WO1996027500A1 - Feuille de marquage en chlorure de vinyle portant un motif - Google Patents

Feuille de marquage en chlorure de vinyle portant un motif Download PDF

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Publication number
WO1996027500A1
WO1996027500A1 PCT/JP1995/000365 JP9500365W WO9627500A1 WO 1996027500 A1 WO1996027500 A1 WO 1996027500A1 JP 9500365 W JP9500365 W JP 9500365W WO 9627500 A1 WO9627500 A1 WO 9627500A1
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WO
WIPO (PCT)
Prior art keywords
vinyl chloride
marking sheet
resin
pattern
sheet
Prior art date
Application number
PCT/JP1995/000365
Other languages
English (en)
Japanese (ja)
Inventor
Yasukichi Ogasawara
Takashi Morikawa
Naoki Hasegawa
Keizo Ogata
Yasunori Kimura
Motohiko Kashioka
Original Assignee
Toyo Ink Manufacturing Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyo Ink Manufacturing Co., Ltd. filed Critical Toyo Ink Manufacturing Co., Ltd.
Priority to PCT/JP1995/000365 priority Critical patent/WO1996027500A1/fr
Publication of WO1996027500A1 publication Critical patent/WO1996027500A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
    • B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
    • B44C1/17—Dry transfer

Definitions

  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the underlying pattern 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.
  • a transfer foil is generally used for a plastic substrate or the like.
  • 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.
  • heat shrinkage of the ripening roll during transfer occurred.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • thermoadhesive resin in the range of 5 to 20 parts by weight.
  • a vinyl chloride masking sheet containing a thermo-adhesive resin 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.
  • the solvent examples 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.
  • 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.
  • the solvent for the solvent examples include:
  • the transferability of the base pattern by the transfer foil can be improved.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the vinyl chloride resin used in the present invention has a degree of polymerization of from 300 to 200, preferably from 600 to 150.
  • 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.
  • 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.
  • a vinyl chloride copolymer resin may be used alone, or two or more of them may be used in combination.
  • rich in toughness and beautification of moderate waist strength required at the time of construction namely the yield stress 1 ⁇ 6 ⁇ 8 ⁇ 2
  • a film thickness of about. 30 to 0.99 m the weather resistance, dimensional stability It has excellent properties such as properties.
  • 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.
  • plasticizer examples 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.
  • 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.
  • coloring colorant examples 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.
  • heat stabilizer examples 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.
  • antistatic agent examples 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.
  • the lubricant can be used as the lubricant.
  • 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.
  • the transfer foil is one in which a desired pattern is provided on a base sheet by gravure printing using ink.
  • the base sheet paper, a plastic film such as polyester, polypropylene, polyethylene, and polyamide, and a metal foil such as aluminum are used.
  • polyesters which are excellent in heat resistance, transparency, ink adhesion, cost and coating properties are preferable.
  • 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.
  • 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.
  • a synthetic resin such as an acrylic resin, a silicon resin, a polyamide resin, or a polyester resin
  • 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.
  • 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.
  • 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.
  • 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.
  • a conventionally known casting method that is, a solution casting method, a sol casting method, a semi-sol casting method, or the like. You can also create a king sheet.
  • 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.
  • 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.
  • T g 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, ⁇ -olefin Z maleic anhydride copolymer, esterified ⁇ -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, n
  • 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.
  • 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.
  • graft grafts with an acryl chain on the backbone of a fluororesin were used.
  • 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.
  • 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.
  • sucrose octabenzoate is effective for improving the weather resistance and is very suitable.
  • sucrose octabenzoate 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a fluorine-containing compound or a silicon-modified resin in combination with the above-mentioned heat-adhesive resin.
  • 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.
  • various fluorine-based surfactants, fluorine-containing waxes and the like are 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.
  • 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.
  • 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.
  • a heat-sensitive recording image receiving layer After forming a pattern pattern with a transfer foil on a vinyl chloride marking sheet.
  • 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.
  • Tg on the vinyl chloride marking sheet with texture is 30 to 30.
  • 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
  • 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
  • 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.
  • 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.
  • an adhesive layer may be provided on the colored ink layer for the purpose of further improving transfer adhesion.
  • polyester film polyethylene terephthalate, polyethylene naphthalate, etc.
  • polyamide film 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • resins obtained by copolymerizing ⁇ -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.
  • 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.
