JP7177776B2 - Laminate and its manufacturing method - Google Patents

Description

The present invention relates to a laminate and its manufacturing method.

Conventionally, in order to give a metallic luster to wheel caps, bumpers, emblems, etc. of resin-made automobiles, it is common to apply a transparent glossy paint after directly plating the resin-made parts with metal. was the method.

However, metal plating and painting are costly and have environmental hygiene problems. In addition, it is difficult to obtain a consistent appearance due to large variations in coating thickness, making it difficult to provide stable quality. In order to solve such problems, instead of metal plating, a metal thin film layer is formed on the base film to produce a metallic decorative film, and instead of painting, the metallic decorative film is applied to the adherend. There is a way to bond.

For example, in Patent Document 1, a biaxially stretched polyethylene terephthalate film, an acrylic resin film or a polycarbonate resin film is used, and the maximum height average R _tm of the back surface is 0.1 to 2.0 μm, and the haze value is 0. .1 to 4.0% transparent resin film having a metal vapor deposition layer containing at least one selected from tin, gold and indium on the back side.

Further, in Patent Document 2, a transparent acrylic film is used as a base sheet, a metal thin film layer is formed thereon, and a plastic sheet is further laminated thereon to form a metal thin film insert film. , discloses a method for manufacturing a metal thin film insert film molded product in which a metal thin film insert film is inserted into a mold and a molding resin is injected onto the plastic sheet side for integration.

Further, in Patent Document 3, a transparent conductive film having a transparent conductive layer on at least one side of a base film containing a main component of an acrylic resin having a ring structure in the main chain and a glass transition temperature of 120° C. or higher is disclosed. disclosed.

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

However, a laminate having a conventional acrylic film layer and a metal layer cracks and/or splits from the cut surface when punching out a desired shape after bonding to an adherend and cutting off the surplus part. was occurring. In addition, depending on the acrylic film used, the metallic luster may be impaired. Furthermore, the transparent conductive film disclosed in Patent Document 3 is highly transparent and lacks 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.

The present inventors have made intensive studies to solve the above problems, and as a result, 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 laminate according to [1] above, wherein the stretched film contains an elastomer, and the content of the elastomer in the stretched film is 30 parts by mass or less with respect to 100 parts by mass of the (meth)acrylic resin. .
[3] The above [ 1] or the laminate according to [2].
[4] The laminate according to any one of [1] to [3] above, 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 [1] to [4] above, 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 laminate according to any one of [1] to [6] above, wherein the metal layer has a thickness of 10 to 500 nm.
[8] The laminate according to any one of [1] to [7] above, which has an impact resistance strength of 4J or more.
[9] The laminate according to any one of [1] to [8] above, wherein the stretched film and the metal layer are in contact with each other.
[10] The laminate according to any one of [1] to [9] above, 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] above.
[12] A molded article comprising the laminate and adherend according to any one of [1] to [10] above.
[13] The method for producing a laminate according to any one of [1] to [10] above, wherein the raw film containing the (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.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the laminated body and the said laminated body which are excellent in punching resistance and metallic luster can be provided.

An example of an embodiment to which the present invention is applied will be described below. Numerical values specified in this specification are values determined by the methods disclosed in the embodiments or examples. It should be noted that other embodiments are also included in the scope of the present invention as long as they match the gist 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. (Meth)acrylic resins include polymethyl methacrylate and styrene-methyl methacrylate resins. In this specification, (meth)acrylic resin refers to methacrylic resin and/or 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. Also, the stretched film may contain one or more of these (meth)acrylic resins.

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

Examples of such monomers other than methyl methacrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, and 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 acid, 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 and itaconic acid; ethene, propylene, 1-butene, isobutene, 1-octene olefins such as butadiene, isoprene, and myrcene; conjugated dienes such as styrene, α-methylstyrene, p-methylstyrene, and m-methylstyrene; aromatic vinyl compounds such as acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, and vinyl acetate , vinylpyridine, vinylketone, vinyl chloride, vinylidene chloride, and vinylidene fluoride. One of these monomers may be used, or two or more thereof may be used in combination.

The (meth)acrylic resin preferably has a triad syndiotacticity (rr) of 65% or more, more preferably 70 to 90%, and still more preferably 72 to 85%. When the syndiotacticity (rr) is 65% or more, the surface hardness and heat resistance of the resulting laminate are enhanced. The syndiotacticity (rr) of the (meth)acrylic resin can be determined by the method described later 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 triad syndiotacticity (rr) of 65% or more, and 40% by mass. % or more, more preferably 50% by mass or more, and even 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 triad syndiotacticity (rr) of 65% or more is preferably 70% by mass or less. , is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

The (meth)acrylic resin has a weight average molecular weight (Mw) of preferably 40,000 to 200,000, more preferably 60,000 to 150,000, and even more preferably 70,000 to 120,000. Further, the molecular weight distribution of the (meth)acrylic resin (ratio of weight average molecular weight (Mw) to number average molecular weight (Mn), Mw/Mn) is preferably 1.0 to 1.8, more preferably 1.0. to 1.4, particularly preferably 1.03 to 1.3. When a (meth)acrylic resin having a molecular weight (Mw) or molecular weight distribution (Mw/Mn) within such a range is used, the stretched film will have 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 the values obtained by converting the chromatogram measured by gel permeation chromatography (GPC) into the molecular weight of standard polystyrene, and specifically can be determined by the method described later in Examples.

The method for producing the (meth)acrylic resin is not particularly limited, and it can be obtained by polymerizing one or more monomers containing preferably 80% by mass or more of methyl methacrylate 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, still more preferably 120° C. or higher, and particularly preferably 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 can be determined by the method described later in Examples.

