TW201811898A - Thermoplastic polymer composition, multilayer film using said composition, and molded article - Google Patents

Abstract

The present invention addresses the problem of providing a thermoplastic polymer composition that exhibits a bipolar adhesiveness, and a multilayer film comprising the thermoplastic polymer composition and a substrate and having an excellent surface smoothness. This problem is solved by a thermoplastic polymer composition containing, relative to 100 parts by mass of (A) a thermoplastic elastomer that is a block copolymer of (S) a polymer block containing an aromatic vinyl compound unit and (D) a polymer block containing a conjugated diene compound unit, or is a hydrogenated product of said block copolymer, 1-20 parts by mass of (C) a (meth)acrylic resin, and 1-50 parts by mass of (B) at least one polypropylene resin, and by a multilayer film having a substrate layer and a layer comprising the thermoplastic polymer composition.

Description

   Thermoplastic polymer composition, multilayer film and formed body using the same   

The present invention relates to a thermoplastic polymer composition excellent in adhesion and surface smoothness, a multilayer film using the composition, and a formed body including the multilayer film.

Ceramics, metals, and synthetic resins that are excellent in design, durability, heat resistance, and mechanical strength are widely used in various applications such as home appliances, electronic parts, mechanical parts, and automotive parts. These members may be used by adhering or compounding different materials depending on the purpose, component configuration, and usage method. For example, exterior appliances such as home appliances, wallpaper, car interiors, etc. are used to provide decorative features such as woody textures, or to give metallic designs or piano black feelings design features and scratch resistance or weather resistance. For the purpose of giving, etc., a decorative film is used.

However, especially when the decorative film and the adherend are different materials with different polarities, there is a problem that the decorative film cannot adhere to the adherend. As described above, in order to adhere the film to the adherend, it is necessary to separately apply an adhesive. In this operation, a solvent coating step, a drying step, and a curing step are required, and it takes a long time to impart adhesiveness. There is a concern that the working environment due to VOC is deteriorated, and poor adhesion caused by uneven coating. Therefore, a decorative film that can be bonded to different materials without an adhesive is desired.

In contrast to the foregoing, Patent Document 1 discloses an adhesive resin composition comprising a vinyl polymer, an adhesive, a polymer block having an ethylene aromatic compound, and a conjugated diene compound polymer in a specific ratio. The block copolymer or its hydride is used when laminating the same or different materials. In addition, Patent Document 2 discloses a resin composition for heat fusion suitable for composite molding, which contains a block copolymer including an ethylene aromatic polymer polymer block and a conjugated diene compound polymer block or a block copolymer thereof A hydride; a copolymer containing a vinyl cyanide monomer component, a rubber component, and an aromatic vinyl compound monomer component; and a non-aromatic rubber softener.

In addition, Patent Document 3 proposes a method for producing a bonded body, in which a film of a thermoplastic polymer composition is bonded to an insert member, and then a resin member is subjected to insert molding. The thermoplastic polymer composition includes A thermoplastic elastomer of a block copolymer of a polymer block of a group ethylene compound unit and a polymer block containing a conjugated diene compound unit or a hydrogenated product thereof, and a polypropylene resin containing a polar group.

Further, Patent Document 4 discloses a laminated body having excellent layer indirect adhesion, which includes a layer (I), wherein the layer (I) is composed of a polyolefin-based polymer and an aromatic vinyl compound-containing polymer block and a copolymer. A block copolymer of a polymer block of a conjugated diene compound or a hydrogenated thermoplastic resin composition thereof.

Prior art literature Patent literature

Patent Document 1 Japanese Patent Application Laid-Open No. 7-207082

Patent Document 2 Japanese Patent Laid-Open No. 2001-247742

Patent Document 3 Japanese Patent Application Publication No. 2014-168940

Patent Document 4 International Publication 2007/066576

The adhesive composition described in Patent Document 1 has high adhesion to the surface due to the adhesion-imparting substance contained therein. Therefore, when the film is formed into a thin film, the handleability is poor, the productivity is low, and the adhesion-imparting substance overflows. Then there is the problem of uneven performance. The resin composition for heat fusion described in Patent Document 2 also has the same problems as described above due to the non-aromatic rubber softener contained therein.

In addition, when the inventors of the present invention examined the thermoplastic polymer composition described in Patent Document 3 and a film including the thermoplastic polymer composition, unevenness or roughness was generated on the surface of the thermoplastic polymer composition, and it was difficult to obtain smoothness. Thin film. In addition, when the film is used for three-dimensional surface decoration molding (Three Dimension Overlay Method: TOM molding), the surface of the thermoplastic polymer composition is roughened and extended to the surface of the film substrate, the surface of the substrate becomes uneven, and the appearance is designed. Deteriorating problem.

Based on the foregoing, an object of the present invention is to provide a thermoplastic polymer composition having bipolar adhesion and excellent surface smoothness; a multilayer film and a decorative film including the thermoplastic polymer composition and a substrate having excellent surface smoothness ; And formed bodies having such films.

The present invention that solves the above problems is the following [1] to [10].

[1] A thermoplastic polymer composition, which comprises 1 to 50 parts by mass of a polypropylene-based resin (B) with respect to 100 parts by mass of the thermoplastic elastomer (A), wherein the thermoplastic elastomer (A ) Is a block copolymer or a hydrogenated product thereof containing a polymer block (S) containing an aromatic vinyl compound unit and a polymer block (D) containing a conjugated diene compound unit, which is characterized in that: The surface of the film was rectangular (8 mm × 0.5 mm) obtained by extruding the thermoplastic polymer composition using a capillary rheometer at a temperature of 50 ° C / minute at a temperature of 50 ° C / minute. The surface roughness of the film was measured according to the following method. (Ra) is 0.15 μm or less. Surface roughness measurement method: A method for measuring the arithmetic average roughness (Ra) by using a stylus shape measuring instrument and a needle with a tip radius of 12.5 μm. [2] The thermoplastic polymer composition according to the above [1], wherein the conjugated diene compound constituting the polymer block (D) is butadiene, isoprene, or butadiene and isoprene Diene, the total amount of 1,2-bonds and 3,4-bonds in the polymer block (D) is 40 mol% or more; [3] as described in [1] or [2] [4] The thermoplastic polymer composition, wherein the polypropylene resin (B) is a non-polar polypropylene resin; [4] The plastic polymer composition according to any one of [1] to [3] above, wherein the thermoplastic The polymer composition contains 1 to 25 parts by mass of the (meth) acrylic resin (C) based on 100 parts by mass of the thermoplastic elastomer (A); [5] The thermoplastic polymer according to the above [4] A composition, wherein the (meth) acrylic resin (C) contains 80% by mass or more of a structural unit derived from methyl methacrylate; [6] a multilayer film having at least a base material layer and containing as described above [1] The layer of the thermoplastic polymer composition according to any one of [1] to [5]; [7] The multilayer film according to the above [6], wherein the base material layer includes an amorphous resin; [8] a decoration film Which system contains the above [6] or [7] The multilayer film according to the; [9] A molded article based comprising multilayer film of [6] or [7] above description of or above [8] The decorative film.

The thermoplastic polymer composition of the present invention has bipolar adhesion and is also excellent in surface smoothness, and therefore can be suitably used as an adhesion layer of a multilayer film. In addition, the multilayer film of the present invention has an adhesive layer containing the thermoplastic polymer composition, and therefore has excellent adhesion to an adherend. Furthermore, the thermoplastic polymer composition has excellent surface smoothness, and thus is a base material for the multilayer film. It is also excellent in surface smoothness, and can be suitably used especially for three-dimensional surface decoration molding. The formed body of the present invention is excellent in designability because it includes the multilayer film.

Implementation of the invention     [Thermoplastic polymer composition]    

The thermoplastic polymer composition of the present invention is 1 to 50 parts by mass of a polypropylene-based resin (B) and 1 to 20 parts by mass of (methyl) based on 100 parts by mass of the thermoplastic elastomer (A). ) Acrylic resin (C), wherein the thermoplastic elastomer (A) is an intercalation comprising a polymer block (S) containing an aromatic vinyl compound unit and a polymer block (D) containing a conjugated diene compound unit Block copolymer or its hydride. Hereinafter, the above-mentioned components (A) to (C) will be described in order.

    [Thermoplastic Elastomer (A)]    

The thermoplastic elastomer (A) contained in the thermoplastic polymer composition is a block copolymer containing a polymer block (S) containing an aromatic vinyl compound unit and a polymer block (D) containing a conjugated diene compound unit. Or its hydride. The said thermoplastic elastomer (A) is a thing which imparts softness | flexibility to a thermoplastic polymer composition, or a favorable mechanical characteristic, moldability, etc., and functions as a matrix in this composition.

    [Polymer block (S) containing aromatic vinyl compound unit]    

Examples of the aromatic vinyl compound constituting the polymer block (S) include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, and 4-methylbenzene. Ethylene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1- Vinylnaphthalene, 2-vinylnaphthalene and the like. The polymer block containing an aromatic vinyl compound unit may include only one type of structural unit derived from such aromatic vinyl compounds, or may include a structural unit derived from two or more types. Among them, styrene, α-methylstyrene, and 4-methylstyrene are preferred.

