JPH0776199A - Marking sheet - Google Patents

Abstract

(57) [Abstract] [Purpose] To provide a marking board with a good design, which is formed by designing a transfer foil. [Structure] A transfer foil having a transfer ink layer provided on a support is used for a plastic sheet containing a heat-adhesive resin,
A vinyl chloride marking sheet on which a desired pattern is transferred.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pressure-sensitive adhesive sheet for decorative display materials used for various decorations and displays, and more particularly to a marking sheet having a design which is excellent in design by using a transfer foil.

[0002]

^2. Description of the Related Art Generally, a polyester resin or urethane resin having high toughness and beauty, and an appropriate waist strength required at the time of construction, that is, a yield stress of 1 to 6 kg / mm ² , a film thickness of about 30 to 150 μm Marking sheets made of polyvinyl chloride resin as described above have excellent properties such as weather resistance and dimensional stability. Therefore, accent stripes and various emblems for automobiles, tank stripes and various emblems for motorcycles, trucks, etc. -Generally used as markings for vehicles such as commercial vehicles, marking members for indoor / outdoor advertisements, various guide plates, and decorative marking materials such as window displays. Such a marking sheet is usually cut directly from the marking sheet with a cutting machine etc. as a means of applying a pattern
The marking object was created by using it as a design or by providing a character / design on a marking sheet by a printing method such as silk screen printing. Among these processing means, the cutting out of the pattern by the cutting machine is limited to the creation of fine or complicated characters / designs because the minimum cutting area that constitutes the target character / design is limited by the accuracy of the cutting machine. That is, it is uneconomical and inefficient because it uses the same number of application films as the hue to fix a large character / design consisting of multiple hues to the construction surface. However, there are drawbacks in that the transfer work is complicated and time-consuming, and that only products with a low design quality can be obtained.

[0003]

Silk screen printing, which is used as a painting processing means, is capable of producing complicated characters and patterns, but it is inferior in immediacy due to the process of making a block copy, proofreading, and printing. At the same time, since the process of preparing the block copy and proofreading accounts for most of the cost, it was not possible to produce at low cost even when a small number of sheets were required. In recent years, ink has been used to meet the demands for cutting and silk-screen printing as means for applying the above-mentioned design, which are inexpensive and capable of multicolor expression, and have immediacy and fine characters and designs. It has been put to practical use by painting the marking sheet using the jet recording method. However, in the ink jet recording method, a pattern having a halftone is obtained because an image is formed by dots, and while it is considerably improved in terms of inexpensiveness and immediacy, at present, it has a low resolution and a small pattern or minute character expression. Is not suitable, and there are drawbacks such that maintenance and inspection are complicated because the ink nozzles are easily clogged. Further, although 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.

On the other hand, gravure printing is generally widely used as a method for continuously performing multicolor printing. However, when gravure printing is performed, particularly in a marking sheet made of polyvinyl chloride resin which is preferable as a marking sheet, gravure printing is performed. The suitability is low, swimming on the printing surface, pinholes, poor leveling, etc. occur, making precise printing difficult.
Furthermore, there are problems such as blocking due to residual solvent and elongation due to tension during printing. In addition, transfer foils are generally used for painting wood grain, marble, etc. on various plastic substrates, but display members for indoor / outdoor advertisements, various guide boards, window displays, etc. There is no suggestion about applying any pattern using a thermal transfer method for painting with a transfer foil on a marking sheet generally used as a decorative display member, and the conventional method as mentioned above. However, it was not possible to form a high-grade, very delicate and fine grain pattern such as wood grain or marble, which is used for highly decorative nameplates.

Therefore, the present inventors prepare a transfer foil on which characters and / or patterns are applied in advance as a processing method for applying characters and / or patterns to the marking sheet, so that the processing can be performed as necessary. We tried to use a transfer foil in consideration of small lot handling and immediate productivity.However, although it was possible to transfer a highly chromatic pattern, the adhesion to the marking sheet surface was poor and the transfer foil It was confirmed that there was a limit only with the adhesive layer. It is considered that the reason is that the marking sheet has a low heat fusion adhesiveness.

In view of the above situation, the inventors of the present invention have made earnest studies, and as a result, by incorporating a heat-adhesive resin into a plastic sheet and transferring a transfer foil on which a desired pattern is printed onto the plastic sheet, designability is improved. The inventors have completed the present invention by finding that characters / designs with good ink adhesion can be applied easily, inexpensively, and immediately.

