JP4172577B2 - Thermocompression-bonding water-discoloring sheet material and water-discoloring processed body using the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a thermocompression-bonding type water discolorable sheet material and a water discolorable processed body using the same. More specifically, a thermocompression-type water discoloration sheet material that effectively fixes and forms a water discoloration layer on a target fabric or fabric processed body by a thermocompression bonding means such as a heat iron or a heat press, and The present invention relates to a water discoloration processed body formed by thermocompression bonding of the sheet material.
[0002]
[Prior art]
Conventionally, a sheet has been disclosed in which a porous layer containing a low refractive index pigment is provided on a support, and the sheet is made transparent by attaching water to the porous layer so that an image appears. Applications include calligraphy practice, image concealment toys, etc. (Japanese Patent Publication No. 50-5097, Japanese Patent Publication No. 5-15389).
[0003]
[Problems to be solved by the invention]
The present invention may be applied to any part of the fabric or fabric processed body is a porous layer Target product described above, by fixing by a relatively simple means such as heat ironing, which expands the application range, the target An object of the present invention is to provide a thermocompression-type water-coloring sheet material capable of obtaining a water-coloring processed body satisfying the stretching adaptability, and various water-coloring processed bodies obtained thereby, even if the object is a stretchable fabric or the like. To do.
[0004]
[Means for Solving the Problems]
The present invention will be described with reference to the drawings (see FIGS. 1 to 6 ).
The present invention has a thickness of 0.02 to 0.4 mm selected from polyamide-based, polyolefin-based, ethylene-vinyl acetate-based, polyurethane-based, or polyester-based resins having a melting point in the range of 60 ° C to 180 ° C as a substrate. Directly or colored on the entire surface 11 of the heat-meltable film surface , a low refractive index pigment fixed in a dispersed state in a binder resin, which is opaque in a non-absorbing state and transparent in the absorbing state. The thermocompression-type water discolorable sheet material 1 is provided as a requirement, which is provided through the layer and fixes the water discoloration layer to the surface of the fabric or fabric processed body that is the object by thermocompression bonding.
Furthermore, a water discoloration processed body formed by fixing the thermocompression-bonding type water discolorable sheet material to the surface of a cloth or a cloth processed body as an object is a requirement.
[0005]
The heat-meltable film 11 serves as a support and bonding medium as a substrate for the porous layer 12, the colored layer 13, or the white hiding layer 14, and has a melting point of 60 ° C. to 180 ° C., preferably 70. A thickness of 0.02 to 0.4 mm, preferably made of a heat-meltable resin selected from polyamide-based, polyolefin-based, ethylene-vinyl acetate-based, polyurethane-based, or polyester-based resins in the range of ℃ to 150 ℃, A film of 0.05 to 0.2 mm is effective.
If the melting point of the heat-meltable film is less than 60 ° C., there is a risk of melting and peeling depending on the environmental temperature or the like. If the melting point is higher than 180 ° C., the heat resistance of the object at the time of thermocompression bonding is limited.
In addition, a thickness of about 0.02 to 0.4 mm satisfies the function as a support and has a homogeneous heat-melting property, satisfies bonding strength and elongation, and can be die-cut into any of various shapes. It is possible and practical.
[0006]
[0007]
In the use in which the above-described object 21 is stretchable and stretchability is required, one having an elongation of about 400% to 600% is appropriately selected and used among the heat-meltable resins. Can do.
[0008]
By blending 10 to 400 parts by weight (preferably 50 to 300 parts by weight) of finely powdered titanium oxide with respect to 100 parts by weight of the above-described hot-melt film 11, it also has a white hiding function in addition to the joining function. Can be made.
[0009]
Further, by combining 10 to 400 parts by weight (preferably 50 to 300 parts by weight) of finely powdered titanium oxide with respect to 100 parts by weight of the hot-melt resin of the hot-melt resin layer 16, the bonding function is the same as described above. In addition to this, a white hiding function can also be provided.
[0010]
By providing the colored layer 13, it is possible to enhance the visual effect by causing the porous layer 12 to show a colored pattern during liquid absorption. The heat-meltable film 11, the heat-meltable resin layer 16, and the white hiding layer 14 blended with the fine powdered titanium oxide are for further enhancing the visual effect of the colored layer 13.
[0011]
As the low refractive index pigment contained in the porous layer, fine silica, barite powder, precipitated sulfuric acid having a refractive index of 1.4 to 1.7 and a particle diameter of 0.03 to 10 μm. Examples thereof include barium, barium carbonate, precipitated calcium carbonate, gypsum, clay, talc, alumina white, and basic magnesium carbonate. Among these, particulate silicic acid is effective in terms of concealability, transparency, workability, and the like.
