WO2017217381A1

WO2017217381A1 - Thermoplastic polymer composition, multilayer film using said composition, and molded article

Info

Publication number: WO2017217381A1
Application number: PCT/JP2017/021698
Authority: WO
Inventors: 圭佑榎本; 貴理博中野; 涼太橋本; 芳朗近藤; 向尾　良樹; 佐々木　啓光
Original assignee: 株式会社クラレ
Priority date: 2016-06-13
Filing date: 2017-06-12
Publication date: 2017-12-21
Also published as: JPWO2017217381A1; TW201811898A; JP7030691B2

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 molded body using the composition

The present invention relates to a thermoplastic polymer composition excellent in adhesiveness and surface smoothness, a multilayer film using the composition, and a molded body comprising the multilayer film.

Ceramics, metals, and synthetic resins with excellent design, durability, heat resistance, and mechanical strength are widely used in various applications such as home appliances, electronic parts, machine parts, and automobile parts. These members may be used by adhering or combining different materials depending on applications, component configurations, and usage methods. For example, the exterior and wallpaper of home appliances, the interior of automobiles, etc. are decorated with patterns such as wood grain, design features such as metallic tone and piano black tone, and functionality such as scratch resistance and weather resistance For the purpose, a decorative film is used.

However, particularly when the decorative film and the adherend are different materials having different polarities, there is a problem that the decorative film does not adhere to the adherend. In such a case, it is necessary to separately apply an adhesive in order to adhere the film to the adherend. This process requires a solvent coating process, a drying process, and a curing process, and it takes a long time to impart adhesiveness, there is a concern about the deterioration of the working environment due to VOCs, and poor adhesion due to coating unevenness. To do. Therefore, there is a need for a decorative film that can adhere to different materials without the need for an adhesive.

In contrast, Patent Document 1 contains an ethylene polymer, a pressure-sensitive adhesive, a block copolymer having a vinyl aromatic compound polymer block and a conjugated diene compound polymer block, or a hydrogenated product thereof in a specific ratio. An adhesive resin composition used when laminating the same or different materials is disclosed. Patent Document 2 discloses a block copolymer composed of a vinyl aromatic compound polymer block and a conjugated diene compound polymer block or a hydrogenated product thereof, a vinyl cyanide compound monomer component, a rubber component, and an aromatic vinyl. There is disclosed a heat-fusing resin composition suitable for composite molding, comprising a copolymer comprising compound monomer components and the like and a non-aromatic rubber softener.

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 and a polar group, which are hydrogenated products thereof. There has been proposed a method for producing an adhesive body in which a film made of a thermoplastic polymer composition containing a contained polypropylene resin is bonded to an insert member, and then the resin member is insert-molded.

Patent Document 4 discloses a polyolefin polymer, a block copolymer containing an aromatic vinyl compound polymer block and a conjugated diene compound polymer block, or a thermoplastic resin composition containing a hydrogenated product thereof. The laminated body excellent in interlayer adhesiveness containing the layer (I) which becomes is disclosed.

JP-A-7-207082 JP 2001-247742 A JP 2014-168940 A International Publication No. 2007/065576 Pamphlet

The adhesive composition described in Patent Document 1 has high surface tackiness due to the tackifying substance contained therein, resulting in poor handling and low productivity when formed into a film, and adhesion performance due to bleeding out of the tackifying substance. There is a problem that it varies. The resin composition for heat fusion described in Patent Document 2 also has the same problem as described above due to the contained non-aromatic rubber softener.

Moreover, when the present inventors examined about the thermoplastic polymer composition of patent document 3, and the film which consists of this thermoplastic polymer composition, the unevenness | corrugation and roughness generate | occur | produce on the surface of the said thermoplastic polymer composition. However, it was difficult to obtain a smooth film. Moreover, when the film was subjected to three-dimensional surface decoration molding (Three dimension Overlay Method: TOM molding), the roughness of the surface of the thermoplastic polymer composition propagated to the surface of the film substrate, and the surface of the substrate was smooth. However, there was a problem that the designability deteriorated.

As described above, an object of the present invention is to provide a thermoplastic polymer composition having ambipolar adhesiveness and excellent surface smoothness, and excellent surface smoothness composed of the thermoplastic polymer composition and a substrate. A multilayer film and a decorative film, and a molded body comprising these films.

The present invention for solving the above-mentioned problems is the following [1] to [10].
[1]
Thermoplastic elastomer (A) 100 which 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 a hydrogenated product thereof A thermoplastic polymer composition containing 1 to 50 parts by mass of at least one polypropylene-based resin (B) with respect to parts by mass, wherein the thermoplastic polymer composition is subjected to conditions of 250 ° C. and 50 mm / min. The film surface roughness (Ra) measured by the following method on a film surface having a rectangular cross section (length 8 mm × width 0.5 mm) obtained by extrusion with a capillary rheometer is 0.15 μm or less. A thermoplastic polymer composition characterized by the above.
Surface roughness measuring method: a method of measuring arithmetic average roughness (Ra) with a stylus shape measuring instrument using a needle having a tip radius of 12.5 μm. ;

[2]
The conjugated diene compound constituting the polymer block (D) is butadiene, isoprene, or butadiene and isoprene, and the total of 1,2-bond amount and 3,4-bond amount in the polymer block (D) The thermoplastic polymer composition according to the above [1], wherein is 40 mol% or more;

[3] The thermoplastic polymer composition according to the above [1] or [2], wherein the polypropylene resin (B) is a nonpolar polypropylene resin;

[4] The thermoplastic polymer composition further comprises 1 to 25 parts by mass of (meth) acrylic resin (C) with respect to 100 parts by mass of the thermoplastic elastomer (A). The thermoplastic polymer composition according to any one of the above [1] to [3];

[5] The thermoplastic polymer composition according to the above [4], 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 a layer comprising the thermoplastic polymer composition according to any one of [1] to [5] above;
[7] The multilayer film according to [6], wherein the base material layer is made of an amorphous resin;
[8] A decorative film comprising the multilayer film of [6] or [7] above;
[9] A molded article comprising the multilayer film according to any one of [6] or [7] or the decorative film according to [8].

Since the thermoplastic polymer composition of the present invention has bipolar adhesiveness and excellent surface smoothness, it can be suitably used as an adhesive layer for multilayer films. In addition, since the multilayer film of the present invention has an adhesive layer made of the thermoplastic polymer composition, it has excellent adhesion to an adherend, and the thermoplastic polymer composition has excellent surface smoothness. Similarly, the base material of the multilayer film is excellent in surface smoothness, and can be suitably used particularly for three-dimensional surface decoration molding. Since the molded body of the present invention comprises the multilayer film, it has excellent design properties.

