JP2927062B2 - Marking film and thermal transfer recording method using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a marking film having heat-melting thermal transfer receptivity and durability, and a thermal transfer recording method using the marking film and a thermal-melting thermal transfer material.

[0002]

2. Description of the Related Art Generally, polyester resins and urethane resins having high toughness and aesthetic appeal, and a yield stress of 1 to 6 kg /
mm ² , a film thickness of about 30 to 150 μm and a marking film made of a vinyl chloride resin having an appropriate stiffness required at the time of construction is weather resistant, ultraviolet absorbent retaining property,
Since it has excellent properties such as dimensional stability, 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, Silk for the purpose of cutting out relatively large characters and simple designs by computer cutting as decorative display materials for various guide boards, window displays, etc., and for forming characters and designs consisting of one or more hues on the marking film surface Painting has been performed by screen printing or ink jet recording and has been put to practical use.

[0003] Of these processing means, pattern cutting by computer cutting is the target character / character.
Since the minimum cutout area that composes the pattern is limited by the precision of the cutting machine, there is a limit to the expressive power, and the same number of applicator films as hues are used to fix large characters and designs consisting of multiple hues on the work surface However, there are disadvantages in that it is uneconomical and inefficient due to the use of, and the operation of transferring cutout characters and designs to an applicator film is complicated and time-consuming. Also, silk screen printing used as a painting process means is inferior in immediacy because it goes through a process of preparing, proofing, and printing a stencil, and at the same time, it was not possible to produce a small number of sheets at low cost. Furthermore, the ink jet recording method forms an image with dots, so that a pattern having a half tone can be obtained, but is not suitable for a small pattern with a low resolution, it is difficult to maintain hardware such as nozzle clogging, and the simplicity is poor. Has a drawback such as low production efficiency due to the time required for recording.

On the other hand, with respect to the material constituting the marking film, JP-A-60-195146 discloses a composition for molding a semi-rigid vinyl chloride resin using a liquid polyester plasticizer and an ethylene / vinyl ester resin as the vinyl chloride resin. In addition, JP-A-63-24619 discloses that
A semi-rigid vinyl chloride resin molding composition using a liquid polyester plasticizer, a low molecular weight acrylic resin or a methacrylic resin for the vinyl chloride resin has been proposed, but in any case, flexibility, weather resistance due to bleed-out of the plasticizer. The purpose of this method is to suppress the problems that occur in the conventional application fields, such as deterioration of the properties, adhesive strength retention, printing ink adhesion, ultraviolet absorbent retention, and the like. It did not suggest the application of the recording method, nor the receptive properties of the thermal transfer ink. In view of the above problems, the present invention provides a marking film as a substrate to be transferred, which can easily and inexpensively form characters and patterns on the surface of the marking film by a thermal transfer recording method and has thermal transfer ink receiving properties. Things.

[0005]

According to the present invention, there is provided a marking film comprising a plastic film containing a vinyl chloride resin and a heat-adhesive resin having a softening point of 40 to 180 ° C., and having a hot-melt type thermal transfer receptivity. And a thermal transfer recording method characterized by patterning the marking film using a thermal transfer material having a heat-meltable ink layer provided on a substrate. The marking film of the present invention is composed of a plastic film containing a heat-adhesive resin having a softening point of 40 to 180 ° C., which is easily melted by the amount of heat given at the time of thermal transfer recording. Is provided. Therefore, with the ink layer of the heat-sensitive transfer material provided with a heat-fusible ink layer on one of the substrates and the surface of the marking film of the present invention, which is the substrate to be transferred, superimposed on each other, When recording is performed from the side using a heating means such as a thermal head or a heat roll, the hot-melt ink layer melts and the contact interface between the hot-melt ink and the marking film is easily heated by the heat and pressure during thermal transfer recording. By melting and adhering, it is possible to obtain an image recorded matter such as a character or a pattern having excellent transferability and adhesiveness directly on the surface of the marking film.

[0006] Since the above image recorded matter can be generally prepared by using a thermal transfer printer which is easy to maintain, desired images such as characters and pictures can be formed at a resolution corresponding to the density of the heating elements of the thermal head. It is inexpensive and can be obtained with immediacy and is useful. In addition, it is possible to obtain a recorded material with excellent expressive power by performing multiple transfers with thermal transfer materials having different hues, use it with existing image forming means such as silk screen printing, or perform computer cutting after thermal transfer recording. The recording surface can be cut out into an arbitrary shape, or the recording surface can be laminated with a transparent plastic film.

