JP2019056045A - Polyvinyl chloride film, marking film, decorative molded article, and method for producing polyvinyl chloride film - Google Patents

Abstract

To provide a polyvinyl chloride film having excellent gasoline resistance, cold impact resistance and processability, to provide a marking film, to provide a decorative molded article and to provide a method for producing the polyvinyl chloride film.SOLUTION: The polyvinyl chloride film includes a vinyl chloride resin, a plasticizer and a cold impact-resistant material. In the polyvinyl chloride film, the content of the plasticizer is 13 pts.wt. to 23 pts.wt. based on 100 pts.wt. of the vinyl chloride resin; the content of the cold impact-resistant material is 5 pts.wt. to 30 pts.wt. based on 100 pts.wt. of the vinyl chloride resin; the cold impact-resistant material comprises a core part and a shell part covering the core part; and the core part includes a rubbery polymer.SELECTED DRAWING: Figure 1

Description

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 several modifiers are added to a resin product such as a polyvinyl chloride film in order to develop the required performance.

As a modifier used for resins such as polyvinyl chloride, for example, Patent Document 1 discloses that vinyl is a rubbery polymer selected from diene rubber, acrylic rubber, silicone rubber, or silicone / acrylic composite rubber. Is a graft copolymer grafted with a system monomer, and includes a resin modifier having a specific average particle diameter. By using the resin modifier, the appearance of the product is good, It is disclosed that sufficient impact strength can be imparted.

In addition, Patent Document 2 discloses that the acrylic rubber-forming component is copolymerized in multiple stages when the acrylic rubber, which is a constituent component of the silicone-modified acrylic rubber particle constituting the silicone-modified acrylic rubber-based graft copolymer particle, is produced. Silicone-modified acrylic rubber particles that are different from each other and have different proportions of polyfunctional monomers are used. By using the above-mentioned silicone-modified acrylic rubber particles, the thermoplastic resin has a high resistance to resistance particularly at low temperatures. It is disclosed that impact properties can be expressed.

Japanese Patent No. 5069857 JP 2000-212231 A

Polyvinyl chloride film, especially polyvinyl chloride film for marking used by printing designs is affixed to bicycles, motorcycles, automobiles, buses, trains and other vehicles, or parts of these parts. Used. From the viewpoint of producing a resin film, the resin film generally requires excellent processability (processability when the film is formed). In particular, the polyvinyl chloride film used in the above-mentioned vehicle or the like is gasoline. In addition to the above processability, gasoline resistance is also required. Furthermore, in recent years, the polyvinyl chloride film used in the above-mentioned vehicles and the like is also required to have cold shock resistance so that it can withstand use in cold regions.

The cold shock resistance of the resin film becomes better as the film becomes more flexible at low temperatures. In the case of a polyvinyl chloride film, generally, flexibility can be imparted to the film by increasing the amount of a plasticizer to be added. However, according to the study of the present inventors, it has been found that the gasoline resistance of the polyvinyl chloride film is lowered when the amount of the plasticizer is increased in order to impart flexibility. The decrease in gasoline resistance is considered to be caused by the decrease in the adhesive strength of the polyvinyl chloride film due to the plasticizer in the polyvinyl chloride film eluting into gasoline or shifting to an adhesive. It is done.

The present inventor further paid attention to a method of adding a cold shock resistant material in addition to the plasticizer to the polyvinyl chloride film in order to improve the cold shock resistance while suppressing a decrease in gasoline resistance. 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 a plasticizer It has been found that the processability of the film decreases as the amount decreases. Therefore, there is room for further study in order to obtain a polyvinyl chloride film having excellent gasoline resistance, cold shock resistance and processability.

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

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

The present inventors conducted various studies on a polyvinyl chloride film having excellent gasoline resistance, cold shock resistance and processability, and a method for producing the same. And by using the cold shock resistant material provided with a core portion containing a rubber-like polymer and a shell portion covering the core portion, the contents of the plasticizer and the cold shock resistant material in the polyvinyl chloride film are respectively in a specific range. The present inventors have found that a polyvinyl chloride film having excellent gasoline resistance, cold shock resistance and processability can be obtained, and have conceived that the above problems can be solved brilliantly, and have reached the present invention. Here, in this specification, gasoline resistance means the difficulty of peeling of the film when the film is exposed to gasoline. The above “peeling of the film” means that the plasticizer contained in the film is dissolved in gasoline, and the film is peeled off from the adherend by deformation due to swelling or the like. Cold shock resistance refers to the difficulty of cracking of the film when subjected to an impact at low temperatures. In this specification, workability means the workability at the time of forming a film.

