JP6694317B2 - Laminated body and molded body, and methods for producing the same - Google Patents

Description

  The present invention relates to a laminated body and a molded body having the laminated body.

  Since (meth) acrylic resins have excellent optical properties such as transparency and light resistance, and have a beautiful appearance, they have been used in various products such as home electric appliances, electronic parts, mechanical parts, and automobile parts. It has been used for decorative purposes. However, since the (meth) acrylic resin is extremely brittle, it may be cracked during secondary processing such as cutting (trimming) or bonding with an adherend.

  As a method for improving the crack resistance of a (meth) acrylic resin, a (meth) acrylic resin composition obtained by alloying or blending various materials has been proposed. For example, in Patent Document 1, a base material composed of a block copolymer containing a (meth) acrylic acid ester polymer block and a conjugated diene polymer block and a methacrylic resin composition containing a methacrylic resin, and an acrylic block. A multilayer film having an adhesive / adhesive layer made of a copolymer is described, and improvement of toughness of a substrate made of a methacrylic resin composition is disclosed by containing a block copolymer.

In addition, three-dimensional surface decorative molding (hereinafter referred to as "TOM molding") has recently been used as a method for adhering a laminate having a base material and an adhesive layer to a three-dimensional adherend to obtain a molded body. However, since the laminate used is stretched and adhered to the adherend, the adhesive strength may be lower than that before stretching.
Therefore, Patent Document 2 has a base material having a storage elastic modulus of 1 × 10 ⁵ to 1 × 10 ⁸ Pa at 100 to 140 ° C. and a tacky adhesive layer containing a (meth) acrylic acid ester polymer block. A decorative sheet is disclosed, and it is disclosed that when the decorative sheet is adhered to an acrylonitrile-butadiene-styrene copolymer (ABS) adherend by TOM molding, the decorative sheet has excellent adhesiveness.

JP 2012-213911 A Japanese Patent Laid-Open No. 2012-077177

  However, the multilayer film described in Patent Document 1 has not been examined for viscous adhesion when stretch-molded, and the decorative sheet having an acrylic resin substrate described in Patent Document 2 has a trimming operation after stretch-molding. There is a problem that cracks sometimes occur, resulting in poor handleability and productivity. Further, a molded product obtained by bonding these films to an adherend made of a resin such as polycarbonate has a problem that the adhesive strength is lowered when placed in a high temperature environment of 100 ° C. or higher.

  An object of the present invention is to provide a laminate excellent in tacky adhesiveness and trimming property and a molded article excellent in heat resistance.

According to the invention, said object is
[1] 5 to 45% by mass of (meth) acrylic acid ester polymer block (a1) having a glass transition temperature of 50 ° C. or higher and (meth) acrylic acid ester polymer block (a2) having a glass transition temperature of 20 ° C. or lower. ) An adhesive layer comprising the thermoplastic resin composition (A) containing the (meth) acrylic block copolymer (a) containing 55 to 95 mass% of the adhesive layer,
A laminate having a substrate comprising a methacrylic resin (b) containing 80% by mass or more of a structural unit derived from methyl methacrylate and a methacrylic resin composition (B) containing a rubber component (c).
[2] The rubber component (c) comprises a methacrylic acid ester polymer block (d1) of 10 to 45 mass% and a structural unit of 50 to 90 mass derived from an acrylate ester having no substituent derived from an aromatic compound. % And an acrylic acid ester polymer block (d2) containing 55 to 90 mass% of a structural unit derived from a (meth) acrylic acid ester having a substituent derived from an aromatic compound (d2) A laminate of [1], which is a polymer (d),
[3] The rubber component (c) is an outer layer (e1) containing 80 to 100% by mass of a methacrylic acid ester, 70 to 99.8% by mass of an acrylic acid ester, and 0.2 to 30% by mass of a crosslinkable monomer. A multilayer structure (e) having an inner layer (e2) containing 1%, [1],
[4] A method for producing a laminate according to any one of [1] to [3], wherein the thermoplastic resin composition (A) and the methacrylic resin composition (B) are coextruded.
[5] A step of accommodating the laminate and the adherend of any one of [1] to [3] in a chamber box;
Depressurizing the chamber box;
Dividing the inside of the chamber box into two by the laminate; and applying the pressure in the chamber box without the adherend higher than the pressure in the chamber box with the adherend. Coating a body with said laminate;
A method for producing a molded body having
[6] The method for producing a molded product according to [5], further including a step of heating the laminate to a range of 90 to 150 ° C. to soften it.
[7] The method for producing a molded article according to [5] or [6], wherein the adherend is a polycarbonate resin, an ABS resin or an ABS / polycarbonate resin,
[8] A molded product having the laminate according to any one of [1] to [3] and an adherend,
[9] A molded product of [8] obtained by the method of [5], [6] or [7],
It is achieved by providing.

  The laminate of the present invention has excellent tackiness and trimming properties, and the molded product having the laminate of the present invention has excellent heat resistance.

[Thermoplastic resin composition (A)]
The thermoplastic resin composition (A) contains at least one (meth) acrylic block copolymer (a). The content of the (meth) acrylic block copolymer (a) in the thermoplastic resin composition (A) is preferably 30% by mass or more, more preferably from the viewpoint of tackiness and heat resistance of the molded product. Is 70% by mass or more, and more preferably 90% by mass or more.

  The (meth) acrylic block copolymer (a) has one or more (meth) acrylic acid ester polymer block (a1) having a glass transition temperature of 50 ° C. or higher and a glass transition temperature of 20 ° C. or lower (meth ) It is preferable to have one or more acrylic acid ester polymer blocks (a2). The adhesive layer made of the thermoplastic resin composition (A) containing such a (meth) acrylic block copolymer (a) is excellent in tackiness and adhesiveness.

  Examples of the (meth) acrylic acid ester used in the (meth) acrylic acid ester polymer block (a1) include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, and tert methacrylic acid. -Butyl, cyclohexyl methacrylate, isobornyl methacrylate, phenyl methacrylate, methacrylic acid esters such as 2-hydroxyethyl methacrylate; tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, phenyl acrylate, 2-hydroxy acrylate. An acrylic acid ester such as ethyl can be used. These may be used alone or in combination of two or more. Among these, methyl methacrylate is more preferable from the viewpoint of moldability and adhesiveness of the adhesive layer.

  Examples of the (meth) acrylic acid ester used in the (meth) acrylic acid ester polymer block (a2) include n-propyl methacrylate, n-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, and n-hexyl methacrylate. Methacrylic acid esters such as 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, phenoxyethyl methacrylate, and 2-methoxyethyl methacrylate; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, N-Butyl acrylate, isobutyl acrylate, sec-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, acrylate Dodecyl, benzyl acrylate, phenoxyethyl acrylate, acrylic acid esters such as 2-methoxyethyl acrylate. These may be used alone or in combination of two or more. Among these, from the viewpoint of adhesiveness of the adhesive layer, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, phenoxyethyl acrylate, acrylic acid 2-methoxyethyl is preferred.

