JPH0524371A - Thermal transfer recording method and marking film - Google Patents

Abstract

PURPOSE:To provide a marking film and a thermal transfer recording method which uses a thermal transfer material and a marking film having thermal transfer acceptability. CONSTITUTION:A thermal transfer recording method which performs patterning on a surface of a heat adhesive resin layer of a substrate to be selected among polyvinyl chloride resin, polyester resin, and urethane resin composed by providing the heat adhesive resin layer to one side surface and an adhesive layer to the other side surface by using a thermal transfer material composed by providing a heat fusible ink layer to the substrate, and a marking film useful for the thermal transfer recording method are provided.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive transfer recording method and a marking film using a heat-sensitive transfer material and a marking film having heat-sensitive transfer acceptance, and more particularly, a heat-adhesive resin having heat-sensitive transfer acceptance characteristics and durability. The present invention relates to a marking film in which a layer is provided on one surface and a substrate is selected from vinyl chloride resin, polyester resin, and urethane resin.

[0002]

2. Description of the Related Art Generally, a polyester resin or urethane resin having excellent toughness and durability, and a yield stress of 1 to 6 kg.
/ Mm ² , film thickness of about 30 to 150 μm, and a marking film made of a vinyl chloride resin having an appropriate elasticity required at the time of construction are excellent in weather resistance, ultraviolet absorbent retention, dimensional stability, etc. Due to its characteristics, accent stripes and various emblems for automobiles, tank stripes and various emblems for motorcycles, vehicle markings for trucks and commercial vehicles, surface finishing materials for indoor and outdoor advertisements, various guide boards, window displays, etc. As a decorative display material for computer, relatively large letters by computer cutting and simple pattern cutting out, and silk screen printing or ink jet recording method for the purpose of forming letters and pictures consisting of one or more hues on the surface of marking film Has been subjected to painting processing by .

Among these processing means, the cutting out of a pattern by computer cutting is a target character / character.
There is a limit to the expressiveness because the minimum cutting area that constitutes the design is limited by the accuracy of the cutting machine, and the same number of applicators as the hue is used to fix a character / design consisting of multiple hues on the work surface. Since a film is used, it is uneconomical and inefficient, and further, the work of transferring cutout characters and patterns to the applicator film is complicated and time-consuming. In addition, silk screen printing used as a painting process means plate making, proofing,
Immediateness was inferior because it went through the printing process, and at the same time, it was not possible to inexpensively produce a small number of sheets. Further, the ink jet recording method forms an image with dots, so that a pattern having a halftone can be obtained, but the resolution is low and it is not suitable for small patterns, and it is difficult to maintain hardware such as nozzle clogging, and inferior in simplicity. Has a drawback that production efficiency is low because it takes time to record.

On the other hand, regarding the material constituting the marking film, in JP-A-60-195146, a semi-rigid vinyl chloride resin molding composition using a liquid polyester plasticizer and ethylene / vinyl ester resin as vinyl chloride resin is disclosed. JP-A-63-24619 proposes a semi-rigid vinyl chloride resin molding composition in which a liquid polyester plasticizer, a low molecular weight acrylic resin or a methacrylic resin is used as a vinyl chloride resin. Also aims to suppress problems that occur in conventional fields of use such as flexibility, weather resistance, adhesive strength retention, adhesiveness of printing ink, deterioration of ultraviolet absorbent retention, etc. due to bleed-out of plasticizer. It was something that was done. Also, in gravure printing and offset printing on a vinyl chloride resin substrate, a urethane resin substrate or a polyester resin substrate, generally, the purpose of improving the adhesion of the printing ink to the urethane resin substrate or the polyester resin substrate, In order to suppress the migration of the liquid plasticizer in the vinyl chloride base material, measures such as applying an undercoat have been taken, but what is necessary is to apply the thermal transfer recording method as a painting means, It did not suggest the receptive property of the thermal transfer ink. In view of such a problem, the present invention provides a simple and inexpensive method for printing characters on the surface of a marking film by a thermal transfer recording method.
It is intended to provide a marking film as a transfer base material capable of forming a pattern and having a heat-sensitive transfer ink receiving property.

