JP2002059500A - Water discoloration laminate and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new toy element for visually deciding an image of a latent image state in a normal state by exposing the image with water as a medium. SOLUTION: A water discoloration laminate 1 comprises a porous resin layer 3 provided on a support 2 to be clarified in a water absorption state, and a water repellent resin layer 4 of a co-existing state in a part of the layer 3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a water-discolorable laminate and a method for producing the same. More specifically, the present invention relates to a water-discolorable laminate that allows an image that is normally in a latent image state to be visually distinguished by using water as a medium, and an effective manufacturing method thereof.

[0002]

2. Description of the Related Art Conventionally, a porous resin layer containing a low-refractive-index pigment is laminated on a support, and a liquid such as water is absorbed by the porous resin layer to make it transparent, so that the color tone of the underlayer is expressed. Disclosed processed paper and sheets are disclosed (Japanese Patent Publication No. 50-5097).
And Japanese Patent Publication No. 5-15389).

[0003]

SUMMARY OF THE INVENTION The present invention utilizes the characteristics of the above-described porous resin layer to make a latent image in an invisible state in a normal state visible using water as a medium to visually distinguish the latent image. Water discoloration that can be applied to various fields such as toys, doll costumes, educational materials, picture books, coloring, artificial flowers, clothing, swimwear, umbrellas, raincoats, rain boots, other rain gear, etc. It is an object of the present invention to provide a functional laminate and an effective production method thereof.

[0004]

The present invention will be described with reference to the drawings (see FIGS. 1 to 10). According to the present invention, a porous resin layer 3 in which a low refractive index pigment is fixed in a binder resin in a dispersed state and which is opaque in a non-water absorbing state and transparent in a water absorbing state is laminated on a support 2. A water-repellent resin layer 4 is provided in a part of the porous resin layer 3 and coexisting therewith, and the porous resin layer 3 in a non-disposed portion of the water-repellent resin layer 4 is in a water-absorbing state. A requirement is a water-discolorable laminate 1 which is made transparent so that both layers can be visually distinguished. Further, the porous resin layer 3 and / or the water-repellent resin layer 4 may be any image selected from characters, symbols, alphanumeric characters, dots, lines, and patterns. The colored layer 5 is provided between the resin layer 3 and the colored layer 51 is provided on the water-repellent resin layer 3. The colored layer 51 is composed of characters, symbols, alphanumeric characters, dots, , A line, a pattern, selected from the images, the low-refractive-index pigment is a particulate silica, the binder resin is selected from a urethane-based resin, the low-refractive-index pigment is manufactured by a wet method. 1-30 g in the porous resin layer.
/ M ² , the support 2 is a fabric, and the fabric is subjected to a water-repellent treatment. Further, after the porous resin layer 3 is provided on the support 2, printing, coating, spraying, writing, or stamping is performed on the porous resin layer 3 using a water-repellent processing liquid containing a water-repellent resin. After the water-repellent processing liquid is adhered to the porous resin layer 3, the liquid-repellent liquid is permeated into the porous resin layer 3, and then dried to form the water-repellent resin layer 4 which is present in the porous resin layer 3 and coexists. A method for producing a water-discolorable laminate, characterized in that:

The support 2 is not limited to a sheet made of various materials such as paper, synthetic paper, metal such as rubber, plastic, and aluminum, a stone, a glass, a cloth, etc., but may be a three-dimensional or uneven material made of various water-resistant materials. Shaped bodies are also effective. A general-purpose pressure-sensitive adhesive applied to the pressure-sensitive adhesive sheet may be applied to the back surface of the support 2 so as to function as a pressure-sensitive adhesive sheet.

The low refractive index pigment includes finely divided silica, barite powder, precipitated barium sulfate, barium carbonate,
Precipitated calcium carbonate, gypsum, clay, talc, alumina white, basic magnesium carbonate, etc., which have a refractive index in the range of 1.4 to 1.7, exhibit good transparency when absorbing water and the like. It shows. The particle size of the low refractive index pigment is not particularly limited, but may be 0.03 or less.
〜10.0 μm is preferably used. Further, two or more low refractive index pigments may be used in combination.

[0007] A low refractive index pigment which is preferably used includes finely divided silica. Fine-particle silicic acid is produced as an amorphous amorphous silicic acid, and is produced by a dry method using a gas phase reaction such as thermal decomposition of silicon halide such as silicon tetrachloride (hereinafter referred to as a dry-method silicic acid). ) And those obtained by a wet method using a liquid phase reaction such as decomposition with an acid such as sodium silicate (hereinafter referred to as wet method particulate silica), and any of them can be used. In the case of using the wet method particulate silica, the concealing property in the normal state is larger than that of the dry method particulate silica,
Since the compounding ratio of the binder resin with respect to the particulate silica can be increased, and the film strength of the porous resin layer 3 itself can be improved, it is more preferably used. As described above, the fine particulate silica used to satisfy the concealing property of the porous resin layer 3 in the normal state is preferably a wet particulate silica. This is because the dry process particulate silica and the wet process particulate silica have different structures, whereas the dry process particulate silica forms a three-dimensional structure in which silicic acid is tightly coupled as shown below. ,

Embedded image The wet-processed particulate silica has a so-called two-dimensional structure in which the silica is condensed to form a long molecular arrangement as shown below. Therefore, since the molecular structure becomes coarser than that of the dry method particulate silica, when the wet method particulate silica is applied to the porous layer, the light in a dry state is lower than the system using the dry method particulate silica. It is presumed that it has excellent irregular reflection properties, and thus has a large concealing property under normal conditions.

