JP2017165864A - Polyvinyl chloride substrate and marking film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyvinyl chloride substrate which has excellent flexibility and gasoline resistance and hardly causes blocking.SOLUTION: The polyvinyl chloride substrate contains a vinyl chloride resin, a polyester-based plasticizer, and a hydrogenated nitrile rubber. The number average molecular weight of the polyester-based plasticizer is 2,000 or more. The content of the polyester-based plasticizer is 30 pts.wt. or less based on 100 pts.wt. of the vinyl chloride resin. The content of the hydrogenated nitrile rubber is 1 to 30 pts.wt. inclusive based on 100 pts.wt. of the vinyl chloride resin.SELECTED DRAWING: Figure 1

Description

The present invention relates to a polyvinyl chloride substrate and a marking film.

The marking film is used by being affixed to a part of a vehicle such as a bicycle, a motorcycle, an automobile, a bus, a train, or the like, a part thereof, a home appliance, or the like. Since these sticking objects have a curved surface shape, the marking film is required to have followability to the curved surface shape. Furthermore, when the marking film is used in the above vehicle or these parts, since it may be exposed to gasoline, in addition to flexibility to a curved surface, gasoline resistance is required.

For example, in Patent Document 1, in a pressure-sensitive adhesive sheet having a base film and a pressure-sensitive adhesive layer provided on one surface thereof, as the base film, ethylene- ( A film using a metal salt of a (meth) acrylic acid copolymer is disclosed. Patent Document 2 discloses a decorative pressure-sensitive adhesive sheet in which a base material layer, a metal thin film layer, and a pressure-sensitive adhesive layer are laminated and integrated in this order, and the base material layer includes a predetermined amount of vinyl chloride resin, adipine. A decorative adhesive sheet, which is a vinyl chloride resin film containing an acid polyester plasticizer, a specific alkyl tin mercapto compound, an organic phosphite ester, and a benzophenone ultraviolet absorber, is disclosed.

JP 2006-8835 A JP 2008-213387 A

In general, a plasticizer is added to the vinyl chloride resin in order to impart flexibility. However, when the plasticizer is dissolved in gasoline, the film may swell or shrink. On the other hand, if the amount of the plasticizer added is decreased in order to obtain gasoline resistance, the flexibility of the film is lowered, so that it is difficult to achieve both gasoline resistance and flexibility. In view of the above, there has been a demand for a marking film substrate having both excellent flexibility and gasoline resistance.

In order to achieve both flexibility and gasoline resistance in a polyvinyl chloride base material, the present inventors have studied the types of plasticizers, have good compatibility with vinyl chloride resins, and are relatively soluble in gasoline. Because it is difficult, we focused on using polyester plasticizers. Furthermore, by examining the amount of polyester plasticizer added and reducing the amount of polyester plasticizer, the gasoline resistance of the polyvinyl chloride base material is improved and the amount of plasticizer added decreases. It has been found that the flexibility of the polyvinyl chloride substrate can be compensated by adding hydrogenated nitrile rubber. On the other hand, the present inventors have found that when the addition amount of hydrogenated nitrile rubber is excessive, blocking occurs in the polyvinyl chloride base material, and by adding the addition amount of hydrogenated nitrile rubber to a predetermined amount. The present inventors have found that a polyvinyl chloride base material that is flexible and hardly generates blocking can be obtained. As a result, by adding a predetermined amount of polyester plasticizer and a predetermined amount of hydrogenated nitrile rubber to vinyl chloride resin, it has excellent flexibility and gasoline resistance, and blocking occurs. It was found that a difficult polyvinyl chloride substrate was obtained, and the present invention was completed.

The polyvinyl chloride base material of the present invention contains a vinyl chloride resin, a polyester plasticizer, and a hydrogenated nitrile rubber. The polyester plasticizer has a number average molecular weight of 2000 or more, and the polyester plastic The content of the agent is 30 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin, and the content of the hydrogenated nitrile rubber is 1 part by weight or more with respect to 100 parts by weight of the vinyl chloride resin. It is 30 parts by weight or less.

