JPH05287686A - Steric pattern transfer sheet - Google Patents

Abstract

PURPOSE:To prevent the lowering of color density and the whitening caused by a protrusion and to widely achieve the desired color and design on a steric protruded pattern transferred to an object to be transferred. CONSTITUTION:The objective sheet for the transfer of a steric protruded pattern on an object to be transferred by pressure and heat is composed of a base sheet 1, a pattern layer 3 containing a thermoplastic polymer capable of forming a soft film and optionally a colorant, a swelling layer 4 containing a thermoplastic polymer capable of forming a soft film, granules expanding with heat and optionally a colorant and an adhesive layer 5 in the order.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a three-dimensional pattern transfer sheet for transferring a three-dimensional raised pattern on a transfer object by applying pressure and heat.

[0002]

2. Description of the Related Art Conventionally, as a method of printing a three-dimensional raised pattern on a sheet-like material such as cloth, a method similar to a pigment resin printing method and a transfer having a multilayer structure are used. A method using a printing sheet is known. The former method is, for example, to prepare a base paste containing a film-forming resin and a thermoplastic polymer granule containing a substance that causes a volume expansion by heating as a main component, and printing this on a sheet-like material after printing. , Low temperature drying for film formation and high temperature treatment for bulge formation are required. However, since the original paste is directly printed on a cloth or the like having an uneven surface, it is also difficult to obtain a sharp line drawing because the surface of the raised design pattern is inevitably uneven. Further, since the process itself has several steps, careful process control is required and it is extremely complicated.

Therefore, usually, the latter method which can overcome most of the drawbacks of the former method, for example, Japanese Patent Publication No.
A method using a transfer printing sheet as disclosed in Japanese Patent No. 36114 has been preferred and used. This transfer printing sheet has a release resin layer, a film-forming elastic polymer compound, a colorant, and a thermoplastic polymer particle containing a substance that causes volume expansion by heating, on a base sheet. A layer and a white pigment resin layer containing an elastic polymer compound and a white pigment are provided in that order, and a three-dimensional raised pattern can be formed on a transfer object by a single step by applying pressure and heating. ..

However, it has been found that such a transfer printing sheet should be further improved. That is, since the particulate matter contained in the bulging resin layer that expresses colors and patterns is volume-expanded by heating to bulge the layer itself, the bulging resin layer also bulges and has a large surface area. Was increasing. Therefore, the coloring density of the coloring agent also included in the layer is lowered, and the surface of the swelling resin layer tends to be white. Such a decrease in the coloring density and whitening of the raised resin layer imposes great restrictions not only on the hue of the raised design pattern but also on its design.

Further, since the film-forming elastic polymer compound contained in the bulging resin layer has a relatively low softening point or melting point, bulging formation simultaneously with thermal transfer by heat and pressure is used. In the process, the protruding resin layer was more fluid than necessary. Therefore, even if the particulate matter contained in the swelling resin layer expands in volume by heating, the proportion of the film-forming elastic polymer compound that flows laterally or penetrates into the transferred material rather than swelling. There were many Therefore, not only a sufficient three-dimensional uplifting effect cannot be obtained, but also accurate and clear expression of color and pattern is difficult, and in particular, fine expression such as delicate drawing lines and photo-decomposed patterns is crushed by the flow. Therefore, it has been extremely difficult to realize a desired sufficient sharpness. In addition, the permeation of the polymer compound into the transferred material causes the colorant in the raised resin layer to diffuse into the transferred material, resulting in a further decrease in the coloring density.

Further, the decrease in the coloring density of the raised resin layer as described above is caused by the white pigment for concealing the transferred material as the base in the adhesive layer for adhering the raised pattern to the transferred material. If it is essential to include. Therefore, not only the step of mixing the white pigment into the adhesive layer is required, but also the adhesive strength of the adhesive layer is reduced, and various fastnesses such as friction fastness and washing fastness may be insufficient. Was also caused.

The present invention has been made in view of the above problems existing in the prior art, and an object of the present invention is to provide a three-dimensional raised pattern to be transferred onto an object to be transferred, A three-dimensional pattern transfer sheet that can prevent a decrease in coloring density and whitening due to a ridge and can achieve a wide range of desired hues and designs, and a three-dimensional pattern that is sufficient for the pattern transferred onto the transferred material. It is an object of the present invention to provide a three-dimensional pattern transfer sheet which can obtain a raised effect and can accurately and clearly express both color and pattern.