Embedded image The low-refractive-index pigment contained in the porous resin layer 3 is mainly composed of water as a medium for absorbing liquid, so that the wet-process fine-particle silicic acid has a silanol group on the particle surface as compared with the dry-process fine-particle silicic acid. It is preferably used because it has a large number of hydroxyl groups and therefore has an appropriate hydrophilicity.

When the wet-processed particulate silica is used as a low refractive index pigment, the type, particle size,
Specific surface area, will depend on the nature of the oil absorption, etc., in order to satisfy both the transparency in the hiding properties and liquid absorption state at normal, it applied amount is 1g / m ² ~30g / m ² by weight, more preferably from ^{5g / m 2 ~20g / m 2} . If it is less than 1 g / m ² , it is difficult to obtain sufficient concealing properties under normal conditions, and if it exceeds 30 g / m ² , it is difficult to obtain sufficient transparency when absorbing liquid. The low-refractive-index pigment is dispersed in a vehicle containing a binder resin as a binder to form a dispersion ink, and the porous resin layer 3 is formed on the surface of the target support 2 by printing, coating, spraying, or the like.
To form

The binder resin includes urethane resin, nylon resin, vinyl acetate resin, acrylate resin, acrylate copolymer resin, acryl polyol resin, vinyl chloride-vinyl acetate copolymer resin, maleic acid 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 emulsions, casein, starch, cellulose derivatives, polyvinyl alcohol, urea resins, phenol resins, epoxy resins and the like. Among them, it is effective to use a urethane-based resin or to include at least a urethane-based resin. By containing a urethane-based resin in the binder resin, the film strength of the porous resin layer 3 can be improved, and it can be applied to various uses requiring durability. The transparency in the liquid absorbing state is not impaired.

As the urethane resin, a polyester urethane resin, a polycarbonate urethane resin,
There are polyether urethane resins and the like, and two or more kinds can be used in combination. Further, a urethane emulsion resin in which the resin is emulsified and dispersed in water, or a colloid dissolved or dispersed in water by self-emulsifying by an ionic group of a urethane resin (urethane ionomer) itself without requiring an emulsifier. Dispersion type (ionomer type)
Urethane resins can also be used. Incidentally, the urethane-based resin may be any of an aqueous urethane-based resin or an oil-based urethane-based resin, but in the present invention, an aqueous urethane-based resin, among them, a urethane-based emulsion resin and a colloid-dispersed urethane-based resin are preferable. Used for The urethane-based resin is preferably used alone, but other binder resins may be used in combination depending on the material and form of the support 2 or the required film strength. When a binder resin other than the urethane resin is used in combination, in order to obtain a practical film strength, the binder resin of the porous resin layer 3 should contain the urethane resin in a solid content ratio of 30% by weight or more. preferable. In the porous resin layer 3 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 The color change can be diversified by adding a metallic luster pigment such as lead arsenate or bismuth oxychloride, or by adding a general dye or pigment, a fluorescent dye or pigment. Furthermore, a reversible thermochromic material that changes color reversibly with a change in temperature can be blended.

The water-repellent resin layer 4 is coated on the porous resin layer 3 with a water-repellent liquid containing a water-repellent resin selected from water-repellent resins such as silicon, paraffin, polyethylene, alkylethylene urea, and fluorine. This is a layer that is present in the porous resin layer 3 and coexists, which is obtained by adhering to form an image having an appropriate shape and drying by permeation and drying. Among the water-repellent resins, a fluorine-based water-repellent is effective in terms of water repellency and workability, and as a solid content, 1 g / m ^{2 to} 50 g / m ² , preferably 2 g / m ^2. An adhesion amount in the range of ３０30 g / m ² is effective.

The coloring layer 5 is a layer formed directly on the surface of the support 2, and when the porous resin layer 3 is in a water absorbing state,
It is intended to enhance the visual effect by seeing through, is not limited to solid printing, may be an appropriate image, not limited to those formed by a coloring material including a coloring agent such as a general-purpose dye or pigment, It may be a reversible thermochromic material formed of a coloring material containing a reversible thermochromic material. The support 2 itself may be in a colored state in which the general-purpose colorant or the reversible thermochromic material is blended.

Colored layer 5 disposed on water-repellent resin layer 4
1 functions to make more diverse images visible.

The reversible thermochromic material imparting reversible thermochromic properties includes, for example, an electron-donating color-forming organic compound, an electron-accepting compound, and an organic compound medium which reversibly causes a color reaction between the two. , A liquid crystal, Ag ₂ HgI ₄ , Cu ₂ HgI _4, etc. are used. As a reversible thermochromic composition containing three components of an organic compound medium that reversibly causes a color reaction between the electron-donating color-forming organic compound and the electron-accepting compound, specifically,
JP-B-51-35414, JP-B-51-4470
No. 6, JP-B-51-44708, JP-B-52
JP-A-77764, JP-B-1-29398, and JP-A-7-186546. The color changes before and after a predetermined temperature (discoloration point) as a boundary, and only one specific state can exist in a normal temperature range between the two states before and after the change. That is, the other state is maintained while the heat or cold required for the state to develop is applied, but returns to the state exhibited in the normal temperature range if the application of the heat or cold disappears, so-called, This type changes color by showing a small hysteresis width (ΔH) for temperature-color density due to temperature change.

