JPS63237984A - Method of imparting pattern to high molecular weight material composition - Google Patents

Abstract

PURPOSE:To impart an extremely clear pattern by applying a viscous aqueous solution of a thermally reversible high molecular weight compound comprising a coloring material to a high molecular weight material composition maintained at or above the phase transition temperature of the thermally reversible high molecular weight material, in an arbitrary pattern, followed by drying. CONSTITUTION:A viscous aqueous solution of a thermally reversible high molecular weight compound comprising a coloring material is applied to a high molecular weight material composition maintained at or above the phase transition temperature of the thermally reversible high molecular weight compound in an arbitrary pattern, followed by drying, or followed by color development and fixation by an ordinary method or by a post processing. The thermally reversible high molecular weight compound may be polyvinyl methyl ether, N-isopropyl acrylamide, N,N-diester acrylamide or the like. The high molecular weight material composition may be in the form of fibers, yarns, a collection thereof, a cloth, a nonwoven fabric, a sewn product or other textile product, a film, a sheet or the like.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is applicable to fibers or threads, or aggregates thereof, textile products such as cloth foils, nonwoven fabrics, and sewn products, and molding of polymeric materials such as films and sheets. This invention relates to a novel method for imparting designs to products and polymeric compositions such as paper. In more detail, various printing methods such as hand-drawn Yuzen, hand printing, automatic screen printing, and roller printing, which have been widely used in the past, as well as photoelectric methods, electrostatic photography, which are expected to be rapidly put into practical use in the future, Among various innovative textile printing or printing methods such as electrophotography or electrophotographic copying method, dye printing method, spray dyeing method and inkjet printing method, it is applied in combination with the method in which water-based colored glue paste is adopted for imparting the design pattern. Both significantly increase productivity in the process of applying the design,
A new high-performance technology that promotes energy-saving effects, promotes sharper edges and higher quality of the resulting designs, improves the working environment, and significantly reduces the burden on air and drainage measures. The present invention relates to a method for imparting a pattern to a molecular composition.

[Conventional technology]

Among the many textile processing techniques, such as dyeing textile products in multiple colors and adding patterns to fabrics, the most widely used method is called stencil dyeing, which is compared to plain dyeing. This is a textile printing method. The basic printing method is to use a screen type or engraved roll, etc. to print various materials such as sodium alginate, carrageenan, marine products such as chitin and funori, starches such as wheat starch, buriti, sugar, and rice flour, gum arabic, gum tragacanth, and locust bean. gums and gum systems such as guar gum; cellulose derivatives such as methylcellulose, hydroxyethylcellulose and carboxymethylcellulose;
Dye, pigment or other coloring material is added to a viscous aqueous solution of a polymer compound called a synthetic sizing agent such as polyvinyl alcohol, partially saponified polyvinyl alcohol, acrylic acid copolymer, and vinyl acetate/maleic anhydride copolymer, and Generally, a paste called a color printing paste containing various desired chemicals is transferred and printed onto the above-mentioned textile product, dried, and then subjected to color fixation and post-treatment. Regarding these production methods, there are many factors such as the target fiber material and structure, the color paste composition to be applied or the printing method to be adopted, the structure or color scheme of the design, the quality of the product or properties such as color fastness, production quantity and processing cost. It is well known that the selection is determined by the following factors. In particular, the flow and dynamic behavior of colored paste containing the required composition is extremely important, and in order to alleviate the fluctuations in printing conditions that are unavoidable in on-site work, the fluidity of the colored paste must be such that there is little thixotropic phenomenon. There has been a demand for something that does not change over time or is temperature dependent.

On the other hand, the traditional methods for imparting patterns to molded products made from polymeric compounds such as films and sheets, or paper, etc. are the letterpress method, the flat plate method called offset printing, the intaglio method called gravure printing, and the stencil method called screen printing. It is a well-known fact that printing methods and printing inks that are compatible with each printing material have been used depending on the printing material, and that printing has been performed by transfer, printing, and drying. Problem (1)
Printmaking takes too much time and cost.

(2) The glue used in post-processing after color development and fixation must be washed and removed. (3) Transfer printing methods combined with printing methods have also been put into practical use in order to improve problems such as the need to separate removed glue from wastewater. However, it has not become widely accepted in the general public because it is limited to specific uses, mainly because the materials are restricted to polyester fibers that can use a thermosol mechanism for dyeing, and there are problems with the color density.