[Thermoplastic polymer composition]
The thermoplastic polymer composition of the present invention comprises 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 hydrogen. It contains at least one polypropylene resin (B) 1 to 50 parts by mass and (meth) acrylic resin (C) 1 to 20 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A) as an additive. Is. Hereinafter, the 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 containing a polymer block (S) containing an aromatic vinyl compound unit and a polymer block (D) containing a conjugated diene compound unit. A copolymer or a hydrogenated product thereof. The thermoplastic elastomer (A) imparts flexibility, good mechanical properties and molding processability to the thermoplastic polymer composition, and serves as a matrix in the composition.

-Polymer block containing aromatic vinyl compound unit (S)-
Examples of the aromatic vinyl compound constituting the polymer block (S) include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene. 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene, 2-vinylnaphthalene and the like. 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 (S) containing an aromatic vinyl compound unit is preferably 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 further preferably 95 of an aromatic vinyl compound unit. It is a polymer block containing at least mass%. The polymer block (S) may have only an aromatic vinyl compound unit, but unless the effect of the present invention is impaired, the aromatic vinyl compound unit and other copolymerizable monomer units. You may have. Examples of other copolymerizable monomers include 1-butene, pentene, hexene, butadiene, isoprene, methyl vinyl ether, and the like. 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 at most 5% by mass, more preferably at most 5% by mass.

-Polymer block (D) containing conjugated diene compound units-
Examples of the conjugated diene compound constituting the polymer block (D) include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. Of these, butadiene and isoprene are preferable.
The polymer block (D) containing a conjugated diene compound unit may consist of a structural unit derived from only one of these conjugated diene compounds, or may consist 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 (D) containing the conjugated diene compound unit is preferably 80% by mass or more of the conjugated diene compound unit, more preferably 90% by mass or more, more preferably 95% by mass or more of the conjugated diene compound unit. It is a polymer block to contain. The polymer block (D) may have only a conjugated diene compound unit, but has another copolymerizable monomer unit 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 bond form of the conjugated diene constituting the polymer block (D) containing the conjugated diene compound unit 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. Among them, when the polymer block (D) containing the conjugated diene compound unit is composed of butadiene, isoprene, or is composed of both butadiene and isoprene, 1,2-in the polymer block (D), The total of the bonding amount and the 3,4-bonding amount is preferably 40 mol% or more from the viewpoint of developing particularly high adhesive performance. The total amount of 1,2-bond and 3,4-bond in the polymer block (D) is preferably 40 to 90 mol%, and more preferably 50 to 80 mol%.
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 to 5.5 derived from 1,4-bond units. It can be calculated from the ratio with the integrated value of the peak existing at 45 ppm.

The bond form of the polymer block (S) containing an aromatic vinyl compound unit and the polymer block (D) containing a conjugated diene compound unit in the thermoplastic elastomer (A) is not particularly limited, and is linear or branched. , Radial, or a combined form in which two or more of these are combined, but a linear combined form is preferred.
As an example of a linear bond 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, a A diblock copolymer represented by -b, a triblock copolymer represented by aba or b-a-b, a tetrablock copolymer represented by abbab, a pentablock copolymer represented by abababa or bababa, an (а-b) nX copolymer (X represents a coupling residue, and n Represents an integer of 2 or more), and mixtures thereof. Among these, a triblock copolymer is preferable, and a triblock copolymer represented by aba is more preferable.

In the thermoplastic elastomer (A), from the viewpoint of improving heat resistance and weather resistance, a part or all of the polymer block (D) containing the conjugated diene compound is hydrogenated (hereinafter abbreviated as “hydrogenated”). It is preferable that The hydrogenation rate of the polymer block containing the conjugated diene compound 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 content of the polymer block (S) containing the aromatic vinyl compound unit in the thermoplastic elastomer (A) is preferably 5 with respect to the entire thermoplastic elastomer (A) from the viewpoint of flexibility and mechanical properties. It is ˜75% by mass, more preferably 5 to 60% by mass, and further preferably 10 to 40% by mass.
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 viewpoints of mechanical properties and moldability. 000 to 200,000, more preferably 70,000 to 200,000, particularly preferably 70,000 to 190,000, and most preferably 80,000 to 180,000. In addition, in this specification, a weight average molecular weight is a weight average molecular weight of polystyrene conversion calculated | required by the 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.

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.

In the anionic polymerization, by adding an organic Lewis base, the amount of 1,2-bond and 3,4-bond of the polymer block (D) in the thermoplastic elastomer (A) can be increased, The amount of 1,2-bond and 3,4-bond can be easily controlled by the amount of organic Lewis base added.
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 groups such as pyridine. Aromatic compounds; Amides such as dimethylacetamide; Ethers such as dimethyl ether, diethyl ether, tetrahydrofuran (THF) and dioxane; Glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; Sulphoxides such as dimethyl sulfoxide; Ketones such as acetone and methyl ethyl ketone Can be mentioned.

Furthermore, the hydrogenated 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, as a thermoplastic elastomer (A), a commercial item can also be used.

[Polypropylene resin (B)]
When the polypropylene resin (B) is contained in the thermoplastic polymer composition, the molding processability is improved, and a film made of the thermoplastic polymer composition is easily produced. In addition, the mechanical properties of the film are improved and handling becomes easy. Furthermore, the adhesiveness of the thermoplastic polymer composition mainly to the nonpolar resin is improved, and it becomes possible to adhere well to the substrate or the adherend.

Examples of the polypropylene 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, the α-olefin in the copolymer may be ethylene, butene-1, isobutene, pentene-1, hexene-1, 4-methylpentene. -1, octene-1 and the like. 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 thereof include a pentene random copolymer, a propylene-hexene random copolymer, a propylene-octene random copolymer, a propylene-ethylene-pentene random copolymer, and a propylene-ethylene-hexene random copolymer. The proportion of the structural units derived from the α-olefin other than propylene in the total structural units of the polypropylene resin (B) is preferably 0 to 45 mol% from the viewpoint of affinity with the thermoplastic elastomer (A). More preferably, it is 0 to 35 mol%, and further preferably 0 to 25 mol%. In other words, the content of the structural unit derived from propylene in the polypropylene resin (B) is preferably 55 mol% or more, more preferably 65 mol% or more, and further preferably 75 mol% or more.
A polypropylene resin (B) may be used individually by 1 type, and may be used in combination of 2 or more type.

