JPS6117275B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides heat-transferable dyes and dihydric alcohols,
Alternatively, use an ink whose main component is trihydric alcohol, monohydric alcohol with a boiling point of 200°C or higher at room temperature, or a mixture of these, and fix it without deforming the plastic by irradiating it with a flash of xenon strobe. , which relates to the instantaneous formation of a penetrating image on the surface. Conventionally, plastic molded bodies, such as films,
For coloring and dyeing sheets and molded products, there are methods such as fixing by adhering ink to the printing material, or methods of dissolving or dispersing pigments in the plastic itself and uniformly coloring the plastic at the same time as the molding process. However, in the former case, various durability is poor due to fixing by adhesion, and a coating layer may be required for further protection after fixing. In the latter case, the dye is dissolved or dispersed in the plastic before molding, which not only makes it difficult to obtain multiple colors, but also causes a large amount of dye loss. The present invention has been made to solve such problems, and the plastic surface to be marked is mainly coated with heat-transferable dyes and dihydric alcohols, or trihydric alcohols, or with a boiling point of 200°C under normal pressure.
An ink image is formed using the ink made of the above monohydric alcohol or a mixture thereof directly or using a transfer sheet, and a penetration image is instantly created without deforming the plastic by irradiation with a flash of xenon light strobe. It is something that forms. To explain the present invention in more detail, the ink used here mainly contains a heat transferable dye and a dihydric alcohol, a trihydric alcohol, a monohydric alcohol with a boiling point of 200°C or higher under normal pressure, or a mixture thereof. As a component, it is non-drying or extremely slow-drying at room temperature, and can be easily colored with heat-transferable dyes on the printing material by heating with flash irradiation from a xenon strobe.
It is characterized by forming a penetrating image inside dyeable plastic. The heat-transferable dye used here is preferably a disperse dye or oil-soluble dye from the viewpoint of rapid processing such as fixing, and due to the unique composition of the ink, it is more tolerant than conventional inks in terms of dispersion stability. Therefore, the dye can be used without special dispersion stabilization treatment. The dye should be selected appropriately taking into account the type of solvent, the fixing capacity of the fixing machine, etc. Specifically, for example, the product names include Sumikalon Violet 3BL, Yellow E-FG, Orange F-
G, Violet RL, Blue E-FBL (manufactured by Sumitomo Chemical Co., Ltd.), Diaceritone First,
Violet B, Dianex Yellow 5R-
E, Red RE-E, Brilliant Red BS-
E, Navy Blue ER-FS (Mitsubishi Kasei Corporation)
(made by Ciba), Oranthene Red 2G, Oranthene Red B, Oranthene Blue B, Oranthene Scarlet 2G, Oranzole Yellow 3G (manufactured by Ciba), Miketon First Scarlet B, Miketon Polyester Red FB (manufactured by Mitsui Toatsu) KK)
(manufactured by Nippon Kayaku Co., Ltd.), Kayaset Blue FR (manufactured by Nippon Kayaku Co., Ltd.)
