JP7148231B2 - Polyvinyl chloride film, marking film, decorative molding, and method for producing polyvinyl chloride film - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polyvinyl chloride film, a marking film, a decorative molded product, and a method for producing a polyvinyl chloride film.

One or more modifiers are added to resin products such as polyvinyl chloride films in order to develop required performance.

As modifiers used for resins such as polyvinyl chloride, for example, Patent Document 1 discloses that vinyl It is a graft copolymer grafted with a system monomer and has a specific average particle size. It is disclosed that sufficient impact strength can be imparted.

Further, in Patent Document 2, during the production of acrylic rubber, which is a constituent component of silicone-modified acrylic rubber particles constituting silicone-modified acrylic rubber-based graft copolymer particles, copolymerization of acrylic rubber-forming components is carried out in multiple stages. In addition, silicone-modified acrylic rubber particles in which the proportion of the polyfunctional monomer used is different in each stage are mentioned. It is disclosed that impact properties can be expressed.

Japanese Patent No. 5069857 JP-A-2000-212231

Polyvinyl chloride film, especially polyvinyl chloride film for marking that is used by printing a design, is attached to vehicles such as bicycles, motorcycles, automobiles, buses, trains, etc., or parts of these used for From the viewpoint of producing resin films, resin films are generally required to have excellent processability (processability when forming films). In addition to the above processability, gasoline resistance is also required. Furthermore, in recent years, the polyvinyl chloride film used in the above vehicles and the like is required to have cold impact resistance so that it can withstand use in cold regions.

The cold impact resistance of the resin film is better as the film is more flexible at low temperatures. In the case of polyvinyl chloride films, flexibility can generally be imparted to the film by increasing the amount of plasticizer added. However, according to the study of the present inventors, it was found that the gasoline resistance of the polyvinyl chloride film was lowered when the amount of the plasticizer was increased in order to impart flexibility. The decrease in gasoline resistance is thought to be caused by the plasticizer in the polyvinyl chloride film eluting into the gasoline or migrating to the adhesive, resulting in a decrease in the adhesive strength of the polyvinyl chloride film. be done.

In order to improve the cold impact resistance while suppressing the deterioration of the gasoline resistance, the present inventor paid attention to a method of adding a cold impact resistant material to the polyvinyl chloride film in addition to the plasticizer. As a result, by adding a cold shock resistant material, it is possible to improve cold shock resistance even if the amount of plasticizer is suppressed, and it is possible to achieve both gasoline resistance and cold shock resistance, but the addition of plasticizer It has been found that the processability of the film decreases as the amount decreases. Therefore, there is room for further investigation in order to obtain a polyvinyl chloride film having excellent gasoline resistance, cold impact resistance and workability.

From the above, there is a demand for a polyvinyl chloride film having excellent gasoline resistance, cold impact resistance and workability. However, Patent Documents 1 and 2 do not disclose any technique for improving the gasoline resistance, cold impact resistance and workability of the film.

The present invention has been made in view of the above-mentioned current situation, and provides a polyvinyl chloride film, a marking film, a decorative molded product, and a polyvinyl chloride film having excellent gasoline resistance, cold impact resistance and workability. The object is to provide a manufacturing method.

The present inventors conducted various studies on a polyvinyl chloride film having excellent gasoline resistance, cold impact resistance and workability, and a method for producing the same. Then, by setting the contents of the plasticizer and the cold shock resistant material in the polyvinyl chloride film to specific ranges, respectively, and using the cold shock resistant material having a core portion containing a rubber-like polymer and a shell portion covering the core portion The inventors have found that a polyvinyl chloride film having excellent gasoline resistance, cold impact resistance and workability can be obtained, conceived that the above problems can be solved admirably, and arrived at the present invention. Here, in this specification, gasoline resistance refers to the difficulty of peeling the film when the film is exposed to gasoline. The above-mentioned "peeling of the film" means that the plasticizer contained in the film dissolves in gasoline, and the film is deformed due to swelling or the like, thereby peeling from the adherend. The term "cold impact resistance" refers to the resistance to cracking of the film when subjected to impact at low temperatures. As used herein, workability refers to workability when forming a film.

The polyvinyl chloride film of the present invention contains a vinyl chloride resin, a plasticizer, and a cold shock resistant material, and the content of the plasticizer is 13 parts by weight or more with respect to 100 parts by weight of the vinyl chloride resin. The content of the cold shock resistant material is 5 parts by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin, and the cold shock resistant material includes the core part and the core and a shell covering the core, wherein the core comprises a rubber-like polymer.

The rubbery polymer preferably contains at least one selected from diene rubbers, acrylic rubbers, silicone rubbers and silicone-acrylic rubbers.

The polyvinyl chloride film preferably has a thickness of 60 μm or less.

The marking film of the present invention is characterized by having the polyvinyl chloride film of the present invention and an adhesive layer.

The decorative molded article of the present invention is characterized by having the polyvinyl chloride film of the present invention, an adhesive layer, and a molded article in this order.

The method for producing a polyvinyl chloride film of the present invention includes a step of forming a polyvinyl chloride film by calendering using a resin composition, the resin composition comprising a vinyl chloride resin, a plasticizer, and a cold-resistant The content of the plasticizer is 13 parts by weight or more and 23 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin, and the content of the cold shock resistant material is the vinyl chloride 5 parts by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the resin, the cold shock resistant material includes a core part and a shell part covering the core part, and the core part contains a rubber-like polymer. It is characterized by

According to the polyvinyl chloride film of the present invention, it is possible to realize excellent gasoline resistance, cold impact resistance and workability. According to the method for producing a polyvinyl chloride film of the present invention, a polyvinyl chloride film (polyvinyl chloride film of the present invention) having excellent gasoline resistance, cold impact resistance and workability can be produced.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which showed typically an example of the marking film provided with the polyvinyl chloride film of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which showed typically an example of the decorative molding provided with the polyvinyl chloride film of this invention.