[0007] The plastic film constituting the marking film of the present invention contains a vinyl chloride resin having high flexibility of the film and excellent suitability for attaching to a curved surface as a base resin, and contains a heat-adhesive resin having a softening point of 40 to 180 ° C.

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, esterified product of α-olefin / maleic anhydride copolymer, 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, polyes Examples thereof include a tellurium resin, a fluorine-containing copolymer resin, and the like. However, the resin is not limited thereto, and another resin may be used in combination as needed. The above-mentioned heat-adhesive resin is, for example, 1 to 40 parts by weight, based on 100 parts by weight of a base resin made of a vinyl chloride resin, and furthermore, sticking of a film at the time of a heat molding process such as a calendaring method of a marking film or of a marking film. In order to maintain appropriate flexibility required at the time of construction, it is preferable to use 5 to 10 parts by weight. In order to maintain the tensile strength of the marking film itself, the number average molecular weight of the heat-adhesive resin is preferably 2,000 to 2,
00000, preferably 3,000 to 50,000, more preferably 5,000 to 30,000, and desirably solid at room temperature. In the case of a liquid at room temperature, the fixability and adhesion of the hot-melt ink are reduced, And easily cause troubles such as blocking. Further, the thermo-adhesive resin which exhibits tackiness at room temperature causes inconveniences such as deposition of soot in the atmosphere by an outdoor exposure test and easy contamination of the surface, so that the resin needs to be solid at room temperature. In order to improve blocking resistance and soot contamination resistance, fluorine-containing polymers such as graft polymers in which acrylic branches are arranged in the backbone of fluororesin and copolymer resins of polyfluoro group-containing vinyl monomers and other vinyl monomers It is preferable to use a copolymer resin, various fluorine-based surfactants, fluorine-containing waxes and the like in combination. In particular, when a marking film is produced by a casting method using a vinyl chloride resin organosol, the heat-adhesive resin is used in an amount of 1 to 40 parts by weight, preferably 5 to 40 parts by weight, in an organic solvent to be used.
A substance that dissolves in a range of not less than part by weight is used, but may contain a partially swollen undissolved substance.

As the vinyl chloride resin in the present invention,
The degree of polymerization is 300 to 2000, preferably 600 to 150.
0 vinyl chloride resin.

The marking film of the present invention may further contain various additives known as additives for vinyl chloride resins for molding, such as plasticizers, coloring agents, stabilizers, ultraviolet absorbers, antistatic agents, oxidizing agents, and the like. Inhibitors, lubricants and the like can be used in combination. Examples of the plasticizer include a basic carboxylic acid compound such as phthalic acid, isophthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid, maleic acid, fumaric acid, trimellitic acid, and oleic acid, and a monovalent or polyvalent compound. And a low-molecular-weight ester plasticizer with an alcohol compound, an alkyd-type liquid plasticizer, and an oxirane oxygen-containing epoxy plasticizer. Examples of the coloring colorant include colored organic pigments and inorganic pigments which have been conventionally used in printing inks, and colorless extender pigments for the purpose of improving the fluidity and imparting an anchoring effect of a hot-melt ink. Can be used. As the heat stabilizer, calcium stearate, barium stearate,
Dioctyltin malate stabilizers such as lead stearate, basic lead sulfite, dibasic lead phosphite, dibutyltin dimaleate, dibutyltin laurate, dibutyltin mercaptide, etc., dioctyltin laurate stabilizer, dioctyltin mercapto Stabilizers, stabilizers such as stannane diol derivatives and / or complexes thereof may be mentioned. As the above-mentioned ultraviolet absorber, 290-4
Compounds that absorb light having a wavelength of 00 nm include, for example, benzophenone, benzotriazole, salicylic acid phenyl ester, cyanoacrylate, cinnamic acid,
Examples of the aminobutadiene-based compound and the like and an ultraviolet blocking agent include fine particles of titanium oxide, zinc white, talc, kaolin, calcium carbonate, iron oxide and the like. Examples of the antistatic agent include polyoxyethylene alkylamine, polyoxyalkylamide, polyoxyethylene alkyl ether, glycerin fatty acid ester, sorbitan fatty acid ester, alkyl sulfonate, alkylbenzene sulfonate, alkyl sulfate alkyl phosphate, and quaternary ammonium sulfate. In particular, the effect of preventing dust collection due to static electricity, which causes defective transfer in thermal transfer recording, is recognized. Known materials can be used as the lubricant, for example, liquid lubricants such as liquid paraffin and polyethylene wax, fatty acid lubricants such as stearic acid and oxy fatty acids, fatty acid amides, natural or synthetic ester waxes, and alcohol lubricants. Lubricants, fluorine-containing waxes, fluororesin powders, etc., can be used to improve the film transportability of the marking film within the thermal transfer printer and improve the abrasion resistance of the marking film surface, as long as the transferability is not adversely affected. Used for purposes.

