WO1996027500A1

WO1996027500A1 - Pattern-carrying vinyl chloride marking sheet

Info

Publication number: WO1996027500A1
Application number: PCT/JP1995/000365
Authority: WO
Inventors: Yasukichi Ogasawara; Takashi Morikawa; Naoki Hasegawa; Keizo Ogata; Yasunori Kimura; Motohiko Kashioka
Original assignee: Toyo Ink Manufacturing Co., Ltd.
Priority date: 1995-03-07
Filing date: 1995-03-07
Publication date: 1996-09-12

Abstract

A pattern-carrying vinyl chloride marking sheet obtained by transferring a pattern from transfer foil, on which a pattern is formed, onto a surface of a heat adhesive resin-containing vinyl chloride marking sheet or onto a heat adhesive resin layer provided on one surface of a vinyl chloride marking sheet. This invention further relates to a pattern-carrying vinyl chloride marking sheet obtained by casting a vinyl chloride resin on a pattern-carrying transfer ink layer of transfer foil. This invention further relates to a pattern-carrying vinyl chloride marking sheet obtained by transferring a letter or a figure from a heat-sensitive transfer ribbon onto a pattern on a pattern-carrying vinyl chloride marking sheet material.

Description

Description Vinyl chloride marking sheet with design pattern

In the present invention, a vinyl chloride marking sheet for decorative display materials used for various decoration and display is used. More specifically, a vinyl chloride marking plate with an excellent design by applying a pattern using a transfer foil, and a thermal transfer ribbon on the pattern of the vinyl chloride marker with a pattern Use vinyl chloride marking sheet with design pattern that can be used for any patterning. Background art

In general, polyester resins and urethane resins rich in toughness and beautification of, Oh Rui moderate waist strength required at the time of construction, namely the yield stress l~6 Kg / mm ^2, the film thickness of about 3 0-1 5 A marking sheet made of polyvinyl chloride resin having a thickness of 0 m has excellent characteristics such as weather resistance and dimensional stability. For this reason, accent stripes and various emblems for automobiles, tank stria and various emblems for motorcycles, trucks-markings for vehicles such as commercial vehicles, signage members for indoor and outdoor advertisements, various inner panels, window displays It is commonly used as a decorative marking material for, etc. Such a marking sheet is generally made of a single-color solid color, and as a means for applying a decorative graphic, the marking sheet is directly cut out with a cutting machine or the like and used as a character or a pattern, or a character or a pattern is used. The sign was created by providing a printing method such as silk screen printing on the marking sheet.

Of these processing means, the cutting out of the pattern by the cutting machine is performed by cutting the minimum cutout area that constitutes the target character / design. There is a limit to the creation of fine or complicated characters and patterns because of the limitations of the accuracy of the printing machine. Also, fixing large characters and designs consisting of multiple hues to the surface to be processed requires the same number of application films as hues, which is uneconomical and inefficient. In addition, there is a problem that the work of transferring cutout characters and designs to the application film is complicated and time-consuming, and that only those with low designability can be obtained.

Silk screen printing, which is used as a painting process, is capable of creating complex characters and patterns, but is inferior in immediacy due to the process of making, proofing, and printing. In particular, there is a problem in that even if only a small number of sheets are required, it cannot be produced at low cost because the process of making and proofing the plate accounts for most of the cost.

In recent years, in order to solve the problems in power-pressing and silk-screen printing as a means for applying patterns, to meet the demands for inexpensive and multi-color expression, and to obtain immediacy and fine characters and patterns The marking process has been applied to the markin sheet by the ink jet recording method and has been put to practical use.

In the ink jet recording method, since an image is formed by dots, a pattern having a halftone can be obtained, and the cost and the immediacy are considerably improved. However, at present, the resolution is low and it is not suitable for displaying small designs and minute characters, and the maintenance and inspection such as the clogging of the ink nozzles is complicated, which has problems. In addition, since a dye is generally used as an ink, it has poor weather resistance, heat resistance, and water resistance, and is not suitable for long-term outdoor use.

The present inventors have conducted intensive studies in view of such a problem, and have disclosed in Japanese Patent Application Laid-Open Nos. 5-850 and 5-22471 a marking sheet using a thermal transfer method. By presenting a patterning method and using a thermal transfer ribbon and a markinda sheet having ripening transfer receptivity, it is possible to dramatically improve the adhesion, thermal resistance, scratch resistance, and other various resistances of the thermal transfer ink. thing And disclosed the technology.

However, in recent years, various kinds of display materials and the like have been upgraded, and a marking sheet to be subjected to arbitrary patterning is desired to be a single-color solid color to have a higher quality and higher decorativeness. In such a point, the above-described thermal transfer technology is useful for patterning on a single-color, plain marking sheet, but it has a high-grade woodgrain or marble tone used for a highly decorative nameplate or the like. In order to perform patterning including patterns, the underlying pattern not only required a half-tone hue, but also was extremely delicate and could not be realized at all.

For this reason, the use of conventionally known silk screen printing or gravure printing is considered in order to form a pattern. Silk screen printing is generally very difficult to perform high-definition and full-color printing including halftones. In some cases, the ink thickness of the part becomes thicker, resulting in inferior fineness and luxury. On the other hand, gravure printing has almost eliminated the disadvantages of silk screen printing. However, in the case of gravure printing, especially in the case of a polyvinyl chloride marking sheet made of a polyvinyl chloride resin which is preferable as a marking sheet, additives generally added to impart flexibility, especially heat stabilizers and plasticizers Due to bleeding on the surface, the suitability for gravure printing is low, and printing is difficult due to swimming, pinholes, poor leveling, etc. on the printing surface. Further, there are problems such as blocking due to a residual solvent and elongation due to tension during printing.

As another pattern forming means, a transfer foil is generally used for a plastic substrate or the like. However, there is no application example for forming a design pattern on a marking sheet which is generally used as a display member for an indoor / outdoor public notice or the like, a variety of guide boards, a display member for a window display or the like. When the present inventors actually tried the transfer foil on a vinyl chloride marking sheet, heat shrinkage of the ripening roll during transfer occurred. In addition, if the transfer was performed at a lower temperature to avoid this, it was possible to transfer a highly colorful pattern. It was confirmed that the adhesion to the surface of the vinyl chloride marking sheet was poor, and that there was a limit to the adhesive layer of the transfer foil alone. This is probably due to the low melt adhesion of the vinyl chloride marking sheet.

Further, on a marking sheet including a pattern pattern such as a woodgrain pattern or a marble pattern pattern having a high sensation used for a nameplate or the like having a high decorative property as described above, patterning of a finer character-pattern by a ripening transfer method may be performed. Is also conceivable. However, in this case, in the case of a pattern other than the above, for example, in forming a pattern by silk screen printing, the printed surface after printing the base pattern is subjected to heat transfer because the thickness of the printed portion is large. Has a problem that the unevenness is remarkable and the thermal transfer receptivity is remarkably low. As described above, the patterning including the delicate and fine woodgrain-like and marble-like base patterns, which are used for nameplates with high decorativeness in the conventional method, can be carried out on the masking sheet. Did not.

Therefore, the present invention is directed to a marking sheet having a pattern that is small in size, can be produced at a low cost, has high production efficiency, and has a high-class feeling and high decorativeness, without requiring complicated processing steps. It is intended to be provided. Further, the present invention aims at providing a marking sheet having a pattern pattern in which characters and patterns are clearly and easily formed on the marking sheet with the pattern, and the present invention is further required for marking work. The purpose of the present invention is to provide a marking sheet having a design pattern that has excellent flexibility, dimensional stability, and weather resistance, and also has excellent adhesion of designs and characters. Disclosure of the invention

In the present invention, a pattern is formed on a surface of a vinyl chloride marking sheet containing a mature adhesive resin, or on a mature adhesive resin layer of a vinyl chloride marking sheet provided with a thermal adhesive resin on one surface. An elaborate pattern obtained by transferring a pattern from a transfer foil with a transfer transfer layer provided on the support Inspect on a vinyl chloride marking sheet that has been subjected to the same procedure.

Also, the present invention provides a method for producing a vinyl chloride marker by using a transfer foil having a transfer ink layer provided on a support as a process paper, casting a vinyl chloride resin solution on the transfer foil, and heating the film to form a film. The design is transferred to the dasheet and the PVC pattern marking sheet is printed with a sophisticated pattern. Further, the present invention provides a thermal transfer recording method using a thermal transfer recording type printer on the pattern of the vinyl chloride marking sheet obtained in this manner, thereby enabling arbitrary characters, designs, etc., which are rich in multicolor expression. The present invention relates to a vinyl chloride marking sheet formed easily, inexpensively, and instantly on a high-quality, fine and finely grounded vinyl chloride marking sheet with a base pattern. BEST MODE FOR CARRYING OUT THE INVENTION

The present invention relates to a method for manufacturing a vinyl chloride marking sheet containing a mature adhesive resin, or on a mature adhesive resin layer of a vinyl chloride marking sheet having a mature adhesive resin layer provided on one surface thereof, A pattern obtained by superimposing the transfer ink layer surface of the transfer foil provided on the support and melting and transferring the transfer ink layer by, for example, heating using a hot roll or a mature plate, or a pressure bonding means was applied. Check with vinyl chloride marking sheet.

Furthermore the glass transition temperature of該熟adhesive resin (hereinafter, referred to as T g) gar 3 0 ° (: ~ 1 2 0 e C or a softening or melting point is 1 0 ^{^e} C~2 0 0 ^e C der, The present invention relates to a vinyl chloride marking sheet provided with a pattern made of a vinyl chloride resin having transferability and adhesion of a transfer ink, that is, using the heat-adhesive resin which can be easily melted by the heat given at the time of transfer. In this way, the contact interface between the transfer ink and the vinyl chloride marking sheet is easily hot-melt-bonded with heat and pressure during transfer, so that a pattern having excellent transferability and adhesion can be obtained.