The polyvinyl chloride film of the present invention includes 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. 23 parts by weight or less, and 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. A shell part covering the part, wherein the core part includes a rubber-like polymer.

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

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 product of the present invention is characterized by having the polyvinyl chloride film of the present invention, an adhesive layer, and a molded product 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, and the resin composition comprises a vinyl chloride resin, a plasticizer, and cold resistance. The plasticizer content 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, and the cold shock resistant material includes a core part and a shell part covering the core part, and the core part includes a rubbery polymer. It is characterized by that.

According to the polyvinyl chloride film of the present invention, excellent gasoline resistance, cold shock resistance and workability can be realized. According to the method for producing a polyvinyl chloride film of the present invention, a polyvinyl chloride film having excellent gasoline resistance, cold shock resistance and processability (polyvinyl chloride film of the present invention) can be produced.

It is sectional drawing which showed typically an example of the marking film provided with the polyvinyl chloride film of this invention. It is sectional drawing which showed typically an example of the decorative molded product provided with the polyvinyl chloride film of this invention.

<Polyvinyl chloride film>
The polyvinyl chloride film of the present invention includes 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. 23 parts by weight or less, and 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. A shell part covering the part, wherein the core part includes 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 that it can be easily attached to a three-dimensional curved surface. Moreover, since it is excellent in printability and is excellent in decorative molding because it softens at a relatively low temperature of about 130 ° C., it is suitable as a substrate for a marking film. 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 shock resistance can also be improved. The polyvinyl chloride resin itself is hardly affected by gasoline, but the adhesive strength of the polyvinyl chloride film is reduced by the elution of the plasticizer into the gasoline or the transfer to the adhesive. May decrease. In the present invention, in order to maintain gasoline resistance, the amount of plasticizer added is adjusted to a specific range, and the cold impact resistance is reduced due to a decrease in the amount of plasticizer added, and a specific amount of cold shock resistant material is added. I make up for that.

The upper limit of the film thickness (thickness) of the polyvinyl chloride film of the present invention is preferably 60 μm. By setting it as such an aspect, the softness | flexibility and moldability suitable for a marking film can be obtained. Since the polyvinyl chloride film of the present invention has a plasticizer content adjusted to a predetermined range and is excellent in workability, even a film having a film thickness of 60 μm or less can be easily processed. In addition to cost reduction, the weight of the polyvinyl chloride film can be reduced to reduce the weight and reduce the environmental load due to the reduction of waste. Furthermore, it becomes possible to reduce the calorific value at the time of combustion by organic substance reduction. The lower limit of the film thickness of the polyvinyl chloride film of the present invention is preferably 20 μm from the viewpoints of workability and cold shock resistance. Among the processability, the present invention is particularly excellent in calendar workability when a film is formed by calendering.

The polyvinyl chloride film of the present invention may be transparent or colored. If the polyvinyl chloride film is transparent, it can be decorated by utilizing the decoration of the surface of the molded product to which the marking film is attached.

[Vinyl chloride resin]
Examples of the vinyl chloride resin include vinyl chloride homopolymers and copolymers of vinyl chloride and other monomers. From the viewpoint of obtaining dimensional stability, a homopolymer of vinyl chloride is preferable.

Examples of the other monomer include vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene and styrene; (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; Examples thereof include vinyl ethers such as methyl vinyl ether and ethyl vinyl ether. 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, within the above range, it is presumed that the higher the average degree of polymerization of the vinyl chloride resin, the less the occurrence of defects such as curling and undulation of the polyvinyl chloride film, even if the added plasticizer is eluted in gasoline. The When the average degree of polymerization of the vinyl chloride resin is less than 800, the melt tension when dissolved by heating may be lowered, and it may be difficult to form into a film. Moreover, since it becomes easy to bleed out another material on the film surface, there exists a possibility that the quantity of the other material which can be added decreases. On the other hand, when the average degree of polymerization of the vinyl chloride resin exceeds 1400, the entanglement of the polymer chains becomes strong, so that the shearing force is increased when the film is drawn and formed into a film by calendering or the like, and the film forming property is increased. May decrease. A more preferable lower limit of the average degree of polymerization of the vinyl chloride resin is 1000, which can further enhance gasoline resistance. The average degree of polymerization of the vinyl chloride resin means the average degree of polymerization measured according to JIS K 6721 “Testing method for vinyl chloride resin”.

