JP4786564B2 - Water discoloration drawing toy and water discoloration drawing toy set using the same - Google Patents

Description

  The present invention relates to a water-coloring drawing toy configured to make a multicolor image appear by applying a writing tool or applicator to which water is applied, and a water-coloring drawing toy set using the same.

Conventionally, there has been disclosed a pen brush paper in which a low refractive index pigment is fixed on a support in a dispersed state in a binder resin, and a porous layer having different transparency in a liquid absorbing state and a non-liquid absorbing state is provided (for example, Patent Document 1).
When the porous layer is in a dry state (non-liquid-absorbing state), the lower layer of the paper is concealed. When the porous layer absorbs a liquid such as water, it becomes transparent and an image with the color tone of the lower layer appears. Even if it can, only an image of a single color tone can be obtained, and even if it can be used repeatedly, the image that appears is a reproduction of the image and does not satisfy the unexpectedness and the taste of change.
Japanese Patent Publication No. 52-44103

  The present invention is intended to solve the problem of the water-image sheet, and is a water-coloring drawing toy that displays a multicolor image and satisfies the unexpectedness and taste of change, and water-coloring using the same. A sex drawing toy set is to be provided.

The present invention is a drawing toy configured such that a handwriting by applying a writing instrument or an applicator to which water is attached causes a multicolor image to appear, and has a particle diameter of 0.01 to 10 μm as a colorant on a support. A large number of non-linear belt - like non-color-change images including colored pigments and different color tones are adjacent to each other, and the boundary portions of the adjacent images are arranged in gradation, and the location where the non-color-change image is provided is 100 cm ^2. A liquid absorbing state in which at least two colors or more are visually recognized, and a low-refractive-index pigment that hinders normal vision of the non-discolored image is fixed to the binder resin in a dispersed state on the upper surface of the non-discolored image. and Ri is Na is different porous layer disposed transparency in a non-liquid absorbing state, the brightness value V _B of the support is 8.0 or more and the band-shaped non-developed image with brightness value V _C in _relation, a V B _-V C> 0 water The color of the drawing toy and requirements.
Furthermore, the band width before Symbol strip non-developed image is a requirement and Dearuko 0.3～10Cm.
Furthermore, a water discoloration drawing toy set comprising the water discoloration drawing toy and a writing instrument or applicator for adhering water is a requirement.
Furthermore, it is a writing instrument or applicator to which the plastic porous body or fiber processed body having the continuous pores is applied as a pen tip member, and a handwriting width formed by application of the writing instrument or applicator is 0.3 to 15 cm. Requirement to be in range.

  The present invention eliminates the monotonousness in which a conventional single-color image appears by causing a multicolor image with different color tones to appear at an adjacent portion of a non-discolored image by applying a writing instrument or an applicator that attaches water. It is possible to provide a water discoloration drawing toy rich in unexpectedness and change and a water discoloration drawing toy set using the same.

  The substrate is effective if it is a substrate having printability, for example, paper, synthetic paper, woven fabric, knitted fabric, braid, non-woven fabric, natural or synthetic leather, plastic, glass, ceramics, metal Wood, stone, etc. are used. The shape is preferably a planar shape, but may be an uneven shape.

