JPWO2019039550A1 - Laminated body and manufacturing method thereof - Google Patents

Abstract

A laminate having a stretched film and a metal layer and having a total light transmittance of 50% or less, wherein the stretched film contains a (meth)acrylic resin and has a haze of 1% or less. The content of the elastomer in the stretched film is preferably 30 parts by mass or less based on 100 parts by mass of the (meth)acrylic resin. The stretched film preferably has a dimensional change rate of 0.1% or less before and after being held at 85° C. for 30 minutes. It is preferable that the stretched film contains an ultraviolet absorber, and the content of the ultraviolet absorber in the stretched film is 0.1 to 10 parts by mass with respect to 100 parts by mass of the (meth)acrylic resin.

Description

The present invention relates to a laminate and a method for manufacturing the same.

Conventionally, in order to give a metallic luster to resin-made automobile wheel caps, bumpers, emblems, etc., it is common to apply a transparent luster paint after directly plating a resin member with metal. Was the way.

However, metal plating and coating are costly and have problems in environmental hygiene. Further, since the coating has a large variation in thickness, it is difficult to obtain a uniform appearance and it is difficult to provide stable quality. As a solution to such a problem, instead of metal plating, a metal thin film is formed on a base film to produce a metal decorative film, and instead of painting, the metal decorative film is applied to an adherend. There is a method of pasting.

For example, Patent Document 1, a biaxially stretched polyethylene terephthalate film, made of an acrylic resin film or a polycarbonate resin film, and the maximum height average R _tm of the rear surface is 0.1 to 2.0 [mu] m, the haze value is 0 There is disclosed a metal-tone sheet having a metal vapor deposition layer containing at least one selected from tin, gold and indium on the back surface of a transparent resin film of 0.1 to 4.0%.

In Patent Document 2, a transparent acrylic film is used as a base sheet, a metal thin film layer is formed on the base sheet, and a metal thin film insert film obtained by laminating a plastic sheet on the base film is preformed into a desired shape. , A method of manufacturing a metal thin film insert film molded article in which a metal thin film insert film is inserted into a mold and a molding resin is injected onto the plastic sheet side to be integrated.

In addition, Patent Document 3 discloses a transparent conductive film having a transparent conductive layer on at least one surface of a base film having a ring structure in the main chain and having an acrylic resin having a glass transition temperature of 120° C. or more as a main component. It is disclosed.

JP, 2008-110518, A JP, 10-180795, A JP, 2008-179677, A

However, when a conventional laminate having an acrylic film layer and a metal layer is attached to an adherend and then punched out into a desired shape to cut off the remaining portion, cracks (flaps) and/or cracks are formed from the cut surface. Was occurring. Further, depending on the acrylic film used, the metallic luster may be impaired. Furthermore, the transparent conductive film as disclosed in Patent Document 3 has high transparency and lacks in metallic luster, and is therefore unsuitable as a metallic decorative film.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a laminate having excellent punching resistance and metallic luster, and a method for producing the laminate.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention including the following aspects. That is, the present invention relates to the following [1] to [12].

[1] A laminate having a stretched film and a metal layer and having a total light transmittance of 50% or less, wherein the stretched film contains a (meth)acrylic resin and has a haze of 1% or less. body.
[2] The laminated body according to the above [1], wherein the stretched film contains an elastomer, and the content of the elastomer in the stretched film is 30 parts by mass or less based on 100 parts by mass of the (meth)acrylic resin. ..
[3] The stretched film contains an ultraviolet absorber, and the content of the ultraviolet absorber in the stretched film is 0.1 to 10 parts by mass with respect to 100 parts by mass of the (meth)acrylic resin. 1] or the laminated body as described in [2].
[4] The laminate according to any one of the above [1] to [3], wherein the stretched film has a dimensional change rate of 0.1% or less before and after being held at 85° C. for 30 minutes.
[5] The laminate according to any one of the above [1] to [4], wherein the stretched film has a thickness of 5 to 200 μm.
[6] The laminate according to any one of [1] to [5] above, wherein the metal layer contains at least one selected from the group consisting of indium, aluminum, chromium, gold, silver and tin.
[7] The layered product according to any one of the above [1] to [6], wherein the metal layer has a thickness of 10 to 500 nm.
[8] The laminate according to any one of [1] to [7], which has an impact strength of 4 J or more.
[9] The laminated body according to any one of the above [1] to [8], wherein the stretched film and the metal layer are in contact with each other.
[10] The laminate according to any one of the above [1] to [9], which has a thickness of 5 to 500 μm.
[11] A metallic decorative film comprising the laminate according to any one of [1] to [10].
[12] A molded product including the laminate and the adherend according to any one of the above [1] to [10].
[13] The method for producing a laminate according to any one of the above [1] to [10], wherein a raw film containing a (meth)acrylic resin is stretched 1.5 to 8.0 times. A method for producing a laminate, comprising: a step of producing the stretched film; and a step of forming a metal layer on the stretched film.

According to the present invention, it is possible to provide a laminate excellent in punching resistance and metallic luster and a method for producing the laminate.

Hereinafter, an example of an embodiment to which the present invention is applied will be described. Numerical values specified in this specification are values obtained by the methods disclosed in the embodiments or examples. Other embodiments are also included in the scope of the present invention as long as they match the spirit of the present invention.

The laminate of the present invention has a stretched film and a metal layer and has a total light transmittance of 50% or less. The stretched film contains a (meth)acrylic resin and has a haze of 1% or less.

(Stretched film)
The stretched film contains a (meth)acrylic resin. Examples of the (meth)acrylic resin include polymethyl methacrylate and styrene-methyl methacrylate resin. In addition, in this specification, a (meth)acrylic resin refers to a methacrylic resin and/or an acrylic resin. The (meth)acrylic resin may be a heat-resistant (meth)acrylic resin modified by imide cyclization, lactone cyclization, methacrylic acid modification or the like. Further, the stretched film may contain one kind or two or more kinds of these (meth)acrylic resins.

The ratio of the structural unit derived from methyl methacrylate in the (meth)acrylic resin is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and further It is preferably 99% by mass or more, and particularly preferably 100% by mass. That is, the ratio of the structural unit derived from a monomer other than methyl methacrylate is preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and further It is preferably 1% by mass or less, and particularly preferably 0% by mass.

Examples of the monomer other than methyl methacrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, acrylic acid. t-butyl, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, acrylic acid Acrylic esters such as 2-hydroxyethyl, 2-ethoxyethyl acrylate, glycidyl acrylate, allyl acrylate, cyclohexyl acrylate, norbornyl acrylate, isobornyl acrylate; ethyl methacrylate, n-propyl methacrylate, methacryl Isopropyl acetate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid Pentadecyl, dodecyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-ethoxyethyl methacrylate, glycidyl methacrylate, allyl methacrylate, cyclohexyl methacrylate, norbornyl methacrylate. , Methacrylic acid esters other than methyl methacrylate such as isobornyl methacrylate; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, maleic acid, itaconic acid; ethene, propylene, 1-butene, isobutene, 1-octene Olefins such as butadiene; isoprene, myrcene and other conjugated dienes; styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene and other aromatic vinyl compounds; acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, vinyl acetate , Vinyl pyridine, vinyl ketone, vinyl chloride, vinylidene chloride, vinylidene fluoride and the like. These monomers may be used alone or in combination of two or more.

The (meth)acrylic resin has a syndiotacticity (rr) in triplet display of preferably 65% or more, more preferably 70 to 90%, further preferably 72 to 85%. When the syndiotacticity (rr) is 65% or more, the surface hardness and heat resistance of the obtained laminate are increased. The syndiotacticity (rr) of the (meth)acrylic resin can be determined by the method described below in Examples.

From the viewpoint of heat resistance and surface hardness, the stretched film preferably contains 10% by mass or more of a (meth)acrylic resin having a syndiotacticity (rr) of 65% or more in triplets, and 40% by mass. % Or more, more preferably 50% by mass or more, still more preferably 55% by mass or more. On the other hand, from the viewpoint of moldability and product cost, the content of the (meth)acrylic resin having a syndiotacticity (rr) of 65% or more in triplets is preferably 70% by mass or less. Is more preferably 50% by mass or less, and further preferably 30% by mass or less.