In addition, printed wiring technology for producing integrated circuit boards with higher precision has improved significantly, and the current state of affairs is that the level of composite technology in the boundary area between textile printing and printing is rising even further.

Against this background, many proposals have been made for textile printing and printing-related technologies that incorporate new elements. For example, a textile is treated with a resin liquid containing a photoelectric semiconductor, the surface of the textile is charged in an electric field, and then a desired light image is projected through a lens to partially increase or decrease the conductivity of the semiconductor depending on the intensity of the light. A photoelectric method (Japanese Patent Publication No. 38-2
0643), by applying electrostatic photography, a pattern is photographed on a charged plate, dye powder is spread and deposited on it, and this image is transferred onto a cloth and then fixed using a glue or the like. ,
Electrostatic photography method for dyeing
:55), electrofax method or zero,
An electrophotographic copying method (Japanese Patent Publication No. 47-12237) in which a dye-containing image on a photoconductor layer is transferred to an object to be printed and then dyed using an electrophotographic method known as the printing method (Japanese Patent Publication No. 47-12237); Method of developing color with dye after applying a solution (Japanese Patent Application Laid-Open No. 18975-1989)
Post-processing steps such as lamination or protective film coating are performed to prevent surface smoothness from deteriorating due to toner adhering to the surface of the printing material and improve the abrasion resistance of the surface during conventional electrophotography. Dry dye printing method using powder ink made of heat-transferable dye, release agent and thermoplastic resin proposed for the purpose of simplification (Japanese Patent Publication No. 59-2199)
3) Spray dyeing method (Japanese Patent Application Laid-open No. 61-215
It is also known that there are many new technologies that exist in the boundary area between textile printing and printing, such as 787).

[Problem that the invention seeks to solve]

Both in conventional textile printing and printing technologies, and in the above-mentioned innovative technology fields whose practical application is expected to expand rapidly in the future, the common challenges are (1) promoting rationalization of production processes; (2) Plan to improve the working environment. (3) It can be easily inferred from many of the proposed technologies that the focus is on improving the quality of the resulting designs.

Regarding the first item, the plate-making process is omitted (Special Publication Publication No. 59-634
), etc., and the various innovative methods mentioned above have been suggested as improvement measures, but in each of these methods, the first concrete challenge has been to increase the printing speed. For example, in conventional designs that are composed of multiple colors, it is necessary to wait for the pattern to dry for each hue before proceeding with the printing of other colors.
' This was an essential condition for suppressing blurring at the edge of the image, which is called ``sulsion'' or ``bleeding.'' Of course, as a countermeasure to these problems, the use of organic solvents to increase the drying speed of the printing paste was necessary. It is also true that improvements have been made to the composition of color pastes, such as by combining them with each other, and by sending hot air to the printing surface.Also, in order to relatively speed up the drying speed, efforts have been made to reduce the printing paste layer, and to improve the color paste composition for each hue. Measures have been taken to prevent "bleeding" by selecting the polymeric compounds that make up the paste and inducing cohesive forces between molecules in the heavily colored areas, but this is not at a fully satisfactory level. For paste compositions,
Problems have been pointed out, such as relatively frequent clogging of molds or nozzles, and large changes in flow behavior over time.

Regarding the second item, it is desirable to further strengthen it from the viewpoint of environmental protection and occupational safety and health, and there is a tendency to restrict the use of organic solvents in combination and the introduction of hot air, which increases the discomfort of the working environment. For example, in place of emulsion-type pastes, various methods have been tried, such as using turpenless or meter-pen type pastes using low-concentration aqueous solutions of highly polymerized polymer compounds, and printing on heating tables. This is an example. In addition, in processes that use large amounts of water-soluble sizing agents, such as textile printing, the sizing agents flow into wastewater during the washing process after color development and fixation, and the large burden of separating and removing them has a significant impact on processing costs. It is also well known that

