JP7406969B2 - Water-soluble sheet color materials, water-soluble sheet sets, and paint sets - Google Patents

Description

The present invention relates to a water-soluble sheet-like coloring material and a manufacturing method. More specifically, the present invention relates to a water-soluble sheet-like coloring material containing colored resin particles and a manufacturing method. This water-soluble sheet coloring material can be used as a watercolor paint by dissolving it in water.

Watercolor paints are generally in liquid or paste form, but there are also other forms such as powder, granule, or solid fixed on a palette. Furthermore, sheet-like paints have also been proposed (Patent Documents 1 and 2). Sheet-shaped paints are particularly required to have good film-forming properties, to have appropriate self-supporting properties and flexibility, and to quickly become uniform when dissolved in water. Improvements were required in this regard.

In addition, like regular paint, it is required to have high concealment properties and good color development so that handwriting can be easily recognized even when drawing on paper with a dark hue, such as black paper. There is.
Furthermore, like ordinary paints, there is a demand for increasing color variations, and fluorescent colors are particularly preferred because they can give an impression that was not seen before.

Japanese Unexamined Patent Publication No. 59-84955 Japanese Patent Application Publication No. 4-225076

In view of the above-mentioned problems, the present invention has good film forming properties, has appropriate self-supporting properties and flexibility, and can quickly become uniform when dissolved in water. Furthermore, the present invention provides a water-soluble sheet-like coloring material containing colored resin particles, which provides handwriting with good color development and hiding properties even when drawn on paper with a dark hue such as black paper.

The water-soluble sheet coloring material according to the present invention is
water-soluble polymer,
It contains colored resin particles and a physical material.

The water-soluble sheet coloring material set according to the present invention includes:
water-soluble polymer,
a first coloring agent, and a first water-soluble sheet coloring material containing a substance;
water-soluble polymer,
a second coloring agent; and a second water-soluble sheet coloring material containing an extender, the first coloring agent being colored resin particles, and the second coloring agent being the colored resin particles. It is a different coloring agent.

A paint set according to the present invention includes the water-soluble sheet-like coloring material described above and a brush.

The water-soluble sheet-like coloring material according to the present invention has good film-forming properties, has appropriate self-supporting properties and flexibility, and is excellent in handleability. In particular, since it is in the form of a sheet, it is easy to adjust the concentration by tearing it apart by hand or cutting it with scissors before dissolving it. In addition, the water-soluble sheet-like coloring material according to the present invention quickly becomes uniform when dissolved in water, so when drawing with a brush, it is possible to obtain good handwriting without uneven color, and it is not only white. Even when used on black paper, it has excellent coloring properties and excellent hiding properties.

Embodiments of the present invention will be described in detail below. In this specification, unless otherwise specified, "parts", "%", "ratio", etc. indicating formulations are based on mass, and content is based on the mass of the water-soluble sheet coloring material. is the mass % of the constituent components.

<Water-soluble sheet coloring material>
The water-soluble sheet-like coloring material (hereinafter sometimes referred to as sheet-like coloring material) according to the present invention includes a water-soluble polymer, colored resin particles, and an extender.

The sheet-like coloring material according to the present invention is a solid having appropriate self-supporting properties and flexibility. Since it is sheet-like, it is easy to cut, and there is no need for a container to house it, and it can be handled individually, so it is easy to handle. A typical example of the sheet-like shape is a film with a uniform thickness, but the thickness may be partially changed to facilitate cutting at thinner parts. However, since the sheet-like coloring material according to the present invention has high coloring properties, sufficient coloring can be obtained even in a relatively thin shape, and therefore sufficient characteristics can be exhibited even in a thin film shape with a uniform thickness. The average film thickness of such a sheet-like coloring material is not particularly limited, but is preferably 5 to 300 μm, more preferably 10 to 150 μm. In the case of a manufacturing method using a bar coater, the average film thickness is preferably 10 to 60 μm. Here, the average film thickness can be measured with a microgauge. A sheet-like coloring material having such an average film thickness has flexibility even in a dry state and can realize sufficient strength for handling. Further, the sheet-like coloring material according to the present invention has low adhesiveness, and when held by hand, the ingredients are unlikely to stick to the hand. Furthermore, even if a plurality of sheets are stacked and stored, they are difficult to stick to each other.