The marking film of the present invention can be formed by a known extrusion method, calendering method, solution casting method, sol casting method, semi-sol casting method or the like. A sol-cast method or a semi-sol-cast method that does not involve hot roll processing at the time of film forming is suitable because it contains a conductive resin. For example, when using the casting method, first, a vinyl chloride resin, a heat-adhesive resin, a plasticizer, and a suitable solvent such as butanol, butyl acetate, ethylene glycol monomethyl ether acetate, diisobutyl ketone, xylol, aromatic petroleum naphtha, Solvent naphtha, a solvent for sol in which a solvent such as trichlene alone or a mixture of a plurality of types is mixed, and, if necessary, various additives described above are mixed and stirred to prepare a paste-like sol-like high-viscosity coating solution, and then released. After casting onto a support having an adhesive property, for example, a silicon-containing release process paper or a stainless plate whose surface has been release-treated, about 160 ° C. to 220 ° C. and about 1 minute to 1 minute
Heated and melted under the condition of 0 min.
A marking film of 50 μm can be obtained.

The marking film of the present invention is provided with a pressure-sensitive adhesive, for example, an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a silicon-based pressure-sensitive adhesive, with a thickness of 10 μm to 200 μm on the back side of the surface to be patterned by the thermal transfer material. An agent release substrate can be laminated. The adhesive strength is usually 1000 to 2000 gr / 25 according to the material and surface condition of the adherend.
mm adhesive (JIS Z0237 Adhesive tape / Adhesive sheet test method) is used.
000gr / 25mm width, preferably 500-900gr /
By setting the width to 25 mm, it is possible to impart a clean peeling property that allows the used pasted marking film to be easily peeled off without leaving unnecessary adhesive on the surface of the adherend.

As the material of the thermal transfer material of the present invention, conventionally known materials can be used. For example, a base film used as a base material is a polyester film (eg, polyethylene terephthalate, polyethylene naphthalate), a polyamide film (eg, nylon), a polyolefin film (eg, polypropylene), a cellulose film (eg, triacetate) having excellent heat resistance and mechanical strength. And polycarbonate films. The polyester film is most preferably excellent in heat resistance, mechanical strength, tensile strength, tensile stability and the like. The thinner this substrate is, the better the thermal conductivity is, but from the viewpoint of strength and ease of application of the ink layer, 3 μm to 5 μm
0 μm is most preferred. Further, a back coat layer made of a heat-resistant resin may be provided on the surface of the substrate opposite to the ink layer. In addition, the heat-meltable ink has an organic pigment as a coloring material,
As the inorganic pigment and the vehicle, materials such as plant-based, animal-based, mineral-based petroleum-based natural waxes, synthetic waxes, fatty acids, and thermoplastic resins having a softening point of 200 ° C. or lower are used.
In addition, in order to increase the mechanical strength of the hot-melt ink particularly after the transfer, a colored ink layer mainly composed of a thermoplastic resin containing a coloring material was provided on a substrate via a release layer mainly composed of wax. It is preferable to use a heat-sensitive transfer material. Examples of the thermoplastic resin used for the colored ink layer include polyvinyl acetate, vinyl chloride / vinyl acetate copolymer, polyethylene, polypropylene, polyacetal, and ethylene / vinyl acetate copolymer. , Ethylene / acrylic acid copolymer, α
-Olefin / maleic anhydride copolymer, esterified product of α-olefin / maleic anhydride copolymer, polystyrene, polyacrylate, polyamide, cellulose resin, epoxy resin, xylene resin, ketone resin,
Petroleum resin, rosin or its derivatives, coumarone indene resin, terpene resin, polyurethane resin, styrene /
Examples include butadiene rubber, polyvinyl butyral, nitrile rubber, acrylic rubber, synthetic rubber such as ethylene / propylene rubber, and polyester resin. The thermoplastic resin / wax weight ratio is preferably 90/10 to 60/40. If necessary, additives such as a softener such as oil, a surfactant, and an ultraviolet absorber can be used in the hot-melt ink.

[0014]

The present invention will be described in more detail with reference to the following examples. In order to explain the marking film of the present invention and a thermal recording method using the same, first, a method for processing a thermal transfer material and a marking film used below and an image recording method using a thermal transfer printer will be described. Parts in the examples are parts by weight.