[0005]

The present invention provides a heat-adhesive resin layer on one surface of a substrate selected from vinyl chloride resin, polyester resin and urethane resin, and an adhesive layer on the other surface. In the heat-sensitive transfer recording method, a marking film provided with a heat-sensitive ink layer is provided on the surface of the heat-adhesive resin layer using a heat-sensitive transfer material provided on a support. The heat-adhesive resin of a marking film composition having an ink layer of a heat-sensitive transfer material having a heat-meltable ink layer provided on one side of a support and a heat-adhesive resin layer on one side of a substrate to be transferred. With the layer surfaces superposed, the heat-meltable ink layer is melted and transferred from the other side of the substrate by using a heating means such as a thermal head, and characters and patterns are directly applied to the surface of the marking film composition. The present invention relates to a thermal transfer recording method for forming images such as. Further, the present invention relates to a marking film made of a vinyl chloride resin, urethane resin or polyester resin having a transfer property and an adhesive property for a heat-meltable ink, wherein the softening point of the heat-adhesive resin layer is 40 to 180 ° C. . That is, by providing the surface of the marking film with the heat-adhesive resin layer which can be easily melted by the heat amount applied during the heat-sensitive transfer recording, the contact interface between the heat-sensitive transfer ink and the marking film causes the heat amount and the pressure during the heat-sensitive transfer recording to be the same. It is possible to easily obtain an image-recorded material excellent in transferability and adhesion by heat-melt adhesion.

Examples of the marking film base material of the present invention include vinyl chloride resin film, urethane resin film and polyester resin film, but it is preferable that the marking film base material has high flexibility and is suitable for curved surface sticking. A vinyl resin film is particularly preferable.

Since the above marking film recorded matter can be generally prepared by using a thermal transfer printer which is easy to maintain, it is possible to obtain an image of a desired character, pattern or the like at a resolution corresponding to the density of heating elements of the thermal head. Is useful because it can be obtained at low cost and with immediacy. In addition, it is possible to easily obtain a printed material with excellent expressiveness by transferring multiple times with thermal transfer materials of different hues, and to use it together with existing image forming means such as silk screen printing, or after thermal transfer recording. It can be cut by computer cutting into an arbitrary shape, or laminated on the recording surface with a transparent plastic film.

The heat-adhesive resin in the present invention is a resin having a softening point of 40 ° C. to 180 ° C., preferably 60 ° C. to 150 ° C., 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-olefin / maleic anhydride copolymer esterification product, polystyrene, poly Acrylic ester, polyamide, epoxy resin, xylene resin, ketone resin, petroleum resin, rosin or its derivative, coumarone indene resin, terpene resin, polyurethane resin, styrene / butadiene rubber, polyvinyl butyral, nitrile rubber, acrylic rubber, ethylene / Synthetic rubber such as propylene rubber, polys Examples of the resin include a ter resin and a fluorine-containing copolymer resin, but the present invention is not limited to these, and other resins may be used in combination as necessary. The above heat-adhesive resin is 0.1 to 5.0 μm, preferably 0.3 to 2 μm on either surface of the marking film substrate, and the substrate is a vinyl chloride copolymer resin or urethane resin. In this case, it is preferable to provide the heat-adhesive resin layer with a thickness of 0.5 to 1.0 μm in order to maintain appropriate flexibility required when applying the marking film and obtain a stable coating thickness. In order to maintain the tensile strength of the marking film itself, it is desirable that the number average molecular weight of the heat-adhesive resin is 2000 to 200,000, preferably 5,000 to 50,000. If the heat-adhesive resin is tacky at room temperature, blocking may occur when the marking films are piled up and stored, or the outdoor exposure test may deposit soot in the atmosphere and cause the surface to become dirty. Therefore, it must be solid at room temperature, and further, in order to improve these blocking resistance and soot stain resistance, a graft polymer in which an acrylic branch chain is arranged on the backbone chain of a fluororesin or a polyfluoro group-containing vinyl It is preferable to use a fluorine-containing copolymer resin such as a copolymer resin of a monomer and another vinyl monomer, various fluorine-based surfactants, and fluorine-containing wax in combination.