Among these, the polypropylene resin (B) is preferably a nonpolar polypropylene resin having no polar functional group. Use of a nonpolar polypropylene resin is excellent in that the melt fracture phenomenon hardly occurs during extrusion molding, and the surface of the multilayer film becomes smooth.

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, random or block propylene and an α-olefin can be synthesized. The copolymer can be synthesized. Moreover, you may use a commercial item for a polypropylene resin (B).

230 degreeC of a polypropylene-type resin (B), a load 2.16kg (21.18)
The melt flow rate (MFR) under the condition of N) is preferably 0.1 to 300 g / 10 minutes, more preferably 0.1 to 100 g / 10 minutes, and further preferably 0.1 to 70 g / 10 minutes. . If the MFR of the polypropylene resin (B) under the above conditions is 0.1 g / 10 min or more, good moldability can be obtained. On the other hand, if the MFR is 300 g / 10 min or less, the mechanical characteristics are easily developed. 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 more preferably 8 to 50 g / 10 minutes. More preferably. From the viewpoint of improving the adhesiveness 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 more preferably 3 to 30 g / 10 minutes. Is more preferable. In addition, it is preferable to use two or more types of polypropylene resins (B) having different MFRs because both surface smoothness and adhesiveness may be improved.
The melting point of the polypropylene 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 adhesion by heat treatment.

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

[(Meth) acrylic resin (C)]
The (meth) acrylic resin (C) is for improving the adhesiveness of the thermoplastic polymer composition, and the (meth) acrylic resin (C) is contained in the thermoplastic polymer composition. The adhesion of the thermoplastic polymer composition mainly to the polar resin is improved, and in the multilayer film using the thermoplastic polymer composition, the thermoplastic polymer composition and the substrate layer described below are strengthened. It becomes possible to adhere.

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

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 t-acrylate. Butyl, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate; phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 2-acrylate Hydroxyethyl, 2-ethoxyethyl acrylate, glycidyl acrylate, allyl acrylate; acrylate esters such as cyclohexyl acrylate, norbornenyl acrylate, isobornyl acrylate; ethyl methacrylate, n-promethacrylate , Isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, t-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; unsaturated compounds such as acrylic acid, methacrylic acid, maleic anhydride, maleic acid and itaconic acid Carboxylic acid; Olefin such as ethylene, propylene, 1-butene, isobutylene and 1-octene; Conjugated dienes such as butadiene, isoprene and myrcene; Aromatics such as styrene, α-methylstyrene, p-methylstyrene and m-methylstyrene Examples of the vinyl compound include acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl pyridine, vinyl ketone, vinyl chloride, vinylidene chloride, and vinylidene fluoride.

The stereoregularity of the (meth) acrylic resin (C) 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 (meth) acrylic resin (C) is preferably 20,000 to 180,000, more preferably 30,000 to 150,000, and particularly preferably 30,000 to 130,000. is there. When the weight average molecular weight is small, the mechanical strength of the resulting thermoplastic polymer composition tends to decrease. When the weight average molecular weight is large, the fluidity of the thermoplastic polymer composition tends to be lowered and the moldability tends to be lowered.
The molecular weight and molecular weight distribution of the (meth) acrylic resin (C) can be controlled by adjusting the types and amounts of the polymerization initiator and the chain transfer agent.

The production method of the (meth) acrylic resin (C) is not particularly limited, and a monomer (mixture) containing 80% by mass or more of methyl methacrylate is polymerized or copolymerized with a monomer other than methyl methacrylate. It is obtained by doing. Moreover, you may use a commercial item as (meth) acrylic-type resin (C). Examples of such commercially available methacrylic resins include “Parapet H1000B” (MFR: 22 g / 10 min (230 ° C., 37.3 N)) and “Parapet GF” (MFR: 15 g / 10 min (230 ° C., 37.3 N). )), “Parapet EH” (MFR: 1.3 g / 10 min (230 ° C., 37.3 N)), “Parapet HRL” (MFR: 2.0 g / 10 min (230 ° C., 37.3 N)), “ Parapet HRS ”(MFR: 2.4 g / 10 min (230 ° C., 37.3 N)) and“ Parapet G ”(MFR: 8.0 g / 10 min (230 ° C., 37.3 N))) Kuraray Co., Ltd.].

The thermoplastic polymer composition preferably contains 1 to 25 parts by weight of (meth) acrylic resin (C), preferably 3 to 20 parts by weight, per 100 parts by weight of the thermoplastic elastomer (A). Is more preferable. When the (meth) acrylic resin (C) is less than 1 part by mass, it may be difficult to adhere to the adherend by heat treatment. On the other hand, when the amount of the (meth) acrylic resin (C) is more than 25 parts by mass, the thermoplastic polymer composition becomes hard, and it may be difficult to express flexibility and mechanical properties.
From the above viewpoint, the content of the (meth) acrylic resin (C) is preferably 1 to 18 parts by mass, more preferably 3 to 15 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A).

[Other ingredients]
The thermoplastic polymer composition of the present invention can be used as long as it does not significantly impair the effects of the present invention, as required by other thermoplastic heavy polymers such as olefin polymers, styrene polymers, polyphenylene ether resins, and polyethylene glycol. It may contain a coalescence. 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 of the present invention is an antioxidant, a lubricant, a light stabilizer, a processing aid, a colorant such as a pigment or a dye, a flame retardant, and the like, as long as the effects of the invention are not impaired. It may contain 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, a fragrance and the like.
Examples of the antioxidant include hindered phenol-based, phosphorus-based, lactone-based, and hydroxyl-based antioxidants. Among these, hindered phenol antioxidants are preferable.

[Method for producing thermoplastic polymer composition]
The method for preparing the thermoplastic polymer composition of the present invention is not particularly limited, but in order to improve the dispersibility of each component constituting the thermoplastic polymer composition, for example, a method of melt kneading and mixing is recommended. The In this case, the thermoplastic elastomer (A), the polypropylene resin (B) and the (meth) acrylic resin (C) and other components added as necessary may be mixed and melt-kneaded at the same time. Good. The mixing operation can be performed using a known mixing or kneading apparatus such as a kneader ruder, an extruder, a mixing roll, or a Banbury mixer. In particular, it is preferable to use a twin screw extruder from the viewpoint of improving the kneadability and compatibility between the thermoplastic elastomer (A) and the (meth) acrylic resin (C). The temperature during mixing and kneading should be appropriately adjusted according to the melting temperature of the thermoplastic elastomer (A), polypropylene resin (B), (meth) acrylic resin (C), etc. Mixing at a temperature in the range of 110 ° C to 300 ° C is recommended.