Among the fine-particle silicic acids, wet-method fine-particle silicic acid has a so-called two-dimensional structure part in which silicic acid is condensed to form a long molecular arrangement, and compared with a dry-method fine-particle fine-silicic acid having a three-dimensional structure. Since the molecular structure becomes rough, the system using wet process fine particle silicic acid is superior in the diffuse reflection of light in the dry state compared to the system using dry process fine particle silicic acid, and has a concealing property in the normal state. In addition, the wet method fine particle silicic acid has more hydroxyl groups present as silanol groups on the particle surface than the dry method fine particle silicic acid, and therefore has a moderate hydrophilicity and therefore has a large water absorption effect. Most preferred.
[0012]
In the system using the wet method fine particle silicic acid, it depends on the type of wet method fine particle silicic acid, the particle diameter, the specific surface area, the oil absorption amount, etc., but the concealability in the normal state and the transparency in the water absorption state are affected. to satisfy both the (more ^{preferably, 0.05g / 100cm 2 ~0.2g / 100cm} 2) coating amount to the substrate surface 0.01g ^/ 100cm ² ~0.3g ^/ 100cm 2 is. If it is less than 0.01 g / 100 cm ² , sufficient concealability cannot be obtained in a normal state. On the other hand, if it exceeds 0.3 g / 100 cm ² , it is difficult to obtain sufficient transparency upon water absorption.
The particulate silicic acid is dispersed in a vehicle containing a binder resin to form a dispersed ink, and a porous layer 12 is formed on the heat-meltable film or support by coating, printing, spraying, or other application means. Is done.
[0013]
Examples of the binder resin include urethane resin, nylon resin, vinyl acetate resin, acrylic ester resin, acrylic ester copolymer resin, acrylic polyol resin, vinyl chloride-vinyl acetate copolymer resin, maleic resin, polyester resin, styrene. Resin, styrene copolymer resin, polyethylene resin, polycarbonate resin, epoxy resin, styrene-butadiene copolymer resin, acrylonitrile-butadiene copolymer resin, methyl methacrylate-butadiene copolymer resin, butadiene resin, chloroprene resin, melamine resin, and the above Resin emulsion selected from each resin, casein, starch, cellulose derivative, polyvinyl alcohol, urea resin, phenol resin, epoxy resin and the like.
In particular, urethane resin is effective, the film strength of the porous layer 12 can be improved, and the concealability in the dry state and the transparency in the water absorption state are not impaired.
[0014]
The urethane-based resin is preferably used alone, but other binder resins can be used in combination depending on the required degree of film strength. In order to obtain practical film strength, It is preferable that urethane resin is present in an amount of 30% by weight (solid content ratio) or more.
In the porous layer 12 formed as described above, conventionally known titanium dioxide-coated mica, iron oxide-titanium dioxide-coated mica, iron oxide-coated mica, guanine, sericite, basic lead carbonate, acidic arsenic acid Metal luster pigments such as lead and bismuth oxychloride can be added, and general dyes and pigments, fluorescent dyes and fluorescent pigments can be added in appropriate amounts to diversify the color change and improve toy and realism. Furthermore, a reversible thermochromic material that changes color reversibly with temperature can be blended.
[0015]
In the system in which the reversible thermochromic material is blended, the weight ratio of the reversible thermochromic material and the particulate silicic acid in the porous layer 12 is 1: 9 to 9: 1 (preferably 2: 8 to The range of 8: 2) can effectively satisfy both the thermochromic property, the concealment property during drying, and the transparency during water absorption.
The reversible thermochromic material is practically used as a pigment in the form of microcapsules having a particle size of 0.1 to 30 μm, preferably 0.1 to 20 μm.
The thermochromic pigment in the form of the microcapsule is blended in a vehicle containing a binder resin to form an ink, similar to various non-thermochromic pigments or colorants such as dyes. The colored layer 13 can be formed on the upper layer to make various color changes visible.
Further, a water repellent treatment liquid containing a water repellent resin selected from silicon-based, paraffin-based, polyethylene-based, alkylethyleneurea-based, and fluorine-based water repellent resins is formed on the porous layer 12. It is also possible to form a water repellent pattern by adhering it to form an image of an appropriate shape and osmotically drying it.
The water-repellent resin pattern is a layer that exists in the porous layer 12 and coexists, and the porous layer 12 at the coexisting location is not formed with a water absorption state due to a water repellent effect, and is kept in an opaque state. (Since the water repellent resin is transparent, the opaque state of the porous layer 12 can be seen through.)
