JPS6024867B2 - Dye sublimation transfer printing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is aimed at completely preventing contamination of non-patterned areas of paper, cloth, etc. caused by diffusion and penetration of sublimated dyes when carrying out the dye sublimation transfer printing method. This article relates to a dye sublimation transfer printing method that can be used.

In recent years, sublimation transfer printing carriers (hereinafter abbreviated as carriers) made of sheet-like materials such as paper or films have been developed using sublimable dyes.
Dye sublimation transfer is a technique that allows you to create any vivid color pattern by printing a pattern on the surface of the dye in advance, then bringing the dye into contact with a dyeable cloth, etc., and applying heat treatment at the same time. Textile printing method (hereinafter abbreviated as sublimation printing method)
This method is widely used and has the great advantage that it does not require the complicated steps of general textile printing methods, since the operation of coloring cloth etc. itself is extremely simple. However, this sublimation printing method has many problems as follows.

First, the sublimable dye printed on the carrier diffuses in a highly concentrated gaseous state during the heat transfer process and dyes the fabric, etc., so it is possible to dye the fabric with the original size of the printed pattern. It never wears out and always shows a tendency to expand.

Therefore, the printed pattern size must be formed in advance as a printed pattern that can always be appropriately reduced from the desired size on the fabric. However, in such an embodiment, it is difficult today to use sublimable dyes to express extremely delicate and deep-colored fine line patterns or extremely delicate Shirayu Tsumugi lines (non-dyed Tsumugi line patterns). This is impossible due to plate-making and printing technology.

Therefore, printed products based on the sublimation printing method on the market, even if the carrier is obtained through a precise printing process such as gravure printing or offset printing, cannot be used on the actual dyed fabric. It is difficult to obtain a clear color pattern.

On the other hand, when a conventional carrier printed with a sublimable dye is stored, the sublimable dye in the printed pattern easily sublimates and diffuses around the sheet forming the carrier and condenses in a contaminating manner, resulting in poor repulsion. form the cause of. Conventionally, as a remedy for the above drawbacks,
First of all, in order to express a delicate pattern, prepare the anti-discharge dyeing paste (hereinafter abbreviated as "discharge dyeing paste") according to the well-known discharge printing method in the general textile printing method, and apply the desired pattern on the fabric to be dyed. A means of printing on the fabric to prevent beams, prepare a beam-proofing paste by mixing powder such as extender pigments in a high concentration and density in a normal polymer glue solution, and coat the fiber surface of the fabric to be dyed. Depending on the method, measures are taken to prevent contact with the dye, or to prevent the intrusion of water that can dissolve the dye by using water-repellent agents, waterproofing agents, gel-like pastes, and the like. However, all of the above methods are insufficiently effective in sublimation printing.

This is because the sublimation transfer process involves heat transfer of sublimable dyes at high temperatures and within a short period of time, and the activity of these dyes is so great that they easily penetrate obstacles such as resist dyeing paste films. .
In addition, in the above-mentioned sublimation printing method, it is necessary to form a resist dyeing paste layer containing an extremely large amount of resisting components, and the threads of the fabric to be dyed are absolutely not allowed to be exposed.

Therefore, the beam-preventing glue is unusually bulky, and in some cases, it must be applied in a thick film several times to the same location to prevent dye vapor from entering or passing through. In addition, there is a risk that the resist dye layer may peel, crack, or scatter during handling of the cloth or high-temperature transfer; Powder-containing glues have drawbacks such as the drying film being extremely hard and hanging, causing irreversible deformation and wrinkles on the transfer cloth, and very poor removability when washed with water after transfer. arise. Moisture absorbers and plasticizers have been added for the purpose of imparting flexibility to the beam barrier coating, but as a reaction, there is a strong possibility that the ability to prevent dye intrusion may deteriorate or the fabric may become stiff. In short, the conventional sublimation printing method's barrier beam technology is only carried out by hand-printing on a scale of 4 using an adsorbent on a part of plain woven fabric, and on strong twist fabric georgette and knit fabric. It was considered extremely difficult.