<Polyvinyl chloride film>
The polyvinyl chloride film of the present invention contains a vinyl chloride resin, a plasticizer, and a cold shock resistant material, and the content of the plasticizer is 13 parts by weight or more with respect to 100 parts by weight of the vinyl chloride resin. The content of the cold shock resistant material is 5 parts by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin, and the cold shock resistant material includes the core part and the core and a shell covering the core, wherein the core comprises a rubber-like polymer.

The polyvinyl chloride film of the present invention contains a vinyl chloride resin, a plasticizer, and a cold shock resistant material. A polyvinyl chloride film has good elongation and is difficult to break, so it can be easily attached to a three-dimensional curved surface. In addition, it is suitable as a base material for marking films because it has excellent printability and is excellent in decorative molding because it softens at a relatively low temperature of about 130°C. In the present invention, a plasticizer is added to the vinyl chloride resin in order to impart flexibility suitable for film processing and decorative molding. By imparting flexibility, cold impact resistance can also be improved. The vinyl chloride resin itself is hardly affected by gasoline, but the plasticizer is eluted into gasoline or migrates to the adhesive, which reduces the adhesive strength of the polyvinyl chloride film. It may reduce sexuality. In the present invention, in order to maintain gasoline resistance, the amount of plasticizer added is adjusted to a specific range, and the decrease in cold impact resistance due to the decrease in the amount of plasticizer added is corrected by adding a specific amount of cold impact resistant material. It makes up for it.

The upper limit of the film thickness (thickness) of the polyvinyl chloride film of the present invention is preferably 60 μm. By adopting such an aspect, it is possible to obtain flexibility and formability suitable for the marking film. Since the polyvinyl chloride film of the present invention has a plasticizer content adjusted within a predetermined range and is excellent in workability, even a film having a thickness of 60 μm or less can be easily processed. In addition, it is possible to reduce the cost, and by reducing the weight of the polyvinyl chloride film, it is possible to reduce the weight and reduce the environmental load by reducing the amount of waste. Furthermore, it is possible to reduce the amount of heat generated during combustion due to the reduction of organic matter. The lower limit of the film thickness of the polyvinyl chloride film of the present invention is preferably 20 μm from the viewpoint of workability and cold impact resistance. Among the workability, the present invention is particularly excellent in calendering workability when forming a film by calendering.

The polyvinyl chloride film of the present invention may be transparent or colored. When the polyvinyl chloride film is transparent, it is possible to decorate the surface of the molded article to which the marking film is attached.

[vinyl chloride resin]
Examples of the vinyl chloride resin include homopolymers of vinyl chloride and copolymers of vinyl chloride and other monomers. A homopolymer of vinyl chloride is preferable because it provides dimensional stability.

Examples of the other monomers include vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene and styrene; and (meth)acrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate. ; Maleic acid diesters such as dibutyl maleate and diethyl maleate; Fumaric acid diesters such as dibutyl fumarate and diethyl fumarate; Vinyl cyanides such as acrylonitrile and methacrylonitrile; Vinyl halides such as vinylidene chloride and vinyl bromide; Vinyl ethers such as methyl vinyl ether and ethyl vinyl ether can be mentioned. These may be used alone or in combination of two or more.

The vinyl chloride resin preferably has an average degree of polymerization of 800 or more and 1400 or less. In general, the higher the average degree of polymerization of the vinyl chloride resin, the greater the amount of other materials such as plasticizers, fillers and pigments that can be added to the vinyl chloride resin. Therefore, it is speculated that the higher the average degree of polymerization of the vinyl chloride resin within the above range, the more likely it is that even if the added plasticizer is eluted into gasoline, problems such as curling and waving of the polyvinyl chloride film can be suppressed. be. If the average degree of polymerization of the vinyl chloride resin is less than 800, the melt tension may decrease when the vinyl chloride resin is heated and melted, making it difficult to form a film. In addition, since other materials tend to bleed out onto the film surface, the amount of other materials that can be added may decrease. On the other hand, when the average degree of polymerization of the vinyl chloride resin exceeds 1,400, the entanglement of the polymer chains becomes strong, so that the shear force when forming a film by stretching by calendering or the like becomes large, and the film formability is deteriorated. may decrease. A more preferable lower limit of the average degree of polymerization of the vinyl chloride resin is 1000, and the gasoline resistance can be further improved. In addition, the average polymerization degree of a vinyl chloride resin means the average polymerization degree measured based on JISK6721 "vinyl chloride-type resin test method."