[0008]

In order to achieve the above object, the three-dimensional pattern transfer sheet of the present invention is a transfer sheet for transferring a three-dimensional raised pattern on a transfer object by applying pressure and heat. A base sheet, a release material layer, a pattern layer, a raised layer and an adhesive layer in this order, wherein the pattern layer comprises a thermoplastic polymer capable of forming a flexible film and a colorant, The raised layer contains a thermoplastic polymer capable of forming a flexible film, particles that cause volume expansion by heating, and a colorant if necessary.

As the above-mentioned base sheet, for example, cellulose paper, synthetic fiber paper, synthetic paper, cellophane, synthetic resin film and the like can be appropriately used. When the base sheet itself has releasability, for example, when it is made of a material having releasability for the pattern layer or the protective layer described later such as tetrafluoroethylene resin, or when the base sheet is peeled for the pattern layer or the protective layer. When it is coated with a material having properties, the release material layer described below is not required. The base sheet is preferably transparent or translucent, for example, a polyester film or translucent paper with a smooth surface so that the pattern can be seen through it.

The release material layer can be formed on the entire surface or a part of the base sheet, if necessary. The release material layer may be, for example, one having releasability with respect to the pattern layer (protective layer when a protective layer is provided) and adhesiveness with respect to the base sheet. In this case, it may have adhesiveness to the protective layer) and releasability from the base sheet. Examples of the material for the release material layer include cellulose derivatives such as methyl cellulose and acetyl butyl cellulose, natural resins such as carnauba wax and rosin, polyolefin resins, vinyl resins, amide resins, silicone resins, synthetic resins such as fluororesins, etc. The above simple substance or a mixture of one or two or more thereof may be appropriately selected and used according to the material of the base sheet, the pattern layer or the protective layer.

The peeling substance layer can be formed, for example, by applying the above-mentioned materials in a state of being dissolved in a solvent or in a molten state onto the base sheet entirely or partially. The release material layer has a function of smoothly separating the base sheet from the pattern layer or the protective layer at the time of transfer, but at the same time, the release layer is a thermoplastic polymer, a coloring agent or a protective layer contained in the pattern layer. It also acts to prevent the contained synthetic resin or the like from entering the base sheet.
The pattern layer contains a thermoplastic polymer capable of forming a flexible film and a colorant, and can be formed on the base sheet or the release material layer.
When a protective layer is provided, it can be formed on the protective layer.

Examples of thermoplastic polymers that can be preferably used are vinyl chloride resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic ester resin, acrylic ester resin, chlorosulfonated polyethylene resin, chlorinated polyolefin resin, Examples thereof include synthetic resins such as saturated polyester resin, polyamide resin and polyurethane resin, and elastomers such as synthetic rubber such as SBR and NBR. This thermoplastic polymer promotes the ridged effect of the ridged layer by heating and also fixes the colorant on the ridged layer or the material to be transferred, giving a soft feel without impairing the feeling, good friction fastness and washing fastness. It realizes sex.
Examples of colorants that can be used in the pattern layer include inorganic pigments such as iron oxide, ultramarine blue, carbon black, and titanium white, organic pigments such as azo-based, anthraquinone-based, and phthalocyanine-based pigments, lakes, dye solid solution pigments, and metal powders. , Metal deposition powder, oil-soluble dye, disperse dye, JP-A-58-3267
1, JP-A-2-34686, JP-A-3-5
Examples thereof include various thermochromic materials and photochromic materials disclosed in Japanese Patent Publication No. 0291, etc., simple substances such as various ultraviolet light emitting materials, and mixtures thereof. Besides that, for example, any of those used as coloring components in printing inks can be used.

The pattern layer is formed, for example, by preparing a printing ink of a normal formulation containing a thermoplastic polymer and a colorant, and using it, on the base sheet, the release material layer or the protective layer. It can be carried out by printing a desired pattern on the whole surface or a part with a plate reverse to the usual printing. In addition to the above two main components, this printing ink includes a vehicle made of water, an organic solvent, etc., and if necessary, a thermosetting resin, a plasticizer, a surfactant, a stabilizer, a lubricant, an ultraviolet absorber, A fluorescent whitening agent, an antioxidant, a viscosity modifier, oils and fats and the like can be added. Note that, for example, when the color of the transferred object is relatively dark and the color of the design pattern in the design pattern layer is relatively light, it is necessary when the color of the transferred object easily affects the design pattern. Accordingly, a white pigment layer for hiding the color of the transferred material can be provided on the pattern layer or the raised layer. The white pigment layer can be formed, for example, by using a printing ink containing a thermoplastic polymer and a white pigment such as titanium white, which is similar to that for forming the pattern layer.