In the present invention, when the marking film substrate is a vinyl chloride resin, the degree of polymerization is 300 to 20.
00, preferably 600 to 1500, as a vinyl chloride resin simple substance or a copolymerization component of vinyl chloride, as an olefin monomer, a diene monomer, a vinyl halide monomer, an acrylic acid ester monomer, Examples of the resin include vinyl ester-based monomers, vinyl ether-based monomers, and styrene derivatives. More specifically, vinyl chloride resin, ethylene-vinyl chloride resin, vinyl acetate-
Examples thereof include copolymer resins such as vinyl chloride resin, ethylene-vinyl acetate-vinyl chloride resin, urethane-vinyl chloride resin, and graft copolymer resins. The vinyl chloride copolymer resin may be used alone, or may be used in combination of two or more kinds, and has a thickness of 30 to 150.
A μm substrate is used. On the other hand, when the base material is a polyurethane resin, as a polyol component, for example, a polyether polyol such as polytetramethylene glycol or polypropylene glycol, or a dibasic acid such as succinic acid, adipic acid, sebacic acid, orthophthalic acid or isophthalic acid. And a polyester diol obtained by an esterification reaction of ethylene glycol, propylene glycol, etc.
Further, as the isocyanate component, for example, tolylene diisocyanate, diphenylmethane diisocyanate,
Examples thereof include polyaddition products or polycondensation products using aromatic diisocyanates such as trizine diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and aliphatic diisocyanates such as isophorone diisocyanate, and a base material having a thickness of 30 to 150 μm is used. To be done. Furthermore, as the polyester resin base material, there is no particular limitation, and a thickness of 30 to 20 which is usually available in the market
A 0 μm substrate is used.

As the ultraviolet absorber in the present invention, 2
Examples of the compound that absorbs light having a wavelength of 90 to 400 nm include benzophenone-based compounds, benzotriazole-based compounds, salicylic acid phenyl ester-based compounds, hindered amine-based compounds, cyanoacrylate-based compounds, cinnamic acid-based compounds, and aminobutadiene-based compounds. 0.5 parts by weight
To 40 parts by weight, preferably 2 to 20 parts by weight,
Further, examples of the ultraviolet blocking agent include fine particles of titanium oxide, zinc oxide, talc, kaolin, calcium carbonate, iron oxide and the like, and 1 to 80 parts by weight relative to 100 parts by weight of the heat adhesive resin. It is possible to reduce the ultraviolet deterioration of the organic pigment or the low-fading pigment such as fluorescent color contained in the heat-adhesive resin layer and the marking film for outdoor use by preferably using in the range of 15 to 40 parts by weight. Becomes

The heat-adhesive resin layer of the present invention further comprises various known additives such as plasticizers, coloring materials for coloring, antistatic agents,
A lubricant etc. can be used together. Examples of the plasticizer include phthalic acid, isophthalic acid, tetrahydrophthalic acid,
Low molecular weight ester plasticizers of basic carboxylic acid compounds such as adipic acid, sebacic acid, maleic acid, fumaric acid, trimellitic acid, oleic acid and monovalent or polyhydric alcohol compounds, alkyd liquid plasticizers, An oxirane oxygen-containing epoxy plasticizer or the like can be freely selected. As the coloring agent for coloring, a colored organic pigment, an inorganic pigment, which has been conventionally used in printing inks, and a colorless extender pigment for the purpose of imparting an effect of anchoring a heat-meltable ink, and further improving fluidity. Can be used.
Examples of the antistatic agent include polyoxyethylene alkylamine, polyoxyalkyl amide, polyoxyethylene alkyl ether, glycerin fatty acid ester, sorbitan fatty acid ester, alkyl sulfonate, alkyl benzene sulfonate, alkyl sulfate alkyl phosphate, and quaternary ammonium sulfate. In particular, it is particularly effective in preventing dust collection due to static electricity that causes defective transfer in thermal transfer recording. 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, etc. can be mentioned. Used for the purpose of improving the transportability of marking film in the thermal transfer printer and improving the abrasion resistance of marking film surface, etc. within the range where transferability is not adversely affected. To be done.

