JP2005125123A - Water-discoloring fabric web sheet and toy set using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-discoloring fabric web sheet, and a discoloring toy set of setting the sheet and a water sticking means, capable of forming a sharp fluoroscopic image, and preventing supersaturate water from oozing out of a sheet back part by satisfying water resistance and folding-up resistant strength. <P>SOLUTION: This water-discoloring fabric web sheet 1 is constituted by forming a porous layer 3 of fixing a particulate-like silicic acid and the other low refractive index pigment to a binder resin in a dispersion state, on a support 2 composed of a fabric web falling within a range of basis weight of 30 to 1,000 g/m<SP>2</SP>. The water-discoloring toy set is constituted by setting the fabric web sheet 1 and the water sticking means 6. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a water-discoloring fabric sheet and a toy set using the same. More specifically, the present invention relates to a water-discoloring fabric sheet that exhibits different aspects in a dry state and a state in which water is impregnated through water adhering means, and a toy set using the same.

Conventionally, a processed paper or water image in which a porous layer containing a low refractive index pigment is provided on a support, and the porous layer is made transparent by absorbing liquid to reveal an image provided in the lower layer. A sheet is disclosed (for example, see Patent Documents 1 and 2).
As a main application field of the above proposal, it has been conventionally applied to calligraphy practice, image concealment toys, etc., mainly using paper as a support, and has poor durability.
Japanese Patent Publication No. 50-5097 Japanese Patent Publication No. 5-15389

By applying a fabric with a specific basis weight as a support, the present invention has an appropriate water absorbability, can display a sharp perspective image, and can eliminate the above-mentioned conventional lack of durability. To increase the commercial value of this type of image forming element.
The seat of the present invention is not only applied to the above-mentioned conventional calligraphy practice, but also has a large area that allows an infant or the like to play on it, and allows the infant or the like to freely form various images with graffiti. It is possible to provide a new water-coloring sheet that is possible and satisfies the toy property and endurance, and a water-coloring toy set that is combined with water adhering means.

The present invention will be described with reference to the drawings (see FIGS. 1 to 5).
In the present invention, a porous layer 3 in which fine particle silicic acid and other low refractive index pigments are fixed to a binder resin in a dispersed state is provided on the surface of the support 2 to provide transparency in a liquid absorbing state and a non-liquid absorbing state. in differing water discoloring sheet, the support member 2, is required for the water-metachromatic cloth sheet 1, characterized in that the fabric is in the range of basis weight ^{30g / m 2 ~1000g / m 2} .
Further, the binder resin is urethane resin, nylon resin, vinyl acetate resin, acrylate resin, acrylate copolymer resin, acrylic 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 It is selected from the resin emulsions, a colored layer 4 is provided in the lower layer, upper layer, or the vicinity of the porous layer 3, and a water-impermeable sheet material 5 is pasted on the back surface of the fabric. The water-impermeable shim The sheet 5 is required to be a sheet having a thickness of 1 μm to 3 mm selected from a soft thermoplastic resin or a thermoplastic elastomer.
Furthermore, a water discolorable toy set including the water discolorable fabric sheet 1 and the water adhering means 6 as a set is required.
Further, the water adhering means 6 is selected from any of a plastic porous body or fiber processed body having continuous pores, or a writing or applicator form in which the plastic porous body or fiber processed body is applied as a nib member. Etc. as requirements.

Since the water discolorable fabric sheet of the present invention uses a fabric having a specific basis weight as a support, the water penetration and retention from the porous layer is more appropriate than a system using paper as a support. In addition, a sharp fluoroscopic image can be quickly formed and viewed, and the strength does not decrease even in a water absorption state. Moreover, it is rich in water resistance and folding strength and can satisfy repeated practicality.
Furthermore, in a system in which a water-impermeable sheet material is adhered to the back surface of the fabric, even if the fabric accidentally spills some amount of water on the sheet or the fabric absorbs supersaturated water, Water oozes or leaks from the back, and contamination of the floor and tatami can be avoided.
In addition, a toy set that easily displays various images can be provided by combining the water adhering means and the water discoloring fabric sheet as a set.