Further, the present invention provides a method in which a resin pattern is cast on a process paper on which a desired pattern pattern has been formed by a transfer ink and heated, whereby the pattern pattern is formed simultaneously with film formation. The present invention relates to a vinyl chloride marking sheet with a design to be transferred. Further, in the present invention, an arbitrary character / pattern is patterned on a surface of the vinyl chloride masking sheet having a pattern formed with a transfer foil using the above-mentioned method or the like using a ripening image transfer ribbon. The present invention relates to a vinyl chloride marking sheet with a design pattern.

A sheet containing a thermo-adhesive resin in the vinyl chloride marking sheet of the present invention containing a heat-adhesive resin in order to improve the transferability of the design pattern by the transfer foil is 1 to 40 parts by weight based on 100 parts by weight of the resin. The resin composition containing a part of the mature adhesive resin can be produced by sheet molding. Examples of the sheet forming method include a known extrusion method, for example, a calendar method, a solution casting method, a sol casting method, a semi-sol casting method, and the like. Among them, a sol-cast method or a semi-sol-cast method that does not involve hot roll processing at the time of sheet molding is suitable because the resin composition contains a mature adhesive resin. Further, in order to prevent sticking of the vinyl chloride marking sheet when the sheet is manufactured by a heat molding process such as a calendar method, or to secure appropriate flexibility required at the time of applying the thermal transfer recording material of the present invention. It is preferable to include a thermoadhesive resin in the range of 5 to 20 parts by weight.

For example, when manufacturing a vinyl chloride masking sheet containing a thermo-adhesive resin using the casting method, first, a polyvinyl chloride resin, a mature adhesive resin, a plasticizer, a suitable solvent, Accordingly, various additives are mixed and stirred to form a paste-like sol-like high-viscosity coating liquid, and a support having a release property, such as a silicon-containing release process paper or a stainless steel whose surface has been release-treated. After casting on a sheet, heat and melt under the conditions of about 160 to 22 CTC and about 1 to 10 minutes, a vinyl chloride marking sheet with the desired thickness of 30 to 150 um Can be obtained. Examples of the solvent include organic solvents such as butanol, butyl acetate, ethylene glycol monomethyl ether acetate, diisobutyl ketone, xylol, cyclohexanone, aromatic petroleum naphtha, sorbent naphtha, tricrene, and the like. Examples of the solvent for the solvent include:

Further, in the present invention, by providing a transfer image-receiving layer containing a heat-adhesive resin as a main component on the vinyl chloride marking sheet, the transferability of the base pattern by the transfer foil can be improved. Examples of the method for producing the transfer image receiving layer include the following production methods. Solvent coating method in which a coating solution in which the composition for forming the transfer image receiving layer is dissolved or dispersed in a solvent or water is coated on a vinyl chloride marking sheet and then dried, or the composition constituting the image receiving layer is ripened and melted Hot-melt coating method for coating on vinyl chloride marking sheet. The thickness of the image receiving layer is 0.1 to

It is preferably about 1 Om, more preferably about 0.2 to 2 m.

The vehicle image-receiving layer contains a heat-adhesive resin as a main component, and may contain various additives as necessary, for example, a plasticizer, a coloring material, an ultraviolet absorber, an antistatic agent, and the like.

Further, in the present invention, a marking sheet manufacturing method by a casting method in which a solvent in the resin liquid is dried by heating after casting the resin liquid, and an image by a transfer ink on a casting process paper. It can also be combined with pattern formation. By this method, the pattern on the process paper can be easily transferred to the marking sheet by the effect of the high temperature and the thermal solvent during the film formation. This causes a problem when forming a design pattern using a transfer foil on the above-mentioned vinyl chloride resin-made marker sheet, such as shrinkage of the marking sheet due to high temperature during transfer or transfer during transfer at low temperature. Improper transfer and poor transfer adhesion can be solved at once. Furthermore, since the production of the marking sheet and the formation of the pattern can be performed at the same time, it is very useful in terms of production efficiency and cost.

By the above manufacturing method, it is possible to form a high-quality design pattern with high decorativeness and designability on the marking sheet without causing heat shrinkage or poor adhesion of the marking sheet. Thermal bonding for better adhesion The conductive resin may be contained in the resin solution for casting or in the transfer ink on the process paper, or the mature adhesive resin layer may be further provided on the transfer ink waste on the process paper.

Further, the present invention is characterized in that arbitrary characters and patterns are patterned by using a thermal transfer ribbon on the pattern pattern forming surface of a vinyl chloride marking sheet on which a pattern pattern is formed in advance using a transfer foil. To provide a vinyl chloride marking sheet with a design pattern.

In the present invention, in a state in which the pattern forming surface of the vinyl chloride marking sheet with a pattern and the heat-meltable ink layer surface of the thermal transfer ribbon are overlapped, heat is applied from the opposite surface of the heat-meltable ink layer surface of the heat-sensitive transfer ribbon to the thermal transfer ribbon. The heat-meltable ink layer is transferred using a heating means by a pad, and an image such as a character or a figure is formed directly on the pattern of the vinyl chloride marking sheet. In addition, the vinyl chloride marking sheet with a pattern obtained by the sensitized transfer recording method of the present invention can be specifically produced using a thermal transfer printer that is easy to maintain. It is possible to obtain images of desired characters and designs at a resolution according to the ripening element density of the thermal head on a high-grade decorative and highly decorative pattern-patterned vinyl chloride marking sheet with low cost and immediateness. Very useful. In this case, it is possible to obtain a recorded matter having excellent expressive power by performing the transfer many times with the thermal transfer ribbons having different hues. Of course, it is also possible to use in combination with existing image forming means such as silk screen printing, to perform cutting after ripening transfer recording, to cut into an arbitrary shape, or to laminate the recording surface with a transparent plastic film.

The vinyl chloride resin used in the present invention has a degree of polymerization of from 300 to 200, preferably from 600 to 150. In the present invention, as the vinyl chloride resin, as a vinyl chloride resin alone or as a copolymer component of vinyl chloride, an olefin monomer, a gen monomer, a vinyl halide monomer, an acrylate ester monomer can be used. Body, vinyl ester monomer, vinyl ester Resins containing one-ter monomer, styrene derivative and the like can be mentioned. More specifically, a copolymer resin such as a vinyl chloride resin, an ethylene-vinyl chloride resin, a vinyl acetate-vinyl chloride resin, an ethylene monoacetate-vinyl chloride resin, and a polyurethane vinyl chloride resin, or a graft copolymer resin may be used. Can be The vinyl chloride copolymer resin may be used alone, or two or more of them may be used in combination. Generally, rich in toughness and beautification of moderate waist strength required at the time of construction, namely the yield stress 1~6 Κ ₈ ιηΓη ^2, a film thickness of about. 30 to 0.99 m, the weather resistance, dimensional stability It has excellent properties such as properties.

Further, in the present invention, the vinyl chloride marking sheet substrate may be any of colored, non-colored, color-transparent, and color translucent, and can be colored as necessary. Is used. If it is colorless, it can be applied to the show window of a store or the like to enhance the aesthetics.

The vinyl chloride marking sheet of the present invention contains a vinyl chloride resin as a main component, and further includes various known additives such as a plasticizer, a coloring material, a ripening stabilizer, an ultraviolet absorber, an ultraviolet ray blocking agent, and an antistatic agent. Agents, lubricants and the like can be used in combination.

Examples of the plasticizer include a low-molecular-weight ester plasticizer of a basic carboxylic acid compound and a monohydric or polyhydric alcohol compound, a liquid polyester plasticizer, an alkyd-type liquid plasticizer, and an oxysilane oxygen-containing epoxy plasticizer. It can be freely selected with the agent. Among them, liquid plasticizers, alkyd liquid plasticizers, and oxysilane oxygen-containing epoxy plasticizers are preferable from the viewpoints of weather resistance and flexibility. Examples of the basic carboxylic oxide compound include phthalic acid, isophthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid, maleic acid, fumaric acid, trimellitic acid, and oleic acid.

Examples of the coloring colorant include colored coloring agents which have been conventionally used in printing inks. Machine pigments, inorganic pigments, and colorless extender pigments can also be used for the purpose of improving fluidity, imparting an anchoring effect to the transfer ink, and the like. Examples of the above heat stabilizer include calcium stearate, barium stearate, lead stearate, lead sulfite, lead phosphite, dibutyltin malate, dibutyltin laurate, dibutyltin mercaptide, dioctylssumaleate-based stabilizer, octyltin Examples thereof include a laurate-based stabilizer, a octyl tin mercaptide-based stabilizer, a tin'diol derivative, and a complex thereof.

Examples of the ultraviolet absorber include compounds that absorb light having a wavelength of 290 to 400 nm, such as benzophenone, benzotriazole, phenyl salicylate, hindered amine, cyanoacrylate, and cinnamon Examples thereof include acid compounds and aminobutadiene compounds. The ultraviolet absorber is added in an amount of 0.5 to 40 parts by weight, preferably 2 to 20 parts by weight, based on 100 parts by weight of the polyvinyl chloride resin. Examples of the ultraviolet blocking agent include fine particles of titanium oxide, zinc white, talc, kaolin, calcium carbonate, iron oxide and the like. The ultraviolet ray blocking agent is blended in an amount of 1 to 80 parts by weight, preferably 15 to 40 parts by weight G0 per 100 parts by weight of the polyvinyl chloride resin. By using an ultraviolet absorber and / or an ultraviolet ray blocking agent, it becomes possible to reduce ultraviolet degradation of organic pigments, fluorescent pigments and the like contained in a vinyl chloride marking sheet for outdoor use.