Regarding the third item, in response to the increasingly multipolar consumer needs, there is a demand for higher quality that corresponds to a richer sense of color, and it is required to sharpen the edge of the image and deepen the color hue. . As a countermeasure for the former, the above-mentioned measures are taken for conventional printing methods, and for various innovative technologies that are being proposed in response to the rationalization of the printing process, it goes without saying that water-based printing methods for cloth foils and recording sheets, etc. There are many proposals for sharpening the edge of a picture when applying a pattern using paste. For example, if an inkjet recording sheet contains a basic latex polymer (Japanese Unexamined Patent Publication No. 57-36
692), inkjet recording base paper is impregnated with at least one of polyvinylpyrrolidone, polyvinylpyrrolidone-vinyl acetate, polyvinyl alcohol, carboxymethyl cellulose, polyacrylamide, and methacrylic acid ester (JP-A-59-951A6);
A surface coating layer containing at least a pigment, a binder, and a water-soluble salt of a metal having an ionic valence of two or more as a water resistance improver is provided on the surface of the substrate (JP-A-59-9-E-98).
a) Also, applying a water-based ink containing a specific dye to a recording medium containing at least one of water-soluble salts of metals with an ionic valence of two or more, alkylamines, polyamines, and quaternary ammonium salts. Method (Unexamined Japanese Patent Publication No. 1983-
106989), before the dyeing section of the cloth foil dyeing device in the inkjet method, the cloth foil is subjected to water-repellent treatment,
Paint with water-based ink that has an appropriate viscosity and surface tension, or apply a gelling agent to the fabric and use dye ink that contains a sizing agent that gels with the gelling agent. (Japanese Unexamined Patent Publication No. 61-75870), a printing method in which a recording liquid containing a water-soluble dye is applied to a fabric by an inkjet method, and then dyed if necessary, the recording liquid is received on the fiber. (Japanese Patent Laid-Open No. 61-138783). When inkjet dyeing or spray dyeing, the fibers are pretreated with a cationic compound or metal salt, and the ink is coated with a receptive layer that can coagulate with the fibers. A method using a water-insoluble pigment ink containing an anionic dispersant (JP-A-6L-2157
Although many techniques such as 87) are known, they are expected to be effective under specific conditions and are inevitably accompanied by considerable limitations in terms of versatility.

On the other hand, in order to improve the color development hue or deep dyeing, for example, by using a strong penetrant in combination with the color paste to promote internal penetration from the printing surface, the printing paste layer can be laminated thickly on the printing surface. Prepare the printing base or use a high-solid gold-containing paste, relax the drying conditions to promote the penetration of the color paste from the printing surface, use a carrier or a deep dyeing agent, and In reality, when it comes to improving the color hue, we are forced to take the exact opposite direction of improving the sharpness of the edge of the image, such as the recommendation to fix the coloring of designs applied using the dry method using the wet method. There is. In particular, the process of applying patterns has been greatly improved. For example, in the electrostatic photographic transfer method, an electrostatic latent image created on a photoreceptor is developed with dye powder, transferred to a cloth sheet, and then a glue is applied on top of the electrostatic latent image. Or, as seen in electrophotographic copying methods, an electrostatic latent image is developed with a toner that contains a disperse dye in a binder resin whose main component is a special resin, and then the polyester In many cases, it is unavoidable to use a wet method to improve the quality, such as transferring the dye to a cloth mainly made of , and then dyeing the polymer material with the dye using steam heat.

[Means for solving problems]

It is known that some water-soluble polymer compounds have the behavior of precipitating or becoming cloudy when the aqueous solution falls below a certain temperature, and redissolving when the temperature falls below that temperature. For example, compared to carboxymethyl cellulose, which is widely used for textile printing among cellulose derivatives, methyl cellulose and hydroxyprobyl methyl cellulose exhibit a unique phenomenon in which they form a gel structure when the aqueous solution is heated, resulting in one-heat gelation. This is because these polymers exist in solution as an aggregate of long colloidal molecules, and the molecules are tightly hydrated with solvent water in a layered manner through hydrogen bonds, forming these chain polymers. It imparts smoothness to the molecules and exhibits good fluidity, but as the temperature rises, hydrogen bonds with water molecules weaken, interactions between chains become stronger, and eventually a gel structure is formed. Unlike many other chemical gels, the gel is produced by phase separation, and it is susceptible to even a small shear and can be mechanically collapsed without changing the molecular weight.Furthermore, the flow behavior can be improved by cooling. It can reversibly return to the original solution without any change.