The fine particle silicic acid may be obtained by a dry method, but fine particle silicic acid produced by a wet method (hereinafter referred to as wet method fine particle silicic acid) is particularly effective and satisfies practicality.
This point will be described below.
Particulate silicic acid is produced as amorphous amorphous silicic acid, and is produced by a dry process using a gas phase reaction such as thermal decomposition of silicon halide such as silicon tetrachloride (hereinafter referred to as dry process particulate silicic acid). And by a wet method using a liquid phase reaction such as decomposition by an acid such as sodium silicate, in order to function as a concealable porous layer intended by the present invention, The fine particulate silicic acid is optimal. This is because the dry process fine particle silicic acid and the wet process fine particle silicic acid have different structures, whereas the dry process fine particle silicic acid forms a three-dimensional structure in which silicic acid is closely bound as shown below.

As shown below, the wet method fine particle silicic acid has a so-called two-dimensional structure part in which a long molecular arrangement is formed by condensation of silicic acid. Accordingly, since the molecular structure is coarser than that of the above-mentioned dry method fine particle silicic acid, when wet method fine particle silicic acid is applied to the porous layer, the light in the dry state compared to the system using the dry method fine particle silicic acid. Therefore, it is presumed that the concealability in the normal state is increased.

Further, since the porous layer 3 of the present invention absorbs water, 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 is hydrophilic. The degree of is large and is preferably used.
In addition, in order to adjust the concealability in the normal state of the porous layer and the transparency in the liquid absorption state, other general-purpose low refractive index pigments are used in combination with the wet method fine particle silicic acid.

The wet process fine particulate silicic acid in the porous layer 3 depends on properties such as particle diameter, specific surface area, oil absorption, etc., in order to satisfy both the concealing property in the normal state and the transparency in the liquid absorbing state. is preferably applied amount is ^{1g / m 2 ~30g / m 2} , more ^{preferably 5g / m 2 ~20g / m 2} . If it is less than 1 g / m ² , it is difficult to obtain sufficient concealability in a normal state, and if it exceeds 30 g / m ² , it is difficult to obtain sufficient transparency during liquid absorption.
The particle size of the particulate silicic acid is not particularly limited, but 0.03 to 10.0 μm is preferably used.
The particulate silicic acid is dispersed in a vehicle containing a binder resin as a binder, applied to the support 2, and then the volatile matter is dried to form the porous layer 3.
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 Each resin emulsion, casein, starch, cellulose derivative, polyvinyl alcohol, urea resin, phenol resin and the like can be mentioned.
The mixing ratio of the particulate silicic acid and these binder resins depends on the kind and properties of the particulate silicic acid, but preferably 0.5 to 2 parts by weight of the binder resin solid content with respect to 1 part by weight of the particulate silicic acid. More preferably, it is 0.8 to 1.5 parts by weight. When the solid content of the binder resin is less than 0.5 parts by weight with respect to 1 part by weight of the particulate silicic acid, it is difficult to obtain a practical film strength of the porous layer 3 and the amount exceeds 2 parts by weight. However, the water permeability into the porous layer 3 is deteriorated.
Since the porous layer 3 has a small mixing ratio of the binder resin to the colorant as compared with a conventionally known general coating film, it is difficult to obtain a sufficient film strength. Therefore, in order to increase the scratch resistance, it is effective to use a nylon resin or a urethane resin among the binder resins, or use it in combination with other resins.
Examples of the urethane resin include a polyester urethane resin, a polycarbonate urethane resin, and a polyether urethane resin, and two or more of them can be used in combination. In addition, a urethane emulsion resin in which the resin is emulsified and dispersed in water, or a colloid in which the resin is self-emulsified without requiring an emulsifier due to the ionic group of the urethane resin (urethane ionomer) itself and dissolved or dispersed in water. A dispersion type (ionomer type) urethane resin can also be used.
The urethane-based resin may be either an aqueous urethane-based resin or an oil-based urethane-based resin. In the present invention, an aqueous urethane-based resin, in particular, a urethane-based emulsion resin or a colloidally dispersed urethane-based resin is suitable. Used for. The urethane resin can be used alone, but other binder resins can be used in combination depending on the type of support and the performance required for the coating. When a binder resin other than the urethane resin is used in combination, in order to obtain a practical film strength, it is preferable to contain 30% or more of the urethane resin in a solid content weight ratio in the binder resin of the porous layer.
In the binder resin, the crosslinkable resin can be further improved in film strength by adding an arbitrary crosslinking agent and crosslinking.
The binder resin has a large or small affinity for water. By combining these, the penetration time into the porous layer 3, the degree of penetration, and the slow speed of drying after the penetration can be adjusted. Furthermore, the said adjustment can be controlled by adding a dispersing agent suitably.