Therefore, in the normal state (non-water-absorbing state), the water-repellent resin pattern and the porous layer 22 that are difficult to discriminate can be discriminated by absorbing water into the porous layer 22 in the non-arranged portion of the water-repellent resin pattern. The aspect change is tautomatic.
Of the water-repellent resins, the fluorine-based water repellent is effective in terms of the water-repellent effect and processability, and the solid content is 1 g / m ^{2 to} 50 g / m ² , preferably 2 g / m ^2. An adhesion amount in the range of ˜30 g / m ² is effective.
[0016]
Thermal compression type water-discoloring sheet material obtained as described above, by fixing the Target piece surface to form a water-discoloring workpiece.
For said object, knitted product as a material, fabric, braided, a fabric such as a nonwoven fabric can be exemplified.
In addition, the sheet material may be fixed to various objects formed of the material. For example, as a processed body using a fabric, a swimsuit, a raincoat, a diaper, or a garment, a doll swimsuit, a rain Examples include coats and diapers.
In addition, umbrellas, rain boots, waterproof books, coasters, artificial flowers, etc. can be used as processed bodies.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
The present invention includes a thermocompression-type water color-changing sheet material using a specific heat-meltable film or a heat-meltable resin as an adhesive medium, and a form of a water-coloring processed body formed by thermocompression bonding of the sheet material. The sheet material or processed body of each of the above forms can be prepared by applying general-purpose means, and is not specified in the following examples.
Examples are described below. Here, the part in an Example is a weight part.
[0018]
【Example】
Example 1 (see FIGS. 1 and 2)
15 parts of wet process fine particle silica [trade name: NIPSEAL E-220, manufactured by Nippon Silica Kogyo Co., Ltd.] on the surface of polyurethane-based hot-melt film 11 (thickness 100 μm, melting temperature 80 ° C.) colored in blue, urethane emulsion [Product name: Hydran AP-10, manufactured by Dainippon Ink & Chemicals, Inc., solid content 30% by weight] 45 parts, water 40 parts, silicone antifoam 0.5 parts, aqueous ink thickener 3 parts Using a white screen printing ink obtained by uniformly mixing and stirring 1 part of ethylene glycol and 3 parts of an isocyanate-based crosslinking agent, the entire surface was solid-printed on a 100-mesh screen plate and dried and cured at 60 ° C. for 30 minutes. A porous layer 12 was formed to obtain a thermocompression-bonding water-coloring sheet material 1 (see FIG. 1).
The water-meltable film 11 side of the sheet material 1 is brought into close contact with a T-shirt (target object 21) made of spandex and excellent in stretchability, and is thermocompression bonded by a heating body heated to about 100 ° C. (Water discoloration processed body 2) was obtained (see FIG. 2).
The water discolorable T-shirt normally exhibits white, but when water is attached, the porous layer 12 changes from white to transparent, so it changes from white to blue, and when water is attached, blue. Although it was present, it returned to its original white color once the water evaporated. The change in appearance was reversibly repeated and reproduced. Further, the water discoloring T-shirt was excellent in stretchability, and the porous layer 12 could be used many times without being lost.
[0019]
Example 2 (see FIGS. 3 and 4)
Colorless and transparent heat-meltable polyester film 11 (thickness 25 μm, heat melting temperature 180 ° C.), polyester-based white ink [ink in which 30 parts of titanium oxide are dispersed in 100 parts of a polyester resin solution (solid content 30% by weight)] Is applied to the entire surface and dried to form a white opaque white hiding layer 14, and then a colored layer 13 having a floral pattern of blue, red, and yellow is formed with an ultraviolet curable non-color-changing offset ink. did.
Next, 15 parts of wet method fine particle silica [trade name: Nipsil E-220, manufactured by Nippon Silica Industry Co., Ltd.], urethane emulsion [trade name: Hydran AP-10, manufactured by Dainippon Ink & Chemicals, Inc., solid content 30 Weight screen] White screen comprising 45 parts, 40 parts of water, 0.5 part of a silicone-based antifoaming agent, 3 parts of a thickener for water-based ink, 1 part of ethylene glycol, and 3 parts of an isocyanate-based crosslinking agent. Using a printing ink, the entire surface of the colored layer 13 is solid-printed with an 80-mesh screen plate, and is dried and cured at 130 ° C. for 5 minutes to form the porous layer 12. 1 was obtained (see FIG. 3).
