JPWO2019198827A1 - Multilayer film and molded article containing it - Google Patents

Abstract

An object of the present invention is a multilayer film and a decorative film having excellent chipping resistance, which are composed of an adhesive layer made of a specific thermoplastic polymer composition and a base material layer, and a molded product comprising these films. Is to provide. According to the present invention, the above object is a multilayer film including a base material layer and an adhesive layer, wherein the adhesive layer is a polymer block (S) containing an aromatic vinyl compound unit. Polypropylene resin (B) 0 with respect to 100 parts by mass of a thermoplastic elastomer (A) which is at least one block copolymer containing a polymer block (D) containing a conjugated diene compound unit or a hydrogenated product thereof. It is characterized by being composed of a thermoplastic polymer composition containing ~ 30 parts by mass, and having a loss tangent (tan δ) at 11 Hz in the range of −50 to −20 ° C. of 3 × 10-2 or more. This is achieved by providing a multilayer film.

Description

The present invention relates to a decorative multilayer film and a decorative film used for a vehicle exterior and the like, and a molded product provided with them.

Conventionally, a vehicle exterior paint applied by a spray method has been used to decorate the vehicle exterior. These paints are used for the purpose of protecting the vehicle substrate and giving the vehicle aesthetics. In particular, in the vehicle exterior member, the coating film may be partially lost due to the splashing of pebbles and snowmelt salt and applying an impact to the coating film. Such damage is called chipping, and the protection against chipping is called chipping resistance. When pebbles collide with a coating film having insufficient chipping resistance, the base material is exposed due to damage to the coating film and the aesthetic appearance is impaired, which is a problem. Among vehicle exterior members, bumpers are particularly prone to chipping, so the coating film used is required to have high chipping resistance.

By the way, polypropylene resin is widely used as a material for vehicle bumpers. The polypropylene-based resin has various advantages such as strong impact resistance, low specific gravity, and low cost. On the other hand, the non-polar polypropylene-based resin easily repels the paint, and it is difficult to maintain high adhesion with the coating film resin. When the adhesion between the coating film and the resin forming the bumper is low, the chipping resistance tends to deteriorate.
On the other hand, Patent Document 1 discloses a primer composition having a predetermined composition, which can achieve both chipping resistance of a coating film and adhesion to polypropylene which is an automobile bumper material. Further, in Patent Document 2, by forming a predetermined multi-layer coating film, it is possible to obtain a multi-layer coating film having excellent curability, chipping resistance and finished appearance at a low temperature in a short time. The method is disclosed.

In recent years, a method of using a decorative film has been proposed instead of decorating the exterior of the vehicle and protecting the base material with paint. The method using the decorative film eliminates the need for a long drying furnace, which is indispensable in the painting process, and thus can save a large amount of energy. As a decoration method using such a film, in Patent Document 3, protection for an automobile exterior including a film-like base material made of an olefin-based elastomer and an adhesive layer applied to the adherend side of the base material. The film is disclosed.

Further, Patent Document 4 discloses a functional film composed of an adhesive material, a predetermined urethane resin, and a paint applied to the surface of the urethane resin layer. However, a step of applying the adhesive material is required, which is complicated.

Japanese Unexamined Patent Publication No. 2012-67197 International Application Publication No. 2014/045657 Japanese Unexamined Patent Publication No. 2004-115657 Japanese Unexamined Patent Publication No. 2004-148508

However, the method using the coating composition described in Patent Document 1 and the method for forming a multi-layer coating film described in Patent Document 2 require a large amount of energy for drying and curing the coating film, which causes a large environmental load, which is a problem. ..

Further, in the protective film for automobile exterior described in Patent Document 3, the presence of a primer layer is required in order to improve the adhesiveness between the base material layer and the pressure-sensitive adhesive layer, which increases the number of steps and is complicated. Is. Further, since the elastic modulus of the base material layer is relatively low and the base material thickness needs to be 250 to 1000 μm, there is a problem that the weight is large. The method described in Patent Document 4 requires a step of applying an adhesive material and is complicated.

From the above, an object of the present invention is to provide a multilayer film and a decorative film having excellent chipping resistance, and a molded product provided with these films.

The present invention that achieves the above object is a multilayer film including a base material layer and an adhesive layer, wherein the adhesive layer is formed.
At least one block copolymer containing a polymer block (S) containing a structural unit derived from an aromatic vinyl compound and a polymer block (D) containing a structural unit derived from a conjugated diene compound, or a hydrogenated product thereof. It is composed of a thermoplastic polymer composition containing 1 to 50 parts by mass of a polypropylene resin (B) with respect to 100 parts by mass of the thermoplastic elastomer (A) composed of the same, at 11 Hz in the range of -50 to -20 ° C. It is a multilayer film characterized by comprising a composition having a loss tangent (tan δ) of 3 × 10 ^{−2 or more.}
Further, the structural unit derived from the conjugated diene compound constituting the polymer block (D) is preferably a structural unit derived from at least one selected from butadiene and isoprene.
Further, the base material layer is preferably made of an amorphous resin, and the amorphous resin is more preferably any one of a (meth) acrylic resin, an ABS resin, a polycarbonate resin and a polyester resin.
Another invention is a decorative film made of the above-mentioned multilayer film, and is a molded product further comprising the above-mentioned multilayer film or the decorative film.

The multilayer film containing the adhesive layer and the base material layer of the present invention has excellent chipping resistance. Therefore, it can be suitably used as a multilayer film particularly used for the exterior of a vehicle.

[Thermoplastic polymer composition]
The multilayer film of the present invention comprises a base material layer and an adhesive layer composed of the following thermoplastic polymer composition.
The thermoplastic polymer composition is at least one block containing a polymer block (S) containing a structural unit derived from an aromatic vinyl compound and a polymer block (D) containing a structural unit derived from a conjugated diene compound. It is composed of a thermoplastic polymer composition containing 1 to 50 parts by mass of a polypropylene-based resin (B) (at least one kind) with respect to 100 parts by mass of a thermoplastic elastomer (A) composed of a copolymer or a hydrogenated product thereof. , -50 to -20 ° C., characterized in that the composition comprises a loss tangent (tan δ) at 11 Hz of 3 × 10 ^{-2 or more.} Hereinafter, the above components (A) and (B) will be described in order.

[Thermoplastic Elastomer (A)]
The thermoplastic elastomer (A) contained in the thermoplastic polymer composition is a polymer block (S) containing a structural unit derived from an aromatic vinyl compound and a polymer block (D) containing a structural unit derived from a conjugated diene compound. ) And a block copolymer or a hydrogenated product thereof. The thermoplastic elastomer (A) imparts flexibility, good mechanical properties, molding processability, and the like to the thermoplastic polymer composition, and plays a role of a matrix in the composition.

-Polymer block (S) containing an aromatic vinyl compound unit-
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 containing structural units. The polymer block made of an aromatic vinyl compound 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 kinds. Of these, those composed of structural units derived from styrene, α-methylstyrene, and 4-methylstyrene are preferable.

The polymer block (S) containing a structural unit derived from an aromatic vinyl compound preferably has a structural unit derived from an aromatic vinyl compound of 80% by mass or more, more preferably 90% by mass or more of the structural unit, and even more preferably. It is a polymer block containing 95% by mass or more of the structural unit. The polymer block (S) may have only structural units derived from an aromatic vinyl compound, but as long as the effects of the present invention are not impaired, the polymer block (S) may have other copolymerizable monomers together with the structural units. It may have a structural unit derived from. Other copolymerizable monomers include, for example, 1-butene, pentene, hexene, butadiene, isoprene, methyl vinyl ether and the like. If it has structural units derived from other copolymerizable monomers, its proportions are relative to the total amount of structural units derived from aromatic vinyl compounds and structural units derived from other copolymerizable monomers. It is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less.

