JPS597595B2 - Tenshiyakushiyokuhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention applies a thermal transfer printing method to dyed materials that do not have good affinity for sublimation dyes, such as amorphous polymer molded products such as plastics, particle boards, fake leather, and synthetic rubber. The purpose is to obtain a stable pattern, color value, clear hue, and sufficient fastness.

More specifically, the present invention applies to sublimable dyes.
−:=:nee 〒:τ; at least one general formula of medium % (
1) CH2=CX-C00Y (1) (wherein, X is a hydrogen atom or a methyl group, Y is a hydrogen atom,
Indicates a hydrocarbon group having 1 to 8 carbon atoms or an oxygen-containing hydrocarbon group.

) and an ethylenically unsaturated hydrocarbon having 2 to 20 carbon atoms at most 60 mol % is coated as an intermediate layer, and a resin having an affinity for sublimable dyes is coated as an intermediate layer. This is a transfer coloring method characterized by coating the surface of the dyed material as a dyed layer, then superimposing it on a carrier having a pattern made of sublimable dye ink and heating it to form a dyed pattern on the dyed material.

Traditionally, methods for coloring amorphous polymer molded products such as plastics, particle boards, fake leather, and synthetic rubber include coloring by kneading pigments into them during manufacturing, or dyeing by dip dyeing using dyes. method is being carried out.

In addition, as a method of giving a pattern similar to textile printing, there is a method of partially applying resist dyeing paste to the surface of the material to be dyed, and then dyeing it in an aqueous bath (Japanese Patent Publication No. 8154/1989), There is a method of printing on the surface using ink. However, all of these known methods are generally complex in operation, require a large amount of equipment and manufacturing steps, and are not of good quality. Furthermore, as an attempt to perform thermal transfer printing, there is a method (Japanese Unexamined Patent Publication No. 47-42964) in which dyed materials containing organometallic compounds are colored using sublimable dyes that can chelate with metals. However, if the material to be dyed does not have sufficient dye affinity, the dye will bleed or migrate over time, and the phenomenon of "blurring" of the pattern cannot be completely prevented, and the light fastness is also significantly inferior. are doing.

As described above, thermal transfer printing can be used to easily dye materials that do not have sufficient affinity for sublimation dyes, such as plastics, particle boards, fake leather, synthetic rubber, and other amorphous polymer molded products. However, it is extremely difficult to form a stable pattern, and a solution to this problem has been strongly desired.

In order to solve these problems, the present inventors conducted intensive research and found a new coloring method that does not have the above-mentioned drawbacks.

Generally, when dyed materials such as those mentioned above are colored with a dispersion material, the dye easily moves within the dyed material, and as a result, the pattern fades within a few days after coloring, and the original vividness of the dye is lost. I end up.

This is because dyeing with disperse dyes is not based on strong chemical bonds such as ionic bonds or covalent bonds, but rather on a mechanism in which the dye is adsorbed and diffused into the amorphous portion of the polymer material. Therefore, disperse dyes can be dyed even at relatively low temperatures in polymeric substances with a low glass transition point, but conversely, even dyes that have been dyed once can easily bleed or migrate if a small amount of heat is applied. In order to eliminate this drawback, we use a resin on the surface of the material to be dyed that has an affinity for sublimable dyes, is dyed clearly and firmly, and does not cause bleeding or migration of the dye dyed at room temperature. A possible method is to apply it as a dyed layer and perform thermal transfer printing.

However, in this case, since the dye does not move in the resin that forms the dyed layer at room temperature, there is no problem as long as the dyed layer is thick enough to prevent the sublimable dye from passing through the dyed layer during the heat treatment during transfer printing. However, if the sublimable dye passes through this dyeing layer and reaches the dyed material that does not have sufficient affinity for the sublimable dye, the dye in the dyed material will naturally bleed and the pattern will become blurred. Put it away. As a result of repeated studies in order to improve these drawbacks, the inventors of the present invention have found that by providing an intermediate layer that blocks or catches the dye between the material to be dyed and the dyed resin layer, dyes that are transferred and printed can be improved. It was found that the dye does not penetrate into the material to be dyed, and therefore a colored product with stable quality without dye bleeding or migration can be obtained.