In this way, the thermoplastic polymer composition of the present invention can be obtained in any form such as pellets or powder. The obtained thermoplastic polymer composition can be formed into various shapes such as a film, a sheet, a plate, a pipe, a tube, a rod-like body, and a granular body. These production methods are not particularly limited, and can be formed by various conventional molding methods such as injection molding, blow molding, press molding, extrusion molding, and calendar molding.

[Multilayer film]
The multilayer film of this invention has at least the layer which consists of a base material layer and the thermoplastic polymer composition of this invention. Hereinafter, the base material layer used in the multilayer film of the present invention will be described.

[Base material layer]
Although it does not specifically limit as a base material layer, What consists of an amorphous resin is preferable. In the present specification, “amorphous resin” means a resin having no 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, polyester resin, and (meth) acrylic resin. Of these, (meth) acrylic resins, ABS resins, polycarbonate resins and polyester resins are preferred from the viewpoints of weather resistance, surface gloss and scratch resistance, and (meth) acrylic resins from the viewpoint of transparency and surface gloss. Is preferred. 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.
As the monomer other than the methyl methacrylate, those similar to those mentioned as the monomer other than methyl methacrylate in the (meth) acrylic resin (C) can be used.

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).
The (meth) acrylic resin (C) used for the thermoplastic polymer composition and the methacrylic resin (F) used for the base layer may be the same, comonomer ratio, molecular weight, MFR. Etc. may be different.

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. It can be polymerized in combination with at least species. Among these, from the viewpoint 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 block copolymer (G) has a plurality of methacrylate polymer blocks (g1), the composition ratio and molecular weight of the structural units constituting the respective methacrylate polymer blocks (g1) are the same. It may be different or different.

The proportion of the methacrylic ester polymer block (g1) in the block copolymer (G) is preferably in the range of 10% by mass to 70% by mass from the viewpoint of transparency, flexibility, molding processability and surface smoothness. More preferably, it is 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 above ratio is calculated based on the total mass of all methacrylate 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 acrylate 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 alone 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 viewpoint 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.

(Aromatic ester of (meth) acrylic acid means an aromatic ester of acrylic acid or an aromatic ester of methacrylic acid, 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. . Among these, from the viewpoint of transparency, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, and benzyl acrylate are preferable.

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 derived from the acrylic acid alkyl ester from the viewpoint of transparency. It preferably contains 50 to 90% by mass of structural units and 50 to 10% by mass of structural units derived from (meth) acrylic acid aromatic ester, and 60 to 80% by mass of structural units derived from alkyl acrylate and (meth) More preferably, it contains 40 to 20% by mass of a structural unit derived from an acrylic acid aromatic ester.

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

The proportion of the acrylate polymer block (g2) in the block copolymer (G) is preferably in the range of 30 to 90% by mass from the viewpoint of transparency, flexibility, molding processability, and surface smoothness. More preferably, it is in the range of 40 to 75% by 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 block copolymer (G) is not particularly limited. For example, at one end of the methacrylic ester polymer block (g1) A structure in which one end of the acrylate polymer block (g2) is connected ((g1)-(g2) structure); an acrylate polymer block (g2) at both ends of the methacrylate polymer block (g1). Structure in which one end is connected ((g2)-(g1)-(g2) structure); Structure in which one end of methacrylic ester polymer block (g1) is connected to both ends of acrylate polymer block (g2) ((G1)-(g2)-(g1) structure), etc., methacrylic acid ester polymer block (g1) and acrylate weight Body 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 end.

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. If the weight average molecular weight of the block copolymer (G) is less than 60,000, sufficient melt tension cannot be maintained in melt extrusion molding, making it difficult to obtain a good film, and mechanical properties such as breaking strength of the obtained film. When the viscosity is larger than 400,000, the viscosity of the molten resin increases, and the surface of the film obtained by melt extrusion molding has fine grain-like irregularities and irregularities due to unmelted material (high molecular weight). This tends to be difficult to obtain a good film.

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. By having the molecular weight distribution within such a range, the content of unmelted material that causes the generation of scum in the base material layer can be reduced. 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 obtained base material layer becomes high. 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) includes 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 cross-linked elastic body obtained by copolymerizing a monomer mixture having an acrylic acid alkyl ester and a cross-linkable monomer. As such an acrylic acid alkyl ester, an acrylic acid 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 ratio of the alkyl acrylate 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 to 90% by 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 from the viewpoint of improving the impact resistance, heat resistance and surface hardness of the base material layer. The range of 10% by mass is more preferable.

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, from the viewpoint of improving the impact resistance of the base material layer. is there.

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 from the viewpoint of heat resistance of the base material layer. The hard thermoplastic resin contains other monofunctional monomer in an amount of 20% by mass or less, preferably 10% by mass or less. Other monofunctional monomers include, for example, 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 determined from the viewpoint of impact resistance, heat resistance, surface hardness, handleability, ease of melt kneading and the like of the obtained base material layer. The content of the inner layer is selected from the range of 40 to 80% by mass, and the content of the outer layer is selected from the range of 20 to 60% by mass, based on the mass (for example, the total amount of the inner layer and outer layer in the case of two layers) It is preferable that

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

When a base material layer is comprised from the (meth) acrylic-type resin composition containing a methacryl resin (F) and an elastic body (R), content of each component is a methacryl resin (F) and an elastic body (R). It is preferable that the content of the methacrylic resin (F) is 10 to 99 parts by mass and the content of the elastic body (R) is 90 to 1 part by mass with respect to 100 parts by mass in total. 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 with respect to a total of 100 parts by mass 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, the content of the methacrylic resin (F) is 70 to 90 parts by mass, and the content of the elastic body (R) is 30 to 10 parts by mass.

The amorphous resin constituting the base material layer preferably has an elastic modulus of 2 to 600 MPa at an arbitrary temperature in the range of 110 to 160 ° C. If the elastic modulus is less than 2 MPa, the elongation during vacuum forming tends to be non-uniform, and if the elastic modulus is greater than 600 MPa, cracking or fracture tends to occur during vacuum forming. The elastic modulus is a value obtained by rounding off the first decimal place when expressed in [MPa] units.

The amorphous resin constituting the base layer is various additives such as antioxidants, heat stabilizers, lubricants, processing aids, antistatic agents, heat deterioration inhibitors, ultraviolet absorbers, light stabilizers, polymers. A processing aid colorant, an impact resistance aid and the like may be contained.