  • adhesive with an adhesive strength of usually 50 to 500 grZ 25 mm width J IS-Z023 7 Adhesive tape ⁇ Adhesive sheet test method
  • 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.
  • 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.
  • 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.
  • a transparent film such as a resin film may be laminated, or a fluorine-containing resin paint may be coated.
  • 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.
  • the fluorine-containing compound examples 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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)
  • 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
  • Example 1 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.
  • 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 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
  • Vinyl chloride resin (Zeon 24, manufactured by Nippon Zeon, degree of polymerization 1 300)
  • 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.
  • 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
  • This vinyl chloride marking sheet is printed on a 25 ⁇ m thick polyester terephthalate film substrate with an acryl resin.
  • 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.
  • 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)
  • Mature adhesive resin manufactured by Toyobo Co., Ltd. Byron 103 softening point 1 55 polyester resin
  • 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
  • Liquid phthalate plasticizer DOP made by Chisso
  • Ripe stabilizer barium / zinc
  • UV absorber benzotriazole type
  • Xylene Diisobutyl ketone 40 parts
  • One adhesive One adhesive
  • a vinyl chloride marking sheet having a thickness of 5 ⁇ 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.
  • Vinyl chloride resin (Zeon 24, manufactured by Nippon Zeon, degree of polymerization 1300)
  • Example 4 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.
  • 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.
  • the pattern protection layer was provided by drying for 30 seconds to obtain a vinyl chloride marking sheet with a marble pattern.
  • FT-1030 manufactured by Asahi Glass
  • UV absorber benzotriazole type
  • a white vinyl chloride marking sheet having a thickness of 10 ⁇ 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.
  • 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 resin (Zeon 24, Nippon Zeon, polymerization degree 1300)
  • 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
  • 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.
  • 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.
  • 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.
  • a vinyl chloride marking sheet having a heat-adhesive resin layer on the surface was obtained.
  • the marble pattern was transferred in the same manner as described above to obtain a vinyl chloride marking sheet with a marble pattern.
  • Vinyl chloride resin (Zeon 24, manufactured by Nippon Zeon) Degree of polymerization: 1300
  • Liquid plasticizer Ada Denka Kogyo Adeniki Sizer-1 PN2600
  • Liquid phthalate plasticizer DOP made by Chisso
  • Liquid ethoxy plasticizer 5 parts
  • Heat stabilization barium / Zinc
  • UV absorber benzotriazole
  • Lubricant stearic acid
  • Example 10 Using the same vinyl chloride marking sheet raw materials as in Example 10, a transparent vinyl chloride marking sheet having a thickness of 100 ⁇ m 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- ⁇ m 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 8 Using the same vinyl chloride marker sheet material as in Example 8, a white vinyl chloride marking sheet having a thickness of 100 ⁇ m 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.
  • Vinyl chloride resin (Zeon 24, manufactured by Nippon Zeon, degree of polymerization 1 300)
  • 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.
  • Example 14 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.
  • Vinyl chloride resin (Zeon 24, manufactured by Nippon Zeon, degree of polymerization 1 300)
  • Example 16 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)
  • Example 14 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 20 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
  • 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.
  • 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.
  • 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.
  • JISL-0823 Gakushin-type dyeing fastness test
  • 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.
  • 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.
  • Example 1 Example 20. Evaluation results of Comparative Examples 1 to 2 Evaluation Pattern Scratch resistance 3 ⁇ 4_ property Adhesion Removability Example Transferability
  • 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 ⁇ m on the marking sheet or on the pattern formation surface of the vinyl chloride marking sheet with the above-mentioned pattern
  • 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.
  • ⁇ Coating solution for thermal recording image receiving layer a
  • 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
  • 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 ⁇ m-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.
  • 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.
  • 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)
  • Polyester resin (Byron 103, manufactured by Toyobo Eve) 10 parts Blue pigment (Lionol Blue FG 7330, manufactured by Toyo Inki)
  • Thermal transfer ribbon 3 was created in exactly the same way as 1.
  • Acrylic resin Mitsubishi Rayon Dianal BR 112 7 parts Sucrose octabenzoate (Daiichi Kogyo Seiyaku Monobet SB)
  • 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.
  • a thermal transfer ribbon ⁇ was prepared in exactly the same manner as the thermal transfer ribbon ⁇ , 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. .
  • 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.
  • 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.
  • 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 ⁇ m according to the method, a ripening ink layer was provided, and a thermal transfer ribbon was prepared.
  • 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
  • the recording part was subjected to a pencil hardness test to evaluate the easiness of scratching.
  • 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.
  • 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.
  • 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.
  • 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.

