JP2018020487A - Multilayer film and molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multilayer film which is suitable for three-dimensional coating molding and has a smooth surface when bonded to an adherend, and to provide a molded body to which the multilayer film is bonded and that is excellent in appearance.SOLUTION: A multilayer film has at least a layer (A) and a layer (B), where the layer (A) is formed of a thermoplastic polymer composition which contains 1-50 pts.mass of a polypropylene-based resin (b) with respect to 100 pts.mass of a thermoplastic elastomer (a) that is a block copolymer containing a polymer block (a1) composed of an aromatic vinyl compound unit and a polymer block (a2) composed of a conjugated diene compound unit or its hydrogenation product, a loss tangent (tanδ) measured at a frequency of 1 Hz and a temperature of 250°C by dynamic viscoelasticity measurement of the thermoplastic resin composition is 1.0 or more, and the layer (B) is composed of a (meth)acrylic resin.SELECTED DRAWING: None

Description

  The present invention relates to a multilayer film having a layer composed of a thermoplastic polymer composition and a molded body to which the multilayer film is bonded.

  For exterior and wallpaper of home appliances, interior decoration of automobiles, decoration with patterns such as woodgraining, addition of design such as metallic tone and piano black tone, and addition of functionality such as scratch resistance and weather resistance For the purpose, a decorative resin film is used.

  As a method for decorating the three-dimensional shape using these films, for example, a film insert molding method in which a film is inserted into a mold and injection molded is used. In this method, it is necessary to press-shape the film in advance so as to match the mold shape. As another decoration method, there is three-dimensional covering molding in which a film is coated on a three-dimensional shape product. In this method, it is not necessary to press-form the film in advance, but when the film is bonded to the adherend, it may be necessary to separately apply an adhesive. This work requires a solvent coating process, a drying process, and a curing process, and it takes a long time to impart adhesiveness, and there is a concern about deterioration of the working environment due to VOC, so there is no need for an adhesive. There is a need for a decorative film that can be bonded.

  Patent Document 1 discloses a composition comprising one or more block copolymers in which at least two monoalkenyl arene blocks are separated by a saturated conjugated diene block, a tackifier resin such as a polyolefin, a hydrogenated hydrocarbon resin, and the like. There has been proposed a pressure sensitive adhesive sheet comprising: In Patent Document 2, a block copolymer comprising at least two polymer blocks A mainly made from vinyl aromatic compounds and at least one polymer block B mainly made from conjugated diene compounds, and / or Copolymer comprising a block copolymer obtained by hydrogenation, a vinyl cyanide compound monomer component, a rubber component, an aromatic vinyl compound monomer component and any other copolymerizable monomer component A resin composition for heat fusion comprising a coalesced, non-aromatic rubber softener is disclosed.

  Patent Document 3 discloses a block copolymer having a polymer block containing an aromatic vinyl compound unit and a polymer block containing a conjugated diene compound unit, or a thermoplastic elastomer which is a hydrogenated product thereof, a polyvinyl acetal resin, and A method for producing an adhesive body is disclosed in which a film made of a thermoplastic polymer composition containing a polar group-containing polypropylene resin is bonded to an insert member, and then the resin member is insert-molded.

JP-A-2005-48195 Japanese Patent No. 4428793 JP 2014-168940 A

The pressure-sensitive adhesive sheet described in Patent Document 1 has a problem that the surface tackiness is high due to the tackifier, and the handleability is poor and the productivity is low, and the adhesive performance varies due to bleeding out of the tackifier. is there. Similarly, the film made of the resin composition for heat fusion described in Patent Document 2 has a problem due to the contained non-aromatic rubber softener.
When the present inventors examined the thermoplastic polymer composition described in Patent Document 3 and a film made of the thermoplastic polymer composition, the surface of the thermoplastic polymer composition was roughened and smooth. It was difficult to obtain a film. Further, when the film is subjected to three-dimensional coating, the surface roughness of the thermoplastic polymer composition propagates to the surface of the film substrate, the surface of the substrate is not smooth, and the design property is deteriorated. was there.

  As described above, an object of the present invention is to provide a multilayer film that is suitable for three-dimensional coating and has a smooth surface when adhered to an adherend and excellent surface properties. Moreover, the further objective of this invention is to provide the molded object which is excellent in the external appearance to which the said multilayer film adhered.

According to the present invention, the above object is
[1] A multilayer film having at least a layer (A) and a layer (B), wherein the layer (A) is a polymer block (a1) composed of an aromatic vinyl compound unit and a polymer block composed of a conjugated diene compound unit. From the thermoplastic polymer composition containing 1 to 50 parts by mass of the polypropylene resin (b) with respect to 100 parts by mass of the block copolymer containing (a2) or the hydrogenated thermoplastic elastomer (a). The loss tangent (tan δ) measured at a frequency of 1 Hz and a temperature of 250 ° C. by dynamic viscoelasticity measurement of the thermoplastic polymer composition is 1.0 or more, and the layer (B) is a (meth) acrylic resin. A multilayer film composed of
[2] The multilayer film according to [1], wherein the thermoplastic elastomer (a) has an order-disorder transition temperature (ODT) of 300 ° C. or lower.
[3] The multilayer film according to [1] or [2], wherein the thermoplastic polymer composition does not contain a (meth) acrylic resin.
[4] The multilayer film according to any one of [1] to [3], which is produced by a coextrusion molding method at a molding temperature of 240 to 260 ° C.
[5] A molded body in which the multilayer film according to any one of [1] to [4] is adhered to the surface of an adherend,
[6] The method for producing a molded body according to [5], wherein the multilayer film is adhered to an adherend using vacuum molding and / or pressure molding.
[7] The method for producing a molded article according to [6], further comprising a step of heating and softening the multilayer film in a range of 100 to 160 ° C.
Is achieved by providing

  The multilayer film of the present invention is suitable for three-dimensional coating, has a smooth surface when adhered to an adherend, and has excellent surface properties. Moreover, the molded article of the present invention to which the multilayer film is adhered is excellent in appearance due to the surface properties of the film.

[Layer (A)]
The layer (A) in the multilayer film of the present invention is a block copolymer containing a polymer block (a1) composed of aromatic vinyl compound units and a polymer block (a2) composed of conjugated diene compound units, or a hydrogenated product thereof. It is comprised from the thermoplastic polymer composition containing the thermoplastic elastomer (a) which is these, and a polypropylene resin (b). In the multilayer film, the layer (A) mainly functions as an adhesive layer.

<Thermoplastic elastomer (a)>
Examples of the aromatic vinyl compound constituting the polymer block (a1) composed of the aromatic vinyl compound unit contained in the thermoplastic elastomer (a) include styrene, α-methylstyrene, 2-methylstyrene, and 3-methyl. Styrene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, etc. Can be mentioned. The polymer block containing the aromatic vinyl compound unit may be composed of a structural unit derived from only one of these aromatic vinyl compounds, or may be composed of a structural unit derived from two or more types. . Of these, styrene, α-methylstyrene, and 4-methylstyrene are preferable.

  The polymer block (a1) comprising aromatic vinyl compound units is preferably 80% by mass or more of aromatic vinyl compound units, more preferably 90% by mass or more of aromatic vinyl compound units, and still more preferably 95% by mass of aromatic vinyl compound units. % Is a polymer block containing at least%. The polymer block (a1) may have only an aromatic vinyl compound unit, but has other copolymerizable monomer units together with the aromatic vinyl compound unit as long as the effects of the present invention are not impaired. You may do it. Examples of other copolymerizable monomers include 1-butene, pentene, hexene, butadiene, isoprene, and methyl vinyl ether. When it has another copolymerizable monomer unit, the proportion thereof is preferably 20% by mass or less, more preferably 10%, based on the total amount of the aromatic vinyl compound unit and the other copolymerizable monomer unit. It is not more than mass%, more preferably not more than 5 mass%.