[Plasticizer]
The polyvinyl chloride film of the present invention contains a plasticizer, and the content of the plasticizer is 13 parts by weight or more and 23 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin. If the content of the plasticizer is less than 13 parts by weight, sufficient workability cannot be obtained. On the other hand, if the content of the plasticizer exceeds 23 parts by weight, the amount of the plasticizer that dissolves or swells with gasoline increases, and the gasoline resistance of the polyvinyl chloride film decreases. In general, when the content of the plasticizer is small, the workability of the polyvinyl chloride film is lowered. However, in the present invention, since the cold shock resistant material is further contained, the workability is further lowered. In the present invention, by adjusting the content of the plasticizer within the above range, excellent workability and gasoline resistance can be obtained by adjusting the content of the plasticizer while obtaining the cold impact resistance of the cold impact resistant material. Obtainable. A preferable upper limit of the content of the plasticizer is 20 parts by weight. A preferable lower limit of the content of the plasticizer is 15 parts by weight. When the content of the plasticizer is 15 parts by weight or more with respect to 100 parts by weight of the polyvinyl chloride resin, the plasticizer is a polyester plasticizer (for example, a polyester plasticizer having a number average molecular weight of 2000 or more ), workability can be improved. A more preferable lower limit for the content of the plasticizer is 18 parts by weight.

Any plasticizer can be used as long as it can facilitate the processing of polyvinyl chloride films. As the plasticizer, those commonly used in the field of polyvinyl chloride films can be used. In addition to phthalate plasticizers such as octyl acid (di-2-ethylhexyl phthalate), dibutyl phthalate, dinonyl phthalate, and diisononyl phthalate (DINP), polyester plasticizers as dephthalic acid plasticizers; adipine Aliphatic dibasic diester plasticizers such as dioctyl acid and dioctyl sebacate; phosphate triester plasticizers such as tricresyl phosphate and trioctyl phosphate; epoxy plasticizers such as epoxidized soybean oil and epoxy resins; mentioned. As the plasticizer, it is preferable to use a phthalate-free plasticizer, and it is more preferable to use a polyester-based plasticizer.

The above polyester plasticizer has good compatibility with vinyl chloride resin. In addition, the above polyester plasticizer is a polymer, so it is less likely to dissolve and swell in gasoline than the phthalic acid plasticizer generally used as a plasticizer for vinyl chloride resins. Therefore, by using a polyester-based plasticizer, it is possible to impart flexibility to the polyvinyl chloride film and further improve the cold impact resistance, and further improve the gasoline resistance. As the polyester plasticizer, for example, ADEKA CIZER PN7535 (manufactured by ADEKA), ADEKA CIZER PN7230 (manufactured by ADEKA), or the like can be used.

The polyester-based plasticizer can be used, for example, by a method of direct polycondensation of a dibasic acid or its anhydride and a dihydric alcohol, or by a method of dibasic acid methyl ester, ethyl ester or other lower alkyl ester with a dihydric alcohol. It can be produced by, for example, a method of conducting an ester exchange reaction.

Examples of the dibasic acid or its anhydride include adipic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, and phthalic anhydride. The dibasic acid or its anhydride may be used alone, or two or more of them may be mixed.

Examples of the dihydric alcohol include ethylene glycol, propylene glycol, butanediol, 1,6-hexanediol, and the like.

Among them, the polyester-based plasticizer is preferably an adipic polyester-based plasticizer. Adipic acid polyester-based plasticizers are highly compatible with vinyl chloride resins, and thus can be suitably used. Adipic acid polyester plasticizers are reaction products of adipic acid and one or more of the above dihydric alcohols.

The polyester plasticizer has a number average molecular weight of 2,000 or more. If the polyester plasticizer has a number average molecular weight of less than 2,000, it may easily dissolve and swell in gasoline, resulting in insufficient gasoline resistance. A preferable lower limit of the number average molecular weight of the polyester plasticizer is 2,500. The polyester plasticizer preferably has a number average molecular weight of 3,500 or less. When the number average molecular weight of the polyester plasticizer exceeds 3500, the gasoline resistance is improved, but the entanglement of the polymer chains is strengthened, so the shear force when stretching and forming a film by calendering or the like is increased. It may become large, and the film formability may deteriorate. In addition, when the shearing force increases, heat is generated during film formation, and the vinyl chloride resin may decompose, which may reduce the heat resistance of the polyvinyl chloride film. In addition, since the melt viscosity increases, the fluidity of the molten resin decreases, and there is a risk that the appearance of the polyvinyl chloride film will be poor, such as the generation of flow marks and the surface roughening. A more preferable upper limit of the number average molecular weight of the polyester plasticizer is 3,000. The above number average molecular weight is a measured value in terms of polystyrene by GPC (gel permeation chromatography) measurement. The GPC measurement method described above is carried out according to a standard method. A dilute tetrahydrofuran solution of the polyester plasticizer to be measured is prepared and measured using a GPC measuring device "HLC-8220GPC" manufactured by Tosoh Corporation at a flow rate of 0.6 ml/min. "KF606M" and "KF603" manufactured by Showa Denko Co., Ltd. are used as columns.

As the polyester-based plasticizer, an adipic polyester-based plasticizer having a number average molecular weight of 2,000 or more and 3,500 or less is suitable. Specifically, Adekasizer (PN-7535, PN-350, P-300) manufactured by ADEKA Corporation can be used.

[Cold impact resistant material]
The polyvinyl chloride film of the present invention contains a cold shock resistant material. The content of the cold shock resistant material is 5 parts by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin. By setting it as such an aspect, the cold impact resistance of the said polyvinyl chloride film can be improved. If the content of the cold impact resistant material is less than 5 parts by weight per 100 parts by weight of the vinyl chloride resin, the cold impact resistance is deteriorated. Moreover, when the content of the cold shock resistant material exceeds 30 parts by weight with respect to 100 parts by weight of the vinyl chloride resin, workability deteriorates. In the present invention, since a material having a core-shell structure is used for the cold shock resistant material, high filling is possible and workability can be improved.