Examples of the antistatic agent include boroxyethylene alkylamine, polyoxyalkylamide, polyoxyethylene alkyl ether, glycerin fatty acid ester, sorbitan fatty acid ester, alkyl sulfonate, alkylbenzene sulfonate, alkyl sulfate alkyl phosphate, and quaternary ammonium. Musulfate and the like are exemplified. The antistatic agent is particularly effective in preventing dust collection due to static electricity, which causes transfer failure.

Known materials can be used as the lubricant. For example, Boriechile Examples include hydrocarbon-based lubricants such as waxes, fatty acid-based lubricants such as stearic acid and oxy fatty acids, fatty acid amide-based lubricants, natural or synthetic waxes, alcohol-based lubricants, fluorine-containing waxes, and fluorine resin powders. The lubricant is used for the purpose of improving the abrasion resistance of the surface of the vinyl chloride mercury sheet and the processability of film formation, as long as the transferability is not adversely affected. In the present invention, the transfer foil is one in which a desired pattern is provided on a base sheet by gravure printing using ink. As the base sheet, paper, a plastic film such as polyester, polypropylene, polyethylene, and polyamide, and a metal foil such as aluminum are used. Among them, polyesters which are excellent in heat resistance, transparency, ink adhesion, cost and coating properties are preferable. When printing on Bolister film, the coating temperature, difficulty in controlling the coating tension, swimming on the printed surface, pinholes, and poor leveling, which are observed when gravure printing is applied directly to vinyl chloride resin, are observed. A little dense and highly colorful pattern can be printed. Those having a thickness of 10 m to 250 jum are preferably used. It is preferable that such a base sheet is subjected to a peeling treatment such as coating with a synthetic resin such as an acrylic resin, a silicon resin, a polyamide resin, or a polyester resin as necessary. As a printing ink, a binder prepared by adding and kneading a colorant such as a binder, a pigment, a dye, and the like, other necessary additives and solvents, and the like is used. As the binder, a conventionally known fluorine-based, vinyl-based, urethane-based, cellulose-based, polyester-based resin or the like may be used alone or as a mixture. When a release layer is provided on the substrate sheet using the obtained printing ink, a transfer foil is formed by gravure printing on the release layer.

Generally, a thermoplastic resin is contained in the ink layer of the transfer foil. Further, the same heat-adhesive resin as that of the mature adhesive resin provided on the surface of the vinyl chloride marking sheet of the present invention is contained in the ink layer, or the mature adhesive resin is laminated on the surface of the transfer foil printing ink layer. By doing so, the compatibility at the time of heating is further improved, and the transferability and adhesion can be remarkably improved. further Ellipses that are usually performed, such as adding an ultraviolet absorber to the transfer foil printing ink layer or laminating it on the surface of the transfer foil printing ink layer, or providing a single concealment layer, are necessary. Next, a method for transferring a transfer foil in which the transfer ink of the present invention is provided on a support will be described. To the surface of the vinyl chloride marking sheet containing the heat-adhesive resin, or to the surface of the heat-adhesive resin layer of the vinyl chloride marker sheet provided with the heat-adhesive resin layer on one side. A method is used in which the symbols are set together and the pattern is transferred by a mature roll or a mature press. As the transfer method, an up-down transfer method, a roll transfer method, a roll transfer method for a cylinder, a rotary transfer method, a multi-sided continuous transfer method, an in-mold transfer method during injection molding (in-mold transfer method), and the like are employed. Among them, up-down transfer method and rotary transfer method are most suitable.

In the present invention, a transfer pattern foil is used as a process paper, and a resin solution is formed on the film by a conventionally known casting method, that is, a solution casting method, a sol casting method, a semi-sol casting method, or the like, to thereby form a patterned patterned chloride polymer. You can also create a king sheet.

For example, a case where a sol-cast method is used in forming a vinyl chloride copolymer film will be described. First, a vinyl chloride copolymer resin, a plasticizer, a suitable solvent, and, if necessary, the above-mentioned various additives are mixed and stirred to prepare a paste-like high-viscosity sol coating liquid. Examples of the solvent include a solvent for sol in which one or a plurality of solvents such as butanol, butyl acetate, ethylene glycol monomethyl ether acetate, diisobutyl ketone, xylol, aromatic petroleum naphtha, solvent naphtha, and trichlene are mixed. Is done. The process of printing and forming the pattern as shown in the figure by the above-mentioned transfer ink. Approx. C, it is possible to obtain about 1 minute to 1 0 thickness 3 and an object is heated and melted at 0 minutes condition M ~ L 5 0 m, the marking sheet subjected to the design pattern of the yield stress l~6 KgZmm ² . In addition, transfer ink and shape When it is desired to improve the adhesion with the formed vinyl chloride marking sheet, a mature adhesive resin may be contained in the high viscosity sol coating liquid.

As the mature adhesive resin used in the present invention, those having a T g of −30: to 120 ° C. or a softening point or a melting point of 10 T: to 200 ° C. are used. Is done. More preferably, T g is −10. C to 80, or a resin having a softening point or melting point of 50 to 15 (TC is preferably used. Preferred resins are exemplified below. Styrene / maleic anhydride copolymer, styrene Z acrylic acid Ester copolymer, Styrene / methacrylic acid ester copolymer, Polyvinyl acetate, Vinyl chloride Z Vinyl acetate copolymer, Polyethylene, Polypropylene, Polyacetal, Ethylene vinyl acetate copolymer, Ethylene Z acrylate copolymer Copolymer, α-olefin Z maleic anhydride copolymer, esterified α-olefin / maleic anhydride copolymer, polystyrene, polyallolactone, polyacrylate, polymethacrylate, polyamide, epoxy Resin, xylene resin, ketone resin, petroleum resin, sucrose ester, rosin Or its derivatives, coumarone indene resin, terpene resin, polyurethane resin, styrene / butadiene rubber, polyvinyl butyral, nitrile rubber, acrylic rubber, ethylene-propylene rubber and other synthetic rubbers, polyester resin, fluorine-containing Examples thereof include copolymer resins, etc. However, the present invention is not limited to these, and other resins that do not fall within the above-mentioned range of ripening characteristics may be applied, if necessary, to suitability for application, cost, weather resistance, etc. They can be used together for the purpose of improving durability.

If the mature adhesive resin shows tackiness at room temperature, blocking may occur when vinyl chloride marking sheets are stacked and stored, or soot in the atmosphere may be deposited by outdoor exposure tests and the surface may be easily stained. Is generated. For this reason, those which are solid at room temperature and do not show tackiness are preferred. In addition, in order to improve the blocking resistance and soot pollution resistance of the vinyl chloride marking sheet, graft grafts with an acryl chain on the backbone of a fluororesin were used. It is also possible to use a fluorine-containing copolymer resin such as a copolymer resin formed of a vinyl monomer having a limmer or polyfluoro group and another vinyl monomer, various fluorine-based surfactants, and a fluorine-containing wax.

As a result of various studies among the above preferred mature adhesive resins, a resin having high crystallinity or partial crystallinity is particularly preferred. Epoxy resins, sucrose esters, and polyproprolactone crystalline polyester resins having such characteristics are exemplified. Among them, sucrose esters and polyfunctional prolactone represented by the following general formula (1) (melting point: about 60 ° C) were found to be effective.

_{_{- (CH2-CH 2 -CH 2}} -CH 2 -CH 2 COO) n i (1) in particular, sucrose Okuta benzoate (melting point 78 C) and sucrose O Kuta acetate (melting point 72), previously It satisfies the conditions that it is hard and hard at room temperature and does not have tackiness, and ripening sensitivity, which is an important property in ripening, is satisfied by a sharp melting point and a low melting viscosity similar to wax. In addition, sucrose octabenzoate is effective for improving the weather resistance and is very suitable. When sucrose octabenzoate is used for the heat-adhesive resin layer, the film strength is slightly weaker when used alone, so that it can be more suitably used by using it together with another resin with high film strength. it can. In this case, the ratio of the sucrose octabenzoate to the resin having a high film-forming strength is preferably 10 to 9% by weight i%, more preferably 30 to 90% by weight.

When the softening point or melting point of the heat-adhesive resin is 10 or more, blocking resistance can be improved by adding a filler such as silica. However, when the softening point or the melting point is less than 1 °, the blocking resistance is not significantly improved even when a filler such as silica is added, and the softening point or the melting point is 200. When the value exceeds C, it was confirmed that the adhesion between the vinyl chloride marking sheet after transfer and the transfer foil ink layer was reduced. If the transfer temperature is too high, the size of the vinyl chloride marking sheet will be lower. This causes problems such as deterioration of qualitative properties and the inability to transfer high-resolution pattern designs.

Further, in order to improve blocking resistance and smoke pollution resistance, it is preferable to use a fluorine-containing compound or a silicon-modified resin in combination with the above-mentioned heat-adhesive resin. Examples of the fluorine-containing compound include a fluorine-containing copolymer resin such as a graft polymer in which an acryl side chain is arranged on the main chain of a fluororesin, or a copolymer resin of a vinyl monomer having a polyolefin group and another vinyl monomer. And various fluorine-based surfactants, fluorine-containing waxes and the like. The silicon-modified resin is a resin obtained by introducing a polyorganosiloxane into the main chain of the base polymer or into the side chain. Among them, a silicon-modified polyurethane resin having a polyorganosiloxane chain in the main chain, or a polyorganosiloxane in the side chain Silicon-modified acryl resins having chains are preferred.