[0007]

The present invention is characterized in that a desired pattern is provided on a plastic sheet containing a heat-adhesive resin by using a transfer foil having a transfer ink layer provided on a support. And the plastic sheet. Melt the transfer ink layer by heating, using a heat roll or heat plate, for example, with the plastic sheet containing the heat-adhesive resin and the transfer ink layer surface of the transfer foil provided with the transfer ink layer superposed. -Regarding a marking sheet provided with a pattern obtained by transferring. Furthermore, the glass transition temperature of the heat-adhesive resin (hereinafter referred to as Tg)
Is -30 ° C to 80 ° C, or has a softening point or melting point of 10
The present invention relates to a marking sheet having the transferability and the adhesiveness of a transfer ink at a temperature of ℃ to 180 ℃. That is, the contact interface between the transfer foil and the plastic sheet containing the heat-adhesive resin, which can be easily melted by the amount of heat given at the time of transfer, is easily melt-bonded by heat and pressure at the time of transfer to improve transferability and adhesion. It is possible to obtain an excellent design.

Next, the components used in the present invention will be described in detail. The thermoadhesive resin in the present invention has a Tg of −30 ° C. to 120 ° C., or a softening point or melting point of 10.
℃ to 200 ℃, preferably Tg -10 ℃ -80
A resin having a softening point or melting point of 50 ° C. to 150 ° C. is preferable. For example, polyvinyl acetate, vinyl chloride / vinyl acetate copolymer, polyethylene, polypropylene, polyacetal, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, α-olefin / maleic anhydride copolymer, α -Esterification product of olefin / maleic anhydride copolymer, polystyrene, polyacrylic acid ester, polyamide, epoxy resin, xylene resin, ketone resin, petroleum resin, rosin or its derivative, coumarone indene resin, terpene resin, polyurethane resin ,
Examples thereof include styrene / butadiene rubber, polyvinyl butyral, nitrile rubber, acrylic rubber, synthetic rubber such as ethylene / propylene rubber, polyester resin, fluorine-containing copolymer resin, etc., but are not limited thereto and may be used as necessary. Accordingly, other resins which do not fall within the above-mentioned thermal property range can be used together for the purpose of improving coating suitability, cost, weather resistance and other durability. The above heat-adhesive resin is, for example, 1 to 40 parts by weight with respect to 100 parts by weight of a base resin such as vinyl chloride copolymer resin, polyester resin, polyurethane resin, and acrylic resin, and further heated by a calendar method of a marking sheet. It is desirable to use within the range of 5 to 20 parts by weight in order to retain the appropriate flexibility required for sticking the film at the time of molding and applying the marking sheet. If it is a liquid at room temperature, the transferability and adhesion of the transfer ink will decrease, blocking will occur when the marking sheet changes over time and is stored repeatedly, and the outdoor exposure test will deposit soot in the atmosphere and the surface In order to cause problems such as easy fouling, it is necessary that it is preferably solid at room temperature. Furthermore, in order to improve these blocking resistance and soot pollution resistance, an acrylic branch chain is arranged in the backbone chain of the fluororesin. It is possible to use a fluorine-containing copolymer resin such as a graft polymer or a polyfluoro group-containing vinyl monomer and a copolymer resin of another vinyl monomer, various fluorine-based surfactants, and fluorine-containing wax in combination.

As a result of various studies among the above-mentioned preferable heat-adhesive resins, resins having high crystallinity or partial crystallinity are particularly preferable, and epoxy resins, sucrose esters, and polycaprolactone crystalline polyester resins are preferable. Among them, sucrose esters and polycaprolactone represented by the following general formula (1) (melting point of about 60
C) was effective.