The polymer block (S) containing an aromatic vinyl compound unit is preferably a polymer block containing 80% by mass or more of an aromatic vinyl compound unit, more preferably 90% by mass or more of an aromatic vinyl compound unit, and more preferably 95% by mass or more of the aromatic vinyl compound unit. The polymer block (S) may have only an aromatic vinyl compound unit, and as long as the effect of the present invention is not impaired, the polymer block (S) may have both the aromatic vinyl compound unit and other copolymerizable monomer units. Examples of other copolymerizable monomers include 1-butene, pentene, hexene, butadiene, isoprene, methyl vinyl ether, and the like. When there are other copolymerizable monomer units, the proportion is preferably 20% by mass or less, and more preferably 10% by mass or less, based on the total amount of the aromatic vinyl compound unit and other copolymerizable monomer units. It is more preferably 5 mass% or less.

    [Polymer block (D) containing conjugated diene compound unit]    

Examples of the conjugated diene compound constituting the polymer block (D) include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3 -Pentadiene, 1,3-hexadiene and the like. Among them, butadiene and isoprene are preferred.

The polymer block (D) containing a conjugated diene compound unit may include only one type of structural unit derived from such a conjugated diene compound, or may include a structural unit derived from two or more types. Particularly preferred are structural units derived from butadiene or isoprene, or structural units derived from butadiene and isoprene.

The polymer block (D) containing a conjugated diene compound unit is preferably a polymer block containing 80% by mass or more of the conjugated diene compound unit, and more preferably 90% by mass or more of the conjugated diene compound unit. Still more preferably, the conjugated diene compound unit is 95% by mass or more. The polymer block (D) may have only a conjugated diene compound unit, but as long as the present invention is not hindered, it may have both a conjugated diene compound unit and other copolymerizable monomer units. Examples of other copolymerizable monomers include styrene, α-methylstyrene, and 4-methylstyrene. When there are other copolymerizable monomer units, the proportion is preferably 20% by mass or less, and more preferably 10% by mass or less, based on the total amount of the conjugated diene compound unit and other copolymerizable monomer units. It is further more preferably 5 mass% or less.

The bonding form of the conjugated diene which comprises the polymer block (D) containing a conjugated diene compound unit is not specifically limited. For example, in the case of butadiene, 1,2-bond, 1,4-bond can be adopted, and in the case of isoprene, 1,2-bond, 3,4-bond, 1,4 can be adopted. -Bonding. Here, when the polymer block (D) containing a conjugated diene compound unit contains butadiene, when isoprene is contained, or when both butadiene and isoprene are contained, the aforementioned polymer The total of the 1,2-bond amount and the 3,4-bond amount of the block (D) is particularly preferably 40 mol% or more from the viewpoint of exhibiting high bonding performance. The total of the 1,2-bond amount and 3,4-bond amount of the polymer block (D) is preferably 40 to 90 mole%, and more preferably 50 to 80 mole%.

The total amount of 1,2-bond and 3,4-bond can be calculated by 1H-NMR measurement. Specifically, it can be calculated from an integral value of a peak of 4.2 to 5.0 ppm derived from a 1,2-bond and 3,4-bond unit and an integral of a peak of 5.0 to 5.45 ppm derived from a 1,4-bond unit. The ratio of the values is calculated.

The bonding form of the polymer block (S) containing the aromatic vinyl compound unit of the thermoplastic elastomer (A) and the polymer block (D) containing the conjugated diene compound unit is not particularly limited, and may be linear. Any one of the bonding forms of branching, radial, or a combination of two or more of these is preferably a linear bonding form.

As an example of a linear bonding form, when a polymer block (S) containing an aromatic vinyl compound unit is represented by a, and a polymer block (D) containing a conjugated diene compound unit is represented by b, Examples include diblock copolymers represented by ab, triblock copolymers represented by aba or bab, tetrablock copolymers represented by abab, pentablock copolymers represented by ababa or babab, (ab) nX-type copolymer (X represents a coupling agent residue, n represents an integer of 2 or more), and a mixture thereof. Among these, a triblock copolymer is preferable, and a triblock copolymer shown by a-b-a is more preferable.

From the viewpoint of improving the heat resistance and weather resistance of the thermoplastic elastomer (A), it is preferred that part or all of the polymer block (D) containing a conjugated diene compound is hydrogenated (hereinafter referred to as "hydrogenation"). The hydrogenation rate of the polymer block containing the conjugated diene compound at this time is preferably 80% or more, and 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 content of the polymer block (S) containing the aromatic vinyl compound unit of the thermoplastic elastomer (A) is preferably 5 to 75 from the viewpoint of its flexibility and mechanical properties relative to the entire thermoplastic elastomer (A). Mass%, more preferably 5 to 60 mass%, and still more preferably 10 to 40 mass%.

The weight average molecular weight of the thermoplastic elastomer (A) is preferably from 30,000 to 500,000, more preferably from 50,000 to 400,000, more preferably from 60,000 to 200,000, and even more preferably from the viewpoint of its mechanical characteristics and formability. 70,000 ~ 200,000, particularly preferably 70,000 ~ 190,000, and most preferably 80,000 ~ 180,000. In addition, in this specification, a weight average molecular weight is a polystyrene conversion weight average molecular weight calculated | required by colloidal permeation chromatography (GPC) measurement.

The thermoplastic elastomer (A) may be used singly or in combination of two or more kinds.

The manufacturing method of a thermoplastic elastomer (A) is not specifically limited, For example, it can manufacture by an anion polymerization method. Specifically, (i) a method of using the alkyl lithium compound as a starter, sequentially polymerizing the aromatic vinyl compound, the conjugated diene compound, and then sequentially polymerizing the aromatic vinyl compound; (ii) A method of using an alkyllithium compound as a starter, sequentially polymerizing the aromatic vinyl compound and the conjugated diene compound, and then adding a coupling agent to perform coupling; (iii) using a dilithium compound as a starter, The method of successively polymerizing the conjugated diene compound and the aromatic vinyl compound, and the like.

During the above anionic polymerization, by adding an organic Lewis base, the amount of 1,2-bonds and 3,4-bonds of the polymer block (D) of the thermoplastic elastomer (A) can be increased. The amount of organic Lewis base added can easily control the 1,2-bond and 3,4-bond.

Examples of the organic Lewis base include esters such as ethyl acetate; amines such as triethylamine, N, N, N ', N'-tetramethylethylenediamine (TMEDA), and N-methylmorpholine. ; Nitrogen-containing heterocyclic aromatic compounds such as pyridine; fluorene such as dimethylacetamide; dimethyl ether, diethyl ether, tetrahydrofuran (THF), two Ethers such as alkane; glycol ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; fluorene such as dimethyl sulfene; ketones such as acetone, methyl ethyl ketone, and the like.

Furthermore, a hydrogenated plastic elastomer (A) can be produced by subjecting the unhydrogenated thermoplastic elastomer (A) obtained above to a hydrogenation reaction. The hydrogenation reaction can be carried out by dissolving the unhydrogenated thermoplastic elastomer (A) obtained above in a solvent that is inert to the reaction and the hydrogenation catalyst, or without unhydrogenating the thermoplastic elastomer (A). The reaction liquid is separated from the aforementioned reaction liquid and used as it is, and reacts with hydrogen in the presence of a hydrogenation catalyst.

As the thermoplastic elastomer (A), a commercially available product can be used.

    [Polypropylene resin (B)]    

The polypropylene resin (B) is contained in the thermoplastic polymer composition to improve moldability, and it is easy to form a film containing the thermoplastic polymer composition. In addition, the mechanical properties of the film are improved, and handling is facilitated. In addition, the adhesion of the thermoplastic polymer composition to the non-polar resin is mainly improved, and it can adhere well to the substrate or the adherend.

Examples of the polypropylene-based resin (B) include a propylene homopolymer or a copolymer of propylene and an α-olefin having 2 to 8 carbon atoms. In the case of a copolymer of propylene and an α-olefin having 2 to 8 carbon atoms, examples of the α-olefin in the copolymer include ethylene, butene-1, isobutylene, pentene-1, hexene-1, 4-methylpentene-1, octene-1 and the like. Examples of the polypropylene-based resin (B) include homopolypropylene, propylene-ethylene random copolymer, propylene-ethylene block copolymer, propylene-butene random copolymer, and propylene-ethylene-butene random copolymer. , Propylene-pentene random copolymer, propylene-hexene random copolymer, propylene-octene random copolymer, propylene-ethylene-pentene random copolymer, propylene-ethylene-hexene random copolymer, and the like. Among all the structural units of the polypropylene resin (B), the proportion of the structural units derived from the aforementioned α-olefin other than propylene is preferably 0 to from the viewpoint of affinity with the thermoplastic elastomer (A). 45 mol%, more preferably 0 to 35 mol%, even more preferably 0 to 25 mol%. In other words, the content of the structural unit derived from propylene of the polypropylene-based resin (B) is preferably 55 mol% or more, more preferably 65 mol% or more, and still more preferably 75 mol% or more.

The polypropylene resin (B) may be used singly or in combination of two or more kinds.

Among these, the polypropylene resin (B) is preferably a non-polar polypropylene resin having no polar functional group. By using a non-polar polypropylene-based resin, melt fracture is less likely to occur during extrusion, and it is excellent in that the surface of the multilayer film becomes smooth.

The polypropylene resin (B) can be synthesized by a conventionally known method. For example, a propylene homopolymer, random, or block propylene can be synthesized using a Ziegler-Natta catalyst or a metal aromatic catalyst. Copolymers with alpha-olefins. As the polypropylene resin (B), a commercially available product may be used.