<Thermal Transfer Material> Release Layer Ink A A coating liquid having the following composition was dispersed at room temperature with an attritor to obtain a release layer ink A. 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 having the following composition is dispersed at room temperature by an attritor, and heated. A meltable ink B was obtained. Carbon black (MA-7 manufactured by Mitsubishi Kasei Kogyo) 10 parts Urethane resin (Desmocoll 500 manufactured by Sumitomo Bayer Urethane) 9 parts Carnauba wax 1 part Toluene 70 parts Methyl isobutyl ketone 10 parts

As described above, using the inks of the compositions A and B, first, the other surface of a 6 μm polyethylene terephthalate film on which a back coat layer was previously provided with the ink A at a coating thickness of 0.8 g / m ^2. The resultant was coated by a gravure coating method, and then ink B was applied in the same manner as above at 0.5 g / m ² to obtain a thermal transfer material C which was overcoated.

<Manufacturing Method of Marking Film> 1) Casting Method A predetermined amount of a pigment and a plasticizer are mixed and then mixed and kneaded with three rolls to produce a colored paste. Next, a vinyl chloride resin powder and the above-mentioned coloring paste are added to a resin solution in which the thermoadhesive resin, the heat stabilizer, and the ultraviolet absorber are previously dissolved in a sol solvent so that the total solid content is about 60%. A sol paste was obtained by adding it appropriately and stirring it well with a disper while cooling. Next, the sol paste was defoamed, applied on an release paper with an applicator so that the thickness after drying was about 100 μm, and dried at 190 ° C. for 3 minutes to prepare a target marking film. 2) Calendering method After a predetermined amount of pigment and plasticizer are premixed with two rolls, the thermoadhesive resin, stabilizer, ultraviolet absorber, vinyl chloride resin, and lubricant are added.
The mixture was kneaded well at 20 ° C. for 20 minutes, and rolled with a calender roll at a temperature of 170 ° C. to 200 ° C. so as to have a thickness of about 100 μm to prepare a target marking film. 3) Coating method of pressure-sensitive adhesive The following predetermined pressure-sensitive adhesive is applied on release paper so that the coated amount after drying is 25 gr / m ² , dried at 100 ° C. for 2 minutes, and then the above-mentioned marking film Was laminated with a surface on which no image was formed to form a marking film with release paper.

Adhesive A: The following ingredients are mixed well after mixing. Initial adhesive strength is 1200gr / 25mm width (JIS-Z
0237 adhesive tape / adhesive sheet test method) at 65 ° C,
80% RH, the adhesive strength with time after 168 hours is 1500 gr /
An adhesive having a width of 25 mm was used. Acrylic adhesive (Olivine BPS4 089B manufactured by Toyo Ink Mfg.) 100 parts Isocyanate-based curing agent (Olivine BHS4 089B manufactured by Toyo Ink Mfg.) 0.87 parts

Adhesive B: The following ingredients 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, adhesion with time after 168 hours is 750 gr / 25
An adhesive having a width of mm was used. Acrylic adhesive (Oliven BPS4 294 manufactured by Toyo Ink Manufacturing Co., Ltd.) 100 parts Isocyanate-based curing agent (Olivine BHS4089B manufactured by Toyo Ink Manufacturing Co., Ltd.) 2 parts

<Thermal Transfer Recording Method> The patterning using the thermal transfer material C is set so that the surface to be transferred of the marking film and the heat-meltable ink surface of the thermal transfer material C face each other, and a full-color printer ( Using Fuji Xerox Co., Ltd.'s "Palette EC-10"), desired character and picture patterns were transcribed to obtain the desired recorded matter.

The raw material formulations and pressure-sensitive adhesives used in Examples 1 to 3 and Comparative Examples 1 to 4 are shown below, and the evaluation results are shown in Table 1 below.

[0022]

Example 1 A recording film A was obtained by using the above-described calendering method with the following composition to obtain a marking film using an adhesive B, and then performing the above-described thermal transfer. Titanium oxide (Taipage CR80, manufactured by Ishihara Sangyo) 30 parts Vinyl chloride resin (Zeon 24, manufactured by Nippon Zeon Co., Ltd., degree of polymerization: 1300) 100 parts Thermal adhesive saturated polyester resin (Vylon 103, manufactured by Toyobo Co., Ltd., softening point: 158 ° C.) Asahi Denka Kogyo Adecaizer PN260) 20 parts Liquid phthalate plasticizer (DOP made by Daihachi Chemical Industry) 15 parts Heat stabilizer (BZ100C made by Katsuta Kako) 3 parts UV absorber (Tinuvin 326 made by Ciba Geigy) 2 parts Lubricant ( Stearyl alcohol) 1 copy

[0023]