The polyester film side of the sheet material 1 was brought into intimate contact with a black polyester satin fabric and pressure-bonded with a hot roll having a surface temperature of about 230 ° C. to obtain a water discolorable polyester satin fabric (water discoloration processed body 2) (FIG. 4).
The fabric is normally white, but in a water adhering state (water absorption state), the porous layer 12 changes from white to transparent, and the floral pattern of blue, red, and yellow of the colored layer 13 is visually recognized. When the water was attached, it had a floral pattern, but when the water evaporated by drying, the original white color was visible again. Further, in the water absorption state, the polyester satin fabric as a base was not affected at all by the black color, and a vivid blue, red and yellow floral pattern could be seen.
[0020]
Example 3 (see FIGS. 5 and 6)
The surface of the polyamide-based hot-melt film 11 colored in white (the content of fine powdered titanium oxide in the film is 50% by weight, the thickness is 150 μm, the melting temperature is 130 ° C.) is coated on the entire surface using a pink aqueous screen ink. A colored layer 13 is provided by screen printing, and further 15 parts of wet method fine particle silica [trade name: NIPSEAL E-220, manufactured by Nippon Silica Industry Co., Ltd.], blue pigment [trade name: Brilliant Blue FLR CONC. , Manufactured by Dainichi Seika Kogyo Co., Ltd.] 0.5 parts, urethane emulsion [trade name: Hydran AP-10, manufactured by Dainippon Ink & Chemicals, Inc., solid content 30%] 45 parts, water 40 parts, silicone 100 mesh screen plate using white screen printing ink prepared by uniformly mixing and stirring 0.5 part of defoaming agent, 3 parts of thickener for water-based ink, 1 part of ethylene glycol and 3 parts of isocyanate-based crosslinking agent The entire surface was solid-printed at 100 ° C. and dried and cured at 100 ° C. for 30 minutes to form a porous layer 12 to obtain a thermocompression-type water discolorable sheet material 1 (see FIG. 5).
The heat-meltable film side of the sheet material 1 is brought into intimate contact with a red T-shirt (object 21) and thermocompression bonded with a heating body heated to about 160 ° C. (See FIG. 6).
The water discolorable T-shirt normally exhibits a light blue color. However, when water is attached, the porous layer 12 changes from a light blue color to a transparent blue color. The color changed to purple, and when the water was attached, the color was purple, but when the water evaporated, it returned to the original light blue color. The change in the appearance was reversibly repeated and reproduced, and the purple color at the time of liquid absorption was vivid purple without being affected by the red color of the T-shirt.
[0021]
[0022]
[0023]
Example 4
Fully solid screen printing using yellow water-based screen ink on the surface of white colored polyurethane-based heat-meltable film (content of finely powdered titanium oxide in film 50% by weight, thickness 150 μm, melting temperature 130 ° C.) Further, a wet process fine particle silica [trade name: Nipseal E-220, manufactured by Nippon Silica Industry Co., Ltd.] 15 parts, urethane emulsion [trade name: Hydran AP-10, Dainippon Ink & Chemicals, Inc. Co., Ltd., solid content 30%] 45 parts, water 40 parts, silicone antifoaming agent 0.5 parts, aqueous ink thickener 3 parts, ethylene glycol 1 part, isocyanate crosslinking agent 3 parts uniformly Using a white screen printing ink obtained by mixing and stirring, the entire surface is solid-printed on a 100 mesh screen plate, dried and cured at 70 ° C. for 30 minutes, and porous. Form to obtain a thermal compression type water-discoloring sheet material.
The sheet material is cut into an oval shape, the heat-meltable film side is brought into close contact with the inside of a doll diaper made of white polyester brushed cloth, and thermocompression bonded by a heating body heated to about 160 ° C. A diaper (water discoloration processed body) was obtained.
The porous layer provided on the inner side of the diaper is changed from white to transparent by water absorption by attaching the water-changing doll diaper to a milk drinking doll, allowing the doll to drink water, and then discharging it. The oval shape of the yellow colored layer was visible, and the puppet was clearly visible.
This aspect is maintained in a state where the porous layer absorbs liquid, but when the water evaporates, it returns to the original white color again.
The modal change can be repeated, and since the film is interposed, it is difficult for water to adhere to the diaper and the water attached to the porous layer easily evaporates. I was able to satisfy the toy.
[0024]
Example 5
On the surface of a colorless and transparent heat-meltable polyurethane film (thickness 25 μm, heat-melting temperature 110 ° C.), polyurethane-based white ink [ink in which 30 parts of titanium oxide are dispersed in 100 parts of polyurethane resin solution (solid content 30% by weight)] After coating on the entire surface and drying to form a white opaque white concealing layer, a photographic floral pattern (colored) by process printing using UV-curable non-color-changing offset ink (yellow, cyan, magenta, black) Layer).