The non-color-change image provided on the support is provided with a large number of non-color-change images having different color tones adjacent to each other, and the portion provided with the non-color-change image has a color tone of at least two colors per 100 cm ^2. Is configured to be visible.
This type of drawing toy has its size and the writing width at the tip of the writing instrument or applicator limited to a practical range, so that it can effectively display a multicolored image at any location during use. Therefore, a non-color-change image is arranged so that at least two colors appear per 100 cm ² . In a system in which a multicolor image appears by changing the area larger than 100 cm ^2, the probability that a multicolor image appears at an arbitrary position is poor, and the color change effect is reduced.
The non-color-changing image is band-shaped non-developed image.
The strip non-color-changing image provided on the support, the color tone is disposed adjacent to each other curve-shaped strip non-color-changing image that different from each other.
The shape of the strip non-color-changing image, even if writing from various directions Ri strip non-developed image der of easily forming a multi-color image non-linear (curved), also for the band width 0.3 A belt-like non-color-change image comprising a combination of the same dimension or different dimensions selected from 10 cm, preferably 0.3 to 5 cm, more preferably 0.5 to 5 cm is suitable.
Also, the portion where the non-developed image is adjacent to each other Ri Gradient der by tone of adjacent image which has a heavy becomes part, non-developed by and difference in color tone is relaxed porous layer between non-color-changing image by the structure The hiding property of the image can be made easy, and as a result, a water discoloration drawing toy excellent in contrast between the dry state and the liquid absorption state can be obtained.
Furthermore, the color tone of the non-color-change image is selected from any two mixed colors selected from yellow, blue, pink, yellow, blue and pink, and the lightness value V _B of the support is 8.0 or more. a white or light-colored, and, in relation to the brightness value _{V C} of the non-color-changing _image, V B _-V C> Ru 0 der.
Here, yellow has a maximum absorption wavelength (λmax) of 430 nm to 480 nm, blue has a maximum absorption wavelength of 580 nm to 600 nm, and pink has a maximum absorption wavelength of 480 nm to 500 nm.
By satisfying the lightness value, the color tone of the non-discolored image is clearly and clearly visible.
In particular, when the boundary portion between adjacent images is gradation, the color density becomes thin, so that the contrast between the dry state and the liquid absorption state of the porous layer becomes poor. Therefore, satisfying the brightness value is an important requirement for visually recognizing the clear tone of the gradation portion. Furthermore, by forming a gradation portion using a non-color-changing ink having light permeability, a color tone becomes clear, and a drawing toy rich in variability between a dry state and a liquid absorption state is obtained.
When the lightness value V _B of the support is less than 8.0, or when V _B −V _C ≦ 0, the color tone of the non-color-changed image becomes dark and it is difficult to conceal it by the porous layer, or vivid color change Since it is difficult to show, it becomes easy to impair merchantability.
The non-color-change image is constituted by a colored pigment having a particle diameter of 0.01 to 10 μm, preferably 0.05 to 5.0 μm, fixed in a binder resin, has an appropriate transparency, and is particularly constituted by color mixing. Even in this case, a clear color tone can be visually recognized.
If the particle diameter is less than 0.01 μm, the transparency is too high and it is easily affected by the background color. Moreover, when water is applied to the porous layer, migration into the porous layer is likely to occur. When the particle diameter exceeds 10 μm, the transparency is poor and it becomes difficult to obtain a clear color mixture. In addition, the smoothness is poor, hiding failure due to the porous layer is likely to occur, and it is difficult to obtain a sufficient discoloration effect.

The porous layer provided on the non-color-change image is a layer in which a low refractive index pigment is fixed in a dispersed state together with a binder resin, and is a layer having different transparency in a dry state and a liquid absorption state.
Examples of the low refractive index pigment include silicic acid and salts thereof, barite powder, barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, talc, alumina white, magnesium carbonate, and the like. It is in the range of 1.8, and shows good transparency when water is absorbed.
Examples of the silicic acid salts include aluminum silicate, aluminum potassium silicate, sodium aluminum silicate, aluminum calcium silicate, potassium silicate, calcium silicate, calcium sodium silicate, sodium silicate, magnesium silicate, and magnesium potassium silicate.
Two or more of the low refractive index pigments can be used in combination.
The particle size of the low refractive index pigment is not particularly limited, but 0.03 to 10.0 μm is preferably used.
In addition, silicic acid is mentioned as a low refractive index pigment used suitably.
The silicic acid may be a silicic acid produced by a dry process, but a silicic acid produced by a wet process (hereinafter referred to as a wet process silicic acid) is particularly effective. To explain this point, silicic acid is amorphous. Amorphous silicic acid 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 silicic acid), and sodium silicate. It is roughly divided into those using a wet method using a liquid phase reaction such as decomposition by an acid such as a dry method, and the structure of a dry method silicic acid is different from that of a wet method silicic acid. The dry method silicic acid has a three-dimensional structure in which silicic acid is closely bound. In contrast, wet-process silicic acid has a so-called two-dimensional structure part in which silicic acid is condensed to form a long molecular arrangement.
Therefore, since the molecular structure becomes rough compared to the dry method silicic acid, when wet method silicic acid is applied to the porous layer, it is excellent in the diffused reflection of light in the dry state compared to the system using the dry method silicic acid, Therefore, it is guessed that the concealment property in a normal state becomes large.
Moreover, in the porous layer, since water is absorbed, the wet process silicic acid has more hydroxyl groups present as silanol groups on the particle surface than the dry process silicic acid, and the degree of hydrophilicity is large. 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 can be used in combination with the wet method silicic acid.