The polyester plasticizer is preferably an adipic acid polyester plasticizer.

The number average molecular weight of the polyester plasticizer is preferably 3500 or less.

The amount of bound acrylonitrile in the hydrogenated nitrile rubber is preferably 35% or more and 60% or less.

The iodine value of the hydrogenated nitrile rubber is preferably 25 mg / 100 mg or less.

The marking film of the present invention is characterized by having the polyvinyl chloride base material of the present invention, an adhesive layer, and a separator in this order.

Furthermore, it is preferable to have a printing layer on the side opposite to the pressure-sensitive adhesive layer of the polyvinyl chloride base material.

The polyvinyl chloride base material of the present invention has excellent flexibility and gasoline resistance and is less likely to cause blocking. Since the marking film of the present invention has the polyvinyl chloride base material of the present invention, it can follow a curved surface shape, has gasoline resistance, and is unlikely to cause blocking.

It is sectional drawing which showed the marking film of this embodiment typically. It is sectional drawing which showed an example of the decorative molded product typically.

The polyvinyl chloride base material of the present invention contains a vinyl chloride resin, a polyester plasticizer, and a hydrogenated nitrile rubber. The polyester plasticizer has a number average molecular weight of 2000 or more, and the polyester plastic The content of the agent is 30 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin, and the content of the hydrogenated nitrile rubber is 1 part by weight or more with respect to 100 parts by weight of the vinyl chloride resin. It is 30 parts by weight or less.

The polyvinyl chloride base material of the present invention contains a vinyl chloride resin, a polyester plasticizer, and a hydrogenated nitrile rubber. Since the polyvinyl chloride base material has good elongation and is difficult to break, it can be easily attached to a three-dimensional curved surface. Moreover, since it is excellent in printability and softens at a relatively low temperature, it is suitable as a substrate for a marking film. In the present invention, a polyester plasticizer is added to the vinyl chloride resin in order to impart flexibility. The polyvinyl chloride resin itself is hardly affected by gasoline, but the polyester plasticizer may dissolve in gasoline and the polyvinyl chloride base material may swell or shrink. Therefore, the addition amount of the polyester plasticizer is adjusted, and the decrease in flexibility due to the decrease in the addition amount of the polyester plasticizer is compensated by adding the hydrogenated nitrile rubber.

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 a degree of polymerization of 800 or more and 1400 or less. In general, the higher the 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, as the degree of polymerization of the vinyl chloride resin is higher, even if the added polyester plasticizer is swollen by gasoline, the occurrence of problems such as curling and undulation of the polyvinyl chloride base material can be suppressed. Inferred. If the degree of polymerization of the vinyl chloride resin is less than 800, the melt tension when dissolved by heating may be reduced, making it 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 polymerization degree of the vinyl chloride resin exceeds 1400, the entanglement of the polymer chain becomes strong, so that the shearing force is increased when the film is drawn and formed into a film by calendaring or the like, and the film formability is lowered. There is a risk. The minimum with more preferable polymerization degree of the said vinyl chloride resin is 1200, and can improve gasoline resistance more.

The polyvinyl chloride base material of the present invention contains a polyester plasticizer as a plasticizer. The polyester plasticizer has good compatibility with the vinyl chloride resin. Further, since it is a polymer as compared with a phthalic acid plasticizer generally used as a plasticizer for vinyl chloride resin, it is difficult to dissolve and swell in gasoline. Therefore, by using a polyester plasticizer, gasoline resistance can be improved while imparting flexibility to the polyvinyl chloride base material.

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. When the number average molecular weight of the polyester plasticizer is less than 2,000, the polyester plasticizer tends to 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 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. The film forming property may be increased and the film formability may be reduced. 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 base material. 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 base material 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 were 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.

