0.1 g/10 minutes or more, more preferably 1 g/10 minutes or more, even more preferably 3 g/10 minutes or more, On the other hand, it is preferably 100 g/10 minutes or less, more preferably 50 g/10 minutes or less, and even more preferably 20 g/10 minutes or less. If the MFR of the acrylic resin composition (I) is equal to or higher than the lower limit value, the moldability during melt molding will be good, and the surface smoothness of the melt molded film will tend to improve and the appearance will be better. . If the MFR of the acrylic resin composition (I) is less than or equal to the above upper limit, the moldability during melt molding tends to be better. MFR can be measured by the method described in Examples below.

In the present invention, a layer is formed from the acrylic resin composition (I), and this is laminated with a layer made of the thermoplastic resin composition (II) described later. The layer may be formed by a known method (for example, coating, melt extrusion, etc.).

The tensile modulus of the layer made of acrylic resin composition (I) is preferably 900 MPa or more, more preferably 1,200 MPa or more, 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 higher than the above lower limit, appropriate rigidity is imparted and the handleability tends to be better. On the other hand, when it is below the above upper limit, flexibility is imparted and processability and handleability tend to be better. The tensile modulus of the layer made of acrylic resin composition (I) can be measured by the method described in the Examples below.

[Thermoplastic resin composition (II)]
The layer made of thermoplastic resin composition (II) is a film or sheet made of thermoplastic resin composition (II) having a different composition from acrylic resin composition (I). Thermoplastic resins are not particularly limited, and include, for example, polyvinyl chloride resins, polyvinylidene chloride resins, polyolefin resins, thermoplastic polyurethane resins, acrylic resins, polyvinylidene fluoride resins, polystyrene resins, and ABS. Examples include 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 these, 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 with the acrylic resin composition (I). , polyvinyl chloride resin, and polyvinylidene fluoride resin are more preferred, and polyvinyl chloride resin is 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.

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, while it is preferably 95% by mass or less, and more preferably 90% by mass or less.

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

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 from 800 to 1,500, and even more preferably from 900 to 1,300.

Examples of the polyvinylidene fluoride resin include polyvinylidene fluoride, which is a homopolymer of vinylidene fluoride.
Commercially available polyvinylidene fluoride products include, for example, Kynar 720 (vinylidene fluoride content: 100% by mass, crystal melting point: 169°C) manufactured by Arkema, Kynar 710 (vinylidene fluoride content: 100% by mass, crystalline). Melting point: 169°C); KFT#850 manufactured by Kureha (vinylidene fluoride content: 100% by mass, crystal melting point: 173°C); Solef 1006 manufactured by Solvay Specialty Polymers (vinylidene fluoride content: 100% by mass) , crystal melting point: 174°C), and Solef 1008 (vinylidene fluoride content: 100% by mass, crystal melting point: 174°C).

When the thermoplastic resin contained in the thermoplastic resin composition (II) having a different composition from the acrylic resin composition (I) is a polyvinyl chloride resin, the thermoplastic resin composition (II) contains a plasticizer. It is desirable to contain. Examples of the plasticizer include phthalate ester plasticizers such as di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisodecyl phthalate, dibutyl phthalate, and dihexyl phthalate; dioctyl adipate, diisononyl adipate, and diisodecyl adipate. , adipic acid plasticizers such as adipic acid esters such as dibutoxyethyl adipate and bis(butyl triglycol) adipate, and adipic acid polyester; epoxy plasticizers such as epoxidized linseed oil and liquid epoxy resin; Examples include phosphate ester plasticizers such as phenyl phosphate, tricylyl phosphate, and tricresyl phosphate; other plasticizers such as dioctyl sebacate, trimellitic acid ester, citric acid ester, and benzoic acid ester. Among these, adipic acid plasticizers are preferred, and dioctyl adipate is more preferred, in view of good weather resistance. These may be used alone or in combination of two or more.

When the thermoplastic resin composition (II) contains a plasticizer, the content thereof is 40% by mass or less, preferably 35% by mass or less, and 30% by mass or less, based on the total amount of the thermoplastic resin composition (II). It is more preferably at most 25% by mass, particularly preferably at most 25% by mass. 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 content is 40% by mass or less, the polyvinyl chloride resin has good handling properties during molding, and the laminate of the present invention has good water resistance and interlayer adhesion. In addition, when the plasticizer content is 5% by mass or more, the flexibility and moldability of the polyvinyl chloride resin tend to improve, and the weather resistance of the laminate of the present invention tends to improve.