A protective layer may be provided between the release material layer and the pattern layer, or between the base sheet and the pattern layer. When the protective layer is provided in this way, when the three-dimensional raised pattern is transferred onto the transfer target, the pattern layer is protected by the protective layer, so that various fastnesses such as friction fastness and washing fastness can be obtained. Is further improved. The material of the protective layer, for example, polyacrylic acid ester-based copolymer resin,
Examples thereof include saturated polyester resins, polyurethane resins, polyvinyl-based copolymer resins, synthetic resins such as polyolefin resins, natural resins such as ethyl cellulose and dammar, and simple substances or mixtures of sizing agents. The formation of the protective layer can be performed, for example, by preparing a commonly-used printing ink containing the above-mentioned material as a main component, and printing it on the entire surface or a part of the release material layer or the base sheet.

The raised layer comprises a thermoplastic polymer capable of forming a flexible film, particles which cause volume expansion by heating, and a coloring agent if necessary, and is formed on the pattern layer. can do. The particles used in the raised layer have a particle size before expansion of 0.1 to 100 μm.
It is preferable that the maximum expansion ratio in free expansion under normal pressure is about 30 to 200 times. The granules are further: -The particle size is as uniform as possible-Stable in the raised layer-forming material, eg in the printing ink, and does not disintegrate or disappear-Machine during the raised layer forming operation, eg during the printing operation It should not be destroyed by a specific force.-It should expand sensitively and sufficiently at the transfer temperature.-It is preferable to have various conditions such as being difficult to shrink easily after the raised layer rises due to expansion.
For example, it is necessary to consider various conditions such as the printing method and its conditions, the pressure and heating conditions at the time of transfer, the swelling effect of the transferred three-dimensional swelling pattern and its robustness.

Examples of such a granular material include a granular material of a substance which is heated to easily generate a gas, or a thermally expansive substance such as such a gas generating substance or a substance which is easily vaporized by heating. Granules and the like contained in the thermoplastic polymer can be adopted. As a substance which easily generates a gas when heated, a substance which decomposes by heat to generate a large amount of nitrogen, carbon dioxide, etc., for example, azobisinbutyronitrile, azodicarbonamide, benzenesulfonyl hydrazide, inorganic carbonate And so on.
Examples of the substance that easily evaporates by heating include low boiling point liquid substances such as ether, pentane, and hexane. When included in the thermoplastic polymer, those in the latter group are preferable from the viewpoint of sensitive reaction to heating for a short time.

Examples of the thermoplastic polymer that constitutes the particulate material containing the heat-expandable substance include synthetic pastes such as polyvinyl methyl ether, polyvinyl alcohol, polyacrylic acid copolymers and maleic acid copolymers; Dammar; , Natural resins such as ethyl cellulose or pastes; synthetic resins such as polyolefin resins, polyvinyl resins, polyacrylic acid ester resins, polyurethane resins, polycarbonate resins, polyacrylonitrile copolymer resins, vinylidene chloride resins; natural rubber and Examples include synthetic rubber. These, alone or in a mixed state, form a wall film of the particulate matter, and the surface area thereof is enlarged with the generation of gas from the encapsulating heat-expandable substance or the vaporization of the heat-expandable substance. In the case of forming such a granular material, for example, granulation is performed while encapsulating the heat-expandable substance during an operation such as polymerization or gelation of these thermoplastic polymers, and a thermoplastic polymer forming a wall film is further added. It is also possible to increase the film strength by cross-linking and to shield the contained thermally expansive substance from the outside more completely.
As a specific method for forming the granular material, for example, a well-known microencapsulation method such as a phase separation method, an interfacial polymerization method, a porous rotary cylinder method, an in-situ method, and a spray drying method can be appropriately adopted.

These thermoplastic polymers are not dissolved in the heat-expandable substance contained therein or swollen thereby, are not affected by the solvent constituting the printing ink, and the expansion easily occurs. On the other hand, a material having a small contraction rate after expansion is selected. Therefore, the synthetic resin group is particularly preferable among the above. The raised layers often do not contain colorants, but can include the aforementioned colorants if desired. Different tones are produced when the same colorant is used in the pattern layer and in the raised layer. That is, when a colorant is used for the raised layer, the color density is lowered and the color is whitish, and a pastel color is obtained. Further, a color rich in variety can be obtained by the color mixture of the color of the raised layer and the color of the pattern layer.

Next, the thermoplastic polymer used for the raised layer and capable of forming a flexible film may be selected from the same thermoplastic polymers as those contained in the above-mentioned pattern layer. It is particularly preferable to use the same kind of resin in order to ensure sufficient adhesive strength between the pattern layer and the raised layer on the transferred material. The thermoplastic polymer contained in the raised layer firmly adheres to the transferred material together with the adhesive layer and is raised by heating, and at the same time, the coloring agent is fixed to the raised layer or the transferred material so that the texture is not deteriorated. It provides a good feel and good abrasion and wash fastnesses.