The gelation temperature is determined by the amount of methyl and hydroxyprobyl substitution, and is used as a measure of the hydrophobicity of these derivatives. It is well known that derivatives with a high degree of substitution generally have a low gelation temperature, and this temperature is influenced by the addition of solutes and electrolytes, but the temperature ranges from about 50°C to 85°C. That's right.

In addition to the above-mentioned cellulose derivatives, such thermoreversible polymers include partially saponified polyvinyl alcohol, polyethylene oxide, and polyvinyloxylidinone. It is also a well-known fact that similar behavior is observed in nonionic activators, and is called the "cloud point" and is used in practical use as a factor indicating the properties of activators.

The present inventors focused on the temperature dependence of the flow behavior of viscous aqueous solutions of these thermoreversible polymer compounds, and as a result of intensive research into the printing characteristics thereof, the present invention was achieved. In other words, we apply a printing paste whose main component is a viscous aqueous solution of a thermoreversible polymer compound whose phase transition temperature can be regulated extremely sharply within a range that does not significantly impede production conditions and working environments. It has been discovered that the behavior of the color paste on the printing surface can be freely controlled by the surface temperature of the printing substrate.

According to the method of the present invention, the viscosity of the color paste composed of a viscous aqueous solution of a thermoreversible polymer containing a coloring material can be maintained at a relatively low viscosity by keeping it at a low temperature. At the same time, the color paste that reaches the printing surface prepared at a specified temperature easily induces a phase transition on the printing surface, resulting in an extremely clear and sharp color paste. This allows the design to be retained. For example, when this function is applied to designs composed of multiple colors, it can greatly improve productivity by allowing color pastes of other colors to be superimposed on top of undried printed color pastes. It also comes with the following features: These environments are at least 50°C or below, more preferably 20°C to 40°C.
Under these conditions, any printing method will not suffer from the drawback of clogging and will not impair the working environment; rather, it can be said that the environment is being purified. It is also possible to use a thermoreversible polymer aqueous solution with a phase transition temperature of 20°C or less by keeping the color paste cool, but if the solubility or stability of the coloring material used in combination at low temperatures is taken into consideration. However, it is not necessarily recommended.

As thermoreversible polymer compounds that can utilize such properties, polymers of polyvinyl methyl ether and N-isoprobyl acrylamide or N-improbyl methacrylamide, or copolymers of both, N-n-
Examples include polyacrylamide derivatives which are polymers such as probyl acrylamide, N,N-diethylacrylamide, acrylamide having a pyrrolidyl group or piperidyl group, and tetrahydrofurfurylacrylamide. These thermoreversible polymers can be used alone or in combination, but general sizing agents and other auxiliary agents can also be used in combination to adjust and stabilize the flow behavior of the paste. However, since the phase transition temperature generally changes due to the addition of a coloring material or a third component, it is necessary to investigate in advance and adjust the temperature on the printing substrate surface within an appropriate temperature range. Further, the solid amount of the thermoreversible polymer compound to be adjusted to a predetermined viscosity is determined by the degree of polymerization of the compound, and can be selected depending on the purpose of printing.

Furthermore, for thermoreversible polymer compounds that exhibit remarkable stringiness due to the fluidity characteristic of linear polymer compounds, crosslinking may be appropriately introduced to impart plastic fluidity to the paste. Note that thermoreversible polymer compounds that exhibit a clear phase transition temperature are polymers produced by polymerization from monomers, rather than those derived from polymer compounds such as the above-mentioned cellulose derivatives or partially saponified polyvinyl alcohol. It can be seen that polyvinyl methyl ether and the above-mentioned polyacrylamide derivatives are most suitable.