-Polymer block (D) containing a conjugated diene compound unit-
Examples of the structural unit derived from the conjugated diene compound constituting the polymer block (D) include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. Those derived from such as. Of these, those derived from butadiene or isoprene are preferable.
The polymer block (D) containing a structural unit derived from a conjugated diene compound may consist of a structural unit derived from only one of these conjugated diene compounds, or may be composed of a structural unit derived from two or more of these conjugated diene compounds. It may be. 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 a structural unit derived from the conjugated diene compound preferably has a structural unit derived from the conjugated diene compound in an amount of 80% by mass or more, more preferably 90% by mass or more, and further preferably the structure. It is a polymer block containing 95% by mass or more of units. The polymer block (D) may have only structural units derived from the conjugated diene compound, but is derived from other copolymerizable monomers together with the structural units as long as it does not interfere with the present invention. It may have a structural unit to be used. Examples of other copolymerizable monomers include styrene, α-methylstyrene, 4-methylstyrene and the like. If it has structural units derived from other copolymerizable monomers, its proportions are relative to the total amount of structural units derived from the conjugated diene compound and structural units derived from other copolymerizable monomers. It is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less.

The bonding form of the conjugated diene constituting the polymer block (D) containing the structural unit derived from the conjugated diene compound is not particularly limited. For example, in the case of butadiene, 1,2-bonds and 1,4-bonds can be taken, and in the case of isoprene, 1,2-bonds, 3,4-bonds and 1,4-bonds can be taken. Among them, when the polymer block (D) containing a structural unit derived from a conjugated diene compound is composed of a structural unit derived from butadiene, is composed of a structural unit derived from isoprene, or is derived from both butadiene and isoprene. When composed of structural units, the total amount of 1,2-bonding amount and 3,4-bonding amount in the polymer block (D) is preferably 40 mol% or more from the viewpoint of exhibiting high adhesive performance. .. The total ratio of the 1,2-bonding amount and the 3,4-bonding amount to the total bonding amount in the polymer block (D) is preferably 40 to 90 mol%, preferably 50 to 80 mol%. Is more preferable.
The total amount of 1,2-bonding amount and 3,4-bonding amount ^{can be calculated by 1 1} H-NMR measurement. Specifically, the integral value of the peaks present at 4.2-5.0 ppm derived from the 1,2-bonded and 3,4-bonded structural units and 5 derived from the 1,4-bonded structural units. It can be calculated from the ratio of the integrated values of the peaks existing at .0 to 5.45 ppm.

The bonding form of the polymer block (S) containing a structural unit derived from an aromatic vinyl compound in the thermoplastic elastomer (A) and the polymer block (D) containing a conjugated diene compound is not particularly limited, and is linear. It may be in the form of a form, a branch form, a radial form, or a bond form in which two or more of these are combined, but a linear bond form is preferable.
As an example of the linear bonding form, the polymer block (S) containing a structural unit derived from an aromatic vinyl compound is a, and the polymer block (D) containing a structural unit derived from a conjugated diene compound is used. Is represented by b, a diblock copolymer represented by ab, a triblock copolymer represented by a-b-a or b-а-b, and a-b-ab. Tetrablock copolymer, pentablock copolymer represented by a-b-a-ba or b-a-b-ab, (а-b) nX type copolymer (X is coupling) Represents a residue, where n represents an integer greater than or equal to 2), and mixtures thereof. Among these, a triblock copolymer is preferable, and a triblock copolymer represented by a-ba-a is more preferable.

The content of the polymer block (S) containing the structural unit derived from the aromatic vinyl compound in the thermoplastic elastomer (A) is different from that of the entire thermoplastic elastomer (A) from the viewpoint of its flexibility and mechanical properties. It is preferably 5 to 75% by mass, more preferably 5 to 60% by mass, and even more 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, and more preferably 60 from the viewpoint of its mechanical properties and molding processability. It is 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. Is. Here, the weight average molecular weight is a polystyrene-equivalent weight average molecular weight obtained by gel permeation chromatography (GPC) measurement.
The thermoplastic elastomer (A) may be used alone or in combination of two or more.

The method for producing the thermoplastic elastomer (A) is not particularly limited, but the thermoplastic elastomer (A) can be produced, for example, 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 the alkyllithium compound as an initiator; (ii) using the alkyllithium compound as an initiator. A method of sequentially polymerizing the aromatic vinyl compound and the conjugated diene compound, and then adding a coupling agent for coupling; (iii) using the dilithium compound as an initiator, the conjugated diene compound, and then the aromatic vinyl. Examples thereof include a method of sequentially polymerizing compounds.

By adding an organic Lewis base during the anionic polymerization, the 1,2-bonding amount and 3,4-bonding amount of the polymer block (D) in the thermoplastic elastomer (A) can be increased. The 1,2-bonding amount and the 3,4-binding amount can be easily controlled by the addition amount of the organic Lewis base.
Examples of the organic Lewis base include esters such as ethyl acetate; amines such as triethylamine, N, N, N', N'-tetramethylethylenediamine (TMEDA) and N-methylmorpholin; and nitrogen-containing heterocyclic formulas such as pyridine. Aromatic compounds; amides such as dimethylacetamide; ethers such as dimethyl ether, diethyl ether, tetrahydrofuran (THF), dioxane; glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; sulfoxides such as dimethyl sulfoxide; ketones such as acetone and methyl ethyl ketone. Can be mentioned.

From the viewpoint of improving heat resistance and weather resistance of the thermoplastic elastomer (A), a part or all of the polymer block (D) containing the conjugated diene compound is hydrogenated (hereinafter, abbreviated as "hydrogenation"). There is). At that time, the hydrogenation ratio of the polymer block containing the conjugated diene compound is preferably 80% or more, more preferably 90% or more. Here, in the present specification, the hydrogenation rate is a value obtained by measuring the iodine value of the block copolymer before and after the hydrogenation reaction.

The hydrogenated thermoplastic elastomer (A) can be produced by subjecting the unhydrogenated thermoplastic elastomer (A) to a hydrogenation reaction. The hydrogenation reaction involves dissolving the unhydrogenated thermoplastic elastomer (A) obtained above in a solvent inert to the reaction and hydrogenation catalyst, or the unhydrogenated thermoplastic elastomer (A). Can be used as it is without being isolated from the above reaction solution, and reacted with hydrogen in the presence of a hydrogenation catalyst.
Further, as the thermoplastic elastomer (A), a commercially available product can also be used.

[Polypropylene resin (B)]
By including the polypropylene-based resin (B) in the thermoplastic polymer composition, the molding processability is improved, and it becomes easy to produce a film made of the thermoplastic polymer composition. In addition, the mechanical properties of the film are improved, making it easier to handle. Further, it imparts adhesiveness to the adherend, and can be satisfactorily adhered to the adherend by heat treatment.

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, the α-olefin in the copolymer includes ethylene, butene-1, isobutene, pentane-1, hexene-1, 4-methylpentene. -1, Octen-1 and the like can be mentioned. Examples of the polypropylene-based resin (B) include homopolypropylene, propylene-ethylene random copolymer, propylene-ethylene block copolymer, propylene-butene random copolymer, propylene-ethylene-butene random copolymer, and propylene-. Examples thereof include a penten random copolymer, a propylene-hexene random copolymer, a propylene-octen random copolymer, a propylene-ethylene-penten random copolymer, a propylene-ethylene-hexene random copolymer and the like. 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 compatibility with the thermoplastic elastomer (A). It is more preferably in the range of 0 to 35 mol%, and further preferably in the range of 0 to 25 mol%. In other words, the content of the structural unit derived from propylene in the polypropylene-based resin (B) is preferably 55 mol% or more, more preferably 65 mol% or more, still more preferably 75 mol% or more.
As the polypropylene-based resin (B), one type may be used alone, or two or more types may be used in combination.