In addition, the thermoplastic resin composition (II) may contain antioxidants, matting agents, stabilizers, lubricants, antistatic agents, weathering aids, colorants, It may contain known additives such as processing aids and ultraviolet absorbers. These may be used alone or in combination of two or more.

Examples of the matting agent include those explained in the above-mentioned matting agent (C), and among them, the hydroxyl group-containing polymer (C1) is preferable. Containing a matting agent tends to reduce the glossiness of the film surface and improve the design.

The stabilizer is not particularly limited, but includes, for example, zinc stearate, zinc palmitate, zinc laurate, zinc octoate, zinc ricinoleate, zinc 2-ethylhexoate, zinc naphthenate, and tin stearate. Metal soaps such as lead stearate, dibasic lead stearate, lead naphthenate; lead white, basic lead silicate, tribasic lead sulfate, tribasic lead phosphite, tribasic lead maleate, Lead-based stabilizers such as basic lead phthalate, silica gel co-precipitated lead silicate, and lead n-salicylate; Organotin-based stabilizers such as dibutyltin dilaurate, dibutyltin malate, and dibutyltin mercaptide; Barium-zinc composite stabilizers, calcium- Zinc composite stabilizer, aluminum-magnesium-zinc composite stabilizer, cadmium-barium-zinc composite stabilizer, cadmium-barium-lead composite stabilizer, calcium-magnesium-zinc composite stabilizer, etc., epoxidized vegetable oil, bisphenol type epoxy compound , epoxy group-containing acrylic polymers, and other epoxy compounds can be used, and these can be used alone or in combination of two or more.

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 and bisfatty acid amides. Fatty acid amide series such as lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids such as glycerides, polyglycol esters of fatty acids, aliphatic alcohol esters of fatty acids (ester waxes), etc.; Metallic soaps, fatty alcohols, Examples include hydrohydric 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 inhibiting properties, are particularly preferred. These can be used alone or in combination of two or more.

As the weathering aid, organic carboxylic acid copper, copper chelate complex compounds, and inorganic copper compounds are preferable. Examples of organic copper carboxylates include copper stearate, copper palmitate, copper laurate, copper octylate, copper acetate, copper benzoate, copper pt-butylbenzoate, copper 1,2-hydroxystearate, and maleic acid. Examples include copper and copper naphthenate. Examples of the copper chelate complex compound include copper dialkylthiocarbamates 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, copper hydroxide, and the like.

The thermoplastic resin composition (II) is obtained by blending these components to a predetermined content and mixing them using a known mixing method (for example, dry blending, melt kneading, etc.). Moreover, as a method for forming a layer from the thermoplastic resin composition (II), a layer may be formed by a known method (for example, melt extrusion, etc.).

The laminate of the present invention is obtained by laminating a layer made of the acrylic resin composition (I) and a layer made of the thermoplastic resin composition (II), but the lamination method is not particularly limited. For example, known methods such as pressurization, heating and pressurization may be used. Alternatively, the acrylic resin composition (I) may be coated on the surface of the layer made of the thermoplastic resin composition (II) to form a laminate.

The applications of the laminate of the present invention thus obtained are not particularly limited, and include, for example, roofing materials, siding materials, rain gutters, flooring materials, skin materials for building materials such as bathrooms and kitchens, and interior and exterior materials for automobiles. It can be used for skin materials, furniture skin materials, and agricultural vinyl houses.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited by the following description. In the examples, "parts" represent "parts by mass."