The stretched film may contain a resin other than the (meth)acrylic resin. Examples of resins other than (meth) acrylic resins include polycarbonate resins such as bisphenol A type polycarbonate; polystyrene, styrene-acrylonitrile resins, styrene-maleic anhydride resins, styrene-maleimide resins, styrene thermoplastic elastomers, Aromatic vinyl resins or their hydrogenated products; Polyolefin resins such as amorphous polyolefins, transparent polyolefins with fine crystal phases, and ethylene-methyl methacrylate resins; 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; A resin etc. are mentioned. The stretched film may contain only one kind of these resins, or may contain two or more kinds. Among these, the stretched film preferably contains a polycarbonate-based resin and/or a phenoxy-based 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 excellent, and the metallic gloss 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. 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 contain an elastomer. Examples of elastomers include (meth)acrylic elastic particles, (meth)acrylic block copolymers in which an acrylic ester polymer block (b1) and a methacrylic ester polymer block (b2) are bonded together ( meth) acrylic elastomers; silicone elastomers; styrene thermoplastic elastomers such as SEPS, SEBS and SIS; olefin elastomers such as IR, EPR and EPDM. These elastomers may be used individually by 1 type, and may use 2 or more types together. Among these, the (meth)acrylic elastomer is preferred, and the (meth)acrylic elastic particles are more preferred, since the laminate is more excellent in punching resistance and metallic gloss. Moreover, when the stretched film contains an ultraviolet absorber, it preferably contains a (meth)acrylic block copolymer as an elastomer. By including the (meth)acrylic block copolymer in the stretched film, it is possible to suppress mold contamination and roll contamination due to the ultraviolet absorber, and to improve continuous productivity.

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, and particularly preferably 4 parts by mass with respect to 100 parts by mass of the (meth)acrylic resin. It is below. When the content of the elastomer is within the range, the laminate tends to have more excellent metallic luster and improved surface hardness. On the other hand, from the viewpoint of improving the punching resistance of the laminate and suppressing mold contamination and roll contamination due to the ultraviolet absorber when it contains an ultraviolet absorber and improving continuous productivity, the content of the elastomer in the stretched film is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more.
In addition, the range of the above-mentioned content includes the aspect which does not contain an elastomer.

Examples of (meth)acrylic elastomers include elastic acrylic polymers containing structural units derived from acyclic alkyl acrylates as main components. The (meth)acrylic elastomer may consist only of the elastic acrylic polymer, or may contain an elastic acrylic polymer, such as the (meth)acrylic elastic particles described later. . In the elastic acrylic polymer, the content of structural units derived from acyclic alkyl acrylate is preferably 50 to 100% by mass, more preferably 70 to 99.8% by mass. The noncyclic alkyl group in the acrylic acid noncyclic alkyl ester has 4 to 8 carbon atoms, specifically, for example, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n -octyl group and isomeric groups thereof are preferred. Further, the acrylic elastic polymer may contain a structural unit derived from a monomer other than the acyclic alkyl acrylate. Examples of such monomers include methyl methacrylate and ethyl methacrylate. methacrylic acid alkyl esters such as styrene; styrene monomers such as 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; etc.

The acrylic elastic polymer may randomly have structural units derived from the acyclic alkyl acrylate and 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, 1 ,9-nonanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate. 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, still more preferably 0.3 to 10% by mass, from the viewpoint of toughness. It is 0.5 to 5% by mass.

The (meth)acrylic elastic particles, which is a 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 a polymer containing a structural unit derived from a diene monomer as a main component and/or the acrylic elastic polymer ( It is preferable that the core-shell particles have a multilayer structure comprising a layer containing a polymer containing a structural unit derived from an acrylic acid acyclic alkyl ester as a main component and a layer containing another polymer. A core-shell particle having a two-layer structure consisting of a layer containing coalescence and a layer containing a methacrylic polymer covering the outer side, or a layer containing a methacrylic polymer and an elastic acrylic polymer covering the outer side. It is more preferable that the core-shell particles have a three-layer structure consisting of a layer containing the methacrylic polymer and a layer containing the methacrylic polymer that covers the outside thereof. From the viewpoint of heat resistance, the core-shell particles have a three-layer structure. More preferred.

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

The (meth)acrylic elastic particles preferably have a number average particle diameter of 10 to 250 nm, more preferably 20 to 150 nm, and even more preferably 40 to 130 nm. When the number average particle size of the (meth)acrylic elastic particles is in the range, the laminate is more excellent in punching resistance and metallic luster, and whitening is less likely to occur when stretched. The number-average particle diameter of the (meth)acrylic elastic particles is based on a microscopic photograph observed by dyeing a sample obtained by melt-kneading the (meth)acrylic elastic particles into a methacrylic resin with ruthenium oxide. can be determined by Here, ruthenium oxide dyes the layer containing the elastic acrylic polymer, but does not dye the layer containing the methacrylic polymer. The average particle size is assumed to correspond to a value that does not include the thickness of the outermost methacrylic polymer-containing layer.

The method for producing (meth)acrylic elastic particles is not particularly limited, and can be produced by a method according to known methods (for example, WO 2016/121868, WO 2014/167868, etc.). .