  The (meth) acrylic block copolymer (a) has other polymer blocks in addition to the (meth) acrylic acid ester polymer block (a1) and the (meth) acrylic acid ester polymer block (a2). You may. Examples of the other polymer block include methacrylic acid, acrylic acid, styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, acrylonitrile, methacrylonitrile, ethylene, propylene, isobutene, butadiene, isoprene, octene, (Co) polymer block composed of monomer units such as vinyl acetate, maleic anhydride, vinyl chloride, vinylidene chloride and / or hydrogenated products thereof; polyethylene terephthalate, polybutylene terephthalate, polylactic acid, polyurethane, poly Examples thereof include polymer blocks made of dimethylsiloxane.

  The bonding form of the (meth) acrylic acid ester polymer block (a1) and the (meth) acrylic acid ester polymer block (a2) is not particularly limited, but from the viewpoint of easy production and adhesiveness of the adhesive layer, A triblock copolymer of the (meth) acrylic acid ester polymer block (a1)-(meth) acrylic acid ester polymer block (a2)-(meth) acrylic acid ester polymer block (a1) is preferable.

The glass transition temperatures of the (meth) acrylic acid ester polymer block (a1) and the (meth) acrylic acid ester polymer block (a2) are different from those of the (meth) acrylic block copolymer (a) by a differential scanning calorimeter (DSC). ) Is the extrapolation onset temperature of the transition region of the (meth) acrylic acid ester polymer block (a1) and the (meth) acrylic acid ester polymer block (a2) observed in the curve obtained by the analysis of FIG. Based on the curve obtained by the DSC measurement, in the (meth) acrylic block copolymer (a) used in the present invention, the (meth) acrylic acid ester polymer block (a1) and the (meth) acrylic acid ester polymer block A plurality of glass transition temperatures derived from (a2) are observed. The glass transition temperatures derived from the (meth) acrylic acid ester polymer block (a1) and the (meth) acrylic acid ester polymer block (a2) have the same chemical structure (monomer composition, stereochemistry) as those of the respective polymer blocks. Since the glass transition temperature is the same as or close to the glass transition temperature of a polymer having regularity), it can be easily attributed to which polymer block these glass transition temperatures originate. A polymer having the same chemical structure as that of the (meth) acrylic acid ester polymer block (a1) and the (meth) acrylic acid ester polymer block (a2) is obtained by converting the acrylic block copolymer (C) into ¹ H. -Chemical structure such as monomer composition and stereoregularity of the (meth) acrylic acid ester polymer block (a1) and the (meth) acrylic acid ester polymer block (a2) analyzed by NMR or ¹³ C-NMR And can be appropriately polymerized so that its chemical structure is reproduced.

  The weight average molecular weight of the (meth) acrylic block copolymer (a) is not particularly limited, but from the viewpoint of the moldability of the adhesive layer, it is preferably in the range of 10,000 to 500,000, more preferably 50, It is in the range of 000 to 200,000. The weight average molecular weight is a value calculated by gel permeation chromatography (hereinafter, referred to as “GPC”) analysis as a conversion value using standard polystyrene for preparing a calibration curve.

  The value of weight average molecular weight / number average molecular weight (hereinafter, referred to as “molecular weight distribution”) of the (meth) acrylic block copolymer (a) is 1.01 from the viewpoint of stickiness and molding processability of the adhesive layer. It is preferable that it is in the range of 2.20 to 2.20, and it is more preferable that it is in the range of 1.05 to 1.50. When the molecular weight distribution is larger than the above range, the adhesion of the adhesive layer tends to increase. If the molecular weight distribution is smaller than the above range, stretch moldability tends to deteriorate.

  The method for producing the (meth) acrylic block copolymer (a) is not particularly limited, and examples thereof include living anion polymerization disclosed in JP 2012-213911 A and JP 11-335432 A.

  The (meth) acrylic block copolymer (a) contains (meth) acrylic acid ester polymer block (a1) 5 to 45 mass% and (meth) acrylic acid ester polymer block (a2) 55 to 95 mass%. However, it preferably contains 20 to 30% by mass of the (meth) acrylic acid ester polymer block (a1) and 70 to 80% by mass of the (meth) acrylic acid ester polymer block (a2). When the (meth) acrylic acid ester polymer block (a1) is less than 5% by mass, the handleability tends to decrease, and when it is more than 45% by mass, the tackiness of the adhesive layer tends to decrease.

  The thermoplastic resin composition (A) is a polymer other than the (meth) acrylic block copolymer (a), a softening agent, a plasticizer, a lubricant, an adhesive, a tackifier, a processing aid, a heat stabilizer, Additives such as antioxidants, light stabilizers, antistatic agents, flame retardants, foaming agents, colorants, dyes, pigments and fillers may be included.

  The thickness of the adhesive layer is preferably in the range of 10 to 300 μm, more preferably 25 to 200 μm. If it is thicker than 300 μm, the flexibility and molding processability tend to decrease, and if it is thinner than 10 μm, the visco-adhesiveness tends to deteriorate.

  Examples of the method for molding the adhesive layer include a melt extrusion molding method, a melt injection molding method and a solution casting method, and the melt extrusion molding method is preferable from the viewpoint of productivity.

[Base material]
The base material is composed of a methacrylic resin (b) containing 80% by mass or more of a structural unit derived from methyl methacrylate and a methacrylic resin composition (B) containing a rubber component (c), and the methacrylic resin (b) is from 50 to 95. Preferably, the methacrylic resin composition (B) contains 5 to 50% by mass of the rubber component (c) and 70 to 90% by mass of the methacrylic resin (b) and 10 to 30% by mass of the rubber component (c). It is more preferable that the methacrylic resin composition (B) contains The methacrylic resin (b) contains 80% by mass or more, preferably 90% by mass or more, of a structural unit derived from methyl methacrylate.

  Examples of the monomer contained in the methacrylic resin (b) other than methyl methacrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and acrylic acid. sec-butyl, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, hexadecyl acrylate, dodecyl acrylate, acrylic Octadecyl acid, tetradecyl acrylate, behenyl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-ethoxyethyl acrylate, glycidyl acrylate, acrylate Acrylic esters such as allyl acid, cyclohexyl acrylate, norbornyl acrylate, isobornyl acrylate; ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-methacrylate. Butyl, tert-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxy methacrylate. Ethyl, 2-hydroxyethyl methacrylate, 2-ethoxyethyl methacrylate, glycidyl methacrylate, allyl methacrylate, cyclohexyl methacrylate, norbomethacrylate Methacrylic acid esters other than methyl methacrylate such as nil and isobornyl methacrylate; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, maleic acid and itaconic acid; ethylene, propylene, 1-butene, isobutene, 1- Olefins such as octene; conjugated dienes such as butadiene, isoprene, myrcene; styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, 1-vinylnaphthalene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecyl Aromatic vinyl compounds such as styrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, halogenated styrene; acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, vinyl acetate, vinylpyridine, vinyl. Ton, vinyl chloride, vinylidene chloride, vinylidene fluoride and the like.