[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. When the content of the plasticizer is less than 13 parts by weight, sufficient processability cannot be obtained. On the other hand, when 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 plasticizer content is low, the processability of the polyvinyl chloride film is lowered, but in the present invention, since the cold shock resistant material is further contained, the processability is further lowered. In the present invention, by making the content of the plasticizer within the above range, by obtaining the cold shock resistance by the cold shock resistant material, by adjusting the content of the plasticizer, excellent workability and gasoline resistance can be obtained. Can be obtained. The upper limit with preferable content of the said plasticizer is 20 weight part. The minimum with preferable content of the said plasticizer is 15 weight part. 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). ), The workability can be improved. The minimum with more preferable content of the said plasticizer is 18 weight part.

The plasticizer is not particularly limited as long as it can easily process the polyvinyl chloride film. As the plasticizer, those usually used in the field of polyvinyl chloride film can be used. In addition to phthalic acid plasticizers such as octyl acid (di-2-ethylhexyl phthalate), dibutyl phthalate, dinonyl phthalate, diisononyl phthalate (DINP), polyester plasticizers as dephthalic acid plasticizers; adipine Aliphatic dibasic acid 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 resin Can be mentioned. As the plasticizer, it is preferable to use a dephthalic acid plasticizer, and it is more preferable to use a polyester plasticizer.

The polyester plasticizer has good compatibility with the vinyl chloride resin. The polyester plasticizer is a polymer compared to a phthalic acid plasticizer generally used as a plasticizer for the vinyl chloride resin, and thus hardly dissolves and swells in gasoline. Therefore, by using a polyester plasticizer, it is possible to further improve gasoline resistance while imparting flexibility with a polyvinyl chloride film to further improve cold shock resistance. As said polyester plasticizer, Adekasizer PN7535 (made by ADEKA), Adekasizer PN7230 (made by ADEKA), etc. can be used, for example.

The polyester plasticizer is, for example, a method of directly polycondensing a dibasic acid or an anhydride thereof with a dihydric alcohol, or a lower alkyl ester such as a methyl ester or an ethyl ester of a dibasic acid and a dihydric alcohol. It can be produced by a method of performing a transesterification reaction or the like.

Examples of the dibasic acid or anhydride thereof include adipic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, and phthalic anhydride. The said dibasic acid or its anhydride may be used independently, and may mix 2 or more types.

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

Especially, it is preferable that the said polyester plasticizer is an adipic acid polyester plasticizer. Adipic acid polyester plasticizers can be suitably used because of their high compatibility with vinyl chloride resins. The adipic acid polyester plasticizer is a reaction product of adipic acid and one or more dihydric alcohols.

The number average molecular weight of the polyester plasticizer is 2000 or more. If the number average molecular weight of the polyester plasticizer is less than 2,000, the polyester plasticizer tends to dissolve and swell in gasoline, and the gasoline resistance may be insufficient. A preferable lower limit of the number average molecular weight of the polyester plasticizer is 2500. The number average molecular weight of the polyester plasticizer is preferably 3500 or less. If the number average molecular weight of the polyester plasticizer exceeds 3500, the gasoline resistance is improved, but the entanglement of the polymer chain becomes strong, so that the shearing force at the time of drawing into a film by calendaring or the like is increased. It may become large and film forming property may fall. Moreover, when the shearing force is increased, heat is generated during film formation, and the vinyl chloride resin may be decomposed, which may reduce the heat resistance of the polyvinyl chloride film. Moreover, since melt viscosity becomes high, the fluidity | liquidity of molten resin falls, there exists a possibility that the appearance defect of a polyvinyl chloride film may generate | occur | produce, such as a flow mark generating and the surface becoming rough. A more preferable upper limit of the number average molecular weight of the polyester plasticizer is 3000. The number average molecular weight is a measured value in terms of polystyrene by GPC (gel permeation chromatograph) measurement. The GPC measurement method is performed 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 under a flow rate condition of 0.6 ml / min. As the column, “KF606M” and “KF603” manufactured by Showa Denko KK are used.

The polyester plasticizer is preferably an adipic acid polyester plasticizer and having a number average molecular weight of 2000 or more and 3500 or less. Specifically, Adeka Co., Ltd. Adeka Sizer (PN-7535, PN-350, P-300) or the like can be used.

[Cold 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. When the content of the cold shock resistant material is less than 5 parts by weight with respect to 100 parts by weight of the vinyl chloride resin, the cold shock resistance is deteriorated. On the other hand, 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, the 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 that covers the core portion. A structure including the core part and the shell part is also referred to as a core-shell structure. The rubber-like polymer contained in the core part is not particularly limited as long as it is a polymer exhibiting rubber elasticity. Here, the rubber elasticity refers to the elasticity caused by the expansion and contraction of the polymer chain. By including the rubber-like polymer in the core part, it is possible to absorb the impact applied to the polyvinyl chloride film and improve the cold shock resistance.