The conjugated diene compound constituting the polymer block (a2) composed of the conjugated diene compound unit contained in the thermoplastic elastomer (a) is preferably a conjugated diene compound having 4 to 20 carbon atoms. Examples of the conjugated diene compound having 4 to 20 carbon atoms include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 1, Examples include 3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, myrcene, and terpenes.
The polymer block (a2) containing a conjugated diene compound unit may be composed of a structural unit derived from only one of these conjugated diene compounds, or may be composed of a structural unit derived from two or more types. Good. In particular, it is preferably composed of a structural unit derived from butadiene or isoprene or a structural unit derived from butadiene and isoprene.

  The polymer block (a2) composed of conjugated diene compound units preferably contains 80% by mass or more of conjugated diene compound units, more preferably 90% by mass or more, more preferably 95% by mass or more of conjugated diene compound units. It is a polymer block. The polymer block (a2) may have only a conjugated diene compound unit, but has other copolymerizable monomer units together with the conjugated diene compound unit, as long as it does not interfere with the present invention. May be. Examples of other copolymerizable monomers include styrene, α-methylstyrene, 4-methylstyrene, and the like. When it has another copolymerizable monomer unit, the proportion thereof is preferably 20% by mass or less, more preferably 10% by mass with respect to the total amount of the conjugated diene compound unit and the other copolymerizable monomer unit. % Or less, more preferably 5% by mass or less.

The bonding form of the conjugated diene constituting the polymer block (a2) is not particularly limited. For example, in the case of butadiene, 1,2-bond and 1,4-bond can be formed, and in the case of isoprene, 1,2-bond, 3,4-bond and 1,4-bond can be formed.
The total amount of 1,2-bond and 3,4-bond can be calculated by ¹ H-NMR measurement. Specifically, the integrated value of the peak existing at 4.2 to 5.0 ppm derived from 1,2-bond and 3,4-bond units and 5.0-5. It can be calculated from the ratio with the integrated value of the peak existing at 45 ppm.

The bonding form of the polymer block (a1) and the polymer block (a2) is not particularly limited, and may be linear, branched, radial, or a combination of two or more thereof. Especially, the form which each block couple | bonded linearly is preferable, When a polymer block (a1) is represented by a1 and a polymer block (a2) is represented by a2, (a1-a2) _l , a1- (a2-a1 ) A bond form represented by _m or a2- (a1-a2) _n is preferred. In addition, said l, m, and n represent an integer greater than or equal to 1 each independently.
Among them, the thermoplastic elastomer (a) is preferably a block copolymer containing two or more polymer blocks (a1) and one or more polymer blocks (a2). From the viewpoint, a triblock copolymer or a pentablock copolymer is more preferable.

  The content of the polymer block (a1) composed of the aromatic vinyl compound unit in the thermoplastic elastomer (a) is preferably 5 to 5 with respect to the entire thermoplastic elastomer (a) from the viewpoint of flexibility and mechanical properties. It is 75 mass%, More preferably, it is 5-60 mass%, More preferably, it is 10-40 mass%.

  From the viewpoint of improving heat resistance and weather resistance, the thermoplastic elastomer (a) is a hydrogen obtained by hydrogenating a part or all of the polymer block (a2) (hereinafter sometimes referred to as “hydrogenation”). It may be an additive. The hydrogenation rate at that time is preferably 80% or more, more preferably 90% or more. Here, in this specification, the hydrogenation rate is a value obtained by measuring the iodine value of the block copolymer before and after the hydrogenation reaction.

The weight average molecular weight of the thermoplastic elastomer (a) is preferably 30,000 to 500,000, more preferably 50,000 to 400,000, more preferably 60, from the viewpoint of its mechanical properties and molding processability. , 000-300,000. Here, the weight average molecular weight is a polystyrene-reduced weight average molecular weight determined by gel permeation chromatography (GPC) measurement.
A thermoplastic elastomer (a) may be used individually by 1 type, and may be used in combination of 2 or more type.

  The thermoplastic elastomer (a) preferably has an order-disorder transition temperature (ODT) of 300 ° C. or lower, more preferably 280 ° C. or lower, and further preferably 250 ° C. or lower. When the ODT of the thermoplastic elastomer (a) is 300 ° C. or less, the surface smoothness of the resulting multilayer film is further improved. The order-disorder transition temperature (ODT) of the thermoplastic elastomer (a) is the weight average molecular weight or molecular weight distribution (Mw / Mn) of the thermoplastic elastomer (a), or the polymer block (a1) and the polymer block (a2). ) Can be set to a desired value by adjusting or the like. In addition, when using combining 2 or more types of thermoplastic elastomers (a), what contains 50 mass% or more of thermoplastic elastomers (a) whose ODT is 300 degrees C or less is preferable, and what contains 70 mass% or more is more preferable. In this specification, ODT is a value obtained by the method described in the examples.

  Although it does not specifically limit as a manufacturing method of a thermoplastic elastomer (a), For example, it can manufacture by an anionic polymerization method. Specifically, (i) a method of sequentially polymerizing the aromatic vinyl compound, the conjugated diene compound, and then the aromatic vinyl compound using an alkyl lithium compound as an initiator; (ii) using an alkyl lithium compound as an initiator A method of sequentially polymerizing the aromatic vinyl compound and the conjugated diene compound, and then coupling by adding a coupling agent; (iii) using the dilithium compound as an initiator, the conjugated diene compound, and then the aromatic vinyl Examples include a method of polymerizing compounds sequentially.

Furthermore, the hydrogenated product of the thermoplastic elastomer (a) can be produced by subjecting the unhydrogenated thermoplastic elastomer (a) obtained above to a hydrogenation reaction. In the hydrogenation reaction, the unhydrogenated thermoplastic elastomer (a) obtained above is dissolved in a solvent inert to the reaction and the hydrogenation catalyst, or the unhydrogenated thermoplastic elastomer (a) is dissolved. Can be used as is without isolation from the reaction solution, and reacted with hydrogen in the presence of a hydrogenation catalyst.
Moreover, a commercial item can also be used as a thermoplastic elastomer (a).

<Polypropylene resin (b)>
As the polypropylene resin (b), a known polypropylene resin can be used, but the content of structural units derived from propylene (hereinafter sometimes referred to as propylene content) is 60 mol% or more. Some are preferred. The content of the structural unit derived from propylene is preferably 80 mol% or more, more preferably 80 to 100 mol%, still more preferably 90 to 100 mol%, and particularly preferably 95 to 99 mol%. Examples of structural units derived from other than propylene include structural units derived from ethylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 1-nonene and 1-decene. In addition to structural units derived from α-olefins such as those described above, structural units derived from modifiers described later are also included.

Examples of the polypropylene resin (b) include homopolypropylene, propylene-ethylene random copolymer, propylene-ethylene block copolymer, propylene-butene random copolymer, propylene-ethylene-butene random copolymer, propylene- Examples include pentene random copolymers, propylene-hexene random copolymers, propylene-octene random copolymers, propylene-ethylene-pentene random copolymers, propylene-ethylene-hexene random copolymers, and modified products thereof. It is done. Examples of the modified product include those obtained by graft copolymerizing a modifier with a polypropylene resin, and those obtained by copolymerizing a modifier with the main chain of the polypropylene resin.
Among these, the polypropylene-based resin (b) is preferably a nonpolar polypropylene-based resin having no polar functional group. From the viewpoint of being relatively inexpensive and easily available, homopolypropylene, propylene-ethylene random A copolymer and a propylene-ethylene block copolymer are preferred.