  The method for producing the methacrylic resin (b) is not particularly limited, and a commercially available product may be used. As commercially available products, for example, "Parapet H1000B" (MFR: 22g / 10 minutes (230 ° C, 37.3N)), "Parapet GF" (MFR: 15g / 10 minutes (230 ° C, 37.3N)), "Parapet "EH" (MFR: 1.3g / 10min (230 ° C, 37.3N)), "Parapet HRL" (MFR: 2.0g / 10min (230 ° C, 37.3N)), "Parapet HRS" (MFR : 2.4 g / 10 minutes (230 ° C., 37.3 N)) and “Parapet G” (MFR: 8.0 g / 10 minutes (230 ° C., 37.3 N)) [Brand name, manufactured by Kuraray Co., Ltd.] Etc.

  The rubber component (c) is preferably a block copolymer or a multilayer structure which does not include a polymer block composed of a constitutional unit derived from a conjugated diene compound, and has a light resistance, a trimming property, a stretch moldability and a resistance to a base material. From the viewpoint of impact resistance, the block copolymer (d) or the multilayer structure (e) is more preferable. A block copolymer containing a polymer block composed of constitutional units derived from a conjugated diene compound is inferior in light resistance and thus not preferable.

  The block copolymer (d) is derived from the methacrylic acid ester polymer block (d1), 50 to 90% by mass of the structural unit derived from an acrylate ester having no substituent derived from an aromatic compound, and the aromatic compound. It contains an acrylic acid ester polymer block (d2) containing 10 to 50% by mass of a structural unit derived from a (meth) acrylic acid ester having a substituent. The proportion of the methacrylic acid ester polymer block (d1) in the block copolymer (d) is preferably in the range of 10 to 45% by mass, more preferably 20 to 30% by mass, from the viewpoint of stretch formability of the substrate. % Range. In addition, the proportion of the acrylic acid ester polymer block (d2) in the block copolymer (d) is preferably in the range of 55 to 90 mass% from the viewpoint of flexibility of the substrate, stretch formability, and impact resistance. Yes, and more preferably in the range of 70 to 80 mass%. When the block copolymer (d) contains a plurality of methacrylic acid ester polymer blocks (d1) and a plurality of acrylic acid ester polymer blocks (d2), the ratio is all methacrylic acid ester polymer blocks (d1) or It is calculated based on the total mass of the acrylate polymer block (d2).

  The methacrylic acid ester polymer block (d1) preferably contains 80% by mass or more, and more preferably 98% by mass or more of a structural unit derived from a methacrylic acid ester from the viewpoint of improving the trimming property of the substrate.

  Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate. , Isoamyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, 2-methacrylate Examples include hydroxyethyl, 2-methoxyethyl methacrylate, glycidyl methacrylate, and allyl methacrylate, which improve the trimming property of the base material. Methyl methacrylate is preferable from the viewpoint that.

  The methacrylic acid ester polymer block (d1) is, for example, acrylic acid ester, unsaturated carboxylic acid, aromatic vinyl compound, olefin, conjugated diene, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl acetate, vinyl pyridine, vinyl ketone, Structural units derived from monomers other than methacrylic acid esters such as vinyl chloride, vinylidene chloride, and vinylidene fluoride may be contained.

  The acrylic acid ester polymer block (d2) is, from the viewpoint of the trimming property of the base material, 50 to 90% by mass of the structural unit derived from an aromatic ester-free acrylic ester and derived from an aromatic compound. It is preferable to contain 10 to 50% by mass of a structural unit derived from a (meth) acrylic acid ester containing a substituent, and a structural unit derived from an acrylic acid ester having no substituent derived from an aromatic compound 60 to It is more preferable to contain 80% by mass and 20 to 40% by mass of a structural unit derived from a (meth) acrylic acid ester having a substituent derived from an aromatic compound.

  Examples of the acrylate ester having no substituent derived from an aromatic compound include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-acrylate. Butyl, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate , 2-methoxyethyl acrylate, glycidyl acrylate, allyl acrylate and the like.

  As the (meth) acrylic acid ester having a substituent derived from an aromatic compound, for example, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, styryl acrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, Examples thereof include styryl methacrylate, and from the viewpoint of trimming property, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, and benzyl acrylate are preferable.

  The method for producing the block copolymer (d) is not particularly limited, and a known method such as a method of living polymerization of the monomers forming each polymer block can be adopted.

  The multilayer structure (e) preferably has two layers, an inner layer (e2) and an outer layer (e1), and the inner layer (e2) and the outer layer (e1) are arranged in this order from the center layer to the outermost layer. It is more preferable to have at least one structure. The multilayer structure (e) may further have a crosslinkable resin layer (e3) inside the inner layer (e2) or outside the outer layer (e1).

  The inner layer (e2) is a mixture of 70 to 99.8% by mass of alkyl acrylate, 0.2 to 30% by mass of a crosslinkable monomer, and 0 to 29.8% by mass of another monofunctional monomer. It is preferably a layer composed of a crosslinked elastic body obtained by copolymerization.

  As such an acrylic acid alkyl ester, the number of carbon atoms of the alkyl group is in the range of 2 to 8, for example, butyl acrylate, 2-ethylhexyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n acrylate. -Butyl, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, 1-methylheptyl acrylate, acrylic acid 2-ethylhexyl and the like can be mentioned. From the viewpoint of trimming property, the alkyl acrylate is more preferably used in a proportion of 70 to 99.8% by mass in the total monomer mixture used for forming the crosslinked elastic body of the inner layer (e2). preferable.

  The crosslinkable monomer may be one having at least two polymerizable carbon-carbon double bonds in one molecule, and examples thereof include unsaturated carboxylic acid diesters of glycols such as ethylene glycol dimethacrylate and butanediol dimethacrylate; Alkenyl esters of unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, allyl cinnamate; polyalkenyl esters of polybasic acids such as diallyl phthalate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate; Examples thereof include unsaturated carboxylic acid esters of polyhydric alcohols such as methylolpropane triacrylate; divinylbenzene and the like, and alkenyl esters of unsaturated carboxylic acids and polyalkenyl esters of polybasic acids are preferable. From the viewpoint of improving the impact resistance and surface hardness of the substrate, the amount of the crosslinkable monomer is more preferably used in the range of 0.5 to 10% by mass in the total monomer mixture.

  Other monofunctional monomers that copolymerize with alkyl acrylates are, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, pentyl methacrylate. Methacrylic acid such as hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, myristyl methacrylate, palmityl methacrylate, stearyl methacrylate, behenyl methacrylate, phenyl methacrylate and benzyl methacrylate. Ester; styrene, α-methylstyrene, 1-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-d -4-benzyl styrene, 4- (phenylbutyl) styrene, aromatic vinyl monomers and halogenated styrene; acrylonitrile, methacrylonitrile; butadiene, and conjugated dienes such as isoprene and the like. From the viewpoint of improving the trimming property of the base material, the other monofunctional monomer is preferably 24.5% by mass or less in the total monomer mixture used for forming the polymer of the inner layer (e2).