The content of the polyester plasticizer is 30 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin. If the polyester plasticizer is not added, the polyvinyl chloride base material is not flexible enough to follow the curved surface shape. On the other hand, when the content of the polyester plasticizer exceeds 30 parts by weight, the amount of the polyester plasticizer that dissolves or swells with gasoline increases, and the gasoline resistance of the polyvinyl chloride base material decreases. The polyester plasticizer may be added, and the lower limit is not particularly limited, but is preferably 0.1 parts by weight or more. The minimum with more preferable content of the said polyester plasticizer is 1 weight part, A preferable upper limit is 25 weight part, Furthermore, a preferable minimum is 5 weight part.

The polyvinyl chloride base material of the present invention contains hydrogenated nitrile rubber. Hydrogenated nitrile rubber has good compatibility with vinyl chloride resin and has gasoline resistance, so adding it to vinyl chloride resin not only gives flexibility to the resulting polyvinyl chloride base material. Can improve gasoline resistance. Moreover, since it has heat resistance, weather resistance, and cold impact resistance, the heat resistance, weather resistance, and cold impact resistance of the polyvinyl chloride substrate can be improved.

The hydrogenated nitrile rubber is obtained by hydrogenating an unsaturated bond contained in a copolymer of butadiene and acrylonitrile. The method for producing the hydrogenated nitrile rubber is not particularly limited. For example, acrylonitrile and butadiene are emulsion-polymerized, solidified and dried to produce acrylonitrile butadiene rubber (NBR), and the obtained NBR is treated with, for example, sulfur. Or the method of hydrogenating using an organic peroxide and obtaining hydrogenated nitrile rubber is mentioned. Moreover, you may use a commercial item.

The amount of bound acrylonitrile in the hydrogenated nitrile rubber is preferably 35% or more and 60% or less. If the amount of bound acrylonitrile is less than 35%, gasoline resistance may be insufficient. On the other hand, if the amount of bound acrylonitrile exceeds 60%, flexibility and cold shock resistance may be reduced. A more preferred upper limit for the amount of bound acrylonitrile is 50%, and a more preferred lower limit is 40%. The amount of the combined acrylonitrile can be measured by a measuring method based on JIS K 6384.

The iodine value of the hydrogenated nitrile rubber is preferably 25 mg / 100 mg or less. When the iodine value exceeds 25 mg / 100 mg, the amount of residual double bonds increases, so that the weather resistance may be deteriorated. A more preferable upper limit of the iodine value is 23 mg / 100 mg. When double bonds that are not hydrogenated are present in the main chain of the hydrogenated nitrile rubber, the weather resistance of the resulting polyvinyl chloride substrate is lowered. Therefore, the lower the iodine value, the better. The iodine value can be measured by a measuring method based on JIS K 6235.

As the hydrogenated nitrile rubber, those having a bound acrylonitrile amount of 35% to 60% and an iodine value of 25 mg / 100 mg or less are suitable. Specifically, Zetpol0020, Zetpol1000L, Zetpol1010, Zetpol1020, etc. manufactured by Nippon Zeon Co., Ltd. can be used.

The content of the hydrogenated nitrile rubber is 1 part by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin. When the content of the hydrogenated nitrile rubber is less than 1 part by weight, the gasoline resistance of the polyvinyl chloride base material is lowered. Moreover, the flexibility which can follow a curved surface shape cannot be obtained. On the other hand, when the content of the hydrogenated nitrile rubber exceeds 30 parts by weight, blocking occurs in the polyvinyl chloride base material. The minimum with preferable content of the said hydrogenated nitrile rubber is 5 weight part, and a more preferable minimum is 10 weight part.

The polyvinyl chloride base material may be transparent or colored. When the polyvinyl chloride base material is transparent, it is possible to decorate using the decoration of the surface of the molded product to which the marking film is attached. The polyvinyl chloride base material may further contain titanium oxide. By containing titanium oxide, it is possible to improve the concealment property when pasted on a sticking object. Moreover, when the printing layer mentioned later is formed, since a polyvinyl chloride base material can be colored white, the coloring of a printing layer can be made favorable. Moreover, the weather resistance of a polyvinyl chloride base material can be improved more.