The melt flow rate (MFR) of the polypropylene resin (B) at 230 ° C and a load of 2.16 kg (21.18 N) is preferably 0.1 to 300 g / 10 minutes, and more preferably 0.1 to 100 g / 10 minutes. It is more preferably 0.1 to 70 g / 10 minutes. If the MFR of the polypropylene-based resin (B) under the above conditions is 0.1 g / 10 minutes or more, good moldability can be obtained. On the other hand, if the MFR is 300 g / 10 minutes or less, it is easy to exhibit mechanical properties. From the viewpoint of improving the surface smoothness of the thermoplastic polymer composition, the MFR of the polypropylene resin (B) under the above conditions is more preferably 5 to 60 g / 10 minutes, and still more preferably 8 to 50 g / 10 minutes. From the viewpoint of improving the adhesion of the thermoplastic polymer composition, the MFR of the polypropylene resin (B) under the above conditions is more preferably 1 to 50 g / 10 minutes, and still more preferably 3 to 30 g / 10 minutes. Moreover, it is preferable to improve both surface smoothness and adhesiveness by using two or more types of polypropylene resins (B) having different MFRs.

The melting point of the polypropylene-based resin (B) is preferably 100 ° C or higher, more preferably 100 to 170 ° C, and still more preferably 110 to 140 ° C from the viewpoints of heat resistance and adhesiveness by heat treatment.

The thermoplastic polymer composition contains 1 to 50 parts by mass of a polypropylene-based resin (B) based on 100 parts by mass of the thermoplastic elastomer (A). When the polypropylene-based resin (B) is less than 1 part by mass, it is difficult to adhere the adherend by heat treatment. On the other hand, when the polypropylene-based resin (B) becomes more than 50 parts by mass, the thermoplastic polymer composition becomes hard, and it becomes difficult to exhibit flexibility and mechanical properties. The content of the polypropylene-based resin (B) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, more preferably 40 parts by mass or less, more preferably 100 parts by mass of the thermoplastic elastomer (A). It is 30 parts by mass or less.

The content of the polypropylene-based resin (B) is preferably 5 to 40 parts by mass, and more preferably 10 to 30 parts by mass based on 100 parts by mass of the thermoplastic elastomer (A).

    [(Meth) acrylic resin (C)]    

The (meth) acrylic resin (C) is used to improve the adhesiveness of the thermoplastic polymer composition. By including the (meth) acrylic resin (C) in the thermoplastic polymer composition, the thermoplastic polymer composition can be improved. The adhesiveness of the substance is mainly relative to the polar resin, and in the multilayer film using the thermoplastic polymer composition, the thermoplastic polymer composition can be strongly adhered to the substrate layer described below.

The (meth) acrylic resin (C) used in the present invention has a structural unit derived from methyl methacrylate of 80% by mass or more, and preferably 90% by mass or more. In other words, the structural units derived from monomers other than methyl methacrylate (C) acrylic resin (C) are set to 20% by mass or less, and preferably 10% by mass or less. The (meth) acrylic resin (C) may be a polymer using only methyl methacrylate as a monomer.

Examples of the monomer other than the methyl methacrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, secondary butyl acrylate, and acrylic acid. Tertiary butyl, pentyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate; phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate Esters, 2-hydroxyethyl acrylate, 2-ethoxyethyl acrylate, propylene acrylate, allyl acrylate; cyclohexyl acrylate, norbornyl acrylate, isopropyl acrylate and other acrylates; methacrylic acid Ethyl ester, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, secondary butyl methacrylate, tertiary butyl methacrylate, methacrylic acid Amyl ester, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate; phenyl methacrylate, benzene methacrylate Methyl ester Phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-ethoxyethyl methacrylate, glycidyl methacrylate, allyl methacrylate; cyclohexyl methacrylate Methacrylates other than methyl methacrylate such as norbornene methacrylate and isoamyl methacrylate; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, maleic acid, and iconic acid ; Olefins such as ethylene, propylene, 1-butene, isobutylene, 1-octene, etc .; conjugated dienes of butadiene, isoprene, myrcene, etc .; styrene, α-methylstyrene, p- Aromatic ethylene compounds such as methylstyrene and m-methylstyrene; acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, vinyl acetate, vinylpyridine, ketene, vinyl chloride, dichloromethane Vinylidene, difluoroethylene, etc.

The stereoregularity of the (meth) acrylic resin (C) is not particularly limited. For example, those having isotacticity, heterotacticity, syndiotacticity, and the like can also be used.

The weight average molecular weight of the (meth) acrylic resin (C) is preferably 20,000 or more and 180,000 or less, more preferably 30,000 or more and 150,000 or less, and still more preferably 30,000 or more and 130,000 or less. If the weight average molecular weight is small, the mechanical strength of the obtained thermoplastic polymer composition tends to decrease. When the weight average molecular weight is large, the flowability of the thermoplastic polymer composition is reduced, and the moldability tends to be reduced.

The molecular weight or molecular weight distribution of the (meth) acrylic resin (C) can be controlled by adjusting the types or amounts of a polymerization initiator and a chain transfer agent.

The method for producing the (meth) acrylic resin (C) is not particularly limited, and a monomer (mixture) containing 80% by mass or more of methyl methacrylate may be polymerized or a monomer other than methyl methacrylate may be used. It is obtained by bulk copolymerization. As the (meth) acrylic resin (C), a commercially available product can also be used. Examples of the commercially available methacrylic resin include "PARAPET H1000B" (MFR: 22g / 10 minutes (230 ° C, 37.3N)), "PARAPET GF" (MFR: 15g / 10 minutes (230 ° C, 37.3N)), "PARAPET EH" (MFR: 1.3g / 10 minutes (230 ° C, 37.3N)), "PARAPET HRL" (MFR: 2.0g / 10 minutes (230 ° C, 37.3N)), "PARAPET HRS "(MFR: 2.4g / 10 minutes (230 ° C, 37.3N)) and" PARAPET G "(MFR: 8.0g / 10 minutes (230 ° C, 37.3N)) [Both are trade names, manufactured by Kuraray Co., Ltd.] Wait.

The thermoplastic polymer composition preferably contains 1 to 25 parts by mass of the (meth) acrylic resin (C) based on 100 parts by mass of the thermoplastic elastomer (A), and more preferably contains 3 to 20 parts by mass. If the (meth) acrylic resin (C) is less than 1 part by mass, it is difficult to adhere the adherend by heat treatment. On the other hand, when the (meth) acrylic resin (C) becomes more than 25 parts by mass, the thermoplastic polymer composition becomes hard, and it becomes difficult to exhibit flexibility and mechanical properties.

From the above viewpoint, the content of the (meth) acrylic resin (C) is preferably 1 to 18 parts by mass, and more preferably 3 to 15 parts by mass, based on 100 parts by mass of the thermoplastic elastomer (A).

    [Other ingredients]    

The thermoplastic polymer composition of the present invention may contain an olefin-based polymer, a styrene-based polymer, a polyphenylene ether-based resin, polyethylene glycol, or the like, as long as it does not significantly impair the effects of the present invention, and others Thermoplastic polymer. Examples of the olefin-based polymer include polyethylene, polypropylene, polybutene, block copolymers and random copolymers with other α-olefins such as propylene and ethylene or 1-butene.

When other thermoplastic polymers are contained, the content is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, still more preferably 20 parts by mass or less, based on 100 parts by mass of the thermoplastic elastomer (A). It is preferably 10 parts by mass or less, and particularly preferably 5 parts by mass or less.

The thermoplastic polymer composition of the present invention may contain an antioxidant, a slip agent, a light stabilizer, a processing aid, a colorant such as a pigment or a pigment, a flame retardant, and Electrostatic agent, matting agent, silicone oil, anti-adhesive agent, ultraviolet absorber, release agent, foaming agent, antibacterial agent, antifungal agent, perfume, etc.

Examples of the antioxidant include hindered phenol-based, phosphorus-based, lactone-based, and hydroxyl-based antioxidants. Among these, a hindered phenol antioxidant is preferable.

    [Manufacturing method of thermoplastic polymer composition]    

The method for preparing the thermoplastic polymer composition of the present invention is not particularly limited. In order to improve the dispersibility of each component constituting the thermoplastic polymer composition, for example, a method of mixing and kneading is recommended. In this case, the thermoplastic elastomer (A), the polypropylene-based resin (B), and the (meth) acrylic-based resin (C) may be simultaneously mixed with other components added as necessary to perform melt-kneading. The mixing operation can be performed using, for example, a known mixing or kneading device such as a Kneader-Ruder, an extruder, a mixing roll, a Banbury mixer, or the like. In particular, from the viewpoint of improving the kneadability and compatibility of the thermoplastic elastomer (A) and the (meth) acrylic resin (C), it is preferable to use a biaxial extruder. The temperature at the time of mixing and kneading can be appropriately adjusted according to the melting temperature of the thermoplastic elastomer (A), polypropylene resin (B), (meth) acrylic resin (C), etc., and is usually 110 ° C ~ Mix at a temperature in the range of 300 ° C.

As described above, the thermoplastic polymer composition of the present invention can be obtained in any form such as pellets and powder. The obtained thermoplastic polymer composition can be formed into various shapes such as a film, a sheet, a flat plate, a pipe, a tube, a rod, and a granular body. These manufacturing methods are not particularly limited, and they can be molded by various conventional molding methods, such as injection molding, blow molding, pressure molding, extrusion molding, and roll molding.

    [Multilayer film]    

The multilayer film of the present invention has at least a substrate layer and a layer containing the thermoplastic polymer composition of the present invention. Hereinafter, the base material layer used for the multilayer film of this invention is demonstrated.