The raised layer is formed by, for example, preparing a printing ink of a normal formulation containing a thermoplastic polymer, particles which cause volume expansion by heating, and optionally a coloring agent, and using the ink, a pattern layer This can be done by printing on the entire surface or a part of the top. To this printing ink, a vehicle made of water, an organic solvent or the like, and if necessary, the additives described for the printing ink for forming the pattern layer can be added.

The above-mentioned adhesive layer is melted by heating at the time of transfer and then solidified by cooling and solidifying so that the transferred material is firmly held on the transferred material. On the other hand, various components contained in the pattern layer and the raised layer are prevented from penetrating into the tissue of the transferred object by transfer, improving the raising efficiency of the raised layer and unnecessary irregularities on the surface of the transferred article. The surface of the raised portion is smoothed by preventing the occurrence of Natural cooling is of course sufficient for cooling. This adhesive layer is, for example, on the entire surface of the raised layer and on the pattern layer (the portion on which the raised layer is not formed), and, if necessary, on the peeling substance layer or the peelable base sheet (on top of it). It can be formed by coating a portion where the pattern layer and the raised layer are not formed) with a hot melt adhesive. As the hot melt adhesive used for forming the adhesive layer, polyamide-based, saturated polyester-based, polyurethane-based, ethylene-vinyl acetate copolymer-based, vinyl chloride-vinyl acetate copolymer-based, polyvinyl chloride-based, polyacrylic ester-based, etc. It is preferred to use the thermoplastic polymers of. Particularly preferred is one having a softening point of 60 to 160 ° C.

In order to coat the entire surface of the raised layer or the like with such a thermoplastic polymer, for example, the thermoplastic resin is dissolved in water or an organic solvent, or it is emulsified or dispersed and suspended. This can be done by preparing a printing ink and using it to print over the raised layer or the like. If necessary, a thermosetting resin, a plasticizer, a surfactant, a stabilizer, a lubricant, a viscosity modifier and the like can coexist in this printing ink. The thermoplastic polymer dispersed and suspended in the printing ink preferably has a particle size of about 10 to 100 μm.

As another method of coating the entire surface of the raised layer with the thermoplastic polymer, the thermoplastic polymer powder is directly sprinkled on the entire surface of the raised layer before it is dried. You can also do it. In this case, the particle size of the resin powder is preferably about 30 to 300 μm.

Furthermore, a holding layer containing the above-mentioned thermoplastic polymer capable of forming a flexible film is formed on the raised layer or the like by printing with a printing ink containing, for example, the thermoplastic polymer, When the layer is not dried but still in a wet state, the thermoplastic polymer powder preferably having a particle size of about 30 to 300 μm may be directly sprinkled on the protective layer to form an adhesive layer. It is also possible to form the adhesive layer with the above printing ink after the holding layer has dried. With respect to the adhesive layer thus formed, according to the three-dimensional pattern transfer sheet that has been once heat-treated at a temperature lower than the temperature at which the thermal expansion of the particulate matter that causes volumetric expansion by heating, And various fastnesses such as wash fastness are significantly improved.

Examples of materials to be transferred to which the three-dimensional pattern transfer sheet of the present invention is transferred include natural fibers such as cotton, hemp, silk and wool; recycled or semi-synthetic fibers such as rayon, cupra, polynosic and acetate; polyamide. -Based, polyester-based, polyacrylic-based, polyurethane-based, polyolefin-based, polyvinyl-based, and other synthetic fibers and glass fibers, and other woven fabrics, interwoven fabrics, interwoven knitted fabrics, knits and nonwoven fabrics; leather; natural rubber Sheet materials such as films or sheets of synthetic rubber, vinyl chloride resin, polyurethane resin and the like can be mentioned. Of course, it can also be transferred to a three-dimensional molded article made of synthetic resin, ceramics, metal or the like. Even if the surface of the material to be transferred is subjected to various kinds of processing or the material to be transferred is porous, it becomes a transfer target.

The adhesive layer of the three-dimensional pattern transfer sheet as described above is brought into contact with the surface of the transferred material, and the base sheet is heated at 80 to 180 ° C. for 2 to 30 seconds by using an iron or a hot press. After pressing, only the base sheet is peeled off from the transferred material, or the base sheet and the peeling material layer are peeled off integrally. Then, the granular material of the raised layer expands in volume, the raised layer rises, the adhesive layer melts, and the three-dimensional pattern is transferred onto the transferred material, and then the adhesive layer is cooled and solidified to be transferred onto the transferred material. Objects are held firmly.