The weight average molecular weight (Mw) of the (meth)acrylic resin is preferably 40,000 to 200,000, more preferably 60,000 to 150,000, and further preferably 70,000 to 120,000. The molecular weight distribution (ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), Mw/Mn) of the (meth)acrylic resin is preferably 1.0 to 1.8, more preferably 1.0. ˜1.4, particularly preferably 1.03 to 1.3. When a (meth)acrylic resin having a molecular weight (Mw) or a molecular weight distribution (Mw/Mn) within the above range is used, the stretched film has excellent mechanical strength. Mw and Mw/Mn can be controlled by adjusting the type and/or amount of the polymerization initiator used during production.
Mw and Mn are values obtained by converting the chromatogram measured by gel permeation chromatography (GPC) into the molecular weight of standard polystyrene, and can be specifically obtained by the method described later in the examples.

The method for producing the (meth)acrylic resin is not particularly limited, and it can be obtained by polymerizing one or more kinds of monomers containing methyl methacrylate, preferably 80% by mass or more, under suitable conditions.

From the viewpoint of heat resistance, the glass transition temperature (Tg) of the (meth)acrylic resin is preferably 100° C. or higher, more preferably 110° C. or higher, further preferably 120° C. or higher, and particularly preferably It is 122° C. or higher. The glass transition temperature (Tg) of the (meth)acrylic resin can be determined according to JIS K 7121 (2012), and specifically, it can be determined by the method described below in Examples.

The stretched film may contain a resin other than the (meth)acrylic resin. Examples of the resin other than the (meth)acrylic resin include polycarbonate resins such as bisphenol A type polycarbonate; polystyrene, styrene-acrylonitrile resin, styrene-maleic anhydride resin, styrene-maleimide resin, styrene-based thermoplastic elastomer, and the like. Aromatic vinyl resins or hydrogenated products thereof; amorphous polyolefins, transparent polyolefins with a finer crystal phase, polyolefin resins such as ethylene-methyl methacrylate resin; polyethylene terephthalate, cyclohexanedimethanol, isophthalic acid, etc. Polyester resins such as modified polyethylene terephthalate, polyethylene naphthalate and polyarylate; polyamide resins; polyimide resins; polyether sulfone resins; cellulose resins such as triacetyl cellulose resins; polyphenylene oxide resins; phenoxy resins Resin etc. are mentioned. The stretched film may contain only one kind of these resins, or may contain two or more kinds thereof. Among these, the stretched film preferably contains a polycarbonate resin and/or a phenoxy resin. When the stretched film contains a polycarbonate-based resin and/or a phenoxy-based resin, the dimensional change rate of the film is reduced, the stretchability of the film is improved, and the metallic luster of the laminate is further improved.

When the stretched film contains a resin other than the (meth)acrylic resin, the content thereof is preferably 20 parts by mass or less, more preferably 10 parts by mass or less with respect to 100 parts by mass of the (meth)acrylic resin. Yes, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less. When the content of the resin other than the (meth)acrylic resin is within the range, the laminate has excellent surface hardness and weather resistance.

The stretched film may include an elastomer. Examples of the elastomer include (meth)acrylic elastic particles, a (meth)acrylic block copolymer in which an acrylic acid ester polymer block (b1) and a methacrylic acid ester polymer block (b2) are bonded ( (Meth)acrylic elastomers; silicone elastomers; styrene thermoplastic elastomers such as SEPS, SEBS, SIS; olefin elastomers such as IR, EPR and EPDM. These elastomers may be used alone or in combination of two or more. Among these, (meth)acrylic elastomers are preferable, and (meth)acrylic elastic particles are more preferable, from the viewpoint that the laminated body is further excellent in punching resistance and metallic luster. When the stretched film contains an ultraviolet absorber, it is preferable that the elastomer contains a (meth)acrylic block copolymer. When the stretched film contains the (meth)acrylic block copolymer, mold stains and roll stains due to the ultraviolet absorber can be suppressed, and continuous productivity can be improved.

The content of the elastomer in the stretched film is preferably 30 parts by mass or less, more preferably 19 parts by mass or less, still more preferably 9 parts by mass or less, particularly preferably 4 parts by mass with respect to 100 parts by mass of the (meth)acrylic resin. It is as follows. When the content of the elastomer is within such a range, the laminate has a more excellent metallic luster and the surface hardness tends to be improved. On the other hand, from the viewpoint of improving the punching resistance of the laminate and suppressing the mold stains and roll stains due to the ultraviolet absorber to improve continuous productivity when the ultraviolet absorber is contained, the content of the elastomer in the stretched film Is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more.
In addition, the range of the above content includes an embodiment in which the elastomer is not included.

As an example of the (meth)acrylic elastomer, an acrylic elastic polymer containing a structural unit derived from an acrylic acid acyclic alkyl ester as a main component can be given. The (meth)acrylic elastomer may be composed only of the acrylic elastic polymer, or may contain an acrylic elastic polymer, such as (meth)acrylic elastic particles described later. .. In the acrylic elastic polymer, the content of the structural unit derived from the acrylic acid acyclic alkyl ester is preferably 50 to 100% by mass, more preferably 70 to 99.8% by mass. The acyclic alkyl group in the acrylic acid acyclic alkyl ester has a carbon number of 4 to 8, specifically, for example, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n. -Octyl group and isomer groups thereof are preferable. Further, the acrylic elastic polymer may include a structural unit derived from a monomer other than the acrylic acid acyclic alkyl ester, and examples of such a monomer include methyl methacrylate and ethyl methacrylate. Methacrylic acid alkyl esters such as; styrene monomers such as styrene and alkylstyrene; unsaturated nitriles such as acrylonitrile and methacrylonitrile; 2-chloroethyl vinyl ether; ethylene glycol (meth)acrylate, ethoxy-diethylene glycol acrylate, methoxy -Alkylene glycol (meth)acrylates such as triethylene glycol acrylate, 2-ethylhexyl-diglycol acrylate, methoxy-polyethylene glycol acrylate, methoxydipropylene glycol acrylate, phenoxydiethylene glycol acrylate, phenoxy-polyethylene glycol acrylate, nonylphenol ethylene oxide adduct acrylate And so on.

The acrylic elastic polymer may have randomly the structural units derived from the acyclic alkyl ester of acrylic acid and the structural units derived from the crosslinkable monomer. Examples of the crosslinkable monomer include allyl (meth)acrylate, methallyl (meth)acrylate, diallyl maleate, triethylene glycol diacrylate, polyethylene glycol diacrylate, 1.6-hexanediol diacrylate, and 1-hexanediol diacrylate. , 9-nonanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate and the like can be mentioned. From the viewpoint of toughness, the content of the structural unit derived from the crosslinkable monomer in the acrylic elastic polymer is preferably 0.2 to 30% by mass, more preferably 0.3 to 10% by mass, and further preferably It is 0.5 to 5 mass %.

The (meth)acrylic elastic particles, which are one preferred embodiment of the (meth)acrylic elastomer, may be particles composed of a single polymer, or particles in which at least two layers of polymers having different elastic moduli are formed. May be The (meth)acrylic elastic particles are, from the viewpoint of further punching resistance of the laminate, a polymer containing a structural unit derived from a diene monomer as a main component and/or the above-mentioned acrylic elastic polymer ( A core-shell particle having a multilayer structure composed of a layer containing a polymer containing a structural unit derived from an acyclic alkyl ester of acrylic acid as a main component) and a layer containing another polymer is preferable. A core-shell particle having a two-layer structure composed of a layer containing a polymer and a layer containing a methacrylic polymer covering the outer layer, or a layer containing a methacrylic polymer and an acrylic elastic polymer coating the outer layer. It is more preferable that the core-shell particles have a three-layer structure composed of a layer containing the methacrylic polymer and a layer containing a methacrylic polymer covering the outside thereof. From the viewpoint of heat resistance, the core-shell particles having the three-layer structure are preferable. More preferable.

The methacrylic polymer forming the core-shell particles is preferably a polymer containing a structural unit derived from a non-cyclic methacrylic acid alkyl ester as a main component. In the methacrylic polymer, the content of the structural unit derived from the methacrylic acid acyclic alkyl ester is preferably 50 to 100% by mass, more preferably 80 to 100% by mass from the viewpoint of fluidity and heat resistance. is there. The methacrylic acid acyclic alkyl ester is preferably methyl methacrylate from the viewpoints of fluidity and heat resistance, and the methacrylic polymer forming the core-shell particles contains 80 to 100% by mass of methyl methacrylate unit. Is most preferred.