As a resin for the intermediate layer capable of preventing penetration of such a dye, at least 40 mol% of at least one acrylic acid derivative represented by the general formula (1) and at most 6
0 mole? It has been found that a copolymer consisting of an ethylenically unsaturated hydrocarbon having 2 to 20 carbon atoms is preferable. Among the raw materials for the copolymer of the present invention, acrylic acid derivatives are compounds that are extremely effective in preventing dye transfer, while ethylenically unsaturated hydrocarbons are effective in imparting appropriate hydrophobicity. By appropriately selecting the composition, a copolymer consisting of these two components can not only prevent dye transfer but also provide properties such as hydrolysis resistance, adhesion, heat resistance, and weather resistance. I can do it.

Although such copolymers can be obtained by direct copolymerization, even more diverse copolymers can be obtained if methods such as graft polymerization and block polymerization are also used.

In the general formula (1), which is one of the components necessary to obtain the copolymer of the present invention, Y other than hydrogen atoms includes alkyl having 1 to 8 carbon atoms, alkenyl, aryl, aralkyl, alkylaryl, cyclo Examples include alkyl, cycloalkenyl, or hydroxy, epoxy, alkoxy, alkyl ketone derivatives or cyclic ether groups thereof.

Further, specific examples of the compound represented by the general formula (1) include acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, Allyl acrylate, crotyl acrylate, isobutenyl acrylate,
Phenyl acrylate, benzyl acrylate, phenethyl acrylate, cyclohexyl acrylate, acrylic acid-
3-cyclopentenyl, 2-hydroxyethyl acrylate, 2-methoxyethyl acrylate, acrylic acid-
These include 2-ethoxyethyl, glycidyl acrylate, furfuryl acrylate, methacrylic acid, and esters of methacrylic acid similar to the above-mentioned acrylic acid. As the ethylenically unsaturated hydrocarbon having 2 to 20 carbon atoms, which is the other component necessary to obtain the copolymer of the present invention, aliphatic, aromatic, and alicyclic compounds are widely used, and terminally unsaturated hydrocarbons are widely used. Both saturated compounds and internally unsaturated compounds can be used.

Particularly preferred are aliphatic α-olefins; specific examples include propylene, isobutylene, ethylene, butene-1
, pentene-1,2-methylbutene-1,2-methylbenzene-1, hexene-1, butene-2,4-methylbenzene-1,2-methyl-4-phenylbutene-1, octadecene-1, norbornene, indene, styrene,
Examples include α-methylstyrene and vinyltoluene. Among these, propylene and isobutylene are particularly useful.

Note that acrylic acid or methacrylic acid halide may be further used depending on the case.

Examples of these include acrylic acid chloride and acrylic acid bromide. In addition, in the present invention, the amount of ethylenically unsaturated hydrocarbon is at most 60 mol? I use it, but
60 moles? If more than that is used, the performance of preventing dye transfer may become insufficient, reducing the effect of the present invention.

When applying the copolymer of the present invention to dyed materials that do not have sufficient affinity for sublimable dyes, such as amorphous polymer molded products such as plastic, particle board, fake leather, and synthetic rubber. can use any method, but
Particularly preferred is a method in which the resin is applied in a state dissolved in a solvent. The solvents used here include aromatic hydrocarbons,
Preferably used are halogenated hydrocarbons, ketones, ethers, esters, amides, and the like. Examples include benzene, xylene, perchlorethylene, trichlorethylene, acetone, methyl ethyl ketone, ethyl acetate, tetrahydrofuran, 1,4-dioxane, cyclohexanone, dimethylformamide and the like. There is no particular limit to the solution concentration, but for example, 1 to 50% by weight. , preferably 5 to 30% by weight solutions are advantageously used. The solution viscosity is preferably 1 to 100,000 centipoise, particularly 10 to 1,000 centipoise. The solid content is 0.01 per square meter for the material to be dyed.
-1009, preferably 1-1009 by various methods such as brush coating, spraying, dipping or knife coating, and drying at room temperature to 200°C. Alternatively, it can be applied using an aqueous or oil dispersion,
Alternatively, it may be directly melted and applied like hot melt. The surface-treated material thus obtained is further coated with a resin as a dyeing layer. The resin forming the dyed layer is preferably a polymer having a melting point of 100° C. or higher, a glass transition point of 0° C. or higher, preferably 15° C. or higher, and an affinity for sublimable dyes.