In a (meth)acrylic block copolymer in which an acrylic ester polymer block (b1) and a methacrylic ester polymer block (b2) are bonded, which is another aspect of the (meth)acrylic elastomer, the polymer block There is no particular limitation on the bonding form of (b1) and polymer block (b2), for example, a diblock copolymer represented by (b1)-(b2); (b1)-(b2)-(b1) or ( b2)-(b1)-(b2) triblock copolymer; (b1)-((b2)-(b1))n, (b1)-((b2)-(b1))n- (b2), (b2)-((b1)-(b2)) n (n is an integer) multi-block copolymer represented by; ((b1)-(b2)) nX, ((b2 )-(b1)) nX (X is a coupling residue), and the like. From the viewpoint of productivity, the diblock copolymer represented by (b1)-(b2), (b2)-(b1)-(b2) or (b1)-(b2)-(b1) A triblock copolymer is preferred, and from the viewpoint of the fluidity of the resin composition when melted and the surface smoothness and haze of the laminate, the triblock copolymer represented by (b2)-(b1)-(b2) coalescence is more preferred. In this case, the two polymer blocks (b2) bonded to both ends of the polymer block (b1) are determined by the type of the constituting monomers, the proportion of structural units derived from methacrylic acid esters, the weight average molecular weight and the stereoregularity. Each gender may independently be the same or different. In addition, the (meth)acrylic block copolymer may further contain other polymer blocks.

The polymer block (b1) constituting the (meth)acrylic block copolymer has a structural unit derived from an acrylic acid ester as a main structural unit. The proportion of structural units derived from an acrylic acid 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.

Such acrylic esters include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, t-butyl acrylate, acrylic amyl acrylate, 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. The polymer block (b1) can be formed by polymerizing these acrylic acid esters singly or in combination of two or more. Among them, polymer block (b1) obtained by polymerizing n-butyl acrylate alone is preferable from the viewpoint of economic efficiency and further punching resistance.

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

Examples of monomers other than acrylic acid esters include methacrylic acid esters, unsaturated carboxylic acids, aromatic vinyl compounds, olefins, conjugated dienes, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl acetate, vinylpyridine, 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 acid ester alone or two or more of them in combination with the acrylic acid ester described above.

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, It is preferably 60% by mass or less, more preferably 57% by mass or less, and still more preferably 53% by mass or less with respect to the total 100% by mass of the polymer block (b1) and the polymer block (b2). . Also, it is preferably 30% by mass or more, more preferably 35% by mass or more, and still more preferably 40% by mass or more.

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

Such methacrylates include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, and 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. Among them, methacrylic acids such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate and isobornyl methacrylate, from the viewpoint of improving transparency and heat resistance. Alkyl esters are preferred, and methyl methacrylate is more preferred. The polymer block (b2) can be formed by polymerizing these methacrylic acid esters singly or in combination of two or more.

The polymer block (b2) may contain a structural unit derived from a monomer other than the methacrylate ester, and from the viewpoint of fluidity and heat resistance, the proportion thereof is preferably 20% by mass or less, more preferably 10% by mass. % by mass or less, more preferably 5% by mass or less, and particularly preferably 0% by mass.

Examples of monomers other than methacrylic acid esters include acrylic acid esters, unsaturated carboxylic acids, aromatic vinyl compounds, olefins, conjugated dienes, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl acetate, vinylpyridine, vinyl ketone, vinyl chloride, vinylidene chloride, vinylidene fluoride and the like. The polymer block (b2) can be formed by copolymerizing these monomers other than the 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 determined from the viewpoint of transparency, surface hardness of the laminate, moldability, surface smoothness of the laminate, and impact resistance. It is preferably 40% by mass or more, more preferably 43% by mass or more, and still more preferably 47% by mass or more relative to the total 100% by mass of (b1) and polymer block (b2). Also, it is preferably 70% by mass or less, more preferably 65% by mass or less, and even more preferably 60% by mass or less.

The method for producing the (meth)acrylic block copolymer is not particularly limited, and a method according to known techniques (for example, WO 2016/121868, JP 2017-78168, etc.) can be adopted. 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. method of anionic polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organic aluminum compound; method of polymerization using an organic rare earth metal complex as a polymerization initiator; α-halogenated ester compound as an initiator and radical polymerization in the presence of a copper compound. Further, a method of producing a mixture containing a (meth)acrylic block copolymer by polymerizing the monomers constituting each block using a polyvalent radical polymerization initiator or a polyvalent radical chain transfer agent. .

The stretched film may contain additives. The types of additives are not particularly limited, and examples include ultraviolet absorbers, infrared absorbers, polymer processing aids, light stabilizers, antioxidants, heat stabilizers, lubricants, antistatic agents, pigments, dyes, and matting agents. agents, fillers, impact resistance aids, plasticizers, and the like. An additive may be used individually by 1 type, and may use 2 or more types together by arbitrary ratios. The stretched film preferably contains a polymer processing aid from the viewpoint of improving the moldability of the stretched film. These additives may be organic compounds or inorganic compounds, but from the viewpoint of dispersibility in the resin composition, organic compounds are preferred.

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 still more 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 range, a laminate having excellent impact resistance and surface hardness can be obtained.

Here, when a single-layer transparent film is used as a decorative film or the like, light is normally irradiated only from one surface. On the other hand, since the laminate of the present invention has a metal layer, the stretched film is exposed to incident light and light reflected by the metal layer, and is easily deteriorated by light. Therefore, since the stretched film is required to have higher weather resistance than a normal transparent film, it preferably 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 still more 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 the range, it is possible to obtain a laminate that has excellent weather resistance and is less likely to whiten even after long-term storage. Examples of ultraviolet absorbers include benzophenone compounds, salicylate compounds, benzoate compounds, triazole compounds and triazine compounds. One type of ultraviolet absorber may be used alone, or two or more types may be used in combination at an arbitrary ratio. Among these, triazole-based compounds and/or triazine-based compounds are preferable from the viewpoint of long-term stability. Moreover, from the viewpoint of further improving weather resistance, it is also preferable to use a light stabilizer and/or an antioxidant in combination with the ultraviolet absorber. Examples of light stabilizers include hindered amine light stabilizers. Examples of antioxidants include phenolic antioxidants.