Since the pattern layer and the raised layer are provided as separate layers, when the particulate matter contained in the raised layer expands in volume and the raised layer rises, the pattern layer is accompanied by it. Although raised, its surface area does not increase significantly.
Therefore, the coloring density of the colorant contained in the pattern layer does not almost decrease, and the surface of the pattern layer does not have a white color. Therefore, the obtained three-dimensional pattern is colored in a clear and high density, and the desired hue and design can be achieved in a wide range. Further, since the pattern layer itself does not expand, the surface of the raised portion in the transferred pattern becomes relatively smooth as compared with the conventional case. Furthermore, the texture of the transfer is flexible because sufficient fastness can be achieved with a relatively small amount of resin. Of course, the pattern layer in the portion where the raised layer is not provided is not raised.

The fluidity of the raised layer and the pattern layer at the transfer temperature is such that the pattern layer and the raised layer flow almost to the side when the three-dimensional raised pattern is transferred onto the transfer object by pressing and heating. It is desirable not to do so. This is such a fluidity that the surface of the transferred pattern does not reflect the shape of the texture when it is transferred to a woven fabric, for example. If the fluidity is low to that extent, when the particulate matter contained in the raised layer expands in volume by heating, the thermoplastic polymer contained in the raised layer and the pattern layer also has a small rate of penetrating into the transferred material, which is sufficient. It is possible to surely obtain such a three-dimensional raised effect and to make the surface of the raised portion in the transfer pattern smoother. In addition, accurate and clear expression can be easily made in terms of color and pattern, and even if it is a fine expression such as a delicate drawing line or a photo-decomposed pattern, it is hardly crushed by the flow, so the desired sharpness is sufficient. Precision can be realized. Normal transfer temperature is 80
Since it is from 180 to 180 ° C., if a thermoplastic polymer having a softening point of 100 ° C. or higher is used, the fluidity condition is almost satisfied. Specifically, it is particularly preferable to use a polyurethane resin whose formed film is flexible and has rubber elasticity or elasticity close to that.

[0029]

According to the three-dimensional pattern transfer sheet of the first aspect, it is possible to prevent the three-dimensional swelling pattern transferred onto the transferred object from being reduced in color density and whitening due to the swelling.
The desired hue and design can be broadly achieved without necessarily requiring the white pigment-containing layer that hides the base, and the surface of the raised portion in the transfer pattern becomes relatively smooth. Also, the material of the base sheet can be widely selected.
According to the three-dimensional pattern transfer sheet of claim 3, the three-dimensional swelling pattern transferred onto the transferred object is prevented from being reduced in color density and whitening due to swelling, and contains a white pigment for hiding the base. The desired hue and design can be achieved extensively without necessarily requiring layers, and the surface of the raised portions in the transfer pattern is relatively smooth. Moreover, since it is not necessary to provide a peeling substance layer, the manufacturing process is simple.

In the three-dimensional pattern transfer sheet according to the second and the fourth aspects, the pattern layer of the three-dimensional raised pattern transferred onto the transferred material is protected by the protective layer, so that various fastnesses are improved. According to the three-dimensional pattern transfer sheet of claim 5, a sufficient three-dimensional uplifting effect can be obtained in the pattern pattern transferred onto the transferred object, and the color and the pattern can be expressed accurately and clearly, and a delicate image line can be obtained. It is possible to realize sufficient sharpness and precision even for fine expressions such as a photograph disassembly pattern, and the surface of the raised portion in the transfer pattern becomes even smoother.

[0031]

EXAMPLES In the following description, "parts by weight" means
Abbreviated as “part”. Example 1 A releasable resin layer 2 was formed by applying a 5% toluene solution of a silicone resin to a 64 g / m ² glassine paper 1 (base sheet) using a gravure coater. After the releasable resin layer 2 is dried, RISVON 315 is formed on it.
From 6 parts (trade name of polyurethane resin [softening point: 130 ° C., manufactured by Dainippon Ink & Co., Inc.) 60 parts, MIBK 20 parts, isophorone 18 parts and Lionol Blue SL (trade name of blue pigment, manufactured by Toyo Ink Co., Ltd.) By using the 225 mesh screen plate, which is the opposite of the actual design, with the blue ink, an M-shaped pattern consisting of diagonal lines with a width of 2 mm at intervals of 1 mm is printed by a normal silk screen method to form the pattern layer 3. did.

After the pattern layer 3 is dried, Superflex E-2000 (polyurethane resin [softening point: 140 ° C., trade name, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.] 7
0 parts, 20 parts Kanebinol LX-50 (trade name of microcapsules containing a thermally expansive substance, manufactured by Kanebo)
An ink consisting of 5 parts of CMC, 3 parts of titanium oxide powder and 2 parts of water gives 100 m of the same M-shaped pattern as the pattern layer.
Overprinting was performed using an esh screen plate to form the raised layer 4.