Next, when the resisting material is printed on a carrier sheet on which dyes can be printed in advance to form a resist beam, the sheet is smooth unlike cloth, so the resist dyeing paste adheres evenly, which is preferable. On the other hand, there is another problem.

That is, one of the advantages of the transfer process is that the carrier sheet is normally supplied in the form of a roll and is dyed continuously.During printing, the paper is always handled as a roll, and therefore, it is difficult to prevent If the beam glue layer is raised on the carrier sheet, it will cause irregular partial spaces in the paper web layer, resulting in poor pattern matching due to meandering during the printing process and uneven deformation of the paper surface. In addition, when a large number of beam barriers are used, the coating layer becomes extremely thick, and the drying operation takes a long time, resulting in fatal practical defects. Incidentally, when the beam-preventing glue layer is thin, the effect of preventing the intrusion of high-temperature gaseous dyes is significantly reduced, as in the case of the dyed fabric. In this way, it has been unexpectedly difficult to obtain the desired vivid lines and clear fine white patterns in the sublimation printing process as easily and efficiently as in general printing.

On the other hand, in order to solve the above-mentioned conventional problems during storage of carrier sheets, a contamination prevention treatment is applied in advance at the time of papermaking of carrier sheets. There is almost no effect, and almost no effect is observed.

Therefore, after printing, the carrier sheet is often coated with a thin layer of sublimation stain preventive material over the entire surface.

However, the purpose of this anti-staining layer (called a top coat) is to improve the frictional strength of the ink film and temporarily adhere it to the fabric during the transfer process. Since the metastasis rate of the drug is significantly reduced, we cannot expect much from it. In short, all conventional sublimation printing methods have extremely large drawbacks, which is why an effective sublimation printing method has been desired.

The inventors of the present invention should fundamentally improve the drawbacks of the above conventional method.
As a result of various studies, a metal or metal compound having specific properties, a polymer compound that chelates with the metal ion, and a substance that inhibits or promotes the chelation were formed on a sheet-like material such as cloth or paper. It has been discovered that if a dense chelated polymer film is formed by applying a substance that can be formed by reacting in the coexistence, the penetration or passage of dye vapor can be strongly prevented at both room temperature and high temperature. The present invention was completed.

Next, the configuration of the present invention will be explained in detail.

The present invention is characterized in that a water-insoluble or elutriation-soluble metal or metal compound, or a complex metal compound, alone or in a mixture, and the above-mentioned metal or metal are added to a sheet material forming either a dyed cloth or a carrier. A film of a chelating polymer substance obtained by a reaction between a polymer compound that chelates with the metal ion of the compound and a substance that suppresses or promotes the chelation is formed to a film thickness of 500 mm or less, and the coating is applied to the dyed fabric and This is a sublimation printing method characterized by carrying out sublimation transfer printing by bringing carriers into contact with each other.

The sheet material used in the present invention includes woven fabrics, knitted fabrics, blended fabrics, mixed woven fabrics, mixed green fabrics, non-woven fabrics, etc. made of natural fibers, recycled fibers, semi-synthetic fibers, or synthetic fibers. On the other hand, examples of the carrier include cellulose fiber paper, cellophane, synthetic resin film, metal foil, etc. Among them, cellulose paper is the most useful.

When applying the method of the present invention to a cloth to be dyed, the material described below is applied in advance to a pattern that requires non-stainability to sublimation dyes, and after drying or heat treatment if necessary, the sublimation dyes are printed. let

A heat transfer method is carried out in contact with a carrier sheet, but in the case of application to a carrier sheet on which sublimation dyes are applied, patterns are similarly applied and dried or heat treated. On the other hand, in the case of preventing dye transfer during storage of a carrier sheet, a substance described below is applied over the entire surface of the sheet to cover it.
In some cases, if the sheet is made of paper or the like, it may be impregnated during papermaking. In addition, treatment on both sides or the front surface of the sheet is performed as appropriate, but it is difficult to say that the treatment on the front surface is very effective. Water-insoluble or water-soluble metals used in the method of the present invention include magnesium, aluminum,
Examples include metals such as zinc, cadmium, tin, lead, manganese, chloride, nickel, iron, cobalt, copper, titanium, and shelf elements, as well as solid solutions and alloys thereof, and these may be used alone or in mixtures, but in particular Preferably, a material is selected that can be made into a fine powder and does not leave any undesirable coloring caused by the ions after ionization.