The rubbery polymer preferably contains at least one selected from diene rubber, acrylic rubber, silicone rubber and silicone-acrylic rubber. It is more preferable that the rubber-like polymer contains a silicone-acrylic rubber because it has excellent cold shock resistance.

The diene rubber can be obtained by polymerizing 1,3-butadiene and, if necessary, one or more vinyl monomers copolymerizable therewith. Examples of the vinyl monomer include aromatic vinyl such as styrene and α-methylstyrene, alkyl methacrylate such as methyl methacrylate and ethyl methacrylate, alkyl ester 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 Examples thereof include vinyl monomers having a glycidyl group such as glycidyl ether and ethylene glycol glycidyl ether.

Furthermore, aromatic polyfunctional vinyl compounds such as divinylbenzene and divinyltoluene, polyhydric alcohols such as ethylene glycol dimethacrylate and 1,3-butanediol diacrylate, trimethacrylic acid esters, triacrylic acid esters, allyl acrylate, methacrylic acid Crosslinkable monomers such as di- and triallyl compounds such as carboxylic acid allyl esters such as acid allyl, diallyl phthalate, diallyl sebacate, and triallyl triazine can also be used in combination. The vinyl monomer and the crosslinkable monomer may be used alone or in combination of two or more. As the chain transfer agent, t-dodecyl mercaptan, n-octyl mercaptan, 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. The alkyl (meth) acrylate is not particularly limited. For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, i-butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, ethoxyethoxyethyl acrylate, Examples include methoxytripropylene glycol acrylate, 4-hydroxybutyl acrylate, lauryl methacrylate, stearyl methacrylate and the like.

The silicone rubber is not particularly limited, but polyorganosiloxane containing a vinyl polymerizable functional group is preferably used. Examples of dimethylsiloxane used for the production of polyorganosiloxane include dimethylsiloxane-based cyclic bodies having 3 or more member rings, and those having 3 to 7 members are preferable. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like. These may be used alone or in combination of two or more.

Also, the vinyl polymerizable functional group-containing siloxane used for the production of polyorganosiloxane is one that contains a vinyl polymerizable functional group and can be bonded to dimethylsiloxane via a siloxane bond, and has a reactivity with dimethylsiloxane. In consideration, various alkoxysilane compounds containing a vinyl polymerizable functional group are preferable. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropylethoxydiethoxymethylsilane and δ-methacryloyloxybutyldiethoxymethylsilane and other methacryloyloxysilane, tetramethyltetravinylcyclotetrasiloxane and other vinylsiloxanes, p-vinylphenyldimethoxymethylsilane and other vinylphenylsilanes Furthermore, mercaptors such as γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane, etc. Siloxane, and the like. In addition, these vinyl polymerizable functional group containing siloxane can be used individually or in mixture of 2 or more types.

The silicone-acrylic rubber is a rubber obtained by combining an alkyl (meth) acrylate rubber with the silicone rubber. The silicone-acrylic rubber can be prepared by adding an alkyl (meth) acrylate component to the latex of the polyorganosiloxane component and polymerizing with the action of a normal radical polymerization initiator. As a method of adding alkyl (meth) acrylate, there are a method of mixing with a latex of a polyorganosiloxane component at once and a method of dropping at a constant rate into a latex of a polyorganosiloxane component.

Examples of the alkyl (meth) acrylate 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 may be used alone or in combination of two or more. In view of the impact resistance and molding gloss of the resin composition containing the graft copolymer, it is particularly preferable to use n-butyl acrylate.

Examples of the polyfunctional alkyl (meth) acrylate include allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, triallyl cyanurate, and triallyl. Isocyanurate etc. are mentioned, These can be used individually or in combination of 2 or more types. As the radical polymerization initiator used for polymerization, a peroxide, an azo initiator, or a redox initiator combined with an oxidizing agent / reducing agent is used. Among these, a redox initiator is preferable, and a system in which ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, Rongalite, and hydroperoxide are combined is particularly preferable.