The polypropylene-based resin (B) may contain a polar group. By containing a polar group, a molded product obtained by adhering the thermoplastic polymer composition of the present invention to ceramics, metal or synthetic resin can be adhered well to ceramics, metal or synthetic resin. High adhesiveness is maintained even when exposed to a temperature environment of 60 ° C. or higher.
Examples of the polar group include (meth) acryloyloxy group; hydroxyl group; amide group; halogen atom such as chlorine atom; carboxyl group; acid anhydride group and the like. The method for producing the polar group-containing polypropylene-based resin is not particularly limited, but the propylene and the polar group-containing copolymerizable monomer can be obtained by random copolymerization, block copolymerization or graft copolymerization by a known method. .. Among these, random copolymerization and graft copolymerization are preferable, and graft copolymers are more preferable.
In addition to this, it can also be obtained by subjecting a polypropylene-based resin to a reaction such as oxidation or chlorination by a known method.

The polar group-containing polypropylene-based resin may be obtained by copolymerizing an α-olefin other than propylene with a polar group-containing copolymerizable monomer together with propylene. Examples of the α-olefin include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, cyclohexene and the like. The α-olefin can be copolymerized with a polar group-containing copolymerizable monomer by a known method, and examples thereof include random copolymerization, block copolymerization, and graft copolymerization. The ratio of the structural units derived from α-olefins other than propylene to the total structural units of the polar group-containing polypropylene-based resin is preferably 0 to 45 mol%, more preferably 0 to 35 mol%, still more preferably. It is 0 to 25 mol%.

Examples of the polar group-containing copolymerizable monomer include vinyl acetate, vinyl chloride, ethylene oxide, propylene oxide, acrylamide, unsaturated carboxylic acid or an ester or anhydride thereof. Among these, unsaturated carboxylic acids or esters or anhydrides thereof are preferable. Examples of unsaturated carboxylic acids or esters or anhydrides thereof include (meth) acrylic acid, (meth) acrylic acid ester, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, hymic acid, and hymic anhydride. Examples include acid. Among these, maleic acid and maleic anhydride are more preferable. These polar group-containing copolymerizable monomers may be used alone or in combination of two or more.

As the polar group-containing polypropylene-based resin, polypropylene containing a carboxyl group as a polar group, that is, a carboxylic acid-modified polypropylene-based resin is preferable from the viewpoint of adhesiveness, and maleic acid-modified polypropylene-based resin and maleic anhydride-modified polypropylene-based resin are preferable. More preferable.

The polypropylene-based resin (B) can be synthesized by a conventionally known method, for example, using a Ziegler-Natta type catalyst or a metallocene type catalyst with a propylene homopolymer, random or block propylene and α-olefin. Copolymer can be synthesized. Further, as the polypropylene-based resin (B), a commercially available product may be used.

The melt flow rate (MFR) of the polypropylene resin (B) under the conditions of 230 ° C. and a load of 2.16 kgf (21.18 N) is preferably 0.1 to 300 g / 10 minutes, more preferably 0.1 to 100 g. / 10 minutes, more preferably 0.1 to 70 g / 10 minutes, more preferably 0.1 to 50 g / 10 minutes, more preferably 1 to 30 g / 10 minutes, still more preferably 1 to 20 g / 10 minutes, particularly preferably. Is 1 to 15 g / 10 minutes. When the MFR of the polypropylene resin (B) under the above conditions is 0.1 g / 10 minutes or more, good molding processability can be obtained. On the other hand, when the MFR is 300 g / 10 minutes or less, mechanical properties are likely to be exhibited.
From the viewpoint of heat resistance, the melting point of the polypropylene-based resin (B) is preferably 100 ° C. or higher, more preferably 100 to 170 ° C., and even more preferably 110 to 145 ° C.

[Polar Olefin Resin (C)]
The polar olefin resin (C) can be contained in the thermoplastic polymer composition to enhance the adhesiveness to the highly polar adherend, and can be satisfactorily adhered to the adherend by heat treatment. ..

Examples of the polar olefin resin (C) include those in which an olefin resin, which is a copolymer of ethylene or propylene and an α-olefin having 2 to 8 carbon atoms, contains a polar group. Examples of the α-olefin in the copolymer include ethylene, propylene, butene-1, isobutene, pentene-1, hexene-1, 4-methylpentene-1, octene-1 and the like. For example, propylene-ethylene random copolymer, propylene-ethylene block copolymer, propylene-butene random copolymer, propylene-ethylene-butene random copolymer, propylene-pentene random copolymer, propylene-hexene random copolymer. Examples thereof include coalescence, propylene-octene random copolymer, propylene-ethylene-pentene random copolymer, propylene-ethylene-hexene random copolymer and the like.

Examples of the polar group include (meth) acryloyloxy group; hydroxyl group; amide group; halogen atom such as chlorine atom; carboxyl group; acid anhydride group and the like. The method for producing the polar group-containing polypropylene-based resin is not particularly limited, but the propylene and the polar group-containing copolymerizable monomer can be obtained by random copolymerization, block copolymerization or graft copolymerization by a known method. .. Among these, random copolymerization and graft copolymerization are preferable, and graft copolymers are more preferable.
In addition to this, it can also be obtained by subjecting an olefin resin to a reaction such as oxidation or chlorination by a known method.

Examples of the polar group-containing copolymerizable monomer include vinyl acetate, vinyl chloride, ethylene oxide, propylene oxide, acrylamide, unsaturated carboxylic acid or an ester or anhydride thereof. Among these, unsaturated carboxylic acids or esters or anhydrides thereof are preferable. Examples of unsaturated carboxylic acids or esters or anhydrides thereof include (meth) acrylic acid, (meth) acrylic acid ester, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, hymic acid, and hymic anhydride. Examples include acid. Among these, maleic acid and maleic anhydride are more preferable. These polar group-containing copolymerizable monomers may be used alone or in combination of two or more.
As the polar olefin resin (C), an olefin resin containing a carboxyl group as a polar group, that is, a carboxylic acid-modified olefin resin is preferable from the viewpoint of adhesiveness, and a maleic acid-modified olefin resin and a maleic anhydride-modified olefin are preferable. The based resin is more preferable.

The thermoplastic polymer composition of the present invention contains 0 to 30 parts by mass of the polypropylene resin (B) with respect to 100 parts by mass of the thermoplastic elastomer (A). When the polypropylene-based resin (B) is more than 30 parts by mass, the thermoplastic polymer composition becomes hard, and flexibility and mechanical properties may be difficult to be exhibited. The content of the polypropylene-based resin (B) is preferably 5 parts by mass or more, and more preferably 25 parts by mass or less with respect to 100 parts by mass of the thermoplastic elastomer (A).
From these, the content of the polypropylene-based resin (B) is preferably 0 to 30 parts by mass, and more preferably 5 to 25 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A).
When the polar olefin resin (C) is further contained, 1 to 50 parts by mass of the polar olefin resin (C) is contained with respect to 100 parts by mass of the thermoplastic elastomer (A). If the amount of the polar olefin resin (C) is less than 1 part by mass, the adhesiveness to the substrate may be insufficient. On the other hand, when the amount of the olefin resin is more than 50 parts by mass, the phase separation with the thermoplastic elastomer (A) becomes easy, and there may be a problem in thermal stability.

[Other ingredients]
The thermoplastic polymer composition of the present invention contains, if necessary, a tackifier resin, a softener, an antioxidant, a lubricant, a light stabilizer, a processing aid, a pigment, a dye, etc., as long as the effects of the invention are not impaired. It may contain a colorant, a flame retardant, an antistatic agent, a matting agent, a silicone oil, an antiblocking agent, an ultraviolet absorber, a mold release agent, a foaming agent, an antibacterial agent, an antifungal agent, a fragrance and the like.