In the production of the marking film of the present invention, a coating solution is prepared by previously dissolving the heat-adhesive resin and the above-mentioned various additives in an organic solvent, or by dissolving or dispersing in water to prepare a marking film substrate. The thickness of one surface is 0.1 μm to 5 μm, preferably 0.3 μm by a solvent coating method such as a gravure coater or a roll coater.
The heat-adhesive resin layer having a thickness of m to 2 μm is formed.

The marking film of the present invention is provided with an adhesive, for example, an acrylic adhesive, a urethane adhesive, a silicon adhesive, etc., in a thickness of 10 μm to 200 μm on the back side of the surface which is patterned by the heat-sensitive transfer material, and is further adhered. An agent release base material can be laminated. Adhesive strength is usually 1000 to 2000 gr / 25 depending on the material and surface condition of the adherend.
A pressure-sensitive adhesive having a width of mm (JIS Z0237 pressure-sensitive adhesive tape / pressure-sensitive adhesive sheet test method) is used.
000gr / 25mm width, preferably 500-900gr /
By setting the width to 25 mm, it is possible to provide a clean peel property capable of easily peeling the used sticking marking film without leaving unnecessary adhesive on the surface of the adherend.

As the material of the heat-sensitive transfer material of the present invention, conventionally known materials can be used. For example, as a base film used as a support, a polyester film (polyethylene terephthalate, polyethylene naphthalate, etc.) having excellent heat resistance and mechanical strength, a polyamide film (nylon, etc.), a polyolefin film (polypropylene, etc.), a cellulose film (triacetate, etc.) , Polycarbonate film, etc. The polyester film is most preferable because it is particularly excellent in heat resistance, mechanical strength, tensile strength and tensile stability. The thinner this support is, the better the thermal conductivity is, but the strength is 3 μm and the ink layer is easy to apply.
Most preferred is 50 μm. A back coat layer made of a heat resistant resin may be provided on the surface of the support opposite to the ink layer. Further, in the heat-meltable ink, organic pigments, inorganic pigments as a coloring material and natural waxes such as plant-based, animal-based, mineral petroleum-based, etc. as vehicles, synthetic waxes, fatty acids,
A material such as a thermoplastic resin having a softening point of 200 ° C. or lower is used. Further, in order to increase the mechanical strength of the hot-melt ink after transfer, a colored ink layer mainly composed of a thermoplastic resin containing a coloring material is provided on a support through a release layer mainly composed of wax. It is preferable to use a heat-sensitive transfer material, and as the thermoplastic resin used for the colored ink layer, 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-
Ester of olefin / maleic anhydride type copolymer, polystyrene, polyacrylic acid ester, polyamide, fibrous resin, epoxy resin, xylene resin, ketone resin, petroleum resin, rosin or its derivative, coumarone indene resin, terpene Resin, polyurethane resin, styrene / butadiene rubber, polyvinyl butyral, nitrile rubber, acrylic rubber, synthetic rubber such as ethylene / propylene rubber, polyester resin and the like are mentioned, and the thermoplastic resin / wax weight ratio is 90/10 to 60 /. 40
Is preferred. Further, if necessary, additives such as a softening agent such as oil, a surfactant, and an ultraviolet absorber can be used in the above heat-meltable ink.

[0015]

EXAMPLES The present invention will be described in more detail below with reference to examples. In order to describe the heat-sensitive recording method and the marking film according to the present invention, first, the heat-sensitive transfer material and the method for processing the marking film used below, and the image recording method using the heat-sensitive transfer printer will be described. Parts in the examples are parts by weight.