The shell part in the cold shock resistant material of this invention is not specifically limited, It is preferable that a polymer is included. The polymer contained in the shell part is preferably a polymer obtained by polymerizing an acrylic monomer copolymerizable with the rubbery polymer. That is, the shell part preferably contains an acrylic polymer. Examples of the polymer contained in the shell part include a polymer obtained by polymerizing at least one monomer selected from the group consisting of acrylic monomers, vinyl monomers, and nitrile monomers. Can be mentioned. Here, a polymer obtained by polymerizing an acrylic monomer is also called an acrylic polymer, a polymer obtained by polymerizing a vinyl monomer is also called a vinyl polymer, and a polymer obtained by polymerizing a nitrile monomer. Is also referred to as 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 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 monomer include unsaturated nitriles such as acrylonitrile and methacrylonitrile.

The cold shock resistant material of the present invention can be copolymerized with one or more kinds in the presence of a rubber polymer containing at least one selected from the above-mentioned diene rubber, acrylic rubber, silicone rubber and silicone-acrylic rubber, for example. It can be obtained by adding an acrylic monomer and graft polymerization. In the 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 when the total amount of the core part and the total amount of the shell part is 100% by mass, the total amount of the shell part is 5% by mass or more and 50% by mass or less. It is preferable that

As the cold shock resistant material whose core portion is a diene rubber, for example, Metablen (registered trademark) C-223 (manufactured by Mitsubishi Chemical Corporation), Kaneace (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, Methbrene (registered trademark) W-300 (manufactured by Mitsubishi Chemical Corporation), Kaneace (registered trademark) FM-40 (manufactured by Kaneka Corporation) or the like can be used. . As the cold shock resistant material whose core part is a silicone-acrylic rubber, for example, Methbrene (registered trademark) S-2001 (manufactured by Mitsubishi Chemical Corporation) or the like can be used.

The total amount 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 setting it as such an aspect, gasoline resistance and cold impact resistance can be improved more.

Moreover, it is preferable that content of the said plasticizer in the polyvinyl chloride film of this invention is larger than content of the said cold shock resistant material.

[Other additives]
The polyvinyl chloride film is added within the range not impairing the effects of the present invention, if necessary, stabilizers, ultraviolet absorbers, lubricants, modifiers, fillers such as inorganic particles and inorganic fibers, and diluents. An agent may be contained. As these additives, those generally blended with vinyl chloride resin 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 stabilizer, epoxy stabilizer; barium stabilizer; calcium stabilizer; tin stabilizer; zinc stabilizer; calcium-zinc-based (Ca-Zn-based), barium-zinc-based (Ba Composite stabilizers such as —Zn-based ”can also be used.

When the stabilizer is contained, the content 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 exerted. On the other hand, if the content exceeds 5.0 parts by weight, the stabilizer is bloomed (spouted). )

Moreover, when it contains the said ultraviolet absorber, the content has 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 not much effect. On the other hand, if the content exceeds 2.0 parts by weight, the surface of the polyvinyl chloride film may be bleed.

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

<Marking film>
The marking film of the present invention has a polyvinyl chloride film 11 and an adhesive layer 12. Below, the marking film provided with the polyvinyl chloride film of this invention is demonstrated using FIG. FIG. 1 is a cross-sectional view schematically showing an example of a marking film provided with the polyvinyl chloride film of the present invention. The marking film 10 shown in FIG. 1 has a printing 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 shock resistance.

[Adhesive layer]
The pressure-sensitive adhesive layer 12 can contain a pressure-sensitive adhesive usually used in the field of marking films. When the marking film is affixed to a vehicle such as a bicycle, a motorcycle, an automobile, a bus, or a train, or to these parts, an adhesive that exhibits sufficient adhesive strength at room temperature (21 ° C. to 25 ° C.) is preferable. As said adhesive, an acrylic adhesive is mentioned, for example. The acrylic pressure-sensitive adhesive may be solvent-based or solvent-free as long as it can exhibit adhesive force at room temperature. Examples of the solvent system include a solvent type adhesive and a non-aqueous emulsion type adhesive. Examples of the solventless system include an emulsion type adhesive and an ultraviolet curable adhesive.

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

[separator]
As the separator 13, those usually used in the field of film can be used. The separator 13 may be a release film or a release paper. Examples of the release film include those obtained by subjecting a resin film such as polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, and polypropylene to easy release treatment. Examples of the release paper include those obtained by subjecting paper such as high-quality paper or glassine paper to easy release treatment. Examples of the easy release treatment include a method of coating the surface of the resin film or paper that contacts the pressure-sensitive adhesive layer with a silicone-based, alkyd-based, or fluorine-based release agent. The separator 13 may be surface-treated only on the surface on the pressure-sensitive 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 of 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 pressure-sensitive 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, and the like. Moreover, the polyvinyl chloride film 11 may have fine unevenness | corrugation by the embossing etc. on the surface on the opposite side to an adhesive layer.