In the porous layer 3, conventionally known titanium dioxide-coated mica, iron oxide-titanium dioxide-coated mica, iron oxide-coated mica, guanine, sericite, basic lead carbonate, lead acid arsenate, bismuth oxychloride. It is possible to diversify the color change by adding metallic luster pigments such as general dyes, pigments, fluorescent dyes and fluorescent pigments.
In addition, conventionally known reversible thermochromic pigments that reversibly change color according to temperature change can be mixed, and the color can be changed depending on the environmental temperature or the water temperature to be adhered.
Furthermore, the color change 4 can be disposed in the upper layer, the lower layer, and / or the vicinity of the porous layer 3 to further diversify the appearance change.
The porous layer 3 and the colored layer 4 are not limited to solid prints, and may be images of characters, symbols, designs, and the like.
The porous layer 3 and the colored layer 4 are conventionally known means, for example, printing means such as screen printing, offset printing, gravure printing, coater, tampo printing, transfer, brush coating, spray coating, electrostatic coating, electric coating, and the like. It can be appropriately formed by coating, flow coating, roller coating, dip coating, or the like.

The support 2 is required to be applied with a fabric such as a woven fabric, a knitted fabric or a non-woven fabric. More specifically, the fabric is in the range of basis weight ^30g / ^{m 2 ~1000g} / m 2 and requirements. In the system having a basis weight of less than 30 g / m ² , water absorbability is inhomogeneous and insufficient, and it is difficult to form a sharp perspective image. On the other hand, in the system exceeding 1000 g / m ² , the thickness of the fabric is unnecessarily thick, and in the case where the sheet itself is in a large area system, the folding storage property and the lightness are impaired and it is uneconomical. .
Among the above-mentioned fabrics, a woven fabric excellent in smoothness is suitably used from the viewpoint of uniform formability of the porous layer.
By applying the fabric, the paper is rich in water absorption and can easily form a sharp fluoroscopic image as compared with a system in which conventional paper is applied as a support. Even in a system that is excellent and has a large area sheet, it satisfies the repeated folding preservation.
On the back surface of the fabric sheet 1, heat such as polyolefin resin, softening plastic such as vinyl chloride resin obtained by blending a plasticizer, styrene, urethane, polyester, polyamide, polybutadiene, fluorine, etc. A water-impermeable sheet material 5 made of a plastic elastomer and having a thickness of about 1 μm to 3 mm can be pasted by conventional means to form a laminated form. In the above, in the system of less than 1 μm, the endurance is insufficient, while in the system of more than 3 mm, the foldability is difficult.
By making the fabric sheet 1 into a laminated form, it is possible to avoid contamination due to water leakage from the back of the sheet when water is accidentally zeroed or supersaturated water is absorbed. Can be fulfilled.
Thus, the seat itself has a large area that an infant or the like can ride on and play, and the toy can freely form various images in a graffiti sense and can be applied with peace of mind by avoiding water pollution problems. Water discolorable fabric sheet 1 can be formed.

The second invention requires a water color changing toy set in which the water color changing fabric sheet 1 and the water adhering means 6 are set.
Examples of the water adhering means 6 include a plastic porous body or fiber processed body having continuous pores, or a writing or applicator using the plastic porous body or fiber processed body as a nib member.
The plastic porous body or fiber processed body having continuous pores in the above may be any one that absorbs and discharges water in an appropriate amount, and has been conventionally used for continuous pores and fibers of general-purpose polyolefin-based, polyurethane-based, and other various plastics. Brush-like ones in which the fibers are focused, those obtained by resin processing or heat welding of fibers, felts, and non-woven fabrics. The shape and dimensions can be arbitrarily set according to the purpose.
Further, a writing instrument or applicator in which the various materials described above are applied as a pen tip member and attached to the tip of the water container is effective.
By setting the water adhering means 6 as a set, an arbitrary fluoroscopic image can be formed freely and easily, and the toy property can be further enhanced.