Examples of the tackifying resin include aliphatic unsaturated hydrocarbon resins, aliphatic saturated hydrocarbon resins, alicyclic unsaturated hydrocarbon resins, alicyclic saturated hydrocarbon resins, aromatic hydrocarbon resins, and hydrogenated aromatic carbides. Hydrogen resin, rosin ester resin, hydrogenated rosin ester resin, terpene phenol resin, hydrogenated terpene phenol resin, terpene resin, hydrogenated terpene resin, aromatic hydrocarbon modified terpene resin, kumaron inden resin, phenol resin, xylene resin, etc. Can be mentioned.

Examples of the softener include softeners generally used for rubber and plastics. For example, paraffin-based, naphthen-based, and aromatic process oils; phthalic acid derivatives such as dioctyl phthalate and dibutyl phthalate; white oil, mineral oil, ethylene and α-olefin oligomers, paraffin wax, liquid paraffin, polybutene, and low molecular weight polybutadiene. , Low molecular weight polyisoprene and the like.

Examples of the antioxidant include hindered phenol-based, phosphorus-based, lactone-based, and hydroxyl-based antioxidants. Of these, hindered phenolic antioxidants are preferred.

The thermoplastic polymer composition of the present invention contains, if necessary, antioxidants, lubricants, light stabilizers, processing aids, colorants such as pigments and pigments, flame retardants, as long as the effects of the invention are not impaired. It may contain an antistatic agent, a matting agent, a silicone oil, an antiblocking agent, an ultraviolet absorber, a mold release agent, a foaming agent, an antibacterial agent, an antifungal agent, a fragrance and the like.

[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 enhance the dispersibility of each component constituting the thermoplastic polymer composition, for example, a method of melt-kneading and mixing is recommended. To. In this case, the thermoplastic elastomer (A) and the polypropylene-based resin (B) may be simultaneously mixed and melt-kneaded with other components added as needed. The mixing operation can be performed using a known mixing or kneading device such as a needle rudder, extruder, mixing roll, Banbury mixer or the like. 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 polypropylene-based resin (B). The temperature at the time of mixing and kneading should be appropriately adjusted according to the melting temperature of the thermoplastic elastomer (A), polypropylene resin (B), etc. used, and is usually at a temperature within the range of 110 ° C to 300 ° C. It is good to mix.

In this way, the thermoplastic polymer composition of the present invention can be obtained in any form such as pellets and powders. The obtained thermoplastic polymer composition can be molded into various shapes such as films, sheets, plates, pipes, tubes, rods, and granules. These manufacturing methods are not particularly limited, and can be molded by various conventional molding methods such as injection molding, blow molding, press molding, extrusion molding, and calendar molding.

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

[Base layer]
The base material layer is not particularly limited, but one made of an amorphous resin is preferable. As used herein, the term "amorphous resin" means a resin that does not have a clear melting point in the 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 (meth) acrylic resin and the like. Among them, (meth) acrylic resin, ABS resin, polycarbonate resin and polyester resin are preferable from the viewpoint of weather resistance, surface gloss resistance and scratch resistance, and (meth) acrylic resin from the viewpoint of transparency or surface glossiness. Is preferable.

As the (meth) acrylic resin used for the base material layer, a (meth) acrylic polymer can be used. Further, as the (meth) acrylic resin used for the base material layer, a (meth) acrylic resin composition containing a (meth) acrylic polymer and an elastic body (R) and the like is more preferable.

The (meth) acrylic polymer has 80% by mass or more, preferably 90% by mass or more, of structural units derived from methyl methacrylate. In other words, the structural unit derived from the monomer other than methyl methacrylate of the (meth) acrylic polymer is 20% by mass or less, preferably 10% by mass or less. The (meth) acrylic polymer may be a polymer having only methyl methacrylate as a monomer.

Examples of the monomer other than methyl methacrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, s-butyl acrylate, and t-butyl acrylate. Butyl, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethyl hexyl acrylate, pentadecyl acrylate, dodecyl acrylate; phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 2-ethyl acrylate Hydroxyethyl, 2-ethoxyethyl acrylate, glycidyl acrylate, allyl acrylate; acrylic acid esters such as cyclohexyl acrylate, norbornenyl acrylate, isobonyl acrylate; ethyl methacrylate, n-propyl methacrylate, 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, norbornenyl methacrylate, methacrylic Methacrylic acid esters other than methyl methacrylate such as isobonyl acid; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, maleic acid, itaconic acid; ethylene, propylene, 1-butene, isobutylene, 1-octene, etc. Olefins; conjugated diene such as butadiene, isoprene, milsen; aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene; acrylamide, methacrylicamide, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl Examples thereof include pyridine, vinyl ketone, vinyl chloride, vinylidene chloride and vinylidene fluoride.

The stereoregularity of the (meth) acrylic polymer 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 polymer is preferably 30,000 or more and 180,000 or less, more preferably 40,000 or more and 150,000 or less, and particularly preferably 50,000 or more and 130,000 or less. If the weight average molecular weight is small, the mechanical strength of the obtained equipment layer tends to decrease. When the weight average molecular weight is large, the fluidity of the thermoplastic polymer composition tends to decrease, and the molding processability tends to decrease. The weight average molecular weight is a standard polystyrene-equivalent value measured by GPC (gel permeation chromatography).
Further, the molecular weight and the molecular weight distribution of the (meth) acrylic polymer can be controlled by adjusting the types and amounts of the polymerization initiator and the chain transfer agent.

The method for producing the (meth) acrylic polymer is not particularly limited, and a monomer (mixture) containing 80% by mass or more of methyl methacrylate is polymerized, or a monomer other than methyl methacrylate is copolymerized. Obtained by.

Further, a commercially available methacrylic resin may be used as the (meth) acrylic resin. Examples of such commercially available methacrylic resins include "Parapet H1000B" (MFR: 22 g / 10 minutes (230 ° C., 37.3N)) and "Parapet GF" (MFR: 15 g / 10 minutes (230 ° C., 37.3N)). )), "Parapet EH" (MFR: 1.3 g / 10 minutes (230 ° C, 37.3N)), "Parapet HRL" (MFR: 2.0 g / 10 minutes (230 ° C, 37.3N)), " Parapet HRS "(MFR: 2.4 g / 10 minutes (230 ° C, 37.3N)) and" Parapet G "(MFR: 8.0 g / 10 minutes (230 ° C, 37.3N)) [Both trade names, Made by Kurare Co., Ltd.] and so on.

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

The methacrylic acid ester polymer block (g1) has a structural unit derived from a methacrylic acid ester as a main structural unit. The proportion of the structural unit derived from the methacrylic acid ester in the methacrylic acid ester polymer block (g1) is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95, from the viewpoint of stretchability and surface hardness. By mass or more, particularly preferably 98% by mass or more.

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 the monomers constituting each polymer block is generally used. .. As such a living polymerization method, for example, an organic alkali metal compound is used as a polymerization initiator and anionic polymerization is carried out in the presence of a mineral salt such as an alkali metal or an alkaline earth metal salt; the polymerization of the organoalkali metal compound is started. 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-halogen ester compound as an initiator. And so on. Further, there is also a method of polymerizing the monomers constituting each block using a polyvalent radical polymerization initiator or a polyvalent radical chain transfer agent to produce a mixture containing an acrylic block copolymer (G). Among these methods, an acrylic block copolymer (G) can be obtained with high purity, the molecular weight and composition ratio can be easily controlled, and it is economical. Therefore, an organoalkali metal compound is used as a polymerization initiator. A method of anionic polymerization in the presence of an organoaluminum compound is preferable.

The multilayer structure (E) contains at least two layers, 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 central layer to the outermost layer. The multilayer structure (E) may further have a crosslinkable resin layer inside the inner layer or outside the outer layer.