When the sheet-like coloring material according to the present invention comes into contact with water, it dissolves into a liquid composition. This liquid composition can be used in the same way as commonly used paints, paints prepared by dispersing them in water, and paints. The temperature of the water used is not particularly limited, but it may be sufficient as long as it can be dissolved in water at about room temperature. The method of contacting with water is not particularly limited, but examples include: bringing a brush soaked in water into contact with the sheet-like coloring material and rubbing it, dropping water onto the sheet-like coloring material with a dropper, etc.; For example, immersing a sheet-like coloring material of a large size, etc. If necessary, the sheet-like coloring material may be placed in water and stirred using a brush or the like.

Since the sheet-shaped coloring material according to the present invention has colored resin particles uniformly dispersed therein, it can be quickly turned into a uniform liquid paint when it comes into contact with water. When a brush or the like is impregnated with the paint and drawn, good handwriting with no uneven color can be obtained.

The components used in the water-soluble sheet-like coloring material according to the present invention will be explained below.

<Water-soluble polymer>
The water-soluble polymer used in the present invention is a main material for maintaining the shape of the sheet-like coloring material, and can be dissolved in water after the film is formed. Further, when a sheet-like color material is dissolved in water and drawn, it can also serve to form a colored film.
The water-soluble polymer is preferably selected from the group consisting of nonionic linear polymers and polysaccharides, and preferably comprises a nonionic linear polymer. Moreover, it is more preferable that the water-soluble polymer is a combination of a nonionic chain polymer and a polysaccharide.
The content of the water-soluble polymer is preferably 5 to 45% by mass, more preferably 10 to 35% by mass, and still more preferably 10 to 30% by mass, based on the total mass of the sheet-like coloring material. be.

The nonionic water-soluble linear polymer does not contain a cyclic structure in its main chain. Specific examples include polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, and polyethylene oxide, with polyvinyl alcohol being preferred. The degree of polymerization of polyvinyl alcohol is particularly preferably from 200 to 1,400, more preferably from 200 to 800.
The content of the nonionic water-soluble chain polymer is preferably 1 to 40% by mass, more preferably 5 to 35% by mass, even more preferably 10% by mass, based on the total mass of the sheet-like coloring material. ~25% by mass.

Examples of polysaccharides include glucan whose main constituent sugar is glucose. Glucan can be classified into α-glucan and β-glucan. Here, α-glucan has a basic structure in which glucose is linked in a chain through α-1,4-bonds, and may have a structure branched from the 6-position of some glucose. β-glucan refers to a polymer, and β-glucan has a basic structure in which glucose is linked in a chain with β-1,3-bonds, although it may have a structure branched from the 6-position of some glucose. It refers to a polymer with a good structure. Examples of α-glucan include amylose and pullulan. Examples of β-glucan include cellulose and derivatives thereof such as fermented cellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, and carboxymethylcellulose. More preferred is α-glucan.
Other polysaccharides that can be used include alginic acid and its salts (eg, sodium alginate), xanthan gum, welan gum, succinoglycan, guar gum, locust bean gum, carrageenan, and diutan gum.
In the present invention, it is particularly preferable to use pullulan, considering that the water-soluble sheet-like coloring material has excellent self-supporting properties and flexibility, and further excellent re-dissolution properties can be obtained.
Note that two or more types of polysaccharides may be combined.

The mass average molecular weight of the polysaccharide is preferably 10,000 to 6,000,000, more preferably 100,000 to 1,500,000, and still more preferably 200,000 to 600,000. Within this range, a highly self-supporting film can be formed and has high resolubility in water. Here, in the present invention, the mass average molecular weight can be measured by a conventional method using gel permeation chromatography.
The content of polysaccharide is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass, particularly preferably 0.5% by mass, based on the total mass of the sheet-like coloring material. ~5% by mass. .

<Colored resin particles>
The sheet-like coloring material according to the present invention includes colored resin particles. In the present invention, colored resin particles refer to resin particles colored with a colorant. The colorant here is not particularly limited as long as it can color the resin particles, and any pigment or dye can be used.

Resin particles have excellent alkali resistance, acid resistance, and heat resistance, and are highly stable even in the presence of various additives, and are not easily affected by thermal environments. Styrene-acrylonitrile resin particles (hereinafter sometimes referred to as SA resin particles) are preferable.