  The outer layer (e1) is composed of a thermoplastic resin obtained by polymerizing a monomer mixture containing 80% by mass or more, and more preferably 85% by mass or more of methyl methacrylate, from the viewpoint of the trimming property of the base material. Is preferred. The monomer mixture is preferably 20 mass% of another monofunctional monomer such as alkyl acrylate such as methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate; acrylic acid; methacrylic acid. % Or less, more preferably 15% by mass or less.

  The ratio of the inner layer (e2) and the outer layer (e1) constituting the multilayer structure (e) to the multilayer structure (e) is determined by the mass of the multilayer structure (e) (from the viewpoint of trimming property of the obtained substrate). For example, when it is composed of two layers, the inner layer (e2) is preferably in the range of 40 to 70 mass% based on the total amount of the inner layer (e2) and the outer layer (e1), and the outer layer (e1) is 30 to 60 mass%. It is preferably in the range of%.

  The method for producing the multilayer structure (e) is not particularly limited, but it is preferably produced by emulsion polymerization from the viewpoint of controlling the layer structure of the multilayer structure (e).

  In the methacrylic resin composition (B), the proportion of the methacrylic resin (b) is preferably in the range of 50 to 95% by mass, more preferably 70 to 90% by mass. The proportion of the rubber component (c) is preferably in the range of 5 to 50 mass%, more preferably 10 to 30 mass%. When the ratios of the methacrylic resin (b) and the rubber component (c) are in the above ranges, the base material made of the methacrylic resin composition (B) has excellent trimming property.

  The methacrylic resin composition (B) contains various additives such as an anti-sticking agent, an ultraviolet absorber, a light stabilizer, an antiaging agent, a plasticizer, a heat stabilizer, a lubricant, a processing aid, an antistatic agent and an antioxidant. , A colorant, a dye, a pigment, and an impact resistance auxiliary agent may be contained.

The methacrylic resin composition (B) is preferably melt-kneaded using a known mixing or kneading device such as a kneader ruder, an extruder, a mixing roll, a Banbury mixer or the like in order to enhance the dispersibility of each constituent component.
Further, the rubber component (c) is dissolved in a solution of methyl methacrylate constituting the methacrylic resin (b), and the methyl methacrylate is polymerized to prepare a methacrylic resin composition (B) containing the rubber component (c). You can also do it.

  The base material can be manufactured by a known method such as a T-die method, an inflation method, a melt casting method, and a calender method.

  The thickness of the substrate is preferably 500 μm or less, more preferably 50 to 200 μm. If it is thicker than 500 μm, the handling property and the trimming property tend to deteriorate.

  The substrate may be colored. The coloring method is not particularly limited, and examples thereof include a method of incorporating a colorant into the methacrylic resin composition (B), a dyeing method of immersing a substrate in a liquid in which the colorant is dispersed, and coloring.

  From the viewpoint of scratch resistance, the surface of the base material preferably has a pencil hardness of a base material having a thickness of 75 μm measured according to JIS-K5600, which is harder than B and more preferably harder than F.

[Laminate]
The laminate of the present invention has at least one adhesive layer made of the thermoplastic resin composition (A) and at least one base material made of the methacrylic resin composition (B). From the viewpoint of handleability, the thickness of the laminate is preferably 500 μm or less.

  The laminate of the present invention may have a metal layer and / or a metal oxide layer. As the metal, for example, aluminum, silicon, magnesium, palladium, zinc, tin, nickel, silver, copper, gold, indium, stainless steel, chromium, titanium or the like can be used. Examples of the metal oxide include aluminum oxide, zinc oxide, antimony oxide, indium oxide, calcium oxide, cadmium oxide, silver oxide, gold oxide, chromium oxide, silicon oxide, cobalt oxide, zirconium oxide, tin oxide, and oxide. Titanium, iron oxide, copper oxide, nickel oxide, platinum oxide, palladium oxide, bismuth oxide, magnesium oxide, manganese oxide, molybdenum oxide, vanadium oxide, barium oxide and the like can be used. These metals and metal oxides may be used alone or as a mixture of two or more kinds. A vacuum deposition method is usually used as a method for providing these metal layers and / or metal oxide layers, but methods such as ion plating, sputtering, and CVD (Chemical Vapor Deposition) may also be used.

  The laminate of the present invention may have a pattern layer, and preferably has a pattern layer between the base material and the adhesive layer. The pattern layer is formed by a known printing method such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, sublimation transfer printing, and inkjet printing.

  The method for producing the laminate is, for example, a method of laminating a film or sheet made of the thermoplastic resin composition (A) and a substrate between heating rolls, a method of thermocompression bonding with a press, a pressure molding or a vacuum molding or a TOM molding. A method of laminating at the same time, a method of laminating with an adhesive layer interposed (wet lamination); a method of laminating a thermoplastic resin composition (A) melt-extruded from a T die onto a substrate; a thermoplastic resin composition Examples thereof include a method of coextruding (A) and the methacrylic resin composition (B). Among these methods, the method of co-extruding the thermoplastic resin composition (A) and the methacrylic resin composition (B) is preferable because the step of separately molding the base material is unnecessary.

  From the viewpoint of chemical resistance and scratch resistance, the laminate of the present invention preferably has a cured resin layer on the surface layer of the substrate. The cured resin layer is obtained by curing a curable resin. As the curable resin, for example, acrylic resin, urethane acrylate resin, silicone acrylate resin, epoxy resin, ester resin or the like can be used.

  The method of forming the cured resin layer is preferably a printing method or a coating method from the viewpoint of productivity. In this case, a curable resin is dissolved or dispersed in a solvent to prepare a coating material, which is applied to a substrate and dried by heating to form a cured resin layer.

  Examples of the printing method include known printing methods such as a gravure printing method, a screen printing method, and an offset printing method. Examples of the coating method include a flow coating method, a spray coating method, a bar coating method, a gravure coating method, a gravure reverse coating method, a kiss reverse coating method, a micro gravure coating method, a roll coating method, a blade coating method, a rod coating method, and a roll. Known methods such as a doctor coat method, an air knife coat method, a comma roll coat method, a reverse roll coat method, a transfer roll coat method, a kiss roll coat method, a curtain coat method and a dipping coat method can be mentioned.