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

The outer layer is made 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. Further, the hard thermoplastic resin contains 20% by mass or less, preferably 10% by mass or less of other monofunctional monomers. Examples of other monofunctional monomers include acrylic acid alkyl esters such as methyl acrylate, butyl acrylate and 2-ethylhexyl acrylate; acrylic acid; methacrylic acid and the like.

The content of the inner layer and the outer layer in the multi-layer structure (E) is determined from the viewpoints of impact resistance, heat resistance, surface hardness, handleability, ease of melt-kneading, etc. 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 of (for example, the total amount of the inner layer and the outer layer in the case of two layers). Is preferable.

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).

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 larger than 600 MPa, cracks or breaks tend to occur during vacuum forming. The elastic modulus is a value rounded off to the first decimal place when expressed in [MPa] units.

Amorphous resins constituting the base material are various additives such as antioxidants, heat stabilizers, lubricants, processing aids, antistatic agents, heat deterioration inhibitors, ultraviolet absorbers, light stabilizers, and polymers. It may contain a processing aid, a colorant, an impact resistant aid, and the like.

Moreover, the above-mentioned amorphous resin can be used by mixing with other polymers. Other such polymers include, for example, polyolefin resins such as polyethylene, polypropylene (PP), polybutene-1, poly-4-methylpentene-1, polynorbornene; ethylene-based ionomers; polystyrene, styrene-maleic anhydride copolymers. , High impact polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-ethylene-styrene copolymer, acrylonitrile-acrylic acid ester-styrene copolymer resin, acrylonitrile-chlorinated polyethylene Styrene resins such as -styrene copolymers, methyl methacrylate-butadiene-styrene copolymers; methyl methacrylate-styrene copolymers; polyester resins such as polyethylene terephthalates (PET) and polybutylene terephthalates; nylon 6, nylon 66, Polyamides such as polyamide elastomers; polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymers, polyacetals, vinylidene fluoride, polyurethanes, modified polyphenylene ethers, polyphenylene sulfides, silicone modified resins; acrylic rubber, silicones. Rubber; styrene-based thermoplastic elastomers such as styrene-ethylene / propylene-styrene copolymer, styrene-ethylene / butadiene-styrene copolymer, styrene-isoprene-styrene copolymer; isoprene rubber, ethylenepropylene rubber, ethylenepropylenediene Examples thereof include olefin-based rubbers such as 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 enhance the dispersibility of each component constituting the amorphous resin. For the mixing operation, a known mixing or kneading device such as a kneader luder, an extruder, a mixing roll, or a Banbury mixer can be used, and it is preferable to use a twin-screw extruder from the viewpoint of improving kneadability and compatibility. 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 the like, and is usually in the range of 110 to 300 ° C. When melt-kneading using a twin-screw extruder, it is preferable to melt-knead under reduced pressure and / or in a nitrogen atmosphere using a vent from the viewpoint of suppressing coloration.

[Other layers]
The multilayer film of the present invention may be used as a decorative film by printing a pattern or color such as a pattern, characters, or figures on a base material layer and / or an adhesive layer. 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, which is generally used in the printing method, as a binder and a pigment or a dye as a colorant. It is preferable to use.

The multilayer film of the present invention may be a decorative film in which the base material layer is colored. As a coloring method, the amorphous resin itself is impregnated with a pigment or a dye to color the resin itself before film formation; the amorphous resin film is immersed in a liquid in which the dye is dispersed to color the resin itself. Dyeing methods and the like can be mentioned, but the method is not particularly limited thereto.

The multilayer film of the present invention may be a decorative film in which a metal or a metal oxide is vapor-deposited on a base material layer. As the metal or metal oxide, a metal or metal oxide used for sputtering, vacuum deposition, etc. can be used without particular limitation. For example, gold, silver, copper, aluminum, zinc, nickel, chromium, indium and oxides thereof can be used. And so on. Moreover, these metals or metal oxides may be used alone or as a mixture of two or more. Examples of the method for depositing a metal or metal oxide on the base material layer include a vacuum film forming method such as vapor deposition and sputtering, electrolytic plating, and electroless plating.

The surface of the multilayer film of the present invention on the substrate layer side is preferably HB or harder than HB in terms of pencil hardness, and more preferably H or harder than that. If the pencil hardness is harder than HB, the multilayer film is not easily scratched, and it is suitably used as a decorative and protective film on the surface of a molded product that requires design.

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 even more preferably in the range of 100 to 250 μm. When the thickness of the multilayer film is 20 μm or more, the production is easy, the impact resistance and the warp reduction at the time of heating are excellent, and the multilayer film has a hiding property at the time of coloring. When 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 500 μm, secondary processability such as laminateability, handleability, cutability 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. It is not preferable because it exists. The thickness of the base material layer is more preferably 40 to 300 μm, and 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 adhesive layer is preferably in the range of 0.2 to 5, and more preferably 0.5 to 4. It is in the range of 0.8 to 3, and more preferably in the range of 0.8 to 3. If the value of the ratio (y / x) is less than 0.2, the surface hardness tends to be low, if it is larger than 5, the multilayer film tends to break easily, and if it is larger than 4, the stretchability becomes lower. It becomes a tendency.

[Manufacturing method of multilayer film]
The multilayer film of the present invention has a base material layer and an adhesive material layer, and can be obtained by laminating the adhesive material layer on one surface of the base material layer.

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

The base material layer may be a film that has been stretched. The stretching process increases the mechanical strength and makes it less likely 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 adhesive layer on the substrate layer obtained as described above is a method of applying a solution of a thermoplastic polymer composition constituting the adhesive layer to the substrate layer, a substrate layer. Examples thereof include a method of laminating a film made of the thermoplastic polymer composition. The film made of the thermoplastic polymer composition can be obtained in the same manner as the method for producing the base material layer exemplified above.
Further, the amorphous resin constituting the base material layer and the thermoplastic polymer composition constituting the adhesive layer can be produced by coextrusion using the T-die method. In particular, a coextrusion molding method using a multi-manifold die is preferable. At this time, the multilayer film is a roll in which the side in contact with the base material layer is a metal roll and the side in contact with the adhesive layer is a silicone roll whose roll surface is made of silicone resin or coated with silicone. It is suitable because it is easy to prevent troubles that wrap around.

[Molded product]
The molded product of the present invention includes the multilayer film of the present invention or a decorative film made of the multilayer film on the surface of the adherend. More preferably, the multilayer film of the present invention is provided on the surface of an adherend made of another thermoplastic resin, thermosetting resin, wood base material, non-wood fiber base material, or the like.

Examples of other thermoplastic resins used for the adherend include polycarbonate resin, polyethylene terephthalate resin, polyamide resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, other (meth) acrylic resin, and ABS (acrylonitrile). -Butadiene-styrene copolymer) resin and the like can be mentioned. Examples of other thermosetting resins include epoxy resins, phenol resins, melamine resins and the like. Further, the molded body may be formed by providing the multilayer film of the present invention on the surface of an adherend made of a non-wood fiber such as a wooden base material or kenaf. Since the adhesive layer of the present invention is particularly excellent in adhesion to an olefin resin, it is highly effective when the adherend is made of a polypropylene resin.

The manufacturing method of the molded product is not particularly limited. For example, the multilayer film of the present invention is vacuum-formed, pressure-molded, or compression-molded on the surface of an adherend such as another thermoplastic resin, thermosetting resin, wooden base material, or non-wood fiber base material under heating. Thereby, the molded product of the present invention can be obtained. In the molded product, the base material layer in the multilayer film of the present invention is provided on the outermost surface layer of the molded product, whereby the surface hardness, surface gloss and the like are excellent.

Another preferred method for producing the molded product is a method generally called an injection molding simultaneous bonding method.
In this injection molding simultaneous bonding method, the multilayer film of the present invention is inserted between male and female molds for injection molding, and the molten thermoplastic resin is injected into the mold from the surface on the adhesive layer side of the film, and injection molding is performed. This is a method of forming a body as an adherend and at the same time laminating the multilayer film on the surface of the injection molded product.