Mihara Oil Yellow 5G, Mihara Oil Orange G, Mihara Oil Orange R, Mihara Oil Red 5B, Mihara Oil Green AX (manufactured by Mihara Kako Co., Ltd.), Oil Yellow G, Oil Black FBB (manufactured by Toyo Ink) A variety of general disperse dyes and oil-soluble dyes can be used. The medium for such heat-transferable dyes is dihydric alcohol, trihydric alcohol, monohydric alcohol with a boiling point of 200°C or higher under normal pressure, or a mixture thereof, which does not dry at room temperature and dries extremely slowly, making it difficult to ink. It has been found that the solvent can be sufficiently evaporated at a heating temperature that causes the heat-transferable dye to migrate into the interior of the substrate without changing the fluidity of the dye. Among the solvents used in general stamp inks, high-boiling petroleum solvents, and other solvents, it has not been possible to find a solvent that satisfies both stability at room temperature and quick drying properties when heated. Since the dye may decompose at a temperature of about 300°C, it is necessary to be able to evaporate the solvent at a temperature lower than that and within a short time. For example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, butylene glycol 1, 4-, butylene glycol 2, 3, hexylene glycol, octylene glycol, polyethylene glycol, glycerin,
Such as benzyl alcohol. The above-mentioned dye and solvent are arbitrarily selected according to the purpose of use, and the ink is made by kneading in the usual manner. However, taking into consideration heat fixing conditions, etc., a small amount of infrared absorber is added to this ink. It's okay. Specific examples of infrared absorbers include those having the following formulas () and (). In the formula, A represents a quaternary ammonium group, and in the formula (), A is a tetrabutylammonium salt, bis(1-thio-2-phenolate)nickel-
For tetrabutylammonium, the following formula ()
When A is bis(1-thio-2-naphtholate)nickel-tetrabutylammonium, which is a tetrabutylammonium salt, it is represented by the following formula (). Here, bis(1-thio-2
-naphthlate) Nickel-tetrabutylammonium has absorption maximums at wavelengths of 730 nm, 1110 nm, and 1370 nm, and has the property of absorbing near-infrared rays over a wide wavelength range of 1000 to 1600 nm.
The amount to be added should be 1 to 20% by weight based on the amount of dye in the ink, taking into consideration not only the fixing effect of the ink due to the addition of these infrared absorbers, but also changes in the hue of the ink and economic efficiency. is preferred. Other infrared absorbers include N, N, N',
N'-tetrakis(P-substituted phenyl)-P-phenylenediamines, benzidines and their aluminum salts and diimonium salts, with the general formula () Compounds represented by the following are preferred. In the formula, R is hydrogen or a lower alkyl group; , an integer of 2, A is

[Formula] Also teeth

[Formula] is shown, n is an integer of 1 or 2, and when m is 2, A is

[Formula] is shown. Among them, N-tetraphenyl-benzoquinone-
Diimonium salts, particularly those having the following general formula, are preferred. In this general formula, XX'YY' each represents an alkyl group containing up to 6 carbon atoms, RR' each represents a substituted or unsubstituted phenyl group, and A represents an anion, if any. Examples include chloride, nitrate, chlorate, sulfate, sulfonate, hexafluoroarsenate, hexafluoroantimonate, and the like. Fluorenol salts also absorb infrared radiation, and the general formula is given as follows. In this general formula, R ₁ R ₂ R ₃ each represents a hydrogen atom, O-CnH ₂ n+1 (n is between 1 and 6), or an amino group. At least 2 of these
One is an amino group, X represents an anion if it is present at all, and one or more hydrogen atoms can be substituted with the following substituents. In other words, alkoxy, alkyl, chlorine, bromine,
Examples include fluorine, nitro, acyl, acylamide, and sulfonamide. Others include first iron or second iron.
Chelates of O-quinone monooximes of iron, such as ferrous 1,2-naphtho-quinone oximate, ferrous 6-bromo-1,2-naphtho-quinone oximate, 3,5-hydroxy or 3,5-7'-hydroxy-naphtho-quinone ferrous oximate, ferrous oximate in which 0.5 to 2 moles of dinitrosoresorcin are mixed per mole of 1-nitroso-2-naphthol. and so on. As is clear from the purpose of the present invention, infrared absorbers are not limited to those described above. Infrared absorbers such as carbon black and iron oxide can also be used. Furthermore, it is also effective to use a mixture of these infrared absorbers. Next, the plastic molded body to be printed needs to have physical properties that allow it to be easily colored and dyed with heat-transferable dyes.