The (meth)acrylic elastic particles have a number average particle diameter of preferably 10 to 250 nm, more preferably 20 to 150 nm, and further preferably 40 to 130 nm. When the number average particle diameter of the (meth)acrylic elastic particles is within the range, the laminate has further excellent punching resistance and metallic luster, and whitening hardly occurs when stretched. The number average particle size of the (meth)acrylic elastic particles is based on a micrograph observed by staining a sample prepared by melt-kneading the (meth)acrylic elastic particles with a methacrylic resin with ruthenium oxide. Can be decided. Here, ruthenium oxide dyes the layer containing the acrylic elastic polymer, but does not dye the layer containing the methacrylic polymer, so the number of core-shell particles of the above-mentioned two-layer structure or three-layer structure The average particle size is estimated to correspond to a value that does not include the thickness of the outermost layer containing the methacrylic polymer.

The method for producing the (meth)acrylic elastic particles is not particularly limited, and the (meth)acrylic elastic particles can be produced by a method according to a known method (for example, International Publication No. 2016/121868, International Publication No. 2014/167868, etc.). ..

A polymer block in a (meth)acrylic block copolymer in which an acrylic acid ester polymer block (b1) and a methacrylic acid ester polymer block (b2) which are another embodiment of the (meth)acrylic elastomer are bonded. There is no particular limitation on the bonding form of (b1) and the polymer block (b2), and for example, a diblock copolymer represented by (b1)-(b2); (b1)-(b2)-(b1) or ( triblock copolymer represented by b2)-(b1)-(b2); (b1)-((b2)-(b1))n, (b1)-((b2)-(b1))n- (B2), (b2)-((b1)-(b2))n (n is an integer) or other multiblock copolymers; ((b1)-(b2))n-X, ((b2 )-(B1)) n-X (X is a coupling residue) and the like. From the viewpoint of productivity, a diblock copolymer represented by (b1)-(b2), (b2)-(b1)-(b2) or (b1)-(b2)-(b1). A triblock copolymer is preferable, and the triblock copolymer represented by (b2)-(b1)-(b2) from the viewpoints of fluidity of the resin composition at the time of melting, and surface smoothness and haze of the laminate. Coalescence is more preferred. In this case, the two polymer blocks (b2) bonded to both ends of the polymer block (b1) are composed of the types of the constituent monomers, the ratio of structural units derived from methacrylic acid ester, the weight average molecular weight and the stereoregularity. Each sex may independently be the same or different. Further, the (meth)acrylic block copolymer may further contain another polymer block.

The polymer block (b1) constituting the (meth)acrylic block copolymer has a structural unit derived from an acrylate ester as a main constituent unit. The proportion of the structural unit derived from an acrylate ester in the polymer block (b1) is preferably 50% by mass or more, more preferably 70% by mass or more, from the viewpoint of further punching resistance of the laminate. It is more preferably 90% by mass or more, and particularly preferably 100% by mass.

Examples of the acrylate ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, t-butyl acrylate, and acrylic. Amyl acid, isoamyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, isobornyl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, acrylic acid 2-hydroxyethyl, 2-methoxyethyl acrylate, glycidyl acrylate, allyl acrylate and the like can be mentioned. The polymer block (b1) can be formed by polymerizing these acrylates alone or in combination of two or more. Among them, the polymer block (b1) is preferably a polymer obtained by polymerizing n-butyl acrylate alone, from the viewpoints of economic efficiency and further punching resistance.

The polymer block (b1) may contain a structural unit derived from a monomer other than an acrylic acid ester, and the ratio thereof is preferably 50% by mass or less from the viewpoint of further punching resistance of the laminate. It is preferably 30% by mass or less, more preferably 10% by mass or less, and particularly preferably 0% by mass.

As the monomer other than the acrylic ester, for example, methacrylic acid ester, unsaturated carboxylic acid, aromatic vinyl compound, olefin, conjugated diene, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl acetate, vinyl pyridine, Examples thereof include vinyl ketone, vinyl chloride, vinylidene chloride, vinylidene fluoride and the like. The polymer block (b1) can be formed by copolymerizing one of these monomers other than the acrylic ester alone or in combination of two or more with the above-mentioned acrylic ester.

The ratio of the polymer block (b1) in the (meth)acrylic block copolymer is from the viewpoint of transparency, surface hardness of the laminate, moldability, surface smoothness of the laminate, impact resistance, and heat resistance. The total amount of the polymer block (b1) and the polymer block (b2) is 100% by mass, preferably 60% by mass or less, more preferably 57% by mass or less, and further preferably 53% by mass or less. .. Further, it is preferably 30% by mass or more, more preferably 35% by mass or more, and further preferably 40% by mass or more.

The polymer block (b2) constituting the (meth)acrylic block copolymer has a structural unit derived from methacrylic acid ester as a main structural unit. From the viewpoint of fluidity and heat resistance, the proportion of structural units derived from methacrylic acid ester in the polymer block (b2) is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably It is 95% by mass or more, and particularly preferably 100% by mass.

Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, methacrylic acid. Amyl acid, isoamyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, methacrylic acid 2-hydroxyethyl, 2-methoxyethyl methacrylate, glycidyl methacrylate, allyl methacrylate and the like can be mentioned. Among these, from the viewpoint of improving transparency and heat resistance, methacrylic acid such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate and isobornyl methacrylate. Alkyl esters are preferred, and methyl methacrylate is more preferred. The polymer block (b2) can be formed by polymerizing these methacrylic acid esters alone or in combination of two or more.

The polymer block (b2) may contain a structural unit derived from a monomer other than a methacrylic acid ester, and the ratio thereof is preferably 20% by mass or less, more preferably 10 from the viewpoint of fluidity and heat resistance. The content is preferably not more than 5% by mass, more preferably not more than 5% by mass, and particularly preferably 0% by mass.

As the monomer other than the methacrylic acid ester, for example, acrylic acid ester, unsaturated carboxylic acid, aromatic vinyl compound, olefin, conjugated diene, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl acetate, vinyl pyridine, Examples thereof include vinyl ketone, vinyl chloride, vinylidene chloride, vinylidene fluoride and the like. The polymer block (b2) can be formed by copolymerizing one of these monomers other than methacrylic acid ester alone or in combination of two or more with the above-mentioned methacrylic acid ester.

The proportion of the polymer block (b2) in the (meth)acrylic block copolymer is from the viewpoint of transparency, surface hardness of the laminate, moldability, surface smoothness of the laminate, and impact resistance. The total amount of (b1) and the polymer block (b2) is 100% by mass, preferably 40% by mass or more, more preferably 43% by mass or more, still more preferably 47% by mass or more. Further, it is preferably 70% by mass or less, more preferably 65% by mass or less, and further preferably 60% by mass or less.

The method for producing the (meth)acrylic block copolymer is not particularly limited, and a method according to a known method (for example, International Publication No. 2016/121868, JP-A-2017-78168, etc.) may be adopted. it can. For example, a method of living polymerization of monomers constituting each polymer block is generally used, and an organic alkali metal compound is used as a polymerization initiator in the presence of a mineral acid salt such as an alkali metal salt or an alkaline earth metal salt. Anionic polymerization in the presence of an organic aluminum compound using an organic alkali metal compound as a polymerization initiator; a polymerization method using an organic rare earth metal complex as a polymerization initiator; an α-halogenated ester compound And a radical polymerization in the presence of a copper compound. Moreover, the method of polymerizing the monomers forming each block using a polyvalent radical polymerization initiator or a polyvalent radical chain transfer agent, and producing a mixture containing a (meth)acrylic block copolymer can also be mentioned. ..

The stretched film may include additives. The type of additive is not particularly limited, and examples thereof include an ultraviolet absorber, an infrared absorber, a polymer processing aid, a light stabilizer, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a pigment, a dye, and a matting agent. Agents, fillers, impact resistance aids, plasticizers and the like. One kind of the additive may be used alone, or two or more kinds thereof may be used in combination at an arbitrary ratio. The stretched film preferably contains a polymer processing aid from the viewpoint of enhancing the moldability of the stretched film. Although these additives may be organic compounds or inorganic compounds, organic compounds are preferable from the viewpoint of dispersibility in the resin composition.

The content of the additive in the stretched film is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and further preferably 3 parts by mass or less with respect to 100 parts by mass of the (meth)acrylic resin. .. When the content of the additive is within the above range, the laminate has excellent impact resistance and surface hardness.