Also, Japanese Patent Publication No. 4-171 proposed by the present applicant.
No. 54, JP-A-7-179777, JP-A-7-179777
The thermosensitive color-changing color memory composition which exhibits large hysteresis characteristics and discolors described in, for example, JP-A-339997, that is, the shape of a curve plotting a change in coloring density due to a temperature change indicates a temperature in a discoloration temperature range. A type of discoloring material that changes color following a significantly different path when the temperature is increased from a lower temperature side and conversely, when the temperature is decreased from a higher temperature side than the discoloration temperature range. A reversible thermochromic composition having a characteristic of being able to memorize and retain a state changed at a temperature below the low-temperature side discoloration point or above the high-temperature side discoloration point in a normal temperature range between the color change points is also effective. or,
A specific alkoxyphenol having a straight-chain or side-chain alkyl group having 3 to 18 carbon atoms as an electron-accepting compound according to the proposal of the present applicant, which develops a color by heating from a decolored state as a heat-colorable composition. Systems to which compounds are applied (JP-A-11-129623, JP-A-11-59)
No. 73) or a system to which a specific hydroxybenzoic acid ester is applied (Japanese Patent Application No. 11-286202).

The reversible thermochromic composition containing the above three components of an organic compound medium which reversibly causes a color reaction between the electron-donating color-forming organic compound and the electron-accepting compound is effective even as it is. However, it is preferably used as a microcapsule pigment encapsulated in microcapsules. That is, under various use conditions, the reversible thermochromic composition is maintained at the same composition and can exert the same function and effect. By being encapsulated in the microcapsules, a chemically and physically stable pigment can be constituted,
Particle size 0.1-50 μm, preferably 0.1-30 μm
m, more preferably in the range of 1 to 20 μm satisfies practicality. The microencapsulation is carried out by a conventionally known interfacial polymerization method, in situ polymerization method, in-liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melting dispersion cooling method, air suspension. There are a coating method, a spray drying method, and the like, which are appropriately selected according to the application. Further, a secondary resin film may be further provided on the surface of the microcapsule according to the purpose to impart durability, or the surface characteristics may be modified for practical use.

Next, the action of the above components of the water discolorable laminate 1 of the present invention will be described. Porous resin layer 3
Is opaque in a non-water-absorbing state, becomes transparent in a water-absorbing state, and can see through the lower layer. Therefore, the colored layer 5
In the system in which the coloring layer 5 is provided, the color and image thereof can be viewed, and in the system in which the coloring layer 5 is not provided, the color of the support itself can be viewed.
Here, since the water-repellent resin layer 4 is included in a part of the porous resin layer 3 and is arranged in a coexisting state, the porous resin layer 3 at the coexisting portion of the water-repellent resin layer 4 is The water absorbing state is not formed due to the water repellent effect, and the opaque state is maintained. (Since the water-repellent resin layer 4 is transparent, the opaque state of the porous resin layer 3 can be seen through.) Therefore, in the normal state (non-water-absorbing state), it is difficult to distinguish the porous resin layer 3 from the water-repellent resin layer 4. The porous resin layer 3 can be distinguished from the porous resin layer 3 by absorbing water in the portion where the water-repellent resin layer 4 is not provided. Said aspect changes are tautomeric. Water absorption into the porous resin layer 3 is performed by immersing in water, spraying with water, wetting a desired portion with a brush, a brush, a pen, a stamp, or the like.
Can be achieved. Incidentally, in a system to which a reversible thermochromic material is applied,
A change in environment temperature, a change in color due to heating or cooling is visually recognized, and the manner of the change is diversified.

The second invention of the present invention relates to an effective method for manufacturing the water-discolorable laminate 1 described above. The method comprises the steps of: providing a porous resin layer 3 on a support 2; After printing, coating, spraying, writing, or stamping with a water-repellent solution containing a water-repellent resin, the water-repellent solution is applied and allowed to penetrate into the porous resin layer 3.
By drying, the water-repellent resin layer 4 which is present in the porous resin layer 3 and coexists is formed. In the above, examples of the printing means include screen printing, gravure printing, offset printing, and the like. Among them, screen printing means, by adjusting the aperture ratio of the screen, hole diameter, wire diameter, etc., according to the purpose, characters, symbols, alphanumeric characters, dots, lines, arbitrary patterns such as patterns and halftone dots An image can be formed relatively easily, and it is also effective in adjusting the thickness of the water-repellent resin layer 4 (the amount of the water-repellent processing liquid applied).

[0019]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The support of the present invention is not limited to a sheet, but a three-dimensional one, a three-dimensional one and the like are all effective, and are not limited to the specific sheet material shown in the following examples. .

[0020]

Examples are shown below. The parts in the examples are parts by weight.