The metal compounds used in the method of the present invention include hydroxides such as magnesium hydroxide and aluminum hydroxide, oxides such as magnesium oxide, lead dioxide, and cobalt oxide, carbonates such as magnesium carbonate, calcium carbonate, and basic carbonate steel. , sulfates such as calcium sulfate and lead sulfate, and other salts, phosphates, and sulfides such as barium citrate, stannous phosphate, zinc sulfide, etc., and these may be used alone or in combination. These are generally water-insoluble or poorly water-soluble at room temperature, and other metal compounds that are generally chlorinated are also used with the same effects as those described above.

It is desirable that these metal compounds be used in the form of fine powder, like the above-mentioned metals. Among metal compounds, nitrates, chlorides, etc. are generally water-soluble, so when used directly, the polymer compound instantly gels, and only the surface layer of the polymer becomes water-insoluble, leaving water inside. When contained in a large amount, it exhibits a hydrogel-like appearance and only forms a highly heterogeneous gelled film of a polymer compound, and after drying, pores are formed irregularly. Since it is difficult to use, it cannot be used directly in the sublimation printing method.Next, as used in the present invention, a chelation reaction occurs with a metal ion based on a metal or a metal compound to form a delicate chelate film. Examples of polymer compounds include natural ionic polymer compounds such as casein, alginates, arabic acid thickening agents, and tannic acid derivatives, and semi-synthetic ionic polymer compounds such as carboxylmethyl cellulose and carboxylmethyl guar gum. ,
Synthetic ionic polymer compounds such as vinyl/maleic acid copolymer salts, polyaminocarboxylic acid condensates, phenol formaldehyde condensates, and the sulfonate salts may be mentioned, and these may be used alone or in combination depending on the purpose. It performs chelation with the metal ions mentioned above.

In this case, the above-mentioned polymer compounds having ionic atomic groups in the polymer are particularly effective because they produce stable chelate compounds, but non-ionic polymers such as polyvinyl alcohol, methylcellulose, etc. Compounds may also be used, although with less effectiveness. Next, substances that suppress or promote the chelation reaction, which are necessary for the purpose of effectively regulating the formation of a strong and delicate chelated polymer film, which is a feature of the present invention, include glycine, Amino acids or derivatives thereof such as hippuric acid, inorganic acids such as sulfamic acid, phosphorous acid, etc., acidic compounds such as ammonium chloride, urea hydrochloride, organic acids such as oxalic acid, salicylic acid, ammonia, triethanolamine,
Alkali or amines such as ethylenediamine, basic compounds such as urotropin, diphenylguanidine, etc., alkali-generating compounds such as sodium acetate, tertiary sodium phosphate, etc., and metal hiding substances such as ethylenediaminetetraacetate, pyrophosphate, etc. These are essential for reducing or activating the reaction rate of metals or metal compounds, and by their combination,
The metal ions are generally inactivated at room temperature and can be easily controlled to be activated at high temperatures, thus gradually
Alternatively, a highly dense chelated polymer film can be rapidly formed.