[0010] Formula _{(1) - (CH 2 -CH} 2 -CH 2 -CH 2 -CH 2 -COO) n -

In particular, sucrose octabenzoate (melting point 78 ° C.) and sucrose octaacetate (melting point 72)
(° C) is a hard solid at room temperature and has no tackiness as mentioned above, and also has the thermal sensitivity, which is an important characteristic in thermal transfer, with a sharp melting point and low melting similar to wax. Satisfied with viscosity, and in sucrose octabenzoate, it is also effective in improving weather resistance,
Very suitable. When sucrose octabenzoate is used in the heat-adhesive resin layer, it has a slightly weaker film forming strength when used alone. Therefore, it can be more preferably used in combination with another resin having a high film forming strength. In this case, the ratio of sucrose octabenzoate is preferably 10 to 90% by weight, more preferably 30 to 90% by weight. When the softening point or melting point of the heat-adhesive resin is 10 ° C. or higher, a blocking resistance can be improved by adding a filler such as silica, which can be used. But,
If the softening point or melting point is less than 10 ° C, even if a filler such as silica is added, the blocking resistance is not significantly improved, and if the softening point or melting point exceeds 200 ° C, the plastic sheet and transfer foil ink after transfer are transferred. It was confirmed that the adhesion to the layer was lowered, and when the transfer temperature was raised too high, the dimensional stability of the plastic sheet was lowered, and a high-resolution pattern could not be transferred. Further, in order to improve the blocking resistance and the smoke pollution resistance, it is preferable to use a fluorine-containing compound or a silicon-modified resin in combination with the above heat-adhesive resin. As the fluorine-containing compound, a fluorine-containing copolymer resin such as a graft polymer in which an acrylic side chain is arranged in the main chain of a fluorine resin or a copolymer resin of a polyfluoro group-containing vinyl monomer and another vinyl monomer, and various fluorine-based compounds Surfactants, fluorine-containing wax, etc. are used. As silicone modified resin,
A polymer in which polyorganosiloxane is introduced into the main chain or side chain of the base polymer, and among them, a silicon-modified polyurethane resin having a polyorganosiloxane chain in the main chain or a silicon-modified acrylic resin having a polyorganosiloxane chain in the side chain is preferable. In addition, other resins may be used in combination with the heat-adhesive resin, if necessary.

As the plastic sheet of the present invention, for example, vinyl chloride copolymer resin, polyester resin, polyurethane resin, polyamide resin, polyimide resin, acrylic resin and the like can be mentioned, preferably vinyl chloride copolymer resin, A polyurethane resin may be mentioned. Particularly, vinyl chloride-based copolymer resin, which has a high flexibility of a sheet and an excellent suitability for sticking to a curved surface, is praised.

The vinyl chloride copolymer resin has a degree of polymerization of 300 to 2000, preferably 600 to 1500,
Vinyl chloride resin simple substance or vinyl chloride copolymer component as olefin monomer, diene monomer, vinyl halide monomer, acrylic ester monomer, vinyl ester monomer, vinyl ether monomer Examples of the resin include monomers and styrene derivatives. More specific examples include copolymer resins such as vinyl chloride resin, ethylene-vinyl chloride resin, vinyl acetate-vinyl chloride resin, ethylene-vinyl acetate-vinyl chloride resin, urethane-vinyl chloride resin, and graft copolymer resins. To be
The vinyl chloride-based copolymer resin can be used alone, or two or more kinds thereof can be used in combination, and in general, it is rich in toughness and aesthetics, and has an appropriate waist strength required at the time of construction, That is, a base material made of a polyvinyl chloride resin having a yield stress of 1 to 6 kg / mm ² , a film thickness of about 30 to 150 μm, and excellent properties such as weather resistance and dimensional stability is used. Furthermore, the plastic sheet used in the present invention may be colored, colorless, color transparent, or color translucent, and can be colored as necessary, but normally a colored vinyl chloride marking sheet substrate is used. When it is colorless, it is installed on a show window of a store or the like to enhance its aesthetic appeal.