  The polypropylene resin (b) can be synthesized by a conventionally known method. For example, using a Ziegler-Natta type catalyst or a metallocene type catalyst, a propylene homopolymer, a random or block propylene and an α-olefin The copolymer can be synthesized.

  A polypropylene resin (b) may be used individually by 1 type, and may use 2 or more types together. Moreover, a commercial item can also be used for polypropylene resin (b).

<Thermoplastic polymer composition>
The thermoplastic polymer composition constituting the layer (A) contains 1 to 50 parts by mass of the polypropylene resin (b) with respect to 100 parts by mass of the thermoplastic elastomer (a). By containing the polypropylene resin (b) in this range, the thermoplastic polymer composition exhibits strong adhesive strength, excellent flexibility and mechanical properties. Thereby, the adhesive force and handling property of the resulting multilayer film are further improved. A more preferable range is 1 to 30 parts by mass of the polypropylene resin (b) with respect to 100 parts by mass of the thermoplastic elastomer (a), and still more preferably a polypropylene resin (100 parts by mass of the thermoplastic elastomer (a). b) 5 to 25 parts by mass.

  In the present invention, the loss tangent (tan δ) of the thermoplastic polymer composition constituting the layer (A) measured by dynamic viscoelasticity measurement at a frequency of 1 Hz and a temperature of 250 ° C. is 1.0 or more. When the loss tangent (tan δ) is 1.0 or more, unevenness due to elastic recovery of the thermoplastic polymer composition that can occur during the formation of the multilayer film can be suppressed. Thereby, the surface of the layer (A) made of the thermoplastic polymer composition becomes smooth, so that the surface when adhered to the adherend is smooth and has excellent surface properties. Appearance is also excellent. On the other hand, when the loss tangent (tan δ) is less than 1.0, the surface shape of the layer (A) made of the thermoplastic resin composition is rough, and therefore, when adhered to the adherend, an orange peel-like surface is formed on the surface of the multilayer film. As a result, the resulting molded article is inferior in appearance. From the above viewpoint, the loss tangent (tan δ) of the thermoplastic polymer composition measured by dynamic viscoelasticity measurement at a frequency of 1 Hz and a temperature of 250 ° C. is more preferably 2.0 or more. The upper limit of the loss tangent (tan δ) is not particularly limited, but is usually 10 or less.

The thermoplastic polymer composition constituting the layer (A) is an olefin-based material in addition to the thermoplastic elastomer (a) and the polypropylene resin (b), as necessary, within a range that does not significantly impair the effects of the present invention. Other thermoplastic polymers such as a polymer, a styrene polymer, a polyphenylene ether resin, and polyethylene glycol may be contained. Examples of the olefin polymer include polyethylene, polypropylene, polybutene, block copolymers of propylene and other α-olefins such as ethylene and 1-butene, and random copolymers.
When other thermoplastic polymer is contained, the content thereof is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, more preferably 20 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (a). Hereinafter, it is more preferably 10 parts by mass or less, particularly preferably 5 parts by mass or less.
The thermoplastic polymer composition constituting the layer (A) preferably does not contain a (meth) acrylic resin.

The thermoplastic polymer composition constituting the layer (A) is colored within the range that does not impair the effects of the present invention, as necessary, such as antioxidants, lubricants, light stabilizers, processing aids, pigments and pigments. An agent, a flame retardant, an antistatic agent, a matting agent, silicone oil, an antiblocking agent, an ultraviolet absorber, a release agent, a foaming agent, an antibacterial agent, an antifungal agent, and a fragrance may be contained.
Examples of the antioxidant include hindered phenol-based, phosphorus-based, lactone-based, and hydroxyl-based antioxidants.

  The method for preparing the thermoplastic polymer composition constituting the layer (A) is not particularly limited and may be prepared by any method as long as the above components can be uniformly mixed. Used. Melt-kneading can be performed using, for example, a melt-kneading apparatus such as a single-screw extruder, a twin-screw extruder, a kneader, a batch mixer, a roller, a Banbury mixer, and the melt-kneading is usually preferably performed at 170 to 270 ° C. As a result, a thermoplastic polymer composition can be obtained.

[Layer (B)]
The layer (B) in the multilayer film of the present invention is composed of a (meth) acrylic resin. In the multilayer film, the layer (B) mainly functions as a base material layer. As the (meth) acrylic resin, a (meth) acrylic resin composition containing a methacrylic resin (F) and an elastic body (R) is more preferable.

  The methacrylic resin (F) has a structural unit derived from methyl methacrylate, preferably 80% by mass or more, more preferably 90% by mass or more. In other words, the methacrylic resin (F) has a structural unit derived from a monomer other than methyl methacrylate, preferably 20% by mass or less, more preferably 10% by mass or less, and only methyl methacrylate is used as a monomer. It may be a polymer.

  Examples of monomers other than methyl methacrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, s-butyl acrylate, and tert-acrylate. Butyl, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 2-acrylate Acrylic esters such as hydroxyethyl, 2-ethoxyethyl acrylate, glycidyl acrylate, allyl acrylate, cyclohexyl acrylate, norbornenyl acrylate, isobornyl acrylate, etc .; ethyl methacrylate, n-methacrylate Pill, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate , Pentadecyl methacrylate, dodecyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-ethoxyethyl methacrylate, glycidyl methacrylate, allyl methacrylate, cyclohexyl methacrylate, Methacrylic acid esters other than methyl methacrylate such as norbornenyl methacrylate and isobornyl methacrylate; acrylic acid, methacrylic acid, maleic anhydride, maleic acid, itaconic acid Unsaturated carboxylic acids of olefins; olefins such as ethylene, propylene, 1-butene, isobutylene and 1-octene; conjugated dienes such as butadiene, isoprene and myrcene; styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, etc. And aromatic vinyl compounds such as acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl pyridine, vinyl ketone, vinyl chloride, vinylidene chloride, and vinylidene fluoride.

  The stereoregularity of the methacrylic resin (F) is not particularly limited, and for example, those having stereoregularity such as isotactic, heterotactic and syndiotactic may be used.

  The weight average molecular weight of the methacrylic resin (F) is preferably in the range of 20,000 to 180,000, more preferably in the range of 30,000 to 150,000. When the weight average molecular weight is less than 20,000, impact resistance and toughness tend to decrease, and when it exceeds 180,000, the fluidity of the methacrylic resin (F) decreases and molding processability tends to decrease.

  The production method of the methacrylic resin (F) is not particularly limited, and it is obtained by polymerizing a monomer (mixture) containing 80% by mass or more of methyl methacrylate or copolymerizing with a monomer other than methyl methacrylate. Moreover, you may use a commercial item as a methacryl resin (F).

  Examples of the elastic body (R) include butadiene rubber, chloroprene rubber, block copolymer, multilayer structure and the like, and these may be used alone or in combination. Among these, from the viewpoint of transparency, impact resistance, and dispersibility, a block copolymer or a multilayer structure is preferable, and an acrylic block copolymer (G) or a multilayer structure (E) is more preferable.

The acrylic block copolymer (G) has a methacrylic acid ester polymer block (g1) and an acrylic acid ester polymer block (g2). The acrylic block copolymer (G) may have only one methacrylic acid ester polymer block (g1) and one acrylic acid ester polymer block (g2), or a plurality thereof.