The multilayer film to be inserted into the mold may be a flat one as it is, or may be preformed by vacuum forming, compressed air forming or the like and shaped into an uneven shape.
The pre-molding of the multilayer film may be performed by a separate molding machine, or may be pre-molded in the mold of the injection molding machine used in the injection molding simultaneous bonding method.

The multilayer film of the present invention or a molded product having the multilayer film on the surface of the adherend can be designed by taking advantage of the good stretchability and molding processability of the multilayer film, excellent bipolar adhesiveness and surface smoothness. It can be applied to the required goods. For example, signboard parts such as advertising towers, stand signs, sleeve signs, column signs, roof signs; display parts such as showcases, dividers, and store displays; fluorescent light covers, mood lighting covers, lamp shades, light ceilings, and light walls. , Lighting parts such as chandeliers; Interior parts such as furniture, pendants, mirrors; Doors, dome, safety window glass, partitions, staircase wainscots, balcony wainscots, building parts such as roofs of leisure buildings, automobile interior / exterior parts, Transporter-related parts such as automobile exterior parts such as bumpers; electronic equipment parts such as sound and image signboards, stereo covers, vending machines, mobile phones, and personal computers; incubators, rulers, dials, greenhouses, large water tanks, box water tanks , Bathroom parts, clock panels, bathtubs, sanitary, desk mats, game parts, toys, wallpaper; marking films, suitable for decoration of various home appliances. Since the multilayer film of the present invention has the above characteristics, it can be particularly preferably used 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 each physical property were carried out as follows.

[Evaluation of viscoelasticity of thermoplastic polymer composition]
The pellets of the thermoplastic polymer composition shown in each of the examples and comparative examples described later are compression-molded using a compression molding machine at 200 ° C. and a load of 50 kgf / cm ² for 2 minutes to obtain a thermoplastic weight. A 150 × 150 mm sheet made of the coalesced composition was obtained. A test piece of 10 × 20 mm was cut out from the obtained sheet, and the temperature dispersion was measured with a dynamic viscoelasticity measuring device (Rheogel-4000 of UBM Co., Ltd.). Tan δ at 20 ° C. was measured.

[Adhesive strength (PP) of thermoplastic polymer composition]
Pellets of the thermoplastic polymer composition obtained in Examples and Comparative Examples and the methacrylic resin composition obtained in Production Example 5 were subjected to 2 at 200 ° C. and a load of 50 kgf / cm ^{2 using a compression molding machine.} By compression molding for 1 minute, a sheet made of a thermoplastic polymer composition and a sheet made of a methacrylic resin composition were obtained. Sheet (length 150 mm x width 150 mm x thickness 0.5 mm), polyimide film (Kapton film manufactured by Toray DuPont, length 75 mm x width 150 mm x thickness 0.05 mm) made of a 150 x 150 mm thermoplastic polymer composition. , Polypropylene sheet (MA3 manufactured by Japan Polypropylene Corporation, length 150 mm x width 150 mm x thickness 0.4 mm) is stacked in this order and placed in the center of a metal spacer with internal dimensions of 150 mm x 150 mm and thickness of 0.8 mm. did. The stacked sheet and the metal spacer are sandwiched between polytetrafluoroethylene sheets, further sandwiched between metal plates from the outside, and compression-molded at 130 ° C. and a load of 50 kgf / cm ² for 2 minutes using a compression molding machine. A multilayer film of a thermoplastic polymer composition and a methacrylic resin composition was obtained.
The multilayer film is cut into a width of 25 mm to obtain a test piece for measuring adhesive strength, and the peel strength between the thermoplastic polymer composition and the methacrylic resin composition is determined according to JIS K 6854-2, a peel tester (Shimadzu Seisakusho Co., Ltd.). AGS-X) was measured under the conditions of a peeling angle of 90 °, a tensile speed of 300 mm / min, and an environmental temperature of 23 ° C. to obtain the adhesive strength (PP) of the thermoplastic polymer composition.

[Evaluation of chipping resistance of molded product]
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 placed in the hopper of a single-screw extruder (VGM25-28EX manufactured by GM ENGINEERING), respectively. The film was charged and co-extruded using a multi-manifold die at 240 ° C. and a flow rate of 5 kg / h to obtain a multilayer film having a width of 30 cm. Further, polypropylene (J708UG manufactured by Prime Polymer Co., Ltd.) is put into an injection molding machine (SG-100 manufactured by Sumitomo Heavy Industries, Ltd.) and injected at 230 ° C. to obtain polypropylene having a length of 100 mm, a width of 40 mm, and a thickness of 3 mm. A molded product was obtained.
A multilayer film composed of a 100 × 40 mm thermoplastic polymer composition and a base material, and a polypropylene molded product (length 100 mm × width 40 mm × thickness 3 mm) were laminated in this order. The stacked sheets are sandwiched between polytetrafluoroethylene sheets, further sandwiched between metal plates from the outside, and compressed for 2 minutes at ^{a load of 50 kgf / cm 2 using a compression molding machine heated to the temperatures shown in each example and comparative example.} By molding, a molded product composed of a multilayer film and a polypropylene molded product was obtained.

A test piece was placed on the methacrylic resin composition side of the molded product under the conditions of a test piece temperature of -20 ° C, 90 degrees with respect to the shot material spraying shaft, and an air pressure of 0.4 MPa using a Grabello tester manufactured by Suga Test Instruments. 50 g of No. 7 crushed stone was collided from a distance of 350 mm. The surface of the molded product after the collision was visually observed.
X: 10 or more peeling points were observed Δ: 1 to 9 peeling points were observed ○: No peeling was observed

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

<Production Example 1> [Synthesis of Thermoplastic Elastomer (A-1)]
The pressure-resistant container was dried by substituting the pressure-resistant container with nitrogen in advance. In the pressure-resistant container, 50.0 kg of cyclohexane as a solvent, 94.1 g of a 10.5 mass% cyclohexane solution of sec-butyllithium as an anionic polymerization initiator (equivalent to 9.9 g of sec-butyllithium), and 300 g of tetrahydrofuran as a Lewis base were placed. I prepared it. The temperature of the solution was raised to 50 ° C. After adding 1.25 kg of styrene (1) to the solution, a polymerization reaction was carried out for 1 hour. Subsequently, 10.00 kg of isoprene was added to the solution, and then a polymerization reaction was carried out for 2 hours. Further, 1.25 kg of styrene (2) was added to the solution, and then a polymerization reaction was carried out for 1 hour. From the above, a reaction solution containing a styrene-isoprene-styrene triblock copolymer was obtained.

Palladium carbon was added to this reaction solution as a hydrogenation catalyst in an amount of 5% by mass per 100% by mass of the block copolymer. The amount of palladium supported per 100% by mass of palladium carbon is 5% by mass. The reaction was carried out for 10 hours in an environment of hydrogen pressure of 2 MPa and 150 ° C. The reaction solution was allowed to cool and then released under pressure. Then, palladium carbon is removed from the reaction solution by filtration, the filtrate is concentrated, and the concentrated solution is vacuum dried to block copolymer (a-1) which is a hydrogenated additive of styrene-isoprene-styrene triblock copolymer. ) Was obtained.