The plastic sheet used in the present invention may further contain various known additives such as a plasticizer, a coloring material, a heat stabilizer, an ultraviolet absorber, an antistatic agent and a lubricant. Examples of the plasticizer include basic carboxylic acid compounds such as phthalic acid, isophthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid, maleic acid, fumaric acid, trimellitic acid, oleic acid, etc. Low molecular weight ester plasticizers with alcohol compounds, liquid polyester plasticizers, alkyd liquid plasticizers, oxirane oxygen-containing epoxy plasticizers, etc. can be freely selected, but weather resistance, flexibility retention From this viewpoint, liquid polyester plasticizers, alkyd liquid plasticizers, and oxirane oxygen-containing epoxy plasticizers are preferable. As the coloring material for coloring, a colored organic pigment or inorganic pigment that has been used in conventional printing inks, or a colorless extender pigment for the purpose of imparting fluidity improvement, anchoring effect of transfer ink, or the like is used. be able to. As the heat stabilizer, calcium stearate, barium stearate, lead stearate, lead sulfite, lead phosphite, dibutyltin malate, dibutyltin laurate,
Dibutyl tin mercaptide, dioctyl tin malate stabilizer, dioctyl tin laurate stabilizer, dioctyl tin mercaptide stabilizer, tin diol derivative,
Also, mention may be made of these complexes. Examples of the ultraviolet absorber include compounds that absorb light having a wavelength of 290 to 400 nm, such as benzophenone-based, benzotriazole-based, salicylic acid phenyl ester-based, hindered amine-based, cyanoacrylate-based, cinnamic acid-based compounds,
Aminobutadiene-based compound or the like is used as the thermoadhesive resin 100.
0.5 to 40 parts by weight, preferably 2 parts by weight
In the range of up to 20 parts by weight, further as an ultraviolet blocking agent,
Examples thereof include fine particles of titanium oxide, zinc oxide, talc, kaolin, calcium carbonate, iron oxide, etc., and 1 to 80 parts by weight relative to 100 parts by weight of the heat-adhesive resin,
It is preferably used in an amount of 15 to 40 parts by weight to reduce ultraviolet deterioration of the heat-adhesive resin layer for outdoor use and the organic pigments and low brown pigments such as fluorescent colors contained in the vinyl chloride marking sheet. Is possible. Examples of the antistatic agent include polyoxyethylene alkylamine, polyoxyalkylamide, polyoxyethylene alkyl ether, glycerin fatty acid ester, sorbitan fatty acid ester, alkyl sulfonate, alkyl benzene sulfonate, alkyl sulfate alkyl phosphate, and quaternary ammonium sulfate. Particularly, the effect is recognized to prevent dust collection due to static electricity which causes transfer failure. Further, as the lubricant, known materials can be used, for example, hydrocarbon lubricants such as polyethylene wax, stearic acid, fatty acid lubricants such as oxyfatty acid lubricants, fatty acid amide lubricants, natural or synthetic waxes, alcohol lubricants, Fluorine-containing wax, fluororesin powder and the like can be mentioned, and they are used for the purpose of improving the abrasion resistance of the marking sheet surface, improving the film forming processability, etc. within the range where the transferability is not adversely affected.

The plastic sheet of the present invention can be formed into a sheet by a publicly known extrusion method, calendering method, solution casting method, sol casting method, semi-sol casting method or the like, but the plastic sheet of the present invention is preferred. Since it contains a heat-adhesive resin, a sol-cast method or a semi-sol-cast method that does not involve hot roll processing during sheet molding is suitable. For example, when using the casting method in a vinyl chloride copolymer film, first, a vinyl chloride copolymer resin, a heat-adhesive resin, a plasticizer and a further suitable solvent such as butanol, butyl acetate, ethylene glycol monomethyl ether acetate. , A solvent for sol in which solvents such as diisobutyl ketone, xylol, aromatic petroleum naphtha, solvent naphtha, and trichlene are mixed alone or in plural kinds, and if necessary, various additives described above are mixed and stirred to form a paste sol. After a high-viscosity coating liquid is prepared and cast on a support having releasability, for example, a silicon-containing releasable process paper or a stainless plate whose surface is release-treated, the temperature is about 160 ° C to 220 ° C. , About 1 minute to 1
Target thickness of 30 μm-1 by heating and melting under the condition of 0 minutes
A 50 μm plastic sheet can be obtained.

The marking sheet of the present invention has a pressure-sensitive adhesive such as an acrylic pressure-sensitive adhesive on the pattern surface or the surface opposite to the pattern.
Adhesives such as urethane adhesives and silicone adhesives
It can be provided with a thickness of up to 200 μm, and an adhesive release substrate can be further laminated. Depending on the material and surface condition of the adherend, the adhesive strength is usually 50-5000 gr / 25 mm width (JIS-Z0
237 Adhesive of adhesive tape / adhesive sheet test method) is used, but the pasted marking sheet that has been used does not leave unnecessary adhesive on the surface of the adherend and exceeds the breaking strength of the marking sheet. In order to impart removability that can be easily peeled without requiring such peeling force, it is particularly preferable that the adhesive force is 50 to 1500 gr / 25 mm width, and more preferably 500 to 900 gr / 25 mm width. Good. Further, with an adhesive force of 1500 gr / 25 mm width or more, a strong adhesive property can be imparted to an adherend as a permanent adhesive type.