In addition, a UV-absorbing agent or UV-blocking agent is applied to the mature adhesive resin to reduce the UV deterioration of the vinyl chloride resin, organic pigments, fluorescent pigments, etc. contained in the vinyl chloride marking sheet, and the transfer foil is transferred to the ink. It may be added within a range that does not adversely affect the properties and adhesion, and other resins may be used in combination as needed.

For the purpose of enhancing the sensitized transfer recording characteristics with a ripened transfer ribbon to a vinyl chloride mercury sheet with a design pattern, it is preferable to provide a heat-sensitive recording image receiving layer after forming a pattern pattern with a transfer foil on a vinyl chloride marking sheet. As a means for forming the heat-sensitive recording image-receiving layer, a solvent coating method of coating a coating solution obtained by dissolving or dispersing the composition constituting the image-receiving layer in a solvent or water, followed by drying, or a composition forming the image-receiving layer A hot melt coating method or the like for coating by heating and melting is usually used. The thickness of the heat-sensitive recording image-receiving layer is preferably about 0.1 to 1 O jum, and more preferably about 0.2 to 2 m.

In addition, in order to further improve the outdoor weather resistance and smoke pollution resistance of a vinyl chloride marking sheet with a patterned pattern provided with a ripening record image receiving layer, Tg on the vinyl chloride marking sheet with texture is 30 to 30. (: Or a softening point or melting point of 40 to 8 (a first heat-sensitive recording image-receiving layer having a high thermal sensitivity mainly composed of a mature adhesive resin of TC is provided, and T _g is 30 To 8 (TC: or a mature adhesive resin with a softening point or melting point of 80 to 18 CTC as a main component, or a mature adhesive resin containing a fluorine-containing compound or a silicon-modified resin, weather resistance Alternatively, a second heat-sensitive recording image receiving layer having excellent stain resistance may be sequentially laminated, provided that the second heat-sensitive recording image receiving layer, which is the outermost layer, is sensitized. The thickness is preferably as thin as possible so as not to lower the property, and is preferably about 0.5> m or less, more preferably 0.1 jum or less.

The ripened recording image-receiving layer contains a ripened adhesive resin as a main component, and may contain the above-mentioned various additives as necessary, such as a plasticizer, a coloring material, an ultraviolet absorber, and an antistatic agent. it can.

As the thermal transfer ribbon used in the present invention, a conventionally known one such as a single-layer type in which a heat-fusible ink layer is provided on a substrate or a multilayer type in which a plurality of layers having different compositions and functions are laminated can be used. . A multi-layer type is more preferable than a single-layer type, and a structure in which a release layer and a colored ink layer substantially composed of a coloring material and a resin are sequentially laminated on a base material is more preferable as a mature melting layer. This is because if waxes are contained in the ink layer, various properties such as weather resistance, adhesion, and abrasion resistance may be adversely affected. Further, an adhesive layer may be provided on the colored ink layer for the purpose of further improving transfer adhesion.

As the base material, polyester film (polyethylene terephthalate, polyethylene naphthalate, etc.) with excellent heat resistance and mechanical strength, polyamide film (nylon, etc.), polyolefin film (polypropylene, etc.), cellulose film (polypropylene, etc.) Triacetate etc.). Polycarbonate film etc. are mentioned. Polyester film is most preferable because of its excellent heat resistance, mechanical strength, tensile strength and tensile stability. The thinner the substrate Although the aging conductivity is good, it is most preferably 3 to 5 in view of the strength and the ease of coating the hot-melt ink layer. Further, a back coat layer made of a maturing resin may be provided on the surface of the substrate opposite to the hot-melt ink layer.

The hot-melt ink layer is composed of coloring materials such as organic pigments and inorganic pigments and natural waxes such as vegetable, animal and mineral petroleum, synthetic waxes, higher fatty acids, higher fatty acids, and softening points of 20 CTC. It is composed of the following resins and other vehicles. If a heat-sensitive image-receiving layer is provided on the surface of a vinyl chloride marking sheet with a pattern, or if a heat-adhesive resin is contained in the ink layer of the transfer foil used to paint the pattern, a heat-sensitive transfer ribbon is used. The adhesiveness of the ripened ink layer to a vinyl chloride marking sheet with a pattern can be remarkably improved. In order to further enhance the surface strength and outdoor weather resistance of the recorded portion after transfer, a colored ink that is substantially formed of a coloring material and a resin via a wax-containing release layer on a base material and does not contain waxes is used. It is preferable to use a ripened transfer ribbon provided with a layer. Actually, if a tincture is contained in the colored ink, it affects the resistance of the recorded material in a high-temperature environment (around 4 CTC), especially the abrasion resistance and adhesion. For example, when the content is about 5% in the coloring ink, it is slightly lower than when no wax is contained, and when the content is about 20% i% in the coloring ink, it clearly decreases. If it is more than 50%, each of the above resistances will be reduced to less than half.

A more preferable fusible ink layer is formed by a colored ink layer and a release layer, and the colorant / resin weight ratio of the colored ink layer particularly affects the base concealing property, the color uniformity, and the resolution. . The weight ratio of the colorant Z resin is preferably 0.5 to 4 in the case of an organic pigment, and is preferably 0.5 to 6 in the case of an inorganic pigment because of its large specific gravity. If it is smaller than this range, the concealing property and the color intensity are reduced, the film forming strength of the colored ink layer is increased, and the sharpness at the time of transfer, that is, the resolution is reduced. If it is larger than this range, the adhesion and the friction resistance decrease. Various conventionally known additives such as a pigment dispersant may be added to the colored ink layer only when necessary if the solid content is 5% by weight or less. Colored ink layer thickness Is preferably from 0.3 to 5 m, more preferably from 0.5 to 3 m.

The release layer is made of a wax or a resin, but may be added with other known additives such as a coloring material, a pigment dispersant, an antistatic agent, a plasticizer, and an ultraviolet absorber as needed. The thickness of the release layer affects the transferability, and is preferably from 0.1 to 3 m, more preferably from 0.3 to 2 / m.

A resin having a softening point of 20 CTC or less is used as the resin for the fusible ink layer. For example, polyvinyl acetate, vinyl chloride Z-vinyl acetate copolymer, polyethylene, polypropylene, polyacetal, ethylene Z-vinyl acetate copolymer, ethylenenoacrylic acid copolymer, α-olefin / maleic anhydride copolymer Coalescing, α-refining Ζesterified maleic anhydride copolymer, polystyrene, polyacrylate, polymethacrylate, α-refining / maleic anhydride / vinyl group-containing monomer copolymer, styrene Ζ Maleic anhydride copolymer, styrene-noacrylate copolymer, polyamide, silicone resin, epoxy resin, xylen resin, ketone resin, petroleum resin, rosin or its derivatives, cumarone indene resin, terpene resin, Polyurethane resin, styrene-butadiene rubber, polyvinyl Butyral, nitrile rubber, acrylic rubber, synthetic rubbers such as Echire down Ζ propylene rubber, a polyester resin, a two-Bok Roseru port one scan, cellulose derivatives, and sucrose esters. Among them, resins obtained by copolymerizing α-olefins having 6 or more carbon atoms, maleic anhydride and (meth) acrylic acid ester, and sucrose octabenzoate and sucrose, which are a kind of sucrose ester Octaacetic ester is particularly suitable for the hot-melt ink layer due to its excellent ripening properties. In order to provide a fusible ink layer on a substrate, a commonly used coating method, that is, a hot melt coating method or more preferably a gravure coating method is used.

The vinyl chloride marking sheet of the present invention is provided with a design surface by a transfer foil. Adhesive on the opposite side of the design, for example acrylic adhesive, urethane A pressure-sensitive adhesive such as a pressure-sensitive adhesive or a silicon-based pressure-sensitive adhesive may be provided in a thickness of 10 to 2 ° m, and a pressure-sensitive adhesive release substrate may be further laminated. Depending on the material and surface condition of the adherend, adhesive with an adhesive strength of usually 50 to 500 grZ 25 mm width (J IS-Z023 7 Adhesive tape · Adhesive sheet test method) is used. . The used vinyl chloride marking sheet can be easily peeled off without leaving unnecessary adhesive on the surface of the adherend and without requiring a peeling force exceeding the breaking strength of the vinyl chloride marking sheet. In order to impart excellent releasability, it is particularly preferable to set the adhesive force to a width of 50 to 150 Ogr / 25 mm, and more preferably to a width of 500 to 900 grZ25. do it. Further, in the case of an adhesive strength of more than 1505, a strong adhesive property can be given to the adherend as a permanent adhesive type.

The PVC sheet marked with the above materials and processing methods may be subjected to post-processing which is usually performed according to the intended use. For example, for the purpose of further improving the weather resistance, an additive having an ultraviolet blocking effect such as an ultraviolet absorber may be contained in the outermost layer of the vinyl chloride marking sheet, and polyester, polypropylene, polyethylene, and a fluorine-containing resin may be used. For example, a transparent film such as a resin film may be laminated, or a fluorine-containing resin paint may be coated. In particular, laminating a fluorine-containing compound in the form of a film or a coating film is preferable because not only weather resistance but also antifouling property and abrasion resistance are improved. Examples of the fluorine-containing compound include a graft polymer in which the side chain of an acrylic resin is arranged on the main chain of a fluororesin (even a low molecular weight oligomer) or a copolymer of a vinyl monomer having a polyfluoro mouth group and another vinyl monomer. Bolimers (which may be low molecular oligomers) are preferred. In addition, the vinyl chloride marking sheet with the graphic pattern obtained as described above is processed to the required form by force-pressing and silk-screen printing for the purpose of further enhancing the design, and, if necessary, by projecting the surface by mechanical embossing. May be. Furthermore, to further enhance the design, a further adhesive resin layer is provided on the outermost surface of the vinyl chloride marking sheet with the pattern. It is permissible to apply characters and designs to the image by patterning means such as a sensitized transfer recording method.