    [Substrate layer]    

Although it does not specifically limit as a base material layer, It is preferable to contain an amorphous resin. In this specification, "amorphous resin" means a resin which does not have a clear melting point in a differential scanning calorimetry (DSC) curve.

Examples of the amorphous resin include polystyrene resin, polyvinyl chloride resin, acrylonitrile styrene resin, ABS resin (acrylonitrile butadiene styrene resin), polycarbonate resin, and polyester resin. , (Meth) acrylic resin, etc. Among them, from the viewpoints of weather resistance, surface gloss, and abrasion resistance, (meth) acrylic resins, ABS resins, polycarbonate resins, and polyester resins are preferred, and from the viewpoints of transparency and surface gloss Is preferably a (meth) acrylic resin. The (meth) acrylic resin is more preferably a (meth) acrylic resin composition containing a methacrylic resin (F) and an elastomer (R).

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

As this monomer other than methyl methacrylate, the same thing as the said (meth) acrylic-type resin (C) mentioned as a monomer other than methyl methacrylate can be used.

The stereoregularity of the methacrylic resin (F) is not particularly limited. For example, those having isotacticity, heterotacticity, and syndiotacticity may be used.

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

The manufacturing method of a methacrylic resin (F) is not specifically limited, It is obtained by superposing | polymerizing the monomer (mixture) containing 80 mass% of methyl methacrylate, or copolymerizing with monomers other than methyl methacrylate. Moreover, as a methacrylic resin (F), a commercial item can also be used.

The (meth) acrylic resin (C) used in the thermoplastic polymer composition may be the same as the methacrylic resin (F) used in the substrate layer, and may also have a comonomer ratio, molecular weight, and MFR And so on.

Examples of the elastomer (R) include a butadiene-based rubber, a chloroprene-based rubber, a block copolymer, and a multilayer structure, 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 methacrylate polymer block (g1) and an acrylate polymer block (g2). The acrylic block copolymer (G) may have only one methacrylate polymer block (g1) and one acrylate polymer block (g2), or a plurality of them.

A methacrylate polymer block (g1) is a structure which has the structural unit derived from a methacrylate as a main structural unit. The proportion of the methacrylate-derived structural unit derived from the methacrylate polymer block (g1) is preferably 80% by mass or more, more preferably 90% by mass or more, from the viewpoint of extensibility and surface hardness. It is more preferably 95% by mass or more, and still more preferably 98% by mass or more.

Examples of the methacrylate include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate. Ester, secondary butyl methacrylate, tertiary butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethyl methacrylate Hexyl hexyl, pentadecyl methacrylate, dodecyl methacrylate, isoamyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, methacrylic acid 2-hydroxyethyl ester, 2-methoxyethyl methacrylate, glycidyl methacrylate, allyl methacrylate, and the like can be polymerized individually or in combination of two or more kinds. Among these, from the viewpoint of transparency and heat resistance, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and tertiary butyl methacrylate are preferred. Alkyl methacrylates such as cyclohexyl methacrylate and isoamyl methacrylate, more preferably methyl methacrylate.

The methacrylate polymer block (g1) may include structural units derived from monomers other than methacrylate, and from the viewpoint of extensibility and surface hardness, the proportion thereof is preferably 20% by mass or less, and more preferably The content is 10% by mass or less, more preferably 5% by mass or less, and even more preferably 2% by mass or less.

Examples of monomers other than the aforementioned methacrylates include acrylates, unsaturated carboxylic acids, aromatic vinyl compounds, olefins, conjugated dienes, acrylonitrile, methacrylonitrile, acrylamide, and formazan. Acrylamide, vinyl acetate, vinylpyridine, ketene, vinyl chloride, dichloroethylene, difluoroethylene and the like can be used alone or in combination of two or more.

When the block copolymer (G) has a plurality of methacrylate polymer blocks (g1), the composition ratio or molecular weight of the structural units constituting the respective methacrylate polymer blocks (g1) may be the same, It can be different.

The proportion of the methacrylate polymer block (g1) of the block copolymer (G) is preferably from 10% by mass to 70% by mass from the viewpoints of transparency, softness, moldability, and surface smoothness. The range is more preferably in the range of 25% by mass to 60% by mass. When the block copolymer (G) includes a plurality of methacrylate polymer blocks (g1), the aforementioned ratio is calculated based on the total mass of all the methacrylate polymer blocks (g1).

An acrylate polymer block (g2) is a structure which has the structural unit derived from an acrylate as a main structural unit. The proportion of the structural unit derived from the acrylate polymer block (g2) from the acrylate is preferably 45% by mass or more, more preferably 50% by mass or more, and more preferably 60% by mass or more, more preferably 90% by mass or more.

Examples of the acrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, secondary butyl acrylate, tertiary butyl acrylate, Amyl acrylate, isoamyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, isoamyl acrylate, phenyl acrylate, benzyl acrylate, Phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-methoxyethyl acrylate, propylene acrylate, allyl acrylate, etc. can be polymerized alone or in combination of two or more .

The acrylic polymer block (g2) preferably contains an alkyl acrylate and an (meth) acrylic acid aromatic ester from the viewpoint of extensibility and transparency. Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and dodecyl acrylate. Among these, n-butyl acrylate and 2-ethylhexyl acrylate are preferred.

The (meth) acrylic acid aromatic ester means an acrylic acid aromatic ester or a methacrylic acid aromatic ester, and a compound containing an aromatic ring is bonded to a (meth) acrylic acid ester. Examples of the (meth) acrylic acid aromatic ester include phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, styrene acrylate, phenyl methacrylate, benzyl methacrylate, Phenoxyethyl methacrylate, styrene methacrylate and the like. Among these, from the viewpoint of transparency, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, and benzyl acrylate are preferred.

When the acrylate polymer block (g2) contains an alkyl acrylate and an (meth) acrylic acid aromatic ester, the acrylate polymer block (g2) preferably contains 50 to 90% by mass from the viewpoint of transparency. The structural unit derived from the alkyl acrylate and 50 to 10% by mass of the structural unit derived from the (meth) acrylic acid aromatic ester, more preferably 60 to 80% by mass of the structural unit derived from the alkyl acrylate and 40 to 20% by mass % Of the structural units derived from the aromatic (meth) acrylic acid ester.

The acrylate polymer block (g2) may include structural units derived from monomers other than acrylate. The content of the acrylate polymer block (g2) is preferably 55% by mass or less, and more preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 10% by mass or less.

Examples of monomers other than acrylate include methacrylate, unsaturated carboxylic acid, aromatic vinyl compound, olefin, conjugated diene, acrylonitrile, methacrylonitrile, acrylamide, and methyl Acrylamide, vinyl acetate, vinylpyridine, ketene, vinyl chloride, dichloroethylene, difluoroethylene, etc. may be used alone or in combination of two or more.

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

The proportion of the acrylate polymer block (g2) of the block copolymer (G) is preferably in the range of 30 to 90% by mass from the viewpoints of transparency, softness, moldability, and surface smoothness, and more preferably The range is 40 to 75% by mass. When the block copolymer (G) includes a plurality of acrylate polymer blocks (g2), the ratio is calculated based on the total mass of all the acrylate polymer blocks (g2).

The bonding form of the methacrylate polymer block (g1) and the acrylate polymer block (g2) of the block copolymer (G) is not particularly limited, and examples thereof include a methacrylate polymer block A structure in which one end of (g1) is connected to one end of the acrylate polymer block (g2) ((g1)-(g2) structure); the two ends of the methacrylate polymer block (g1) are connected to acrylic acid Structure ((g2)-(g1)-(g2) structure) connected at one end of the ester polymer block (g2); methacrylate polymer is embedded at both ends of the acrylate polymer block (g2) Structure in which one end of segment (g1) is connected (such as (g1)-(g2)-(g1) structure) methacrylate polymer block (g1) and acrylate polymer block (g2) are connected in series . Among these, a diblock copolymer having a (g1)-(g2) structure or a triblock copolymer having a (g1)-(g2)-(g1) structure is preferred.

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

The weight average molecular weight of the acrylic block copolymer (G) is preferably in the range of 60,000 to 400,000, and more preferably in the range of 60,000 to 200,000. If the weight average molecular weight of the block copolymer (G) is less than 60,000, sufficient melt tension cannot be maintained during melt extrusion, and it is difficult to obtain a good film, and mechanical properties such as breaking strength of the obtained film are reduced. If it is more than 400,000, the viscosity of the molten resin will increase, and fine corrugated unevenness or unmelted (high molecular weight) particles will be produced on the surface of the film obtained by melt extrusion, and it will be difficult to obtain it. Good film tendency.

The molecular weight distribution of the acrylic block copolymer (G) is preferably in the range of 1.0 to 2.0, and more preferably in the range of 1.0 to 1.6. Since there is a molecular weight distribution in the above-mentioned range, the content of unmelted matter that is a cause of particles in the base material layer can be reduced. The weight average molecular weight and the number average molecular weight are molecular weights in terms of standard polystyrene measured by GPC.

The refractive index of the acrylic block copolymer (G) is preferably in the range of 1.485 to 1.495, and more preferably in the range of 1.487 to 1.493. When the refractive index is within this range, the transparency of the obtained base material layer becomes high. The refractive index is a value measured at a wavelength of 587.6 nm (d-ray).