The low refractive index pigment in the porous layer depends on properties such as particle diameter, specific surface area, oil absorption, etc., in order to satisfy both the concealability in the normal state and the transparency in the liquid absorption state, preferably the coating amount is 1 to 30 g / ^{m 2,} more preferably 5 to 20 g / ^{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 low refractive index pigment is dispersed in a vehicle containing a binder resin as a binder, applied to a support, and then the volatile matter is dried to form a porous layer.
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 low refractive index pigment and these binder resins depends on the kind and properties of the low refractive index pigment, but preferably the binder resin solid content is 0.5 to 1 part by weight with respect to 1 part by weight of the low refractive index pigment. 2 parts by weight, more preferably 0.8 to 1.5 parts by weight. When the binder resin solid content is less than 0.5 parts by weight with respect to 1 part by weight of the low refractive index pigment, it is difficult to obtain a practical film strength of the porous layer, and the content exceeds 2 parts by weight. In this case, the water permeability into the porous layer is deteriorated.
Since the porous layer has a smaller mixing ratio of the binder resin to the colorant than a general coating film, it is difficult to obtain 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.
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 the need for an emulsifier by an ionic group of the ionic 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, but 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 with water. By combining these, the penetration time into the porous layer, 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 and surfactant suitably.

  The porous layer is formed by screen printing, offset printing, gravure printing, coater, tampo printing, transfer printing, brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, dip coating, etc. It can be formed on a non-discolored image.

  The drawing toy displays a multicolor image composed of at least two or more different colors when a handwriting having a length or size crossing an adjacent non-color-changed image is formed by application of a writing instrument or an applicator that attaches water. Let In addition, the multicolor image is erased by drying, and returns to the normal state.

As means for adhering water to the porous layer of the drawing toy, a writing or applicator having a brush tip or a fiber pen body at the tip part, containing water in the container, and deriving the water in the container Examples include a writing instrument or applicator provided with a fibrous body or a brush, a roller-type applicator, and the like.
A water discoloration drawing toy set is obtained by combining the writing instrument or applicator and the water discoloration drawing toy.
As a preferred writing instrument or applicator, a writing instrument or applicator in which water is contained in a container and a plastic porous body or fiber processed body having continuous pores for leading out the water in the container is applied as a pen tip member. Yes, handwriting can be easily formed, and practicality can be enhanced.
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, such as polyolefin-based, polyurethane-based, polyester-based and other various plastic continuous pores and fibers. Examples include a focused brush-like one, a fiber-processed resin-processed or heat-welded one, a felt, and a non-woven fabric. The shape and dimensions can be arbitrarily set according to the purpose.
The handwriting width formed in the porous layer of a drawing toy by application of a writing instrument or applicator is 0.3 to 15 cm, preferably 0.5 to 10 cm, more preferably 0.5 to 5 cm.
If it is less than 0.3 cm, the visibility of a multicolor image tends to be impaired, and if it exceeds 15 cm, the variability in which a multicolor image is formed may be hindered by writing.
A stamp tool, a spray container, a stencil sheet or the like can be used in combination with the writing instrument or the applicator.

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. In addition, the brightness value was measured using a color difference meter [TC3600 type color difference meter, manufactured by Tokyo Denshoku Co., Ltd.].
Example 1 (see FIG. 1)
Using a non-color-changing ink of purple, blue, green, yellow, orange and red on the upper surface of a white nylon taffeta fabric (lightness value: 9.6) as a support, a 2 cm wide bent belt-like image is formed. Wave-shaped band-like non-discolored images arranged in close proximity to each other were formed.
The lightness value of the place where the purple non-color-changed image is provided is 4.7, the lightness value of the place where the blue non-color-changed image is provided is 4.2, and the lightness value of the place where the green non-color-changed image is provided is 6.0, the brightness value of the portion where the yellow non-color-changed image is provided is 9.2, the brightness value of the location where the orange non-color-changed image is provided is 6.0, and the brightness value of the location where the red non-color-changed image is provided The value is 5.0, and the non-color-change image is expressed by gradation of halftone dots on adjacent boundary surfaces.
Subsequently, 15 parts of wet-process silicic acid [trade name: NIPSEAL E-200, manufactured by Nippon Silica Industry Co., Ltd.], urethane emulsion [trade name: Hydran HW-930, Dainippon Ink & Chemicals, Inc. ), 50% solids] 30 parts, 40 parts water, 0.5 parts silicone antifoam, 3 parts thickener for water-based ink, 1 part ethylene glycol, 3 parts blocked isocyanate crosslinking agent Using a white screen printing ink obtained by stirring, solid printing is performed on the entire surface with a 100-mesh screen plate, followed by drying and curing at 130 ° C. for 5 minutes to form a porous layer 2 to form a water discoloration drawing toy 1. Got.
The drawing toy has a white color when the porous layer is in a dry state, thereby preventing the non-discolored image from being visually recognized. Next, when the writing instrument 3 filled with water is applied to the porous layer, the porous layer in that portion becomes transparent, and a multicolor image 4 (handwriting) in which purple, blue, green, yellow, orange and red are connected. Appeared.
In the drawing toy, as the porous layer dries, the image becomes invisible, and when water is attached to the porous layer again, a multicolor image is visually recognized.