This is thought to be the reason why the rust ionic compounds generated from the above reaction are particularly effective. For example, ammoniacal tetraammine zinc chloride rust salts are remarkable as a means of mildly contributing water-soluble zinc chloride to the chelation reaction. It has the effect of liberating zinc ions very gradually at room temperature and releasing ammonia at high temperatures to quantitatively perform the chelation. In the case of zinc powder, it has the effect of promoting the gradual release of zinc ions and effectively forming a dense chelate film. Furthermore, calcium sulfate in the coexistence of sodium pyrophosphate can hide the calcium ion and make it inactive, allowing the chelation reaction to be extremely advantageously controlled, and the present invention shows that the reaction can be attenuated or activated by the combination thereof. This is one of the remarkable features of Therefore, the composition of the substance is
It is selected and increased or decreased depending on the temperature condition, the type and combination of chelating agents, the concentration, etc., without being too much or not too little. The method of forming a dense and strong chelated polymer compound film in the present invention is as follows: 1) The above three components are simultaneously applied to a sheet-like material in a mixed state.

(2) A reaction inhibiting or accelerating substance is applied to a sheet together with one of the chelating agents, and the sheet is further treated with the other chelating agent.

The method of the present invention can be carried out safely and easily by any of the above-mentioned methods. For example, the polymer compound is dissolved or dispersed in a solvent or prepared by dipping, and the polymer compound is dissolved or dispersed in a solvent. The compound and the reaction inhibitor and promoter are dissolved, dispersed, emulsified, or prepared in a microcapsule form in a solvent, and then screened,
It is applied to a pattern or the entire area using a coating process such as lo-fu, rotary, gravure, offset, flexo, etc., padding, coating, splendid, etc., and then it is delicately chelated at room temperature or under heating. A film can be formed appropriately.

The quantitative relationship of the chelation reaction main ingredients of the present invention is determined by the required reaction amount of functional groups with each other based on the molecular weight of both, but in general, when the polymer compound side is in excess, it is difficult to form a strong chelation film. Desirable in terms of formation. However, the setting of the conditions should be determined empirically in view of the variety of chelation reactions, and therefore there is no particular need for quantitative limitations on both. However, if excessive unreacted solid components remain and cause pores in the coating, the amount should be kept to a minimum.Also, when targeting very light-colored sublimation dyes, the coating should be made into a thin layer. is sufficient to reach your goal. The film thickness of the chelating polymeric material in the method of the present invention is less than 500 µm, and anything more than that is unnecessary and harmful.

For example, 5 to 100 for paper, 25 to 50 for cloth
A value of 0 French is desirable, and its specific value is determined by the density, smoothness, drying property of the sheet-like material, shrinkability of the chelate film, type of sublimation dye, concentration, etc. Therefore, the film of the present invention has a chemical form based on pure chelation, which transcends the physical form of ordinary polymer compounds such as gelation and coagulation, and is capable of smoothly carrying out the reaction and forming a fiber. Suppression to achieve a dense, strong, uniform, and homogeneous state,
It is essential to incorporate the accelerator component, and the film thus formed has excellent resistance to sublimation dyes. Next, the treated fabric is in contact with the general sublimation printing paper, and if the treatment is applied to a carrier sheet, the carrier and the dyed fabric are in contact with each other, and both are usually 190-220 qo, 20-49 qo. In the meantime, a high temperature transfer process is performed, followed by washing with water, de-sizing, and cleaning in the former case, and in the latter case, the cloth is taken out as it is as a sublimation printed cloth.

In this way, on the dyed cloth obtained, a fresh iron and delicate resist-dyed pattern clearly appears. On the other hand, an unprinted carrier sheet is subjected to the treatment of the present invention in advance, and a printing ink made of a sublimation dye is applied onto the treated surface. If carried out, the transfer rate of the dye to the fabric will be significantly higher, and in this respect it is incomparably superior to commercially available unprinted carrier sheets for transfer, and the transferred carrier sheet can be reused. Moreover, even if the carrier sheet is stored for a long period of time, no dye bleeding is observed on the surface coated with printing ink, and a clear transfer printed fabric can be obtained. The special effects of the invention can be fully demonstrated. In addition, the sublimable dye printed on the carrier in the present invention is preferably one that exhibits sublimation behavior at 360 qo or less under normal pressure.
Pigments that do not contain sulfonic acid groups and carboxyl groups, such as organic pigments such as azo, quinone, and berynone; disperse dyes such as azo, quinone, and coumarin; and quinone, thiondigo, and berylene. Examples include constructional dyes such as Jianliang dyes, oil-soluble dyes such as azo dyes, nitro dyes, etc., and light brighteners such as naphthalimide dyes, oxazole dyes, imidazole dyes, and the like.