Next, wet process fine particle silica [trade name: Nipseal E-220, manufactured by Nippon Silica Industry Co., Ltd.] 15 parts, urethane emulsion [trade name: Hydran AP-30, manufactured by Dainippon Ink & Chemicals, Inc., solid content 30 Weight screen] White screen comprising 45 parts, 40 parts of water, 0.5 part of a silicone-based antifoaming agent, 3 parts of a thickener for water-based ink, 1 part of ethylene glycol, and 3 parts of an isocyanate-based crosslinking agent. Using a printing ink, the entire surface of the colored layer is solid-printed with an 80-mesh screen plate, and is dried and cured at 80 ° C. for 5 minutes to form a porous layer, thereby obtaining a thermocompression-type water discolorable sheet material. It was.
The sheet material is cut along the floral pattern, and the polyurethane film side is brought into close contact with a doll swimsuit made of a spandex fabric having excellent pink elasticity, and is crimped by an iron having a surface temperature of about 160 ° C. A sex doll swimsuit (water discoloration processed body) was obtained.
In the swimsuit, a white floral pattern is normally visible on a pink background, but in a water-attached state (water-absorbing state), the porous layer changes from white to transparent, and the photographic-like floral pattern of the colored layer is visible. When the water was attached, it had a floral pattern, but when the water evaporated by drying, the original white color was visible again. Moreover, in the water absorption state, it was not affected at all by the pink color of the spandex fabric as a base, and a vivid floral pattern could be visually observed.
The aspect change can be repeated, and the decorativeness is excellent, so that the toy property is sufficiently satisfied.
[0025]
【The invention's effect】
The water-color-changing sheet material of the present invention is a water-color-changing processed material that is firmly bonded to an arbitrary portion of the fabric or fabric processed product by applying a relatively simple thermocompression bonding means such as a thermal iron. Can provide. Even in Shin compression resistance object to Koto, meet stretchable conformable it is possible to obtain water discoloring processed body, the scope of the water metachromatic member can be greatly expanded.
[Brief description of the drawings]
FIG. 1 is an enlarged cross-sectional explanatory view of an embodiment of a thermocompression-bonding type water discolorable sheet material of the present invention.
FIG. 2 is an enlarged cross-sectional explanatory view of a water-color-change processed body formed using the thermocompression-bonding type water-color-change sheet material of FIG.
FIG. 3 is an enlarged cross-sectional explanatory view of another embodiment of the thermocompression-bonding type water discolorable sheet material of the present invention.
4 is an enlarged cross-sectional explanatory view of a water-color-change processed body formed using the thermocompression-bonding type water-color-change sheet material of FIG.
FIG. 5 is an enlarged cross-sectional explanatory view of another embodiment of the thermocompression-bonding type water discolorable sheet material of the present invention.
6 is an enlarged cross-sectional explanatory view of a water color changeable processed body formed using the thermocompression bonding type water color change sheet material of FIG.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Thermocompression-type water discolorable sheet material 11 Heat-meltable film 12 Porous layer 13 Colored layer 14 White hiding layer 2 Water discolorable processed body 21 Object

Claims (5)

The surface of a heat-meltable film having a thickness of 0.02 to 0.4 mm selected from a polyamide-based, polyolefin-based, ethylene-vinyl acetate-based, polyurethane-based, or polyester-based resin having a melting point of 60 to 180 ° C as a substrate. On the entire surface , a low refractive index pigment was fixed in a dispersed state in a binder resin, and a non-liquid-absorbing and opaque porous layer that was transparent in the liquid-absorbing state was provided directly or via a colored layer . A thermocompression-type water discolorable sheet material in which a water discoloration layer is fixed to the surface of a fabric or fabric processed body by thermocompression bonding. The thermocompression-bonding type water discolorable sheet material according to claim 1, wherein 10 to 400 parts by weight of finely powdered titanium oxide is blended with 100 parts by weight of the heat-meltable film in the heat-meltable film. The thermocompression-bonding water-color-changing sheet material according to claim 1 or 2, wherein a white concealing layer in which finely powdered titanium oxide is fixed to a binder resin in a dispersed state is provided under the colored layer. A water-color-change processed body obtained by fixing the thermocompression-bonding type water-color-change sheet material according to any one of claims 1 to 3 to a surface of a fabric or a fabric processed body as an object. The water discoloration processed body according to claim 4, wherein the object is doll clothing.

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