Polymer particles having a particle size of 0.05 to 0.5 μm, which can be produced by an emulsion polymerization method, can be used as the polymer processing aid. When the stretched film contains the polymer processing aid, the thickness accuracy and film-forming stability are improved when the resin composition is molded, and fish-eye defects can be reduced. Representative products of polymer processing aids 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, 60 to 90% by mass of methyl methacrylate and 10 to 10% of alkyl acrylate are used from the viewpoint of reducing the fish-eye defects of stretched films and improving the molding stability during film formation, especially the molding stability of film edges. Polymer processing aids containing 40% by mass are preferred, Metabrene (registered trademark) P530A, P550A and Paraloid K125 are more preferred, and Metabrene (registered trademark) P550A is particularly preferred.

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

When the polymeric processing aid is a monolayer particle, it preferably has an intrinsic viscosity of 3 to 6 dl/g. If the intrinsic viscosity is too low, the effect of improving moldability is low. If the intrinsic viscosity is too high, the melt fluidity of the resin composition tends to be lowered.

Although the method for forming the original film containing the (meth)acrylic resin, which is the basis of the stretched film, is not particularly limited, a preferred example thereof is a melt extrusion method. The melt-extrusion method is not particularly limited, and can be performed by any melt-extrusion method known in the art, such as the T-die method, the inflation method, and the like. At this time, the molding temperature is preferably 150 to 350°C, more preferably 200 to 300°C, even more preferably 240 to 280°C.

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

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 resulting resin composition can be improved. Also, the extruder preferably has a polymer filter to remove foreign matter. Structures of the polymer filter include, for example, leaf disk type and candle type. Furthermore, the extruder preferably has a gear pump in order to stabilize the discharge amount of the resin composition. A known gear pump can be used. When the extruder has an open vent section, a gear pump and a polymer filter, it is preferable to connect them in the order extruder-gear pump-polymer filter-die from the viewpoint of reducing foreign matter and suppressing vent-up. Moreover, in order to prevent deterioration of the resin composition in the extruder, it is preferable to carry out molding while passing nitrogen through the extruder.

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

Further, as another embodiment for producing a raw film, the extruded film-like molten resin is brought into contact with and adheres to a mirror roll by a contact auxiliary means from the viewpoint of the surface smoothness and thickness uniformity of the stretched film, Cooling and solidification are preferred. Examples of adhesion assisting devices include electrostatic adhesion devices, air knives, air chambers, and vacuum chambers. Among these, from the viewpoint of production stability, it is preferable to use an electrostatic adhesion device as the adhesion auxiliary device.

When edge pinning and wire pinning are used together as the adhesion assisting device, it is preferable to arrange the edge pinning and wire pinning in this order from the upstream side. Further, the wire pinning is preferably arranged downstream of the position where the temperature of the molten resin on the mirror-finished roll reaches the glass transition temperature, and upstream of the position where the resin is peeled from the mirror-finished roll.

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

After the original film is formed into a film, it is stretched to obtain 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 increasing the punching resistance of the laminate. The stretching treatment improves the mechanical strength of the film and improves the punching resistance. The stretching method is not particularly limited, and includes a simultaneous biaxial stretching method, a sequential biaxial stretching method, a tubular stretching method, a rolling method and the like. The stretching process preferably includes a preheating step, a stretching step, and a heat setting step in this order, and more preferably includes 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 film is preferably at least the glass transition temperature of the raw film and 40°C higher than the glass transition temperature, more preferably at least 5°C higher than the glass transition temperature of the raw film and It is not more than 30° C. higher than the glass transition temperature. When the temperature of the original film in the preheating step is within the range, breakage is less likely to occur in the stretching step in the production of the stretched film, productivity is improved, and the laminate has excellent stretchability. If the raw film has multiple glass transition temperatures, the highest value can be taken as the reference for the temperature range of the raw film.

In the stretching step, the temperature of the raw film (stretching temperature) is preferably 5°C higher than the glass transition temperature of the raw film and 40°C higher than the glass transition temperature, more preferably the glass of the raw film. It is 10°C higher than the transition temperature and 35°C higher than the glass transition temperature, more preferably 20°C higher than the glass transition temperature of the original film and 30°C higher than the glass transition temperature. Particularly preferably, the temperature is at least 22°C higher than the glass transition temperature of the original film and at most 27°C higher than the glass transition temperature. When the temperature of the raw film in the stretching process is in the range, breakage is less likely to occur in the stretching process, productivity is improved, and the laminate has excellent stretchability. If the raw film has multiple glass transition temperatures, the highest value can be taken as the reference for the temperature range of the raw film.

In the stretching step, the stretching ratio is preferably 1.5 to 8.0 times, more preferably 2.0 to 6.0 times, still more 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. In addition, when the draw ratio is 8.0 times or less, particularly 4.0 times or less, the laminate has excellent stretchability, and the laminate can be subjected to three-dimensional surface decoration molding (Three dimension Overlay Method: TOM molding). Even if it is used for 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 100-5000%/min, more preferably 500-2000%/min. When the stretching speed is within the range, breakage is less likely to occur in the stretching process during production of the stretched film, and productivity is improved.

The stretching process 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 at least 40°C lower than the glass transition temperature of the raw film and at most the glass transition temperature, more preferably at least 30°C lower than the glass transition temperature of the raw film and higher than the glass transition temperature. 10°C lower temperature or less.

It is preferable that the stretching process further includes a relaxation step after the heat setting step. A laminate having excellent stretchability can be obtained by the relaxation step. The relaxation rate is preferably 0.1-5%, more preferably 0.5-2%.

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, from the viewpoint of cost and surface hardness. .

The stretched film has a haze of 1% or less, preferably 0.8% or less, more preferably 0.5% or less, and still more preferably 0.4% or less. If the stretched film has a haze of more than 1%, the resulting laminate may have a metallic luster. 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, as well as the stretching temperature and stretching ratio. The haze of the stretched film can be determined according to JIS K 7136 (2000), and specifically by the method described later in Examples.