Example 1 (See FIGS. 1 and 6) Fluorescent pink pigment 1 was coated on the surface of a support 2 composed of a white broad cloth made of a blend of polyester and cotton (65%: 35%).
5 parts, acrylic ester emulsion 50 parts, aqueous ink thickener 3 parts, leveling agent 0.5 part, defoamer 0.3
Part, and 5 parts of a blocked isocyanate-based cross-linking agent are uniformly mixed and stirred, and the solid color is printed with a 120-mesh screen plate using a fluorescent pink screen printing ink, and dried and cured at 130 ° C. for 5 minutes to obtain a colored layer. 5 was obtained. Next, 15 parts of wet-processed particulate silica (trade name: Nip Seal E-220, manufactured by Nippon Silica Industry Co., Ltd.) and urethane emulsion [trade name: Hydran AP-10, Dainippon Ink & Chemicals, Ltd.] Manufactured by
Solid content 30% by weight] 45 parts, water 40 parts, silicone-based antifoaming agent 0.5 parts, thickener for water-based ink 3 parts, ethylene glycol 1 part, and blocked isocyanate-based crosslinking agent 3 parts are uniformly mixed and stirred. The entire surface was solid-printed on a 100-mesh screen plate using the white screen printing ink thus obtained, and dried and cured at 130 ° C. for 5 minutes to form a porous resin layer 3. Next, 50 parts of a fluororesin water repellent (trade name: NK Guard NDN-7, manufactured by Nikka Chemical Co., Ltd., solid content: 22% by weight) and 1.5 parts of sodium alginate from the porous resin layer 3 , 48.5 parts of water, 0.5 parts of a silicone-based antifoaming agent, and 5 parts of a blocked isocyanate-based cross-linking agent are uniformly mixed and stirred. The pattern was printed, dried and cured at 170 ° C. for 2 minutes to form a water-repellent resin layer 4 having a star pattern in the porous resin layer 3 to obtain a water-discolorable cloth (water-discolorable laminate 1). (See FIG. 1). The water discolorable cloth 1 is a porous resin layer 3 in a normal state (non-water absorbing state).
Is white and the water-repellent resin layer 4 itself is colorless and transparent, so that the star pattern image in which the two coexist is also white and in a latent image state (see FIG. 6A). When water is sprayed on the surface of the water-discolorable cloth 1 by a spray, the water-repellent resin layer 4 repels water and does not absorb liquid, and the porous resin layer excluding the portion of the water-repellent resin layer 4 (star pattern) 3 is due to the absorption of water
It became transparent, and a bright fluorescent pink color was visually recognized by the lower colored layer 5, and a white star pattern 4 and a fluorescent pink background 5 (background) appeared [FIG. 6 (2)]. When water adhered, the appearance was as described above, but when the water evaporated from the cloth, the entire surface became white again, and the star pattern 4 returned to the latent image state (FIG. 5 (1)).

Example 2 (See FIGS. 2 and 7) As a support 2, a blend of polyester and cotton (65%: 3)
(5%) white broad cloth, using the same fluorescent pink screen printing ink as in Example 1, using a 120 mesh screen printing plate, and printing at 130 ° C. for 5 hours.
After drying and curing for 5 minutes, a colored layer 5 was obtained. Then, the entire surface of the colored layer 5 was solid-printed with a 100-mesh screen plate using the same white screen printing ink as in Example 1, and dried and cured at 130 ° C. for 5 minutes to form a porous resin layer 3. Was formed. Next, on the porous resin layer 3,
Fluorine-based resin water repellent [trade name: NK Guard NDN-7,
50 parts, sodium alginate 1.5 parts, water 48.5 parts, silicone-based defoamer 0.5 part, blocked isocyanate-based cross-linking agent 5 parts uniformly. Using a colorless and transparent screen printing ink formed by mixing and stirring, a star pattern was printed on a 100-mesh screen plate, and dried and cured at 170 ° C. for 2 minutes.
The water-repellent resin layer 4 (star-cut pattern) was formed in the porous resin layer 4 in an internal state to obtain a water-discolorable fabric (water-discolorable laminate 1) (see FIG. 2). In the water-discolorable fabric 1, the porous resin layer 3 is white in a normal state (non-water-absorbing state), and the water-repellent resin layer 4 itself is colorless and transparent. It is in a state [FIG. 7 (1)]. When water is sprayed on the surface of the water-discolorable fabric 1, the water-repellent resin layer 4 repels water and does not absorb liquid, and the porous resin layer 3 excluding the water-repellent resin layer 4 absorbs water. The liquid makes it transparent, and a bright fluorescent pink color due to the lower colored layer 5 becomes visible, and a fluorescent pink star pattern (colored layer 5) and a white back (water-repellent resin layer 4) appear. [FIG. 7 (2)].
When water adhered, the appearance was as described above, but when the water evaporated from the cloth, the entire surface became white again, and the star pattern returned to the latent image state (FIG. 7 (1)).