The method for producing the acrylic block copolymer (G) is not particularly limited, and a method according to a known method may be adopted. For example, a method of livingly polymerizing monomers constituting each polymer block is generally used. Examples of the aforementioned living polymerization method include a method in which an organic alkali metal compound is used as a polymerization initiator and anionic polymerization is performed in the presence of a mineral acid salt such as an alkali metal or an alkaline earth metal salt; and an organic alkali metal is used. A method in which a compound is used as a polymerization initiator and anionic polymerization is performed in the presence of an organoaluminum compound; a method in which an organic rare earth metal complex is used as a polymerization initiator and polymerization is performed; an α-halogenated ester compound is used as a initiator Use, a method of performing radical polymerization in the presence of a copper compound, and the like. In addition, a method of polymerizing monomers constituting each block using a polyvalent radical polymerization initiator or a polyvalent radical chain transfer agent and producing the mixture as a mixture containing an acrylic block copolymer (G) can also be mentioned. Wait. Among these methods, an acrylic block copolymer (G) is obtained with high purity, and the molecular weight or composition ratio is easily controlled and economical. Therefore, it is preferable to use an organic alkali metal compound as a polymerization initiator. A method for performing anionic polymerization in the presence of an organoaluminum compound.

The multilayer structure (E) includes at least two layers of an inner layer and an outer layer, and has a layer structure in which at least one inner layer and an 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 elastomer obtained by copolymerizing an alkyl acrylate and a monomer mixture having a crosslinkable monomer. As the alkyl acrylate, an alkyl acrylate having a carbon number in the range of 2 to 8 can be particularly used, and examples include butyl acrylate and 2-ethylhexyl acrylate. The proportion of the alkyl acrylate of the entire monomer mixture used to form the copolymer of the inner layer is preferably in the range of 70 to 99.8% by mass, and more preferably 80 to 90% by mass from the viewpoint of impact resistance.

The crosslinkable monomer used in the inner layer may be one having at least two polymerizable carbon-carbon double bonds in one molecule, and examples thereof include ethylene glycol dimethacrylate and butanediol. Unsaturated carboxylic acid diesters of diols such as dimethacrylate; allyl acrylates of unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, allyl cinnamate; diallyl phthalate Esters, polyallyl maleates, triallyl cyanurate, triallyl isocyanate and other polyacrylic acid polyacrylates; trimethylolpropane triacrylate and other unsaturated polyesters Carboxylic acid esters; divinylbenzene and the like, and preferably an alkenyl ester of an unsaturated carboxylic acid or a polyene ester of a polybasic acid. The amount of the crosslinkable monomer in the entire monomer mixture is preferably in the range of 0.2 to 30% by mass, and more preferably 0.2 to 10% by mass from the viewpoint of improving the impact resistance, heat resistance, and surface hardness of the base material layer. Range.

The monomer mixture forming the inner layer may further contain other monofunctional monomers. Examples of the monofunctional monomer include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate. Ester, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, myristyl methacrylate Esters, palmyl methacrylate, stearyl methacrylate, taracosyl methacrylate and other alkyl methacrylates; methacrylic acid and phenolic esters such as phenyl methacrylate; phenyl methyl methacrylate Methacrylic acid esters such as methacrylic acid and aromatic alcohols; styrene, α-methylstyrene, 1-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexyl Aromatic vinyl monomers such as styrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, and halogenated styrene; acrylonitrile, methyl Vinyl cyanide-based monomers such as acrylonitrile; conjugated diene-based monomers such as butadiene and isoprene. The amount of other monofunctional monomers in the entire monomer mixture is preferably 24.5% by mass or less, more preferably 20% by mass or less, from the viewpoint of improving the impact resistance of the base material layer.

From the viewpoint of the heat resistance of the base material layer, the outer layer is composed of a hard thermoplastic resin obtained by polymerizing a monomer mixture containing 80% by mass or more of methyl methacrylate, and preferably contains 90% by mass or more. The rigid thermoplastic resin contains 20% by mass or less of other monofunctional monomers, and preferably contains 10% by mass or less. Examples of other monofunctional monomers include alkyl acrylates such as methyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; acrylic acid; and methacrylic acid.

The content of the inner layer and the outer layer of the multilayer structure (E) is preferably a multilayer structure from the viewpoints of impact resistance, heat resistance, surface hardness, handleability, and ease of melt-kneading of the obtained base material layer. The mass of (E) (for example, the total amount of the inner layer and the outer layer when two layers are included) is used as a reference. The content rate of the inner layer is selected from the range of 40 to 80% by mass, and the content rate of the outer layer is selected from 20 to 60. Range of mass%.

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

When the base material layer is composed of a (meth) acrylic resin composition containing a methacrylic resin (F) and an elastomer (R), the content of each component is preferably based on the methacrylic resin (F) and elasticity. The total amount of the body (R) is 100 parts by mass, the content of the methacrylic resin (F) is 10 to 99 parts by mass, and the content of the elastomer (R) is 90 to 1 part by mass. When the content of the methacrylic resin (F) is less than 10 parts by mass, the surface hardness of the base material layer tends to decrease. More preferably, the content of the methacrylic resin (F) is 55 to 90 parts by mass and the content of the elastomer (R) is 45 to 100 parts by mass based on the total of the methacrylic resin (F) and the elastomer (R). 10 parts by mass. Still more preferably, the content of the methacrylic resin (F) is 70 to 90 parts by mass, and the content of the elastomer (R) is 30 to 10 parts by mass.

The amorphous resin constituting the substrate layer is preferably an arbitrary temperature in the range of 110 to 160 ° C, and the elastic modulus is 2 to 600 MPa. If the elastic coefficient is less than 2 MPa, there is a tendency that the elongation becomes uneven during vacuum forming, and if the elastic coefficient is larger than 600 MPa, there is a tendency that cracks or breaks may occur during vacuum forming. The coefficient of elasticity is a value rounded to the first decimal place when expressed in [MPa].

The amorphous resin constituting the base material layer may also contain various additives such as antioxidants, heat stabilizers, slip agents, processing aids, antistatic agents, anti-thermal deterioration agents, ultraviolet absorbers, light stabilizers, Polymer processing aids, colorants, impact additives, etc.

The amorphous resin may be used in combination with other polymers. Examples of the other polymers include polyolefin resins such as polyethylene, polypropylene (PP), polybutene-1, poly-4-methylpentene-1, and polynorbornene; and ethylene-based resins. Ionic polymers; polystyrene, styrene-maleic anhydride copolymer, impact-resistant polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile- Styrene such as ethylene-styrene copolymer, acrylonitrile-acrylate-styrene copolymer resin, acrylonitrile-chlorinated polyethylene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, etc. Resin; methyl methacrylate-styrene copolymer; polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, etc .; nylon 6, nylon 66, polyamide Polyamines such as elastomers; polycarbonates, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymers, polyacetals, polydifluoroethylene, polyurethanes , Modified polyphenylene ether, polyphenylene sulfide, silicone modified resin; acrylic rubber, silicone; styrene-ethylene / propylene-styrene copolymer, Styrene-based thermoplastic elastomers such as ethylene-ethylene / butadiene-styrene copolymer, styrene-isoprene-styrene copolymer; olefins such as isoprene rubber, ethylene propylene rubber, and ethylene propylene diene rubber Department of rubber and so on.

The method for preparing the amorphous resin constituting the base material layer is not particularly limited, but in order to improve the dispersibility of the components constituting the amorphous resin, a method of melt-kneading and mixing is preferred. For the mixing operation, for example, a known mixing or kneading device such as Kneader-Ruder, extruder, mixing roll, Banbury mixer, etc. can be used. From the viewpoint of improving kneading and compatibility, it is preferable. To use a twin-shaft extruder. The temperature at the time of mixing and kneading may be appropriately adjusted according to the melting temperature of the amorphous resin to be used, and is usually in the range of 110 to 300 ° C. When melt-kneading is performed using a biaxial extruder, from the viewpoint of coloration suppression, it is preferable to use an exhaust port, and perform melt-kneading under reduced pressure and / or under a nitrogen atmosphere.

    [Other layers]    

The multilayer film of the present invention may also be printed on the substrate layer and / or the layer containing the thermoplastic polymer composition with patterns or colors such as patterns, characters, and graphics. The pattern can be colored or achromatic. Examples of the printing method include known printing methods such as gravure printing, lithographic printing, screen printing, transfer printing, and inkjet printing. In printing, it is preferable to use resins containing polyethylene resins, polyester resins, acrylic resins, polyvinyl acetal resins, and cellulose resins as binders, and pigments or dyes as colorants generally used in this printing method. Resin composition.

The base material layer used in the multilayer film of the present invention may be colored. Examples of the coloring method include a method in which the amorphous resin itself contains a pigment or a dye, and the resin itself is colored before being formed into a thin film; a dyeing method in which an amorphous resin film is dipped in a dye-dispersed liquid and colored; , But it is not limited to these.

In the multilayer film of the present invention, a metal or a metal oxide may be deposited on a substrate layer. The metal or metal oxide is not particularly limited, and a metal or metal oxide used for sputtering or vacuum deposition can be used. Examples include gold, silver, copper, aluminum, zinc, nickel, chromium, and indium. Or such oxides. These metals or metal oxides may be used alone or as a mixture of two or more. Examples of a method for vapor-depositing a metal or a metal oxide on a substrate layer include a vacuum film-forming method such as vapor deposition or sputtering, or electroplating or electroless plating.

The surface of the substrate layer side of the multilayer film of the present invention is preferably pencil hardness HB or harder, and more preferably H or harder. If the pencil hardness is harder than HB, the multilayer film is less likely to be damaged, and it can be suitably used as a decorative and protective film on the surface of a molded product that requires design.