Examples of suitable polymers include polyethylene terephthalate, polysulfone, polycarbonate, polytrimethylene terephthalate, polyethylene-2,7-naphthalate, polyvinyl alcohol, polyacrylonitrile, nylon 6, nylon 6,6, cellulose acetate, and aminoalkyds. It will be done. When treating the dyed material having the copolymer layer of the present invention using these polymers, any method may be used, such as brush coating, spraying, dipping, knife coating in a state dissolved or dispersed in a solvent. Methods such as coating, melt coating, and pressure bonding are possible, and the coating is applied to the material to be dyed at a solid content of 0.019 or more per square meter. A carrier having a pattern made of sublimable dye ink is applied to a dyed material that does not have sufficient affinity for sublimable dyes, which has a resin layer and a dyeing layer that can prevent penetration of the dye thus obtained. They are stacked and heated to transfer the sublimable dye to the resin as a dyeing layer. Materials to be dyed that do not have sufficient affinity for sublimable dyes in the present invention include plastics such as polyethylene, polypropylene, and polyvinyl chloride, fake leather, natural leather, synthetic rubber, natural rubber, particle board, nonwoven fabric, etc. It also includes metal plates, inorganic plates, wood, etc. that have been given characteristics that do not have sufficient affinity for sublimable dyes.

In the present invention, sublimable dye ink refers to oil-based and water-based printing inks containing sublimable dyes, and usually consists of oil, binder, solvent, etc. in addition to sublimable dyes, and further contains a sublimable dye to promote sublimation. It may also contain a filler. Sublimable dyes have a temperature of 100°C to 300°C under atmospheric pressure.
Dyes that sublime under transfer conditions of 1 second to 5 minutes, preferably 15 seconds to 120 seconds, and even lower temperatures under reduced pressure are desirable; typical examples include disperse dyes, vat dyes, etc. Examples include dyes, oil-soluble dyes, and cationic dyes modified to have sublimation properties. Furthermore, since the vehicles and auxiliary agents constituting the printing ink, such as binders and solvents, differ depending on the printing method employed, it is sufficient to prepare and use a printing ink suitable for the printing method. The carrier having a pattern made of sublimable dye ink used in the present invention is cellophane, metal foil, plastic film, etc., and paper is more preferred.

Printing is commonly used as a method for providing designs on carriers, but the method is not limited to this. The printing method may be lithographic, letterpress, intaglio, or stencil, and examples include offset, flexo, gravure, screen process, and special printing methods. Transfer conditions are atmospheric pressure, temperature 100℃ to 300℃, time 1 second to 5 seconds.
minutes, preferably from 15 seconds to 120 seconds. Furthermore, under reduced pressure, the temperature conditions may be even lower. In order to efficiently transfer the design on the carrier as it is and the sublimable dye on the carrier to the material to be dyed, the carrier and the material to be dyed must be in reliable contact, and methods such as pressurization and suction are required. It is better to use Furthermore, if the melting point of the resin forming the dyed layer is close to the transfer conditions and the resin and carrier will adhere to each other, it may be advisable to apply an arbitrary release agent to the material to be dyed or the carrier in advance. According to the method of the present invention, it has become possible to perform thermal transfer printing of dyed materials that do not have sufficient affinity for sublimable dyes, which has been difficult to put into practical use until now.

Furthermore, the quality of the product is that it has a delicate design with a clear, dark, and stable hue that has never been available before, and has excellent fastness, light fastness, and abrasion resistance. In addition, not only has thermal transfer printing become possible, but there is no wastewater generated after conventional dyeing and printing, and processing has become extremely easy. Next, specific examples of the present invention will be shown by way of Examples, but the content of the present invention is not limited thereto.
Example 1 The copolymer solution obtained in Reference Example 1 described below was applied onto a white PVC sheet to a thickness of 4 mil using an applicator, and the temperature was 10.
It was dried at 0°C for 1 minute.

Next, polycarbonate resin (Teijin Panlight L-1
225 (Teijin Kasei) was dissolved in chloroform to make a 15% solution.

This was applied to a white PVC sheet coated with the copolymer described above using an applicator to a thickness of 8 mils, and dried at 70° C. for 5 minutes to obtain a white PVC sheet for transfer printing. Separately, create gravure ink using an ink prescription, and use a gravure proofing machine (
(manufactured by Toshiba Machine) on high-quality single-sided roll paper and dried to obtain transfer paper.

Next, using a transfer printing machine (Nao Printer NP-1F: Naomoto Kogyo), a transfer paper was placed over the PVC white sheet for transfer printing, and transfer printing was performed at a temperature of 150° C. for 60 seconds under a pressure of 1209/Cril. As a result, a PVC sheet having a clear reddish-blue pattern was obtained. For comparison, a white PVC sheet that had not been treated according to the present invention was similarly subjected to transfer printing, but no good results were obtained in terms of sharpness, color value, and hue.