The stretched film preferably has a dimensional change rate of 0.1% or less, more preferably 0.08% or less, still more preferably 0.06% or less before and after being held at 85 ° C. for 30 minutes. More preferably 0.05% or less, particularly preferably 0.04% or less. Moreover, it is preferably 0.005% or more, more preferably 0.01% or more, and still more preferably 0.02% or more. When the dimensional change rate of the stretched film is within the range, the laminate has excellent stretchability, and even if the laminate is subjected to TOM molding or insert molding, breakage is less likely to occur. In addition, the punching resistance is further improved. The dimensional change rate before and after holding the stretched film at 85° C. for 30 minutes can be determined using a stress/strain control type thermomechanical analyzer, and specifically can be determined 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, as well as the stretching temperature, stretch ratio, heat setting temperature, relaxation rate, etc. You can control it.

At least one surface of the stretched film can be surface-treated in order to improve the adhesive strength with the functional layer described below. As such surface treatment, methods known in the art, such as corona discharge treatment, plasma treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, and activation treatment such as ozone treatment are used. be able to.

(metal layer)
Examples of the metal layer of 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 oxides 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, and tin oxide. , titanium oxide, iron oxide, copper oxide, nickel oxide, platinum oxide, palladium oxide, bismuth oxide, magnesium oxide, manganese oxide, molybdenum oxide, vanadium oxide, and barium oxide. These metals and/or metal oxides may be used alone or as a mixture of two or more. Among them, the metal layer is at least one selected from the group consisting of indium, aluminum, chromium, gold, silver and tin, from the viewpoint of having excellent metallic luster and excellent stretchability of the laminate. It preferably contains seeds, more preferably indium. The total content of the metal and metal oxide in the metal layer is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 99% by mass or more, and even more preferably 99% by mass. .99% by mass or more, and may be 100% by mass.

The thickness of the metal layer is preferably 10-500 nm, more preferably 30-300 nm, even more preferably 40-250 nm, still more preferably 50-200 nm. When the thickness of the metal layer is within the range, the metallic gloss of the laminate is further excellent, and the beautiful metallic gloss can be maintained even when the laminate is stretched by TOM molding and insert molding. A molded article having a laminate of is excellent in metallic gloss.

(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, and still more preferably 10% or less. If the total light transmittance exceeds 50%, there is a risk that the laminate will have a poor metallic luster. On the other hand, the total light transmittance is preferably 0.1% or more, more preferably 0.5% or more, and still more preferably 1% or more from the viewpoint of the formability of the laminate. The total light transmittance of the laminate can be determined according to JIS K 7136 (2000), and specifically can be determined by the method described later in Examples.

The laminate of the present invention preferably has an impact resistance 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, and even more preferably 6 J or more. be. When the impact resistance is within the range, the laminate tends to be more excellent in punching resistance. The impact resistance strength of the laminate can be determined by the method described later in Examples.

In the laminate, the stretched film and the metal layer are preferably in contact with each other because of low cost and low environmental load, but an anchor layer may be provided 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. The stretched film can be protected from the adhesive and whitening of the stretched film can be suppressed. Materials for the anchor layer include, for example, two-component curable urethane resin, thermosetting urethane resin, melamine resin, cellulose ester resin, chlorine-containing rubber resin, chlorine-containing vinyl resin, acrylic resin, epoxy resin, Examples include vinyl copolymer resins. Examples of methods for forming the anchor layer include coating methods such as gravure coating, roll coating and comma coating, gravure printing and screen printing.

The laminate of the present invention may consist only of the stretched film and the metal layer, but may further have layers other than the stretched film and the metal layer. Layers other than the stretched film and the metal layer include, for example, 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. is preferably provided in Also, 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 an adhesive layer, because the stretchability of the laminate is improved.

As the material of the printing layer, resins such as polyvinyl resin, polyamide resin, polyester resin, acrylic resin, polyurethane resin, polyvinyl acetal resin, polyester urethane resin, cellulose ester resin, and alkyd resin are used as binders. It is preferred to use colored inks containing pigments or dyes of appropriate colors as colorants. Examples of methods for forming the printed layer include ordinary printing methods such as offset printing, gravure printing, and screen printing. In particular, offset printing and gravure printing are suitable for multicolor printing and gradation expression. Moreover, 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 employed. Depending on the design to be expressed, the printed layer may be provided entirely or partially.

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

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, from the viewpoint of cost and surface hardness. .

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

(Molded body)
The molded article 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 formed 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 By having the laminate of the present invention on the surface of the adherend, the molded article is excellent in surface smoothness, surface hardness, and metallic gloss. Examples of the adherend include thermoplastic resins, thermosetting resins, woody base materials, and non-woody base materials.

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

Examples of thermosetting resins include epoxy-based resins, phenol-based resins, and melamine-based resins. Examples of non-woody substrates include substrates made of kenaf fibers and substrates made of carbon fibers.

The method for producing the molded body is not particularly limited, and examples thereof include a method of heating the laminate of the present invention and vacuum forming, air pressure forming, compression molding or TOM forming on the surface of an adherend. Alternatively, the laminate of the present invention can be preformed, inserted into a mold, and a molded body can be produced by insert molding or injection molding simultaneous bonding method in which molten resin is injection molded on the metal layer side.

(Application)
Applications of the laminate and molded product of the present invention are not particularly limited, and examples include vehicle decorative parts such as bumpers, emblems, vehicle exteriors, and vehicle interiors; building material parts such as wall materials, window films, window frames, and bathroom wall materials. household goods such as tableware, toys, and musical instruments; home appliance decorative parts such as vacuum cleaner housings, television housings, and air conditioner housings; interior members such as kitchen door covering materials;

Among them, the laminate of the present invention is excellent in punching resistance and metallic luster, and therefore can be suitably used for molded articles that require good design. In addition, the laminate of the present invention can be used as a metal-tone decorative film particularly suitably for metal-tone decorative applications.