  As a solvent for dissolving or dispersing the curable resin, for example, methanol, ethanol, isopropyl alcohol, n-butanol, ethylene glycol, diacetone alcohol, 2-methoxyethanol (methylcellosolve), 2-ethoxyethanol (ethylcellosolve), 2 -Alcohols such as butoxyethanol (butyl cellosolve), diethylene glycol, acetocyanohydrin; aromatic hydrocarbons such as xylene, toluene, benzene; aliphatic hydrocarbons such as hexane, pentane; halogenated hydrocarbons such as chloroform, carbon tetrachloride; phenol , Phenol such as cresol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetone, cyclohexanone; diethyl ether, methoxytoluene, 1,2-dimethoxyethane, 1 Ethers such as 2-dibutoxyethane, 1,1-dimethoxymethane, 1,1-dimethoxyethane, 1,4-dioxane and tetrahydrofuran; fatty acids such as formic acid, acetic acid and propionic acid; acid anhydrides such as acetic anhydride; acetic acid Esters such as ethyl, n-propyl acetate, butyl acetate, butyl formate, 1-acetoxy-2-ethoxyethane, 2-acetoxy-1-methoxypropane; amines such as ethylamine, toluidine, 2-aminoethanol, diethanolamine, morpholine; Examples thereof include amides such as dimethylformamide and dimethylacetamide; thiophene, dimethylsulfoxide; water and the like. These may be used alone or in combination of two or more.

[Molded body]
The molded product of the present invention has the laminate and the adherend of the present invention. Examples of the material forming the adherend include thermoplastic resins, thermosetting resins, ceramics, metals, wood and non-wood fibers, and thermoplastic resins are preferable from the viewpoint of moldability.

  Examples of the thermoplastic resin forming the adherend include polycarbonate (PC) resin, polyethylene terephthalate resin, polyamide resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, (meth) acrylic resin, ABS resin, ABS. / Polycarbonate resin and the like can be mentioned, and from the viewpoint of moldability, impact resistance and heat resistance, polycarbonate resin, ABS resin or ABS / polycarbonate resin is preferable. Examples of the thermosetting resin include epoxy resin, phenol resin, and melamine resin. Examples of non-wood fibers include kenaf base materials.

  The ceramics forming the adherend means a non-metallic inorganic material, and examples thereof include metal oxides, metal carbides, and metal nitrides. Specific examples thereof include glass, cements, alumina, zirconia, zinc oxide ceramics, barium titanate, lead zirconate titanate, silicon carbide, silicon nitride, and ferrites.

  Examples of the metal forming the adherend include iron, copper, aluminum, magnesium, nickel, chromium, zinc, and alloys containing them. Further, it may be a molded product having a metal surface formed by plating such as copper plating, nickel plating, chrome plating, tin plating, zinc plating, platinum plating, gold plating and silver plating.

  The laminate of the present invention has a peel strength of preferably 10 N / 25 mm or more, more preferably 20 N / 25 mm or more, further preferably 25 N / 25 mm when TOM-molded at 110 ° C. by the method described later in Examples. That is all. By having such a property of the laminated body, even when the molded body is heated, for example, in a car under the hot sun, floating or peeling between the laminated body and the adherend is less likely to occur.

  The molded product of the present invention has the laminate of the present invention on the surface of the adherend, and is thereby excellent in surface hardness, surface gloss, heat resistance and the like. When the laminated body has a printed layer, a picture or the like is clearly displayed, and when the laminated body has a metal layer, a mirror-like gloss like metal is obtained.

  Examples of the method for adhering the laminate to the surface of the adherend to obtain the molded article of the present invention include injection molding method, vacuum molding method, pressure molding method, compression molding method, TOM molding and the like. TOM molding is preferable from the viewpoint of shapeability.

  As a preferred embodiment, a method for producing a molded product by TOM molding will be exemplified. As a vacuum forming apparatus for TOM forming the laminate, for example, the vacuum forming apparatus described in JP-A-2002-067137 or the coating apparatus described in JP-A-2005-262502 can be preferably used. Is equipped with a chamber box in which the stack and the adherend are installed and closed to reduce the pressure.

  A method for producing a molded body by TOM molding includes a step of accommodating a laminated body and an adherend in a chamber box; a step of decompressing the inside of the chamber box; a step of dividing the inside of the chamber box by the laminated body; And a step of making the pressure in the chamber box without the adherend higher than the pressure in the chamber box with the adherend to cover the adherend with the laminate. In the step of accommodating the laminated body and the adherend in the chamber box, the step of dividing the inside of the chamber box by the laminated body may be performed at the same time.

  In the step of reducing the pressure inside the chamber box, the pressure inside the chamber box is preferably in the range of 0.1 to 20 kPa, and more preferably in the range of 0.1 to 10 kPa. When the pressure is higher than 20 kPa, it becomes difficult to shape the laminate accurately in the step of covering the adherend with the laminate, and when the pressure is less than 0.1 kPa, the time required for molding increases and the production Sex tends to decrease.

  It is preferable that the above-mentioned method for producing a molded body further includes a step of heating and softening the laminate. In this step, the temperature of the laminated body is preferably heated to a range of 90 to 150 ° C, more preferably 110 to 140 ° C. When the temperature of the laminated body is lower than 90 ° C., the laminated body is not sufficiently softened, resulting in defective molding, or the adhesive strength of the laminated body in the molded body tends to decrease. On the other hand, when the temperature exceeds 150 ° C., excessive softening or deterioration of the laminated body occurs, and the quality of the molded body tends to deteriorate. The step of decompressing the inside of the chamber box and the step of heating and softening the laminated body may be performed at the same time.

In the step of covering the adherend with the laminate by setting the pressure in the chamber box without the adherend higher than the pressure in the chamber box with the adherend, a person without the adherend The pressure inside the chamber box is preferably in the range of 50 to 500 kPa, and more preferably in the range of 100 to 400 kPa. When the pressure in the chamber box having no adherend in the step is less than 50 kPa, it becomes difficult to accurately shape the laminate in the step of covering the adherend with the laminate. When the pressure in the chamber box without the adherend is higher than 500 kPa, it takes time to bring the molded body to atmospheric pressure (about 100 kPa) when taking out the molded body from the chamber box, and the productivity tends to decrease.
As a method of making the pressure in the chamber box without the adherend higher than the pressure in the chamber box with the adherend, for example, open the chamber box without the adherend to the atmospheric pressure. Or a method of supplying compressed air to the chamber box having no adherend. By supplying compressed air, the laminate can be stretch-formed into the form of the adherend more accurately.

  The laminate and the molded article of the present invention utilize the excellent stretch moldability, trimming property, adhesive strength, and heat resistance of the laminate, and are required to have a design property, particularly decorative molding. For example, billboard parts such as advertising towers, stand signs, sleeve signs, transom signs, rooftop signs, etc .; display parts such as showcases, partition boards, store displays; fluorescent light covers, mood lighting covers, lamp shades, light ceilings, light walls, Lighting parts such as chandeliers; interior parts such as furniture, pendants, mirrors; doors, domes, safety window glass, partitions, stair wainscots, balcony wainscots, building parts such as roofs of leisure buildings, automobile interior and exterior parts, bumpers Car exterior parts such as car exterior parts; audiovisual nameplates, stereo covers, vending machines, mobile phones, electronic parts such as personal computers; incubators, fixed , Dial, greenhouse, a large water tank, water tank box, bathroom member, clock panel, bathtub, sanitary, desk mat, game parts, toys, musical instruments, wallpaper; marking film, is suitably used in various consumer electronics products and the like.