The cold shock resistant material includes a core portion and a shell portion covering the core portion. A structure including the core portion and the shell portion is also called a core-shell structure. The rubber-like polymer contained in the core portion is not particularly limited as long as it is a polymer exhibiting rubber elasticity. Here, rubber elasticity refers to elasticity caused by expansion and contraction of polymer chains. By including a rubber-like polymer in the core portion, it becomes possible to absorb the impact applied to the polyvinyl chloride film, and the cold impact resistance can be improved.

The rubbery polymer preferably contains at least one selected from diene rubbers, acrylic rubbers, silicone rubbers and silicone-acrylic rubbers. More preferably, the rubber-like polymer contains a silicone-acrylic rubber because of its excellent cold impact resistance.

The diene rubber can be obtained by polymerizing 1,3-butadiene and, if necessary, one or more vinyl monomers copolymerizable therewith. Examples of vinyl-based monomers include aromatic vinyls such as styrene and α-methylstyrene, methacrylic acid alkyl esters such as methyl methacrylate and ethyl methacrylate, acrylic acid alkyl esters such as ethyl acrylate and n-butyl acrylate, and acrylonitrile. , unsaturated nitriles such as methacrylonitrile, vinyl ethers such as methyl vinyl ether and butyl vinyl ether, vinyl halides such as vinyl chloride and vinyl bromide, vinylidene halides such as vinylidene chloride and vinylidene bromide, glycidyl acrylate, glycidyl methacrylate, allyl Vinyl-based monomers having a glycidyl group such as glycidyl ether and ethylene glycol glycidyl ether are included.

Furthermore, aromatic polyfunctional vinyl compounds such as divinylbenzene and divinyltoluene, polyhydric alcohols such as ethylene glycol dimethacrylate and 1,3-butanediol diacrylate, trimethacrylate, triacrylate, allyl acrylate, and methacryl Crosslinkable monomers such as carboxylic acid allyl esters such as allyl acid, di- and triallyl compounds such as diallyl phthalate, diallyl sebacate, and triallyltriazine can also be used in combination. One or two or more of the above vinyl-based monomers and crosslinkable monomers may be used. As a chain transfer agent, t-dodecylmercaptan, n-octylmercaptan, α-methylstyrene and the like can be used. Preferably t-dodecyl mercaptan can be used.

The acrylic rubber can be obtained by polymerizing one or more alkyl (meth)acrylates and one or more vinyl monomers copolymerizable therewith. Alkyl (meth)acrylates are not particularly limited, and examples include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, i-butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, ethoxyethoxyethyl acrylate, methoxytripropylene glycol acrylate, 4-hydroxybutyl acrylate, lauryl methacrylate, stearyl methacrylate and the like.

Although the silicone-based rubber is not particularly limited, polyorganosiloxane containing a vinyl-polymerizable functional group is preferably used. Examples of dimethylsiloxane used in the production of polyorganosiloxane include dimethylsiloxane-based cyclic bodies having a 3-membered ring or more, with 3- to 7-membered rings being preferred. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, etc. These may be used alone or in combination of two or more.

In addition, the vinyl-polymerizable functional group-containing siloxane used in the production of the polyorganosiloxane contains a vinyl-polymerizable functional group and is capable of bonding with dimethylsiloxane via a siloxane bond, and exhibits reactivity with dimethylsiloxane. In consideration, various alkoxysilane compounds containing vinyl polymerizable functional groups are preferred. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, methacryloyloxysilanes such as γ-methacryloyloxypropylethoxydiethoxymethylsilane and δ-methacryloyloxybutyldiethoxymethylsilane; vinylsiloxanes such as tetramethyltetravinylcyclotetrasiloxane; vinylphenylsilanes such as p-vinylphenyldimethoxymethylsilane; and mercaptosiloxanes such as γ-mercaptopropyldimethoxymethylsilane and γ-mercaptopropyltrimethoxysilane. These vinyl-polymerizable functional group-containing siloxanes can be used alone or as a mixture of two or more.

The above silicone-acrylic rubber is a rubber obtained by compounding the above silicone rubber with an alkyl (meth)acrylate rubber. A silicone-acrylic rubber can be prepared by adding an alkyl (meth)acrylate component to a latex of a polyorganosiloxane component, and polymerizing the mixture with a conventional radical polymerization initiator. Methods for adding the alkyl (meth)acrylate include a method of mixing with the latex of the polyorganosiloxane component all at once, and a method of dropping it into the latex of the polyorganosiloxane component at a constant rate.

Examples of alkyl (meth)acrylates include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate, and alkyl methacrylates such as hexyl methacrylate, 2-ethylhexyl methacrylate and n-lauryl methacrylate. These can be used alone or in combination of two or more. Considering the impact resistance and molding gloss of the resin composition containing the graft copolymer, the use of n-butyl acrylate is particularly preferred.

Examples of polyfunctional alkyl (meth)acrylates include allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, triallyl cyanurate, and triallyl. Examples include isocyanurate and the like, and these can be used alone or in combination of two or more. As the radical polymerization initiator used for polymerization, a peroxide, an azo initiator, or a redox initiator obtained by combining an oxidizing agent and a reducing agent is used. Among these, a redox initiator is preferred, and a system in which ferrous sulfate, disodium ethylenediaminetetraacetic acid, Rongalit, and hydroperoxide are combined is particularly preferred.