In addition, the reason why it is 36,000 or less is that among the above-mentioned sublimable dye group,
Although many organic pigments and architectural dyes have a melting point of 36,000, they exhibit sublimation behavior at around 200°C, and the limit of heat resistance without destruction of the chelated polymer film of the present invention is about 360q○. It is based on the fact that

However, if the cloth to be dyed is polyester fiber, 230
The area around this is the processing limit. In addition, in the method of the present invention, surfactants, drying regulators, oils and fats, waxes, adsorbents, dye solubilizers, pigments, carriers, extender powders, redox agents, redox inhibitors, ultraviolet absorbers, Contains chemicals such as white pigments, thickeners, mold release agents, foaming agents, electrolytes, antifoaming agents, foaming agents, water repellents, insect repellents, preservatives, etc. for purposes other than forming the chelate film. Even if it is, it does not depart from the gist of the present invention. Next, the effects of the present invention will be listed. '
1' When the method of the present invention is used, the relationship between the original pattern, the printing plate, and the dyed pattern dimensions can be freed from the complexity of setting the margin visually and empirically as in the past, and the desired pattern can be obtained. can be expressed freely.

(2) According to the method of the present invention, a sharp pongee line or small dot pattern can be easily obtained. Legs According to the method of the present invention,
By selectively adding pigments, it is possible to prevent the color from being stained.

According to the method of the present invention, the coating work is extremely easy, and it is possible to form a sublimation dye-impermeable, non-beam-like polymer film that adheres uniformly to the surface of a sheet-like object and is extremely dense.
Furthermore, the formation of the chelated polymer film can be controlled as desired. {5} Even though the treatment layer of the present invention is extremely thin, it effectively prevents the penetration of sublimation dyes, so it does not affect printability, and there is no deformation or meandering during the transfer operation, causing peeling or scattering of the film. A strong, effective, and pure chelating polymer compound can be appropriately selected without any problems.

Legs If sublimation printing paper is made using a sheet-like carrier treated entirely by the method of the present invention, the behavior of dyes penetrating into the sheet at room temperature and high temperature, unlike conventional paper, will be improved, and the transfer efficiency will be greatly improved. In addition, the range of usable sheets is expanded, for example, it becomes possible to use paper with a low basis weight, and since it is non-staining, it is also possible to reuse sublimation transfer paper that has already been transferred, which is very economical.

(7) Sublimation printed paper treated by the method of the present invention is completely prevented from generating double patterns after long-term storage.

Next, examples will be shown.

Example 1 Parts by weight of 10% aqueous solution 8 of low viscosity sodium alginate (hereinafter, parts by weight are abbreviated as parts).

), 0.5 parts of sodium tripolyphosphate and 1.5 parts of diammonium phosphate are uniformly mixed and dissolved, and further 2 parts of anhydrous calcium sulfate, 0.5 parts of diammonium phosphate, and 15.5 parts of water are added in advance. The materials to be dispersed into fine particles were quickly mixed together to form a uniform viscous steel solution. (Viscosity 500 ratio.ps). Using this sticky solution, make a diameter of 1
Print on polyester Amundsen cloth through a dense polka dot distribution screen plate (130 mesh) and heat at 80°C.
After drying for 3 minutes, heat treatment was performed for 15 minutes and 0.2 minutes to form a delicate film on the polka dot pattern (average film thickness 200 mm). (color dye) 10% concentration ink plate depth 65, 15
0, the entire surface was placed in contact with normal sublimation printing paper printed with a gravure plate, and heat treated with sand at 205° C. for 3 hours. Next, the cloth was taken out, soaked in warm water at 65°C for 5 minutes, heated to 95°C with a 0.5% caustic soda aqueous solution, soaked in the same solution for 1 minute, thoroughly washed with running water, and air-dried. In this way, a polyester Amundsen transfer printed fabric was obtained in which a clear polka dot pattern with a diameter of 1 skin, densely packed in a deep black base dye, was clearly expressed.