The entire 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, and even more preferably in the range of 100 to 400 μm. When the thickness of the multilayer film is 20 μm or more, production becomes easy, impact resistance and warpage during heating are reduced, and hiding properties are obtained when coloring. When the thickness of the multilayer film is 1,000 μm, the three-dimensional coating moldability tends to be improved.

In the multilayer film of the present invention, the thickness of the substrate layer is preferably 500 μm or less. If it becomes thicker than 500 μm, secondary processability such as lamination, handling, cutting, and machinability will decrease, and it will become difficult to use it as a thin film. At the same time, the unit price per unit area will increase, which is economically disadvantageous. , So it ’s less good. The thickness of the substrate layer is more preferably 40 to 300 μm, and still more preferably 50 to 250 μm.

The ratio (y / x) of the thickness (y) of the substrate layer to the thickness (x) of the layer containing the thermoplastic polymer composition is preferably in the range of 0.2 to 5, and more preferably in the range of 0.5 to 4, A more preferable range is 0.8 to 3. If the value of the above ratio (y / x) is less than 0.2, the surface hardness tends to be lower. If it is larger than 5, the multilayer film tends to be easily broken. If it is larger than 4, the stretchability will be changed. Get a lower tendency.

    [Manufacturing method of multilayer film]    

The multilayer film of this invention is a thing which has a base material layer and the layer containing the thermoplastic polymer composition of this invention, and can be obtained by including the said thermoplastic polymer composition in the area layer of one of the base material layers.

The manufacturing method of the said base material layer is not specifically limited, For example, when an amorphous resin is used, it can be performed using well-known methods, such as a T-die method, an inflation method, a melt casting method, and a rolling method. From the standpoint of obtaining a film with good surface smoothness and low haze, it is preferable that the self-T-die containing the amorphous resin constituting the base material layer is extruded in a molten state, and the both sides and the surface of the mirror roll are extruded. Or the method of forming the surface of the mirror conveyor belt in contact. The rollers or conveyor belts used at this time are preferably made of metal. When the two sides of the extruded melt-kneaded material are brought into contact with a mirror surface to perform film formation, it is preferable to press and hold both sides of the film with a mirror roll or a mirror conveyor belt. The wrapping pressure using a mirror roll or a mirror conveyor belt is preferably the higher, and as the line pressure, it is preferably 10 N / mm or more, and more preferably 30 N / mm or more.

The substrate layer may be a film subjected to a stretching treatment. With the elongation treatment, the mechanical strength is improved and it becomes difficult to crack. The stretching method is not particularly limited, and examples thereof include a simultaneous biaxial stretching method, a sequential biaxial stretching method, a tubular stretching method, and a rolling method.

Examples of the method of laminating the thermoplastic polymer composition-containing layer of the base material layer obtained as described above include a method of applying a solution of the thermoplastic polymer composition to the base material layer, and including the thermoplastic material on the base material layer. Method of thin film of polymer composition, etc. The film containing the said thermoplastic polymer composition can be obtained similarly to the manufacturing method of the base material layer demonstrated above.

The amorphous resin and the thermoplastic polymer composition constituting the base material layer can also be produced by coextrusion using a T-die method. Especially preferred is the co-extrusion molding method using multiple branch tube molds.

    [Formed body]    

The molded article of the present invention is a multilayer film or a decorative film including the multilayer film of the present invention. More preferably, the multilayer film of the present invention is one provided on the surface of an adherend such as a thermoplastic resin, a thermosetting resin, a wood substrate, or a non-wood fiber substrate.

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, Other (meth) acrylic resins, ABS (acrylonitrile-butadiene-styrene copolymerization) resins, and the like. Examples of the thermosetting resin include epoxy resin, phenol resin, and melamine resin. The formed article may be a multilayer film of the present invention provided on the surface of a non-wood fiber such as a wooden substrate or kenaf.

There are no particular restrictions on the method of forming the formed body. For example, the multilayer film of the present invention can be formed on the surface of an adherend such as a thermoplastic resin, a thermosetting resin, a wooden substrate, and a non-wood fiber substrate by heating under vacuum, pressure, and compression to obtain a film. The formed body of the present invention. In the molded body, the base material layer of the multilayer film of the present invention is provided on the outermost layer of the molded body, and according to the foregoing, the surface smoothness, surface hardness, surface gloss, and the like are excellent. Among them, vacuum forming and / or pressure forming are preferred from the viewpoint of forming with good accuracy and adhering to various adherends, and more preferably three-dimensional surface decoration forming combining vacuum forming and pressure forming (Three dimension Overlay) Method: TOM forming). As the vacuum forming apparatus for TOM forming a multilayer film, a vacuum forming apparatus described in Japanese Patent Application Laid-Open No. 2002-067137 or a coating device described in Japanese Patent Application Laid-Open No. 2005-262502 can be suitably used. The device or the covering device includes a chamber box provided with a multilayer film and an adherend, which can be closed and decompressed.

The method for manufacturing a molded body by TOM forming includes the steps of storing a multilayer film and an adherend in a chamber box; a step of decompressing the inside of the chamber box; and dividing the inside of the chamber box into two halves with the multilayer film. A step of making the pressure in the chamber box of the person without the aforementioned adherend higher than that in the chamber box of the person having the aforementioned adherend, and covering the aforementioned adherend with the multilayer film. Furthermore, in the step of accommodating the multilayer film and the adherend in the chamber box, the step of dividing the inside of the chamber box into two halves with the multilayer film may be performed at the same time.

Among the manufacturing methods of the molded body, another preferable method is generally called a method of injection molding and simultaneous bonding.

The simultaneous injection molding method is to insert the multilayer film of the present invention into a male and female mold for injection molding, and inject a molten thermoplastic resin from the surface of the film on the side of the layer to be formed into the injection molded body, and at the same time A method for laminating the aforementioned multilayer film on the surface.

The multilayer film inserted into the mold can be maintained as a flat surface, or it can be formed into a concave-convex shape by preliminary forming such as vacuum forming and pressure forming.

The pre-forming of the multilayer film may be performed by another forming machine, or may be performed in a mold of an injection molding machine which is used for injection molding at the same time.

A multilayer film having a layer containing the thermoplastic polymer composition of the present invention and a molded body having the multilayer film can make use of the good extensibility and molding processability of the multilayer film, excellent bipolar adhesion and surface smoothness, and can be applied. For items that require design. For example, it can be suitably used for advertising parts such as advertising towers, vertical signs, side signs, horizontal signs, roof signs, etc .; display parts such as display cabinets, dividers, and store displays; fluorescent lamp covers, atmosphere lamp covers, lamp covers, light Lighting components such as ceiling panels, illuminated walls, chandelier; interior parts such as furniture, necklaces, mirrors; doors, domes, safety window glass, partition panels, step siding, balcony siding, roofs of leisure buildings, etc. Parts, automobile interior and exterior components, automobile exterior components such as bumpers, and other transport equipment-related parts; audio-visual panels, audio dust covers, vending machines, mobile phones, computers and other electronic equipment parts; baby boxes, rulers, clock faces, Greenhouses, large sinks, aquariums, bathroom components, surface boards, bathtubs, sanitary equipment, table mats, game parts, toys, wallpapers; marking films, and decorative applications for various home appliances. Since the multilayer film of this invention has the said characteristic, it can use suitably as a decorative film especially.

    [Example]    

Hereinafter, the present invention will be described in more detail based on examples and the like, but the present invention is not limited to these examples. The production of test samples and the measurement or evaluation of various physical properties in the examples and comparative examples were performed as follows, and the results are arranged in a table.

    [Surface smoothness of thermoplastic polymer composition]    

A capillary rheometer (CAPIROGRAPH 1C, manufactured by TOYOSEIKI Co., Ltd.) was installed with a slit-shaped capillary having a rectangular cross section (8 mm in length × 0.5 mm in width), and the examples and comparisons were extruded at 250 ° C and a piston speed of 50 mm / min The obtained thermoplastic polymer composition obtained a film-like strand. Using a probe shape measuring device (Dektak-150 manufactured by Bruker), a needle having a tip radius of 12.5 μm was used to measure the arithmetic average roughness (Ra) of the surface of the strand obtained as described above. When Ra is smaller than 0.15 μm, the surface smoothness is excellent.

    [Adhesive strength of thermoplastic polymer composition (PMMA)]    

The thermoplastic polymer composition obtained in Examples and Comparative Examples and the methacrylic resin composition pellets obtained in Production Example 5 were each compression-molded under the conditions of 200 ° C and a load of 50 kgf / cm2 using a compression molding machine. For 2 minutes, a sheet containing a thermoplastic polymer composition and a sheet containing a methacrylic resin composition were obtained. A sheet containing a thermoplastic polymer composition of 150 × 150 mm (150 mm in length × 150 mm in width × 0.5 mm in thickness) and a polyimide film (Kapton film manufactured by Toray‧Du Pont, 75 mm in length × 150 mm in width × 0.05 mm in thickness) A sheet (150 mm in length × 150 mm in width × 0.5 mm in thickness) containing a methacrylic resin composition is stacked in this order, and is arranged at a central portion of a metal spacer having an internal size of 150 mm × 150 mm and a thickness of 0.8 mm. The overlapped sheet and the metal spacer were sandwiched by a polytetrafluoroethylene sheet, and sandwiched by a metal plate from the outside, and compression-molded using a compression molding machine at 130 ° C. and a load of 50 kgf / cm 2 for 2 minutes to obtain A multilayer film of a thermoplastic polymer composition and a methacrylic resin composition.