[Abbreviation]
Abbreviations in Examples are as follows.
[Monomer component]
・MMA: Methyl methacrylate ・BA: n-butyl acrylate ・MA: Methyl acrylate ・HEMA: 2-hydroxyethyl methacrylate ・BDMA: 1,3-butylene glycol dimethacrylate [grafting cross agent]
・AMA: Allyl methacrylate [emulsifier]
・RS610NA: Mono-n-dodecyloxytetraoxyethylene sodium phosphate: "Phosphanol RS-610NA" (trade name) manufactured by Toho Chemical Industry Co., Ltd.
・OTP: Manufactured by Kao Corporation, "Perex OT-P" (product name)
[Chain transfer agent]
・nOM: n-octyl mercaptan ・nDM: n-dodecyl mercaptan [polymerization initiator]
・CHP: Manufactured by NOF Corporation, "Park Mill H" (product name)
・tBH: “Perbutyl H” (product name) manufactured by NOF Corporation
・LPO: Manufactured by NOF Corporation, "Pearloil L" (product name)
[Hindered amine compound]
(Hindered amine compound (B) with a molecular weight of 1,000 or more)
・C2020: Manufactured by BASF Japan, "Chimassorb2020" (trade name) (molecular weight 2,600 to 3,400)
・C944: Manufactured by BASF Japan, "Chimassorb944" (trade name) (molecular weight 2,000 to 3,100)
(Hindered amine compound (B') with molecular weight less than 1,000)
・LA57: Manufactured by ADEKA, "LA-57" (trade name) (molecular weight 791)
[Ultraviolet absorber (E)]
・LA31: Manufactured by ADEKA, "LA-31" (product name)
・Tv1577: Manufactured by BASF Japan, "Tinuvin1577" (product name)
[Additive]
[Hindered phenol compound]
・Irg1076: Manufactured by BASF Japan, "Irganox1076" (product name)
[Polyvinyl chloride resin sheet]
・Semi-rigid vinyl chloride resin sheet: Vinyl chloride resin, plasticizer (dioctyl adipate), stabilizer, and brown pigment are kneaded and molded into a sheet shape, and the amount of plasticizer is 19.7% by mass based on the sheet. , thickness 100μm
- Soft vinyl chloride resin sheet: A sheet made by kneading vinyl chloride resin, a plasticizer (dioctyl adipate), and a stabilizer and molding it into a sheet.The amount of plasticizer is 45% by mass of the sheet, and the thickness is 100μm.
[Polyvinylidene fluoride resin]
・T850: Manufactured by Kureha, "KFT#850" (product name)

Further, various test methods and measurement methods in Examples are as follows.

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

[Average particle diameter]
Core-shell rubber particles are dispersed in ion-exchanged water, diluted to a concentration sufficient for measurement, and the volume is measured using a laser diffraction/scattering particle size distribution analyzer (manufactured by Shimadzu Corporation, product name: "SALD-7100"). The median diameter in terms of average was determined, and the median diameter was taken as the average particle diameter.

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

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

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

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

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

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

[Amount of acrylic acid ester monomer unit having an alkyl group having 2 or more carbon atoms]
The amount of acrylic acid ester monomer units having an alkyl group having a carbon number of 2 or more contained in the total amount of the acrylic resin composition is replaced with the acrylic resin (core shell rubber (A-1), (A- 2), calculated from the production amounts of hydroxyl group-containing polymers (C1-1), (C1-2), additive P, and additive Q).

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

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

[Synthesis Example 1: Core shell rubber (A-1)]
After charging 8.5 parts of deionized water into a container equipped with a stirrer, add the monomer composition shown below (α1-1(1)) while stirring, and stir for 20 minutes to form an emulsion. Prepared.
Next, 191.5 parts of deionized water and component (i) shown below were charged into a polymerization container 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 container over 8 minutes, and the reaction was continued for 15 minutes. Subsequently, a monomer composition (α1-1(2)) shown below was dropped into the polymerization container over a period of 90 minutes, and the reaction was continued for 60 minutes to obtain a core latex. Note that the Tg of the core portion was -48°C.
Subsequently, a monomer composition (α3-1) shown below was dropped into the polymerization container over a period of 45 minutes, and the reaction was continued for 60 minutes to form an intermediate portion on top of the core portion. Note that the Tg of the intermediate portion alone was 20°C.
Subsequently, a monomer composition (α2-1) shown below was dropped into the polymerization container over a period of 140 minutes, and the reaction was continued for 60 minutes to form a shell portion on the middle portion. Through the above steps, latex containing 100 parts of core shell rubber (A-1) was obtained. Note that the Tg of the shell portion alone was 84°C. Further, the average particle diameter of the core-shell rubber (A-1) measured after polymerization was 0.12 μm.
The latex of this core-shell rubber (A-1) was subjected to coagulation, flocculation, 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 unit having an alkyl group having 2 or more carbon atoms contained in the core-shell rubber (A-1) calculated from the amount of production charge of the core-shell rubber (A-1) is 35.7% by mass. there were.