Here, when the single-layer transparent film is used as a decorative film or the like, light is usually emitted from only one surface. On the other hand, since the laminate of the present invention has the metal layer, the stretched film is exposed to the incident light and the light reflected by the metal layer, and the deterioration due to the light is likely to proceed. Therefore, the stretched film is required to have a higher weather resistance than the ordinary transparent film, and therefore it is preferable that the stretched film contains an ultraviolet absorber. The content of the ultraviolet absorber in the stretched film is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, and further preferably 100 parts by mass of the (meth)acrylic resin. Is 0.5 to 3 parts by mass. When the content of the ultraviolet absorber is within such a range, a laminate having excellent weather resistance and hardly causing whitening even after long-term storage can be obtained. Examples of the ultraviolet absorber include benzophenone compounds, salicylate compounds, benzoate compounds, triazole compounds and triazine compounds. The ultraviolet absorbers may be used alone or in combination of two or more at an arbitrary ratio. Among these, triazole compounds and/or triazine compounds are preferable from the viewpoint of long-term stability. Further, from the viewpoint of further increasing the weather resistance, it is also preferable to use a light stabilizer and/or an antioxidant together with the ultraviolet absorber. Examples of the light stabilizer include hindered amine light stabilizers and the like. Examples of antioxidants include phenolic antioxidants.

As the polymer processing aid, polymer particles having a particle diameter of 0.05 to 0.5 μm, which can be produced by an emulsion polymerization method, can be used. When the stretched film contains the polymer processing aid, the thickness accuracy and the film-forming stability are improved when the resin composition is molded, and fisheye defects can be reduced. Representative products of the polymer processing aid include Kane Ace PA series (manufactured by Kaneka), Metabrene (registered trademark) P series (manufactured by Mitsubishi Chemical), and Paraloid K series (manufactured by Dow Chemical). .. Among these, from the viewpoint of reducing fisheye defects of the stretched film, molding stability at the time of film formation, and particularly improving molding stability of the film end portion, methyl methacrylate is 60 to 90% by mass, and alkyl acrylate is 10 to 10% by mass. A polymer processing aid containing 40% by mass is preferable, Metabrene (registered trademark) P530A, P550A and Paraloid K125 are more preferable, and metabrene (registered trademark) P550A is particularly preferable.

The polymer particles constituting the polymer processing aid may be single layer particles composed of a polymer having a single composition ratio and a single intrinsic viscosity, or may be two or more kinds of polymer particles having different composition ratios or intrinsic viscosities. It may be a multi-layered particle composed of coalesced particles. Among these, particles having a two-layer structure having a polymer layer having a low intrinsic viscosity in the inner layer and a polymer layer having a high intrinsic viscosity of 5 dl/g or more in the outer layer are preferable.

When the polymer processing aid is a single layer particle, the intrinsic viscosity is preferably 3 to 6 dl/g. If the intrinsic viscosity is too small, the effect of improving moldability is low. If the intrinsic viscosity is too large, the melt fluidity of the resin composition tends to deteriorate.

The method for molding the raw film containing the (meth)acrylic resin, which is the base of the stretched film, is not particularly limited, but, for example, the melt extrusion method is preferable. The melt extrusion method is not particularly limited, and the melt extrusion method known in the art can be used, and for example, the T die method, the inflation method and the like can be used. At this time, the molding temperature is preferably 150 to 350°C, more preferably 200 to 300°C, and further preferably 240 to 280°C.

When a raw film is formed by the T-die method, a T-die can be connected to the tip of a known single-screw extruder or a twin-screw extruder to obtain a raw film extruded in a film shape.

The extruder preferably has one or more open vents. By using such an extruder, decomposed products and volatile components can be sucked from the open vent portion, and the quality of the obtained resin composition can be improved. Further, the extruder preferably has a polymer filter for removing foreign matters. Examples of the structure of the polymer filter include a leaf disk type and a candle type. Further, the extruder preferably has a gear pump in order to stabilize the discharge amount of the resin composition. Known gear pumps can be used. When the extruder has an open vent part, a gear pump and a polymer filter, it is preferable to connect the extruder, the gear pump, the polymer filter and the die in this order from the viewpoint of reducing foreign matters and suppressing vent up. Further, in order to prevent deterioration of the resin composition in the extruder, it is preferable to mold while passing nitrogen through the extruder.

As one embodiment for producing a raw film, it is preferable to take out and sandwich the extruded film-shaped molten resin between mirror-finished rolls or mirror-finished belts from the viewpoint of surface smoothness and thickness uniformity of the stretched film. Both the mirror surface roll and the mirror surface belt are preferably made of metal. More preferably, the mirror roll is a combination of a metal rigid roll and a metal elastic roll. The linear pressure between the mirror surface roll or the mirror surface belt is preferably 10 N/mm or more, more preferably 30 N/mm or more, from the viewpoint of surface smoothness. The surface temperature of the mirror surface roll or the mirror surface belt is preferably 60° C. or higher, more preferably 70° C. or higher from the viewpoint of surface smoothness, haze, appearance and the like. Further, it is preferably 130° C. or lower, and more preferably 100° C. or lower.

Further, as another embodiment for producing a raw film, the extruded film-like molten resin, from the viewpoint of surface smoothness and thickness uniformity of the stretched film, contact and adhere to a mirror surface roll by an adhesion assisting means, It is preferable to cool and solidify. Examples of the adhesion auxiliary device include an electrostatic adhesion device, an air knife, an air chamber, a vacuum chamber and the like. Among these, from the viewpoint of manufacturing stability, it is preferable to use an electrostatic contact device as the contact auxiliary device.

When both edge pinning and wire pinning are used as the adhesion assisting device, it is preferable to arrange the edge pinning and the wire pinning in this order from the upstream side. Further, it is more preferable that the wire pinning is arranged on the downstream side, including the position where the temperature of the molten resin on the mirror surface roll becomes the glass transition temperature, and on the upstream side of the position where it is separated from the mirror surface roll.

From the viewpoint of productivity, the thickness of the raw film is preferably 40 to 500 μm, more preferably 80 to 400 μm, further preferably 100 to 300 μm, still more preferably 120 to 200 μm. Here, the thickness of the original film is an average value of the central portion of 50 mm with respect to the entire width of the original film.

The raw film is formed into a film and then subjected to a stretching treatment to become a stretched film. The stretched film may be a uniaxially stretched film or a biaxially stretched film, but a biaxially stretched film is preferable from the viewpoint of further enhancing the punching resistance of the laminate. The stretching treatment improves the mechanical strength of the film and improves punching resistance. The stretching method is not particularly limited, and examples thereof include a simultaneous biaxial stretching method, a sequential biaxial stretching method, a tuber stretching method, and a rolling method. The stretching treatment preferably has a preheating step, a stretching step, and a heat setting step in this order, and more preferably has a preheating step, a stretching step, a heat setting step, and a relaxation step in this order.

In the preheating step, the temperature of the raw fabric film is preferably not less than the glass transition temperature of the raw fabric film and not more than 40° C. higher than the glass transition temperature, more preferably not less than 5° C. higher than the glass transition temperature of the raw fabric film and The temperature is not higher than the glass transition temperature by 30°C. When the temperature of the raw film in the preheating step is within the range, breakage is less likely to occur in the stretching step during production of the stretched film, productivity is improved, and the laminate has excellent stretchability. When the raw fabric film has a plurality of glass transition temperatures, the highest value can be adopted as a standard for the temperature range of the raw fabric film.

In the stretching step, the temperature of the raw fabric film (stretching temperature) is preferably not less than 5° C. higher than the glass transition temperature of the raw fabric film and not higher than 40° C. higher than the glass transition temperature, and more preferably glass of the raw fabric film. It is at least 10° C. higher than the transition temperature and at most 35° C. higher than the glass transition temperature, more preferably at least 20° C. higher than the glass transition temperature of the original film and at most 30° C. higher than the glass transition temperature. Particularly preferably, the temperature is not less than 22° C. higher than the glass transition temperature of the raw film and not more than 27° C. higher than the glass transition temperature. When the temperature of the raw film in the stretching step is within the range, breakage is less likely to occur in the stretching step, productivity is improved, and the laminate has excellent stretchability. When the raw fabric film has a plurality of glass transition temperatures, the highest value can be adopted as a standard for the temperature range of the raw fabric film.

In the stretching step, the stretching ratio is preferably 1.5 to 8.0 times, more preferably 2.0 to 6.0 times, and further preferably 2.5 to 4.0 times. When the draw ratio is 1.5 times or more, the punching resistance of the laminate is further improved. Further, when the draw ratio is 8.0 times or less, particularly 4.0 times or less, the laminate is excellent in drawability, and the laminate is subjected to three-dimensional surface decoration molding (Three dimension Overlay Method: TOM molding) or Even when subjected to insert molding, breakage is less likely to occur. The stretch ratio means the ratio of the area after stretching to the area before stretching.

In the stretching step, the stretching speed is preferably 100 to 5000%/min, more preferably 500 to 2000%/min. When the stretching speed is within the above range, breakage is less likely to occur in the stretching process during the production of the stretched film, and the productivity is improved.