  The methacrylic acid ester polymer block (g1) is mainly composed of structural units derived from methacrylic acid esters. The proportion of the structural unit derived from the methacrylic ester in the methacrylic ester polymer block (g1) is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95 from the viewpoints of stretchability and surface hardness. It is at least 98% by mass, particularly preferably at least 98% 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, tert-butyl methacrylate, and methacrylic acid. Amyl, isoamyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, 2 methacrylate -Hydroxyethyl, 2-methoxyethyl methacrylate, glycidyl methacrylate, allyl methacrylate and the like, and these may be used alone or in combination. It can be polymerized or in combination. Among these, from the viewpoints of transparency and heat resistance, alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, and isobornyl methacrylate. Is preferred, and methyl methacrylate is more preferred.

  The methacrylic acid ester polymer block (g1) may contain a structural unit derived from a monomer other than the methacrylic acid ester, and the proportion thereof is preferably 20% by mass or less, more preferably from the viewpoint of stretchability and surface hardness. It is 10 mass% or less, More preferably, it is 5 mass% or less, Most preferably, it is 2 mass% or less.

  Examples of the monomer other than the methacrylic acid ester include acrylic acid ester, unsaturated carboxylic acid, aromatic vinyl compound, olefin, conjugated diene, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl acetate, vinyl pyridine, vinyl ketone. , Vinyl chloride, vinylidene chloride, vinylidene fluoride, and the like. These may be used alone or in combination of two or more.

  When the acrylic block copolymer (G) has a plurality of methacrylate polymer blocks (g1), the composition ratio and molecular weight of the structural units constituting each methacrylate polymer block (g1) are the same. May be different or different.

  The proportion of the methacrylic acid ester polymer block (g1) in the acrylic block copolymer (G) is preferably 10% by mass to 70% by mass from the viewpoints of transparency, flexibility, molding processability and surface smoothness. It is a range, More preferably, it is the range of 25 mass%-60 mass%. When the acrylic block copolymer (G) contains a plurality of methacrylic ester polymer blocks (g1), the above ratio is calculated based on the total mass of all the methacrylic ester polymer blocks (g1).

  The acrylic ester polymer block (g2) is mainly composed of a structural unit derived from an acrylic ester. The proportion of structural units derived from the acrylate ester in the acrylate polymer block (g2) is preferably 45% by mass or more, more preferably 50% by mass or more, further preferably from the viewpoint of three-dimensional coating moldability and stretchability. Is 60% by mass or more, particularly preferably 90% by mass or more.

  Examples of the acrylic ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, and acrylic acid. Amyl, 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, and these can be polymerized singly or in combination of two or more.

  The acrylic ester polymer block (g2) is preferably composed of an acrylic acid alkyl ester and a (meth) acrylic acid aromatic ester from the viewpoints of stretchability and transparency. Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, and the like. Of these, n-butyl acrylate and 2-ethylhexyl acrylate are preferred.

  (Meth) acrylic acid aromatic ester means acrylic acid aromatic ester or methacrylic acid aromatic ester, and a compound containing an aromatic ring is ester-bonded to (meth) acrylic acid. Examples of the (meth) acrylic acid aromatic ester include phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, styryl acrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, and styryl methacrylate. . Of these, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, and benzyl acrylate are preferred.

  When the acrylic acid ester polymer block (g2) is composed of an acrylic acid alkyl ester and a (meth) acrylic acid aromatic ester, the acrylic acid ester polymer block (g2) is a structural unit derived from the acrylic acid alkyl ester 50 to 90. It is preferable to contain 50 to 10% by mass of structural units derived from mass% and (meth) acrylic acid aromatic ester, and 60 to 80% by mass of structural units derived from alkyl acrylate and (meth) acrylic acid aromatic ester. More preferably, it contains 40 to 20% by mass of the structural unit derived from.

  The acrylate polymer block (g2) may contain a structural unit derived from a monomer other than the acrylate ester, and the content of the acrylate polymer block (g2) is preferably 55% by mass or less. More preferably, it is 50 mass% or less, More preferably, it is 40 mass% or less, Most preferably, it is 10 mass% or less.

  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, vinyl pyridine, vinyl ketone, Examples thereof include vinyl chloride, vinylidene chloride, and vinylidene fluoride, and these can be used alone or in combination of two or more.

  When the acrylic block copolymer (G) has a plurality of acrylic ester polymer blocks (g2), the composition ratio and molecular weight of the structural units constituting the respective acrylic ester polymer blocks (g2) are the same. May be different or different.

  The proportion of the acrylate polymer block (g2) in the acrylic block copolymer (G) is preferably in the range of 30 to 90% by mass from the viewpoint of obtaining a multilayer film suitable for three-dimensional coating. More preferably, it is the range of 40-75 mass%. When the block copolymer (G) contains a plurality of acrylic ester polymer blocks (g2), the proportion is calculated based on the total mass of all acrylic ester polymer blocks (g2).

  The bonding form of the methacrylic ester polymer block (g1) and the acrylate polymer block (g2) in the acrylic block copolymer (G) is not particularly limited. For example, one of the methacrylic ester polymer block (g1) A structure in which one end of the acrylate polymer block (g2) is connected to the end ((g1)-(g2) structure); an acrylate polymer block (g2) on both ends of the methacrylate polymer block (g1) ) A structure in which one end is connected ((g2)-(g1)-(g2) structure); one end of the methacrylic acid ester polymer block (g1) is connected to both ends of the acrylate polymer block (g2). Structure ((g1)-(g2)-(g1) structure), etc., methacrylate polymer block (g1) and acrylic acid ester Ether polymer block (g2) can be cited a structure that led to series. Among these, a diblock copolymer having a (g1)-(g2) structure or a triblock copolymer having a (g1)-(g2)-(g1) structure is particularly preferable.

  The acrylic block copolymer (G) may have a functional group such as a hydroxyl group, a carboxyl group, an acid anhydride, or an amino group in the molecular chain or at the molecular chain terminal.

  The weight average molecular weight of the acrylic block copolymer (G) is preferably in the range of 60,000 to 400,000, more preferably in the range of 60,000 to 200,000. The molecular weight distribution of the acrylic block copolymer (G) is preferably in the range of 1.0 to 2.0, more preferably in the range of 1.0 to 1.6. In addition, a weight average molecular weight and a number average molecular weight are molecular weights of standard polystyrene conversion measured by GPC.

  The refractive index of the acrylic block copolymer (G) is preferably in the range of 1.485 to 1.495, more preferably in the range of 1.487 to 1.493. When the refractive index is within this range, the transparency of the layer (B) increases and the appearance of the multilayer film is excellent. The refractive index is a value measured at a wavelength of 587.6 nm (d line).

  The method for producing the acrylic block copolymer (G) is not particularly limited, and a method according to a known method can be adopted. For example, a method of living polymerizing monomers constituting each polymer block is generally used. . Examples of such living polymerization methods include a method of anionic polymerization in the presence of a mineral salt such as an alkali metal or an alkaline earth metal salt using an organic alkali metal compound as a polymerization initiator; A method of anionic polymerization in the presence of an organoaluminum compound used as an agent; a method of polymerization using an organic rare earth metal complex as a polymerization initiator; a method of radical polymerization in the presence of a copper compound using an α-halogenated ester compound as an initiator Etc. Moreover, the method of polymerizing the monomer which comprises each block using a polyvalent radical polymerization initiator and a polyvalent radical chain transfer agent, and manufacturing as a mixture containing an acryl-type block copolymer (G), etc. are mentioned. Among these methods, the acrylic block copolymer (G) can be obtained with high purity, the molecular weight and the composition ratio can be easily controlled, and it is economical. A method in which anionic polymerization is used in the presence of an organoaluminum compound is preferred.

  The multilayer structure (E) contains at least two layers of an inner layer and an outer layer, and has at least one layer structure in which the inner layer and the outer layer are arranged in this order from the center layer toward the outermost layer. The multilayer structure (E) may further have a crosslinkable resin layer inside the inner layer or outside the outer layer.