[Component (i)]
Sodium formaldehyde sulfoxylate: 0.2 part Ferrous sulfate: 0.0001 part Disodium ethylenediaminetetraacetate: 0.0003 part [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 parts [monomer composition (α1 -1(2))]
・MMA: 1.5 parts ・BA: 22.5 parts ・AMA: 0.25 parts ・BDMA: 1.0 parts ・CHP: 0.016 parts [Monomer composition (α3-1)]
・MMA: 6.0 parts ・BA: 4.0 parts ・AMA: 0.075 parts ・CHP: 0.013 parts [Monomer composition (α2-1)]
・MMA: 55.2 parts ・BA: 4.8 parts ・nOM: 0.22 parts ・tBH: 0.075 parts

[Synthesis Example 2: Core shell rubber (A-2)]
After putting 195 parts of deionized water into a polymerization container equipped with a stirrer, a cooling tube, a thermocouple, and a nitrogen introduction pipe, the following monomer composition (α1-2(1)) was added, The temperature was raised to ℃. After raising the temperature, 5 parts of deionized water and component (ii) shown below were added to start polymerization. After confirming the peak temperature, the reaction was continued for 15 minutes to complete the polymerization.
Subsequently, the monomer composition (α1-2(2)) shown below was dropped into the polymerization container over 120 minutes. Thereafter, the reaction was continued for 60 minutes to complete polymerization of the core portion. Note that the Tg of the core portion was -49°C.
Subsequently, a monomer composition (α2-2) shown below was dropped into the polymerization container over 120 minutes, and the reaction was continued for 60 minutes to form a shell portion on the core portion. Through the above steps, a latex-like core-shell rubber was obtained. Note that the Tg of the shell portion alone was 79°C. Further, the average particle diameter of the core-shell rubber (A-2) after polymerization was 0.12 μm.
The latex core-shell rubber was dropped into 300 parts of 70°C hot water containing 3.8 parts of calcium acetate to coagulate the latex. Furthermore, the temperature was raised to 95°C and held for 5 minutes to solidify. The obtained coagulated product was separated and 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 2 or more carbon atoms contained in the core-shell rubber (A-2) calculated from the production amount of the core-shell rubber (A-2) is 55.7% by mass. there were.

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

[Synthesis Example 3: Core shell rubber (A-3)]
After charging 8.5 parts of deionized water into a container equipped with a stirrer, add the monomer composition shown below (α1-3(1)) while stirring, and stir for 20 minutes to form an emulsion. Prepared.
Next, 191.5 parts of deionized water and component (i) shown below were charged into a polymerization container 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 container over 8 minutes, and the reaction was continued for 15 minutes. Subsequently, a monomer composition (α1-3(2)) shown below was dropped into the polymerization container over a period of 90 minutes, and the reaction was continued for 60 minutes to obtain a core latex. Note that the Tg of the core portion was -48°C.
Subsequently, a monomer composition (α3-3) shown below was dropped into the polymerization container over a period of 45 minutes, and the reaction was continued for 60 minutes to form an intermediate portion on top of the core portion. Note that the Tg of the intermediate portion alone was 20°C.
Subsequently, a monomer composition (α2-3) shown below was dropped into the polymerization container over a period of 140 minutes, and the reaction was continued for 60 minutes to form a shell portion above the intermediate portion. Through the above steps, latex containing 100 parts of core shell rubber (A-3) was obtained. Note that the Tg of the shell portion alone was 84°C. Further, the average particle diameter of the core-shell rubber (A-3) measured after polymerization was 0.12 μm.
The latex of this core-shell rubber (A-3) was subjected to coagulation, flocculation, 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 unit having an alkyl group having 2 or more carbon atoms contained in the core-shell rubber (A-3) calculated from the production amount of the core-shell rubber (A-3) is 35.5% by mass. there were.

[Component (i)]
Sodium formaldehyde sulfoxylate: 0.2 part Ferrous sulfate: 0.0001 part Disodium ethylenediaminetetraacetate: 0.0003 part [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 parts [monomer composition (α1 -3(2))]
・MMA: 1.0 part ・BA: 22.5 parts ・AMA: 0.75 parts ・BDMA: 1.5 parts ・CHP: 0.016 parts [Monomer composition (α3-3)]
・MMA: 6.0 parts ・BA: 4.0 parts ・AMA: 0.075 parts ・CHP: 0.013 parts [Monomer composition (α2-3)]
・MMA: 55.2 parts ・BA: 4.8 parts ・nOM: 0.24 parts ・tBH: 0.075 parts