After the raised layer 4 was dried, 5 parts of Superflex E-2000 (supra) and Daiamide 450P-1 (polyamide resin [softening point: 100
[° C.], a hot melt adhesive having a trade name of 30 parts by Daicel Chemical Co., Ltd., 5 parts by CMC (above) and 60 parts by water.
Overprint using a screen plate to form the adhesive layer 5,
The adhesive layer 5 was dried to obtain a three-dimensional pattern transfer sheet A as shown in FIG.

A three-dimensional pattern transfer sheet A obtained by using a thermal transfer machine was used, and the adhesive layer 5 was applied to the red cotton knit 6 which was the transfer target.
Place it on the red cotton knit 6 with it abutting on it,
After heating and pressurizing at 250 g / cm ² at 140 ° C. for 10 seconds, the glassine paper 1 was rapidly peeled off as shown in FIG. 2, and as shown in FIGS. 3 and 4, On the red cotton knit 6, an M-shaped pattern C consisting of 2 mm wide blue diagonal lines B (that is, the raised pattern layer 3) having a height of about 20 times and having a width of 1 mm was obtained. The three-dimensional pattern thus obtained exhibits an extremely clear and dark blue color and is almost faithful to the design of the screen plate, and the surface of the raised portion is extremely smooth,
It had excellent toughness and had a soft feel.

Example 2 Surface-treated with silicone resin and having releasability 1
00g / m ² polyester film (base sheet)
KBK AD4031 (trade name of acrylic ester resin [softening point: 150 ° C., manufactured by Kanebo Ltd.] 60
Parts, ethylene glycol monoethyl ether acetate 30 parts, isophorone 8 parts and Hostaperm Y
yellow H-10G (trade name of yellow pigment, manufactured by Hoechst Co.) 2 parts yellow ink, and Hostaperm Yellow H-10G in the ink
Ostaperm Pink E (trade name of red pigment,
Hoechst), Lionol Blue SL (trade name of blue pigment, Toyo Ink) and Carbon B
black MT40 (trade name of carbon black, manufactured by Mitsubishi Kasei Co., Ltd.) is used to print with four color inks of red, blue and black inks using a color separation plate (300 mesh) of a photographic flower pattern. , A pattern layer was formed.

After the pattern layer is dried, Flex 300 (trade name of polyurethane resin [softening point: 180 ° C., manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.] 70 is placed only on the petals of the pattern layer. Part, Kanebinol LX-75 (trade name of microcapsules encapsulating a heat-expandable substance, manufactured by Kanebo), 5 parts of CMC, 3 parts of titanium oxide powder and 2 parts of water, using a 100 mesh screen plate. Overprinting was performed to form a raised layer.

After the raised layer was dried, a 100 mesh screen having the same pattern as the pattern layer was formed with an ink composed of 90 parts of Flex 300 (previous), 5 parts of CMC (previous) and 5 parts of water. Overprinting was performed using a plate to form a holding layer.

While the holding layer was in a wet state, Daiamide 450P-3 (polyamide resin [softening point: 85
[° C] of hot melt adhesive, manufactured by Daicel Chemical Co., Ltd.) to form an adhesive layer, and then at 95 ° C for 3 hours.
A three-dimensional pattern transfer sheet was obtained by baking for 3 minutes.

Using a thermal transfer machine, the obtained three-dimensional pattern transfer sheet was placed on the blue cotton knit, which was an object to be transferred, in contact with the adhesive layer, and was placed on the blue cotton knit for 20 seconds. After heating and pressurizing at 250 ° C / cm ² at 150 ° C, the base sheet was quickly peeled off. Only the petals were raised about 20 times on the blue cotton knit, and the stem and other parts were raised. An extremely three-dimensional design pattern in a state where it was not obtained was obtained. The three-dimensional pattern thus obtained exhibits an extremely vivid and dark color, is faithful to photographs, and has a surface of a raised portion which is extremely smooth and has excellent fastness. The feel was flexible.

Example 3 Carnauba wax 1 was applied to a portion corresponding to the entire pattern layer formed on parchment paper (60 g / m ² ).
An ink consisting of 5 parts, 80 parts of toluene and 5 parts of Ethocel 100 (trade name of ethyl cellulose, manufactured by Hercules) was screen printed using a 200 mesh screen plate to form a peelable resin layer. After the releasable resin layer has dried, RISVON 30
06 (trade name of polyurethane resin [softening point: 160 ° C., manufactured by Dainippon Ink and Chemicals, Inc.] 60 parts, ethylene glycol monoethyl ether acetate 30 parts, isophorone 8 parts and Carbon Black MT40 (trade name of carbon black, Mitsubishi Kasei) (Manufactured by K.K.) 2 parts black ink, and Carbon Black M in the ink
T40 is used as Hostaperm Pink E (trade name of red pigment, manufactured by Hoechst), Lionol Blue
SL (trade name of blue pigment, manufactured by Toyo Ink Co., Ltd.) and Ho
The pattern pattern layer is printed by using a screen plate with a character pattern with four color inks of red, blue and yellow inks respectively replaced by taperm Yellow H-10G (trade name of yellow pigment, manufactured by Hoechst). Formed.