Furthermore, the thermoreversible polymer that is the subject of the present invention is easily soluble in water below the phase transition temperature, and if it is desired to remove it by washing after the fixation coloring process after printing, it can be easily removed with cold water. It is possible to greatly contribute to water and energy conservation. Furthermore, these thermoreversible polymers that flow into wastewater easily gel and precipitate when heated above the phase transition temperature, so they can be easily separated and removed, significantly reducing the burden of wastewater treatment. can.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 70 parts of a 25% aqueous solution of N-isoprobyl acrylamide polymer having a molecular weight of about 3oo and ooo was taken as a base glue,
Prodione Nevy H3R (IC engineering) 5%, urea 5%
, color paste at 20 °C containing 3% acidic sodium carbonate and Kayadion Scarle, ) P-NA (KYK
) Prepare 2000 colored pastes of the same composition containing 2%. Separately, 300C cotton lawn that has been scoured, bleached and mercerized using conventional methods! After applying the base on a printing table adjusted to C for 15 minutes, and post-process and finish according to the conventional method.Meanwhile, 70 parts of a 7% aqueous solution of sodium alginate and a 9% aqueous solution of highly etherified carboxymethyl cellulose were each used as the base glue, and the above thermoreversible A colored paste with the same composition as a colored paste using a polymer as the base paste is prepared, and the same design is created under the same conditions.Comparing the two obtained prints, the design is similar to that of the one using a thermoreversible polymer as the base paste. It can be seen that the sharpness is extremely excellent.Especially in the case of colored glue using sodium alginate or carboxymethyl cellulose as the base glue, even if you overprint scarlet colored glue after the navy colored glue has completely dried, there will be no dark blue fine lines. A tendency for the disease to "bleed" was clearly observed, confirming the clearing effect and productivity improvement of the thermoreversible polymer.

Example 2 80 parts of a 30% aqueous solution of polyvinyl methyl ether (viscosity 3.400 cps at 25°C) was taken as a base glue, and a color at 25°C containing 5% of Polar-Bun RXL (OGY) was prepared. Prepare the glue. Separately, a 6% aqueous solution of sodium alginate (viscosity at 25°C is approximately 22.900 cps)
Take 70 parts of this as a base glue to prepare a standard color glue of the same composition at 25°C. 3 pieces of silk satin that have gone through the preparation process according to the usual method
The fabric was spread on a printing stand adjusted to 5°C, and a screen-type cloth with polka dots made of polyester hexafilament with a wire diameter of 40 microns and a mesh of warp 200 and weft 230 mesh was arranged on the fabric. Print with both colored glue. Compared to a colored paste made of polyvinyl methyl ether prepared to have a low viscosity, the threadability of a standard colored paste made of sodium alginate is extremely poor, making printing almost impossible.

In addition, it easily becomes clogged, so it cannot be put to practical use. Therefore, by lowering the concentration of sodium alginate, which is the base glue, the viscosity of polyvinyl methyl ether,! : Same-
Comparing the colored paste prepared to the same standard, it can be confirmed that the printing properties are almost the same. However, when comparing designs that have been colored and fixed under the same conditions, it is observed that the outline of the design obtained from sodium alginate is significantly less sharp than that obtained from polyvinyl methyl ether.

In addition, if you print the same design using standard sodium alginate glue and 50 denier polyester monofilament through a 90 mesh gauze screen mold, you can obtain a very good print, but under the same conditions. When compared with the pattern made from polyvinyl methyl ether, "° bleed" in the outline is observed.

Color paste composed of polyvinyl methyl ether, highly pigmented,
Comparing the patterns obtained from mesh screen and low mesh screen, it goes without saying that the former has superior sharpness.

Example 3 Polyisoprobyl acrylamide (molecular weight approximately L OO
Take 70 parts of a 5% aqueous solution of O, OOO) as a base glue, and add Latile Gray 8GFS ('J key' product, DUP)
2%, High Printer HT-100 (■Chuo Giken, H
Prepare a 200C color paste consisting of 2% (deep dyeing agent for TS). For comparison, a 13% aqueous solution of processed starch, a 12% aqueous solution of locust bean gum, and a 9% aqueous solution of highly etherified carboxymethyl cellulose were mixed in the same weight ratios, and 70 parts of the base glue was used, and the color was the same as the above composition. Prepare the glue.

Separately, take 60 parts of a 5% aqueous solution of sodium alginate as a base glue, and add Miketon Polyester Orange SC (MDW).
) 3% and High Printer Qc-x Special 0.5%.

On the other hand, alkali-reduced polyester decine prepared according to a conventional method is placed on a printing stand adjusted to 3o0c. On the deshin, draw 2 thin lines 3 mm wide in the weft direction of the fabric.
Use a stripe mold (100 mesh gauze) arranged at intervals to print gray glue, immediately overprint with "Ishigoki glue", and after air drying, apply 175cm according to the usual method.
High-temperature steam fixation at °C for 6 minutes and post-treatment finishing.