This multilayer film was cut to a width of 25 mm, and the peel strength between the thermoplastic polymer composition and the methacrylic resin composition was used as a test piece for measuring the adhesive strength. A peel tester (manufactured by Shimadzu Corporation) was used in accordance with JIS K 6854-2. AGS-X) was measured under the conditions of a peeling angle of 90 °, a stretching speed of 300 mm / min, and an ambient temperature of 23 ° C, and was used as the adhesion strength (PMMA) of the thermoplastic polymer composition.

    [Adhesive strength (PP) of the thermoplastic polymer composition]    

In the adhesive strength (PMMA) of the thermoplastic polymer composition, a sheet containing a methacrylic resin composition was changed to a polypropylene sheet (MA3 manufactured by Japan Polypropylene Corporation, 150 mm in length × 150 mm in width × 0.4 mm in thickness ), Except for the same procedure, a multilayer film was prepared, and the peel strength between the thermoplastic polymer composition and polypropylene was measured to determine the adhesion strength (PP) of the thermoplastic polymer composition.

    [Evaluation of the surface smoothness of the formed body]    

The multilayer film produced in Example 10 and Comparative Example 7 described later was inserted into a vacuum pressure forming machine (manufactured by Busch Vacuum Co., Ltd .; NGF-0406-T), which was performed in the same manner as in Example 10, and three-dimensionally performed on the sheet glass. Surface decoration molding was performed to prepare a sample for evaluation, and the surface property of the molded body was evaluated. The evaluation system used a probe shape measuring device (Dektak-150 manufactured by Bruker), and used a needle with a tip radius of 12.5 μm to measure the arithmetic mean roughness (Ra). When Ra is smaller than 0.15 μm, the surface smoothness is excellent.

    [Evaluation of Adhesive Strength of the Molded Body]    

On the flat platform of the vacuum pressure forming machine, a sheet-shaped adherend (length: 150 mm × width: 25 mm × thickness: 0.3 mm) containing a polypropylene resin (manufactured by Japan Polypropylene Corporation; MA03) was placed on the polypropylene A polyimide film (Kapton film manufactured by Toray‧Du Pont, 30 mm in length × 30 mm in width × 0.125 mm in thickness) was superposed on the ends of the sheet, and the same procedure as in Example 10 was performed, and three-dimensional surface decoration molding was performed and removed The non-overlapping part of the multilayer film and the polypropylene sheet was used to prepare a test piece. The multilayer film side of the obtained test piece was fixed to a SUS board with a strong tape, and a peel tester (AGS-X manufactured by Shimadzu Corporation) was used at a peel angle of 90 °, a tensile speed of 300 mm / min, and an ambient temperature of 23 ° C. The peel strength between the layer containing the thermoplastic polymer composition and the polypropylene sheet was measured in accordance with JIS K 6854-2.

The components used in the following examples and comparative examples are as follows.

    <Manufacturing example 1> [Synthesis of thermoplastic elastomer (A-1)]    

In a pressure-resistant container substituted with nitrogen and dried, 64 L of cyclohexane as a solvent, 0.20 L of secondary butyl lithium (10% by mass of cyclohexane solution) as a starter were added, and organic Lewis base was added. Tetrahydrofuran 0.46L. After raising the temperature to 50 ° C., 2.3 L of styrene was added and polymerization was performed for 3 hours, and then 23 L of isoprene was added for polymerization for 4 hours, and 2.3 L of styrene was added for polymerization for 3 hours. The obtained reaction solution was poured into 80 L of methanol, and the precipitated solid was filtered and dried at 50 ° C. for 20 hours to obtain a triblock copolymer including polystyrene-polyisoprene-polystyrene.

Next, 10 kg of a polystyrene-polyisoprene-polystyrene triblock copolymer was dissolved in 200 L of cyclohexane, and palladium carbon as a hydrogenation catalyst (palladium supporting amount: 5 mass%) 5% by mass was added to the copolymer, and the reaction was performed at a hydrogen pressure of 2 MPa and 150 ° C. for 10 hours. After being allowed to cool and pressure, the palladium-carbon was removed by filtration, and the filtrate was concentrated and vacuum-dried to obtain a hydrogenated product of a polystyrene-polyisoprene-polystyrene triblock copolymer (hereinafter It is called thermoplastic elastomer (A-1)). The weight average molecular weight of the obtained thermoplastic elastomer (A-1) was 107,000, the styrene content was 21% by mass, the hydrogenation rate was 85%, the molecular weight distribution was 1.04, and 1,2- The total amount of bonding and 3,4-bonding was 60 mol%.

    [Polypropylene resin (B-1)]    

As the non-polar polypropylene resin (B-1), J229E (230 ° C., a load of 2.16 kg (21.18 N) with a MFR of 50 g / 10 minutes and a melting point of 144 ° C.) manufactured by Prime Polymer was used. The melting point is a value read from an endothermic peak of a differential scanning calorimetry curve when the temperature is raised at 10 ° C / min.

    [Polypropylene resin (B-2)]    

As the non-polar polypropylene resin (B-2), WFX4TA (230 ° C., a load of 2.16 kg (21.18 N) with a MFR of 7 g / 10 minutes and a melting point of 124 ° C.) manufactured by Japan Polypropylene Corporation was used. The melting point is a value read from an endothermic peak of a differential scanning calorimetry curve when the temperature is raised at 10 ° C / min.

    <Manufacturing example 2> [Synthesis of polypropylene resin (B-3) containing polar group]    

42 g of polypropylene "Prime Polypro F327" (manufactured by Prime Polymer), 160 mg of maleic anhydride, and 42 mg of 2,5-dimethyl-2,5-di (tributylperoxy) hexane were used in a batch method. The mixer was melt-kneaded under conditions of 180 ° C and a screw rotation speed of 40 rpm to obtain a polar group-containing polypropylene resin (B-3). The MFR [230 ° C, load 2.16kg (21.18N)] of the obtained polar group-containing polypropylene resin (B-3) was 6 g / 10 minutes, the maleic anhydride concentration was 0.3%, and the melting point was 138 ° C. The maleic anhydride concentration is a value obtained by titrating the obtained kneaded product using a methanol solution of potassium hydroxide. The melting point is a value read from an endothermic peak of a differential scanning calorimetry curve when the temperature is raised at 10 ° C / min.

    <Manufacturing Example 3> [Synthesis of (meth) acrylic resin (C-1)]    

To a monomer mixture containing 95 parts by mass of methyl methacrylate and 5 parts by mass of methyl acrylate, 0.1 part by mass of a polymerization initiator (2,2'-azobis (2-methylpropionitrile), Hydrogen abstraction energy: 1%, 1-hour half-life temperature: 83 ° C) and 0.28 parts by mass of a chain transfer agent (n-octyl mercaptan), and dissolved to obtain a raw material liquid.

100 parts by mass of ion-exchanged water, 0.03 parts by mass of sodium sulfate, and 0.45 parts by mass of a suspension dispersant were mixed to obtain a mixed solution. In a pressure-resistant polymerization tank, 420 parts by mass of the mixed solution and 210 parts by mass of the raw material solution were added, and the temperature was set to 70 ° C. while stirring under a nitrogen atmosphere, and a polymerization reaction was started. After the start of the polymerization reaction, the temperature was raised to 90 ° C. after 3 hours had elapsed, and stirring was continued for 1 hour to obtain a solution in which a bead-like copolymer was dispersed. The obtained copolymer dispersion was washed with an appropriate amount of ion-exchanged water, and the bead-like copolymer was taken out using a barrel centrifuge, and dried in a hot-air dryer at 80 ° C. for 12 hours to obtain bead-like (meth) acrylic acid. Series resin (C-1). The weight average molecular weight of the obtained (meth) acrylic resin (C-1) was 30,000, and Tg was 128 degreeC.

    <Manufacturing Example 4> [Synthesis of acrylic block copolymer (G-1)]    

In a three-necked flask that was degassed and replaced with nitrogen, 735 g of dry toluene, 0.4 g of hexamethyltriethylenetetramine, and isobutyl bis (2,6-di-tertiary butyl) were added at room temperature. 39.4 g of a toluene solution of 20 mmol of 4-methylphenoxy) aluminum, and 1.17 mmol of secondary butyllithium were added. 35.0 g of methyl methacrylate was added thereto, and reacted at room temperature for 1 hour to form a first methacrylate polymer block (g1) (hereinafter referred to as "methyl methacrylate polymer block (g1) -1)"). When the polymer contained in the reaction solution was sampled and the weight average molecular weight (hereinafter referred to as Mw (g1-1)) was measured, it was 40,000.

Next, the reaction solution was brought to -25 ° C, and a mixed solution of 24.5 g of n-butyl acrylate and 10.5 g of benzyl acrylate was added dropwise over 0.5 hours. Immediately after the dropwise addition, the polymer contained in the reaction solution was sampled and the weight average molecular weight was measured to be 80,000. Since the weight average molecular weight of the methyl methacrylate polymer block (g1-1) is 40,000, the weight of the acrylate polymer block (g2) including a copolymer of n-butyl acrylate and benzyl acrylate is averaged. The molecular weight Mw (g2) was set to 40,000.