The amorphous resin can be used by mixing with other polymers. Examples of such other polymers include polyolefin resins such as polyethylene, polypropylene (PP), polybutene-1, poly-4-methylpentene-1, and polynorbornene; ethylene ionomers; polystyrene, styrene-maleic anhydride copolymers , High impact polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-ethylene-styrene copolymer, acrylonitrile-acrylic ester-styrene copolymer resin, acrylonitrile-chlorinated polyethylene -Styrene resins such as styrene copolymers, methyl methacrylate-butadiene-styrene copolymers; methyl methacrylate-styrene copolymers; polyethylene terephthalate (PET), polybutyl Polyester resins such as terephthalate; polyamides such as nylon 6, nylon 66, polyamide elastomer; polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, polyvinylidene fluoride, polyurethane, modified polyphenylene Ether, polyphenylene sulfide, silicone modified resin; acrylic rubber, silicone rubber; styrene heat such as styrene-ethylene / propylene-styrene copolymer, styrene-ethylene / butadiene-styrene copolymer, styrene-isoprene-styrene copolymer Plastic elastomers; olefin rubbers such as isoprene rubber, ethylene propylene rubber, and ethylene propylene diene rubber.

The method for preparing the amorphous resin constituting the base material layer is not particularly limited, but a method of melt kneading and mixing is preferable in order to improve the dispersibility of each component constituting the amorphous resin. 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. 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 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.

[Other layers]
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 base layer and / or the layer made of the thermoplastic polymer composition. 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 base material layer used in the multilayer film of the present invention may be colored. As a coloring method, the amorphous resin itself contains a pigment or a dye, and the resin itself before being formed into a film is colored; the amorphous resin film is colored by immersing it in a liquid in which the dye is dispersed. Examples thereof include, but are not limited to, staining methods.

In the multilayer film of the present invention, a metal or metal oxide may be deposited on the base material layer. 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 base material layer include vacuum film formation methods such as deposition and sputtering, electrolytic plating, and electroless plating.

The surface of the multilayer film of the present invention on the base material layer side is preferably HB or higher in pencil hardness, more preferably H or higher. 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, and still more preferably in the range of 100 to 400 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. If the thickness of the multilayer film is 1,000 μm or less, the three-dimensional coating moldability tends to be improved.

In the multilayer film of the present invention, the thickness of the base material layer 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. The thickness of the base material layer is more preferably 40 to 300 μm, particularly preferably 50 to 250 μm.

The ratio (y / x) of the thickness (y) of the base material layer to the thickness (x) of the layer made of the thermoplastic polymer composition is preferably in the range of 0.2 to 5, more preferably 0. The range is from 5 to 4, more preferably from 0.8 to 3. If the value of the ratio (y / x) is less than 0.2, the surface hardness tends to be low, and if it is larger than 5, the multilayer film tends to break, and if it is larger than 4, the stretchability is lowered. It becomes a trend.

[Method for producing multilayer film]
The multilayer film of the present invention has a base material layer and a layer made of the thermoplastic polymer composition of the present invention, and a layer made of the thermoplastic polymer composition is laminated on one surface of the base material layer. Can be obtained.

The method for producing the substrate layer is not particularly limited. For example, when an amorphous resin is used, it can be performed using a known method such as a T-die method, an inflation method, a melt casting method, or a calendar method. From the viewpoint that a film with good surface smoothness and low haze can be obtained, the molten kneaded material of the amorphous resin constituting the base material layer is extruded in a molten state from a T-die, and both surfaces thereof are mirror roll surface or mirror belt surface A method including a step of forming the film by contacting the substrate is preferable. The roll or belt used at this time is preferably made of metal. When forming the film by bringing both sides of the extruded melt-kneaded material into contact with a mirror surface, it is preferable to press and sandwich both surfaces of the film with a mirror roll or a mirror belt. The pinching pressure by the mirror roll or the mirror belt is preferably high, and the linear pressure is preferably 10 N / mm or more, and more preferably 30 N / mm or more.

The base material layer may be a film that has been subjected to stretching treatment. The stretching process increases the mechanical strength and makes it 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 tuber stretching method, and a rolling method. *

Lamination of the layer comprising the thermoplastic polymer composition to the base material layer obtained as described above is a method of applying a solution of the thermoplastic polymer composition to the base material layer, and the thermoplastic layer to the base material layer. Examples include a method of laminating a film made of a polymer composition. A film made of the thermoplastic polymer composition can be obtained in the same manner as in the method for producing a base material layer exemplified above.
Moreover, the amorphous resin and the thermoplastic polymer composition constituting the base material layer can be produced by co-extrusion using a T-die method. In particular, a co-extrusion method using a multi-manifold die is preferable.

[Molded body]
The molded body of the present invention comprises the multilayer film of the present invention or a decorative film made of the multilayer film. More preferably, the multilayer film of the present invention is provided on the surface of an adherend such as a thermoplastic resin, a thermosetting resin, a wooden 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) resin and the like. Examples of the thermosetting resin include an epoxy resin, a phenol resin, and a melamine resin. 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.

The manufacturing method of the molded body is not particularly limited. For example, the multilayer film of the present invention is subjected to vacuum forming, air forming, and compression forming under heating on the surface of an adherend such as a thermoplastic resin, a thermosetting resin, a wooden base material, and a non-wood fiber base material. The molded product of the present invention can be obtained. In the molded body, the base material layer in the multilayer film of the present invention is provided on the outermost layer of the molded body, thereby being excellent in surface smoothness, surface hardness, surface gloss and the like. Among them, vacuum molding and / or pressure molding is preferable because it can be shaped and adhered to various adherends with high accuracy, and three-dimensional surface decoration molding (Three た dimension Overlay Method: TOM molding) is a combination of vacuum molding and pressure molding. More preferred. 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 suitably 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.

Another preferable method among the manufacturing methods of a molded object is the method generally called the injection molding simultaneous bonding method.
In this simultaneous injection molding method, the multilayer film of the present invention is inserted between male and female molds for injection molding, and a molten thermoplastic resin is injected into the mold from the surface on the adhesive layer side of the film. At the same time as forming the body, the multilayer film is bonded to the surface of the molded body.

The multilayer film inserted into the mold may be a flat film as it is, or may be formed into a concavo-convex shape by preforming by vacuum forming, pressure forming or the like.
The preforming of the multilayer film may be performed by a separate molding machine, or may be preformed in a mold of an injection molding machine used for the injection molding simultaneous bonding method.