The stretching treatment preferably has a heat setting step after the stretching step. By heat setting, a laminate having excellent stretchability can be obtained. The temperature at the time of heat setting is preferably 40° C. or more lower than the glass transition temperature of the original film and not more than the glass transition temperature, more preferably 30° C. lower than the glass transition temperature of the original film and more than the glass transition temperature. The temperature is 10° C. or lower.

The stretching treatment preferably further includes a relaxation step after the heat setting step. By the relaxation step, a laminate having more excellent stretchability can be obtained. The relaxation rate is preferably 0.1 to 5%, more preferably 0.5 to 2%.

From the viewpoint of cost and surface hardness, the thickness of the stretched film is preferably 5 to 200 μm, more preferably 10 to 100 μm, still more preferably 20 to 80 μm, still more preferably 30 to 60 μm. ..

The stretched film has a haze of 1% or less, preferably 0.8% or less, more preferably 0.5% or less, still more preferably 0.4% or less. If the haze of the stretched film exceeds 1%, the laminate may have a metallic luster and poor gloss. The haze of the stretched film can be controlled by appropriately adjusting the type and amount of the resin or elastomer contained in the stretched film, the stretching temperature and the stretching ratio. The haze of the stretched film can be determined according to JIS K 7136 (2000), and specifically, it can be determined by the method described later in Examples.

The stretched film has a dimensional change rate before and after being held at 85° C. for 30 minutes of preferably 0.1% or less, more preferably 0.08% or less, still more preferably 0.06% or less, It is more preferably 0.05% or less, and particularly preferably 0.04% or less. Further, it is preferably 0.005% or more, more preferably 0.01% or more, still more preferably 0.02% or more. When the dimensional change rate of the stretched film is within the above range, the laminate has excellent stretchability and is less likely to break even when the laminate is subjected to TOM molding or insert molding. Further, it is more excellent in punching resistance. The dimensional change rate before and after holding the stretched film at 85° C. for 30 minutes can be determined by using a stress/strain controlled thermomechanical analyzer, and specifically by the method described later in Examples. The dimensional change rate before and after holding the stretched film at 85° C. for 30 minutes can be determined by appropriately adjusting the type and amount of the resin or elastomer contained in the stretched film, the stretching temperature, the stretching ratio, the heat setting temperature, the relaxation rate, and the like. You can control.

The stretched film may be subjected to a surface treatment on at least one surface of the stretched film in order to improve the adhesive force with the functional layer described later. As the surface treatment, a method known in the art, for example, an activation treatment such as a corona discharge treatment, a plasma treatment, a glow discharge treatment, a flame treatment, an ultraviolet ray irradiation treatment, an electron beam irradiation treatment, or an ozone treatment is used. be able to.

(Metal layer)
Examples of the metal layer included in the laminate of the present invention include those made of metal and/or metal oxide. Examples of the metal include aluminum, silicon, magnesium, palladium, zinc, tin, nickel, silver, copper, gold, indium, stainless steel, chromium and titanium. 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. , Titanium oxide, 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. These metals and/or metal oxides may be used alone or as a mixture of two or more kinds. Among them, the metal layer has at least one selected from the group consisting of indium, aluminum, chromium, gold, silver and tin, from the viewpoint that it has an excellent metallic luster and the laminate has excellent stretchability. It is preferable to include a seed, and more preferable to include indium. The total content of the metal and the metal oxide in the metal layer is preferably 90 mass% or more, more preferably 95 mass% or more, still more preferably 99 mass% or more, still more preferably 99 mass% or more. It is 0.99 mass% or more, and may be 100 mass %.

The thickness of the metal layer is preferably 10 to 500 nm, more preferably 30 to 300 nm, further preferably 40 to 250 nm, still more preferably 50 to 200 nm. When the thickness of the metal layer is within the above range, the metallic luster of the laminate is further excellent, and the beautiful metallic luster can be maintained even when the laminate is stretched by TOM molding and insert molding. The molded product having the above laminated body is excellent in metallic luster.

(Laminate)
The laminate of the present invention has a total light transmittance of 50% or less, preferably 30% or less, more preferably 20% or less, still more preferably 10% or less. If the total light transmittance exceeds 50%, a laminate having a metallic luster and poor gloss may be formed. On the other hand, in view of the moldability of the laminate, the total light transmittance is preferably 0.1% or more, more preferably 0.5% or more, still more preferably 1% or more. The total light transmittance of the laminate can be determined according to JIS K 7136 (2000), and specifically, it can be determined by the method described below in Examples.

The laminate of the present invention preferably has an impact strength of 2 J or more, more preferably 3 J or more, still more preferably 4 J or more, still more preferably 5 J or more, still more preferably 6 J or more. is there. When the impact resistance is within the range, the laminated body tends to have further excellent punching resistance. The impact strength of the laminate can be determined by the method described later in the examples.

From the viewpoint of low cost and low environmental load, it is preferable that the stretched film and the metal layer are in contact with each other, but the laminate may have an anchor layer between the stretched film and the metal layer. By having an anchor layer between the stretched film and the metal layer, the adhesion between the stretched film and the metal layer can be improved, and in the case where the adhesive layer is provided on the metal layer side of the laminate, the adhesive layer can be used. It is possible to protect the stretched film from the adhesive and suppress whitening of the stretched film. As the material of the anchor layer, for example, a two-component curable urethane resin, a thermosetting urethane resin, a melamine resin, a cellulose ester resin, a chlorine-containing rubber resin, a chlorine-containing vinyl resin, an acrylic resin, an epoxy resin, Examples thereof include vinyl copolymer resins. Examples of the method for forming the anchor layer include a gravure coating method, a roll coating method, a coating method such as a comma coating method, a gravure printing method, and a screen printing method.

The laminate of the present invention may consist of only the stretched film and the metal layer, but may further have layers other than the stretched film and the metal layer. Examples of layers other than the stretched film and the metal layer include functional layers such as a top coat layer, a hard coat layer, an anchor layer, an easily adhesive layer, an adhesive layer, and a printing layer. The positions of these layers in the laminate are not particularly limited, but when the metal layer side of the laminate is attached to an adherend, the top coat layer and the hard coat layer are surfaces of the stretched film opposite to the metal layer. Is preferably provided in the. Further, the anchor layer is preferably provided between the stretched film and the metal layer. Furthermore, the adhesive layer is preferably provided on the surface of the metal layer opposite to the stretched film, and the easily adhesive layer is preferably provided between the metal layer and the adhesive layer. It is preferable for the laminate to have these layers, particularly the tackiness/adhesion layer, because the stretchability of the laminate is improved.

As the material of the printing layer, polyvinyl resin, polyamide resin, polyester resin, acrylic resin, polyurethane resin, polyvinyl acetal resin, polyester urethane resin, cellulose ester resin, resin such as alkyd resin is used as a binder. It is preferable to use a colored ink containing a pigment or dye of an appropriate color as a colorant. Examples of the method for forming the print layer include ordinary printing methods such as an offset printing method, a gravure printing method, and a screen printing method. In particular, the offset printing method and the gravure printing method are suitable for performing multicolor printing and gradation expression. Further, in the case of a single color, a coating method such as a gravure coating method, a roll coating method or a comma coating method can be adopted. The print layer may be provided entirely or partially depending on the design to be expressed.

As the adhesive layer, a heat-sensitive or pressure-sensitive resin suitable for a stretched film can be appropriately used, but an acrylic resin, a polystyrene resin, a polyamide resin or the like is preferable, and an acrylic resin is preferable. More preferable. Examples of the method for forming the adhesive layer include a gravure coating method, a roll coating method, a coating method such as a comma coating method, a gravure printing method, and a screen printing method. The thickness of the adhesive layer after drying is preferably 1 to 200 μm, more preferably 10 to 150 μm, and still more preferably 20 to 100 μm, from the viewpoint of adhesiveness and handleability. More preferably, it is 30 to 70 μm.

From the viewpoint of cost and surface hardness, the thickness of the laminate is preferably 5 to 500 μm, more preferably 10 to 300 μm, still more preferably 20 to 100 μm, still more preferably 30 to 60 μm. ..

The method for producing the laminate of the present invention is not particularly limited and can be produced, for example, by forming a metal layer on the stretched film as described above. The method for forming the metal layer on the stretched film is not particularly limited, and examples thereof include a vacuum vapor deposition method, an ion plating method, sputtering, and chemical vapor deposition. When the vacuum vapor deposition method is used, the degree of vacuum is preferably 0.1 Pa or less, and more preferably 0.01 Pa or less, from the viewpoint of improving the thickness accuracy of the metal layer.