SA resin particles are resin particles obtained by copolymerizing styrene and acrylonitrile as monomers. The blending ratio of styrene and acrylonitrile is not particularly limited, but is generally blended at a ratio of 10 to 90 mol% of styrene and 90 to 10 mol% of acrylonitrile. Note that monomers other than styrene and acrylonitrile can be combined within a range that does not impair the effects of the present invention.

SA resin particles can be obtained by any conventionally known method, but considering the color development and stability of the sheet coloring material, uniform particles are easily obtained by emulsion polymerization of styrene and acrylonitrile. Preferably, they are resin particles, and more preferably, they are used as an SA resin particle dispersion in a state in which they are previously dispersed in a dispersion medium such as water. It is also possible to use a commercially available SA resin particle dispersion.

The size of the resin particles is not particularly limited, but in consideration of improving dispersibility and color development, the average particle size is preferably 0.05 to 3 μm, more preferably 0.1 to 1 μm. Here, the average particle diameter of the SA resin particles is determined by calibrating the average particle size of the SA resin particles using a standard sample or other measurement method using, for example, a laser diffraction particle size distribution analyzer (trade name "MicrotracHRA9320-X100", Nikkiso Co., Ltd.). It can be measured by the particle diameter (D50) at 50% cumulative volume of the particle size distribution measured by a laser diffraction method based on numerical values.

The colorant may be a pigment or a dye. Such coloring agents can be arbitrarily selected from inorganic, organic, processed pigments, and the like. Specific raw materials include ultramarine, yellow lead, iron oxide, phthalocyanine series, azo series, quinacridone series, quinophthalone series, threne series, triphenylmethane series, perinone series, perylene series, gioxazine series, pearl pigments, fluorescent pigments, Examples include phosphorescent pigments and complementary color pigments.

Specific examples of such pigments include Pigment Blue 1, Pigment Blue 15:1, Pigment Blue 15:3, Pigment Blue 17, Pigment Blue 3, Pigment Blue 5, Pigment Blue 22, Pigment Blue 38, Pigment Blue 48, Pigment Blue 49, and Pigment Blue 53, 57, 81, 104, 146, 245, Pigment Yellow 1, 3, 12, 13, 14, 42, 74, Pigment Yellow 83, Pigment Yellow 106, Pigment Orange 117, Pigment Orange 5, Pigment 16, Pigment Violet 1, Pigment 3, Pigment 19, Pigment 23, Pigment Violet 27, Pigment Green 7, Pigment 36, etc.

Moreover, a dye can also be used as a coloring agent. As for dyes, direct dyes, acid dyes, basic dyes, metal-containing dyes, and various salt-forming type dyes can be used.

Various types of such dyes are commercially available, and any one can be selected and used. Specifically, (a) Direct dyes include Direct Yellow 4, Direct Yellow 26, Direct Yellow 44, Direct Yellow 50, Direct Red 85, Direct Red 1, Direct Red 1, Direct Red 2, Direct Red 4, Direct Red 23, Direct Red 31, Direct 37, Direct Red 39. , 75, 80, 81, 83, 225, 226, 227, Direct Blue 1, 3, 15, 41, 71, 86, 106, 119, Direct Orange 6 (b) Acidic dyes include Acid Black 1, 2, 24, 26, 31, 52, 107, Acid Orange 56, Acid Yellow 3, 7, 17, 19, 23, 42, 49, 61, 92, Acid Red 8, 9, 14, 18, 51, 52, 73, 87, 92, 94, Acid Blue 1, 7, 9, 22, 62, 90, 103, Acid Green 3, 9, 16, 25, 27, Acid Violet 15, 17, etc. (c) Basic dyes include: C. I. Basic Yellow-1, 2, 21, 7, 40, C. I. Basic Orange 2, 14, 32, C. I Basic Red 1, 1:1, 2, 9, 14, C. I. Basic Violet 1, 3, 7, 10, 11:1, C.I. I. Basic Blue-3, 7, 26, Basic Green 4, C. I. Basic Brown 12, C. I. Basic Black 2, Methyl Violet, Victoria Blue FB, Malachite Green, Rhodamine series, etc. (d) Other dyes include disperse dyes such as Disperse Yellow 82, Disperse Yellow 121, and Disperse Blue 7.