A multilayer film having a layer comprising the thermoplastic polymer composition of the present invention and a molded body comprising the multilayer film have good stretchability and moldability of the multilayer film, excellent ambipolar adhesion and surface smoothness. It can be applied to articles that require design properties. For example, billboard parts such as advertising towers, stand signboards, sleeve signboards, billboard signs, rooftop signboards; display parts such as showcases, partition plates, store displays; fluorescent lamp covers, mood lighting covers, lamp shades, light ceilings, light walls , Lighting parts such as chandeliers; interior parts such as furniture, pendants, mirrors; doors, domes, safety window glass, partitions, staircases, balconies, building parts such as roofs for 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. Since the multilayer film of the present invention has the above characteristics, it can be suitably used particularly as a decorative film.

Hereinafter, the present invention will be described in more detail with reference to examples and the like, but the present invention is not limited to these examples. Preparation of test samples in Examples and Comparative Examples and measurement or evaluation of physical properties were performed as follows, and the results were summarized in a table.

[Surface smoothness of thermoplastic polymer composition]
A capillary-shaped rheometer (CAPIROGRAPH 1C, manufactured by TOYOSEIKI) is fitted with a slit-shaped capillary having a rectangular cross section (length 8 mm x width 0.5 mm). The obtained thermoplastic polymer composition was extruded to obtain a film-like strand. The arithmetic average roughness (Ra) of the strand surface obtained above was measured with a stylus shape measuring instrument (Dektak-150 manufactured by Bruker) using a needle having a tip radius of 12.5 μm. When Ra is smaller than 0.15 μm, the surface smoothness is excellent.

[Adhesive strength of thermoplastic polymer composition (PMMA)]
The pellets of the thermoplastic polymer compositions obtained in Examples and Comparative Examples and the methacrylic resin composition obtained in Production Example 5 were respectively subjected to conditions of 200 ° C. and a load of 50 kgf / cm ² using a compression molding machine. A sheet made of a thermoplastic polymer composition and a sheet made of a methacrylic resin composition were obtained by compression molding for 2 minutes. Sheet made of 150 × 150 mm thermoplastic polymer composition (length 150 mm × width 150 mm × thickness 0.5 mm), polyimide film (Kapton film manufactured by Toray DuPont, length 75 mm × width 150 mm × thickness 0.05 mm) Sheets made of a methacrylic resin composition (length 150 mm × width 150 mm × thickness 0.5 mm) were stacked in this order, and placed in the center of a metal spacer having an inner dimension of 150 mm × 150 mm and a thickness of 0.8 mm. By sandwiching this overlapped sheet and a metal spacer with a polytetrafluoroethylene sheet, further sandwiching with a metal plate from the outside, using a compression molding machine, compression molding is performed at 130 ° C. and a load of 50 kgf / cm ² for 2 minutes. A multilayer film of a thermoplastic polymer composition and a methacrylic resin composition was obtained.
The multilayer film is cut to a width of 25 mm to form a test piece for measuring adhesive strength, and the peel strength between the thermoplastic polymer composition and the methacrylic resin composition is measured according to JIS K 6854-2 (Shimadzu Corporation). Using AGS-X), the measurement was carried out under the conditions of a peel angle of 90 °, a tensile speed of 300 mm / min, and an environmental temperature of 23 ° C., and was defined as the adhesive strength (PMMA) of the thermoplastic polymer composition.

[Adhesive strength (PP) of thermoplastic polymer composition]
In the adhesive strength (PMMA) of the thermoplastic polymer composition described above, the sheet made of the methacrylic resin composition was changed to a polypropylene sheet (MA3 manufactured by Nippon Polypro Co., Ltd., 150 mm long × 150 mm wide × 0.4 mm thick). Except for the above, a multilayer film was prepared in the same manner, and the peel strength between the thermoplastic polymer composition and polypropylene was measured to obtain the adhesive strength (PP) of the thermoplastic polymer composition.

[Evaluation of surface smoothness of molded product]
The multilayer film produced in Example 12 and Comparative Example 5, which will be described later, is inserted into a vacuum / pressure forming machine (manufactured by Fuse Vacuum Co., Ltd .; NGF-0406-T), and three-dimensional surface decoration molding is performed on the sheet glass. By performing, the sample for evaluation was produced and the surface property of the molded object was evaluated. The evaluation was performed by measuring the arithmetic average roughness (Ra) with a stylus shape measuring instrument (Duktak-150 manufactured by Bruker) using a needle having a tip radius of 12.5 μm. When Ra is smaller than 0.15 μm, the surface smoothness is excellent.

[Evaluation of adhesive strength in compacts]
A sheet-like adherend (length 150 mm × width 25 mm × thickness 0.3 mm) made of polypropylene resin (manufactured by Nippon Polypro Co., Ltd .; MA03) is placed on the flat stage of the above-described vacuum / pressure forming machine, and the polypropylene Three-dimensional surface decorative molding was carried out in the same manner as in Example 10 with a polyimide film (Kapton film manufactured by Toray DuPont, length 30 mm x width 30 mm x thickness 0.125 mm) placed on the edge of the sheet. A test piece was prepared by excising a portion where the multilayer film and the polypropylene sheet did not overlap. The multi-layer film side of the obtained test piece was fixed to a SUS plate with a strong adhesive tape, and using a peel tester (AGS-X, manufactured by Shimadzu Corporation), a peeling angle of 90 °, a tensile speed of 300 mm / min, and an environmental temperature of 23 The peel strength between the layer made of the thermoplastic polymer composition and the polypropylene sheet was measured according to JIS K 6854-2 under the condition of ° C.

In addition, each component used in the following Examples and Comparative Examples is as follows.

<Production Example 1> [Synthesis of thermoplastic elastomer (A-1)]
A pressure-resistant container purged with nitrogen and dried was charged with 64 L of cyclohexane as a solvent, 0.20 L of sec-butyllithium (10 mass% cyclohexane solution) as an initiator, and 0.46 L of tetrahydrofuran as an organic Lewis base. After the temperature was raised to 50 ° C., 2.3 L of styrene was added for polymerization for 3 hours, then 23 L of isoprene was added for polymerization for 4 hours, and 2.3 L of styrene was further added for polymerization for 3 hours. The obtained reaction liquid was poured into 80 L of methanol, and the precipitated solid was separated by filtration and dried at 50 ° C. for 20 hours to obtain a triblock copolymer composed of polystyrene-polyisoprene-polystyrene.
Subsequently, 10 kg of a triblock copolymer composed of polystyrene-polyisoprene-polystyrene was dissolved in 200 L of cyclohexane, and palladium carbon (palladium supported amount: 5% by mass) as a hydrogenation catalyst was 5% by mass with respect to the copolymer. The reaction was carried out for 10 hours under the conditions of hydrogen pressure of 2 MPa and 150 ° C. After allowing to cool and release, palladium carbon is removed by filtration, the filtrate is concentrated, and further dried under vacuum to give a hydrogenated product of a triblock copolymer consisting of polystyrene-polyisoprene-polystyrene (hereinafter, thermoplastic elastomer). (Referred to as (A-1)). The resulting thermoplastic elastomer (A-1) has a weight average molecular weight of 107,000, a styrene content of 21% by mass, a hydrogenation rate of 85%, a molecular weight distribution of 1.04, and a polyisoprene block containing 1,1. The total amount of 2-bond and 3,4-bond was 60 mol%.