Landscapes

  • Laminated Bodies (AREA)
  • Decoration By Transfer Pictures (AREA)

Abstract

L'invention concerne une feuille de marquage en chlorure de vinyle portant un motif obtenu par transfert d'un motif à partir d'une feuille de transfert, sur laquelle un motif est formé, sur une surface d'une feuille de marquage en chlorure de vinyle contenant de la résine thermoadhésive, ou sur une couche de résine thermoadhésive ménagée sur une surface d'une feuille de marquage en chlorure de vinyle. Cette invention concerne également une feuille de marquage en chlorure de vinyle portant un motif obtenu par coulage d'une résine de chlorure de vinyle sur une couche d'encre de transfert d'une feuille de transfert portant un motif. Cette invention concerne en outre une feuille de marquage en chlorure de vinyle portant un motif obtenu par transfert d'une lettre ou d'une figure d'un ruban de transfert thermosensible sur un motif ou sur une matière en feuille de marquage en chlorure de vinyle portant un motif.
PCT/JP1995/000365 1995-03-07 1995-03-07 Feuille de marquage en chlorure de vinyle portant un motif WO1996027500A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP1995/000365 WO1996027500A1 (fr) 1995-03-07 1995-03-07 Feuille de marquage en chlorure de vinyle portant un motif

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP1995/000365 WO1996027500A1 (fr) 1995-03-07 1995-03-07 Feuille de marquage en chlorure de vinyle portant un motif

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WO1996027500A1 true WO1996027500A1 (fr) 1996-09-12

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009234011A (ja) * 2008-03-27 2009-10-15 Lintec Corp マーキングフィルム

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4811408B1 (fr) * 1969-03-29 1973-04-13
JPH04179581A (ja) * 1990-11-14 1992-06-26 Riken Viny Kogyo Kk マーキング材用フィルムの製造法及びそれにより作られるフィルム
JPH06219096A (ja) * 1993-01-28 1994-08-09 Toppan Printing Co Ltd 耐候性保護層を有する転写シート及びその製造方法
JPH078232Y2 (ja) * 1986-08-26 1995-03-01 順一 石川 印刷用フィルム

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4811408B1 (fr) * 1969-03-29 1973-04-13
JPH078232Y2 (ja) * 1986-08-26 1995-03-01 順一 石川 印刷用フィルム
JPH04179581A (ja) * 1990-11-14 1992-06-26 Riken Viny Kogyo Kk マーキング材用フィルムの製造法及びそれにより作られるフィルム
JPH06219096A (ja) * 1993-01-28 1994-08-09 Toppan Printing Co Ltd 耐候性保護層を有する転写シート及びその製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009234011A (ja) * 2008-03-27 2009-10-15 Lintec Corp マーキングフィルム

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