[Protective film layer]
The marking film 10 may further have a protective film layer on the printing layer 14. As said protective film, what is normally used in the field | area of a film can be used. Examples of the protective film include polyethylene terephthalate (PET) resin, polypropylene (PP) resin, and polycarbonate resin.

Although the manufacturing method of the marking film 10 is not particularly limited, for example, the polyvinyl chloride film 11 is obtained by melt-kneading a vinyl chloride resin, a plasticizer, and a cold shock resistant material using a blender or the like, and then calendar processing or the like. Can be formed. 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 apparatus or film forming method such as various coating apparatuses, bar coats, doctor blades, etc., and then drying. can do. The marking film 10 can be obtained by laminating the pressure-sensitive adhesive layer 12 on the polyvinyl chloride film 11. When the marking film 10 has the printing layer 14, the formation of the printing layer 14 may be before or after the pressure-sensitive adhesive layer 12 is laminated on the polyvinyl chloride film 11.

Examples of the method for applying the marking film 10 include a method in which the separator 13 is peeled off from the marking film 10 and attached to the molded product through the pressure-sensitive adhesive layer 12. The marking film 10 can be affixed at room temperature, and may be affixed while being heated with a dryer or the like. Further, the marking film 10 can be attached to the molded product by hand.

The material of the molded product is not particularly limited. For example, a resin such as a polycarbonate resin, an acrylic resin, or a styrene resin, an acrylonitrile-butadiene-styrene copolymer (ABS resin); a metal such as iron, copper, or aluminum An alloy or the like.

Although it does not specifically limit as said molded article, For example, bicycles, motorcycles, cars, buses, trains and other vehicles; helmets; ships; airplanes, helicopters and other aircraft; furniture, household appliances such as home appliances; cabinets, office desks And office supplies such as personal computers; wall surfaces, floor surfaces, ceilings, roofs, pillars, signboards, doors, gates of buildings; or building materials on construction sites, or parts thereof. Especially, since high gasoline resistance is requested | required, it can use suitably with respect to some vehicles, such as a motorbike, a motor vehicle, a bus, and a train.

The marking film can be used as a sticker to decorate a 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 on which a manufacturer logo, an emblem, or a car model name is printed can be attached to a part of a 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 a molded product via the pressure-sensitive adhesive layer.

<Decorated molded products>
Below, the decoration molded product provided with the polyvinyl chloride film of this invention is demonstrated using FIG. FIG. 2 is a cross-sectional view schematically showing an example of a decorative molded product including the polyvinyl chloride film of the present invention.

As shown in FIG. 2, the decorative molded product 100 is obtained by pasting the polyvinyl chloride film 11 on the molded product 20 via the pressure-sensitive adhesive layer 12, and the molded product 20, the pressure-sensitive adhesive layer 12, and the polychlorinated chloride. The vinyl films 11 are laminated in this order. Furthermore, you may have the printing layer 14 on the opposite side to the adhesive layer 12 of the polyvinyl chloride film 11. FIG. 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 shock resistance.

As shown in FIG. 2, the polyvinyl chloride film of the present invention can also be used as a base material for a decorative film. For example, the decorative film is heated to 80 ° C. to 130 ° C., and is used by being attached to a molded product in a state where the film is softened.

The pressure-sensitive adhesive layer 12 preferably contains a hot-melt adhesive because it is suitable for pasting by vacuum / pressure forming. Examples of the hot melt adhesive include polyester hot melt adhesives, acrylic hot melt adhesives, rubber hot melt adhesives, and silicone hot melt adhesives. For example, for example, Hibon 7663 manufactured by Hitachi Chemical Co., Ltd. can be used.

Examples of the method for applying the decorative film include a method in which the separator 13 is peeled off from the marking film 10 and attached to a molded product via the pressure-sensitive adhesive layer 12. Specifically, vacuum molding, pressure molding (TOM molding) is used. ), Vacuum / compressed air molding, in-mold molding, film insert molding, lamination, and the like can be used. Among these, it is preferable to use vacuum / pressure forming.

EXAMPLES Hereinafter, although an Example is hung up and demonstrated in more detail about this invention, this invention is not limited only 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 polymerization degree of 1000, and melt-kneaded for 10 minutes using a blender, and then a molten mixture (PVC compound) Got. The obtained 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 Sizer PN7535 manufactured by ADEKA) was used. As the cold shock resistant material, a cold shock resistant material having a core-shell structure (metabrene (registered trademark) S-2001, manufactured by Mitsubishi Chemical Corp.) including a silicone-acrylic rubber in the core portion and an acrylic polymer in the shell portion was used. . The film thickness (thickness) of the polyvinyl chloride film was 50 μm.