[Polypropylene resin (B-1)]
As the nonpolar polypropylene resin (B-1), J229E (230 ° C., MFR at a load of 2.16 kg (21.18 N) of 50 g / 10 min, melting point 144 ° C.) manufactured by Prime Polymer Co., Ltd. was used. Moreover, melting | fusing point is the value read from the endothermic peak of the differential scanning calorimetry curve at the time of heating up at 10 degree-C / min.

[Polypropylene resin (B-2)]
As the nonpolar polypropylene resin (B-2), WFX4TA (230 ° C., MFR at a load of 2.16 kg (21.18 N), 7 g / 10 min, melting point 124 ° C.) manufactured by Nippon Polypro Co., Ltd. was used. Moreover, melting | fusing point is the value read from the endothermic peak of the differential scanning calorimetry curve at the time of heating up at 10 degree-C / min.

<Production Example 2> [Synthesis of polar group-containing polypropylene resin (B-3)]
42 g of polypropylene “Prime Polypro F327” (manufactured by Prime Polymer Co., Ltd.), 160 mg of maleic anhydride and 42 mg of 2,5-dimethyl-2,5-di (tertiarybutylperoxy) hexane, 180 ° C. and screw using a batch mixer It was melt-kneaded under the condition of a rotation speed of 40 rpm to obtain a polar group-containing polypropylene resin (B-3). MFR [230 ° C., load 2.16 kg (21.18N)] of the obtained polar group-containing polypropylene resin (B-3) was 6 g / 10 min, the maleic anhydride concentration was 0.3%, and the melting point was It was 138 ° C. The maleic anhydride concentration is a value obtained by titrating the obtained kneaded product with a methanol solution of potassium hydroxide. Moreover, melting | fusing point is the value read from the endothermic peak of the differential scanning calorimetry curve at the time of heating up at 10 degree-C / min.

<Production Example 3> [Synthesis of (Meth) acrylic resin (C-1)]
Polymerization initiator (2,2′-azobis (2-methylpropionitrile), hydrogen abstraction capacity: 1%, half-life for 1 hour, in a monomer mixture consisting of 95 parts by weight of methyl methacrylate and 5 parts by weight of methyl acrylate (Temperature: 83 ° C.) 0.1 part by mass and chain transfer agent (n-octyl mercaptan) 0.28 part by mass were added and dissolved to obtain a raw material solution.
100 parts by mass of ion-exchanged water, 0.03 parts by mass of sodium sulfate and 0.45 parts by mass of the suspension / dispersant were mixed to obtain a mixed solution. In a pressure-resistant polymerization tank, 420 parts by mass of the mixed liquid and 210 parts by mass of the raw material liquid were charged, and the polymerization reaction was started at a temperature of 70 ° C. while stirring in a nitrogen atmosphere. After 3 hours from the start of the polymerization reaction, the temperature was raised to 90 ° C. and stirring was continued for 1 hour to obtain a liquid in which the bead copolymer was dispersed. The obtained copolymer dispersion is washed with an appropriate amount of ion-exchanged water, the bead-like copolymer is taken out with a bucket-type centrifuge, and dried with a hot air dryer at 80 ° C. for 12 hours. ) Acrylic resin (C-1) was obtained. The obtained (meth) acrylic resin (C-1) had a weight average molecular weight of 30,000 and Tg of 128 ° C.

<Production Example 4> [Synthesis of acrylic block copolymer (G-1)]
In a three-necked flask purged with nitrogen and purged with nitrogen, 735 g of dry toluene, 0.4 g of hexamethyltriethylenetetramine, and isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum at room temperature 39.4 g of a toluene solution containing 20 mmol was added, and 1.17 mmol of sec-butyllithium was further added. 35.0 g of methyl methacrylate was added to this and reacted at room temperature for 1 hour, whereby the first methacrylate polymer block (g1) (hereinafter referred to as “methyl methacrylate polymer block (g1-1)”). ) Was formed. The polymer contained in the reaction solution was sampled and the weight average molecular weight (hereinafter referred to as Mw (g1-1)) was measured, and 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 dropping, the polymer contained in the reaction solution was sampled and the weight average molecular weight was measured, and it was 80,000. Since the weight average molecular weight of the methyl methacrylate polymer block (g1-1) was 40,000, the weight of the acrylate polymer block (g2) comprising a copolymer of n-butyl acrylate and benzyl acrylate. The average molecular weight (Mw (g2)) was determined to be 40,000.

Subsequently, 35.0 g of methyl methacrylate was added, the reaction solution was returned to room temperature, and stirred for 8 hours, whereby a second methacrylate polymer block (g1) (hereinafter, “methyl methacrylate polymer block (g1 -2) ”). Thereafter, 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 to precipitate an acrylic block copolymer (G-1) as a triblock copolymer, followed by filtration. Then, it was isolated by drying at 80 ° C. and 1 torr (about 133 Pa) for 12 hours. The resulting acrylic block copolymer (G-1) had a weight average molecular weight Mw (G) of 120,000. Since the weight average molecular weight of the diblock copolymer was 80,000, the weight average molecular weight (referred to as Mw (g1-2)) of the methyl methacrylate polymer block (g1-2) was 40,000. Were determined.

<Production Example 5> [Base material layer]
Biaxial extrusion of 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 A methacrylic resin composition pellet was produced by melt kneading at 230 ° C. using a machine (TEM-28 manufactured by Toshiba Machine Co., Ltd.), extruding into a strand, and cutting.