<Production Example 2> [Synthesis of Styrene-based Thermoplastic Elastomer (A-2)]
In a pressure vessel substituted with nitrogen and dried, 50.0 kg of cyclohexane was charged as a solvent, and 61.1 g (sec-butyllithium 6.42 g) of sec-butyl styrene (10.5 mass% cyclohexane solution) was charged as an anionic polymerization initiator. After raising the temperature to 50 ° C., 0.81 kg of styrene (1) was added and polymerized for 1 hour, then 10.87 kg of isoprene was added and polymerized for 2 hours, and 0.81 kg of styrene (2) was further added. Polymerization for 1 hour gave a reaction solution containing a styrene-isoprene-styrene triblock copolymer.
Palladium carbon (palladium-supported amount: 5% by mass) was added to this reaction solution as a hydrogenation catalyst in an amount of 5% by mass based on the block copolymer, and the reaction was carried out under the conditions of hydrogen pressure of 2 MPa and 150 ° C. for 10 hours. ..
After allowing to cool and pressurize, palladium carbon is removed by filtration, the filtrate is concentrated, and further vacuum dried to obtain a hydrogenated styrene-isoprene-styrene triblock copolymer (A-2-1). It was.

Further, in the same procedure as in the procedure for obtaining the hydrogenated product (A-2-1), 50.0 kg of cyclohexane was used as a solvent and sec-butyllithium (10. 420.0 g (sec-butyllithium 44.1 g) (5 mass% cyclohexane solution) was charged, the temperature was raised to 50 ° C., 2.83 kg of styrene (1) was added, and the mixture was polymerized for 1 hour, followed by 19.81 kg of isoprene. Was added and polymerization was carried out for 2 hours to obtain a reaction solution containing a styrene-isopregen block copolymer.
Hydrogenation was carried out in this reaction solution in the same manner as described above to obtain a hydrogenated product (A-2-2) of a styrene-isoprene block copolymer.
The above obtained (A-2-1) and (A-2-2) were used in a twin-screw extruder ZSK26MegaComponder (L / D = 54) manufactured by Coperion Co., Ltd. at a screw of 300 rpm and a kneading temperature of 200 ° C. Melt-kneading was performed to obtain a styrene-based thermoplastic elastomer composition (A-2).

<Production Example 3> [Synthesis of Styrene-based Thermoplastic Elastomer (A-3)]
In a pressure-resistant container substituted with nitrogen and dried, 50.0 kg of cyclohexane was charged as a solvent, and 170.6 g (sec-butyllithium 17.91 g) of sec-butyl lithium (10.5 mass% cyclohexane solution) was charged as an anionic polymerization initiator. After raising the temperature to 50 ° C., 1.87 kg of styrene (1) was added and polymerized for 1 hour, then 8.75 kg of butadiene was added and polymerized for 2 hours, and 1.87 kg of styrene (2) was further added. Polymerization for 1 hour gave a reaction solution containing a styrene-butadiene-styrene triblock copolymer.
Palladium carbon (palladium-supported amount: 5% by mass) was added to this reaction solution as a hydrogenation catalyst in an amount of 5% by mass based on the block copolymer, and the reaction was carried out under the conditions of hydrogen pressure of 2 MPa and 150 ° C. for 10 hours. ..

After allowing to cool and pressurize, palladium carbon is removed by filtration, the filtrate is concentrated, and further vacuum dried to obtain a hydrogenated styrene-butadiene-styrene triblock copolymer (A-3-1). It was.
Further, in the same manner as in (A-3-1), 50.0 kg of cyclohexane was used as a solvent and sec-butyllithium (10.5 mass% cyclohexane solution) was used as an anionic polymerization initiator in a pressure-resistant container that had been replaced with nitrogen and dried. 1 g (32.9 g of sec-butyl lithium) was charged, the temperature was raised to 50 ° C., 3.75 kg of styrene (1) was added and polymerized for 1 hour, and then 8.75 kg of butadiene was added and polymerized for 2 hours. , A reaction solution containing a styrene-butadiene diblock copolymer was obtained.

Hydrogenation was carried out in this reaction solution in the same manner as in (A-3-1) to obtain a hydrogenated product (A-3-2) of a styrene-budazien block copolymer.
(A-3-1) and (A-3-2) obtained above were used in a twin-screw extruder ZSK26MagaCompounder (L / D = 54) manufactured by Coperion Co., Ltd. at a screw of 300 rpm and a kneading temperature of 200 ° C. Melt-kneading was performed to obtain a thermoplastic elastomer composition (A-3).

[Polypropylene resin (B-1)]
As the polypropylene-based resin (B-1), WFX4TA (MFR at 230 ° C. of 7 g / 10 min) manufactured by Japan Polypropylene Corporation was used.

<Production Example 4> [Synthesis of Polar Group-Containing Polypropylene Resin (B-2)]
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 (talshalbutylperoxy) hexane at 180 ° C. and a screw using a batch mixer. It was melt-kneaded under the condition of a rotation speed of 40 rpm to obtain a polypropylene-based resin (B-2) containing a polar group. The obtained polar group-containing polypropylene resin (B-2) had an MFR [230 ° C., a load of 2.16 kgf (21.18 N)] of 6 g / 10 minutes, a maleic anhydride concentration of 0.3%, and a melting point of 0.3%. 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. The melting point is a value read from the endothermic peak of the differential scanning calorimetry curve when the temperature is raised at 10 ° C./min.

[Polypropylene resin (B-3)]
As the polypropylene-based resin (B-3), ^{Toughmer TM} XM7090 manufactured by Mitsui Chemicals, Inc. (MFR at 230 ° C. was 7 g / 10 min) was used.

[Polar Olefin Resin (C-1)]
As the polypropylene-based resin (C-1), ^{Toughmer TM} MA8510 (MFR at 230 ° C. of 5.0 g / 10 min) manufactured by Mitsui Chemicals, Inc. was used.

<Manufacturing Example 5> [Synthesis of (meth) acrylic resin]
Polymerization initiator (2,2'-azobis (2-methylpropionitrile), hydrogen extraction capacity: 1%, 1 hour half-life in a monomer mixture consisting of 95 parts by mass of methyl methacrylate and 5 parts by mass of methyl acrylate. Temperature: 83 ° C.) 0.1 part by mass and 0.28 part by mass of the chain transfer agent (n-octyl mercaptan) were added and dissolved to obtain a raw material solution.
A mixture was obtained by mixing 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. 420 parts by mass of the mixed solution and 210 parts by mass of the raw material solution were charged into the pressure-resistant polymerization tank, 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-like copolymer was dispersed. The obtained copolymer dispersion is washed with an appropriate amount of ion-exchanged water, the beaded copolymer is taken out by a bucket centrifuge, dried in a hot air dryer at 80 ° C. for 12 hours, and beaded (meth). ) Acrylic resin was obtained. The weight average molecular weight of the obtained (meth) acrylic resin was 30,000, and Tg was 128 ° C.

<Manufacturing example 6> [Multilayer structure]
A reactor equipped with a stirrer, thermometer, nitrogen gas inlet tube, monomer introduction tube and reflux condenser, 1050 parts by mass of ion-exchanged water, 0.5 parts by mass of sodium dioctyl sulfosuccinate and 0.7 parts by mass of sodium carbonate. Was charged, and the inside of the container was sufficiently replaced with nitrogen gas, and then the internal temperature was set to 80 ° C. After adding 0.25 parts by mass of potassium persulfate and stirring for 5 minutes, a monomer composed of methyl methacrylate: methyl acrylate: allyl methacrylate = 94: 5.8: 0.2 (mass ratio). 245 parts by mass of the mixture was continuously added dropwise for 50 minutes, and after the addition was completed, a polymerization reaction was further carried out for 30 minutes.
Next, 0.32 parts by mass of potassium peroxo2 sulfate was added to the reactor and stirred for 5 minutes, and then a single amount consisting of 80.6% by mass of butyl acrylate, 17.4% by mass of styrene and 2% by mass of allyl methacrylate. 315 parts by mass of the body mixture was continuously added dropwise over 60 minutes, and after completion of the addition, a polymerization reaction was further carried out for 30 minutes.
Subsequently, 0.14 parts by mass of potassium persulfate was added to the reactor and stirred for 5 minutes, and then 140 parts by mass of a monomer mixture consisting of methyl methacrylate: methyl acrylate = 94: 6 (mass ratio) was added. The dropping was continuously carried out over 30 minutes, and after the dropping was completed, the polymerization reaction was further carried out for 60 minutes to obtain a multilayer structure.