The content of the titanium oxide is preferably 1 part by weight or more and 40 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin. When the content of the titanium oxide is within the above range, the titanium oxide does not bleed on the surface of the polyvinyl chloride base material, and the weather resistance and concealment are improved, and the color of the printing layer is improved. it can. The minimum with more preferable content of the said titanium oxide is 5 weight part, and a more preferable upper limit is 35 weight part.

The polyvinyl chloride base material is within the range not impairing the effects of the present invention, and as necessary, such as stabilizers, ultraviolet absorbers, lubricants, modifiers, fillers such as inorganic particles and inorganic fibers, and diluents. An additive 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 to 5.0 parts by weight 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 the said ultraviolet absorber is contained, the content has preferable 0.3-2.0 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 substrate may be bleed.

The method for producing the polyvinyl chloride base material is not particularly limited. For example, after blending a vinyl chloride resin, a polyester plasticizer, and a hydrogenated nitrile rubber using a blender or the like, it is formed by calendering or the like. can do.

The polyvinyl chloride base material preferably has an elongation represented by the following formula (1) of 100% or more.

（式中、Ｌ_０は、初めの標線間距離（ｍｍ）であり、Ｌ_１は、切断時の標線間距離（ｍｍ）である。）

(In the formula, L ₀ is the initial distance between marked lines (mm), and L ₁ is the distance between marked lines at the time of cutting (mm).)

The elongation of the polyvinyl chloride substrate is measured by a method based on the tensile test of JIS K 6732. The measurement temperature is 21 ° C to 25 ° C. As will be described later, when the polyvinyl chloride base material is used as a marking film base material, it is used by being attached to a molded product at room temperature. Therefore, the polyvinyl chloride base material preferably has sufficient flexibility at room temperature (21 ° C. to 25 ° C.). When the elongation of the polyvinyl chloride base material is less than 100%, the flexibility of the polyvinyl chloride base material is insufficient, and it may be difficult to attach to the molded product. A more preferable lower limit of the elongation of the polyvinyl chloride base material is 150%.

Below, the marking film which concerns on this embodiment is demonstrated using FIG. FIG. 1 is a cross-sectional view schematically showing the marking film of the present embodiment. The marking film 10 shown in FIG. 1 has a polyvinyl chloride base material 11, an adhesive layer 12, and a separator 13 in this order. The marking film 10 further has a printing layer 14 on the opposite side of the polyvinyl chloride substrate 11 from the pressure-sensitive adhesive layer 12.

[Polyvinyl chloride substrate]
The marking film 10 has the polyvinyl chloride base material (polyvinyl chloride base material 11) of the present invention as a base material. Since the polyvinyl chloride base material 11 has excellent flexibility and gasoline resistance and is difficult to cause blocking, the marking film 10 provided with the polyvinyl chloride base material 11 can follow the curved surface shape. Yes, it has gasoline resistance, and blocking hardly occurs.

The preferable minimum of the thickness of the polyvinyl chloride base material 11 is 30 micrometers, and a preferable upper limit is 300 micrometers. When the thickness of the polyvinyl chloride film layer is less than 30 μm, it may become too thin when being attached to a substrate having a three-dimensional curved surface portion, and the base may be transparent. When the thickness of the polyvinyl chloride base material exceeds 300 μm, there is a possibility that the tracking property of the marking film becomes insufficient when it is attached to a base material having a three-dimensional curved surface portion. A more preferred lower limit is 40 μm, a more preferred upper limit is 250 μm, a still more preferred lower limit is 50 μm, and a still more preferred upper limit is 200 μm.

[Adhesive layer]
The pressure-sensitive adhesive layer 12 can contain a pressure-sensitive adhesive usually used in the field of 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 substrate 11 opposite to the pressure-sensitive adhesive layer 12. Printing on the polyvinyl chloride substrate 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 base material 11 may have a fine unevenness | corrugation by the embossing etc. in the surface on the opposite side to an adhesive 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 substrate 11 is obtained by melt-kneading a vinyl chloride resin, a polyester plasticizer, and a hydrogenated nitrile rubber using a blender or the like. It can be formed by calendering or the like. 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 substrate 11. When the marking film 10 has the printing layer 14, the printing layer 14 may be formed before or after the pressure-sensitive adhesive layer 12 is laminated on the polyvinyl chloride substrate 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.