Example 2 A recording film B was obtained by using the above-described casting method and forming a marking film using the pressure-sensitive adhesive B, and then performing the above-described thermal transfer. Titanium oxide (Taipage CR80, manufactured by Ishihara Sangyo) 30 parts Vinyl chloride resin (Zeon 24, manufactured by Zeon Corporation, degree of polymerization: 1300) 100 parts Thermal adhesive acrylic resin (JONCRYL611 manufactured by Johnson Polymer, softening point 105 ° C) 20 parts Liquid polyester plasticizer (Asahi Denka) Industrial Adekizer PN260) 20 parts Liquid phthalate plasticizer (DOP manufactured by Daihachi Chemical Industry) 15 parts Heat stabilizer (BZ100C manufactured by Katsuta Kako) 3 parts UV absorber (Tinuvin 326 manufactured by Ciba Geigy) 2 parts Xylol 142 parts Diisobutyl 142 parts of ketone

[0024]

Example 3 A marking film was obtained under the same conditions as in Example 2 except that the pressure-sensitive adhesive B was changed to pressure-sensitive adhesive A, and then the above-described thermal transfer was performed to obtain a recorded material C.

[0025]

Comparative Example 1 A recording film D was obtained by obtaining the marking film using the pressure-sensitive adhesive A under the same conditions as in Example 2 except that all the heat-adhesive resin was used, and then performing the above-described thermal transfer.

[0026]

Comparative Example 2 In place of the heat-adhesive resin of Example 2, the amount of the liquid polyester resin plasticizer (Adekaizer PN260) was increased by 20 parts. A thermal transfer was performed to obtain a record E.

[0027]

Comparative Example 3 A marking film of an adhesive A was obtained under the same conditions except that 20 parts of a nitrified cotton resin (HIG1 / 2 manufactured by Asahi Kasei Kogyo Co., Ltd.) was used in place of the heat-adhesive resin of Example 1. Thereafter, the above-mentioned thermal transfer was performed to obtain a recorded matter F.

[0028]

Example 4 50 parts of an ethylene / vinyl acetate resin (Evaflex 577-2, softening point 52 ° C., manufactured by Mitsui Polychemicals, Inc.) was used in place of the heat-adhesive resin of Example 1,
Otherwise, a marking film of the pressure-sensitive adhesive A was obtained under the same conditions, and then the above-described thermal transfer was performed to obtain a recorded matter G.

[0029]

[Table 1] <Evaluation> 1. Transferability: The image clarity of the transferred record was visually determined. 2. Ink Adhesion: The degree of ink removal when the surface of the transfer recording was rubbed with a nail was visually determined. 3. Surface dirtiness: The state of surface dirt when the transfer recorded matter was exposed outdoors for one month was visually judged. 4. Removability: The transfer recorded matter is stuck on a stainless steel plate and pressed with a 2 kg roller. Then 65 ° C, 80% R
H for 168 hours, take out, 23 ℃, 65% RH
After 24 hours, the adherend was observed for the presence of residual adhesive by hand peeling.

[0030]

According to the present invention, high-precision images such as characters and pictures can be easily formed on a marking film containing a heat-adhesive resin having a heat-melting ink receptivity by a thermal transfer recording method. Therefore, inexpensive and highly productive patterning can be easily realized 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 the marking film construction, the adhesion of the heat-fusible ink of the heat-sensitive transfer material. Since it is excellent, it can sufficiently withstand practical use.

Continuation of the front page (56) References JP-A-62-66996 (JP, A) JP-A-4-28594 (JP, A) JP-A-61-283595 (JP, A) JP-A-62-294595 (JP, A) JP-A-3-106669 (JP, A) JP-A-2-40564 (JP, U) (58) Fields investigated (Int. Cl. ⁶ , DB name) B41M 5/38-5/40

Claims (5)

(57) [Claims] 1. A vinyl chloride resin and a softening point of 40 to 180 ° C.
From plastic film containing thermal adhesive resin
And a marking film with heat-melting thermal transfer receptivity
Lum. 2. The marking film according to claim 1, further comprising a release substrate on the back side of the surface to be patterned by the thermal transfer material with an adhesive layer interposed therebetween. 3. The pressure-sensitive adhesive layer has a pressure-sensitive adhesive strength of JIS-Z02.
37 50 to 1 in adhesive tape / adhesive sheet test method
000gr / 25mm width.
Or the marking film of 2. 4. The heat-adhesive resin dissolves in an organic solvent.
The method according to any one of claims 1 to 3, wherein
Marking film . 5. The mask according to claim 1, wherein
A hot-melt ink layer on the base film
Characterized by patterning using a thermal transfer material
Thermal transfer recording method.