The transfer foil of the present invention is one in which a desired pattern is provided by gravure printing using an ink on a base material sheet. As the base sheet, paper, or a plastic film such as polyester, polypropylene, polyethylene, polyamide, or a metal foil such as aluminum is used.
It is preferable to use polyester, which is excellent in heat resistance, transparency, ink adhesion, cost, and coatability, and to control the coating temperature and coating tension that can be seen when gravure printing is directly applied to a vinyl chloride copolymer sheet. There are few difficulties. A thickness of 10 μm to 250 μm is preferably used. If necessary, these base material sheets are previously subjected to a peeling treatment such as coating with a synthetic resin such as an acrylic type, a silicon type, a polyamide type, a polyester type, or the like, and then a conventionally known fluorine type, vinyl type, urethane type. -Based, cellulose-based, polyester-based resin or the like, or a mixture of them as a binder, a pigment, a coloring agent such as a dye,
A printing foil prepared by adding and kneading other necessary additives and solvents is gravure-printed to obtain a transfer foil. In general, the transfer foil ink contains a thermoplastic resin, but it contains the same resin as the thermo-adhesive resin contained in the marking sheet, or it is further heated by laminating it on the transfer foil printing ink layer surface. Time compatibility improves, transferability,
Adhesion can be significantly improved. In addition, a configuration that is usually performed, such as further providing a concealing layer, can be taken as necessary.

In the transfer method of the present invention, a method is used in which the pattern surface of the transfer foil is set face-to-face on the marking sheet and the pattern is transferred by a heat roll, a heat press or the like, which is necessary when preparing the marking sheet. May be transferred by using heat, for example, may be transferred at the same time as rolling by a calender method, or may be transferred at the same time by using heat required for heating and film formation by a casting method, etc. A method capable of applying heat or pressure may be used.

The marking sheet provided with the pattern by the constituent materials and the processing method described above may be subjected to the post-processing which is usually carried out depending on the application. For example, for the purpose of further improving the weather resistance, the marking sheet outermost layer may be laminated with a transparent film such as polyester, polypropylene, polyethylene, or a fluorine-containing resin, or may be coated with a fluorine-containing resin coating material, You may contain the additive which has an ultraviolet blocking effect, such as an ultraviolet absorber. In particular, it is preferable to laminate the fluorine-containing compound in the form of a film or a coating film because not only weather resistance but also stain resistance and abrasion resistance are improved. As the fluorine-containing compound, a graft polymer in which a side chain of an acrylic resin is arranged on a main chain of a fluororesin (a low molecular weight oligomer may be used) or a copolymer polymer of a vinyl monomer containing a polyfluoro group and another vinyl monomer (a low molecular weight oligomer) However, it is preferable. In addition, the marking sheet with a pattern obtained as described above may be processed into a required form by cutting or silk screen printing for the purpose of further enhancing the designability, and if necessary, unevenness processing on the surface by mechanical embossing or the like. .. Further, another layer of the heat-adhesive resin layer may be provided on the outermost surface of the vinyl chloride marking sheet with the pattern, and characters / patterns may be applied by a patterning means such as a heat-sensitive transfer recording method in order to enhance the design.

[0020]

The present invention will be described in more detail with reference to the following examples. The number of parts in the examples represents parts by weight.

Example 1 A resin solution composed of the following sheet raw materials was casted by a known casting method, and a release paper of 160 μm thickness obtained by applying a polyester-based release agent to a high-quality paper, which had been clay-coated, had a thickness of 50 μm on the release surface. A film was formed so that the process paper was removed to obtain a marking sheet. Then, release treatment was applied to one surface 17
The initial adhesive strength was 150, which was provided on the release surface of 0 μm thick double-sided polyethylene laminated paper so that the film thickness would be 30 μm.
The adhesive layer consisting of the following adhesive raw materials, which has a 0 gr / 25 mm width (JIS-Z0237 adhesive tape / adhesive sheet test method) and has a aging adhesive strength of 2,000 hours after 65 ° C., 80% RH and 168 hours, is 2000 g / 25 mm width. A layer that is laminated on a white marking sheet, and a 25 μm-thick polyethylene terephthalate film substrate with a peeling layer made of acrylic resin and a gravure-printed marble pattern using a coloring ink containing vinyl acetate resin as the main component. , A vinyl chloride / vinyl acetate copolymer resin was sequentially provided with an adhesive layer, and a marble pattern was transferred onto a marking sheet with a heating roll at 150 ° C. under a pressure of 4 kg to obtain a marking sheet. . -Marking sheet-Vinyl chloride resin (Zeon 24 made by Nippon Zeon 24 degree of polymerization 1300) 100 parts Thermal adhesive resin (John Cryl 611 made by Johnson Polymer, softening point 105 ° C) 20 parts Acid value titanium (Taipec CR80 made by Ishihara Sangyo) 50 parts Liquid Polyester plasticizer (Adeka Sizer PN260 manufactured by Asahi Denka Co., Ltd.) 20 parts Liquid phthalate ester plasticizer (DOP manufactured by Chisso) 15 parts Heat stabilizer (barium / zinc system) 3 parts UV absorber (benzotriazole system) 2 parts Xylene 40 Part Diisobutyl ketone 40 parts-Adhesive-Two-part curable acrylic adhesive 100 parts Curing agent 0.87 parts