【Example】

Hereinafter, the present invention will be described in detail with reference to examples. Parts in the examples are parts by weight unless otherwise specified. Implementation Kiyoshi 1

In accordance with a known casting method, a high quality paper coated with clay is treated with e. A 160 m thick process paper coated with a release-based release agent was prepared. On the release surface of this process paper, a resin solution composed of the following vinyl chloride sheet raw material containing a thermo-adhesive resin was cast so that the thickness after drying was 5 Ojum, and heated to form a film. The process paper was removed to obtain a white vinyl chloride marking sheet. Next, a 170 m-thick double-sided polyethylene laminated paper having one surface subjected to a release treatment was prepared. A pressure-sensitive adhesive layer composed of the following pressure-sensitive adhesive raw materials was provided on the release-treated surface of the double-sided polyethylene laminated paper so as to have a thickness of 30 microns, and was laminated on the previously obtained vinyl chloride marker sheet. A vinyl chloride marking sheet having a layer and a release substrate was obtained. The vinyl chloride marking sheet obtained in this way has an initial adhesive strength of 1,500 gr / 25 mm width (JIS-Z0237 adhesive tape, adhesive sheet test method), and after 65 and 80% RH. The adhesive strength over time was 200 Ogr / 25 mm width. A mold release layer composed of acrylmelamine-based resin and a design layer composed of gravure-printed marble patterns using a colored ink mainly composed of vinyl acetate-based resin were sequentially provided on a 25-jum-thick polyethylene terephthalate film base material. A transfer foil was prepared. Next, the transfer foil and the vinyl chloride marking sheet are thermocompression-bonded with a ripening roll at a roll temperature of 10 (TC, roll pressure of 4 kg pressure, and a conveyance speed of 50 cm / min), and then the transfer foil base material is removed. (4) The pattern of the printing foil was copied to obtain a vinyl chloride marking sheet with a marble pattern.

Polyvinyl chloride marking sheet Vinyl chloride resin (Zeon 24, manufactured by Nippon Zeon, degree of polymerization 1300)

100 parts Thermal adhesive resin (John Krill 61 1 made by Johnson Bolimer Softening point 105 "C) 20 parts Titanium oxide (Taitake CR80 made by Ishihara Sangyo) 50 parts Liquid polyester plasticizer (Aderic sizer PN260 made by Asahi Denka Kogyo 20 parts Liquid phthalate plasticizer (DOP made by Chisso) 15 parts Ripe stabilizer (barium-no-zinc type) 3 parts UV absorber (benzotriazole type) 2 parts Xylene 40 parts Diisobutyl ketone 40 parts

-Adhesive

Two-part curable acrylic adhesive 100 parts Curing agent 0.87 parts Example 2

Using the same vinyl chloride marking sheet raw material as in Example 1, a white PVC marking sheet having a thickness of 5 Ojum was produced in the same manner as in Example 1. The marble pattern was transferred to this vinyl chloride marking sheet in the same manner as in Example 1, using the same transfer foil as in Example 1, to obtain a vinyl chloride marking sheet having a marble pattern. . On the pattern surface of the vinyl chloride marking sheet, in the same manner as in Example 1, using the same adhesive as in Example 1, a marbled chloride having an adhesive layer and a release substrate was used. A vinyl marking sheet was obtained.

Example 3

A transparent vinyl chloride marking sheet having a thickness of 5 Ojm was prepared in the same manner as in Example 1 by using a vinyl chloride marker sheet containing a heat-adhesive resin shown below. Then, in the same manner as in Example 1, Using the same adhesive as in Example 1, a vinyl chloride marking sheet having an adhesive layer and a release substrate was obtained. Further, a marble pattern was transferred to this vinyl chloride marking sheet in the same manner as in Example 1, using the same transfer foil as in Example 1, to obtain a vinyl chloride marking sheet with a marble pattern. —Vinyl chloride marker sheet

Vinyl chloride resin (Zeon 24, manufactured by Nippon Zeon, degree of polymerization 1 300)

100 parts Mature adhesive resin (Toyobo Jippon Byron 103 softening point 1 55.C)

20 parts Liquid polyester plasticizer (Ada Densa Industrial Co., Ltd. PN 260) 20 parts Liquid phthalate plasticizer (DOP made by Chisso) 5 parts Liquid epoxy plasticizer 5 parts Ripe stabilizer (barium Z zinc) 3 Part UV absorber (benzotriazole type) 3 parts Xylene 30 parts Diisobutyl ketone 30 parts Example 4

A 50-jum-thick white vinyl chloride marking sheet was prepared in the same manner as in Example 1 by using the following vinyl chloride marking sheet raw material containing a heat-adhesive resin. Next, a vinyl chloride marking sheet having a pressure-sensitive adhesive layer and a release substrate was prepared in the same manner as in Example 1 using a pressure-sensitive adhesive composed of the following pressure-sensitive adhesive raw materials and having ease of re-peeling. The easily removable vinyl chloride marking sheet obtained in this manner has an initial adhesive strength of 500 grZ 25 mm width (JI SZ0237 Adhesive Tea 'Adhesive Sheet Test Method), 65 ° C. 80% RH, 168 Time-dependent adhesion after 75 hours

It was 5 mm wide. This vinyl chloride marking sheet is printed on a 25 〃m thick polyester terephthalate film substrate with an acryl resin. Using a transfer layer provided with a pattern layer formed by gravure printing a grain pattern using a colored ink mainly composed of styrene-acrylic resin, and an adhesive layer made of polyester resin. In the same manner as in Example 1, the grain pattern was transferred to obtain a vinyl chloride marking sheet with a grain pattern.

Vinyl chloride resin (Zeon 24, manufactured by Nippon Zeon, degree of polymerization 1300)

100 parts Mature adhesive resin (manufactured by Toyobo Co., Ltd. Byron 103 softening point 1 55 polyester resin) 12 parts Mature adhesive resin (Daiichi Kogyo Seiyaku Monopet SB melting point 78 ° C sucrose octabenzoate) 8 parts Titanium oxide (Ishihara Sangyo Taipeta CR80) 50 parts Liquid polyester plasticizer (Ada Densa Kogyo PN 260

20 parts Liquid phthalate plasticizer (DOP made by Chisso) 1 5 parts Ripe stabilizer (barium / zinc) 3 parts UV absorber (benzotriazole type) 2 parts Xylene 40 parts Diisobutyl ketone 40 parts One adhesive One

Two-part curable removable acrylic adhesive 100 parts Curing agent 0.25 parts Example 5

A vinyl chloride marking sheet having a thickness of 5θΛίπι was prepared in the same manner as in Example 1 by using the following raw material of a vinyl chloride marking sheet containing a mature adhesive resin. Then, in the same manner as in Example 1, using the same pressure-sensitive adhesive as in Example 1, vinyl chloride having a pressure-sensitive adhesive layer and a release substrate A marking sheet was used. Further, on the vinyl chloride marking sheet, in the same manner as in Example 1, using the same transfer foil as in Example 4, the grain pattern was copied to obtain a vinyl chloride marking sheet with a grain pattern. Polyvinyl chloride marking sheet

100 parts Rigid adhesive resin (ARAXEL H7, melting point 60.C, polycaprolactone, manufactured by Daicel Chemical Industries, Ltd.) 20 parts Titanium oxide (Taiko CR80, manufactured by Ishihara Sangyo) 50 parts Liquid polyester plasticizer PN260) 20 parts Liquid phthalate plasticizer (DOP made by Chisso) 15 parts Heat stabilizer (barium Z zinc) 3 parts Ultraviolet absorption (benzotriazole) 2 parts Toluene 5 parts Xylene 35 parts Diisobutyl ketone 40 parts Example 6

Using the same vinyl chloride marking sheet raw material as in Example 4, a white vinyl chloride marking sheet having a thickness of 50 m was prepared in the same manner as in Example 1. Next, in the same manner as in Example 1, using the same adhesive as in Example 1, a vinyl chloride marking sheet having an adhesive layer and a release substrate was obtained. Further, in the same manner as in Example 1, a release layer made of an acryl-based resin and a styrene-acrylic-based resin were used as the main components of this vinyl chloride marking sheet on a 25-m-thick polyethylene terephthalate film substrate. Using a transfer foil provided with a pattern layer made by gravure printing a granite pattern using colored ink, and an adhesive layer consisting of a mixture of a polyester resin and sucrose octabenzoate at a ratio of 6Z4, in that order Roll the pattern The sheet was copied to obtain a marking sheet with a granite pattern.

Example 7

On the pattern surface of the vinyl chloride marking sheet with a marble pattern obtained in Example 1, apply a fluorine-containing resin paint composed of the following raw materials to a bar coater so that the film thickness after drying becomes 2.0 / m. 80 ° C,

The pattern protection layer was provided by drying for 30 seconds to obtain a vinyl chloride marking sheet with a marble pattern.