After the pattern layer is dried, CRISVON 3006 (described above) and Kanebinol LX-50 (including a heat-expandable substance are included on the entire surface of the pattern layer excluding so-called kei lines such as outlines of character patterns. The product name of the microcapsules manufactured by Kanebo Co., Ltd.), 100 parts by ink containing 20 parts, xylene 25 parts and titanium oxide powder 5 parts.
Overprinting was performed using an sh screen plate to form a raised layer. After the raised layer was dried, 30 parts of Pandex 5102 (trade name of a hot-melt adhesive made of polyurethane resin [softening point: 50 ° C., manufactured by Dainippon Ink and Chemicals, Inc.) and 70 parts of cyclohexanone were placed on it. The ink was used to form an adhesive layer by overprinting with a screen plate so as to cover the entire pattern layer, and the adhesive layer was dried to obtain a three-dimensional pattern transfer sheet.

Using a thermal transfer machine, the obtained three-dimensional pattern transfer sheet was placed on the red vinyl chloride sheet with its adhesive layer being in contact with the red vinyl chloride sheet as the material to be transferred, and was placed for 5 seconds. After heating and pressurizing 250 g / cm ² at 120 ° C., the base sheet was immediately peeled off. As a result, a very clear and dark color was exhibited on the red vinyl chloride sheet and it had a sharp appearance. A character pattern having irregularities and excellent in three-dimensional effect was obtained. The surface of the raised portion was extremely smooth. In addition, the touch of the character pattern was flexible, and the toughness was excellent.

Example 4 1 g of a silicone resin was placed on a 100 g / m ² polyester film 1 (base sheet) that had been sand matted.
A 0% toluene solution was applied to the entire surface with a knife coater to form a peelable resin layer 2. After the releasable resin layer 2 is dried, CRISVON 3865 (polyurethane resin [softening point: 180 ° C.], trade name, Dainippon Ink Co., Ltd. is applied to a portion corresponding to the entire pattern layer 3 formed thereon. A protective layer 7 was formed by screen printing with an ink consisting of 70 parts of DMF and 20 parts of MIBK. After the protective layer 7 was dried, the black, red, blue and yellow four-color inks used in Example 2 were used to print using a color-separated plate (300 mesh) of a photographic tone fruit pattern to obtain a pattern layer 3 Formed.

After the pattern layer 3 is dried, Teisan resin A-3611 (trade name of acrylic ester resin [softening point: 140 ° C.], is applied on the entire surface of the pattern layer 3.
Teikoku Chemical Co., Ltd.) 70 parts, Microsphere F-80
(Product name of microcapsules containing a heat-expandable substance,
20 parts of Matsumoto Yushi-Seiyaku Co., Ltd., 5 parts of CMC and 5 parts of water were used to perform overprinting using a 100 mesh screen plate to form a raised layer 4. While the raised layer 4 is in a wet state, Byron 902P (trade name of a hot melt adhesive made of saturated polyester resin [softening point: 70 ° C., manufactured by Toyobo Co., Ltd.] is sprayed to form an adhesive layer 5. ,
After that, baking was performed at 130 ° C. for 3 minutes to obtain a three-dimensional pattern transfer sheet D as shown in FIG.

Using a thermal transfer machine, the obtained three-dimensional pattern transfer sheet was placed on the black polyester knit, which was an object to be transferred, with the adhesive layer being in contact with the black polyester knit, and the sheet was left for 5 seconds. 250 g / cm ² at 160 ° C
After heating and pressurizing, and cooling to room temperature, the base sheet was peeled off. Furthermore, a release paper which was lightly release treated than the base sheet was overlaid on the design, and heated and pressed at 160 ° C. for 250 seconds at 250 g / cm ² by a heat press machine to obtain a black polyester knit. above,
A three-dimensional fruit pattern that was raised about 20 times was obtained. The three-dimensional pattern thus obtained has an extremely clear and dark color, is faithful to the photograph, and the surface of the raised portion is extremely smooth, and its texture is flexible. It was Moreover, even if the three-dimensional pattern was ironed, the pattern did not transfer to the iron, and the washing fastness as well as the dry cleaning was endured. The same was true when the release paper was replaced with a commercially available release film.