  Next, the present invention will be described in more detail with reference to Examples and the like, but the present invention is not limited to these. In addition, each evaluation in this invention was performed by the following method.

[Number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (Mw / Mn)]
The gel permeation chromatograph analysis uses a gel permeation chromatograph (manufactured by Tosoh Corp .; HLC-8020) equipped with a column in which one TSKgel G2000HHR manufactured by Tosoh Corp. and two GMHHR-M manufactured by Tosoh Corp. are connected in series and eluted. Tetrahydrofuran was passed as a liquid at 1.0 ml / min, the column temperature was set to 40 ° C., and the measurement was performed with a differential refractive index (RI) meter. The calibration curve was prepared using standard polystyrene.

[Polymerization conversion of monomer]
The polymerization conversion rate of each monomer is GL Sciences Inc. Using a gas chromatograph (manufactured by Shimadzu Corporation; GC-14A) equipped with INERT CAP 1 (df = 0.4 μm, 0.25 mm ID × 60 m) manufactured by Shimadzu Corporation as a column, conditions of an injection temperature of 180 ° C. and a detector temperature of 180 ° C. Was analyzed. The column temperature was maintained at 60 ° C. for 5 minutes after the start of measurement, then increased at 10 ° C./minute, and maintained at 200 ° C. for 10 minutes.

[Constitutional ratio of (meth) acrylic acid ester block]
The composition ratio of each polymer block was determined by dissolving a sample in deuterated chloroform and measuring ¹ H-NMR ( ¹ H-nuclear magnetic resonance) using a nuclear magnetic resonance apparatus (JNM-LA400, manufactured by JEOL Ltd.). Sought by.

[Glass transition temperature (Tg)]
The glass transition temperature (Tg) was the extrapolation start temperature in the curve obtained by DSC measurement using a DSC measuring device (manufactured by Mettler; DSC-822) at a temperature rising rate of 10 ° C./min.

[Peel strength]
The adherend side of the molded body produced by the method described below was fixed to a stainless steel (SUS) plate with a strong adhesive tape (manufactured by Nitto Denko Corp .; Hyper Joint H9004) to improve the peel strength between the adhesive layer and the adherend. Using a tabletop precision universal testing machine (AGS-X manufactured by Shimadzu Corporation), the peeling angle was 90 °, the pulling speed was 300 mm / min, and the environmental temperature was 23 ° C. according to JIS K 6854-1. The adhesiveness of the laminate was evaluated.

[Trimming]
The molded body produced by the method described below was cut with scissors, and the propagation of cracks from the cut portion was visually confirmed in the direction of 20 to 170 ° with respect to the cutting direction.
○: The crack did not propagate from the cut portion.
Δ: A crack propagates less than 3 mm from the cut portion.
X: A crack propagates from the cut portion by 3 mm or more.

[Heat-resistant]
The molded article produced by the method described below was left standing at 100 ° C. for 48 hours using a 3-bath type constant temperature bath (manufactured by Mita Sangyo Co., Ltd .; DE-303), and then the appearance of the molded article was visually observed.
◯: No floating or peeling was observed between the laminate and the adherend.
X: Floating or peeling is observed between the laminate and the adherend.

<< Synthesis Example 1 >> (meth) acrylic block copolymer (a-1)
In a reactor whose inside was degassed and replaced with nitrogen, 1040 parts by mass of dry toluene, 52.0 parts by mass of 1,2-dimethoxyethane, and isobutylbis (2,6-di-tert-butyl-4-methylphenoxy) were added at 25 ° C. ) 60.0 parts by mass of a toluene solution containing 40.2 mmol of aluminum, 5.17 parts by mass of a mixed solution of cyclohexane and n-hexane containing 2.98 mmol of sec-butyllithium, and 25.0 parts by mass of methyl methacrylate. It was added in order and reacted at 25 ° C. for 1 hour. At this time, the polymerization conversion rate of methyl methacrylate was 99.9% or more. Next, the reaction liquid was cooled to −30 ° C., 204.0 parts by mass of n-butyl acrylate was added dropwise over 2 hours, and after completion of the dropwise addition, the mixture was stirred at −30 ° C. for 5 minutes. The polymerization conversion rate of n-butyl acrylate at this time was 99.9% or more. Subsequently, 35.0 parts by mass of methyl methacrylate was added to this reaction liquid, and after stirring overnight at 25 ° C., 3.50 g of methanol was added to stop the polymerization reaction. At this time, the polymerization conversion rate of methyl methacrylate was 99.9% or more. The obtained reaction liquid was poured into a large amount of methanol, and the residue was dried for 12 hours under the conditions of 80 ° C. and 1 torr (about 133 Pa) to obtain pellets of the (meth) acrylic block copolymer (a-1). ..
As a result of ¹ H-NMR measurement and GPC measurement, the obtained (meth) acrylic block copolymer (a-1) was composed of polymethyl methacrylate-n-butyl polyacrylate-polymethyl methacrylate. A block copolymer, the two methyl methacrylate polymer blocks were of equal weight, having 22.5 wt% methyl methacrylate polymer block and 77.5 wt% n-butyl acrylate polymer block. .. The weight average molecular weight (Mw) is 115,000, the number average molecular weight (Mn) is 104,500, the molecular weight distribution (Mw / Mn) is 1.10, and the Tg of the methyl methacrylate polymer block is 110 ° C. The Tg of the n-butyl acrylate polymer block was -47 ° C.

<< Synthesis Example 2 >> (meth) acrylic block copolymer (a-2)
A triblock copolymer composed of poly (methyl methacrylate)-(n-butyl polyacrylate)-(methyl polymethacrylate) was prepared by the same procedure as in Synthesis Example 1 except that the amounts of methyl methacrylate and n-butyl acrylate were changed. , Methyl methacrylate polymer block 23.7% by weight and n-butyl acrylate polymer block 76.3% by weight, Mw 81,000, Mn 73,000, Mw / Mn 1.11. A pellet of a certain (meth) acrylic block copolymer (a-2) was obtained.

<< Synthesis Example 3 >> (meth) acrylic block copolymer (a-3)
A triblock copolymer composed of poly (methyl methacrylate)-(n-butyl polyacrylate)-(methyl polymethacrylate) was prepared by the same procedure as in Synthesis Example 1 except that the amounts of methyl methacrylate and n-butyl acrylate were changed. , 50% by weight of methyl methacrylate polymer block and 50% by weight of n-butyl acrylate polymer block, Mw of 70,000, Mn of 63,000, Mw / Mn of 1.11. Pellets of the acrylic block copolymer (a-3) were obtained.