Example 3 (not shown) As a support, 15 parts of a fluorescent pink pigment, 50 parts of an acrylic ester emulsion, 3 parts of a water-based ink thickener, 3 parts of a water-repellent white polyester tropical cloth were used as a support. Solid printing using a 120-mesh screen stencil using a fluorescent pink screen printing ink prepared by uniformly mixing and stirring 0.5 part of an agent, 0.3 part of an antifoaming agent, and 5 parts of an epoxy crosslinking agent. The mixture was dried and cured at 100 ° C. for 5 minutes to obtain a fluorescent pink colored layer. Next, on the colored layer, 15 parts of wet-processed particulate silica (trade name: Nip Seal E-1009, manufactured by Nippon Silica Industry Co., Ltd.), blue pigment [trade name: Sundai Super Blue GLL, manufactured by Sanyo Dye Co., Ltd.] 5 parts, urethane emulsion [trade name: Hydran AP-20, manufactured by Dainippon Ink and Chemicals, Incorporated.
Solid content 35% by weight] 45 parts, water 40 parts, silicone defoamer 0.5 part, thickener for water-based ink 3 parts, ethylene glycol 1 part, blocked isocyanate cross-linking agent 3 parts are uniformly mixed and stirred. The colored layer was solid-printed on a 100-mesh screen plate using the resulting blue screen printing ink and dried and cured at 130 ° C. for 5 minutes to form a pale blue porous resin layer in a normal state. Next, on the porous resin layer, 50 parts of a fluororesin water repellent [trade name: Asahigard LS-6015, manufactured by Meisei Chemical Co., Ltd., solid content 15% by weight], a thickener for water-based ink 3 Parts, 47 parts of water, 0.5 parts of a silicone-based antifoaming agent, and 5 parts of a blocked isocyanate-based crosslinking agent, using a colorless transparent screen printing ink obtained by uniformly mixing and stirring, using a 120-mesh screen plate. A floral pattern with halftone dots was printed on the porous resin layer, dried and cured at 170 ° C. for 2 minutes, and a water-repellent resin layer was formed inside the porous resin layer to obtain a water-discolorable fabric. . In the water-discolorable fabric, the porous resin layer is pale blue in a normal state (non-water-absorbing state) and the water-repellent resin layer is colorless and transparent, so that the entire surface has a pale blue appearance, but is immersed in water. Then, the porous resin layer except for the coexisting portion of the water-repellent resin layer absorbs water and becomes transparent, and a purple color, which is a mixed color of the fluorescent pink color of the lower colored layer and the blue color of the porous resin layer, is seen, and purple. In the back (background), a floral pattern represented by a light blue halftone dot was visually recognized. When the porous resin layer was in a water-absorbing state, the appearance was as described above. However, when the water was dried, the entire surface returned to the original pale blue color, and the appearance change could be repeatedly reproduced.

Example 4 (not shown) A red PET film (100 μm thick) was used as a support.
m), 15 parts of wet-process particulate silica (trade name: Nip Seal E-1011, manufactured by Nippon Silica Industry Co., Ltd.)
Urethane emulsion [brand name: Neorez R-9]
66, manufactured by Abisia K.K., solid content 33% by weight] 45 parts,
Using a white screen printing ink obtained by uniformly mixing and stirring 40 parts of water, 0.5 part of a silicone-based defoamer, 3 parts of a thickener for water-based ink, 1 part of ethylene glycol, and 3 parts of a blocked isocyanate-based cross-linking agent. Then, the entire surface was solid-printed on an 80-mesh screen plate, and dried and cured at 130 ° C. for 5 minutes to obtain a porous resin layer. Next, a silicone resin water repellent [trade name: SM870] is formed on the porous resin layer.
7, manufactured by Dow Corning Toray Silicone Co., Ltd., solid content 40% by weight], 50 parts, polyethylene oxide 3 parts,
Using a colorless transparent screen printing ink obtained by uniformly mixing and stirring 47 parts of water and 5 parts of a metal-based catalyst, a polka dot pattern is printed on a 100-mesh screen plate, and dried and cured at 150 ° C. for 5 minutes. A water-discolorable film (water-discolorable laminate) was obtained by internally forming a water-repellent resin layer having a polka dot pattern in the porous resin layer. Although the entire surface of the water discolorable film is normally white in the normal state, when the water discolorable film is immersed in water, the porous resin layer except for the coexisting portion of the water repellent resin layer absorbs water and becomes transparent. Thus, the red color of the support itself is seen, and a white polka dot pattern is seen on a red background (background). When the porous resin layer was in a water-absorbing state, the appearance was as described above. However, when the water was dried, the entire surface returned to the original white color, and the appearance change was repeatedly reproduced.

Example 5 (see FIGS. 3 and 8) 5 parts of a green pigment and an acrylate emulsion 45 were placed on a support 2 made of white polyester tricot cloth.
Parts, a silicone-based antifoaming agent 0.5 parts, a water-based ink thickener 3 parts, water 10 parts, and a blocked isocyanate-based cross-linking agent 5 parts, using a green screen printing ink obtained by uniformly mixing and stirring 150 parts. Solid printing was performed on a mesh screen plate, and dried and cured at 130 ° C. for 5 minutes to obtain a green colored layer 5. Next, 15 parts of wet-processed particulate silica (trade name: Nip Seal E-200, manufactured by Nippon Silica Industry Co., Ltd.) and urethane emulsion [trade name: Hydran AP-20, Dainippon Ink and Chemicals, Ltd.] Manufactured by
Solid content 33% by weight] 45 parts, water 40 parts, silicone defoamer 0.5 part, aqueous ink thickener 3 parts, ethylene glycol 1 part, blocked isocyanate cross-linking agent 3 parts uniformly mixed and stirred. Using a white screen printing ink, a heart pattern was printed on an 80-mesh screen plate, and dried and cured at 130 ° C. for 5 minutes to obtain a porous resin layer 3. Next, on the porous resin layer 3, 60 parts of a fluorine-based resin water repellent (trade name: Lifeguard FR-448, manufactured by Kyoeisha Chemical Co., Ltd., solid content 30% by weight), 45 parts of water, polyvinyl alcohol 5 parts, silicone defoamer 0.5
The letter "A" is printed on a 100-mesh screen plate using a colorless and transparent screen printing ink prepared by uniformly mixing and stirring the parts, and dried and cured at 170 ° C. for 2 minutes to form a porous resin. Water repellent resin layer 4 in layer 3
Was formed to obtain a water-discolorable fabric 1 (see FIG. 3). Using the water discolorable cloth 1, a swimsuit for a doll was sewn to obtain a swimsuit for a water discolorable toy doll. In the swimsuit for a water discolorable toy doll, a white heart pattern of the porous resin layer 3 is normally seen with the green colored layer as a back [FIG.
(1)]. When water is adhered to the swimsuit, the portion excluding the water-repellent resin layer 4 (the letter “A”) inside the white heart pattern becomes transparent and green is visualized, and the letter “A” is white. It was visually recognized (FIG. 8 (2)). The appearance was such that the porous resin layer 3 was kept in a water-absorbing state, but when the water was dried, a white heart pattern was seen again, and the appearance change was reciprocal and repeated.