EXAMPLES The present invention will be described more specifically below with reference to examples and comparative examples. In addition, the present invention is not limited to the following examples. In addition, the present invention includes all aspects that arbitrarily combine items representing technical characteristics such as characteristic values, forms, manufacturing methods, and uses as described above.

(Polymerization conversion rate)
A GL Sciences Inc. column was used in a gas chromatograph GC-14A manufactured by Shimadzu Corporation. Inert CAP 1 (df = 0.4 µm, ID = 0.25 mm, length = 60 m) was connected, and the injection temperature was 180 ° C., the detector temperature was 180 ° C., and the column temperature was held at 60 ° C. for 5 minutes. C. to 200.degree. C. at a rate of temperature increase of 10.degree. C./min and held at 200.degree.

(Weight average molecular weight Mw, weight average molecular weight Mw/number average molecular weight Mn)
A chromatogram was measured by gel permeation chromatography (GPC) under the following conditions, and a value converted to the molecular weight of standard polystyrene was calculated. The baseline is the point where the slope of the high molecular weight peak on the GPC chart changes from zero to positive when viewed from the early retention time, and the point where the slope of the low molecular weight peak changes from negative to zero when viewed from the early retention time. A line connecting the points where
GPC device: HLC-8320 manufactured by Tosoh Corporation
Detector: Differential refractive index detector Column: Two TSKgel SuperMultipore HZM-M manufactured by Tosoh Corporation and SuperHZ4000 connected in series were used.
Eluent: Tetrahydrofuran Eluent flow rate: 0.35 mL/min Column temperature: 40°C
Calibration curve: Created using 10 standard polystyrene data

(Syndiotacticity (rr) in triplets)
A ¹ H-NMR spectrum was measured using a nuclear magnetic resonance apparatus (ULTRA SHIELD 400 PLUS, manufactured by Bruker), using deuterated chloroform as a solvent, at room temperature (25° C.), and under the conditions of 64 integrations. . From the spectrum, the area A _O in the region of 0.6 to 0.95 ppm when TMS is 0 ppm and the area A _Y in the region of 0.6 to 1.35 ppm are measured. Syndiotacticity (rr) (%) was calculated by the formula: (A _O /A _Y )×100.

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

(haze)
A 50 mm×50 mm piece was cut out from the stretched film obtained in the example, and the haze was measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., SH7000) in accordance with JIS K 7136 (2000).

(Dimensional change rate)
A test piece of 40 mm×5 mm 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 gripped 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 the film was attached to a thermomechanical analyzer (Q400EM manufactured by TA Instruments).
With the test piece set as described above, the test piece is 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. 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 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 measured before and after holding at 85 ° C. for 30 minutes. rate of change.
Dimensional change rate (%) = ΔL [unit: mm]/24 [unit: mm] x 100 (1)

(Total light transmittance)
A 50 mm × 50 mm piece was cut from the laminate obtained in the example to obtain a test piece, and the total light transmittance was measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., SH7000) in accordance with JIS K 7136 (2000). did.

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

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

(200% stretchability)
A 100 mm × 100 mm test piece was cut out from the laminate obtained in the example, set in a biaxial stretching birefringence measuring device (manufactured by Eto Co., Ltd., SDR-563K), at a temperature of 145 ° C., a stretching rate of 3600%/min and a stretching ratio. Stretched under the condition of 200%. Five test pieces were stretched by such a method and evaluated as follows.
A: Not even one sheet was broken.
B: One or two sheets were broken.
C: Three or more sheets were broken.

(250% stretchability)
A 100 mm × 100 mm test piece was cut out from the laminate obtained in the example, set in a biaxial stretching birefringence measuring device (manufactured by Eto Co., Ltd., SDR-563K), at a temperature of 145 ° C., a stretching rate of 3600%/min and a stretching ratio. Stretched under the condition of 250%. Five test pieces were stretched by such a method and evaluated as follows.
A: Not even one sheet was broken.
B: One or two sheets were broken.
C: Three or more sheets were broken.

(exterior)
The laminate obtained in the example was placed on white paper (C2r, manufactured by Fuji xerox), 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 fitted with a stirrer and sampling tube was purged 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 fed into this raw material liquid to remove dissolved oxygen in the raw material liquid.
A tank-type reactor connected to an autoclave through a pipe was charged with the raw material liquid up to 2/3 of its capacity. While maintaining the temperature at 140° C., the polymerization reaction was first started in a batch mode. When the polymerization conversion rate reached 55% by mass, the raw material solution was supplied from the autoclave to the tank reactor at a flow rate that gave an average residence time of 150 minutes while maintaining the temperature at 140°C. The polymerization reaction was switched to a continuous flow system in which the reaction liquid was extracted 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 reactor in a steady state was supplied to a shell and tube heat exchanger having an internal temperature of 230° C. at a flow rate that gave an average residence time of 2 minutes, and was heated. Then, the heated reaction liquid was introduced into a flash evaporator to remove volatile matter mainly composed of unreacted monomers to obtain a molten resin. The molten resin from which volatile matter was removed was supplied to a twin-screw extruder having an internal temperature of 260° C., extruded in a strand shape, and cut with a pelletizer to obtain a pellet-like (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 a glass reaction vessel equipped with a stirring blade and a three-way cock was purged with nitrogen. To this, 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 0.45M 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 with a concentration of 1.3 M (solvent: 95% by mass of cyclohexane, 5% by mass of n-hexane %) of 0.011 parts by mass. To these raw materials, 100 parts by mass of distilled and purified MMA was added dropwise at 20° C. over 30 minutes while stirring. After the dropwise addition was completed, the mixture 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%. The obtained solution was diluted by adding 2.7 parts by mass of toluene. Then, the diluted solution was poured into 180 parts by mass of methanol to obtain a precipitate. The resulting 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 resins were prepared.
Phenoxy1: manufactured by 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)
(Meth) acrylic resin (X1) 40 parts by mass, (meth) acrylic resin (X2) 60 parts by mass, triblock structure (meth) obtained with reference 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 (manufactured by Mitsubishi Chemical Corporation, Metabrene (registered Trademark) P550A) is mixed with 2 parts by mass in a Henschel mixer, kneaded and extruded using a vented twin-screw extruder with a screw diameter of 41 mm set at 260 ° C., and a methacrylic resin composition having a glass transition temperature Tg of 124 ° C. A pellet of (M1) was obtained.