  The inner layer is a layer composed of a crosslinked elastic body obtained by copolymerizing a monomer mixture having an alkyl acrylate ester and a crosslinking monomer. As the acrylic acid alkyl ester, an alkyl alkyl ester having an alkyl group having 2 to 8 carbon atoms is preferably used, and examples thereof include butyl acrylate and 2-ethylhexyl acrylate. From the viewpoint of impact resistance, the proportion of the acrylic acid alkyl ester in the total monomer mixture used to form the inner layer copolymer is preferably in the range of 70 to 99.8% by mass, more preferably. Is 80-90 mass%.

  The crosslinkable monomer used in the inner layer may be any monomer having at least two polymerizable carbon-carbon double bonds in one molecule. For example, unsaturated glycols such as ethylene glycol dimethacrylate and butanediol dimethacrylate. Polyalkenyl esters of polybasic acids such as carboxylic acid diesters, alkenyl esters of unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, allyl cinnamate, diallyl phthalate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate And unsaturated carboxylic acid esters of polyhydric alcohols such as trimethylolpropane triacrylate, divinylbenzene and the like, and alkenyl esters of unsaturated carboxylic acids and polyalkenyl esters of polybasic acids are preferred. The amount of the crosslinkable monomer in the total monomer mixture is preferably in the range of 0.2 to 30% by mass, and more preferably in the range of 0.2 to 10% by mass.

  The monomer mixture forming the inner layer may further have another monofunctional monomer. Such monofunctional monomers include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, Alkyl methacrylates such as dodecyl methacrylate, myristyl methacrylate, palmityl methacrylate, stearyl methacrylate, and behenyl methacrylate; methacrylates such as phenyl methacrylate and esters of phenols; methacrylates such as esters of methacrylic acid and aromatic alcohols such as benzyl methacrylate Styrene, α-methylstyrene, 1- Aromatic vinyl series such as nylnaphthalene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, halogenated styrene Examples thereof include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; conjugated diene monomers such as butadiene and isoprene. The amount of the other monofunctional monomer in the total monomer mixture is preferably 24.5% by mass or less, more preferably 20% by mass or less.

  The outer layer is composed of a hard thermoplastic resin obtained by polymerizing a monomer mixture containing 80% by mass or more, preferably 90% by mass or more of methyl methacrylate. Further, the hard thermoplastic resin may contain other monofunctional monomer in an amount of 20% by mass or less, preferably 10% by mass or less. Examples of the other monofunctional monomer include acrylic acid alkyl esters such as methyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; acrylic acid; methacrylic acid.

  The content of the inner layer and the outer layer in the multilayer structure (E) is based on the mass of the multilayer structure (E) (for example, the total amount of the inner layer and the outer layer in the case of two layers) from the viewpoint of ease of melt kneading. The content of the inner layer is preferably selected from the range of 40 to 80% by mass, and the content of the outer layer is preferably selected from the range of 20 to 60% by mass.

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

  When the layer (B) is composed of a (meth) acrylic resin composition containing a methacrylic resin (F) and an elastic body (R), the content of each component is a multilayer film suitable for three-dimensional coating molding. From a viewpoint obtained, the content of the methacrylic resin (F) is 10 to 99 parts by mass with respect to 100 parts by mass in total of the methacrylic resin (F) and the elastic body (R), and the elastic body (R) is contained. The amount is preferably 90 to 1 part by mass. More preferably, the content of the methacrylic resin (F) is 55 to 90 parts by mass with respect to 100 parts by mass in total of the methacrylic resin (F) and the elastic body (R), and the content of the elastic body (R). Is 45 to 10 parts by mass. More preferably, content of a methacryl resin (F) is 70-90 mass parts, and content of an elastic body (R) is 30-10 mass parts.

  Layer (B) contains various additives such as antioxidants, thermal stabilizers, lubricants, processing aids, antistatic agents, thermal degradation inhibitors, ultraviolet absorbers, light stabilizers, polymer processing aid colorants, An impact resistance aid or the like may be contained. The layer (B) is composed of at least one resin selected from (meth) acrylic resins, ABS resins, polycarbonate resins and polyester resins, and these resins and other polymers (for example, polyolefin resins) Styrene resin, polyamide, and other thermoplastic elastomers) may be used in combination.

  The method for preparing the resin constituting the layer (B) is not particularly limited, but in order to improve the dispersibility of each component, a method of melt kneading and mixing is preferable. For the mixing operation, for example, a known mixing or kneading apparatus such as a kneader ruder, an extruder, a mixing roll, or a Banbury mixer can be used. From the viewpoint of improving kneadability and compatibility, it is preferable to use a twin screw extruder. What is necessary is just to adjust suitably the temperature at the time of mixing and kneading | mixing according to the melting temperature etc. of resin to be used, and it is the range of 110-300 degreeC normally. When melt-kneading using a twin-screw extruder, it is preferable to use a vent and melt-knead under reduced pressure and / or in a nitrogen atmosphere from the viewpoint of suppressing coloration.

[Multilayer film]
The multilayer film of the present invention may have other layers in addition to the layer (A) and the layer (B) as long as the effects of the present invention are not impaired. For example, you may have a design layer (printing layer, metal layer), a hard-coat layer, an inorganic particle compounding layer, etc. in an outermost layer or an intermediate | middle layer.

  In the multilayer film of the present invention, a pattern or color such as a picture, a character, or a figure may be printed on the layer (A) and / or the layer (B). The pattern may be chromatic or achromatic. Examples of the printing method include known printing methods such as gravure printing, offset printing, screen printing, transfer printing, and ink jet printing. In printing, a resin composition containing a resin such as a polyvinyl resin, a polyester resin, an acrylic resin, a polyvinyl acetal resin, or a cellulose resin as a binder and a pigment or a dye as a colorant, which is generally used in the printing method. Is preferably used.

  The layer (B) used in the multilayer film of the present invention may be colored. As a coloring method, the resin itself constituting the layer (B) is made to contain a pigment or a dye, and the resin itself before film formation is colored; the resin film of the layer (B) is placed in a liquid in which the dye is dispersed. Although the dyeing | staining method etc. which immerse and color are mentioned are mentioned, It does not specifically limit to these.

  In the multilayer film of the present invention, a metal or a metal oxide may be deposited on the layer (B). As the metal or metal oxide, any metal or metal oxide used for sputtering or vacuum deposition can be used without any particular limitation. For example, gold, silver, copper, aluminum, zinc, nickel, chromium, indium and oxides thereof Etc. Further, these metals or metal oxides may be used alone or as a mixture of two or more. Examples of the method for depositing metal or metal oxide on the layer (B) include vacuum film formation methods such as deposition and sputtering, electrolytic plating, and electroless plating.

  The surface on the layer (B) side of the multilayer film of the present invention preferably has a pencil hardness of HB or harder, more preferably H or harder. When the pencil hardness is higher than HB, the multilayer film is hardly damaged, and is suitably used as a decorative and protective film for the surface of a molded product that requires design properties.

  The total thickness of the multilayer film of the present invention is preferably in the range of 20 to 1,000 μm, more preferably in the range of 50 to 500 μm. If the thickness of the multilayer film is 20 μm or more, the production becomes easy, it is excellent in impact resistance and warpage reduction during heating, and has a concealing property during coloring. When the thickness of the multilayer film is 1,000 μm or less, the three-dimensional coating moldability is improved.

  In the multilayer film of the present invention, the thickness of the layer (A) is preferably 30 to 500 μm. If the layer (A) is thicker than this, the moldability deteriorates. On the other hand, if the layer (A) is thinner than this, the adhesive performance is lowered. From the above viewpoint, the thickness of the layer (A) is more preferably 50 μm to 300 μm.