<Thermal Transfer Material> Ink A for Release Layer A coating liquid having the following composition was dispersed at room temperature in an attritor to obtain Ink A for release layer. Carnauba wax 20 parts Ethylene-vinyl acetate copolymer (Evaflex 577-2 manufactured by Mitsui Polychemicals) 3 parts Toluene 77 parts Heat-meltable ink composition B A coating liquid of the following composition is dispersed at room temperature in an attritor to heat-melt. Ink B was obtained. Carbon black (Mitsubishi Kasei Kogyo MA-7) 10 parts Urethane resin (Sumitomo Bayer Urethane Desmocol 500) 9 parts Carnauba wax 1 part Toluene 70 parts Methyl isobutyl ketone 10 parts

As described above, using the inks having the compositions A and B, first, the other surface of the 6 μm polyethylene terephthaleto film having a back coat layer previously formed with the ink A with a coating thickness of 0.8 g / m ² was used. The above was applied by the gravure coating method, and then the ink B was applied by the same method at 0.5 g / m ² to obtain a heat-sensitive transfer material C which was overlaid.

<Method for producing marking film> 1) Formation of heat-adhesive resin layer The heat-adhesive resin and the above-mentioned UV absorber and antistatic agent are mixed and stirred in an organic solvent to dissolve completely, and then dried. The following marking film substrate was coated with a bar coater so that the coating amount afterwards was 1 gr / m ^2, and was heated and dried well at a temperature of 80 ° C. to 100 ° C. for 1 minute to prepare the target marking film. Substrate A: Polyurethane resin marking film (UF made by Nankai Technate) Substrate B: Vinyl chloride copolymer resin marking film (Dynacal DC1001 manufactured by Toyo Ink Mfg. Co., Ltd.) 2) Adhesive coating method The pressure-sensitive adhesive of 1 is applied so that the coating amount after drying becomes 25 gr / m ² , dried at 100 ° C. for 2 minutes, and then laminated on the surface of the marking film opposite to the heat-adhesive resin layer, and then release paper. An attached marking film was prepared.

Adhesive A-The following raw materials are thoroughly stirred after blending. Initial adhesive strength is 1200gr / 25mm width (JIS-Z
0237 adhesive tape / adhesive sheet test method) at 65 ° C.,
80% RH, adhesive strength after 168 hours is 1500 gr /
An adhesive having a width of 25 mm was used. Acrylic adhesive (Olivine BPS4089B manufactured by Toyo Ink Manufacturing) 100 parts Isocyanate curing agent (Olivine BHS4089B manufactured by Toyo Ink Manufacturing) 0.87 parts

Adhesive B-The following raw materials are mixed well after mixing. Initial adhesive strength is 500gr / 25mm width (JIS-Z0
237 adhesive tape / adhesive sheet test method) at 65 ° C, 8
0% RH, adhesive strength after 168 hours is 750gr / 25
An adhesive having a width of mm was used. Acrylic adhesive (Olivine BPS4294 manufactured by Toyo Ink Manufacturing) 100 parts Isocyanate curing agent (Olivine BHS4089B manufactured by Toyo Ink Manufacturing) 2 parts

<Heat-sensitive transfer recording method> The patterning using the heat-sensitive transfer material C is carried out by setting so that the heat-adhesive resin layer surface of the marking film and the heat-meltable ink surface of the heat-sensitive transfer material C face each other, and full color printing is performed. A printer (Fuji Xerox "Palette EC-10") was used to transfer desired patterns of characters and pictures to obtain a desired recorded matter.

The raw material blends, pressure sensitive adhesives and base materials used in Examples 1 to 3 and Comparative Examples 1 to 3 are shown below, and the evaluation results are shown in Table 1 below.