(Production Example 4) Methacrylic resin composition (M2)
(Meth)acrylic resin (X1) 85 parts by mass and 15 parts by mass of a (meth)acrylic block copolymer having a triblock structure obtained with reference to Reference Example 3 of JP 2017-78168 A Henschel mixer and kneaded and extruded using a vented twin-screw extruder with a screw diameter of 41 mm set at 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)
Obtained with reference to Reference Examples 1 and 2 of International Publication No. 2016/139950, 70 parts by mass of (meth)acrylic resin (X3) consisting of 99% by mass of methyl methacrylate and 1% by mass of methyl acrylate, and international 30 parts by mass of three-layer structure (meth)acrylic elastic particles having a particle diameter of 0.23 μm as measured by a dynamic light scattering method obtained with reference to Reference Example 1 of Japanese Patent Application Publication No. 2014/167868 were added to Henschel. The mixture was mixed in a mixer and kneaded and extruded using a vented twin-screw extruder with a screw diameter of 41 mm set at 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)
(Meth) acrylic resin (X1) 80 parts by mass, (meth) acrylic resin (X2) 20 parts by mass, triblock structure (meth) obtained with reference to Reference Example 3 of JP-A-2017-78168 1 part by mass of acrylic block copolymer, 0.8 parts by mass of polycarbonate resin (SD-POLYCA 401-40, manufactured by Sumika Polycarbonate Co., Ltd.), 2.5 parts by mass of phenoxy resin (Phenoxy1), UV absorber (manufactured by ADEKA) , LA-F70) 1 part by mass, and 2 parts by mass of a polymer processing aid (Metabrene (registered trademark) P550A, manufactured by Mitsubishi Chemical Corporation) were mixed in a Henschel mixer, and a screw diameter of 41 mm with a vent set at 260 ° C. The mixture was kneaded and extruded using a screw 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)
A pellet-shaped methacrylic resin composition (M1) was melted at 270° C. in a φ65 mm vented single-screw extruder connected to a T-die, and extruded into a sheet through 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 subjected to electrostatic application (edge pinning, voltage 4 V, contact point with the cast roll 5 mm in the vertical direction and 10 mm on the T-die side), the film was 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. Subsequently, a raw film related to a tenter type simultaneous biaxial stretching machine was introduced and preheated at 147°C. Then, the original film was subjected to simultaneous biaxial stretching of 3.25 times (1.80 times in the longitudinal direction and 1.80 times in the width direction) at 147°C. At this time, the stretching speed was 1000%/min in both the longitudinal direction and the width direction. Then, it was cooled to 105° C. and heat-set for 1 minute to obtain a stretched film of 40 μm.

(Manufacturing of laminate)
An indium layer having a thickness of 50 nm is formed on the obtained stretched film by vacuum deposition using a vacuum deposition apparatus (VE-2030, resistance heating method, manufactured by Vacuum Device Co., Ltd.) to obtain a laminate as a metallic decorative film. 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 deposition conditions were a degree of vacuum of 7×10 ⁻³ Pa and a rate of 0.8 Å/sec for 10 minutes. Table 2 shows the evaluation results. When the appearance of the obtained laminate was observed from the stretched film side, it had a beautiful metallic luster.

(Production of compact)
The obtained laminate was cut into a size of 210 mm×300 mm to obtain a test piece. A polystyrene resin clip case (CP-500, manufactured by Plus Co., Ltd., width 76 mm×depth 62 mm×height 40 mm) was used as an adherend. The adherend and the test piece were set in a TOM forming apparatus (manufactured by Fuse Vacuum Co., Ltd., NGF-0406T) so that the metal layer of the test piece faced the convex side of the adherend. TOM molding was performed under the condition of a pressure difference of 300 kPa to obtain a molded body. The laminate was not broken in the molded article, and the molded article 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. Table 2 shows the evaluation results. When the appearance of the obtained laminate was observed from the stretched film side, 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. Table 2 shows the evaluation results. When the appearance of the obtained laminate was observed from the stretched film side, it had a beautiful metallic luster, but the color of indium was light as a whole.

Example 4
A laminate was produced in the same manner as in Example 1, except that heat setting was not performed in the production of the stretched film of Example 1. Table 2 shows the evaluation results. When the appearance of the obtained laminate was observed from the stretched film side, 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 draw ratio was 4.50 times (2.12 times in the longitudinal direction and 2.12 times in the width direction ) to produce a laminate in the same manner as in Example 1. Table 2 shows the evaluation results. When the appearance of the obtained laminate was observed from the stretched film side, it had a beautiful metallic luster.

Example 6
(Manufacturing of laminate)
In the production of the raw film of Example 1, the thickness of the raw film was changed to 250 μm, and in the production of the stretched film, the draw ratio was 6.25 times (2.50 times in the longitudinal direction and 2.50 times in the width direction ) to produce a laminate in the same manner as in Example 1. Table 2 shows the evaluation results. When the appearance of the obtained laminate was observed from the stretched film side, it had a beautiful metallic luster.