The water discolorable fabric sheet of the present invention is appropriately sized from a size as large as calligraphy paper to a size that allows an infant or the like to ride on top.
A portable water-coloring toy set is formed by combining the water-coloring fabric sheet and water adhering means.
Examples are shown below, but the present invention is not limited to the examples. In addition, the part in an Example shows a weight part.

Example 1
On the entire surface of the pink of basis weight 90 g / m ² polyester satin fabric as the support 2, wet-process fine silica powder [trade name: Nipsil E-200, Nippon Silica Industrial Co., Ltd.] 15 parts of a urethane emulsion [ Product name: Hydran HW-930, manufactured by Dainippon Ink & Chemicals, Inc., solid content 50%] 30 parts, water 50 parts, silicone-based antifoaming agent 0.5 part, water-based ink thickener 3 parts, ethylene 1 part of glycol and 3 parts of blocked isocyanate cross-linking agent are uniformly mixed and stirred using white screen printing ink, solid printed on an 80 mesh screen plate, dried and cured at 130 ° C. for 5 minutes, and porous The quality layer 3 was formed to obtain a water-discoloring fabric sheet 1 (see FIG. 1).
In the water discolorable fabric sheet 1, the pink color of the support 2 is normally concealed, and the entire surface is visually recognized as a white porous layer 3.
When a palm moistened with water is pressed onto the water discolorable fabric sheet 1, the porous layer 3 at that portion becomes transparent, and a pink palm image 7 is made visible.
The pink image is retained when the water is in an undried state. When the water is dried, the original white color is restored, and the image becomes invisible.

Example 2 (see FIG. 2)
On the entire surface of the white of the basis weight 45 g / m ² nylon taffeta fabric as a support 2, a green pigment [trade name: San Die Super Green LXB, Sanyo Color Works Co., Ltd.] 5 parts of acrylic acid ester emulsion [trade name : Movinyl 763, manufactured by Hoechst Synthesis Co., Ltd., solid content 48%] 50 parts, aqueous ink thickener 3 parts, leveling agent 0.5 part, antifoaming agent 0.3 part, epoxy-based crosslinking agent 5 parts Using a green screen printing ink obtained by uniformly mixing and stirring, solid printing was performed on a 180 mesh screen plate, followed by drying and curing at 100 ° C. for 3 minutes to form a colored layer 4.
Next, 15 parts of wet-process fine powder silica [trade name: NIPSEAL E-220, manufactured by Nippon Silica Industry Co., Ltd.], yellow pigment [trade name: Sundai Super Yellow 10GS, Sanyo Dye, are formed on the entire surface of the colored layer 4. 1 part, urethane emulsion [trade name: Hydran AP-20, manufactured by Dainippon Ink & Chemicals, Inc., solid content 30%] 45 parts, water 40 parts, silicone antifoam 0. Using a yellow screen printing ink obtained by uniformly stirring and mixing 5 parts, 3 parts of a thickener for water-based ink, 1 part of ethylene glycol, and 3 parts of a blocked isocyanate crosslinking agent, Printing was performed and dried and cured at 130 ° C. for 5 minutes to form a porous layer 3 to obtain a water-discoloring fabric sheet 1.
The water-discoloring fabric sheet 1 normally has a yellow porous layer 3 visible and a green colored layer 4 in a concealed state.
When water is attached to the brush and the character is drawn on the water discolorable fabric sheet 1, the porous layer 3 at that portion becomes transparent and green characters are visually recognized.
The characters are retained when the water is undried, and when the water dries, the characters become invisible and have the original yellow appearance.