The shell portion in the cold shock resistant material of the present invention is not particularly limited, and preferably contains a polymer. The polymer contained in the shell portion is preferably a polymer obtained by polymerizing the rubber-like polymer with a copolymerizable acrylic monomer. That is, the shell preferably contains an acrylic polymer. Examples of the polymer contained in the shell include a polymer obtained by polymerizing at least one monomer selected from the group consisting of acrylic monomers, vinyl monomers and nitrile monomers. mentioned. Here, a polymer obtained by polymerizing an acrylic monomer is also referred to as an acrylic polymer, a polymer obtained by polymerizing a vinyl monomer is also referred to as a vinyl polymer, and a polymer obtained by polymerizing a nitrile monomer. is also called a nitrile polymer.

Examples of the acrylic monomer include methacrylic acid alkyl esters such as methyl methacrylate and ethyl methacrylate; and acrylic acid alkyl esters such as ethyl acrylate and n-butyl acrylate. Examples of the vinyl-based monomer include aromatic vinyls such as styrene, α-methylstyrene, and various halogen-substituted and alkyl-substituted styrenes; glycidyl groups such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, and ethylene glycol glycidyl ether. and vinyl monomers having a hydroxy group such as hydroxy methacrylate; Examples of the nitrile-based monomer include unsaturated nitriles such as acrylonitrile and methacrylonitrile.

The cold impact material of the present invention comprises, for example, in the presence of a rubber polymer containing at least one selected from the diene rubber, acrylic rubber, silicone rubber and silicone-acrylic rubber, at least one copolymerizable It is obtained by adding an acrylic monomer and graft-polymerizing it. In graft polymerization, a crosslinkable monomer and/or a chain transfer agent can be used together with the acrylic monomer.

The mass ratio of the core part and the shell part in the cold shock resistant material of the present invention is such that the total amount of the shell part is 5% by mass or more and 50% by mass or less when the total amount of the core part and the total amount of the shell part is 100% by mass. is preferably

As the cold shock resistant material whose core part is diene rubber, for example, Metabrene (registered trademark) C-223 (manufactured by Mitsubishi Chemical Corporation), Kane Ace (registered trademark) B-11A (manufactured by Kaneka Corporation), etc. can be used. . As the cold shock resistant material whose core part is acrylic rubber, for example, Metabrene (registered trademark) W-300 (manufactured by Mitsubishi Chemical Corporation), Kane Ace (registered trademark) FM-40 (manufactured by Kaneka Corporation), etc. can be used. . As a cold shock resistant material having a core made of silicone-acrylic rubber, for example, METABLEN (registered trademark) S-2001 (manufactured by Mitsubishi Chemical Corporation) or the like can be used.

The total content of the plasticizer and cold shock resistant material of the present invention is preferably more than 30 parts by weight and less than 45 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. By adopting such an aspect, gasoline resistance and cold impact resistance can be further improved.

Moreover, the content of the plasticizer in the polyvinyl chloride film of the present invention is preferably higher than the content of the cold shock resistant material.

[Other additives]
The polyvinyl chloride film may contain stabilizers, ultraviolet absorbers, lubricants, modifiers, fillers such as inorganic particles and inorganic fibers, diluents, etc. It may contain an agent. As these additives, those generally blended with vinyl chloride resins can be used.

Examples of the stabilizer include metal soaps such as fatty acid calcium, fatty acid zinc and fatty acid barium; hydrotalcite and the like. Examples of the fatty acid component of the metal soap include calcium laurate, calcium stearate, calcium ricinoleate, zinc laurate, zinc ricinoleate, zinc stearate, barium laurate, barium stearate, and barium ricinoleate. In addition, as the above stabilizers, epoxy stabilizers; barium stabilizers; calcium stabilizers; tin stabilizers; zinc stabilizers; -Zn system) can also be used.

When the stabilizer is contained, the content thereof is preferably 0.3 parts by weight or more and 5.0 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin. If the content is less than 0.3 parts by weight, the effect of blending the stabilizer may not be sufficiently exhibited. ).

Moreover, when containing the said ultraviolet absorber, the content is preferable 0.3 to 2.0 weight part with respect to 100 weight part of said vinyl chloride resins. If the content is less than 0.3 parts by weight, there is little effect, while if the content exceeds 2.0 parts by weight, bleeding may occur on the surface of the polyvinyl chloride film.

The method for producing the polyvinyl chloride film is not particularly limited. For example, the polyvinyl chloride film can be formed by mixing a vinyl chloride resin, a plasticizer, and a cold shock resistant material using a blender or the like, and then performing calendering or the like. .

<Marking film>
The marking film of the present invention has a polyvinyl chloride film 11 and an adhesive layer 12. A marking film comprising the polyvinyl chloride film of the present invention will be described below with reference to FIG. FIG. 1 is a cross-sectional view schematically showing an example of a marking film comprising the polyvinyl chloride film of the present invention. The marking film 10 shown in FIG. 1 has a printed layer 14, a polyvinyl chloride film 11, an adhesive layer 12, and a separator 13 in this order. As the polyvinyl chloride film 11, the polyvinyl chloride film of the present invention can be used. The marking film 10 has gasoline resistance and cold impact resistance.

[Adhesive layer]
The adhesive layer 12 may contain an adhesive that is commonly used in the field of marking films. When the marking film is applied to vehicles such as bicycles, motorcycles, automobiles, buses, and trains, or parts thereof, adhesives that exhibit sufficient adhesive strength at room temperature (21° C. to 25° C.) are preferred. As said adhesive, an acrylic adhesive is mentioned, for example. The acrylic pressure-sensitive adhesive may be solvent-based or non-solvent-based, as long as it exhibits adhesive strength at room temperature. Solvent-based adhesives include solvent-type adhesives and non-aqueous emulsion-type adhesives. Examples of solvent-free adhesives include emulsion adhesives and ultraviolet curing adhesives.