For comparison, an attempt was made to prepare a beam paste by adding the same amount of calcium sulfate used in this example and excluding other ingredients, but it gelled into an agar-like state and could not be mixed. , Maprogum NP (trade name) 10% aqueous solution and 1
A 0% sodium alginate aqueous solution was diluted at a ratio of 80:20 and the same treatment as in this example was performed, but no traces of polka dots were found in the deep black background dyeing.

In addition, when a resist dyeing paste containing 6 parts of a 10% mapro gum aqueous solution and 4 parts of calcium sulfate was used in the same manner as in this example, a slight effect was observed, and a gray polka dot pattern was obtained. However, the viscosity of the resist-dyed fabric was 100,000 c. p. s, making the seal lacquer work difficult. Therefore, the same screen version is 7
0 mesh and by squeezing the same resist dye twice, a light grayish brown polka dot pattern was finally obtained, but the thickness of the resist dye layer was 0.5 when dried. Therefore, after the thermal transfer process, the area around the polka dot pattern was deformed and became uneven, and in any case, a clear difference from this example was observed. Example 2 A single-sided coated high-quality paper for gravure that was uniformly gravure printed in advance with 8% density ink of McMillon Navy BP (trade name: sublimation dye) using a full-scale engraving plate with a plate depth of 40 mm and 150 mm. /, 123 inboard roll, Example 1
The same beam-proofing glue was printed at a speed of 20 m/min using a horizontal striped string gravure plate with a plate depth of 60 mm and a diameter of 0.2 at 80 r, and dried with hot air at 150°C for 1 minute, and then printed on the paper. A highly glossy and delicate film (average film thickness: 40 mm) was formed on the surface.

Next, the triacetate knit cloth was brought into contact with the above-mentioned treated sublimation printing paper, heated for 20 mm with a cylinder-type thermal transfer machine, and the knit cloth was taken out.

In this way, a trisenite transfer-printed cloth was obtained in which the bright horizontal line pattern appeared pure white during the dark blue background dyeing and was clearly visible in the 0.2 leg size.

For comparison, Matsumiron Navy Blue BP (product name: sublimation dye) ink with a concentration of 8% was applied to the plain coated paper with a plate depth of 40〃, horizontal stripes of 150 ridges and a diameter of 0.2 ribs in reverse. Although an attempt was made to obtain sublimation printed paper by gravure printing at a speed of 20/min using a ground type gravure plate, a horizontal striped pattern could not be obtained as the ink ran out during printing. At the minute speed, printing was possible although some blurring occurred. A horizontal striped pattern was also obtained when the same pattern was printed at a plate depth of 25 mm and 180'' at a speed of 20 mm/min.Next, both were transferred to triacetate cloth in the same manner as in this example. In both cases, traces of horizontal striped linear patterns were observed on the cloth, colored slightly lighter than the dark blue of the base beam, and the results were incomparable to those of this example.

Further, for comparison, a mixture of 10% maple gum aqueous solution 6 anchors and 40 parts calcium sulfate, which is used as a comparative example in Example 1, was diluted to 50% with water to give a viscosity of 800. p. Although the same treatment as in Example 2 was carried out using a triacetite fabric made of s., only a triacenit fabric with a navy blue background was obtained, and no trace pattern was observed, so it could not be compared with this example.

Example 3 Mamilon Black BRP (product name: sublimable dye) 10
A polka dot pattern with a diameter of 2 mm was printed on the same coated paper as in Example 2 using a gravure printing plate with a plate depth of 30〃 and 150 mm using a gravure printing ink consisting of a low viscosity sodium alginate 10% aqueous solution of 50 mm after drying. part, fine powder metal zinc powder 45
250 parts of anhydrous sodium acetate.
p. Apply beam-protecting glue s inward from the outer periphery of the polka dot pattern at 1.5 skin intervals, and place the same 0 circle pattern on the 1.5 side of the line and 0.2 rib intervals from the same 0 circle pattern. Printed on the inside using a gravure plate with a depth of 60 mm and 150 peaks, consisting of concentric circular patterns of 1.5 ribs in the line, and dried with hot air for 1 minute at 15,000 mm to create a beam-protecting film with an average film thickness of 25 peaks. A sublimation printed paper was obtained.