Comparing the patterns from the two color pastes obtained, it can be seen that the sharpness of the striped pattern using the thermoreversible polymer is significantly superior to that using the natural glue. The degree of this is superior to that obtained by printing a gray paste using a natural blended paste as the base paste, thoroughly drying it, squeezing it with an orange paste, forcing drying, and then finishing with color development using a conventional method.

Furthermore, it can be confirmed that the adhesive according to the present invention, which has a lower solid content, develops a deeper color than that of the naturally formulated adhesive, which is classified as the adhesive with the highest color density when fixed by high-temperature steaming.

Although the finished texture of the two is almost the same, polyisoprobyl acrylamide, which is easily soluble in cold water, is extremely easy to remove after high-temperature steaming, and the amount of adhered glue is also significantly greater than that of natural sizing agents. It is noteworthy that the cleaning process is low and greatly contributes to the rationalization of the cleaning process.

Example 4 Suminol Milling Red R3125% (NSK
) 1 g/l 20'C dye aqueous solution (abbreviated as A),
A dye aqueous solution (abbreviated as B) at the same temperature in which the same dye aqueous solution was combined with 10 l/l of sodium alginate, the same <Example 2
The dye aqueous solution (abbreviated as 0) at the same temperature using polyvinyl methyl ether 10 l/l used in
An aqueous dye solution (abbreviated as D) at the same temperature as that used in Example 3 is prepared in combination with 10 l/l of polyisoprobyl acrylamide. Assuming pull dyeing or spray dyeing, a genuine silk crepe prepared in the usual manner was held horizontally with a needle tension, and 3 drops of each of the above dye aqueous solutions were applied and dripped from a pipette fixed 2 degrees above the surface of the fabric. Dry naturally. The approximate spread of the dye solution at that point, expressed in area (square) based on the average value in the weft and warp directions of the fabric, is as follows: In other words, the fibers that make up the fabric of the dye aqueous solution using water alone or in combination with sodium alginate. The spread area that is diffused due to capillary action in the gaps has almost no relation to the fabric temperature; for example, at 30°C, A is 94% and B is 98%, compared to the case at 15°C. On the other hand, by using a thermoreversible polymer in combination, the spread of the aqueous dye solution on the fabric held above the phase transition temperature is 76% for O and 76% for D compared to the spread on the fabric below the phase transition temperature. A tendency to be suppressed can be confirmed at 73%.

In addition, when the fabric was steamed at 100' (1!) for 30 minutes and then post-treated using a conventional method, the color density was compared, and it was found that the dye was more vividly colored than the dye alone, especially when the dye was not used together with the sizing agent. It is observed that the level dyeing of the dripped thermoreversible polymer is high, and the stain penetrates well into the back of the fabric.

In addition, the color development area of A is extremely narrow, and it is thought that the dye aggregates in the center and only a small amount of dye-containing water diffuses, resulting in the apparent spread seen in the table above. There is a significant difference in color density between the core and the outer layer, and at the same time there are difficulties in penetrating into the back of the fabric.

Based on the above behavior, in both pull dyeing and spray dyeing, an aqueous solution of dye combined with a thermoreversible polymer, which has fluidity similar to that of water alone, is an excellent brush or "komabera" dye.
When the aqueous dye solution comes into contact with the fabric surface, which is maintained at a temperature higher than the phase transition temperature of the thermoreversible polymer, a phase transition occurs, suppressing the spread of the aqueous dye solution and imparting a clear pattern. It becomes possible.

Example 5 When diluting commercially available India India India 30% with water, the following four types of India India India Ink liquid prepared at 20°C were prepared, each containing 5 l/l of various thickening agents in the diluted India India Ink. A is diluted with water only. B
is polyvinyl alcohol partially saponified product (degree of polymerization approximately L100)
) added.

C is the same as in Example 2, except for the combination of polyvinyl methyl ether. D is the diluted India ink to which the polyisopropyl acrylamide used in Example 1 was added.

1 of each of the above ink in accordance with the method detailed in Example 4.
Droplets were placed on high-quality paper horizontally fixed on a table adjusted to 15°C and 35°C, and the behavior was observed.