<Manufacturing Example 7> [Base material layer]
Using a twin-screw extruder (TEM-28 manufactured by Toshiba Machine Co., Ltd.), 20 parts by mass of the multilayer structure obtained in Production Example 6 and 80 parts by mass of the (meth) acrylic resin obtained in Production Example 5 were used. Pellets (P) of the methacrylic resin composition were produced by melt-kneading at 230 ° C., extruding into strands, and cutting.

<Example 1>
The thermoplastic elastomers (A-1) to (A-3) and the polypropylene-based resin (B-1) were charged into a twin-screw extruder (KZW15-30MG manufactured by Technobel Co., Ltd.) at the ratio shown in Table 1 at 225 ° C. , After melt-kneading at 250 rpm, extruded into strands and cut to obtain pellets of the thermoplastic polymer composition.
The viscoelasticity, adhesive strength (PP), and chipping resistance of the molded product of the obtained thermoplastic polymer composition were evaluated by the above-mentioned methods. The results are shown in Table 1.

<Examples 2-9, Comparative Examples 1-5, Reference Example 1>
Performed except that the thermoplastic elastomers (A-1) to (A-3) and the polypropylene resins (B-1) to (B-3) and (C-1) were mixed at the ratios shown in Table 1. Pellets of the thermoplastic elastomer composition were obtained in the same manner as in Example 1. The obtained thermoplastic polymer composition was evaluated by the above-mentioned method. The results are shown in Table 1.

In Example 1, the loss tangent (tan δ) at 11 Hz in the range of −50 to −20 ° C. of the thermoplastic polymer composition was 3 × 10 ⁻² or more, and the composition showed high adhesive strength to polypropylene. .. The molded product using the thermoplastic polymer composition of Example 1 as the adhesive layer showed high chipping resistance. It is considered that this is because the thermoplastic polymer composition is excellent in low temperature impact resistance. From this, it was clarified that the multilayer film of the present invention is suitable as a decorative film having excellent chipping resistance.
On the other hand, the thermoplastic polymer composition of Comparative Example 1 in which the loss tangent (tan δ) at 11 Hz in the range of −50 to −20 ° C. is 3 × 10 ⁻² or less is similar to that of Example 1 with respect to polypropylene. Although it showed excellent adhesive strength, the molded product using this thermoplastic polymer composition as the adhesive layer had poor chipping resistance.
Even when the thermoplastic polymer composition of Comparative Example 1 is used for the adhesive layer, polypropylene is used when the adhesive layer is thick and the temperature at the time of press bonding is high as in Reference Example 1. The adhesive strength to the adhesive was very excellent, and the chipping resistance was also good. From the above, it can be seen that the multilayer film of the present invention can exhibit high chipping resistance even when the thickness of the adhesive layer is thin and the bonding temperature is low.

The thermoplastic polymer composition of Example 2 in which the content of the polypropylene-based resin (B) was changed as compared with Example 1 had a loss tangent (tan δ) of 3 × 10 at 11 Hz in the range of −50 to −20 ° C. ^{It was -2} or more and showed high adhesive strength to polypropylene, and the molded product using the thermoplastic polymer composition as the adhesive layer showed high chipping resistance. Further, in Examples 3 to 6, the same thermoplastic polymer composition as in Example 1 is used to change the adhesive strength with polypropylene, but even when the adhesive strength with polypropylene is relatively low, good resistance is good. It showed chipping property.
Further, the thermoplastic polymer compositions of Examples 7 to 9 in which the type of the polypropylene-based resin (B) was changed and the polar olefin-based resin (C) was added had a loss at 11 Hz in the range of −50 to −20 ° C. The tan δ was 3 × ^10-2 or more, and high adhesive strength to polypropylene was exhibited, and the molded product using the thermoplastic polymer composition as the adhesive layer exhibited high chipping resistance.

On the other hand, the thermoplastic polymer compositions of Comparative Examples 2 to 4 have a loss tangent (tan δ) of 3 × 10 ⁻² or less at 11 Hz in the range of −50 to −20 ° C., and are chipping resistant as in Comparative Example 1. The sex was bad. The thermoplastic polymer composition of Comparative Example 5 has a loss tangent (tan δ) at 11 Hz in the range of −50 to −20 ° C. of 3 × 10 ⁻² or more, but contains an excess of polypropylene resin. When the bonding temperature was low, the adhesive strength to polypropylene was low, and the chipping resistance was also inferior.

As described above, in the multilayer film provided with the adhesive layer made of the thermoplastic polymer composition of the present invention, the thickness of the adhesive layer is thin, and high chipping resistance is obtained even when the bonding temperature is low. Since it can be expressed, it can be suitably used as a multilayer film particularly used for vehicle exteriors.

This application claims priority on the basis of Japanese application Japanese Patent Application No. 2018-077682 filed on April 13, 2018, the entire disclosure of which is incorporated herein by reference.

Claims (14)

A multilayer film including a base material layer and an adhesive layer, wherein the adhesive layer is
At least one block copolymer containing a polymer block (S) containing a structural unit derived from an aromatic vinyl compound and a polymer block (D) containing a structural unit derived from a conjugated diene compound, or a hydrogenated product thereof. It is composed of a thermoplastic polymer composition containing 0 to 30 parts by mass of a polypropylene-based resin (B) with respect to 100 parts by mass of the thermoplastic elastomer (A), and the thermoplastic polymer composition is −50 to −−. A multilayer film comprising a composition having a loss tangent (tan δ) at 11 Hz in the 20 ° C. range of 3 × ^{10-2 or more.} The multilayer film according to claim 1, wherein the structural unit derived from the conjugated diene compound constituting the polymer block (D) is a structural unit derived from at least one selected from butadiene and isoprene. 1 or claim 1, wherein the thermoplastic polymer composition further contains 1 to 50 parts by mass of the polar olefin resin (C) with respect to 100 parts by mass of the thermoplastic elastomer (A). 2. The multilayer film according to 2. The multilayer film according to claim 1, wherein the base material layer is made of an amorphous resin. The multilayer film according to claim 4, wherein the amorphous resin is any one of a (meth) acrylic resin, an ABS resin, a polycarbonate resin, and a polyester resin. The multilayer film according to any one of claims 1 to 5, wherein the multilayer film is a decorative film. The method for producing a multilayer film according to any one of claims 1 to 6, wherein the base material layer and the adhesive adhesive layer are coextruded. The method for producing a multilayer film according to claim 7, wherein the side in contact with the base material layer is formed as a metal roll, and the side in contact with the adhesive layer is formed as a silicone roll. The method for producing a multilayer film according to any one of claims 1 to 6, wherein the adhesive layer is formed on the base material layer by an extrusion lamination method. Production method. A molded product having the multilayer film according to any one of claims 1 to 6 on the surface of the adherend. The molded product according to claim 10, wherein the adherend is a polypropylene resin. The step of accommodating the multilayer film and the adherend according to any one of claims 1 to 6 in a chamber box;
Step of depressurizing the inside of the chamber box;
The step of dividing the inside of the chamber box by the multilayer film; and the pressure in the chamber box having the adherend is made higher than the pressure in the chamber box having the adherend. The step of coating the body with the multilayer film;
A method for producing a molded product having. The method for producing a molded product according to claim 12, further comprising a step of heating the multilayer film according to any one of claims 1 to 6 to a range of 110 to 180 ° C. to soften the multilayer film. A step of preforming the multilayer film according to any one of claims 1 to 6 by vacuum forming;
A step of arranging the preformed multilayer film in the mold so that the base material layer is in contact with the mold;
The process of injection molding the thermoplastic resin that forms the adherend after closing the mold;
A method for producing a molded product having.