The thickness of the adhesive layer 12 is preferably 10 μm or more and 60 μm or less. A more preferable lower limit to the thickness of the adhesive layer 12 is 20 μm, and a more preferable upper limit is 50 μm.

[separator]
As the separator 13, one commonly used in the film field can be used. The separator 13 may be a release film or release paper. Examples of the release film include resin films such as polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, and polypropylene that have undergone an easy peeling treatment. Examples of the release paper include paper such as high-quality paper or glassine paper that has undergone an easy peeling treatment. Examples of the easy peeling treatment include a method of coating the surface of the resin film or paper that comes into contact with the pressure-sensitive adhesive layer with a silicone-based, alkyd-based, fluorine-based release agent, or the like. The separator 13 may be surface-treated only on the adhesive layer side. The thickness of the separator 13 is preferably 12 μm or more and 200 μm or less. A more preferable lower limit to the thickness of the separator 13 is 50 μm, and a more preferable upper limit is 150 μm.

[Print layer]
The printed layer 14 is printed on the surface of the polyvinyl chloride film 11 opposite to the adhesive layer 12 . Printing on the polyvinyl chloride film 11 can be performed by, for example, inkjet printing, gravure printing, screen printing, rotary screen printing, flexographic printing, offset printing, electrostatic printing, or the like. Further, the polyvinyl chloride film 11 may have fine unevenness by embossing or the like on the surface opposite to the adhesive layer.

[Protective film layer]
Marking film 10 may further have a protective film layer over printing layer 14 . As the protective film, one commonly used in the film field can be used. Examples of the protective film include polyethylene terephthalate (PET)-based resins, polypropylene (PP)-based resins, and polycarbonate-based resins.

The manufacturing method of the marking film 10 is not particularly limited, but for example, the polyvinyl chloride film 11 is produced by melt-kneading a vinyl chloride resin, a plasticizer, and a cold shock-resistant material using a blender or the like, followed by calendering or the like. can be formed by The pressure-sensitive adhesive layer 12 is formed by coating the pressure-sensitive adhesive composition on the separator 13 using a general-purpose film-forming device or film-forming method such as various coating devices, bar coaters, and doctor blades, followed by drying. can do. By laminating the adhesive layer 12 on the polyvinyl chloride film 11, the marking film 10 can be obtained. When the marking film 10 has the printed layer 14 , the printed layer 14 may be formed before or after laminating the adhesive layer 12 on the polyvinyl chloride film 11 .

A method of applying the marking film 10 includes, for example, a method of peeling off the separator 13 from the marking film 10 and attaching it to the molded product via the adhesive layer 12 . The marking film 10 can be attached at room temperature, or may be attached while being heated with a dryer or the like. Alternatively, the marking film 10 can be manually applied to the molding.

The material of the molded article is not particularly limited, and examples include resins such as polycarbonate resins, acrylic resins, and styrene resins, acrylonitrile-butadiene-styrene copolymers (ABS resins); metals such as iron, copper, and aluminum. ; alloys and the like.

Examples of the molded article include, but are not limited to, vehicles such as bicycles, motorcycles, automobiles, buses, and trains; helmets; ships; aircraft such as airplanes and helicopters; , office supplies such as personal computers; walls, floors, ceilings, roofs, pillars, signboards, doors, and gates of buildings; In particular, since high gasoline resistance is required, it can be suitably used for parts of vehicles such as motorcycles, automobiles, buses and trains.

The marking film can be used as a sticker to decorate part of the molded product. Examples of the sticker include those obtained by printing a desired pattern, characters, etc. on the marking film and cutting it into a desired shape. Specifically, a sticker printed with a maker's logo, an emblem, a model name, or the like can be attached to a part of the vehicle or the like.

The marking film can be used by being attached to a part of the molded product. Specifically, the separator can be peeled off from the marking film of the present invention and attached to the molded product via the pressure-sensitive adhesive layer.

<Decorative molding>
A decorative molded article comprising the polyvinyl chloride film of the present invention will be described below with reference to FIG. FIG. 2 is a cross-sectional view schematically showing an example of a decorative molded article provided with the polyvinyl chloride film of the present invention.

As shown in FIG. 2, the decorative molded product 100 is obtained by attaching a polyvinyl chloride film 11 to a molded product 20 via an adhesive layer 12. The molded product 20, the adhesive layer 12, the polychlorinated The vinyl films 11 are laminated in this order. Furthermore, the printed layer 14 may be provided on the side of the polyvinyl chloride film 11 opposite to the adhesive layer 12 . As the polyvinyl chloride film 11, the polyvinyl chloride film of the present invention can be used. The decorative molded product 100 has gasoline resistance and cold impact resistance.

The polyvinyl chloride film of the present invention can also be used as a base material for decorative films, as shown in FIG. The decorative film is heated to, for example, 80° C. to 130° C. to soften the film before being applied to a molded product.

The pressure-sensitive adhesive layer 12 preferably contains a hot-melt adhesive because it is suitable for attachment by vacuum/pneumatic molding. Examples of the hot-melt adhesives include polyester-based hot-melt adhesives, acrylic hot-melt adhesives, rubber-based hot-melt adhesives, and silicone-based hot-melt adhesives. For example, Hibon 7663 manufactured by Hitachi Kasei Polymer Co., Ltd. may be used.