The water-coloring drawing toy set is obtained by combining the water-coloring drawing toy and a writing instrument having a fiber pen body made of nylon resin at the tip as a water adhering tool and configured to accommodate water in the shaft tube. It was.
When the water discoloration drawing toy set is written using the writing instrument in which water is contained in a porous layer, a 1.5 cm wide multicolor image (handwriting) is visually recognized.
Furthermore, as the porous layer dries, the image is not visually recognized. When water is again attached to the porous layer, a multicolor image is visually recognized.

Example 2 (see FIG. 1)
On the upper surface of white nylon taffeta fabric (lightness value: 9.6) as a support, yellow, pink, blue, red and orange, which are mixed colors of yellow and pink, and purple which is a mixed color of pink and blue A wave-patterned band-shaped image in which bent-band images with a width of 1.5 cm are arranged close to each other using non-color-changing ink (ink in which a colored pigment having an average particle diameter of 1.0 μm is dispersed in an acrylic resin emulsion). A non-discolored image was formed.
The lightness value of the portion where the yellow non-discolored image is provided is 9.2, the lightness value of the portion where the pink non-discolored image is provided is 5.5, and the lightness value of the portion where the blue non-discolored image is provided 4.2, the lightness value of the place where the red non-color-changed image is provided is 5.0, the lightness value of the place where the orange non-color-changed image is provided is 6.0, and the place where the purple non-color-changed image is provided The lightness value is 4.7, and the non-color-change image is formed by gradation of halftone dots on adjacent boundary surfaces.
Subsequently, 15 parts of wet-process silicic acid [trade name: NIPSEAL E-200, manufactured by Nippon Silica Industry Co., Ltd.], urethane emulsion [trade name: Hydran HW-930, Dainippon Ink & Chemicals, Inc. ), 50% solids] 30 parts, 40 parts water, 0.5 parts silicone antifoam, 3 parts thickener for water-based ink, 1 part ethylene glycol, 3 parts blocked isocyanate crosslinking agent Using a white screen printing ink obtained by stirring, solid printing is performed on the entire surface with a 100-mesh screen plate, followed by drying and curing at 130 ° C. for 5 minutes to form a porous layer 2 to form a water discoloration drawing toy 1. Got.
The drawing toy has a white color when the porous layer is in a dry state, thereby preventing the non-discolored image from being visually recognized. Next, when the writing instrument 3 filled with water is applied to the porous layer, the porous layer in that portion becomes transparent, and a multicolor image 4 in which yellow, orange, red, pink, purple and blue are connected (handwriting). ) Appeared.
In the drawing toy, as the porous layer dries, the image becomes invisible, and when water is attached to the porous layer again, a multicolor image is visually recognized.

The water-coloring drawing toy set is obtained by combining the water-coloring drawing toy and a writing instrument having a fiber pen body made of nylon resin at the tip as a water adhering tool and configured to accommodate water in the shaft tube. It was.
When the water discoloration drawing toy set is written using the writing instrument containing water in a porous layer, a 1 cm wide multicolor image (handwriting) is visually recognized.
Furthermore, as the porous layer dries, the image is not visually recognized. When water is again attached to the porous layer, a multicolor image is visually recognized.