[Synthesis Example 4: Hydroxyl group-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, and the like. Next, after the inside of the container was sufficiently purged with nitrogen gas, the monomer component (1) in the reaction container was heated to 75° C. with stirring, and reacted for 3 hours in a nitrogen gas stream. Thereafter, the temperature inside the reaction vessel was raised to 90° C. and maintained for an additional 45 minutes to complete polymerization, followed by dehydration and drying to obtain a hydroxyl group-containing polymer (C1-1). Since the hydroxyl group-containing polymer (C1-1) does not contain an acrylic acid ester having an alkyl group having 2 or more carbon atoms, the hydroxyl group-containing polymer (C1-1) contains 2 carbon atoms, which is calculated from the production amount. The amount of acrylic acid ester monomer units having the above alkyl group was 0% by mass. Further, the amount of monomer units having a hydroxyl group contained in the hydroxyl group-containing polymer (C1-1) calculated from the production amount was 20.0% by mass.

[Monomer component (1)]
・MA: 1 part ・MMA: 79 parts ・HEMA: 20 parts ・nDM: 0.22 parts ・LPO: 0.53 parts ・Copolymer of methyl methacrylate/potassium methacrylate/2-sulfoethyl sodium methacrylate salt Combined: 0.05 part ・Deionized water: 250 parts

[Synthesis Example 5: Hydroxyl group-containing polymer (C1-2)]
A hydroxyl group-containing polymer (C1-2) was obtained in the same manner as in Synthesis Example 4 except that monomer component (1) was changed to monomer component (2) below. Since the hydroxyl group-containing polymer (C1-2) does not contain an acrylic acid ester having an alkyl group having 2 or more carbon atoms, the hydroxyl group-containing polymer (C1-2) contains 2 carbon atoms, which is calculated from the production amount. The amount of acrylic acid ester monomer units having the above alkyl group was 0% by mass. Further, the amount of monomer units having hydroxyl groups contained in the hydroxyl group-containing polymer (C1-2) calculated from the amount of production was 30.0% by mass.

[Monomer component (2)]
・MA: 10 parts ・MMA: 60 parts ・HEMA: 30 parts ・nDM: 0.25 parts ・LPO: 0.52 parts ・Copolymer of methyl methacrylate/potassium methacrylate/sodium 2-sulfoethyl methacrylate salt Combined: 0.05 part ・Deionized water: 250 parts

[Synthesis Example 6: Additive P]
Additive P was obtained according to the method for producing thermoplastic polymer IV in Preparation Example 4 of International Publication No. 2015/137309. The monomers constituting the additive P have a ratio of MMA/BA=80/20, and the unit amount of acrylic ester monomer having an alkyl group having 2 or more carbon atoms contained in the additive P is calculated from the amount charged. was 20.0% by mass.

[Synthesis Example 7: Additive Q]
Additive Q was obtained according to the method for producing thermoplastic polymer III of Preparation Example 3 of International Publication No. 2015/137309. The monomers constituting Additive Q have a ratio of MMA/BA=84/16, and the unit amount of acrylic acid ester monomer having an alkyl group having 2 or more carbon atoms contained in Additive Q is calculated from the amount charged. was 16.0% by mass.

[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-A-2000-319516. The monomers constituting the additive R are MMA/BA/n-butyl methacrylate = 50/30/20, and have an alkyl group having 2 or more carbon atoms included in the additive R calculated from the amount charged. The amount of acrylic acid ester monomer units was 30.0% by mass.

[Manufacture 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 parts of Irg1076. .1 part was 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 to form pellets. An acrylic resin composition was obtained. The glass transition temperature of the obtained resin composition was 99°C.

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

<Example 1>
The obtained pellets of the acrylic resin composition of Production Example 1 were melt-extruded and extruded using a 40 mmφ (diameter) non-vented screw extruder (L/D = 33) equipped with a 400 mm wide T-die. The resulting film was cooled by sandwiching it between a pair of mirror-finished metal rolls and a rubber roll to form a film with a thickness of 50 μm. The extrusion molding conditions were a cylinder temperature of 240°C and a T-die temperature of 240°C. Further, the temperature of the mirror-finished metal roll was 85°C.
The obtained acrylic resin film was laminated with a semi-rigid vinyl chloride resin sheet, and a laminate was created by heating and pressing at 140° C. and a pressure of 2 MPa for 10 minutes.

<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.

<Example 17>
T850 was plasticized using a 30 mmφ extruder with a cylinder temperature of 240°C, and the pellets of the acrylic resin composition obtained in Production Example 14 were plasticized using a 40mmφ extruder with a cylinder temperature of 240°C. did. Next, an acrylic resin film (laminated film) having a thickness of 50 μm was formed using a 2-type, 2-layer multi-manifold die set at 240°C. Further, 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 with a semi-rigid vinyl chloride resin sheet, and a laminate was created by heating and pressing at 140° C. and a pressure of 2 MPa for 10 minutes.