(Examples 2-9 and Comparative Examples 1-6)
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 shock resistant material (manufactured by Mitsubishi Chemical Co., Ltd., Metabrene (registered trademark) C-223) having a core-shell structure including a diene rubber (butadiene rubber) in the core portion and an acrylic polymer in the shell portion is used. It was. In Example 3, a cold shock resistant material (manufactured by Mitsubishi Chemical Co., Ltd., Metabrene (registered trademark) W-300) having a core-shell structure including 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 prepared in Examples and Comparative Examples, (1) gasoline resistance, (2) cold shock resistance, (3) weather resistance, and (4) workability were evaluated by the following methods. It was. Moreover, comprehensive evaluation was performed from the result of (1)-(4).

(1) Gasoline resistance After applying an adhesive to the polyvinyl chloride films prepared in the Examples and Comparative Examples and affixing them to a polypropylene plate (hereinafter also referred to as PP plate), a mixed solvent of isooctane and toluene (mixed) Dipping ratio 1: 1). Thereafter, the time until each polyvinyl chloride film was peeled off from the PP plate was visually measured to evaluate gasoline resistance.
A: Time required for the polyvinyl chloride film to peel from the PP plate is 25 minutes or more.
X: Time until a polyvinyl chloride film peels from PP board is less than 25 minutes.

(2) Cold shock resistance The polyvinyl chloride films prepared in the examples and comparative examples were left for a while until the temperature reached 5 ° C, 0 ° C, -5 ° C, -10 ° C, -15 ° C, and -20 ° C, respectively. In each temperature, using a DuPont type drop impact tester (manufactured by Yasuda Seiki Seisakusho) with a DuPont type (punching radius 6.35 mm, weight 500 g, drop height 100 mm), it is cracked into a polyvinyl chloride film. The temperature (cold shock resistant temperature) at which the occurrence occurs was evaluated.
◯: Cold shock resistant temperature is 0 ° C. or less.
X: Cold shock resistance temperature exceeds 0 degreeC.

(3) Weather resistance For polyvinyl chloride films prepared in Examples and Comparative Examples, using a weather resistance tester (for example, a sunshine weather meter) conforming to JIS B7753, the method conforming to JIS B7753 is used for 1000 hours. An accelerated weathering test was performed. About each polyvinyl chloride film, the degree of the discoloration after an accelerated weathering test was confirmed visually. The weather resistance was evaluated according to the following evaluation criteria.
○: Discoloration was not confirmed.
(Triangle | delta): The discoloration of the grade which does not influence on use was confirmed.
X: The discoloration of the grade which cannot be used was confirmed.

(4) Processability In Examples and Comparative Examples, a film forming apparatus provided with two rolls of a material containing a vinyl chloride resin, a plasticizer, and a cold shock resistant material prepared when producing a polyvinyl chloride film. Were kneaded for 10 minutes, a gap was formed between the two rolls, and the kneaded material was rolled to form a 0.2 mm thick sheet (film). The apparatus used in the processability evaluation is different from the apparatus provided with the inverted L-type calendar roll used in the manufacture of Example 1, but can evaluate the calendar processability. When forming the said sheet | seat, the following <1>-<4> items were evaluated and the following evaluation criteria evaluated. In addition, when the bank rotation of <1> is uneven, that is, when the bank rotation is not smooth, the thickness of the sheet may be uneven due to bank pulsation. Further, if the material has poor roll adhesiveness and the bank is in a slid state, a pin pole may be generated by entraining air as an appearance defect. Hereinafter, it is possible to determine an air scum or a flow mark according to << 2 >> and << 4 >>. The air scum is a defect that occurs when air remaining in the material draws dents and streaks during stretching, and in an extreme case, a hole is formed. Further, the flow mark is a defect that occurs when thickness unevenness occurs in the width direction and vertical stripes or wood-tone lines are drawn. The streaks change the luster and color, resulting in poor appearance and are also called bank marks.
<Evaluation items>
<1> Whether the sheet can be peeled off from the roll without load <2> Is there any unevenness in the bank rotation? <3> Is the material blown off the roll visually? <4> Appearance of the sheet (dents, streaks) , Presence of holes, etc.) Confirmation <Evaluation criteria>
◯: There were no problems for all the evaluation items of the above << 1 >> to << 4 >>.
Δ: There was no problem with the evaluation item of << 4 >>, but there was a problem with any of the evaluation items of << 1 >> to << 3 >>.
X: There was a problem with the evaluation item <4> above.