Example 3 (see FIG. 2 )
In the center of the upper surface of a white T / C broad cloth (lightness value 9.2) having a size of 80 cm × 80 cm as a support, each non-color-changing ink of blue, yellow, and pink (average particle diameter is 0.10 μm) A non-color-changed belt-like image in which bent belt-like images having a width of 3 cm are arranged adjacent to each other using an ink in which a colored pigment is dispersed in an acrylic resin emulsion) is used alone or in combination, and has a size of 60 cm × 60 cm. Formed as follows.
The lightness value of the purple non-discolored image is 4.5, the lightness value of the blue non-discolored image is 4.2, the lightness value of the blue-green non-discolored image is 5.0, and the lightness value of the green non-discolored image. The value is 6.0, the lightness value of the yellow-green non-discolored image is 7.0, the lightness value of the yellow non-discolored image is 9.1, the lightness value of the orange non-discolored image is 5.9, and the non-discolored image of red The lightness value of the discolored image is 5.0, and the lightness value of the red-purple non-discolored image is 4.7. The non-discolored image is expressed by gradation of halftone dots adjacent to each other.
In addition, letters and pictures were printed around the non-discolored image on the support.
Subsequently, 15 parts of wet-process silicic acid [trade name: NIPSEAL E-200, manufactured by Nippon Silica Industry Co., Ltd.], urethane emulsion [trade name: Hydran HW-930, Dainippon Ink & Chemicals, Inc. ), 50% solids] 30 parts, 40 parts water, 0.5 parts silicone antifoam, 3 parts thickener for water-based ink, 1 part ethylene glycol, 3 parts blocked isocyanate crosslinking agent Using a white screen printing ink obtained by stirring, solid printing is performed on the entire surface with a 100-mesh screen plate, followed by drying and curing at 130 ° C. for 5 minutes to form a porous layer 2 to form a water discoloration drawing toy 1. Got.
The drawing toy has a white color when the porous layer is in a dry state, thereby preventing the non-discolored image from being visually recognized. Next, when the writing instrument 3 filled with water is applied to the porous layer, the porous layer in that portion becomes transparent, and purple, blue, blue-green, green, yellow-green, yellow, orange, red, reddish purple The connected multicolor image 4 (handwriting) appeared.
In the drawing toy, as the porous layer dries, the image becomes invisible, and when water is attached to the porous layer again, a multicolor image is visually recognized.

The water-coloring drawing toy set was obtained by combining the water-coloring drawing toy and an applicator equipped with a 10 cm wide brush as a water adhering tool.
When the water color changing drawing toy set is written with an applicator in which water is included in the brush, a multicolor image (handwriting) having a maximum width of 10 cm is visually recognized.
Furthermore, as the porous layer dries, the image is not visually recognized. When water is again attached to the porous layer, a multicolor image is visually recognized.

It is one Example of this invention water discoloration drawing toy, and shows the state of the image made to appear using a writing implement. It is another Example of this invention water color changeable drawing toy, and shows the state of the image made to appear using a writing implement.

1 Water discoloration drawing toy 2 Porous layer 3 Writing instrument 4 Multicolor image

Claims (5)

A drawing toy configured such that a handwriting by application of a writing instrument or application tool for adhering water causes a multicolor image to appear, and includes a colored pigment having a particle size of 0.01 to 10 μm as a colorant on a support In addition, a large number of non-linear belt - shaped non-color-change images having different color tones are adjacent to each other, and border portions of the adjacent images are arranged in gradation, and the non-color-change image is provided at least two colors per 100 cm ² The above-described color tone is configured to be visible, and the upper surface of the non-color-changed image has a low-refractive-index pigment that prevents normal vision of the non-color-changed image fixed to a binder resin in a dispersed state. Ri Na transparency while is different porous layer disposed, the brightness value V _B of the support is 8.0 or more, and, in relation to the brightness value V _C of the belt-shaped non-developed image, V water-discoloring drawing a _B -V _C> 0 Ingredients. The water-coloring drawing toy according to claim 1, wherein a band width of the band-shaped non-color-change image is 0.3 to 10 cm. A water-color-changing drawing toy set comprising the water-color-changing drawing toy according to claim 1 and a writing instrument or applicator for adhering water. The water discoloration drawing toy set according to claim 3, which is a writing instrument or applicator to which a plastic porous body or a fiber processed body having continuous pores is applied as a pen tip member. The water discoloration drawing toy set according to claim 3 or 4, wherein a handwriting width formed by application of the writing instrument or applicator is in a range of 0.3 to 15 cm.

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