The polyvinyl chloride substrate 11 can also be used as a substrate 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. Therefore, when using the polyvinyl chloride base material 11 also as a base material of a decoration film, the elongation of the said polyvinyl chloride base material may be less than 100% at normal temperature.

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.

FIG. 2 is a cross-sectional view schematically showing an example of a decorative molded product. As shown in FIG. 2, the decorative molded product 100 is affixed to the molded product 20 via the pressure-sensitive adhesive layer 12, and is laminated in the order of the molded product 20, the pressure-sensitive adhesive layer 12, and the polyvinyl chloride base material 11. Is done. Furthermore, you may have the printing layer 14 on the opposite side to the adhesive layer 12 of the polyvinyl chloride base material 11. FIG. The decorative molded product has gasoline resistance.

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 polyester plasticizer, 10 parts by weight of hydrogenated nitrile rubber and 35 parts by weight of titanium dioxide are added to 100 parts by weight of vinyl chloride resin having an average degree of polymerization of 1000, and melted for 15 minutes using a blender. The mixture was kneaded to obtain a molten mixture (PVC compound). The obtained PVC compound was calendered using an inverted L-type calendar roll to obtain a polyvinyl chloride base material of Example 1. As the polyester plasticizer, an adipic acid polyester plasticizer having a number average molecular weight of 2600 (ADEKA PN-7535 manufactured by ADEKA Corporation) was used. As the hydrogenated nitrile rubber, hydrogenated nitrile rubber (Zetpol 0020 manufactured by Nippon Zeon Co., Ltd.) having a combined acrylonitrile amount of 49.2% and an iodine value of 23 mg / 100 mg was used. The film thickness of the polyvinyl chloride substrate was 50 μm.

(Examples 2 to 9 and Comparative Examples 1 to 5)
Polyvinyl chloride substrates according to Examples 2 to 9 and Comparative Examples 1 to 5 were produced in the same manner as in Example 1 except that the formulation was changed as shown in Table 1 below. In Comparative Example 5, an adipic acid polyester plasticizer having a number average molecular weight of 1200 (Adekaizer PN-7230, manufactured by ADEKA Corporation) was used as the polyester plasticizer.

(Evaluation of polyvinyl chloride substrate)
About the polyvinyl chloride base material produced by the Example and the comparative example, the following method evaluated (1) elongation, (2) gasoline resistance, and (3) blocking property. From the results of (1) to (3), comprehensive evaluation was performed. Furthermore, (4) appearance and (5) weather resistance of the polyvinyl chloride base materials produced in Examples and Comparative Examples were evaluated by the following methods.

（式中、Ｌ_０は、初めの標線間距離（ｍｍ）であり、Ｌ_１は、切断時の標線間距離（ｍｍ）である。）
○：基材の伸びが１５０％以上
△：基材の伸びが１００％以上、１５０％未満
×：基材の伸びが１００％未満 (1) Elongation The polyvinyl chloride base materials produced in the examples and comparative examples are subjected to a tensile test by a method based on JIS K 6732, and the elongation L represented by the following formula (1) is evaluated according to the following evaluation criteria. did. The measurement temperature was 23 ° C. and the tensile speed was 200 mm / min.