One pattern protection layer

Fluorine copolymer resin (FT-1030 manufactured by Asahi Glass) 10 parts UV absorber (benzotriazole type) 5 parts Solvent (toluene Z methyl ethyl ketone = 1 1) 85 parts Example 8

From the following vinyl chloride marking sheet raw materials, a white vinyl chloride marking sheet having a thickness of 10θΛί was prepared by a known calendar method. The same adhesive as in Example 1 was used on one side of the vinyl chloride marking sheet, and a vinyl chloride marking sheet having an adhesive layer and a release substrate was produced in the same manner as in Example 1. Further, on the surface opposite to the pressure-sensitive adhesive layer, a thermo-adhesive resin coating solution composed of the following thermo-adhesive resin layer raw materials is applied by a bar coater so that the film thickness after drying becomes 0.5 jum, and then dried. Ripe adhesive A vinyl chloride marking sheet having a resin layer on the surface was obtained. A marble pattern was transferred onto the vinyl chloride marking sheet in the same manner as in Example 1 using the same transfer foil as in Example 1 to obtain a vinyl chloride masking sheet with a marble pattern.

Vinyl chloride marking sheet

Vinyl chloride resin (Zeon 24, Nippon Zeon, polymerization degree 1300)

100 parts Titanium oxide (Taipeta CR80, manufactured by Ishihara Sangyo) 50 parts Liquid plasticizer (Aderic sizer, PN260, manufactured by Asahi Denka Kogyo) 20 parts Liquid phthalate plasticizer (DOP made by Chisso) 1 5 Parts Ripe stabilizer (barium Z zinc) 3 parts UV absorption (benzotriazole) 2 parts Lubricant (stearic acid) 0.5 parts

-Heat-adhesive resin layer

Soft adhesive resin (JONC RYL 6 11 1 made by Johnson Polymer, softening point 105.C styrene-acrylic resin) 10 parts Solvent (toluenenomethylethyl ketone = 1/1) 90 parts Example 9

A marking sheet with a marble pattern was obtained in exactly the same manner as in Example 8, except that the thermal adhesive resin layer of Example 8 was changed as follows.

- heat-adhesive resin layer - Mature adhesive resin (Toyobo緝製Byron 1 0 3 Softening point 1 5 5 ^e C poly ester resin) 6 parts heat-bonding resin (manufactured by Dai-ichi Kogyo Seiyaku Co. mono- pet SB mp 78 ° C sucrose Glyocta benzoate) 4 parts Solvent (toluene / methyl ethyl ketone = 1 Z 1) 90 parts Example 10

A transparent vinyl chloride marking sheet having a thickness of 100 m was prepared from the following vinyl chloride marker sheet raw materials by a known calendar method. The same adhesive as in Example 1 was used on one side of the vinyl chloride marking sheet, and a vinyl chloride marking sheet having an adhesive layer and a release substrate was produced in the same manner as in Example 1. Further, on the opposite side of the pressure-sensitive adhesive layer, apply a thermo-adhesive resin coating liquid consisting of the following mature adhesive resin layer raw materials with a bar coater so that the film thickness after drying becomes 0.5 m, and then dry. As a result, a vinyl chloride marking sheet having a heat-adhesive resin layer on the surface was obtained. Using the same transfer foil as in Example 1 on this vinyl chloride marking sheet, The marble pattern was transferred in the same manner as described above to obtain a vinyl chloride marking sheet with a marble pattern.

Vinyl monochloride marker sheet

Vinyl chloride resin (Zeon 24, manufactured by Nippon Zeon) Degree of polymerization: 1300

100 parts Liquid plasticizer (Ada Denka Kogyo Adeniki Sizer-1 PN2600) 20 parts Liquid phthalate plasticizer (DOP made by Chisso) 5 parts Liquid ethoxy plasticizer 5 parts Heat stabilization (barium / Zinc) 3 parts UV absorber (benzotriazole) 3 parts Lubricant (stearic acid) 0.5 parts

-Resin adhesive resin waste -Resin adhesive resin (Placcel H 7 melting point 6 CTC polyalactolactone manufactured by Daicel Chemical Industries, Ltd.) 10 parts Solvent (toluene / methylethyl ketone = 1 Z1) 90 parts Example 11

Using the same vinyl chloride marking sheet raw materials as in Example 10, a transparent vinyl chloride marking sheet having a thickness of 100 μm was prepared by a known calendar method. On one surface of this vinyl chloride marking sheet, using the same heat-adhesive resin layer raw material as in Example 9, in the same manner as in Example 8, a vinyl chloride marking sheet having a mature adhesive resin layer on the surface was formed. Obtained. The grain pattern was transferred to this vinyl chloride marking sheet in the same manner as in Example 1 using the same transfer foil as in Example 4 to obtain a vinyl chloride marking sheet having a grain pattern. Further, a vinyl chloride marking sheet having an adhesive layer and a release substrate was formed on the wood grain pattern forming surface using the same adhesive as in Example 1 and in the same manner as in Example 1.

Example 1 2 Using the same vinyl chloride mercury sheet raw material as in Example 8, a 100-μm thick white vinyl chloride mercury sheet was prepared by a known calendar method. Next, a vinyl chloride marking sheet having an adhesive layer and a release substrate was obtained in the same manner as in Example 1 using an adhesive having the same ease of removability as in Example 4. Next, a vinyl chloride marking sheet having a heat-adhesive layer on the surface was obtained in the same manner as in Example 8 using a heat-adhesive resin layer made of the same mature adhesive resin raw material as in Example 9. Using the same transfer foil as in Example 4 on the vinyl chloride marking sheet, the grain pattern was transferred in the same manner as in Example 1 to obtain a vinyl chloride marker sheet having a grain pattern.

Example 13

Using the same vinyl chloride marker sheet material as in Example 8, a white vinyl chloride marking sheet having a thickness of 100 μm was prepared by a known calendar method. Using the same pressure-sensitive adhesive as in Example 1 on one surface of this vinyl chloride marking sheet, a vinyl chloride marking sheet having a pressure-sensitive adhesive layer and a release substrate was produced in the same manner as in Example 1. Next, a vinyl chloride marker sheet having a heat-adhesive layer on the surface was obtained in the same manner as in Example 8 using a mature adhesive resin layer made of the same heat-adhesive resin raw material as in Example 9. Using the same transfer foil as in Example 6, the granite pattern was transferred to this vinyl chloride marking sheet in the same manner as in Example 1 to obtain a vinyl chloride marking sheet with a granite pattern.

Example 14

Gravure-printed marble pattern on a 100-m-thick polyethylene terephthalate film substrate with a release layer composed of acrylyl-melamine resin and a colored ink mainly composed of vinyl chloride-vinyl acetate resin A transfer foil provided with a layer in order is used as process paper, and a resin liquid composed of the following vinyl chloride marker sheet material is applied on the transfer foil using an applicator so that the thickness after drying is 50 m. coated Te, dried 3 minutes at 1 9 0 ^e C Then, a marble pattern was transferred and formed at the same time as the film was formed, and a vinyl chloride marking sheet with a marble pattern was created. Next, on the surface opposite to the marble pattern forming surface, in the same manner as in Example 1, using the same adhesive as in Example 1, a vinyl chloride marking sheet having an adhesive layer and a release substrate was obtained. . —PVC marking sheet

100 parts Titanium acid value (Taishi CR80 manufactured by Ishihara Sangyo) 50 parts Liquid plasticizer plasticizer (Aderikisaiza PN 260 manufactured by Asahi Denka Kogyo) 20 parts Liquid phthalate plasticizer (DOP manufactured by Chisso) 1 5 parts Mature stable Agent (barium-no-lead) 3 parts UV absorber (benzotriazole-based) 2 parts Solvent (Xylol Z-diisobutyl ketone = 1/1) 270 parts Example 15

A marble patterned vinyl chloride marking sheet was obtained in the same manner as in Example 14, using the same raw materials as in Example 14, except that the raw materials for the vinyl chloride marking sheet of Example 14 were changed to the following raw materials. Was. —Vinyl chloride marking sheet—

100 parts Titanium oxide (Taibe CR80, manufactured by Ishihara Sangyo) 50 parts Thermo-adhesive resin (Toyo Bojip, Byron 103 with a softening point of 1 55, polyester resin) 20 parts Liquid polyester plasticizer (Adeki Syza, Asahi Denka Kogyo) I PN 260) 20 parts Liquid phthalate plasticizer (DOP made by Chisso) 1 5 parts Ripe stabilizer (barium Z zinc) 3 parts UV absorber (benzotriazole-based) 2 parts Solvent (xylol diisobutyl ketone = 1/1) 80 parts Example 16

A release layer mainly composed of an acryl-based resin on a polyethylene terephthalate film substrate having a thickness of 100 μm, a pattern layer formed by gravure printing a polka dot pattern using a colored ink mainly composed of an acryl-based resin, A polka dot pattern was formed in the same manner as in Example 14 using the same raw materials as in Example 14 except that transfer paper provided with an adhesive layer containing an acrylic resin as a main component in order was used as the process paper. A vinyl chloride marking sheet was obtained. Example 17

Except that the raw material for the vinyl chloride marking sheet of Example 16 was changed to the raw material shown below, the same raw material as in Example 16 was used, and the same method as in Example 16 was used. A vinyl marking sheet was obtained. —PVC marking sheet

Chloride bur resin (Zeon 24, Nippon Zeon polymerization degree 1300)

100 parts Heat-adhesive resin (Toyobo Jippon Byron 10 3 Softening point 15 5. C polyester resin) 20 Parts Liquid polyester plasticizer (Ada Densaiza PN 2 600) 2 0 Part Liquid phthalate plasticizer (DOP made by Chisso) 5 parts Epoxy plasticizer 5 parts Ripe stabilizer (barium / zinc) 3 parts Ultraviolet absorber (benzotriazole) 3 parts Solvent (Xylol Z-diisobutyl ketone) = 1 Z 1) 60 part Example 1 8

Except that the pressure-sensitive adhesive of Example 14 was changed to a pressure-sensitive adhesive having the same removability as in Example 4, using the same raw materials as in Example 14, in the same manner as in Example 14, PVC marking sheet marking with marble pattern I got a sheet.