Next, the polyester tough cloth and the printed paper are brought into contact with each other,
205oo, thermal transfer treatment was carried out across the three existing sands. In this way, there are two clear concentric patterns of white pongee lines in the pure black polka dots on the inner periphery of the circle, and the white fine lines are 0.
The black pongee line D circle pattern sandwiched between two circular patterns is 0.
An excellent polyester lid transfer printed fabric was obtained, which was confirmed to stand out on a fresh coin.

For comparison, a gravure reverse engraving version of the above pattern (30 French,
Although the same operation could be carried out without using the beam-proofing glue in 150 France), the two white pongee lines had the same D circular pattern reduced to about 0.8, and the surrounding area was disordered and took on a zigzag shape. Furthermore, the black thin line concentric circle pattern sandwiched between two white thin line concentric circle patterns is 0 in the line.
．． The skin was enlarged to 4 and had an unpolished appearance, which was extremely inferior to that of this example.

Example 4 1.5 parts of anhydrous subsalt chloride, 5.5 parts of aqueous ammonia, 0.2 parts of sodium ethylenediaminetetraacetate, and 8 parts of a low-viscosity 10% aqueous sodium alginate solution, Isoban (trade name: Vinyl/ Prepare 13.3 parts of maleic anhydride copolymer as a homogeneous clayey aqueous solution (viscosity: 300 p.s.) and apply it to a polyester georgette cloth using a lo-fu, 2-knurling knurling, and 15-diameter willow floret pattern plate. Roller printing is applied to the top, and after drying, steaming at 100 qo for 2 minutes and then dry heat treatment at 190 qo for 1 minute to form a film with an average thickness of 100 〃. :
A full-scale gravure plate obtained with an ink between Olive Green consisting of 5% P (sublimable dye) and 2% Macmillon O-GP (trade name: sublimable dye), 2
Thermal transfer was performed for 000030 seconds, followed by washing and soaping.

In this way, a polyester georgette transfer-printed fabric was obtained, in which a clear floret pattern was clearly visible on a gray-green plain surface.

In addition, when the same operation was carried out with a mixture of 10 anchor parts of the beam-proofing paste of this example and 2 parts of Pigment Red #3 (organic pigment: a sublimable pigment with a melting point of 2 degrees Celsius), a gray-green plain surface was obtained. A polyester georgette colored resist dye transfer-printed fabric was obtained in which a brightly colored floret pattern was observed as if it stood out in sharp contrast to the contours. For comparison, two plates were used to print the same pattern with the same color scheme and the same dye ink using gravure printing, but due to poor mold matching, baby colors or hot water were generated in the left-right and front-back directions. , it is impossible to match the types,
In addition, the transferred product also showed polymerization that gave a brown color around the floret pattern, and in short, it had an extremely poor appearance.
The value was essentially different from that of this example.

In addition, for comparison, barium sulfate, calcium carbonate, activated Shiraki, activated carbon, and kaolin were added to the present Example except for the zinc chloride and aqueous ammonia, that is, 9 parts of the sodium alginate aqueous solution, and 1 part of the sodium alginate solution. When a total of 5 types of glue were prepared by mixing one base part at a time and performing the same operations as in this example, all of them showed fairly good results. A beam-like pattern) was obtained, which was not as clear as the bright white floret pattern of this example, and the cloth was deformed into irregularities.

Example 5 5 parts of magnesium sulfate hexahydrate and 5 parts of low-viscosity sodium alginate were uniformly mixed with 9 $ of water on a pure white roll paper of 65 mm, and the entire surface was coated with a knife coater to 165 mm.
It was applied all over the ship for 5 nights/pillow weight and dried for 3 minutes at 100 qo.