<< Synthesis Example 4 >> Rubber component (c-1)
The reactor in which the inside was degassed and replaced with nitrogen was dried at 25 ° C. at 776 parts by mass of toluene, 46.0 parts by mass of 1,2-dimethoxyethane, and isobutylbis (2,6-di-tert-butyl-4-methylphenoxy). ) 19.6 parts by mass of a toluene solution containing 8.8 mmol of aluminum, 1.8 mmol of sec-butyllithium, and 45.3 ml of methyl methacrylate were added in this order, and the mixture was reacted at 25 ° C for 1 hour. The temperature of the reaction liquid was cooled to −15 ° C., and a mixed liquid of 53.9 ml of n-butyl acrylate and 11.3 parts by mass of benzyl acrylate was added dropwise over 1 hour. Subsequently, 18.8 parts by mass of methyl methacrylate was added and the reaction solution was heated to 25 ° C. and stirred for 5 hours. This reaction liquid was poured into a large amount of methanol, and the residue was dried for 12 hours under the conditions of 80 ° C. and 1 torr (about 133 Pa) to obtain a rubber component (c-1).

<< Synthesis example 5 >> Rubber component (c-2)
In a reactor equipped with a stirrer, a thermometer, a nitrogen gas introduction pipe, a monomer introduction pipe and a reflux condenser, 1050 parts by mass of ion-exchanged water, 0.5 parts by mass of sodium dioctylsulfosuccinate and 0.7 parts by mass of sodium carbonate. Was charged, the inside of the container was sufficiently replaced with nitrogen gas, and then the internal temperature was set to 80 ° C. After 0.25 parts by mass of potassium persulfate was charged into the reactor and stirred for 5 minutes, a simple mixture of methyl methacrylate: methyl acrylate: allyl methacrylate = 94: 5.8: 0.2 (mass ratio) was added. 245 parts by mass of the monomer mixture was continuously added dropwise over 50 minutes, and after completion of the addition, a polymerization reaction was performed for another 30 minutes.
Next, 0.32 parts by mass of potassium peroxodisulfate was put into the same reactor and stirred for 5 minutes, and thereafter, it was composed of 80.6% by mass of n-butyl acrylate, 17.4% by mass of styrene and 2% by mass of allyl methacrylate. 315 parts by mass of the monomer mixture was continuously added dropwise over 60 minutes, and after completion of the addition, a polymerization reaction was performed for another 30 minutes.
Subsequently, 0.14 parts by mass of potassium peroxodisulfate was charged into the reactor and stirred for 5 minutes, and then 140 parts by mass of a monomer mixture composed of methyl methacrylate: methyl acrylate = 94: 6 (mass ratio). It was continuously added dropwise over 30 minutes, and after the completion of the addition, a polymerization reaction was performed for 60 minutes to obtain a rubber component (c-2).

<< Production Example 1 >> Methacrylic resin composition (B-1)
80 parts by mass of methacrylic resin (b-1) (manufactured by Kuraray Co .; Parapet HRS) and 20 parts by mass of the rubber component (c-1) obtained in Synthesis Example 4 were twin-screw extruder (manufactured by Toshiba Machine Co., Ltd .; TEM-28, After melt-kneading at 230 ° C., the pellets of the methacrylic resin composition (B-1) were manufactured by melt-kneading at 230 ° C.

<< Production Example 2 >> Methacrylic resin composition (B-2)
After melt-kneading 88 parts by mass of methacrylic resin (b-2) (manufactured by Kuraray Co .; Parapet EH) and 12 parts by mass of rubber component (c-2) obtained in Synthesis Example 5 at 230 ° C. using a twin-screw extruder. Then, the methacrylic resin composition (B-2) was extruded into a strand shape and cut to obtain pellets of the methacrylic resin composition (B-2).

<< Production Example 3 >> Methacrylic resin composition (B-3)
72 parts by mass of the methacrylic resin (b-2) and 28 parts by mass of the rubber component (c-2) were melt-kneaded at 230 ° C. using a twin-screw extruder, and then extruded into a strand shape and cut to obtain a methacrylic resin composition ( B-3) pellets were produced.

[Example 1]
The pellets of the (meth) acrylic block copolymer (a-1) obtained in Synthesis Example 1 and the pellets of the methacrylic resin composition (B-1) obtained in Production Example 1 were each screwed with an L / D of 32. The single-screw extruder (GM ENGINEERING Co., Ltd .; VGM25-28EX) is charged into the hopper and the coextrusion method using a multi-manifold die in which the extrusion temperature is set to 240 ° C. is a width of 30 cm consisting of two layers, A laminated body having a thickness of 230 μm was obtained. The thickness of each layer of the laminate was controlled by the extrusion flow rate, and the thickness of the adhesive layer was 80 μm and the thickness of the substrate was 150 μm. Table 1 shows the evaluation results of the obtained laminate.

  Subsequently, a molded body was manufactured using the obtained multilayer film. That is, TOM molding was performed using a molding machine (NGF-0406-T manufactured by Fuse Vacuum Co., Ltd.) that forms the chamber box (C) by closing the chamber box (C1) and the chamber box (C2). In the chamber box (C2) of the molding machine, a sheet-shaped adherend (width 25 mm × width 250 mm × width 160 mm × depth 25 mm) and polycarbonate resin (Asahi Glass Co., Ltd .; Carboglass CGPC20) (Length 150 mm × thickness 0.3 mm) and the obtained laminated body are put therein, an adherend is placed at the bottom of the mold, and the laminated body is such that the adhesive layer of the laminated body faces the mold and the adherend. Is placed, and the laminated body is sandwiched between the chamber box (C1) and the chamber box (C2) so that the laminated body divides the chamber box (C) into two, and the chamber box (C1) and the chamber box (C2) are closed and the chamber box ( C) was formed. Then, the pressure in the chamber box (C) was reduced to 0.5 kPa in 90 seconds. At this time, since the laminate bends due to the non-equilibrium of the degree of reduced pressure and the weight of the laminate itself, the pressure inside the chamber box (C1) and the chamber box (C2) was appropriately adjusted to keep the laminate parallel. The laminated body is heated by an infrared heating device in parallel with the depressurization, and when the temperature of the laminated body reaches 110 ° C., the inside of the chamber box (C1) is quickly returned to atmospheric pressure to cover the adherend with the laminated body. Then, a molded body in which the laminate was stretch-bonded to the adherend was molded. The temperature of the laminate was measured with a radiation thermometer. Then, the chamber box (C) was opened, and the mold and the molded body were taken out from the chamber box (C2). The evaluation results of the obtained molded body are shown in Table 1.

[Example 2]
In Example 1, except that the adherend made of ABS resin (Sumitomo Bakelite Co., Ltd .; Tough Ace EAR802) was used instead of the adherend made of polycarbonate resin (width 25 mm x length 150 mm x thickness 0.3 mm). A molded body was obtained in the same manner as in Example 1.

[Example 3]
A molded body was obtained in the same manner as in Example 2 except that the heating temperature of the laminate was changed from 110 ° C to 100 ° C.

[Example 4]
A molded body was obtained in the same manner as in Example 2 except that the heating temperature of the laminate was changed from 110 ° C to 130 ° C.