(Molded body)
The molded product of the present invention has the laminate and the adherend of the present invention. As a preferred embodiment of the molded article, the laminate of the present invention is provided on the surface of the adherend, and the laminate of the present invention is provided so that the metal layer side of the laminate of the present invention faces the surface of the adherend. It is more preferable to provide. Since the molded product has the laminate of the present invention on the surface of the adherend, it has excellent surface smoothness, surface hardness, and metallic luster. Examples of the adherend include a thermoplastic resin, a thermosetting resin, a wood base material, or a non-wood base material.

Examples of the thermoplastic resin used for the adherend include polycarbonate resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, other (meth)acrylic resin, ABS (acrylonitrile-butadiene-styrene copolymer). Combined) type resins, ethylene vinyl alcohol type resins, polyvinyl butyral type resins, vinyl acetal type resins, styrene type thermoplastic elastomers, olefin type thermoplastic elastomers, acrylic type thermoplastic elastomers and the like.

Examples of the thermosetting resin include epoxy resin, phenol resin, melamine resin and the like. Examples of the non-woody base material include a base material made of kenaf fiber and a base material made of carbon fiber.

The method for producing the formed body is not particularly limited, and examples thereof include a method in which the laminate of the present invention is heated to perform vacuum forming, pressure forming, compression forming or TOM forming on the surface of the adherend. Further, a molded body can be manufactured by insert molding or injection molding simultaneous laminating method in which the laminate of the present invention is preformed, inserted into a mold, and molten resin is injection molded on the metal layer side.

(Use)
The use of the laminate and the molded article of the present invention is not particularly limited, and examples thereof include vehicle decorative parts such as bumpers, emblems, vehicle exteriors, vehicle interiors; building material parts such as wall materials, window films, window frames, bathroom wall materials. Household items such as vacuum cleaner housings, television housings, air conditioner housings; interior members such as kitchen doors and cover materials; ship members and the like.

Among them, the laminate of the present invention is excellent in punching resistance and metallic luster, so that it can be suitably used for a molded product requiring designability. Moreover, the laminated body of this invention can be used especially suitably for a metal-like decoration use as a metal-like decorative film.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. The present invention is not limited to the examples below. Further, the present invention includes all modes in which the items representing the technical characteristics such as the characteristic value, the form, the manufacturing method, and the use described above are arbitrarily combined.

(Polymerization conversion rate)
A gas chromatograph GC-14A manufactured by Shimadzu Corporation was used as a column with GL Sciences Inc. Inert CAP 1 (df=0.4 μm, ID=0.25 mm, length=60 m) manufactured by Inert CAP 1 was connected, and the injection temperature was 180° C., the detector temperature was 180° C., and the column temperature was maintained at 60° C. for 5 minutes, 60 The temperature was raised from 200C to 200C at a heating rate of 10C/min, and the measurement was performed under the condition of holding at 200C for 10 minutes, and the polymerization conversion rate was calculated based on the result.

(Weight average molecular weight Mw, weight average molecular weight Mw/number average molecular weight Mn)
The chromatogram was measured by gel permeation chromatography (GPC) under the following conditions, and the value converted into the molecular weight of standard polystyrene was calculated. The baseline shows that the slope of the peak on the high molecular weight side of the GPC chart changes from zero to a positive value when the retention time is early, and the slope of the peak on the low molecular weight side is a negative value to zero when the retention time is early. It is a line connecting the points that change.
GPC device: manufactured by Tosoh Corporation, HLC-8320
Detector: Differential Refractive Index Detector Column: Two TSKgel SuperMultipore HZM-M manufactured by Tosoh Corporation and Super HZ4000 connected in series were used.
Eluent: Tetrahydrofuran Eluent flow rate: 0.35 mL/min Column temperature: 40°C
Calibration curve: Created using the data of 10 points of standard polystyrene

(Syndiotacticity (rr) in triplets display)
Using a nuclear magnetic resonance apparatus (ULTRA SHIELD 400 PLUS manufactured by Bruker), deuterated chloroform was used as a solvent, and ¹ H-NMR spectrum was measured under the conditions of room temperature (25° C.) and an integration number of 64 times. .. The area _{A O} of the area of 0.6~0.95ppm when used as a 0ppm the TMS from the spectrum, and the area _{A Y} region of 0.6~1.35ppm measured, then triad display The syndiotacticity (rr) (%) was calculated by the formula: (A _O /A _Y )×100.

(Glass transition temperature (Tg))
According to JIS K 7121 (2012), using a differential scanning calorimeter (manufactured by Shimadzu Corporation, DSC-50 (product number)), the temperature was once raised to 230° C. and then cooled to room temperature (25° C.). Then, the DSC curve was measured under the condition that the temperature was raised from room temperature (25° C.) to 230° C. at 10° C./min. The midpoint glass transition temperature obtained from the DSC curve measured during the second temperature rise was taken as the glass transition temperature in the present invention.

(Haze)
The stretched film obtained in the example was cut into a piece of 50 mm×50 mm to give a test piece, and the haze was measured using a haze meter (SH7000 manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS K 7136 (2000).

(Dimensional change rate)
A 40 mm×5 mm test piece was cut out from the stretched film obtained in the example. Here, the longitudinal direction of the test piece was parallel to the width direction of the original film. Both ends of the test piece in the longitudinal direction were held by a pair of film chucks. At this time, the distance between the pair of film chucks was set to 24 mm. A tensile load of 2 g was applied to the stretched film by a pair of film chucks, and this was attached to a thermomechanical analyzer (Q400EM, manufactured by TA Instruments).
With the test piece set as described above, the test piece was heated from 25° C. to 85° C. at a heating rate of 2° C./min, and the length (LB) of the test piece immediately after reaching 85° C. was measured. It was measured. After that, the test piece was held at 85° C. for 30 minutes, and the length (LA) of the test piece immediately after the holding was measured. Then, the value of (LA-LB) [unit: mm] is obtained as the value of ΔL, and the dimensional change rate [unit: %] represented by the following formula (1) is maintained for 30 minutes at 85° C. The rate of change was used.
Dimensional change rate (%)=ΔL [unit: mm]/24 [unit: mm]×100 (1)

(Total light transmittance)
The laminate obtained in the example was cut into 50 mm×50 mm to give a test piece, and the total light transmittance was measured using a haze meter (SH70000, manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS K 7136 (2000). did.

(Impact strength)
The laminate obtained in the example was cut into a piece of 80 mm×80 mm to give a test piece, which was set in a film impact tester (NO.181 film impact tester manufactured by Yasuda Seiki Seisakusho Co., Ltd.) and a spherical impact mallet (radius 12.7±). 0.2 mm) was applied to the test piece at a right angle, and the energy [unit: J] required for punching was taken as the impact strength.

(Punching resistance)
The laminate obtained in the example was cut into a test piece of 80 mm×80 mm to form a test piece, and the test piece and a punching jig (Thomson blade) of 40 mm×40 mm were set in a punching device (SDL-200 manufactured by Dumbbell) and tested. Pieces were punched out to 40 mm x 40 mm. The punched test piece was evaluated as A if there was no crack (flame) and C if there was a crack.

(200% stretchability)
The laminate obtained in the example was cut into 100 mm×100 mm to prepare a test piece, which was set in a biaxial stretching birefringence measuring device (EDR, SDR-563K), at a temperature of 145° C., a stretching speed of 3600%/min and a stretching ratio. It was stretched under the condition of 200%. Five test pieces were stretched by the method and evaluated as follows.
A: No piece was broken.
B: One or two sheets were broken.
C: Three or more sheets were broken.

(250% stretchability)
The laminate obtained in the example was cut into 100 mm×100 mm to prepare a test piece, which was set in a biaxial stretching birefringence measuring device (EDR, SDR-563K), at a temperature of 145° C., a stretching speed of 3600%/min and a stretching ratio. It was stretched under the condition of 250%. Five test pieces were stretched by the method and evaluated as follows.
A: No piece was broken.
B: One or two sheets were broken.
C: Three or more sheets were broken.

(appearance)
The laminate obtained in the example was placed on a white paper (C2r manufactured by FUJI xerox Co., Ltd.), and the appearance was visually observed under a fluorescent lamp (200 lux).