Example 6 (see FIGS. 4 and 9) 10 parts of a fluorescent orange pigment and an acrylic ester emulsion 4 were placed on a white polyester tricot cloth (support 2).
5 parts, silicone-based antifoaming agent 0.5 parts, water-based ink thickener 3 parts, water 10 parts, blocked isocyanate-based crosslinking agent 5
Using a fluorescent orange screen printing ink formed by uniformly mixing and stirring the parts, solid printing was performed on a 150-mesh screen plate, followed by drying and curing at 130 ° C. for 5 minutes to obtain a fluorescent orange colored layer 5. Next, on the colored layer 5, 15 parts of wet-processed particulate silica (trade name: Nip Seal E-200, manufactured by Nippon Silica Industry Co., Ltd.) and urethane emulsion [trade name: Hydran AP-10, Dainippon Ink and Chemicals, Ltd.] 45 parts, water 40 parts, silicone defoamer 0.5 part, water-based ink thickener 3 parts,
Using a white screen printing ink prepared by uniformly mixing and stirring 1 part of ethylene glycol and 3 parts of a blocked isocyanate-based crosslinking agent, a heart pattern is printed on an 80-mesh screen plate, and dried and cured at 130 ° C. for 5 minutes. Thus, a porous resin layer 3 was obtained. Next, on the porous resin layer 3,
Fluorinated resin water repellent [trade name: Asahigard AG-48]
0, manufactured by Meisei Chemical Industry Co., Ltd., solid content 20% by weight] 45
Parts, 45 parts of water, 5 parts of a thickening agent for water-based ink, and 0.5 part of a silicone-based antifoaming agent, using a colorless transparent screen printing ink prepared by uniformly mixing and stirring the mixture, using a 100 mesh screen plate. A heart pattern slightly larger than the porous resin layer 3 (heart pattern) is printed with a printed pattern of the letter "A" at the center, and dried and cured at 170 ° C for 2 minutes to form the water-repellent resin layer 4, Water discolorable fabric 1 was obtained (see FIG. 4). The water discolorable cloth 1 was sewn on a swimsuit for a doll to obtain a swimsuit for a water discolorable toy doll. In the swimsuit for a water discolorable toy doll, a white heart pattern is visually recognized with a fluorescent orange background as a normal state [FIG. 9 (1)]. When water is attached to the swimsuit, only the letter “A” becomes transparent and a fluorescent orange color is seen,
A white heart pattern was seen [FIG. 9 (2)]. In the above aspect, the porous resin layer 3 was kept in a water-absorbing state, but returned to the original white heart pattern aspect when the water was dried. The appearance change was tautomeric and was repeated.

Example 7 (not shown) As a support, a blend of polyester and cotton (65%: 35)
%) Broad cloth (white), colorless at 30 ° C or higher, 2
At 8 ° C. or less, 30 parts of a reversible thermochromic microcapsule pigment exhibiting a blue color, 5 parts of a fluorescent pink pigment, 50 parts of an acrylic resin emulsion, 1 part of an antifoaming agent, and a thickener 4 for an aqueous ink 4
Parts, 15 parts of water, and 5 parts of a blocked isocyanate-based cross-linking agent are uniformly mixed and stirred, and solid printing is performed on a 120-mesh screen plate using a reversible thermochromic screen printing ink, followed by drying and curing at 130 ° C. for 5 minutes. Let it be 30 ° C
Thus, a reversible thermochromic coloring layer exhibiting a blue-violet color and a fluorescent pink color at 28 ° C. or less was obtained. Next, on the reversible thermochromic coloring layer, wet-process fine-particle silica (trade name: Nip Seal E)
-220, manufactured by Nippon Silica Industry Co., Ltd.] 15 parts, urethane emulsion [trade name: Hydran AP-10, manufactured by Dainippon Ink and Chemicals, Inc., solid content 30% by weight] 45 parts,
40 parts of water, 0.5 parts of silicone defoamer, 3 parts of thickener for water-based ink, 1 part of ethylene glycol, and 3 parts of blocked isocyanate-based cross-linking agent are uniformly mixed and stirred to obtain a white screen printing ink. The whole was solid-printed on a 100-mesh screen plate and dried and cured at 130 ° C. for 5 minutes to form a porous resin layer. Then, on the porous resin layer, 50 parts of a fluorine-based resin water repellent [trade name: NK guard NDN-7, manufactured by Nika Chemical Co., Ltd., solid content 22% by weight], 1.5 parts of sodium alginate, Water 48.
Using a colorless transparent screen printing ink prepared by uniformly mixing and stirring 5 parts, a silicone-based antifoaming agent 0.5 parts, and a blocked isocyanate-based crosslinking agent 5 parts, a star pattern is printed on a 100-mesh screen plate. After drying and curing at 170 ° C. for 2 minutes, a water repellent cloth was obtained by internally forming a star-patterned water-repellent resin layer in the porous resin layer. The water discolorable fabric,
In the normal state (non-water absorbing state), the entire surface is white,
When water at 24 ° C. is adhered to the surface of the cloth by spraying, the water-repellent resin layer repels water and assumes a white state without absorbing liquid, whereas the porous resin layer absorbs water. Depending on the liquid
The blue-violet color of the lower reversible thermochromic coloring layer is made transparent and the white star pattern is visible with the blue-violet background,
Thereafter, the entire surface was returned to a white appearance by drying with water.
Further, when the water discolorable fabric is immersed in warm water of 40 ° C.,
In addition to the appearance change, the reversible thermochromic coloring layer changes from blue to fluorescent pink, a white star pattern is visible on the fluorescent pink background, removed from warm water and left at room temperature of about 20 ° C. The fluorescent pink background turned blue, and as the water dries, the entire surface turned white again, and the appearance change was repeated and reproduced alternately.