(In the formula, L ₀ is the initial distance between marked lines (mm), and L ₁ is the distance between marked lines at the time of cutting (mm).)
○: Elongation of substrate is 150% or more Δ: Elongation of substrate is 100% or more and less than 150% X: Elongation of substrate is less than 100%

(2) Gasoline resistance The polyvinyl chloride base materials prepared in Examples and Comparative Examples were immersed in a mixed solvent of isooctane and toluene (mixing ratio 1: 1) for 24 hours. Then, each polyvinyl chloride base material was taken out from the mixed solvent, and the state of each polyvinyl chloride base material was confirmed visually. Gasoline resistance was evaluated according to the following evaluation criteria. “Change” in the following evaluation criteria means that the film is wavy or curled.
○: No change △: There was a change that did not affect use ×: There was a change that could not be used

(3) Blocking property Five polyvinyl chloride substrates produced in the examples and comparative examples were stacked one above the other, sandwiched between two glass plates, loaded with 5 kg, and left at 60 ° C. for 1 hour. Thereafter, the laminated polyvinyl chloride base material was peeled off, and the blocking state was confirmed visually. The blocking property was evaluated according to the following evaluation criteria.
○: Blocking was not confirmed Δ: Blocking to the extent that it does not affect use was confirmed ×: Blocking to the extent that it could not be used was confirmed

(4) Appearance of base material The surface of the polyvinyl chloride base material prepared in Examples and Comparative Examples was visually observed using a lighting device under reflected light to confirm the presence or absence of a flow mark. The appearance of the substrate was evaluated according to the following evaluation criteria.
○: No flow mark was observed Δ: A flow mark that did not affect the use was observed ×: A flow mark that could not be used was observed

(5) Weather resistance For the polyvinyl chloride base materials produced in Examples and Comparative Examples, using a weather resistance tester (for example, a sunshine weatherometer) based on JIS B7753, a method based on JIS B7753 is used. A time accelerated weathering test was performed. About each polyvinyl chloride base material, the degree of the discoloration after an accelerated weathering test was confirmed visually. The weather resistance was evaluated according to the following evaluation criteria.
○: No discoloration confirmed △: Discoloration to the extent that does not affect use was confirmed ×: Discoloration to the extent that it could not be used was confirmed

As a result of the evaluation test, ◎ indicates that the evaluation results of (1) to (3) are all ◎, ◯ indicates that the evaluation results of (1) to (3) are ◯ or Δ, and (1 ) To (3) were evaluated as x when any of the evaluation results was x.

Tables 1 and 2 show the configurations and evaluation results of the polyvinyl chloride base materials according to Examples and Comparative Examples.

From the results shown in Tables 1 and 2, Examples 1 and 2 were excellent in film elongation and gasoline resistance, and the occurrence of blocking was sufficiently suppressed. In Examples 3 to 9, although some evaluations of film elongation, gasoline resistance, and blocking properties were somewhat low, they had sufficient quality as a polyvinyl chloride base material. On the other hand, Comparative Examples 1-5 were inadequate as a polyvinyl chloride base material, in which any evaluation of the elongation of a film, gasoline resistance, and blocking property was bad.

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

Claims (7)

Contains vinyl chloride resin, polyester plasticizer, and hydrogenated nitrile rubber,
The polyester plasticizer has a number average molecular weight of 2000 or more,
The polyester plasticizer content is 30 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin.
Content of the said hydrogenated nitrile rubber is 1 to 30 weight part with respect to 100 weight part of said vinyl chloride resins, The polyvinyl chloride base material characterized by the above-mentioned. The polyvinyl chloride substrate according to claim 1, wherein the polyester plasticizer is an adipic acid polyester plasticizer. The polyvinyl chloride base material according to claim 1 or 2, wherein the number average molecular weight of the polyester plasticizer is 3500 or less. The polyvinyl chloride base material according to any one of claims 1 to 3, wherein the amount of bound acrylonitrile of the hydrogenated nitrile rubber is 35% or more and 60% or less. The polyvinyl chloride base material according to claim 1, wherein the hydrogenated nitrile rubber has an iodine value of 25 mg / 100 mg or less. A marking film comprising the polyvinyl chloride substrate according to claim 1, an adhesive layer, and a separator in this order. Furthermore, it has a printing layer on the opposite side to the said adhesive layer of the said polyvinyl chloride base material, The marking film of Claim 6 characterized by the above-mentioned.

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