Comparative Example 5% of silicone resin on glassine paper (64 g / m ² ).
The toluene solution was applied to the entire surface by a gravure coater to form a peelable resin layer. After the releasable resin layer was dried, 70 parts of Sumikaflex 401 (trade name of ethylene-vinyl acetate copolymer-based resin [softening point: 70 ° C., manufactured by Sumitomo Chemical Co., Ltd.], Kanebinol LX-50 (heat (Product name of microcapsule containing expandable substance, manufactured by Kanebo)
20 parts, CMC 5 parts and Lionol Blue SL
(Blue pigment product name, manufactured by Toyo Ink Co., Ltd.) An M-shaped pattern having the same pattern as in Example 1 was formed by using two parts of blue ink.
Printing was carried out in the same manner as in Example 1 by a silk screen method to form a raised pattern layer.

After the raised pattern layer was dried, 25 parts of Byron 200 (trade name of a hot melt adhesive made of a saturated polyester resin [softening point: 80 ° C., manufactured by Toyobo Co., Ltd.] on the entire surface, A conventional raised pattern transfer sheet is formed by overprinting with an ink composed of 18 parts of titanium oxide powder, 50 parts of ethylene glycol monoethyl ether acetate and 7 parts of D.O.P to form a white pigment layer, and drying the white pigment layer. was gotten.

Using this raised pattern transfer sheet, a raised pattern was transferred and formed on a red cotton knit under the same conditions as in Example 1. Table 1 shows the results of comparison between the three-dimensional pattern obtained in Example 1 and the raised pattern obtained in Comparative Example.

[0049]

[Table 1]

Regarding sharpness, in Example 1, M
The distance between the blue diagonal lines in the letter pattern is almost 1 mm
A very sharp three-dimensional pattern kept in the width was obtained, but in the comparative example, the interval between the blue diagonal lines in the M-shaped pattern was about 0.5 mm, and the sharpness was lacking. Regarding the swelling property, in the first embodiment, the swelling layer thickness is 1
In the comparative example, the film having a thickness of 100 μm, which is a pattern having a protuberance pattern, swelled only to about 1 mm. Further, the surface of the raised portion had a conspicuous unevenness and had a rough feel.

[Brief description of drawings]

FIG. 1 is a schematic sectional view of a three-dimensional pattern transfer sheet.

FIG. 2 is a schematic cross-sectional view showing a transfer operation of a three-dimensional pattern transfer sheet.

FIG. 3 is a schematic cross-sectional view showing a transferred three-dimensional pattern.

FIG. 4 is a schematic plan view of a transferred three-dimensional pattern.

FIG. 5 is a schematic cross-sectional view of another three-dimensional pattern transfer sheet.

[Explanation of sign]

 1 Glassine paper 2 Releasable resin layer 3 Design pattern layer 4 Raised layer 5 Adhesive layer 6 Red cotton knit 7 Protective layer A Three-dimensional pattern transfer sheet B Blue diagonal line C M-shaped pattern D M-shaped pattern

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location D06P 5/00 118 D 9160-4H Z 9160-4H

Claims (5)

[Claims] 1. A transfer sheet for transferring a three-dimensional raised pattern on a transfer object by pressurization and heating, comprising a base sheet, a release material layer, a pattern layer, a raised layer and an adhesive layer in this order. The pattern layer has a thermoplastic polymer capable of forming a flexible film and a colorant,
The three-dimensional pattern transfer sheet, wherein the raised layer comprises a thermoplastic polymer capable of forming a flexible film, a granular material that causes volume expansion by heating, and a colorant if necessary. 2. The three-dimensional pattern transfer sheet according to claim 1, further comprising a protective layer between the release material layer and the pattern layer. 3. A transfer sheet for transferring a three-dimensional raised design pattern onto an object to be transferred by applying pressure and heat, which comprises a base sheet having releasability, a design pattern layer, a raised layer and an adhesive layer in this order. And the pattern layer comprises a thermoplastic polymer capable of forming a flexible film and a colorant, and the raised layer comprises a thermoplastic polymer capable of forming a flexible film and a volume by heating. A three-dimensional pattern transfer sheet comprising a swelling granular material and a colorant if necessary. 4. The three-dimensional pattern transfer sheet according to claim 3, further comprising a protective layer between the base sheet and the pattern layer. 5. The fluidity of the pattern layer and the raised layer at a transfer temperature is such that the pattern layer and the raised layer are almost lateral when the three-dimensional raised pattern is transferred onto an object to be transferred by pressing and heating. The three-dimensional pattern transfer sheet according to claim 1, claim 2, claim 3 or claim 4, which does not flow to the outside.