  In the multilayer film of the present invention, the thickness of the layer (B) is preferably 500 μm or less. If it is thicker than 500μm, the secondary processability such as laminating property, handling property, cutting property and punching property will deteriorate, making it difficult to use as a film and increasing the unit price per unit area, which is economically disadvantageous. This is not preferable. As thickness of a layer (B), 40-300 micrometers is more preferable, and 100-300 micrometers is further more preferable.

As a method for producing the multilayer film of the present invention, a method of applying a solution of a thermoplastic polymer composition constituting the layer (A) to the layer (B); a thermoplastic constituting the layer (A) to the layer (B) A method of thermally laminating a film of a polymer composition; a method of thermocompressing layers (B) and (A) with a press; a method of laminating simultaneously with pressure forming, vacuum forming or TOM forming; and interposing an adhesive layer And laminating (wet lamination); a coextrusion molding method in which the resin constituting the layer (B) and the thermoplastic polymer composition constituting the layer (A) are laminated in a die. Of these methods, the coextrusion molding method is preferable because a step of separately forming the layer (B) is unnecessary.
The coextrusion molding method can be performed using a known method such as a T-die method or an inflation method. Examples of the T-die method include a multi-manifold method and a feed block method. In particular, from the viewpoint of thickness accuracy, coextrusion molding by a multi-manifold method is preferable. The molding temperature is preferably 240 to 260 ° C. because a multilayer film can be produced without causing film formation defects such as film breakage and edge wrapping. In addition, from the viewpoint that a film with good surface smoothness can be obtained after coextrusion molding, the melt-kneaded material is extruded from a T-die in a molten state, and both surfaces thereof are brought into contact with a mirror roll surface or a mirror belt surface and molded. A method comprising a step is also preferred. The roll or belt used at this time is preferably made of metal or silicone rubber.

  Since the multilayer film of the present invention has good elongation characteristics and adhesive strength, vacuum forming and / or pressure forming (that is, vacuum forming, pressure forming, vacuum pressure forming) is performed on an adherend without using an adhesive. (Molding) can be suitably used for adhesion. Further, the multilayer film can cover the adherend in a state where the film surface is smooth when adhered to the adherend. Thereby, the molded object which is excellent in an external appearance can be obtained.

[Molded body]
The molded body of the present invention is obtained by bonding the multilayer film to the surface of an adherend. Although it does not specifically limit as a to-be-adhered body, For example, a thermoplastic resin, a thermosetting resin, a metal member, a wooden base material, or a non-wood fiber base material etc. are mentioned.

  Examples of the thermoplastic resin used as the adherend include polycarbonate resin, polyethylene terephthalate resin, polyamide resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, (meth) acrylic resin, ABS (acrylonitrile-butadiene-styrene). (Copolymerization) resin and the like. Examples of the thermosetting resin include an epoxy resin, a phenol resin, and a melamine resin. Examples of the metal member include aluminum, nickel, magnesium, zinc, iron, chromium, and copper. In addition, the molded body may be one in which the multilayer film of the present invention is provided on the surface of a non-wood fiber such as a wooden base material or kenaf.

[Method for producing molded article]
Examples of the method for obtaining the molded body of the present invention include an injection molding method, a vacuum molding method, a pressure molding method, and a compression molding method. Among them, vacuum forming and / or pressure forming is preferable because it can be shaped and adhered to various adherends with high accuracy. Three-dimensional surface decoration forming (Three dimension decoration forming) is a kind of vacuum pressure forming that combines vacuum forming and pressure forming. Overlay Method (TOM molding) is more preferable. Hereinafter, production by TOM molding will be described in detail as an example of the production method.

  As a vacuum forming apparatus for TOM-forming a multilayer film, for example, a vacuum forming apparatus described in JP-A No. 2002-0667137 or a coating apparatus described in JP-A No. 2005-262502 can be preferably used. The molding apparatus or the coating apparatus includes a chamber box that can be closed and decompressed by installing a multilayer film and an adherend.

  A method for producing a molded body by TOM molding includes a step of accommodating a multilayer film and an adherend in a chamber box; a step of reducing the pressure in the chamber box; a step of dividing the interior of the chamber box by the multilayer film; Covering the adherend with the multilayer film by setting the pressure in the chamber box not having the adherend higher than the pressure in the chamber box having the adherend. In addition, in the process of accommodating a multilayer film and a to-be-adhered body in a chamber box, you may implement simultaneously the process of dividing the inside of a chamber box into a multilayer film.

  In the step of reducing the pressure in the chamber box, the pressure in the chamber box is preferably in the range of 0.1 to 20 kPa, and more preferably in the range of 0.1 to 10 kPa. If the pressure is higher than 20 kPa, it becomes difficult to accurately shape the multilayer film in the process of coating the adherend with the multilayer film. If the pressure is lower than 0.1 kPa, the time required for molding increases and the productivity is increased. It tends to decrease.

  It is preferable that the manufacturing method of the molded object by the said TOM shaping | molding further has the process of heating and softening the said multilayer film. In this step, the multilayer film is preferably heated in the range of 100 to 160 ° C, more preferably in the range of 110 to 140 ° C. When the temperature of the multilayer film is less than 100 ° C., the multilayer film is not sufficiently softened, resulting in poor molding, or the adhesive strength of the multilayer film in the molded product tends to be reduced. On the other hand, when it exceeds 160 degreeC, the excessive softening and quality change of a multilayer film will arise, and it will become the tendency for the quality of a molded object to fall. In addition, you may implement simultaneously the process of depressurizing the inside of a chamber box, and the process of heating and softening a multilayer film.

One that does not have an adherend in the process of coating the adherend with a multilayer film by setting the pressure in the chamber box having no adherend higher than the pressure in the chamber box having the adherend. The pressure in the chamber box is preferably in the range of 50 to 500 kPa, more preferably in the range of 100 to 400 kPa. When the pressure in the chamber box having no adherend is lower than 50 kPa, it is difficult to accurately shape the multilayer film in the step of coating the adherend with the multilayer film. When the pressure in the chamber box having no adherend is higher than 500 kPa, it takes time to set the pressure to atmospheric pressure (about 100 kPa) when the molded body is taken out from the chamber box, and the productivity tends to decrease.
As a method of increasing the pressure in the chamber box without the adherend to the pressure in the chamber box having the adherend, for example, the chamber box without the adherend is opened to atmospheric pressure. Or a method of supplying compressed air to the chamber box having no adherend. By supplying compressed air, the multilayer film can be formed in closer contact with the adherend, and the shape of the adherend can be transferred to the multilayer film more accurately.

[Usage]
The multilayer film of the present invention and the molded body to which the multilayer film is bonded can be applied to articles requiring design properties. For example, billboard parts such as advertising tower, stand signboard, sleeve signboard, bamboard signboard, rooftop signboard; display parts such as showcase, partition plate, store display; fluorescent lamp cover, mood lighting cover, lamp shade, light ceiling, light wall Lighting parts such as chandeliers; Interior parts such as furniture, pendants, mirrors; Doors, domes, safety window glass, partitions, staircases, balconies, roofs of leisure buildings, automobile interior and exterior components, Transport equipment-related parts such as automobile exterior parts such as bumpers; electronic equipment parts such as nameplates for audio images, stereo covers, vending machines, mobile phones, personal computers; incubators, rulers, dials, greenhouses, large tanks, box tanks , Bathroom parts, clock panels, bathtubs, sanitary, desk mats, game parts, toys, wallpaper; marking films, various home appliances Suitably used in decorative applications.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further in detail, this invention is not limited to these Examples at all. Production of test samples in Examples and Comparative Examples and measurement or evaluation of each physical property were performed as follows.