Example 19

Using the transfer foil used in Example 6 as the process paper, and using the resin liquid composed of the vinyl chloride marking sheet raw material used in Example 4, in the same manner as in Example 14, the granulated vinyl chloride marking sheet was used. It was created. Then, on the surface opposite to the granite pattern forming surface, in the same manner as in Example 1, using the same adhesive as in Example 1, a vinyl chloride marker sheet having an adhesive layer and a release substrate was prepared. did. Example 20

On a patterned surface of the vinyl chloride marking sheet with a granite pattern obtained in Example 19, a fluorine-containing resin paint composed of the following raw materials was applied to a bar coater so that the film thickness after drying was 2.0 m. After coating, the resultant was dried at 80 ° C. for 30 seconds to provide a pattern protective layer, thereby obtaining a vinyl chloride marking sheet with a granite pattern. One pattern protection layer

Fluorine-based copolymer resin (FT-103, made by Asahi Glass) 10 parts UV absorber (benzotriazole-based) 5 parts Solvent (toluene Z methyl ethyl ketone = 1 18 5 parts Comparative Example 1

A marble-patterned vinyl chloride marking sheet was obtained in the same manner as in Example 1, except that the vinyl chloride marking sheet was prepared by omitting the mature adhesive resin from the raw materials of the vinyl chloride marking sheet in Example 1. Comparative Example 2

A vinyl chloride marking sheet with a marble pattern was obtained in the same manner as in Example 8, except that the mature adhesive resin layer in Example 8 was omitted.

Evaluation of Examples 1 to 20 and Comparative Examples 1 to 2

Example 1 to Example 20 and Comparative Example 1 to Comparative Example 2 were evaluated for the pattern transferability of the transfer foil, the abrasion resistance after transfer, the drag resistance, the adhesion, and the removability of the marker sheet. . Tables 1 and 2 show the results.

-Pattern transferability of transfer foil- The uniform transferability of the transfer pattern by transfer-transfer of the transfer foil and the presence or absence of unevenness in the transfer were evaluated.

(1) Withdrawal resistance-The ease of surface scratching was evaluated by a pencil hardness test.

—Scratch resistance—

Gakushin-type dyeing fastness test (JISL-0823) was used to evaluate the easiness of surface scratching.

One adhesion one

Cellophane tape (Nichiban 18mm wide cellophie ') was attached to the surface, and it was instantaneously peeled off to evaluate the degree of removal of the pattern to the tape side. 1. Removability-Each of the examples is attached to a stainless steel plate having a smooth surface, and pressed with a 2 kg mouth-roller. After leaving it for 168 hours in an environment of 65 and 80% RH, remove it, and then for 24 hours in an environment of 23 and 65% RH, peel it off by hand, and check whether there is any residual adhesive on the stainless steel plate. Was evaluated.

Table 1 Evaluation results of Examples 1 to 11 Evaluation pattern Shochu rub resistance Shrink resistance Adhesion Removability Example Transferability

1 〇〇〇 X

2 〇 ◎ ◎ 〇 X

3 〇 Δ 〇〇 X

4 ◎ 〇〇〇〇

5 〇〇〇〇 X

6 ◎ 〇 ◎ ◎ X

7 〇 ◎ ◎ ◎ X

8 〇〇〇 ο X

9 ◎ 〇〇〇 X

1 0 〇〇〇〇 X

1 1 ◎ ◎ ◎ 〇 X

◎: very good 〇: good Δ:: slightly poor X:

Table 2. Example 1 Example 20. Evaluation results of Comparative Examples 1 to 2 Evaluation Pattern Scratch resistance ¾_ property Adhesion Removability Example Transferability

12 ◎ 〇〇〇 3 1 3 ◎ 〇 ◎ ◎ X

14 △ Δ) 〇 X

1 5 〇〇〇 X

16 △ Δ 〇〇 X

17 〇 Δ 〇〇 X

18 Δ 〇〇〇〇 1 ◎ 〇 ◎ X

20 ◎ ◎ ◎ ◎ X Comparative Example 1 Δ X Δ X X Comparative Example 2 △ X Δ X X

◎: Very good ': Good room:: Somewhat poor X: Poor Example 21 to Example 32

In order to explain Examples 21 to 32, a vinyl chloride marking sheet with a pattern and a ripening transfer ribbon will be described in order, and a ripening copy recording method using these will be described.

Ku PVC marking sheet with a pattern>

Example 1, Example 3, Example 4, Example 8, Example 9 Example 9 Example 12, Example 13, Example 14, Example 15, Example 17, Example 17 The coating thickness of the heat-sensitive recording image receiving layer coating liquid a to f consisting of the following raw materials becomes 0.5 μm on the marking sheet or on the pattern formation surface of the vinyl chloride marking sheet with the above-mentioned pattern As described above, a vinyl chloride marking sheet with a design pattern having a sensitized recording image-receiving layer provided with a heat-sensitive recording image-receiving layer was applied as a transfer object. ー Coating solution for thermal recording image receiving layer a —

Ripe adhesive resin (Toyobo Jippon Byron 103 softening point 155 ° C Polyester resin) 10 parts Solvent (toluene Z methyl ethyl ketone = 1-1) 90 parts

-Sensitive recording image receiving layer coating solution b -Heat-adhesive resin (Byron 200 Tg 67'C polyester resin manufactured by Toyobo Co., Ltd.) 8 parts Ripe-adhesive resin (Monobet SB melting point 78 sucrose octabenzoate ester by Dai-ichi Kogyo Seiyaku Co., Ltd.) 2 parts Solvent (toluene / methyl ethyl ketone-1/1) 90 parts

Thermal adhesive resin (Darcel Chemical Industries, Inc., Araxel H7, melting point 6CTC, polycaprolactone) 10 parts Solvent (toluene Z methyl ethyl ketone = 1/1) 90 parts

-Thermal recording image receiving layer coating solution d-Ripe adhesive resin (Araxel H7, Melting point 60 ° C, Polycaprolactone, manufactured by Daicel Chemical Industries) 10 parts Thermal adhesive resin (Monobet SB, melting point 78, sucrose octabenzoic acid, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Ester) 2 parts

-Sensitive recording image receiving layer coating solution e —

Thermal adhesion resin (Toyobo Jippon's Byron 103 softening point 155 polyester resin) 8 parts Silicon-modified urethane resin (Dainichi Kagaku Kogyo Co., Ltd. Diaromer SP 21 05 Softening point 95.C) 2 parts Solvent (toluene / methyl ethyl ketone = 1 no 1) 90 parts

-Coating solution for sensible recording image receiving layer ί-Ripe adhesive resin (Toyobo Co., Ltd. Byron 130 Tg 15 ^e C polyester resin) 12 parts Fluorine copolymer resin (FT-1030 softening point 955, manufactured by Asahi Glass)

3 parts Solvent (toluene / methyl ethyl ketone = 1 Z1) 8 5 parts Ripe transfer ribbon>

Thermal transfer ribbons I to ® were obtained by the following methods. Thermal transfer ribbon

A release layer coating solution obtained by sufficiently dispersing and mixing a release layer raw material having the following composition in a ball mill is applied to a 4.5 μm-thick polyethylene terephthalate having a heat-resistant back coat layer on one surface. The other side of the back coat layer of the film was coated by gravure coating so that the film thickness after drying was 1> m. Further, a coating liquid for a colored ink layer obtained by sufficiently dispersing and mixing the following raw materials for a colored ink layer with a sand mill on the release layer is coated with a film having a thickness after drying by a gravure coating method. A colored ink layer was provided by coating so as to be 1 jum, and a thermal transfer ribbon ① was prepared.

One release layer

Ethylene monoacetate copolymer resin (Mitsui Dupont Bolichemical Eva Flex V5.77-2) 5 parts Carnauba wax 20 parts Toluene 50 parts Isopropyl alcohol 2 5 parts One colored ink layer

Polyester resin (Toyobo Jippon Byron 200) 4 parts Sucrose octabenzoate (Daiichi Kogyo Seiyaku Monopet SB)

6 parts Carbon black 10 parts Dispersant 0.5 parts Toluene 40 parts Methyl ethyl ketone 40 parts Thermal transfer ribbon

Heat-sensitive except for changing the ingredients of the colored ink layer to the following composition

The same procedure as ① was performed to create thermal transfer ribbon ②.

—Colored ink waste

Polyester resin (Byron 103, manufactured by Toyobo Eve) 10 parts Blue pigment (Lionol Blue FG 7330, manufactured by Toyo Inki)

10 parts Dispersion 剂 0.5 parts Toluene 40 parts Methyl ethyl ketone 40 parts Thermal transfer ribbon③

Thermal transfer ribbon except that the raw material of the colored ink layer is changed to the following composition

Thermal transfer ribbon ③ was created in exactly the same way as ①.

One colored ink layer

Acrylic resin (Mitsubishi Rayon Dianal BR 112) 7 parts Sucrose octabenzoate (Daiichi Kogyo Seiyaku Monobet SB)

3 parts Carbon black 10 parts Dispersant 0.5 parts Toluene 40 parts Methyl ethyl ketone 40 parts Thermal transfer ribbon

A heat-sensitive transfer ribbon (1) was prepared in exactly the same manner as the thermal transfer ribbon (1), except that the raw material of the colored ink layer was changed to the following composition.