Example 2 In the same manner as in Example 1, the following sheet raw materials were used.
A marking sheet having a thickness of μm was prepared, and then the same transfer foil as in Example 1 was used to transfer the marble pattern onto the transparent marking sheet with a heating roll. Furthermore, Example 1
A marking sheet with a marble pattern was obtained by laminating the pressure-sensitive adhesive on the pattern surface using the same pressure-sensitive adhesive as in. -Marking sheet-Vinyl chloride resin (Zeon 24 made by Nippon Zeon 24, degree of polymerization 1300) 100 parts Heat-bonding resin (Byron 103 made by Toyobo, Softening point 155 ° C) 20 parts Liquid polyester plasticizer (Adeka Sizer PN260 made by Asahi Denka Co., Ltd.) 20 Part Liquid phthalate ester plasticizer (Chisso DOP) 5 parts Liquid epoxy plasticizer 5 parts Heat stabilizer (barium / zinc system) 3 parts UV absorber (benzotriazole system) 3 parts Xylene 30 parts Diisobutyl ketone 30 parts

Example 3 The following sheet raw material was used in the same manner as in Example 1
We made a marking sheet with a thickness of μm, made of the following adhesive raw materials and had easy removability, and the initial adhesive strength was 500 gr.
/ 25 mm width (JIS-Z0237 pressure-sensitive adhesive tape / pressure-sensitive adhesive sheet test method), the same processing as in Example 1 was performed using a pressure-sensitive adhesive having a time-dependent adhesive strength of 750 gr / 25 mm width at 65 ° C, 80% RH, and 168 hours. gave. A 25 μm thick polyester terephthalate film base material, a release layer made of an acrylic resin, a colored layer containing styrene-acrylic resin as a main component, a pattern layer formed by gravure-printing a wood pattern, and a polyester resin. A polka dot pattern was transferred in the same manner as in Example 1 by using a transfer foil in which the following adhesive layers were sequentially provided to obtain a marking sheet with a grain pattern. -Marking sheet-Vinyl chloride resin (Zeon 24 made by Nippon Zeon, degree of polymerization 1300) 100 parts Heat-adhesive resin (Toyobo Byron 103, softening point 155 ° C polyester resin) 12 parts Heat-adhesive resin (Daiichi Kogyo Seiyaku Monopet) SB melting point 78 ° C sucrose octabenzoate 8 parts acid value titanium (Ishihara Sangyo Taipaque CR80) 50 parts liquid polyester plasticizer (Asahi Denka Kogyo ADEKA CIZER PN260) 20 parts liquid phthalate plasticizer (Chisso DOP) ) 15 parts Heat stabilizer (barium / zinc-based) 3 parts Ultraviolet absorber (benzotriazole-based) 2 parts Xylene 40 parts Diisobutyl ketone 40 parts-Adhesive-Two-component curable removable acrylic adhesive 100 parts Cured Agent 0.25 part

Example 4 In the same manner as in Example 1, the following sheet raw materials were used.
A marking sheet having a thickness of μm was prepared, and the same adhesive processing as in Example 3 was applied. The same transfer foil as in Example 3 was used for this, and the same process as in Example 1 was carried out to transfer the wood grain pattern to obtain a marking sheet with a wood grain pattern. -Marking sheet- Vinyl chloride resin (Zeon 24 made by Nippon Zeon 24 degree of polymerization 1300) 100 parts Thermal adhesive resin (Placcel H7 manufactured by Daicel Chemical Industries, melting point 60 ° C Polycaprolactone) 20 parts Titanium oxide (Taipeque CR80 manufactured by Ishihara Sangyo) 50 parts Liquid polyester plasticizer (Adeka Sizer PN260 manufactured by Asahi Denka Co., Ltd.) 20 parts Liquid phthalate ester plasticizer (DOP manufactured by Chisso) 15 parts Heat stabilizer (barium / zinc type) 3 parts UV absorber (benzotriazole type) 2 parts Toluene 5 parts xylene 35 parts diisobutyl ketone 40 parts