[Measurement method of tanδ]
A measurement sample was prepared by cutting a 1 mm thick sheet obtained by molding the thermoplastic polymer compositions obtained in Examples and Comparative Examples at 200 ° C. with a press molding machine into a circular shape having a diameter of 25 mm, and a rotational rheometer. Using “ARES” (Rheometric Scientific), sandwiched by parallel disks (diameter 25 mm), strain: 5%, heating rate: 5 ° C./min, measuring temperature: 170 ° C. to 250 ° C. The value of tan δ at 250 ° C. and a shear rate of 10 (1 / s) when measured under the conditions was measured.

[Measurement method of order-disorder transition temperature (ODT)]
For the thermoplastic elastomers obtained in Production Examples 1 to 3, an ARES viscoelasticity measurement system manufactured by Rheometric Scientific was used, parallel plate mode, vibration frequency 10 radians / second, applied strain 0.5%, heating rate 3 ° C. / The storage elastic modulus G ′ in the temperature range of 150 ° C. to 300 ° C. was measured in minutes, and the temperature at which the value of G ′ rapidly decreased was defined as the order-disorder transition temperature (ODT).

[Surface smoothness of thermoplastic polymer composition (capillary strand surface)]
A capillary (8 × 0.5 mm) slit-shaped capillary was attached to a capillary rheometer (CAPIROGRAPH 1C, manufactured by TOYOSEIKI), and the thermoplasticity obtained in the examples and comparative examples at 250 ° C. and a piston speed of 50 mm / min. The polymer composition was extruded to obtain a film-like strand. The surface of the obtained strand was visually observed to evaluate the surface smoothness.
○: The surface was smooth with no irregularities. Δ: The irregularities were small. ×: Wrinkled irregularities were easily recognized on the surface.

[Evaluation of surface properties of compacts]
By inserting the multilayer film obtained in Example 1 into a vacuum / pressure forming machine (NGF0406 forming machine manufactured by Fuse Vacuum Co., Ltd.), and performing three-dimensional surface decoration molding that compresses the sheet glass under vacuum, A molded body in which the multilayer film was adhered to the sheet glass was produced. An evaluation sample was obtained from the molded body, and the surface property was evaluated. The evaluation was performed by measuring the arithmetic average roughness (Ra) with a 12.5 μm stylus using a stylus shape measuring instrument (Dektak-150 manufactured by Bruker).
○: Ra is less than 0.08 μm ×: Ra is 0.08 μm or more

<Production Example 1> Thermoplastic elastomer (a-1)
In a pressure-resistant container purged with nitrogen and dried, 50.0 kg of cyclohexane as a solvent and 125.0 g of sec-butyllithium (10.5 mass% cyclohexane solution) as an anionic polymerization initiator were charged and heated to 50 ° C., By adding 1.12 kg of styrene (1) and polymerizing for 1 hour, subsequently adding 10.25 kg of isoprene and polymerizing for 2 hours, further adding 1.12 kg of styrene (2) and polymerizing for 1 hour, polystyrene- A reaction solution containing a poly (isoprene) -polystyrene triblock copolymer was obtained. To this reaction solution, 5% by mass of palladium carbon (palladium supported amount: 5% by mass) as a hydrogenation catalyst was added to the polystyrene-polyisoprene-polystyrene triblock copolymer, and the conditions were a hydrogen pressure of 2 MPa and 150 ° C. The reaction was carried out for 10 hours. After allowing to cool and release the pressure, palladium carbon is removed by filtration, the filtrate is concentrated, and further dried under vacuum to obtain a hydrogenated polystyrene-poly (isoprene) -polystyrene triblock copolymer (hereinafter referred to as “thermoplastic”). Elastomer (a-1) ") was obtained.
The obtained thermoplastic elastomer (a-1) had a hydrogenation rate of 97.2%, a styrene block content of 18.0% by mass, a peak top molecular weight of the styrene block of 5,500, and a thermoplastic elastomer (a The peak top molecular weight of -1) was 99,000, the molecular weight distribution was 1.04, the total amount of 1,2-bonds and 3,4-bonds contained in the polyisoprene block was 7 mol%, and the ODT was 220 ° C. It was.

<Production Example 2> Thermoplastic elastomer (a-3)
In a pressure-resistant container purged with nitrogen and dried, 50.0 kg of cyclohexane as a solvent and 94.1 g of sec-butyllithium (10.5 mass% cyclohexane solution) as an anionic polymerization initiator were charged and heated to 50 ° C. Styrene (1) 1.25 kg was added and polymerized for 1 hour, then 277 g of tetrahydrofuran was added as a Lewis base to this reaction mixture, then isoprene 10.00 kg was added and polymerization was conducted for 2 hours, and styrene 1.25 kg was further added. In addition, the reaction liquid containing a polystyrene-polyisoprene-polystyrene triblock copolymer was obtained by polymerizing for 1 hour. Subsequently, 10.25 kg of isoprene was added and polymerization was performed for 2 hours, and further 1.25 kg of styrene (2) was added and polymerization was performed for 1 hour, whereby a reaction liquid containing polystyrene-poly (isoprene) -polystyrene triblock copolymer was obtained. Got. To this reaction solution, 5% by mass of palladium carbon (palladium supported amount: 5% by mass) as a hydrogenation catalyst was added to the polystyrene-polyisoprene-polystyrene triblock copolymer, and the conditions were a hydrogen pressure of 2 MPa and 150 ° C. The reaction was carried out for 10 hours. After allowing to cool and release the pressure, palladium carbon is removed by filtration, the filtrate is concentrated, and further dried under vacuum to obtain a hydrogenated polystyrene-poly (isoprene) -polystyrene triblock copolymer (hereinafter referred to as “thermoplastic”). Elastomer (a-3) ") was obtained.
The hydrogenation rate of the obtained thermoplastic elastomer (a-3) is 93.2%, the styrene block content is 20.0% by mass, the peak top molecular weight of the styrene block is 8,100, and the thermoplastic elastomer (a -3) has a peak top molecular weight of 107,000, a molecular weight distribution of 1.06, the total amount of 1,2-bonds and 3,4-bonds contained in the polyisoprene block is 60 mol%, and the ODT is 320 ° C. It was.

<Production Example 3> Thermoplastic elastomer (a-4)
In a pressure vessel that was purged with nitrogen and dried, 50.0 kg of cyclohexane as a solvent and 40.1 g of sec-butyllithium (10.5 mass% cyclohexane solution) as an anionic polymerization initiator were charged and heated to 50 ° C., By adding 1.25 kg of styrene (1) and polymerizing for 1 hour, subsequently adding 10.00 kg of isoprene and polymerizing for 2 hours, further adding 1.25 kg of styrene (2) and polymerizing for 1 hour, polystyrene- A reaction solution containing a poly (isoprene) -polystyrene triblock copolymer was obtained. To this reaction solution, 5% by mass of palladium carbon (palladium supported amount: 5% by mass) as a hydrogenation catalyst was added to the polystyrene-polyisoprene-polystyrene triblock copolymer, and the conditions were a hydrogen pressure of 2 MPa and 150 ° C. The reaction was carried out for 10 hours. After allowing to cool and release the pressure, palladium carbon is removed by filtration, the filtrate is concentrated, and further dried under vacuum to obtain a hydrogenated polystyrene-poly (isoprene) -polystyrene triblock copolymer (hereinafter referred to as “thermoplastic”). Elastomer (a-4) ") was obtained.
The obtained thermoplastic elastomer (a-4) had a hydrogenation rate of 98.1%, a styrene block content of 20.0 mass%, a peak top molecular weight of the styrene block of 18,500, and a thermoplastic elastomer (a -4) has a peak top molecular weight of 275,000, a molecular weight distribution of 1.05, the total amount of 1,2-bonds and 3,4-bonds contained in the polyisoprene block was 8 mol%, and ODT was 360 ° C. It was.