—Colored ink layer

«-Olefin < ⁷ oleic anhydride butyl methacrylate copolymer resin (ratio: 1/1/1, Mw = 50 000) 1 2 parts Carbon black 8 parts Dispersant 0.5 part Methyl isobutyl ketone 40 parts Methyl ethyl ketone 40 parts Thermal transfer ribbon

A thermal transfer ribbon 作成 was prepared in exactly the same manner as the thermal transfer ribbon 以外, except that the release layer was not provided and the colored ink layer was directly gravure coated on the surface opposite to the back coat. .

Sensitive transfer ribbon⑥

A coating liquid for an adhesive layer having the following composition is applied on the colored ink layer of the thermal transfer ribbon by the gravure coating method so that the thickness after drying becomes 0.5 jum. , Thermal transfer ribbon ⑥ was created.

One adhesive layer

α-Olef Z-butyl oleic anhydride (Tacrylate copolymer resin (molar ratio = 1/1/1, Mw = 50 000) 10 parts Toluene 4 5 parts Methyl ethyl ketone 4 5 parts Sensitizing Photo ribbon ⑦

One colored ink layer

Polyvinylpyrrolidone resin (Lubiscol VΕ73 I made by Yuka Birdish) 5 parts Carnauba wax 1 2 parts Carbon black 3 parts Dispersant 0.1 parts Toluene 80 parts Sensitive transfer ribbon

Do not heat and melt the raw material for the hot-melt ink layer having the following composition with three rolls. The hot-melt ink composition obtained by thoroughly dispersing and mixing the mixture is coated with a heat-resistant knock coat layer on one side and a hot-melt coating on the opposite side of the back coat layer of a 4.5 m polyethylene terephthalate film. The coating was applied to a thickness of 4 μm according to the method, a ripening ink layer was provided, and a thermal transfer ribbon was prepared.

Ichijuku meltable ink layer

Ethylene monoacetate copolymer resin (Mitsui Dubon Polychemical Eva Flex V570 7-2) 8 parts Carbon black 20 parts Dispersant 2 parts Carnauba wax 60 parts Paraffin wax (melting point 1555 ° F) 10 parts

A combination of various types of vinyl chloride marking sheet with a patterned pattern, a sensitized recording image receiving layer provided on the patterned vinyl chloride marking sheet, and a ripened ¾ photographic transfer ribbon, a pallet EC-1 of a sensitive transfer copying machine made by Fuji Xerox. Characters and figures were patterned using 0. Table 3 shows the combinations implemented.

Table 3. Combinations in Examples 21 to 32 Sensitized recording image receiving layer with design pattern Sensitive transfer ribbon Presence or absence of vinyl chloride mark

Examples Ng sheet and coating liquid

2 1 Example 1 None ①

2 2 Example 1 None

2 3 Example 3 Yes: a ①

2 4 Example 4 Yes:: b ③

25 Example 8: a ②

2 6 Example 9 Yes: b ⑤

2 7 Example 9 Yes: b ④

2 8 Example 1 2 Yes:: a ①

2 9 Example 13 Yes:: c ⑥

3 0 Example 1 4 Yes:: d ⑦

3 1 Example 1 5 Yes: e ③

3 2 Example 1 有り Yes:: f ①

Examples 21 The transferability, abrasion resistance, resistance to β, adhesion, and removability of the thermal transfer ribbon in Examples 1 to 50 were evaluated, and the results are summarized in Table 4. One pull resistance

The recording part was subjected to a pencil hardness test to evaluate the easiness of scratching.

One transferability

The resolution of the recording part and the sharpness of the recording by the ripening transfer recording were evaluated. One adhesion one

A cellophane tape (Nichiban 18-mm wide cellophane tape) was attached to the recording part, which was instantaneously peeled off, and the degree to which the recording part was taken to the tape side was evaluated. Scratch resistance

The recording section was evaluated by the Gakushin-type dyeing fastness test (JISL-0823) did.

Re-peelability

Each of the examples was attached to a stainless steel plate having a smooth surface, and pressed with a 2 Kg mouthpiece. This is left for 16 hours in an environment of 65 ° C and 80% RH and then taken out.After standing for 24 hours in an environment of 23 ° C and 65% RH, the stainless steel is peeled off by hand to remove stainless steel. Evaluation was made based on the presence or absence of the residual adhesive on the plate.

Table 4. Evaluation results of Examples 21 to 32

Evaluation Thermal Ribo Scratch resistance Scratch resistance Adhesion Adhesion Removability Example Transferability

2 1 △ 〇〇〇 X

2 2 ◎ m Δ 〇 X

2 3 〇〇〇〇 X

2 4 ◎ 〇〇 ◎ 〇 2 5 〇〇〇〇 X

2 6 Δ 〇〇〇 X

2 7 〇 Δ △ ◎ X

2 8 〇〇〇〇〇

2 9 〇〇 ◎ X

3 ϋ 〇〇〇 X

3 1 △ 〇 ◎ X

3 2 △ ◎ ◎ ◎ X

◎: Very good 〇: Good △: Somewhat poor X Poor Industrial applicability

According to the present invention, it is possible to obtain a vinyl chloride marking sheet with a delicate and fine pattern, which can be adapted to a small lot, is inexpensive, has a high production efficiency, has a high quality, and is highly decorative, without going through complicated processing steps. In addition, the character “picture” is transferred to the chlorinated vinyl marking sheet with Since such images can be formed clearly and simply, an inexpensive and highly productive patterning process can be easily realized without going through complicated processing steps. The marking sheet obtained by this study has sufficient flexibility, dimensional stability and weather resistance required for marking work, and has excellent adhesion between letters and patterns, so that it can withstand practical use. is there.

Claims

The scope of the claims

1. Support the transfer ink layer with the pattern formed on the surface of the vinyl chloride marking sheet containing the mature adhesive resin, or on the thermal adhesive resin layer provided on one side of the vinyl chloride marking sheet. A vinyl chloride marking sheet with a design pattern obtained by copying the design pattern from the transfer foil provided on the body.

2. The transfer of the design pattern according to claim 1, wherein the transfer of the design pattern is obtained by casting a vinyl chloride resin on the transfer ink layer with the design pattern of the transfer foil, followed by ripening and forming a film. PVC marking sheet

3. The vinyl chloride marking sheet with a graphic pattern according to claim 2, wherein the vinyl chloride resin contains a mature adhesive resin.

4. The vinyl chloride marking sheet with a graphic pattern according to claim 2, wherein the transfer ink layer has a layer of a mature adhesive resin provided on the layer.

5. The vinyl chloride marker sheet with a pattern according to claim 1, wherein the transfer ink layer contains a heat-adhesive resin.

6. The vinyl chloride marking sheet with a graphic pattern according to claim 5, wherein the mature adhesive resin is the same as the thermal adhesive resin used in the vinyl chloride marking sheet.

7. The vinyl chloride marking sheet with a graphic pattern according to claim 1, wherein the transfer ink layer is provided with a layer of a thermoadhesive resin on the ink layer.

8. The vinyl chloride marking sheet with a graphic pattern according to claim 7, wherein the thermoadhesive resin is the same as the mature adhesive resin used in the vinyl chloride marking sheet.

9. The pattern according to claim 1, wherein the heat-adhesive resin has a glass transition point of 30 to 80 or a softening point or a melting point of 40 to 180 ° C. Vinyl chloride marking sheet.

10. The claimed vinyl chloride marking sheet with a design pattern is a character or pattern transcribed from a ripening transfer ribbon on the design pattern of the sheet. .

11. The pattern according to claim 10, wherein the vinyl chloride marking sheet with the pattern is provided with a thermosensitive recording image-receiving layer mainly composed of a heat-adhesive resin on the pattern of the sheet. PVC marking sheet with

12. The diagram according to claim 11, wherein the thermoadhesive resin has a glass transition point of 30 to 80 ° (: or a softening point or a melting point of 40 to 180′C. With a vinyl chloride marking sheet.

13. The vinyl chloride marking sheet with a pattern according to claim 1 or 11, wherein the ripe adhesive resin contains a sucrose ester and Z or a polyallolactone.

14. The vinyl chloride marking sheet with a graphic pattern according to claim 10 wherein the ripening transfer ribbon is provided with a heat-meltable ink layer on the surface of the substrate.

15 5. When the ripe-melt ink layer contains a coloring agent and a resin, and the coloring agent is an organic pigment, the weight ratio of the coloring agent resin is 0.5 to 4, and the coloring agent is inorganic. The pigment-coated vinyl chloride marking sheet according to claim EB 14, wherein in the case of pigment, the weight ratio of coloring material ^/ resin is 0.5 to 6.

16. The vinyl chloride marking sheet with a graphic pattern according to claim 10, wherein the heat-sensitive transfer ribbon has a release layer and a heat-fusible ink layer sequentially provided on the surface of the base material.

17. When the ripe-melt ink layer contains a colorant and a resin, and the colorant is an organic pigment, the overlap ratio of the colorant // resin is 0.5 to 4, and the colorant is 17. The vinyl chloride marking sheet with a graphic pattern according to claim 16, wherein the weight ratio of the coloring material / resin is 0.5 to 6 in the case of an inorganic pigment.

18. The vinyl chloride masking sheet with a design according to claim 15 or 17, wherein the resin has a softening point of 20 CTC or less.

1 9. The pattern as described on page 11, wherein the vinyl chloride marking sheet with a pattern has a pressure-sensitive adhesive layer and a release base material layer sequentially provided on the pattern surface or on the opposite surface. With vinyl chloride marking sheet.

20. The force of a vinyl chloride marking sheet with a graphic The vinyl chloride marker sheet with a graphic according to claim 1, wherein a layer of a fluorine-containing resin is provided as a surface layer on the side of the graphic pattern.