Example 5 A marking sheet having a thickness of 50 μm made of the same sheet material as in Example 3 was prepared in the same manner as in Example 1, and the same adhesive processing as in Example 1 was performed. A 25 μm thick polyethylene terephthalate film substrate with a release layer made of an acrylic resin, a pattern layer obtained by gravure-printing a granite pattern with a colored ink containing styrene-acrylic resin as a main component, and a polyester resin. Using a transfer foil in which an adhesive layer made of a mixture of sucrose octabenzoate was mixed in a ratio of 6/4, a granite pattern was transferred by a heating roll to obtain a marking sheet with a granite pattern.

Example 6 On the pattern surface of the marking sheet E obtained in Example 5,
Furthermore, a fluorine-containing resin coating consisting of the following raw materials was applied with a bar coater so that the film thickness after drying would be 2.0 μm, and then dried at 80 ° C. for 30 seconds to provide a pattern protective layer and a marking sheet with a granite pattern. Got -Design protection layer-Fluorine-based copolymer resin (FT-1030 manufactured by Asahi Glass) 10 parts UV absorber (benzotriazole-based) 5 parts Solvent (toluene / methyl ethyl ketone = 1/1) 85 parts

Example 7 A marking sheet with a marble pattern was obtained in exactly the same manner as in Example 1 except that the raw materials for the sheet of Example 1 were changed to the following. -Marking sheet- Titanium oxide (Taipaque CR80 manufactured by Ishihara Sangyo) 30 parts Polyurethane resin (dicyclohexylmethane diisocyanate / polyhexamethylene carbonate diol (Mw 1000) / propylene glycol / isophorone diamine = 4/1/1/1 (molar ratio)) 100 Part Thermal adhesive resin (Voyon 103, softening point 158 ° C., saturated polyester resin, manufactured by Toyobo) 20 parts UV absorber (Tinuvin 326, manufactured by Ciba-Geigy) 2 parts Solvent (cyclohexanone / diisobutylketone = 2/1) 400 parts Evaluation of Examples The marking sheets with a pattern pattern obtained in the above examples were evaluated for transferability of transfer foil, scratch resistance after transfer, scratch resistance, adhesion and removability of the marking sheet. The results are shown in Table 1.

[0028]

EFFECTS OF THE INVENTION According to the present invention, it is possible to obtain a marking sheet which is capable of handling a small lot without complicated processing steps, is inexpensive, and has a delicate pattern with good production efficiency.
Further, since the marking sheet obtained by the present invention retains the flexibility, dimensional stability, and weather resistance required for marking work, it has excellent adhesion of characters and patterns,
It can be put to practical use.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Keizo Ogata 2-3-13 Kyobashi, Chuo-ku, Tokyo Toyo Inki Manufacturing Co., Ltd. (72) Yasunori Kimura 2-3-13 Kyobashi, Chuo-ku, Tokyo Toyo Inki Manufacturing Co., Ltd. (72) Inventor Motohiko Kashiwaoka 2-33 Kyobashi, Chuo-ku, Tokyo Toyo Inki Manufacturing Co., Ltd.

Claims (5)

[Claims] 1. A vinyl chloride marking sheet characterized in that a desired pattern is transferred onto a plastic sheet containing a heat-adhesive resin by using a transfer foil having a transfer ink layer provided on a support. 2. The marking sheet according to claim 1, wherein an adhesive layer and a release substrate are provided on the pattern surface or the surface opposite to the pattern surface. 3. The marking sheet according to claim 1, wherein a part or all of the heat-adhesive resin is sucrose ester or polycaprolactone. 4. The marking sheet according to claim 1, wherein the transfer ink layer of the transfer foil contains the same thermal adhesive resin as the thermal adhesive resin layer contained in the marking sheet. 5. The marking sheet according to claim 1, wherein a fluororesin layer is provided on the outermost surface on which the pattern is transferred.