<Production Example 4> Multilayer structure (E-1)
In a reactor equipped with a stirrer, thermometer, nitrogen gas inlet tube, monomer inlet tube and reflux condenser, 1050 parts by mass of ion-exchanged water, 0.5 parts by mass of sodium dioctylsulfosuccinate and 0.7 parts by mass of sodium carbonate After the inside of the container was sufficiently replaced with nitrogen gas, the internal temperature was set to 80 ° C. After adding 0.25 parts by mass of potassium persulfate to the same reactor and stirring for 5 minutes, a simple mixture of methyl methacrylate: methyl acrylate: allyl methacrylate = 94: 5.8: 0.2 (mass ratio) was used. 245 parts by mass of the monomer mixture was continuously added dropwise over 50 minutes, and after completion of the addition, a polymerization reaction was further performed for 30 minutes.
Next, 0.32 parts by mass of potassium peroxodisulfate was added to the reactor and stirred for 5 minutes, and then a single unit consisting of 80.6% by mass of butyl acrylate, 17.4% by mass of styrene and 2% by mass of allyl methacrylate. 315 parts by mass of the body mixture was continuously added dropwise over 60 minutes, and after completion of the addition, a polymerization reaction was further performed for 30 minutes.
Subsequently, 0.14 parts by mass of potassium peroxodisulfate was added to the reactor and stirred for 5 minutes, and then 140 parts by mass of a monomer mixture consisting of methyl methacrylate: methyl acrylate = 94: 6 (mass ratio) was added. It dripped continuously over 30 minutes, and after completion | finish of dripping, superposition | polymerization reaction was performed for 60 minutes and the multilayer structure (E-1) was obtained.

<Production Example 5> Methacrylic resin composition (B-1)
Methacrylic resin “Parapet EH” (MFR: 1.3 g / 10 min (230 ° C., 37.3 N), manufactured by Kuraray Co., Ltd.) 88 parts by mass and multilayer structure (E-1) 12 parts by mass obtained in Production Example 4 After melt-kneading at 230 ° C. using a twin-screw extruder, it was extruded and cut into strands to produce pellets of the methacrylic resin composition (B-1).

<Example 1>
Using 80 parts by weight of the thermoplastic elastomer (a-1) obtained in Production Example 1 and 20 parts by weight of Wintec WFX4TA (random polypropylene, manufactured by Nippon Polypro Co., Ltd.) as the polypropylene resin (b-1), After melt kneading at 225 ° C. and 250 rpm using a shaft extruder (ZSK-25 manufactured by KRUPP WERNER & PFLIDEERER), pellets of a thermoplastic polymer composition were produced by extruding into strands and cutting.
Subsequently, the pellets of the obtained thermoplastic polymer composition and the pellets of the methacrylic resin composition (B-1) obtained in Production Example 5 were each single screw extruder (G. M. ENGINEERING (VGM25-28EX) hopper, layer (A) (thermoplastic polymer composition layer) and layer were prepared by coextrusion using a multi-manifold die with an extrusion temperature set at 250 ° C. A multilayer film having a width of 30 cm and a thickness of 380 μm having (B) (methacrylic resin composition layer) was obtained. The thickness of each layer of the multilayer film was controlled by the extrusion flow rate, and the thickness of the layer (A) was 130 μm and the thickness of the layer (B) was 250 μm.
Using the obtained multilayer film, three-dimensional surface decoration molding was performed by the method described above to prepare a molded body.
The obtained thermoplastic polymer composition and molded product were evaluated by the methods described above. The results are shown in Table 1.

<Example 2>
Example 1 using 80 parts by weight of SIS 5229 (styrene-isoprene-styrene block copolymer, manufactured by JSR) and 20 parts by weight of a polypropylene resin (b-1) as the thermoplastic elastomer (a-2) In the same manner, pellets of the thermoplastic polymer composition were produced. The obtained thermoplastic polymer composition was evaluated by the method described above. The results are shown in Table 1.

<Example 3>
Example 1 using 70 parts by weight of the thermoplastic elastomer (a-1), 10 parts by weight of the thermoplastic elastomer (a-3) obtained in Production Example 2, and 20 parts by weight of the polypropylene resin (b-1). The pellets of the thermoplastic polymer composition were produced in the same manner as described above. The obtained thermoplastic polymer composition was evaluated by the method described above. The results are shown in Table 1.

<Example 4>
The thermoplastic polymer composition was prepared in the same manner as in Example 1 using 80 parts by weight of the thermoplastic elastomer (a-4) obtained in Production Example 3 and 20 parts by weight of the polypropylene resin (b-1). Pellets were produced. The obtained thermoplastic polymer composition was evaluated by the method described above. The results are shown in Table 1.

<Comparative Example 1>
Using 10 parts by weight of the thermoplastic elastomer (a-1), 70 parts by weight of the thermoplastic elastomer (a-3), and 20 parts by weight of the polypropylene resin (b-1), heat was applied in the same manner as in Example 1. Pellets of plastic polymer composition were produced. The obtained thermoplastic polymer composition was evaluated by the method described above. The results are shown in Table 1.

In Example 1, the shape of the strand surface of the caprograph of the thermoplastic polymer composition constituting the layer (A) was smooth. Further, even in a molded article obtained by three-dimensional coating using the multilayer film, the surface property of the multilayer film was maintained and the appearance was excellent. Thus, it was found that the multilayer film of the present invention is suitable for three-dimensional coating molding, and a molded body having a smooth surface when adhered to an adherend and excellent in appearance can be obtained. Similarly, in Examples 2 to 4, the shape of the thermoplastic polymer composition constituting the layer (A) is smooth in the caprograph strand surface or small in irregularities. It is considered that the surface property is maintained and the appearance is excellent.
On the other hand, in Comparative Example 1 where the tan δ of the thermoplastic polymer composition constituting the layer (A) was less than 1, wrinkle-like roughness was easily recognized on the surface of the strand surface of the caprograph. Accordingly, it is considered that the surface of the molded body after the three-dimensional coating is not smooth and the appearance is inferior.

Claims (7)

  A multilayer film having at least a layer (A) and a layer (B), wherein the layer (A) is a polymer block (a1) comprising an aromatic vinyl compound unit and a polymer block (a2) comprising a conjugated diene compound unit. Is composed of a thermoplastic polymer composition containing 1 to 50 parts by weight of a polypropylene resin (b) with respect to 100 parts by weight of a thermoplastic elastomer (a) which is a block copolymer containing or hydrogenated product thereof, The loss tangent (tan δ) measured at a frequency of 1 Hz and a temperature of 250 ° C. by dynamic viscoelasticity measurement of the thermoplastic polymer composition is 1.0 or more, and the layer (B) is composed of a (meth) acrylic resin. Multi-layer film.   The multilayer film of Claim 1 whose order-disorder transition temperature (ODT) of the said thermoplastic elastomer (a) is 300 degrees C or less.   The multilayer film according to claim 1 or 2, wherein the thermoplastic polymer composition does not contain a (meth) acrylic resin.   The multilayer film according to any one of claims 1 to 3, which is produced by a coextrusion molding method at a molding temperature of 240 to 260 ° C.   The molded object which the multilayer film in any one of Claims 1-4 adhere | attached on the surface of the to-be-adhered body.   6. The method for producing a molded body according to claim 5, wherein the multilayer film is adhered to an adherend using vacuum molding and / or pressure molding. The manufacturing method of the molded object of Claim 6 which further has the process of heating and softening the said multilayer film in the range of 100-160 degreeC.