Example 8 (not shown) As a support, 30 parts of a reversible thermochromic microcapsule pigment exhibiting a colorless color at 30 ° C. or more and a pink color at 28 ° C. or less on a white polyester tricot fabric, and an acrylic resin emulsion 50 Part, 1 part of defoamer, thickener for water-based ink 5
Parts, 10 parts of water, and 5 parts of an ethyleneimine cross-linking agent are uniformly mixed and stirred. Using a reversible thermochromic screen printing ink, solid printing is performed on a 100-mesh screen plate and dried at 100 ° C. for 5 minutes. After curing, a reversible thermochromic coloring layer was obtained. Next, on the reversible thermochromic coloring layer, 15 parts of wet-processed particulate silica (trade name: Nip Seal E-200, manufactured by Nippon Silica Industry Co., Ltd.), urethane emulsion [Hydran AP-20, Dainippon Ink and Chemicals, Ltd.] (stock)
45%, water 40 parts, silicone defoamer 0.5 part, water-based ink thickener 3 parts, ethylene glycol 1 part, blocked isocyanate cross-linking agent 3 parts Using a white screen printing ink obtained by stirring, a heart pattern was printed on an 80 mesh screen plate, and dried and cured at 130 ° C. for 5 minutes to obtain a porous resin layer. Then, on the porous resin layer, 60 parts of a fluorine-based resin water repellent [trade name: Lifeguard FR-448, manufactured by Kyoeisha Chemical Co., Ltd., solid content 30% by weight], 45 parts of water, polyvinyl alcohol 5 Part, silicone antifoam 0.5
Using a colorless transparent screen printing ink formed by uniformly mixing and stirring the parts, the letter "A" was printed on a 100-mesh screen plate, and dried and cured at 170 ° C for 2 minutes.
A water-repellent fabric was obtained by internally forming a water-repellent resin layer in the porous resin layer. The water discolorable cloth was cut and sewn to obtain a water discolorable toy doll swimsuit. The swimsuit is usually
The pink color of the reversible thermochromic coloring layer and the white heart pattern of the porous resin layer are visible, but when water at 24 ° C. is adhered, the heart pattern of the porous resin layer becomes transparent and the reversible thermochromic The color of the colored layer changes to pink, and only the letter “A” of the water-repellent layer is seen in white on the pink background. When the water absorbed by the porous resin layer was evaporated, the water was restored to a pink background with a white heart pattern. When the water discolorable toy doll swimsuit is immersed in warm water of 40 ° C., the porous resin layer becomes transparent by liquid absorption, and the reversible thermochromic coloring layer simultaneously changes from pink to colorless, and the entire surface is white. State
When removed from warm water and left at room temperature of about 20 ° C., the entire white state changes to a state in which only the letter “A” is seen in white on a pink background. It became a white heart pattern on the color background. The appearance change was reproduced alternately and repeatedly.

Example 9 (See FIGS. 5 and 10) On a support 2 made of white polyester satin cloth,
Using a green screen printing ink, solid printing was performed on a 120-mesh screen plate, followed by drying and curing at 130 ° C. for 5 minutes to obtain a colored layer 5. Next, the colored layer 5
Using the white screen printing ink of Example 1, the entire surface was solid-printed on a 100-mesh screen plate and dried and cured at 130 ° C. for 5 minutes to form a porous resin layer 3. Then, on the porous resin layer 3, the first embodiment
Using a water-repellent ink for colorless and transparent screen printing,
A star pattern is printed on a 100-mesh screen plate, dried and cured at 170 ° C. for 2 minutes, and the porous resin layer 3
After forming a star pattern (water-repellent resin layer 4) therein, using the fluorescent pink screen printing ink of Example 1,
A heart discoloration pattern having a space in which the star relief pattern is embedded (the periphery thereof forms a pink colored layer 51) is printed so as to be aligned with the star relief pattern, and the water discolorable cloth is formed. (Water-discolorable laminate 1) was obtained (see FIG. 5).
In the water-discolorable fabric, in a normal state (non-water-absorbing state), a white heart pattern (by the porous resin layer 3) is visible with a pink background (colored layer 51), but water is attached by water spray. Then, a green star pattern (colored layer 5) appears from the white heart pattern, and when water adheres, it has this appearance, but when dried, the green star pattern disappears and turns to a white heart pattern It changed and returned to its original state (see FIG. 10).
The appearance change could be repeated.