Examples of the method of applying the decorative film include a method of peeling off the separator 13 from the marking film 10 and attaching it to the molded product via the adhesive layer 12. Specifically, vacuum molding, pressure molding (TOM molding ), vacuum/pneumatic molding, in-mold molding, film insert molding, lamination, and the like can be used. Among them, it is preferable to use vacuum/pressure molding.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples.

(Example 1)
20 parts by weight of a plasticizer and 15 parts by weight of a cold shock resistant material are added to 100 parts by weight of a vinyl chloride resin having an average degree of polymerization of 1000, and melt-kneaded for 10 minutes using a blender to form a molten mixture (PVC compound). got The resulting PVC compound was calendered using an inverted L-shaped calender roll to obtain a polyvinyl chloride film of Example 1. As the plasticizer, a polyester plasticizer having a number average molecular weight of 3000 (ADEKA Cizer PN7535) was used. As the cold shock resistant material, a cold shock resistant material with a core-shell structure containing silicone-acrylic rubber in the core portion and acrylic polymer in the shell portion (METABLEN (registered trademark) S-2001, manufactured by Mitsubishi Chemical Corporation) was used. . The film thickness (thickness) of the polyvinyl chloride film was 50 μm.

(Examples 2 to 9 and Comparative Examples 1 to 6)
Polyvinyl chloride films according to Examples 2 to 9 and Comparative Examples 1 to 6 were produced in the same manner as in Example 1, except that the formulation was changed as shown in Table 1 below. In Example 2, a cold impact resistant material (METABLEN (registered trademark) C-223, manufactured by Mitsubishi Chemical Corporation) having a core-shell structure containing a diene rubber (butadiene rubber) in the core portion and an acrylic polymer in the shell portion was used. board. In Example 3, a cold shock resistant material (METABLEN (registered trademark) W-300, manufactured by Mitsubishi Chemical Corporation) having a core-shell structure containing an acrylic rubber in the core portion and an acrylic polymer in the shell portion was used.

(Evaluation of polyvinyl chloride film)
For the polyvinyl chloride films produced in Examples and Comparative Examples, (1) gasoline resistance, (2) cold impact resistance, (3) weather resistance, and (4) workability were evaluated by the following methods. rice field. Also, a comprehensive evaluation was made from the results of (1) to (4).

(1) Gasoline resistance After applying an adhesive to the polyvinyl chloride film produced in Examples and Comparative Examples and attaching it to a polypropylene plate (hereinafter also referred to as a PP plate), a mixed solvent of isooctane and toluene (mixed ratio 1:1). After that, the time required for each polyvinyl chloride film to peel off from the PP plate was visually measured to evaluate the gasoline resistance.
◯: The time until the polyvinyl chloride film was peeled off from the PP plate was 25 minutes or longer.
x: Less than 25 minutes until the polyvinyl chloride film was peeled off from the PP plate.

(2) Cold impact resistance The polyvinyl chloride films prepared in Examples and Comparative Examples were left for a while until they reached 5°C, 0°C, -5°C, -10°C, -15°C and -20°C, respectively. From, at each temperature, the polyvinyl chloride film is cracked using a DuPont type drop impact tester (manufactured by Yasuda Seiki Seisakusho) at a DuPont type (die radius 6.35 mm, weight 500 g, drop height 100 mm). The temperature (cold resistance shock temperature) at which this occurs was evaluated.
◯: Cold impact resistance temperature is 0° C. or less.
x: The cold impact resistance temperature exceeds 0°C.

(3) Weather resistance The polyvinyl chloride films produced in Examples and Comparative Examples were subjected to 1000 hours of weather resistance test using a JIS B7753-compliant weather resistance tester (e.g., Sunshine Weather Meter) by a JIS B7753-compliant method. An accelerated weathering test was performed. For each polyvinyl chloride film, the degree of discoloration after the accelerated weather resistance test was visually confirmed. Weather resistance was evaluated according to the following evaluation criteria.
◯: No discoloration was observed.
Δ: Discoloration to the extent that it does not affect use was confirmed.
x: Discoloration to the extent that it cannot be used was confirmed.

(4) Processability In the examples and comparative examples, the material containing vinyl chloride resin, plasticizer, and cold shock resistant material prepared when producing the polyvinyl chloride film was applied to a film forming apparatus equipped with two rolls. After kneading for 10 minutes, a gap was formed between the two rolls, and the kneaded material was rolled to form a sheet (film) having a thickness of 0.2 mm. The apparatus used for the evaluation of workability is different from the apparatus equipped with the reverse L-shaped calender rolls used in the production of Example 1, but it is capable of evaluating calender workability. When forming the above sheet, the following items <<1>> to <<4>> were evaluated, and evaluation was made according to the following evaluation criteria. Note that if there is unevenness in the bank rotation described below in <<1>>, that is, if the bank rotation is not smooth, the pulsation of the bank may cause unevenness in the thickness of the sheet. Further, if the roll adhesion of the above material is poor and the bank is in a slippery state, pinholes may occur due to entrainment of air as an appearance defect. From <<2>> and <<4>> below, air blurring and flow marks can be determined. The above-mentioned air blurring is a defect that occurs when air remaining in the material causes dents and streaks during stretching, and in extreme cases, holes are formed. Further, flow marks are defects caused by thickness unevenness occurring in the width direction and vertical streaks or wood grain streaks. The streaks change their luster and color, resulting in poor appearance, and are also called bank marks.
<Evaluation items>
<<1>> Whether the sheet can be peeled from the roll without load <<2>> Whether the bank rotation is uneven <<3>> Visually check whether the material blown out onto the roll is attached <<4>> Appearance of the sheet (dents, streaks) , Presence or absence of holes, etc.) Confirmation <Evaluation criteria>
◯: There were no problems with respect to all of the above evaluation items <<1>> to <<4>>.
Δ: There was no problem with the above <<4>> evaluation item, but there was a problem with any of the above <<1>> to <<3>> evaluation items.
x: There was a problem with the above <<4>> evaluation item.