(Comprehensive evaluation)
As a result of the evaluation test, ◎ indicates that the evaluation results of (1) to (4) are all ◎, ◯ indicates that the evaluation results of (1) to (4) are ◯ or Δ, and (1 ) To (4) were evaluated as x when any of the evaluation results was x.

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

From the result of Table 1, Examples 1-9 were excellent in gasoline resistance, cold impact resistance, and workability. Examples 1, 3 and 5 were excellent in all evaluations of gasoline resistance, cold shock resistance, weather resistance and processability.

Example 1 using a cold shock resistant material containing silicone-acrylic rubber in the core part is more resistant to gasoline than Example 2 using diene rubber in the core part and Example 3 using acrylic rubber in the core part. And cold shock resistance equal to or higher than that of Example 2 and Example 3. Examples 1 and 3 in which the core part 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 part was a diene rubber.

Since the cold shock resistant material is more easily dissolved in gasoline than the vinyl chloride resin alone, the cold shock resistant material of Example 1 having a smaller cold shock resistant material amount is more resistant to the cold shock resistant material of Examples 4 and 9. It is thought that it was excellent in gasoline. Further, in Examples 4 and 9 where the amount of cold shock resistant material is larger than that in Example 1, since the powdered cold shock resistant material increases, the fluidity of the resin is lowered during processing, and the resin tends to be easily decomposed. Air scum and flow marks are likely to occur, and the workability is considered to be slightly lowered.

Since Example 1 has a larger amount of cold shock resistant material than Example 5, it is considered that the cold shock resistance was improved.

In Example 1 to which more plasticizers than Examples 6 to 8 were added, flexibility was imparted by the polyvinyl chloride film, and it was considered that the cold shock resistance was improved. Further, in Examples 6 to 8 in which the amount of the plasticizer is small compared to Example 1, the fluidity of the resin is lowered during processing, and the resin tends to be decomposed, so that air scouring and flow marks are easily generated, It is thought that the workability was slightly lowered.

On the other hand, Comparative Examples 1 to 6 have poor evaluation of at least one of gasoline resistance, cold shock resistance and workability, and obtain a polyvinyl chloride film having excellent gasoline resistance, cold shock resistance and workability. could not.

More specifically, in Comparative Examples 1 and 2 in which the content of the plasticizer exceeds the upper limit value of the present invention and the content of the cold shock resistant material is lower than the lower limit value of the present invention, the plastic that dissolves or swells in gasoline. It is thought 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 scope of the present invention, the workability was lowered.

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

In Comparative Example 5 in which the plasticizer content exceeds the upper limit of the present invention and the content of the cold shock resistant material is within the scope of the present invention, the amount of the plasticizer that is dissolved or swelled by gasoline is increased. Gasoline properties are thought to have declined.

In Comparative Example 6 in which the content of the plasticizer is within the range of the present invention and the content of the cold shock resistant material is lower than the lower limit value of the present invention, it is considered that the cold shock resistant material amount is small and the cold shock resistant property is lowered. It is done.

DESCRIPTION OF SYMBOLS 10 Marking film 11 Polyvinyl chloride film 12 Adhesive layer 13 Separator 14 Print layer 20 Molded product 100 Decorated molded product

Claims (6)

Including a vinyl chloride resin, a plasticizer, and a cold shock resistant material,
The plasticizer content 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 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 includes a core part and a shell part covering the core part,
The polyvinyl chloride film, wherein the core portion includes a rubbery polymer. 2. The polyvinyl chloride film according to claim 1, wherein the rubber-like polymer includes at least one selected from diene rubber, acrylic rubber, silicone rubber, and silicone-acrylic rubber. The polyvinyl chloride film according to claim 1 or 2, wherein the thickness is 60 µm or less. A marking film comprising the polyvinyl chloride film according to claim 1 and an adhesive layer. A decorative molded product comprising the polyvinyl chloride film according to any one of claims 1 to 3, an adhesive layer, and a molded product in this order. Including a step of forming a polyvinyl chloride film by calendering using the resin composition;
The resin composition includes a vinyl chloride resin, a plasticizer, and a cold shock resistant material,
The plasticizer content 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 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 includes a core part and a shell part covering the core part,
The method for producing a polyvinyl chloride film, wherein the core portion includes a rubber-like polymer.

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