General thermoplastic polymers such as polyvinyl chloride, acrylic resin, polyester, polyamide resin, polycarbonate, acetal, urethane, acetate, polyethylene, styrene, etc., and among these, hydroxyethyl methacrylate, cellophane, etc., which have hydrophilic groups, Or a copolymer
Also includes ABS resin, elastomers, and rubber. Next, as methods for printing on various plastic molded bodies as printing materials, there are a method of directly printing an ink image on the printing material and a method of transferring the ink image. Direct printing methods include letterpress printing, dry offset printing, flexographic printing, intaglio offset printing, gravure offset printing, and silk screen printing. In these methods, the blankets used for dry offset printing, concave plate offset printing, and gravure offset printing should have as low a hardness as possible because they have good ink transfer properties and can provide clear printed images. Regarding the transfer method, there are two methods: printing an image on a transfer sheet in advance and transferring the ink image to the printing material under pressure at a low temperature, and applying (impregnating) the ink on the entire surface of the transfer sheet to create the desired image. There is a method in which a mold having an image is used to transfer the image to a printing material under low temperature pressure. The transfer sheet used for ink image formation here includes films such as polyester, cellophane, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, polycarbonate, acetate, coated paper, etc., and laminates thereof, or Examples include metal sheets such as steel and aluminum. In addition to the above-mentioned transfer sheet, cloth, paper, etc. may be used as the transfer sheet used for the entire surface coating (impregnation). Here, the transfer conditions are: temperature is room temperature to 60℃, pressure is 5 to 20Kg/ ^cm3 , and time is
Do this in 0.5 to 2 seconds. In the present invention, as a method for fixing the ink having the composition as described above onto a plastic molded article, a method of instantaneously heating the article by flash irradiation from a xenon strobe is used. In this case, as the plastic material to be printed, as mentioned above, plastics that can be easily colored and dyed with heat-transferable dyes can be used, but specifically, plastics whose glass transition temperature is not so high, such as styrene, Examples include acrylic resin, polyvinyl chloride, acetal, acetate, ABS resin, polyamide resin, polyester, urethane, elastomer, rubber, etc. In this case, it is possible to form an ink image with an ink having the composition as described above and then heat it with a flash of xenon light strobe to form a penetration image on these plastic surfaces. Also, as ink,
When using an ink obtained by adding a small amount of an infrared absorber to the above ink, it is possible to form a penetrating image on the plastic surface with a small amount of xenon flash light compared to an ink with no additive. can. Since the present invention has the above configuration, it has various effects shown below. That is, the present invention provides heat-transferable dyes and dihydric alcohols, or trihydric alcohols,
Or a plastic molded article using an ink whose main component is a monohydric alcohol with a boiling point of 200°C or more under normal pressure, or a mixture thereof, and a flash of xenon light strobe is used as the fixing method for the ink image. Since a penetrating image is instantaneously formed on the surface, deformation of the plastic molded body due to heating during fixing can be prevented. Furthermore,
By adding an infrared absorber to the ink, its effect can be further increased, making it extremely easy to form images on plastic moldings that are subject to severe thermal deformation. Furthermore, the plastic molded article having a penetration image obtained by the present invention has a wide range of applications, such as various cards, sheets, decorative boards, keyboards,
Possible applications include eyeglass frames and nameplates. In addition, because the pigment is instantly permeated into the plastic, the image has excellent resistance such as abrasion resistance, dimensional stability, and chemical resistance, and satisfies the suitability required for each application. is obtained. To name a few, when applied to PVC ID cards, it has excellent abrasion resistance, immersion resistance, chemical resistance,
Machine oil resistance, dimensional stability, etc., for polyester magnetic commuter passes and programming cards, abrasion resistance (number of bahts), chemical resistance, dimensional stability, etc.
In the case of acrylic decorative boards, they can satisfy the resistance aptitude required for each target, such as transparency, abrasion resistance, and chemical resistance. Examples of the present invention will be given below. Example 1 60 parts of Diamond Ceritone Fast Violet B (manufactured by Mitsubishi Chemical Industries, Ltd.) and 50 parts of polyethylene glycol #200 were mixed and mixed, and an ink obtained was used to print a white color using a dry offset printing method. After forming an ink image on a hard vinyl chloride magnetic credit card, a xenon light strobe (Commet Co., Ltd.)