<Example 1>
Thermoplastic elastomer (A-1), polypropylene resin (B-1), and (meth) acrylic resin (C-1) are added to a twin screw extruder (ZSK-25 manufactured by KRUPP WERNER & PFLIDEERER) at the ratio shown in Table 1. The mixture was melted and kneaded at 225 ° C. and 250 rpm, then extruded into strands and cut to obtain thermoplastic polymer composition pellets.
The surface smoothness and adhesive 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 and Comparative Examples 1 to 4>
Examples except that thermoplastic elastomer (A-1), polypropylene resins (B-1) to (B-3) and (meth) acrylic resin (C-1) were mixed in the proportions shown in Table 1. 1 was used to obtain pellets of a thermoplastic polymer composition. The surface smoothness and adhesive 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 respectively placed in the hopper of a single screw extruder (VGM25-28EX manufactured by GM ENGINEERING). Then, it was coextruded at 240 ° C. and a flow rate of 5 kg / h using a multi-manifold die to obtain a multilayer film having a width of 30 cm and a thickness of 350 μm. The thickness of the base material layer (methacrylic resin composition layer) was 230 μm, and the thickness of the adhesive layer (thermoplastic polymer composition layer) was 120 μm.
Then, the molded object was manufactured using the obtained multilayer film. That is, three-dimensional surface decoration using a vacuum / pressure forming machine (manufactured by Fuse Vacuum Co., Ltd .; NGF-0406-T) that forms the chamber box (CB) by closing the chamber box (CB1) and the chamber box (CB2). Molding was performed. As the adherend, a sheet-like adherend (length 150 mm × width 25 mm × thickness 0.3 mm) made of polypropylene resin (manufactured by Nippon Polypro Co., Ltd .; MA03) was used. The multilayer box and the adherend are placed in the chamber box (CB2) of the molding machine so that the adhesive layer of the multilayer film faces the adherend, and the chamber box (CB) is divided into two parts by the multilayer film. The multilayer film was sandwiched between CB1) and a chamber box (CB2), and the chamber box (CB1) and the chamber box (CB2) were closed to form a chamber box (CB). Thereafter, the pressure in the chamber box (CB) was reduced to 0.5 kPa in 90 seconds. At this time, since the multilayer film was bent due to non-equilibrium of the degree of vacuum and the self-weight of the multilayer film, the pressures in the chamber box (CB1) and the chamber box (CB2) were appropriately adjusted to keep the multilayer film parallel. In parallel with decompression, the multilayer film is heated by an infrared heating device for 120 seconds, and when the temperature of the multilayer film reaches 130 ° C., the chamber box (CB1) is quickly returned to atmospheric pressure so that the adherend is coated with the multilayer film. A three-dimensional surface-decorated molded body in which the multilayer film was unstretched and adhered to the adherend was molded. The temperature of the multilayer film was measured with a radiation thermometer. Thereafter, the chamber box (CB) was opened, and the molded body was taken out from the chamber box (CB2). The surface property and adhesive strength of the obtained three-dimensional surface decorative molded body were evaluated by the above-described methods. The results are shown in Table 2.

<Comparative Example 5>
A three-dimensional surface-decorated molded article was produced in the same manner as in Example 12, except that the thermoplastic polymer composition pellets obtained in Comparative Example 1 were used as the thermoplastic polymer composition. The surface property and adhesive strength of the obtained molded body were evaluated by the above-described methods. The results are shown in Table 2.

In order for the multilayer film having a layer made of the thermoplastic polymer composition of the present invention to have a sufficient adhesive strength to the adherend, the adhesive strength (PP) and adhesive strength (PP) of the thermoplastic polymer composition ( PMMA) needs to be larger than 15 N / 25 mm. The thermoplastic polymer composition of Example 1 was excellent in the surface smoothness of the film-like strand, showed high adhesive strength to the methacrylic resin composition and polypropylene, and was excellent in bipolar adhesion. Moreover, since the thermoplastic polymer composition of Example 1 is excellent in surface smoothness, the molded product of Example 12 using the thermoplastic polymer composition of Example 1 has surface smoothness of the obtained molded product. The property was also excellent. Moreover, the adhesive strength to the adherend was also excellent. Thereby, it became 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 that does not contain a (meth) acrylic resin and contains a polar group-modified polypropylene was superior to the methacrylic resin composition and polypropylene as in Example 1. Although the adhesive strength was shown, the surface smoothness of the film-like strand was poor. Therefore, in Comparative Example 5 using the thermoplastic polymer composition of Comparative Example 1, although the adhesive strength to the adherend was excellent, the surface smoothness of the obtained molded product was inferior.

The thermoplastic polymer compositions of Examples 2 and 3 in which the contents of the polypropylene resin (B) and the (meth) acrylic resin (C) are changed as compared with Example 1 are film-like as in Example 1. It was excellent in the surface smoothness of the strand and showed high adhesive strength to the methacrylic resin composition and polypropylene. On the other hand, Comparative Examples 2 and 3 with a high content of polypropylene resin (B-3) have poor surface smoothness of the film-like strands, and Comparative Example 4 with a large amount of (meth) acrylic resin (C). The adhesive strength to (meth) acrylic resin composition and polypropylene was insufficient.
In addition, the thermoplastic polymer compositions of Examples 4 to 7 and 11 using different types of polypropylene resins (B) from Examples 1 to 3 were particularly excellent in adhesive strength to methacrylic resin compositions and polypropylene. . 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 the (meth) acrylic resin (C) had excellent adhesion strength to the (meth) acrylic resin composition and polypropylene.

Claims

Thermoplastic elastomer (A) 100 which 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 a hydrogenated product thereof A thermoplastic polymer composition containing 1 to 50 parts by mass of at least one polypropylene-based resin (B) with respect to parts by mass, wherein the thermoplastic polymer composition is subjected to conditions of 250 ° C. and 50 mm / min. The film surface roughness (Ra) measured by the following method on a film surface having a rectangular cross section (length 8 mm × width 0.5 mm) obtained by extrusion with a capillary rheometer is 0.15 μm or less. A thermoplastic polymer composition characterized by the above.
Surface roughness measuring method: a method of measuring arithmetic average roughness (Ra) with a stylus shape measuring instrument using a needle having a tip radius of 12.5 μm.
The conjugated diene compound constituting the polymer block (D) is butadiene, isoprene, or butadiene and isoprene, and the total of 1,2-bond amount and 3,4-bond amount in the polymer block (D) The thermoplastic polymer composition according to claim 1, wherein is 40 mol% or more.
The thermoplastic polymer composition according to claim 1 or 2, wherein the polypropylene resin (B) is a nonpolar polypropylene resin.
The thermoplastic polymer composition further comprises 1 to 25 parts by mass of (meth) acrylic resin (C) with respect to 100 parts by mass of the thermoplastic elastomer (A). The thermoplastic polymer composition according to any one of 1 to 3.
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 having at least a base layer and a layer comprising the thermoplastic polymer composition according to any one of claims 1 to 5.
The multilayer film according to claim 6, wherein the base material layer is made of an amorphous resin.
A decorative film comprising the multilayer film according to claim 6 or 7.
A molded body comprising the multilayer film according to claim 6 or 7, or the decorative film according to claim 8.