(Production Example 1) [Production of (meth)acrylic resin (X1)]
The inside of the autoclave equipped with the stirrer and the sampling tube was replaced with nitrogen. To this, 100 parts by mass of distilled and purified methyl methacrylate (MMA), 2,2′-azobis(2-methylpropionitrile) (hydrogen abstraction capacity: 1%, 1 hour half-life temperature: 83° C.) 0.0052 Parts by mass and 0.225 parts by mass of n-octyl mercaptan were added and stirred to obtain a raw material liquid. Nitrogen was sent into this raw material liquid to remove dissolved oxygen in the raw material liquid.
The raw material liquid was put into a tank reactor connected to an autoclave through a pipe to a volume of 2/3. With the temperature maintained at 140° C., the polymerization reaction was first started in a batch system. When the polymerization conversion rate reached 55% by mass, while maintaining the temperature at 140°C, the raw material solution was supplied from the autoclave to the tank reactor at a flow rate that would make the average residence time 150 minutes. The polymerization reaction was switched to a continuous flow system in which the reaction solution was withdrawn from the tank reactor at a corresponding flow rate. After switching to the continuous flow system, the polymerization conversion rate in the steady state was 55% by mass.
The reaction liquid extracted from the tank-type reactor in the steady state was supplied to a multi-tube heat exchanger having an internal temperature of 230° C. at a flow rate to give an average residence time of 2 minutes and heated. Next, the heated reaction liquid was introduced into a flash evaporator to remove a volatile component containing an unreacted monomer as a main component to obtain a molten resin. The molten resin from which the volatile components were removed was supplied to a twin-screw extruder having an internal temperature of 260° C., discharged in a strand shape, and cut with a pelletizer to obtain a pellet-shaped (meth)acrylic resin (X1). Table 1 shows the physical properties of the obtained (meth)acrylic resin (X1).

(Production Example 2) [Production of (meth)acrylic resin (X2)]
The inside of the glass reaction vessel equipped with a stirring blade and a three-way cock was replaced with nitrogen. At room temperature (25° C.), 2.9 parts by mass of toluene, 0.0045 parts by mass of 1,1,4,7,10,10-hexamethyltriethylenetetramine, and 0.45 M of isobutylbis( 0.097 parts by mass of a toluene solution of 2,6-di-t-butyl-4-methylphenoxy)aluminum and a solution of sec-butyllithium having a concentration of 1.3 M (solvent: cyclohexane 95% by mass, n-hexane 5% by mass). %) 0.011 part by mass was charged. While stirring, 100 parts by mass of MMA which had been purified by distillation was added dropwise to these raw materials at 20° C. over 30 minutes. After completion of dropping, the solution was stirred at 20° C. for 90 minutes, and the color of the solution changed from yellow to colorless. The polymerization conversion rate of MMA at this point was 100%. 2.7 parts by mass of toluene was added to the obtained solution to dilute it. Then, the diluted solution was poured into 180 parts by mass of methanol to obtain a precipitate. The obtained precipitate was dried at 80° C. and 140 Pa for 24 hours to obtain a (meth)acrylic resin (X2). Table 1 shows the physical properties of the obtained (meth)acrylic resin (X2).

The following phenoxy resin was prepared.
Phenoxy1: Nippon Steel & Sumikin Chemical Co., Ltd., YP-50S (product number), MFR (230° C., 3.8 Kg, 10 minutes; JIS K 7210-1 (2014) compliant)=22 g/10 minutes, Mw=55000, Mw/Mn =2.5

(Production Example 3) Methacrylic resin composition (M1)
40 parts by weight of (meth)acrylic resin (X1), 60 parts by weight of (meth)acrylic resin (X2), and (meth) having a triblock structure obtained by referring to Reference Example 3 of JP-A-2017-78168. 1 part by mass of an acrylic block copolymer, 1 part by mass of a phenoxy resin (Phenoxy1), 1 part by mass of an ultraviolet absorber (LA-F70 manufactured by ADEKA), and a polymer processing aid (metabrene (registered by Mitsubishi Chemical) (Trademark) P550A) 2 parts by mass are mixed with a Henschel mixer, and kneaded and extruded using a twin screw extruder with a vent having a screw diameter of 41 mm set to 260° C., and a methacrylic resin composition having a glass transition temperature Tg of 124° C. (M1) pellets were obtained.

(Production Example 4) Methacrylic resin composition (M2)
85 parts by mass of the (meth)acrylic resin (X1) and 15 parts by mass of the (meth)acrylic block copolymer having a triblock structure obtained by referring to Reference Example 3 of JP-A-2017-78168 are used in a Henschel mixer. Were mixed and extruded using a twin screw extruder with a vent having a screw diameter of 41 mm set to 260° C. to obtain pellets of a methacrylic resin composition (M2) having a glass transition temperature Tg of 118° C.

(Production Example 5) Methacrylic resin composition (M3)
70 parts by mass of (meth)acrylic resin (X3) composed of 99% by mass of methyl methacrylate and 1% by mass of methyl acrylate, obtained by referring to Reference Examples 1 and 2 of WO 2016/139950, and International 30 parts by mass of (meth)acrylic elastomer particles having a three-layer structure and having a particle diameter of 0.23 μm measured by a dynamic light scattering method, obtained by referring to Reference Example 1 of JP-A-2014/167868, is Henschel. The mixture was mixed with a mixer, and kneaded and extruded using a vented twin-screw extruder having a screw diameter of 41 mm set to 260° C. to obtain pellets of a methacrylic resin composition (M3) having a glass transition temperature Tg of 114° C.

(Production Example 6) Methacrylic resin composition (M4)
80 parts by weight of (meth)acrylic resin (X1), 20 parts by weight of (meth)acrylic resin (X2), and (meth) having a triblock structure obtained by referring to Reference Example 3 of JP-A-2017-78168. 1 part by mass of an acrylic block copolymer, 0.8 part by mass of a polycarbonate resin (manufactured by Sumika Polycarbonate Co., Ltd., SD-POLYCA 401-40), 2.5 parts by mass of a phenoxy resin (Phenoxy1), an ultraviolet absorber (manufactured by ADEKA). , LA-F70) 1 part by mass and a polymer processing aid (Metablene (trademark) P550A manufactured by Mitsubishi Chemical Co., Ltd.) 2 parts by mass were mixed by a Henschel mixer, and a vented screw having a screw diameter of 41 mm set at 260° C. The mixture was kneaded and extruded using a shaft extruder to obtain pellets of a methacrylic resin composition (M4) having a glass transition temperature Tg of 122°C.

Example 1
(Production of stretched film)
The pellet-shaped methacrylic resin composition (M1) was melted at 270° C. with a φ65 mm vented single-screw extruder to which a T-die was connected, and extruded into a sheet from a T-die having a width of 700 mm. The distance from the die discharge part until the molten thermoplastic resin composition contacts the cast roll is set to 30 mm, and the extruded thermoplastic resin composition is electrostatically applied (edge pinning, voltage 4 V, contact point with cast roll). 5 mm in the vertical direction and 10 mm on the T-die side) and brought into close contact with a cast roll having a diameter of 225 mm and cooled to obtain a raw film having a thickness of 130 μm. Then, the original film which concerns on a tenter type simultaneous biaxial stretching machine was introduce|transduced, and it preheated at 147 degreeC. Then, the raw film was simultaneously biaxially stretched at 147° C. at 3.25 times (longitudinal direction 1.80 times and width direction 1.80 times). At this time, the stretching speed was 1000%/min in both the longitudinal direction and the width direction. Then, it cooled to 105 degreeC and heat-fixed for 1 minute, and obtained the 40-micrometer stretched film.

(Manufacture of laminated body)
A laminated body which is a metal-like decorative film, in which a 50 nm-thick indium layer is formed on the obtained stretched film by vacuum vapor deposition using a vacuum vapor deposition apparatus (VE-2030 manufactured by Vacuum Device Co., resistance heating method). Got At this time, a basket heater (92% alumina) was used for resistance heating, and indium having a purity of 99.99% and a grain size of 1 mm was used. The vapor deposition conditions were a vacuum degree of 7×10 ⁻³ Pa and a rate of 0.8 Å/sec for 10 minutes. The evaluation results are shown in Table 2. When the appearance of the obtained laminate was observed from the side of the stretched film, it had a beautiful metallic luster.

(Production of molded body)
The obtained laminate was cut into 210 mm×300 mm to obtain a test piece. Also, a polystyrene resin clip case (manufactured by Plus Co., CP-500, width 76 mm x depth 62 mm x height 40 mm) was used as the adherend. The adherend and the test piece were set in a TOM molding device (NGF-0406T manufactured by Fuse Vacuum Co., Ltd.) so that the metal layer of the test piece faces the convex side of the adherend, and the preheating temperature is 130° C. TOM molding was performed under the condition of a pressure difference of 300 kPa to obtain a molded body. In the molded body, the laminate was not broken, and the molded body had a beautiful metallic luster.