[0023]

Example 1 A heat-adhesive resin layer having the following composition was provided on the base material A, a marking film was obtained by the pressure-sensitive adhesive B, and then the above-mentioned heat-sensitive transfer was performed to obtain a recorded material A. Urethane resin (Sumitomo Bayer Urethane Desmocol 8303 softening point 80 ° C) 10 parts Toluene 75 parts Methyl isobutyl ketone 15 parts

[0024]

Example 2 A heat-adhesive resin layer having the following composition was provided on the base material A, a marking film with the pressure-sensitive adhesive B was obtained, and then the above-mentioned heat-sensitive transfer was performed to obtain a recorded matter B. Urethane resin (Sumitomo Bayer Urethane Desmocol 8303 softening point 80 ° C) 10 parts UV absorber (Ciba Geigy Tinuvin 326) 2 parts Toluene 73 parts Methyl isobutyl ketone 15 parts

[0025]

Example 3 A heat-adhesive resin layer having the following composition was provided on the base material B to obtain a marking film with the pressure-sensitive adhesive B, and then the above-mentioned heat-sensitive transfer was performed to obtain a recorded material C. Vinyl chloride / vinyl acetate copolymer resin (MPR-TA, softening point 112 ° C., manufactured by Nisshin Chemical Co., Ltd.) 10 parts Fluorine-based copolymer resin (FT-1030, softening point 95 ° C., manufactured by Asahi Glass) 5 parts Toluene 20 parts Methyl isobutyl ketone 65 Department

[0026]

Comparative Example 1 A recording film D was obtained by obtaining the marking film of the pressure-sensitive adhesive B without providing the heat-adhesive resin layer on the substrate B, and then performing the above-mentioned heat-sensitive transfer.

[0027]

Comparative Example 2 A marking film was obtained under the same conditions except that the pressure-sensitive adhesive B of Example 1 was changed to the pressure-sensitive adhesive A, and then the above-mentioned thermal transfer was performed to obtain a recorded matter E.

[0028]

COMPARATIVE EXAMPLE 3 The thermal adhesive resin layer of Example 1 was changed to the following composition, and a marking film with the adhesive B was obtained under the same conditions except for the above, and the above-mentioned thermal transfer was applied to obtain a recorded material F. Nitrified cotton resin (HIG1 / 2 manufactured by Asahi Kasei Corporation) 10 parts Methyl isobutyl ketone 40 parts Toluene 30 parts Ethyl acetate 20 parts

[0029]

[Table 1]

[0030]

According to the present invention, a highly sensitive image such as characters and pictures can be easily formed on a marking film containing a heat-adhesive resin having a heat-meltable ink receiving property by a heat-sensitive transfer recording method. Therefore, it is possible to easily realize patterning processing which is inexpensive and has high immediate productivity, without going through complicated processing steps. Further, the image recorded matter of the present invention, while maintaining the flexibility, surface smoothness, dimensional stability, weather resistance and the like required in marking film construction, the adhesion of the heat-meltable ink of the heat-sensitive transfer material Since it is excellent, it can withstand practical use.

Claims (5)

[Claims] 1. A vinyl chloride resin, a polyester resin,
A heat-meltable ink layer is provided on the surface of the heat-adhesive resin layer of a marking film having a heat-adhesive resin layer on one surface of a base material selected from urethane resins and an adhesive layer on the other surface. A thermal transfer recording method, which comprises patterning using a thermal transfer material provided on a support. 2. The adhesive strength of the adhesive layer is JIS-Z.
50 in the adhesive tape / adhesive sheet test method
The thermal transfer marking film according to claim 1, which has a width of up to 1000 gr / 25 mm. 3. A heat-sensitive transfer marking film which is a heat-adhesive resin layer made of a heat-adhesive resin having a softening point of 40 to 180 ° C. 4. The heat-sensitive transfer marking film according to claim 3, wherein the heat-adhesive resin layer contains a fluorine-containing compound. 5. The marking film for heat-sensitive transfer according to claim 3, wherein the heat-adhesive resin layer contains an ultraviolet absorber or an ultraviolet blocker.