Next, 6 sheets of PVC white sheet with the colored pattern obtained here were
When left in a dryer at 0°C for one week, the pattern of the untreated PVC white sheet became blurred, but the pattern of the PVC white sheet obtained by the method of the present invention remained intact and no change was observed. .

Reference Example 1 The copolymer of the present invention used in Example 1 was obtained as follows.

101 A separable flask was equipped with a reflux condenser and a thermometer, and after the system was thoroughly purged with nitrogen, ethyl acetate 43739 was charged as a solvent, and the pre-produced 30°C
45 moles of isobutylene whose intrinsic viscosity in toluene solution is 0.91 dψ? - 5 mol% styrene - 40 mol% ethyl acrylate - 5 mol% allyl acrylate - 5 mol % of acrylic acid chloride? A five-element copolymer consisting of 20.8 weight? toluene solution containing 25619, methyl methacrylate 8539, glycidyl methacrylate 2139 and benzoyl peroxide 18.59 as a polymerization initiator.
was added and polymerized at 80°C for 8 hours to obtain the desired copolymer solution.

Example 2 The copolymer solution obtained in Reference Example 2 described later was applied to a hard polyethylene sheet with an applicator to a thickness of 6 mil, and dried at a temperature of 60° C. for 5 minutes.

Next, polysulfon (P-1700 manufactured by Union Carbide) was dissolved in chloroform to prepare a 10% solution. This was applied to a hard polyethylene sheet coated with the above copolymer to a thickness of 10 mils using an applicator, and dried at 60° C. for 5 minutes to obtain a hard polyethylene sheet for transfer printing. Separately, an offset ink was prepared using the ink formulation (B), and this was printed on double-sided specialty paper to obtain a transfer paper.

Then, using a transfer printing machine (Nao Printer 1 NP-1F, manufactured by Naomoto Kogyo), transfer paper was placed over the hard polyethylene sheet for transfer printing, and heated at 140°C under a pressure of 1209/Cd.
Transfer printing was carried out for 60 seconds at a temperature of 100 mL, and a rigid polyethylene sheet with a clear red pattern was obtained.

As in Example 1, this was compared with a rigid polyethylene sheet that had not been treated according to the present invention in terms of dyeability and pattern stability.The colored products obtained by the method according to the present invention had the same color value, sharpness, and sharpness. The quality was extremely good in terms of pattern stability.

Reference Example 2 The copolymer of the present invention used in Example 2 was obtained as follows.

By the same operation as in Reference Example 1, methyl ethyl ketone 112f11 ethanol 1129 was charged as a solvent into a 500ec separable flask, and 30
45 mol % of isobutylene whose intrinsic viscosity in toluene solution is 1.42 d1/9 - 5 mol of styrene? -45 moles of ethyl acrylate? - Quaternary copolymer consisting of 5 mol% allyl acrylate 24.0 weight? Toluene solution containing 739, methyl methacrylate 429, methacrylic acid-2
- Hydroxyethyl 10.59 and benzoyl peroxide 0.69 as a polymerization initiator were added and the mixture was heated to 80°C.
The desired copolymer solution was obtained by polymerization for a period of time.

Example 3 A copolymer solution obtained in the same manner as in Reference Example 1 was applied to a chipboard hardened with urea resin to a thickness of 4 mil using an applicator, and dried at a temperature of 100° C. for 2 minutes.

Next, dissolve the amyl alkyd resin in No. 5 solvent and
A 0% solution was made.

Claims (1)

[Claims] 1. When coloring a material to be dyed that does not have sufficient affinity for sublimable dyes by a thermal transfer printing method, at least 40 mol% of at least one type of general formula CH_2=C is added to the material to be dyed.
X-COOY (wherein, X is a hydrogen atom or a methyl group, Y is a hydrogen atom,
Indicates a hydrocarbon group having 1 to 8 carbon atoms or an oxygen-containing hydrocarbon group. ) and a copolymer consisting of an acrylic acid derivative represented by () and at most 60 mol% of an ethylenically unsaturated hydrocarbon having 2 to 20 carbon atoms as an intermediate layer, and a resin having an affinity for sublimable dyes. A transfer coloring method, which is characterized in that a dyed layer is applied to the surface of the dyed material, and then a carrier having a pattern made of sublimable dye ink is layered and heated to form a dyed pattern on the dyed material.