Light intensity: 10
When irradiated with W Sec/cm ² , clear penetration images could be obtained without instantly deforming the printing material. This card meets the dimensional accuracy required for magnetic cards, and the penetrating image can be removed by chemicals such as alcohol or benzene, or by a reader.
No change occurred after 5000 readings. Example 2 Using an ink obtained by mixing 60 parts of Kayaset Blue FR (manufactured by Nippon Kayaku Co., Ltd.) and 50 parts of polyethylene glycol #200 and kneading the mixture, printing was carried out using a letterpress printing method.
on a polyester magnetic programming card.
After forming the ink image, the light intensity is
When irradiated with 10W Sec/cm ² , clear penetration images could be obtained without instantly deforming the printing material. This card satisfies the dimensional accuracy required for programming cards, and its penetrating image cannot be exposed to chemicals such as alcohol or benzene, or
No change occurred after 5000 parts repetitions. Example 3 Sumikalon Violet 3BL (Sumitomo Chemical Co., Ltd.)
Using the ink obtained by mixing 60 parts of Polyethylene Glycol #200 and 50 parts of polyethylene glycol #200, an ink image was formed on urethane rubber using the letterpress printing method.
CH-2000XT) at a light intensity of 10 W Sec/cm ² , it was possible to obtain a clear penetration image without instantaneously deforming the printing material. Example 4 60 parts of Kayaset Blue FR (manufactured by Nippon Gunpowder Co., Ltd.), 50 parts of polyethylene glycol #200, and bis(1-thio-2-naphthlate) as an infrared absorber.
Using an ink obtained by mixing 0.6 parts of nickel-tetrabutylammonium (1% by weight based on the amount of dye) and kneading, an ink image was formed on a polyester magnetic programming card by a letterpress printing method. Afterwards, a xenon strobe (commet strobe CH-2000XT) was used to increase the light intensity to 6W Sec/
When irradiated at cm ² , a penetration image having the same durability as the penetration image obtained in Example 2 could be obtained without instantaneously deforming the printing material. Example 5 Dianics Brilliant Red BS-E
(manufactured by Mitsubishi Chemical Industries, Ltd.), 50 parts of polyethylene glycol #200, and 0.6 parts of bis(1-thio-2-naphthorate)nickel-tetrabutylammonium as an infrared absorber, 1% by weight based on the amount of dye. Using the ink obtained by mixing and kneading, an ink image was formed on the acrylic resin using the intaglio offset printing method, and then a xenon optical strobe (Commet strobe CH-20000XT) was used to print the ink at a light intensity of 10W.
When irradiated at Sec/cm ² , a clear penetration image could be obtained instantly without deforming the printing material. Example 6 Sumikalon Violet 3BL (Sumitomo Chemical Co., Ltd.)
), 50 parts of polyethylene glycol #200, and as an infrared absorber, bis(1-thio-2-naphthorate)nickel-tetrabutylammonium.
Using the ink obtained by mixing 0.6 parts (1% by weight based on the amount of dye) and kneading, an ink image was formed on a steel plate using a flexo printing method, and then the temperature was 60℃ and the pressure was 15Kg/cm ² After transferring the ink image onto the diacetate plate with
When irradiated with W Sec/cm ² , clear penetration images could be obtained instantly without deforming the printing material.

Claims (1)

[Claims] 1 Heat-transferable dye and dihydric alcohol, trihydric alcohol, or boiling point under normal pressure
An ink image is formed on a plastic molded body that can be easily colored and dyed with the heat-transferable dye using an ink containing monohydric alcohol at 200°C or higher or a mixture thereof, and then A method for forming an image on a plastic molded object, which is characterized in that a penetrating image is instantaneously formed on the surface of the molded object by irradiating the surface of the molded object with flash light from a xenon strobe.