Example 3
A fine powder fluorescent pink color on a white cotton satin fabric with a basis weight of 130 g / m ² , which is cut to a size of 1 m × 1 m as a support 2 and a urethane elastomer sheet having a thickness of 3 μm is pasted on the back. 5 parts of pigment [trade name: Epocolor FP-112, manufactured by Nippon Shokubai Co., Ltd.], 50 parts of acrylic ester emulsion [trade name: Movinyl 763, manufactured by Hoechst Synthesis Co., Ltd., solid content 48%], thickened aqueous ink Solid printing on a 180-mesh screen plate using fluorescent pink ink prepared by uniformly mixing and stirring 3 parts of an agent, 0.5 part of a leveling agent, 0.3 part of an antifoaming agent, and 5 parts of an epoxy crosslinking agent After forming the colored layer 4 by drying and curing at 100 ° C. for 3 minutes, 15 parts of wet-process fine powder silica [trade name: Nipsil E-200, manufactured by Nippon Silica Industry Co., Ltd.] is formed on the colored layer 4. , Retan emulsion [trade name: Hydran HW-930, manufactured by Dainippon Ink & Chemicals, Inc., solid content 50%] 30 parts, water 50 parts, silicone-based antifoaming agent 0.5 part, thickener 3 for water-based ink White screen printing ink obtained by uniformly mixing and stirring 1 part of ethylene glycol, 1 part of ethylene glycol and 3 parts of a block isocyanate-based cross-linking agent using a 80-mesh screen plate, and solidified by drying at 130 ° C. for 5 minutes. Thus, a white porous layer 3 was formed to obtain a water-discoloring fabric sheet 1 (see FIG. 3).
In addition, in the vicinity of the porous layer 3 of the sheet, a display with characters, a message, a design or the like by a general printing ink can be provided to impart merchantability and design.
Although the water discolorable fabric sheet 1 is normally white in its entire state, it can be changed to a pink color by applying a water adhering means 6 such as a marker equipped with a fiber processing pen body or a sponge cut into a toy shape. Can be made visible.

Example 4
The support 2 formed by sticking a 3 μm thick urethane resin sheet to the back of the white cotton satin fabric of Example 3 is applied, and the fluorescent pink ink of Example 3 is applied to a part of the surface of the fabric. As a result, the colored layer 4 was formed, and the colored layer 4 made of a pattern of general printing ink was disposed to obtain a water-discoloring fabric sheet 1 (see FIG. 4).
The seat 1 avoids polluting floors, tatami mats, etc. by water leaking out or leaking from the back of the seat even if a certain amount of water is accidentally zeroed or the fabric is oversaturated. It was.

It is an expansion longitudinal cross-section explanatory drawing of one Example of the water discolorable fabric sheet | seat of this invention. It is an expansion longitudinal cross-section explanatory drawing of the other Example of the water discolorable fabric sheet | seat of this invention. It is an expansion longitudinal cross-section explanatory drawing of the other Example of the water discolorable fabric sheet | seat of this invention. It is an expansion longitudinal cross-section explanatory drawing of the other Example of the water discolorable fabric sheet | seat of this invention. It is explanatory drawing of the use condition of the water discoloration toy set of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Water discolorable fabric sheet 2 Support body 3 Porous layer 4 Colored layer 5 Water impermeable sheet material 6 Water adhesion means 7 Perspective image

Claims (7)

Water discoloration that provides a porous layer with fine particles of silicic acid and other low-refractive-index pigments fixed in a dispersed state in a binder resin on the surface of the support, making the liquid absorption and non-liquid absorption different in transparency. in the sheet, the support is water-metachromatic fabric sheet, characterized in that the fabric is in the range of basis weight ^{30g / m 2 ~1000g / m 2} .   The binder resin is a 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 resins The water discolorable fabric sheet according to claim 1, selected from emulsions.   The water discolorable fabric sheet according to claim 1 or 2, wherein a colored layer is provided in a lower layer, an upper layer, or the vicinity of the porous layer.   The water discolorable fabric sheet according to any one of claims 1 to 3, wherein a water-impermeable sheet material is adhered to the back surface of the fabric.   The water discolorable fabric sheet according to claim 4, wherein the water-impermeable sheet is a sheet having a thickness of 1 μm to 3 mm selected from a soft thermoplastic resin or a thermoplastic elastomer.   A water-coloring toy set comprising the water-coloring fabric sheet according to any one of claims 1 to 5 and water adhering means as a set.   The said water adhesion means is chosen from either the plastic porous body or fiber processed body which has continuous pores, or the writing or applicator form which applied the said plastic porous body or fiber processed body as a nib member. Water discoloration toy set.

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