(Production of compact 1)
The obtained laminate was cut into a size of 210 mm×300 mm to obtain a test piece. A polystyrene resin clip case (CP-500, manufactured by Plus Co., Ltd., width 76 mm×depth 62 mm×height 40 mm) was used as an adherend. The adherend and the test piece were set in a TOM forming apparatus (manufactured by Fuse Vacuum Co., Ltd., NGF-0406T) so that the metal layer of the test piece faced the convex side of the adherend. When TOM molding was performed under the condition of a pressure difference of 300 kPa, the laminate was broken.

(Production of compact 2)
The obtained laminate was cut into a size of 210 mm×300 mm, and an adhesive (Arontac S-1511X manufactured by Toagosei Co., Ltd.) was applied to the metal layer side to form an adhesive layer having a thickness of 50 μm to prepare a test piece. A polystyrene resin clip case (CP-500, manufactured by Plus Co., Ltd., width 76 mm×depth 62 mm×height 40 mm) was used as an adherend. The adherend and the test piece were set in a TOM forming apparatus (manufactured by Fuse Vacuum Co., Ltd., NGF-0406T) so that the metal layer of the test piece faced the convex side of the adherend. TOM molding was performed under the condition of a pressure difference of 300 kPa to obtain a molded body. The laminate was not broken in the molded article, and the molded article 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 (meth)acrylic resin (X1), and the preheating temperature and stretching temperature were changed to 145 ° C. Example 1 A laminate was produced in the same manner. Table 2 shows the evaluation results. When the appearance of the obtained laminate was observed from the stretched film side, 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 stretching temperature were changed to 135°C, and the heat setting temperature was changed to 95°C. Table 2 shows the evaluation results. When the appearance of the obtained laminate was observed from the stretched film side, it had a beautiful metallic luster.

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

Comparative example 1
In the production of the raw film of Example 1, the electrostatic application was changed to sandwiching by metal elastic rolls, the thickness of the raw film was changed to 40 μm, and in the production of the stretched film, stretching was not performed. A laminate was produced in the same manner as in Example 1. Table 2 shows the evaluation results. 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 produced in the same manner. Table 2 shows the evaluation results. When the appearance of the obtained laminate was observed from the stretched film side, the reflected light appeared to flicker 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 produced in the same manner. Table 2 shows the evaluation results. When the appearance of the obtained laminate was observed from the stretched film side, the reflected light was blurred and blurred, and the metallic luster was impaired.

The laminates obtained in Examples 1 to 10 have a stretched film layer with a haze of 1% or less and a total light transmittance of 50% or less, compared to Comparative Examples 1 to 3. and excellent metallic luster. Among them, the laminates obtained in Examples 1 to 5, 7, 9 and 10 are excellent in stretchability by 200%, and the laminates obtained in Examples 1 to 3, 7, 9 and 10 are excellent in stretchability by 250%. 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 dark as a whole.
Since the laminate obtained in Comparative Example 1 did not have a stretched film layer, the punching resistance was poor.
In the laminates obtained in Comparative Examples 2 and 3, the stretched film had a haze of more than 1%, so the metallic luster was impaired.

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

Claims (12)

A laminate having a stretched film and a metal layer and having a total light transmittance of 50% or less,
The stretched film contains 100 parts by mass of a (meth)acrylic resin containing 40% by mass or more and 70% by mass or less of polymethyl methacrylate having a syndiotacticity (rr) of 65% or more in triad display, and acrylic acid It contains 0.5 parts by mass or more and 4 parts by mass or less of a (meth)acrylic block copolymer in which the ester polymer block (b1) and the methacrylic acid ester polymer block (b2) are bonded, and has a haze of 1% or less . , the dimensional change rate before and after holding at 85 ° C. for 30 minutes is 0.05% or less ,
laminate. The laminate according to claim 1, wherein the stretched film contains a phenoxy resin, and the content of the phenoxy resin in the stretched film is 3 parts by mass or less with respect to 100 parts by mass of the (meth)acrylic resin. . Claim 1 or 2, wherein 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 weight with respect to 100 parts by weight of the (meth)acrylic resin. The laminate according to . The laminate according to any one of claims 1 to 3 , wherein the stretched film has a thickness of 5 to 200 µm. 5. The laminate according to any one of claims 1 to 4 , wherein said metal layer contains at least one selected from the group consisting of indium, aluminum, chromium, gold, silver and tin. The laminate according to any one of claims 1 to 5 , wherein the metal layer has a thickness of 10 to 500 nm. The laminate according to any one of claims 1 to 6 , which has an impact resistance strength of 4J or more. The laminate according to any one of claims 1 to 7 , wherein said stretched film and said metal layer are in contact with each other. The laminate according to any one of claims 1 to 8 , having a thickness of 5 to 500 µm. A metallic decorative film comprising the laminate according to any one of claims 1 to 9 . A molded article comprising the laminate according to any one of claims 1 to 9 and an adherend. The method for producing a laminate according to any one of claims 1 to 9 , wherein polymethyl methacrylate having a triad syndiotacticity (rr) of 65% or more is added in an amount of 40% by mass or more and 70% by mass. 100 parts by mass of a (meth)acrylic resin containing the following , and 0.5 parts by mass of a (meth)acrylic block copolymer in which an acrylic ester polymer block (b1) and a methacrylic ester polymer block (b2) are bonded Manufacture of a laminate comprising a step of stretching a raw film containing 4 parts by mass or less to 1.5 to 8.0 times to produce the stretched film, and a step of forming a metal layer on the stretched film Method.