[0030]

The water-discolorable laminate of the present invention can make a latent image, which is normally invisible, appear as a color-developed image using water as a medium. Particularly, the water-repellent resin layer (image) Intermediate and overprinting effects allow the user to visualize a variety of images alternately and add new toy, unexpectedness, decorativeness, detectability, etc. toys, doll costumes, educational materials It can be applied to various fields such as picture books, coloring books, artificial flowers, swimwear, umbrellas, rain gear, etc. Furthermore, by applying the production method of the present invention, an arbitrary image made of a water-repellent resin can be easily formed in a porous resin layer in a coexisting state by a printing means.

[Brief description of the drawings]

FIG. 1 is an explanatory longitudinal sectional view of one embodiment of a water discolorable laminate of the present invention.

FIG. 2 is an explanatory longitudinal sectional view of another embodiment of the water-discolorable laminate of the present invention.

FIG. 3 is an explanatory longitudinal sectional view of another embodiment of the water-discolorable laminate of the present invention.

FIG. 4 is an explanatory longitudinal sectional view of another embodiment of the water-discolorable laminate of the present invention.

FIG. 5 is an explanatory longitudinal sectional view of another embodiment of the water-discolorable laminate of the present invention.

FIG. 6 shows an example of a water-discolorable laminate of the present invention,
It is each explanatory drawing of the visual state in a (1) non-water-absorbing state and (2) water-absorbing state, when a porous resin layer is.

FIG. 7 is an explanatory diagram of (1) a non-water-absorbing state and (2) a visual state in a water-absorbing state of a porous resin layer in another embodiment of the water-discolorable laminate of the present invention.

FIG. 8 is an explanatory view of (1) a non-water-absorbing state and (2) a visual state in a water-absorbing state of a porous resin layer in another embodiment of the water-discolorable laminate of the present invention.

FIG. 9 is an explanatory diagram of (1) a non-water-absorbing state and (2) a visual state in a water-absorbing state of a porous resin layer in another example of the water-discolorable laminate of the present invention.

FIG. 10 is an explanatory diagram of (1) a non-water-absorbing state and (2) a visual state in a water-absorbing state of a porous resin layer in another embodiment of the water-discolorable laminate of the present invention.

[Explanation of symbols]

 Reference Signs List 1 water discolorable laminate 2 support 3 porous resin layer 4 water repellent resin layer 5 colored layer 51 colored layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 3/34 C08K 3/34 C08L 75/04 C08L 75/04 101/14 101/14 F-term (reference) 2C150 BC03 CA18 CA26 DC17 DG22 DG23 FB04 FB18 FB22 FB43 FB46 FB55 4F100 AA03B AJ04 AK01B AK25 AK41 AK51 AT00A BA02 BA03 BA10A BA10B BA44 CA13B DE01B DG11A DJ00B EH112 EH462 EH612 EJ822 EJ863 GB90 HB00B HB00C HB31 JB06A JB06B JD15B JL10 JL10C JM01 JN01B JN02B JN13H JN18B YY00B 4J002 CK021 DE146 DE236 DE266 DJ006 DJ036 DJ046 GC00

Claims (10)

[Claims] 1. A porous resin layer in which a low-refractive-index pigment is fixed in a binder resin in a dispersed state, which is opaque in a non-water-absorbing state and transparent in a water-absorbing state, is laminated on a support, The water-repellent resin layer is disposed in a part of the porous resin layer, and coexists with the water-repellent resin layer. A water-discolorable laminate configured so that both layers can be visually distinguished. 2. The water-discolorable laminate according to claim 1, wherein the porous resin layer and / or the water-repellent resin layer is an image selected from characters, symbols, alphanumeric characters, dots, lines, and patterns. body. 3. Between the surface of the support and the porous resin layer,
The water-discolorable laminate according to claim 1, further comprising a coloring layer. 4. The water-discolorable laminate according to claim 1, wherein a colored layer is provided on the water-repellent resin layer. 5. The coloring layer includes letters, symbols, alphanumeric characters,
The water discolorable laminate according to claim 4, which is any one of images selected from a point, a line, and a design. 6. The low-refractive-index pigment is particulate silica, and the binder resin is selected from urethane-based resins.
The water discolorable laminate according to the above. 7. The low-refractive-index pigment is finely divided silicic acid produced by a wet method, and is contained in the porous resin layer in an amount of 1 to 30 g / m ^2.
The water-discolorable laminate according to claim 1, wherein the laminate is blended at a ratio of: 8. The water-discolorable laminate according to claim 1, wherein the support is a cloth. 9. The water discolorable laminate according to claim 8, wherein the fabric is subjected to a water repellent treatment. 10. After providing a porous resin layer on a support,
On the porous resin layer, the water repellent processing liquid is adhered by printing, coating, spraying, writing, or stamping with a water repellent processing liquid containing a water repellent resin, and penetrates into the porous resin layer. A method for producing a water-discolorable laminate, comprising forming a water-repellent resin layer existing in a coexisting state in a porous resin layer by drying after drying.