Next, a mixture of 2 parts of anhydrous calcium sulfate in a 10% secondary butyl alcohol solution of hydroxypropyl cellulose was applied over the entire surface for 5 days/day, and after drying, water vapor was applied to the coated surface to absorb moisture. ,
It was dried again and used as a processed base paper to form a dense film with a film thickness of 5 mm, and a photo-degraded gravure plate, a fruit pattern consisting of a total of 4 plates of 3 primary colors and black with a maximum depth of 25 mm was printed as usual gravure. , a sublimation printed paper was obtained and compared with untreated sublimation printed paper, the results are shown in Table 1. Table 1 (Note) The transfer printed fabric is polyester blue. As shown above, the storage stability of the sublimation printed paper treated in this example was significantly excellent.

Next, Omotekawa prepared a treated base paper using only the poval and sodium alginate of this example, and used this as a comparative example to compare it with this example after the same treatment.・This shows the superiority of this example.

In this example, when magnesium sulfate was not added, a non-uniform porous gel coagulated film was formed, the printability on the printed paper was poor, and a uniform stain prevention effect could not be obtained.

Table □ (Note) The transfer printing fabric is the same as in Table 1. Example 6 Matsumiron Red PCB (
Product name: Full-surface gravure printing using ink containing 5% (sublimable dye) at a plate depth of 35mm and 50mm.
Further, on the surface, 4 parts of mineral Yu-Pen, 8 parts of sodium alginate, 2 parts of stannous anthranilate (2:1 chelate compound) powder, and Demol N (trade name: dispersant naphthalene formaldehyde condensate sulfon) were added. acid salt) 1
A pale yellow emulsion consisting of 1 part and 2 parts of Emulgen A-60 (trade name: emulsifier) and 47 parts of water was made into a gravure plate with a plate depth of 80 mm and a maximum line length of 3.5 ribs and a medium thickness of 0.2 mm. Gravure printed in a random grid pattern, dried at 100℃ for 1 minute,
A sublimation printed paper was prepared by subjecting it to a heat treatment of 80 mm and 2 mm (film thickness: 40 layers).

On the other hand, cotton/polyester, 35:65 broad cloth was pretreated with Matsumin Fixer #80 and Mutmin Fixer #100 (both product names: agents that pre-treat the cotton side to make it dyeable with disperse dyes). After pretreatment, the cloth and the above-mentioned sublimation printing paper were brought into contact with each other, and heated at 215°C.
Thermal transfer was carried out for 40 seconds, and then the fabric was passed through a cloth containing Mummin Softener TC (trade name: Softener) and dried. In this way, a cotton/polyester transfer-printed fabric was obtained in which a bright white irregular lattice pattern could be clearly seen on the entire plain bluish-red color with its delicate 0.2 side dimension.

Claims (1)

[Scope of Claims] 1. A water-insoluble or poorly water-soluble metal or metal compound, or a complex metal compound, alone or in a mixture, on a sheet material forming either the dyed fabric or the carrier for sublimation transfer printing. and a polymer compound that chelates with the metal ion of the metal or metal compound, and a substance that suppresses or promotes the chelation, forming a film of a chelating polymer substance to a thickness of 500 μm or less, A dye sublimation transfer printing method, characterized in that sublimation transfer printing is carried out by bringing the dyed fabric and the carrier for sublimation transfer printing into contact with each other. 2. The dye sublimation transfer printing method according to claim 1, wherein the water-insoluble or poorly water-soluble metal or metal compound, or the metal compound formed into a complex salt can be made into fine powder. 3. The dye sublimation transfer printing method according to claim 1, wherein the polymer compound that chelates with the metal ion of the metal or metal compound is an ionic polymer compound. 4. The dye sublimation transfer printing method according to claim 1, wherein the sublimable dye printed on the sublimation transfer printing carrier exhibits sublimation behavior at 360° C. or lower under normal pressure.