(Comprehensive evaluation)
As a result of the above evaluation test, ◎ if the evaluation results of (1) to (4) above are all ○, ○ if the evaluation results of (1) to (4) above are ○ or △, and (1) above ) to (4) were rated as x when any one of them was x.

Table 1 shows the structures and evaluation results of the polyvinyl chloride films of Examples and Comparative Examples.

From the results in Table 1, Examples 1 to 9 were excellent in gasoline resistance, cold impact resistance and workability. Moreover, Examples 1, 3 and 5 were excellent in all evaluations of gasoline resistance, cold impact resistance, weather resistance and workability.

Example 1 using a cold shock resistant material containing silicone-acrylic rubber in the core has better gasoline resistance than Example 2 using diene rubber in the core and Example 3 using acrylic rubber in the core. and had a cold impact resistance equal to or higher than that of Examples 2 and 3. Examples 1 and 3, in which the core portion of the cold shock resistant material is silicone-acrylic rubber or acrylic rubber, were superior in weather resistance to Example 2, in which the core portion is diene rubber.

Since the cold shock resistant material is more easily dissolved in gasoline than the vinyl chloride resin itself, Example 1, which contains a smaller amount of the cold shock resistant material, exhibits better resistance than Examples 4 and 9, which contain a larger amount of the cold shock resistant material. It is thought that it was excellent in gasoline resistance. In addition, in Examples 4 and 9, which have a large amount of cold shock resistant material compared to Example 1, the amount of powdered cold shock resistant material increases, so the fluidity of the resin decreases during processing, and the resin tends to decompose easily. Air blurring and flow marks are more likely to occur, and workability is considered to have slightly deteriorated.

In Example 1, since the amount of the cold shock resistant material is larger than that in Example 5, it is considered that the cold impact resistance is improved.

In Example 1, in which a larger amount of plasticizer was added than in Examples 6 to 8, it was possible to impart flexibility to the polyvinyl chloride film, and it is believed that the cold impact resistance was improved. In addition, in Examples 6 to 8, in which the amount of plasticizer is smaller than that in Example 1, the fluidity of the resin decreases during processing, and the resin tends to decompose easily. It is considered that the workability slightly decreased.

On the other hand, in Comparative Examples 1 to 6, at least one of the gasoline resistance, cold impact resistance and processability was poorly evaluated, and it was impossible to obtain a polyvinyl chloride film having excellent gasoline resistance, cold impact resistance and processability. could not.

More specifically, in Comparative Examples 1 and 2, in which the content of the plasticizer exceeds the upper limit of the present invention and the content of the cold shock resistant material is lower than the lower limit of the present invention, a plasticizer that dissolves or swells in gasoline It is considered that the amount of the agent increased and the gasoline resistance decreased.

In Comparative Example 3, in which the content of the plasticizer was below the lower limit of the present invention and the content of the cold shock resistant material was within the range of the present invention, workability was lowered.

In Comparative Example 4, in which the content of the plasticizer was within the range of the present invention and the content of the cold shock resistant material exceeded the upper limit of the present invention, the amount of the cold shock resistant material dissolved in gasoline increased. is thought to have declined.

In Comparative Example 5, in which the content of the plasticizer exceeds the upper limit of the present invention and the content of the cold shock resistant material is within the range of the present invention, the amount of the plasticizer that dissolves or swells with gasoline increases. It is considered that gasoline resistance has decreased.

In Comparative Example 6, in which the content of the plasticizer was within the range of the present invention and the content of the cold shock resistant material was below the lower limit of the present invention, the amount of the cold shock resistant material was small, and the cold impact resistance was reduced. be done.

10 Marking film 11 Polyvinyl chloride film 12 Adhesive layer 13 Separator 14 Printing layer 20 Molded product 100 Decorative molded product

Claims (5)

including a vinyl chloride resin, a polyester plasticizer, and a cold shock resistant material,
The content of the polyester plasticizer is 13 parts by weight or more and 23 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin,
The number average molecular weight of the polyester plasticizer is 2000 or more and 3500 or less,
The content of the cold shock resistant material is 5 parts by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin,
The cold shock resistant material comprises a core and a shell covering the core,
The polyvinyl chloride film, wherein the core portion contains silicone-acrylic rubber. 2. The polyvinyl chloride film according to claim 1, which has a thickness of 60 [mu]m or less. A marking film comprising the polyvinyl chloride film according to claim 1 or 2 and an adhesive layer. A decorative molded product comprising the polyvinyl chloride film according to claim 1 or 2, an adhesive layer, and a molded product in this order. Using the resin composition, including a step of forming a polyvinyl chloride film by calendering,
The resin composition includes a vinyl chloride resin, a polyester plasticizer, and a cold shock resistant material,
The content of the polyester plasticizer is 13 parts by weight or more and 23 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin,
The number average molecular weight of the polyester plasticizer is 2000 or more and 3500 or less,
The content of the cold shock resistant material is 5 parts by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin,
The cold shock resistant material comprises a core and a shell covering the core,
The method for producing a polyvinyl chloride film, wherein the core portion contains silicone-acrylic rubber.

Images