<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.

<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.

<Comparative example 4>
A laminate was obtained in the same manner as in Example 1 except that a soft vinyl chloride resin sheet was used instead of the semi-hard vinyl chloride resin sheet.

<Comparative example 5>
In Example 1, a paper impregnated with semi-cured melamine resin, which is a thermosetting resin, was used instead of the semi-rigid vinyl chloride resin sheet, and a laminate was obtained by heating and pressing at 140° C. and a pressure of 4 MPa for 20 minutes. The acrylic resin film of the laminate and the melamine resin-impregnated paper did not adhere sufficiently and were easily peeled off.

The evaluation results of the laminates of Examples and Comparative Examples are shown in Table 3 below.

The above examples revealed the following. That is, the laminates obtained in Examples 1 to 18 showed no noticeable whitening or coloring after the hot water test, and had good water resistance. Moreover, the cutting workability was also good. In particular, the laminates obtained in Examples 2 to 12, 17, and 18 have low gloss and have good matte appearance, water resistance, and cutting workability, and have high industrial utility value.

On the other hand, the laminate obtained in Comparative Example 1 uses an acrylic resin composition that does not contain a hindered amine compound with a molecular weight of 1,000 or more, so it has poor water resistance and a large change in whiteness after the hot water test. was seen. Since the laminate obtained in Comparative Example 2 uses an acrylic resin composition containing a hindered amine compound whose molecular weight does not satisfy 1,000 or more, the haze value of the film is high and the design of the molded product is affected. It was inferior. In addition, the laminate obtained in Comparative Example 3 showed no discoloration after the hot water test because the acrylic ester monomer unit amount having an alkyl group having 2 or more carbon atoms contained in the acrylic resin composition exceeded 45% by mass. The water resistance was poor. Further, the laminate obtained in Comparative Example 4 had poor water resistance because the amount of plasticizer in the thermoplastic resin composition (II) exceeded 40% by mass. Furthermore, the laminate obtained in Comparative Example 5 had poor interlayer adhesion because it used a melamine resin, which is a thermosetting resin, in place of the thermoplastic resin composition (II).
Furthermore, Examples 1 and 4 had lower ΔE in the weather resistance test than Comparative Examples 3 and 4, and had excellent weather resistance.

Although the present invention has been described above with reference to the embodiments and examples, the present invention is not limited to the above embodiments and examples. The configuration and details of the present invention can be modified in various ways that can be understood by those skilled in the art within the scope of the present invention.

Applications of the laminate of the present invention are not particularly limited, and include, for example, roofing materials, siding materials, rain gutters, flooring materials, skin materials for building materials such as bathrooms and kitchens, skin materials for the interior and exterior of automobiles, and skin materials for furniture. It can be used for agricultural vinyl greenhouses.

Claims (9)

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 different composition from the acrylic resin composition (I). The molecular weight of the hindered amine compound is 1,000 or more, and 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 A laminate in which the thermoplastic resin composition (II) contains a plasticizer in an amount of 45% by mass or less based on the total amount of the material (I), and the thermoplastic resin composition (II) contains a plasticizer of 40% by mass or less based on the total amount of the thermoplastic resin composition (II). . The laminate according to claim 1, wherein the acrylic resin is core-shell rubber (A). The laminate according to claim 1 or 2, wherein the thermoplastic resin composition (II) contains a polyvinyl chloride resin. The laminate according to claim 1 or 2, wherein the layer made of the acrylic resin composition (I) has a tensile modulus of 900 MPa or more and 1,900 MPa or less. The laminate according to claim 1 or 2, wherein the hindered amine compound has a structure represented by the following formula (1).

The laminate according to claim 1 or 2, wherein the acrylic resin composition (I) contains a hydroxyl group-containing polymer (C1). The laminate according to claim 1 or 2, wherein the amount of monomer units having hydroxyl groups contained in the acrylic resin composition (I) is 5% by mass or less based on the total amount of the acrylic resin composition (I). The laminate according to claim 1 or 2, wherein the acrylic resin composition (I) has a glass transition temperature of 80°C or higher. The laminate according to claim 1 or 2, wherein the glossiness of at least one side measured at an incident angle of 60° is 110% or less.