As the colorant for the resin particles, it is particularly preferable to use a fluorescent colorant. This is because when handwriting is formed on black paper or the like, it is highly visible and can give a special aesthetic appearance. Examples of fluorescent colorants include fluorescent dyes and fluorescent pigments. Among fluorescent colorants, it is preferable to use fluorescent dyes because they have high visibility of handwriting on black paper and the like and are highly stable with resin particles containing styrene-acrylonylyl. Specific examples of such fluorescent dyes include basic dyes having a xanthene skeleton, triaryl skeleton, or azo skeleton, or disperse dyes. Among these, basic dyes having a xanthene skeleton or an azo skeleton are preferred because they have higher visibility of handwriting. Such fluorescent dyes include Direct Yellow 85, Basic Yellow 1, 40, Basic Red 1, 1:1, Basic Violet 10, 11:1, Acid Yellow 7, Acid Red 92, Acid Blue 9, and Direct Yellow 1:1. Examples include Spurs Yellow 82 and Spurs Yellow 121.

Particularly preferably, the colored resin particles are a combination of SA resin particles and a fluorescent dye.

Examples of commercially available products containing colored resin particles include the Shinroihi Color series (manufactured by Shinrohi Co., Ltd.), the Lumicol series (manufactured by Nippon Fluoro Chemical Co., Ltd.), and the LM series (Fuji Shiki). (manufactured by Nippon Shokubai Co., Ltd.) and Epocolor series (manufactured by Nippon Shokubai Co., Ltd.). Specifically, the Lumicor series includes NKW-2317H, NKW-6307H, NKW-2308H, NKW-2302H, NKW-2305H, and NKW-6305H. In addition, the Shinrohi color base SW-11, SW-12, SW-13, SW-14, SW15, SW-16, SW-17, SW-18, and SW-27, SW-37, SW-47, SF-1012, SF-1013, SF-1014, SF-1015, SF-1017, SF-1027, SF-1038, SF- 5015 etc. are also mentioned.

The content of the colored resin particles is preferably 20 to 60% by mass, more preferably 30 to 50% by mass, particularly preferably 35 to 45% by mass, based on the total mass of the sheet-like coloring material. be.

<Constitution material>
The sheet-like coloring material according to the present invention contains an extender. Here, in the present invention, the extender material itself has low coloring and hiding properties, but it suppresses the sinking of colored resin particles between paper fibers, etc., and the extender material itself scatters light. It is a substance that can enhance hiding properties and coloring properties when combined with colored resin particles. By including the extender, the strength of the film can be increased, the film thickness can be increased, and the dissolution of the sheet-like coloring material when it comes into contact with water can be promoted. Specific examples include kaolin, talc, mica, clay, bentonite, calcium carbonate, barium sulfate, and aluminum hydroxide, with kaolin being preferred. Kaolin can be classified into hydrated kaolin (wet kaolin), calcined kaolin, and dry kaolin depending on the manufacturing method. Hydrous kaolin has excellent solubility and dispersibility, and is used to manufacture sheet-like coloring materials. Cheap. In addition, it is particularly preferable to use kaolin because it is easy to obtain handwriting with good color development and hiding properties even when drawing on paper with a dark hue such as black paper. Note that some of these physical materials are not colorless, so they also have the function of a coloring agent.

The content of the extender is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and preferably 10 to 30% by mass, based on the total mass of the sheet coloring material. More preferred.
In addition, in the sheet-shaped coloring material, it is possible to obtain handwriting with excellent film strength and excellent coloring and hiding properties, and the content of the extender is 10% based on the total mass of the extender and colored resin particles. It is preferably from 70% by weight, preferably from 20 to 50% by weight, and preferably from 20 to 40% by weight.
Further, the content of the water-soluble polymer is preferably 10 to 100% by mass, more preferably 20 to 50% by mass, based on the total mass of the colorant and extender.

<Others>
The sheet-like coloring material according to the present invention can contain other materials as necessary. Examples of additives that can be used include colorants, fatty acid metal salts, polyhydric alcohols, surfactants, water, viscosity modifiers, coating performance improvers, preservatives, antifoaming agents, and the like. It can also include other materials that can normally be used in water-based paints.