Example 2
A laminate was produced in the same manner as in Example 1 except that the thickness of the indium layer was changed to 40 nm in the production of the laminate of Example 1. The evaluation results are shown in Table 2. When the appearance of the obtained laminate was observed from the side of the stretched film, it had a beautiful metallic luster.

Example 3
A laminate was produced in the same manner as in Example 1 except that the thickness of the indium layer was changed to 30 nm in the production of the laminate of Example 1. The evaluation results are shown in Table 2. When the appearance of the obtained laminate was observed from the side of the stretched film, it had a beautiful metallic luster, but the color of indium was light as a whole.

Example 4
In the production of the stretched film of Example 1, a laminate was produced in the same manner as in Example 1 except that heat setting was not performed. The evaluation results are shown in Table 2. When the appearance of the obtained laminate was observed from the side of the stretched film, it had a beautiful metallic luster.

Example 5
In the production of the raw film of Example 1, the thickness of the raw film was changed to 180 μm, and in the production of the stretched film, the stretching ratio was 4.50 times (2.12 times in the longitudinal direction and 2.12 times in the width direction). A laminated body was manufactured in the same manner as in Example 1 except that the above was changed to ). The evaluation results are shown in Table 2. When the appearance of the obtained laminate was observed from the stretched film side, it had a beautiful metallic luster.

Example 6
(Manufacture of laminated body)
In the production of the raw fabric film of Example 1, the thickness of the raw fabric film was changed to 250 μm, and in the production of the stretched film, the stretching ratio was 6.25 times (longitudinal direction 2.50 times and width direction 2.50 times). A laminated body was manufactured in the same manner as in Example 1 except that the contents were changed to ). The evaluation results are shown in Table 2. When the appearance of the obtained laminate was observed from the side of the stretched film, it had a beautiful metallic luster.

(Manufacture of molded body 1)
The obtained laminate was cut into 210 mm×300 mm to obtain a test piece. Also, a polystyrene resin clip case (manufactured by Plus Co., CP-500, width 76 mm x depth 62 mm x height 40 mm) was used as the adherend. The adherend and the test piece were set in a TOM molding device (NGF-0406T manufactured by Fuse Vacuum Co., Ltd.) so that the metal layer of the test piece faces the convex side of the adherend, and the preheating temperature is 130° C. When TOM molding was performed under the condition that the pressure difference was 300 kPa, the laminate was broken.

(Manufacture of molded body 2)
The obtained laminated body was cut out into 210 mm×300 mm, and an adhesive (Toron Gosei Co., Ltd., Aron Tuck S-1511X) was applied on the metal layer side to form an adhesive layer having a thickness of 50 μm to obtain a test piece. Also, a polystyrene resin clip case (manufactured by Plus Co., CP-500, width 76 mm x depth 62 mm x height 40 mm) was used as the adherend. The adherend and the test piece were set in a TOM molding device (NGF-0406T manufactured by Fuse Vacuum Co., Ltd.) so that the metal layer of the test piece faces the convex side of the adherend, and the preheating temperature is 130° C. TOM molding was performed under the condition of a pressure difference of 300 kPa to obtain a molded body. In the molded body, the laminate was not broken, and the molded body had a beautiful metallic luster.

Example 7
In the production of the stretched film of Example 1, the methacrylic resin composition (M1) was changed to the (meth)acrylic resin (X1), and the preheating temperature and the stretching temperature were changed to 145°C. A laminate was manufactured in the same manner as in. The evaluation results are shown in Table 2. When the appearance of the obtained laminate was observed from the side of the stretched film, it had a beautiful metallic luster.

Example 8
A laminate was produced in the same manner as in Example 7, except that the preheating temperature and the stretching temperature were changed to 135°C and the heat setting temperature was changed to 95°C. The evaluation results are shown in Table 2. When the appearance of the obtained laminate was observed from the side of the stretched film, it had a beautiful metallic luster.

Example 9
A laminate was produced in the same manner as in Example 1 except that the methacrylic resin composition (M1) was changed to the methacrylic resin composition (M4) in the production of the stretched film of Example 1. The evaluation results are shown in Table 2. When the appearance of the obtained laminate was observed from the side of the stretched film, it had a beautiful metallic luster.

Example 10
In the production of the stretched film of Example 1, the methacrylic resin composition (M1) was changed to the methacrylic resin composition (M4), the stretching temperature was changed to 150° C., and the stretching ratio was changed to 5.30 times. A laminate was manufactured in the same manner as in Example 1 except for the above. The evaluation results are shown in Table 2. When the appearance of the obtained laminate was observed from the side of the stretched film, it had a beautiful metallic luster.

Comparative Example 1
In the production of the raw fabric film of Example 1, except that electrostatic application was changed to sandwiching by a metal elastic roll, the thickness of the raw fabric film was changed to 40 μm, and stretching was not performed in the production of the stretched film. A laminated body was manufactured in the same manner as in Example 1. The evaluation results are shown in Table 2. When the appearance of the obtained laminate was observed from the film side, it had a beautiful metallic luster.

Comparative example 2
In the production of the raw film of Example 7, the (meth)acrylic resin (X1) was changed to the methacrylic resin composition (M2), and the thickness of the raw film was changed to 98 μm. A laminate was manufactured in the same manner as in. The evaluation results are shown in Table 2. When the appearance of the obtained laminate was observed from the side of the stretched film, reflected light appeared to fluctuate and the metallic luster was impaired.

Comparative Example 3
In the production of the raw film of Example 7, the (meth)acrylic resin (X1) was changed to the methacrylic resin composition (M3), and the thickness of the raw film was changed to 98 μm. A laminate was manufactured in the same manner as in. The evaluation results are shown in Table 2. When the appearance of the obtained laminate was observed from the side of the stretched film, the reflected light was blurred and appeared blurred, and the metallic luster was impaired.

The laminates obtained in Examples 1 to 10 have a layer of a stretched film having a haze of 1% or less and a total light transmittance of 50% or less, as compared with Comparative Examples 1 to 3, and thus have punching resistance. It was also excellent in metallic luster. Among them, the laminates obtained in Examples 1 to 5, 7, 9 and 10 are excellent in 200% stretchability, and further the laminates obtained in Examples 1 to 3, 7, 9 and 10 are excellent in 250% stretchability. Therefore, it is particularly suitable for drawing, other three-dimensional molding, and bonding to a three-dimensional adherend. In addition, the laminates obtained in Examples 1, 2 and 4 to 10 had a beautiful metallic luster, and the color of indium was deeply visible as a whole.
The laminate obtained in Comparative Example 1 did not have the layer of the stretched film, and thus the punching resistance was poor.
In the laminates obtained in Comparative Examples 2 and 3, the haze of the stretched film was more than 1%, and thus the metallic luster was impaired.

The laminate of the present invention has excellent punching resistance and metallic luster, and can be used as a metallic decorative film.

Claims (13)

A laminate having a stretched film and a metal layer and having a total light transmittance of 50% or less, wherein the stretched film contains a (meth)acrylic resin and has a haze of 1% or less. The laminate according to claim 1, wherein the stretched film contains an elastomer, and the content of the elastomer in the stretched film is 30 parts by mass or less based on 100 parts by mass of the (meth)acrylic resin. The stretched film contains an ultraviolet absorber, and the content of the ultraviolet absorber in the stretched film is 0.1 to 10 parts by mass with respect to 100 parts by mass of the (meth)acrylic resin. The laminated body according to. The laminate according to claim 1, wherein the stretched film has a dimensional change rate of 0.1% or less before and after being held at 85° C. for 30 minutes. The laminate according to claim 1, wherein the stretched film has a thickness of 5 to 200 μm. The laminate according to claim 1, wherein the metal layer contains at least one selected from the group consisting of indium, aluminum, chromium, gold, silver and tin. The laminate according to claim 1, wherein the metal layer has a thickness of 10 to 500 nm. The laminate according to any one of claims 1 to 7, which has an impact strength of 4 J or more. The laminate according to claim 1, wherein the stretched film and the metal layer are in contact with each other. The laminate according to claim 1, which has a thickness of 5 to 500 μm. A metal-like decorative film comprising the laminate according to claim 1. A molded body comprising the laminate according to any one of claims 1 to 10 and an adherend. It is a manufacturing method of the laminated body in any one of Claims 1-10, Comprising: The raw film containing a (meth)acrylic resin is stretched 1.5 to 8.0 times, and the said stretched film is manufactured. A method for producing a laminate, which comprises a step and a step of forming a metal layer on the stretched film.