For A, ``Pa bleed'' occurs on paper at both 15°C and 35°C. For B, no 0 bleed is observed, but it takes a considerable amount of time to complete natural drying. Also, there are drawbacks to the brush strokes, and poor penetration, which tends to cause blurring. In contrast, the "bleeding" of C on paper at 15°0 is remarkable.
1 "Bleeding" is also observed in D, but there is no "bleeding" phenomenon on paper at 35°C, and extremely good brushstrokes can be confirmed. Although there is a tendency for the surface concentration of C to decrease, it is possible to deepen the color by adjusting the ink concentration.

Example 6 A polyester decine which had been subjected to scouring, bleaching and alkaline weight loss processing in a conventional manner was spread on an iron plate printing stand adjusted to 15°C and 30°C, and Miketone polyester was applied onto the fabric.
Spread the Nevy Blue GLSF (MDW) powder evenly. On top of that, (1) water, (2) sodium alginate, (3) the polyvinyl methyl ether used in Example 2 and (4) Overprint the zO/l aqueous solution of Improvir acrylamide used in Example 1. After drying the printed fabric naturally, it was heated at 190°O for 1
Pass it through a roller setter for a minute to fix it with dry heat, then post-process and finish according to the usual method, and compare and observe the color development.

The overprinted version of (1) and (2) is 15
Bleeding was significant for both the fabrics at 30°C and 30°C. On the other hand, in both cases (3) and (4), although there is significant bleeding on the fabric at 15°, a clear border can be seen on the fabric at 30°. In addition, the coloring hue is (1), (2), (3) compared to that produced directly as a powder using a thermosol.
Both samples and (4) are good, with no speck-like unevenly dyed areas, but it can be seen that the color density is clearly deeper when combined with the glue.

Example 7 Liquid fractional dye seri print Bra, Ri KXPM-68
Three types of colored pastes at 15°C were prepared by mixing 7120 parts by weight of 0 (YCL) 40 and 80 parts by weight of the following base glue. (1)
Sodium alginate 2.5% (2) Polyvinyl methyl ether 20% solution used in Example M (3) Isoprobil acrylamide polymer 15% solution used in Example 1 was used as the base glue.

A polka dot pattern was screen printed on a polyester film prepared at 30°C using three different colored pastes with similar apparent viscosity, and after air drying, it was dry heat treated at 195°C for 60 seconds.
7. Post-process in a conventional manner and compare the design and color hue.

Compared to (1), it was observed that the edges of (2) and (3) were more clearly finished and the color density was higher, and the combined effect of thermoreversible polymers was also confirmed in the film printing method.

In addition, when comparing the same color paste used in Example 6 by printing on the polyester decine at 15°C and 30'O and developing thermosol color after natural drying, it was found that (1) the line pattern tended to become thicker at both temperatures. However, in both (2) and (3), it can be confirmed that the bleeding tendency observed on the fabric at 15°C is eliminated on the fabric at 30°C.

〔Effect of the invention〕

By the method of the present invention, it has become possible to apply highly sharp patterns to the surface of a polymer composition at high speed using a low-viscosity printing paste. In addition, forced drying of the printing paste on the printing surface and the use of organic solvents can be omitted, contributing to a significant improvement in the purification of the printing work environment.

The thermoreversible polymer used dissolves in water extremely easily at low temperatures, which simplifies the cleaning process in post-treatment and significantly reduces water usage. This makes it possible to easily agglomerate, precipitate, and remove with difficulty, making it possible to significantly reduce the burden of wastewater treatment.

Claims (3)

[Claims] (1) A viscous aqueous solution of a thermoreversible polymer containing a coloring material is applied in an arbitrary pattern onto a polymer composition maintained at a temperature higher than the phase transition temperature of the thermoreversible polymer and dried, or by a conventional method. A method for imparting a pattern to a polymer composition, characterized by coloring and fixing or post-processing. (2) The method according to claim 1, wherein the thermoreversible polymer is a polyvinyl methyl ether and a polyacrylamide derivative having a phase transition temperature of at least 50°C or lower. (3) The polymer composition is fibers or threads, or aggregates thereof, textile products such as cloth foils, nonwoven fabrics, and sewn products, molded products of polymer materials such as films and sheets, and paper. The method described in Section 1.