[Example 5]
In Example 1, an adherend (width 25 mm x length 150 mm x thickness 0.3 mm) made of ABS / polycarbonate resin (manufactured by Japan A & L Co .; H-270) was used instead of the adherend made of polycarbonate resin. A molded body was obtained in the same manner as in Example 1 except that the above was used.

[Example 6]
A laminate and a molded product were obtained in the same manner as in Example 1 except that the methacrylic resin composition (B-2) obtained in Production Example 2 was used in place of the methacrylic resin composition (B-1). Obtained.

[Example 7]
A laminate and a molded product were obtained in the same manner as in Example 1 except that the methacrylic resin composition (B-3) obtained in Production Example 3 was used in place of the methacrylic resin composition (B-1). Obtained.

[Example 8]
Pellets of (meth) acrylic block copolymer (a-1) obtained in Synthesis Example 1, pellets of methacrylic resin composition (B-3) obtained in Production Example 3 and methacrylic resin composition obtained in Production Example 1 The pellets of the product (B-1) were respectively put into the hopper of a single-screw extruder (GM ENGINEERING; VGM25-28EX) having a screw with L / D of 32, and the extrusion temperature was set to 240 ° C. A multi-manifold die was used to obtain a three-layer laminate having a width of 30 cm and a thickness of 305 μm by a coextrusion method. The thickness of each layer of the laminate is controlled by the extrusion flow rate, the thickness of the adhesive layer made of the (meth) acrylic block copolymer (a-1) is 80 μm, and the thickness of the methacrylic resin composition (B-3) is a base. The thickness of the material was 150 μm, the thickness of the base material made of the methacrylic resin composition (B-1) was 75 μm, and the layers were laminated in this order. Further, a molded body was obtained in the same manner as in Example 1 by using the obtained laminated body.

[Example 9]
A laminated body and a molded body were obtained in the same manner as in Example 1 except that the thickness of the adhesive layer was changed from 80 μm to 30 μm.

[Example 10]
Example 1 except that the (meth) acrylic block copolymer (a-2) obtained in Synthesis Example 2 was used in place of the (meth) acrylic block copolymer (a-1) in Example 1. A laminate and a molded body were obtained in the same manner as in.

[Comparative Example 1]
A laminate and a molded body were obtained in the same manner as in Example 1 except that the methacrylic resin (b-2) was used instead of the methacrylic resin composition (B-1).

[Comparative example 2]
Example 1 except that the (meth) acrylic block copolymer (a-3) obtained in Synthesis Example 3 was used in place of the (meth) acrylic block copolymer (a-1) in Example 1. A laminate and a molded body were obtained in the same manner as in.

[Comparative Example 3]
In Example 5, a thermoplastic resin composition (A'-1) composed of a random copolymer having a structural unit derived from an alkyl acrylate instead of the (meth) acrylic block copolymer (a-1). A laminate and a molded body were obtained in the same manner as in Example 5 except that the thickness of the adhesive layer was changed from 80 μm to 50 μm by using (Nihon Kako Co., Ltd .; MHM-FWD50).

[Reference Example 1]
In Example 1, instead of the laminate composed of the (meth) acrylic block copolymer (a-1) and the methacrylic resin composition (B-1), an acrylic resin (A′-2) having a thickness of 30 μm was used. Same as Example 1 except that 3M wrap film series 1080 (manufactured by 3M; 1080-G54) having an adhesive layer made of and a base material made of polyvinyl chloride resin (B′-1) having a thickness of 90 μm was used. A molded body was obtained.

  From Table 1, it can be seen that the laminate of the present invention is excellent in tackiness and trimming property even after stretch forming. Further, from Comparative Example 3, when an adherend made of a polycarbonate resin is used, even if the peel strength is sufficiently high, when the molded body is heated, floating or peeling may occur between the adherend and the adhesive layer. It can be seen that the molded products having the laminate of the present invention according to Examples 1 to 8 do not cause floating or peeling even when heated, and have excellent heat resistance.

  From the above results, the laminate of the present invention is excellent in adhesiveness and trimming property, and the molded product having the laminate of the present invention is excellent in heat resistance. Therefore, the laminate of the present invention is excellent in decorativeness. It can be suitably used for the production of molded products.

Claims (9)

5 to 45% by mass of (meth) acrylic acid ester polymer block (a1) having a glass transition temperature of 50 ° C. or higher and (meth) acrylic acid ester polymer block (a2) 55 of having a glass transition temperature of 20 ° C. or lower An adhesive layer made of a thermoplastic resin composition (A) containing a (meth) acrylic block copolymer (a) containing 95% by mass;
Methacrylic resin (b) containing 80% by mass or more of a structural unit derived from methyl methacrylate and 10 to 45% by mass of a methacrylic acid ester polymer block (d1), and acrylic acid having no substituent derived from an aromatic compound. Acrylic ester polymer block (d2) containing 50 to 90% by mass of structural unit derived from ester and 10 to 50% by mass of structural unit derived from (meth) acrylic acid ester having a substituent derived from aromatic compound. A laminate having a substrate comprising a methacrylic resin composition (B) containing a rubber component (c) which is a block copolymer (d) containing 55 to 90 mass% . 5 to 45% by mass of (meth) acrylic acid ester polymer block (a1) having a glass transition temperature of 50 ° C. or higher and (meth) acrylic acid ester polymer block (a2) 55 of having a glass transition temperature of 20 ° C. or lower An adhesive layer made of a thermoplastic resin composition (A) containing a (meth) acrylic block copolymer (a) containing 95% by mass;
  Methacrylic resin (b) containing 80% by mass or more of structural units derived from methyl methacrylate, and outer layer (e1) containing 80 to 100% by mass of methyl methacrylate, and 70 to 99.8% by mass of alkyl acrylate and crosslinking. Having a base material composed of a methacrylic resin composition (B) containing a rubber component (c) which is a multilayer structure (e) having an inner layer (e2) containing 0.2 to 30 mass% of a polymerizable monomer. body. Based on the mass of the multilayer structure (e), the inner layer (e2) of the multilayer structure polymer (e) is 40 to 70% by mass, and the outer layer (e1) of the multilayer structure polymer (e) is 30 to 60% by mass. The laminated body according to claim 2 , which is   The method for producing a laminate according to claim 1, wherein the thermoplastic resin composition (A) and the methacrylic resin composition (B) are coextruded. A step of accommodating the laminate and the adherend according to any one of claims 1 to 3 in a chamber box;
Depressurizing the chamber box;
Dividing the inside of the chamber box by the laminated body; and increasing the pressure in the chamber box without the adherend higher than the pressure in the chamber box with the adherend, Coating an adherend with the laminate;
A method for producing a molded article having the following.   The method for producing a molded article according to claim 5, further comprising a step of heating the laminate to 90 to 150 ° C. to soften it.   The method for producing a molded article according to claim 5, wherein the adherend is a polycarbonate resin, an ABS resin, or an ABS / polycarbonate resin.   A molded body comprising the laminate according to any one of claims 1 to 3 and an adherend.   The molded product according to claim 8, which is obtained by the method according to claim 5, 6 or 7.