Next, 35.0 g of methyl methacrylate was added, and the reaction solution was returned to room temperature, followed by stirring for 8 hours to form a second methacrylate polymer block (g1) (hereinafter referred to as "methyl methacrylate" Polymer block (g1-2) "). After that, 4 g of methanol was added to the reaction solution to stop the polymerization, and then the reaction solution was poured into a large amount of methanol, and the acrylic block copolymer (G-1) as a triblock copolymer was precipitated and filtered. It was separated by drying at 1 torr (about 133 Pa) for 12 hours at a temperature of 0 ° C. The weight average molecular weight Mw (G) of the obtained acrylic block copolymer (G-1) was 120,000. Since the weight average molecular weight of the diblock copolymer is 80,000, the weight average molecular weight (referred to as Mw (g1-2)) of the methyl methacrylate polymer block (g1-2) is set to 40,000.

    <Manufacturing example 5> [base material layer]    

20 parts by mass of the acrylic block copolymer (G-1) obtained in Production Example 4 and 80 parts by mass of the (meth) acrylic resin (C-1) obtained in Production Example 2 were used in a biaxial extruder (TEM-28 manufactured by Toshiba Machinery Co., Ltd.) After melt-kneading at 230 ° C, it is extruded into strands and cut to produce pellets of a methacrylic resin composition.

    <Example 1>    

The thermoplastic elastomer (A-1), polypropylene resin (B-1), and (meth) acrylic resin (C-1) were charged into a biaxial extruder (KRUPP WERNER) at the ratio shown in Table 1. & PFLEIDERER ZSK-25), melt-kneaded at 225 ° C, 250 rpm, extruded into strands and cut to obtain pellets of a thermoplastic polymer composition.

The surface smoothness and adhesion strength (PMMA, PP) of the obtained thermoplastic polymer composition were evaluated by the methods described above. The results are shown in Table 1.

    <Examples 2 to 11, Comparative Examples 1 to 4>    

The thermoplastic elastomer (A-1), polypropylene resins (B-1) to (B-3), and (meth) acrylic resin (C-1) were mixed at the ratios shown in Table 1, and In the other systems, pellets of a thermoplastic polymer composition were obtained in the same manner as in Example 1. The surface smoothness and adhesion strength (PMMA, PP) of the obtained thermoplastic polymer composition were evaluated by the methods described above. The results are shown in Table 1.

    <Example 12>    

The pellets of the thermoplastic polymer composition obtained in Example 1 and the pellets of the methacrylic resin composition obtained in Production Example 5 were individually charged into the feed hopper of a uniaxial extruder (VGM25-28EX manufactured by General Engineering Corporation). Using a multi-branch tube mold, co-extrusion was performed at 240 ° C. and a flow rate of 5 kg / h to obtain a multilayer film having a width of 30 cm and a thickness of 350 μm. The thickness of the substrate layer (methacrylic resin composition layer) was 230 μm, and the thickness of the adhesion layer (thermoplastic polymer composition layer) was 120 μm.

Next, a molded body is produced using the obtained multilayer film. That is, a three-dimensional surface is performed using a vacuum pressure forming machine (manufactured by Busch Vacuum Co., Ltd .; NGF-0406-T) forming a chamber box (CB) by closing the chamber box (CB1) and the chamber box (CB2). Decorative molding. As the adherend, a sheet-shaped adherend (length: 150 mm × width: 25 mm × thickness: 0.3 mm) containing a polypropylene resin (manufactured by Japan Polypropylene Corporation; MA03) was used. In the chamber box (CB2) of the molding machine, the multilayer film and the adherend are placed with the adhesive layer of the multilayer film facing the adherend, and the multilayer film is held between the chamber box (CB1) and the chamber box (CB2), so that The multilayer film divides the chamber box (CB) into two halves, and closes the chamber box (CB1) and the chamber box (CB2) to form the chamber box (CB). Thereafter, the inside of the chamber box (CB) was decompressed to 0.5 kPa in 90 seconds. At this time, the multilayer film is bent due to the imbalance of the decompression degree and the weight of the multilayer film, so the pressure in the chamber box (CB1) and the chamber box (CB2) is appropriately adjusted to keep the multilayer films parallel. Using the infrared heating device at the same time as the decompression, the multilayer film was heated for 120 seconds. When the temperature of the multilayer film reached 130 ° C, the chamber box (CB1) was quickly restored to atmospheric pressure, so that the adherend was covered with the multilayer film. The multi-layer film is stretched and then formed on the three-dimensional surface decorative shaped body of the adherend. The temperature of the multilayer film was measured with a radiation thermometer. After that, the chamber box (CB) is opened, and the formed body is taken out of the chamber box (CB2). The surface properties and adhesive strength of the obtained three-dimensional surface decorative molded body were evaluated by the methods described above. The results are shown in Table 2.

    <Comparative example 5>    

Except having used the pellet of the thermoplastic polymer composition obtained in the comparative example 1 as a thermoplastic polymer composition, it carried out similarly to Example 12, and produced the three-dimensional surface decoration molded object. The surface properties and adhesive strength of the obtained molded body were evaluated by the methods described above. The results are shown in Table 2.

The adhesive strength of the adherend of the multilayer film including the layer of the thermoplastic polymer composition of the present invention becomes sufficient. Therefore, the adhesive strength (PP) and the adhesive strength (PMMA) of the thermoplastic polymer composition need to be relatively small. 15N / 25mm larger. The thermoplastic polymer composition of Example 1 had excellent surface smoothness of the film-like strands, exhibited high adhesion strength to the methacrylic resin composition and polypropylene, and had excellent bipolar adhesion. Moreover, the molded article of Example 12 using the thermoplastic polymer composition of Example 1 was excellent in surface smoothness of the thermoplastic polymer composition of Example 1, and therefore the obtained molded article was also excellent in surface smoothness. Moreover, it is also excellent in adhesive strength with respect to an adherend. From this, it is clear that the thermoplastic polymer composition of the present invention is suitable for three-dimensional surface decoration molding. On the other hand, the thermoplastic polymer composition of Comparative Example 1 which does not include a (meth) acrylic resin and contains polypropylene modified with a polar group is the same as Example 1 with respect to the methacrylic resin composition and the polymer. Acrylic shows excellent bonding strength, but the surface smoothness of the film-like strands is poor. Therefore, in Comparative Example 5 using the thermoplastic polymer composition of Comparative Example 1, although the adhesion strength to the adherend was excellent, the obtained molded body had poor surface smoothness.

Compared with Example 1, the thermoplastic polymer composition of Examples 2 and 3 in which the content of the polypropylene resin (B) and (meth) acrylic resin (C) was changed was the same as that of Example 1 The surface of the thread is poor in smoothness and exhibits high adhesion strength to the methacrylic resin composition and polypropylene. On the other hand, Comparative Examples 2 and 3 with a large amount of polypropylene resin (B-3) had poor surface smoothness of the film-like strands, and Comparative Example with a large amount of (meth) acrylic resin (C). 4. Insufficient adhesion strength to the (meth) acrylic resin composition and polypropylene.

In addition, the thermoplastic polymer compositions of Examples 4 to 7 and 11 using different types of polypropylene-based resins (B) from Examples 1 to 3, particularly the adhesion strength to the methacrylic resin composition and polypropylene Excellent. The thermoplastic polymer composition of Example 8 using two types of polypropylene resins (B) was excellent in both surface smoothness and adhesive strength. In addition, the thermoplastic polymer compositions of Examples 9 and 10 that did not contain a (meth) acrylic resin (C) had excellent adhesion strength to the (meth) acrylic resin composition and polypropylene.

Claims (10)

    A thermoplastic polymer composition comprising a thermoplastic polymer composition containing at least one polypropylene resin (B) in an amount of 1 to 50 parts by mass based on 100 parts by mass of the thermoplastic elastomer (A), wherein the thermoplastic elastomer The body (A) is a block copolymer or a hydrogenated product thereof comprising a polymer block (S) containing an aromatic vinyl compound unit and a polymer block (D) containing a conjugated diene compound unit, and is characterized in that: The surface of the film obtained by extruding the thermoplastic polymer composition at 250 ° C. and 50 mm / min with a capillary rheometer having a rectangular cross section (8 mm in length × 0.5 mm in width) was measured according to the following method. The surface roughness (Ra) is 0.15 μm or less; the method for measuring the surface roughness: a method of measuring the arithmetic average roughness (Ra) by using a stylus shape measuring device and a needle with a tip radius of 12.5 μm.         The thermoplastic polymer composition of claim 1, wherein the conjugated diene compound constituting the polymer block (D) is butadiene, isoprene, or butadiene and isoprene, and the polymer The total amount of 1,2-bonds and 3,4-bonds in the block (D) is 40 mol% or more.         The thermoplastic polymer composition according to claim 1 or 2, wherein the polypropylene resin (B) is a non-polar polypropylene resin.         The thermoplastic polymer composition according to claim 1 or 2, wherein the thermoplastic polymer composition further contains 1 to 25 parts by mass of a (meth) acrylic resin (based on 100 parts by mass of the thermoplastic elastomer (A)). C).         The thermoplastic polymer composition according to claim 4, wherein the (meth) acrylic resin (C) contains 80% by mass or more of a structural unit derived from methyl methacrylate.         A multilayer film comprising at least a substrate layer and a layer comprising a thermoplastic polymer composition as claimed in claim 1 or 2.         The multilayer film of claim 6, wherein the substrate layer comprises an amorphous resin.         A decorative film comprising a multilayer film as claimed in claim 6.         A formed body comprising a multilayer film as claimed in claim 6.         A molded article comprising the decorative film according to claim 8.