The sheet-like coloring material according to the present invention can realize different color tones by further containing a coloring agent, thereby further increasing color variations. This coloring agent is different from that used for coloring the colored resin particles.
As this coloring agent, any conventionally known pigments or dyes can be used, but pigments are preferred. Pigments are not particularly limited and include, for example, inorganic, organic, and processed pigments, but specific examples include carbon black, aniline black, ultramarine blue, yellow lead, titanium oxide, iron oxide, and phthalocyanine pigments. , azo pigments, quinacridone pigments, quinophthalone pigments, styrene pigments, triphenylmethane pigments, perinone pigments, perylene pigments, dioxazine pigments, and the like. Incidentally, the pigment may be a water-dispersed pigment product that is previously dispersed in a medium using a pigment dispersant such as a surfactant.
Examples of the dye include phthalocyanine dyes, pyrazolone dyes, nigrosine dyes, anthraquinone dyes, and azo dyes.
Moreover, the same coloring agent as the coloring agent contained in the colored resin particles may be further included.
The content of the coloring agent varies depending on its type, but is preferably 50 to 150% by mass, more preferably 80 to 120% by mass, based on the total mass of colored resin particles contained in the entire sheet-like coloring material.

Fatty acid metal salts are thought to have the effect of promoting dissolution of the sheet-like coloring material when it comes into contact with water, and of uniformly dispersing colored resin particles when the sheet-like coloring material is dissolved in water. .
The fatty acid metal salt is preferably a metal salt of a fatty acid having 12 or more carbon atoms, and specifically, lithium stearate, sodium stearate, potassium stearate, lithium palmitate, sodium palmitate, potassium palmitate, Lithium myristate, sodium myristate, potassium myristate, lithium laurate, sodium laurate, potassium laurate, lithium oleate, sodium oleate, potassium oleate, lithium isostearate, sodium isostearate, potassium isostearate, etc. and preferably potassium oleate.
The content of the fatty acid metal salt is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, and even more preferably 2 to 8% by mass, based on the total mass of the sheet-like coloring material. %. However, since containing fatty acid metal salts may cause foaming when dissolved in water, it is also a preferred embodiment not to contain fatty acid metal salts.

Polyhydric alcohol can be used for the purpose of suppressing overdrying of the sheet-like coloring material and keeping it appropriately moist. It is also thought to have the effect of preventing agglomeration of the colorant in the sheet-like coloring material and imparting plasticity to the film. The polyhydric alcohol is preferably a diol or triol, and specific examples include ethylene glycol, diethylene glycol, propylene glycol, and glycerin, with glycerin being particularly preferred.
In order for the sheet-like coloring material to maintain a sheet shape with sufficient strength, the content of polyhydric alcohol is preferably 0.5 to 30% by mass based on the total mass of the sheet-like coloring material, More preferably, it is 1 to 10% by mass.

The surfactant can be used as a dispersant for colored resin particles, or as a paintability improver during drawing. As the surfactant, nonionic, cationic, anionic, or amphoteric ionic surfactants are known, and they can be appropriately selected and used.
Examples of surfactants include fluorine-based surfactants, silicone-based surfactants, surfactants having an acetylene bond in their structure, and phosphate-based surfactants. Considering the improvement of the coating properties, it is more preferable to select and use one or more types of surfactants from fluorine-based surfactants, silicone-based surfactants, and surfactants having an acetylene bond in their structure. It is more preferable to use a surfactant having in its structure.
Furthermore, examples of the surfactant having an acetylene bond in its structure include acetylene alcohol surfactants and acetylene glycol surfactants, and among them, it is particularly preferable to use an acetylene glycol surfactant.

The sheet-like coloring material according to the present invention can contain water. In addition to being added as a solvent, such water may be added as a solvent or dispersion medium for colorants, surfactants, and the like. Such water may be removed by evaporation in the manufacturing method described below, or a part of it may remain in the water-soluble sheet-like coloring material.

<Method for manufacturing water-soluble sheet coloring material>
Although the method for producing the water-soluble sheet-like coloring material according to the present invention is not particularly limited, it can be produced, for example, as follows.

A mixture comprising a water-soluble polymer, colored resin particles, and extender is stirred to prepare a uniform dispersion. It is preferable to use colored resin particles that have been previously dispersed in a dispersion medium.
Next, a sheet-like coloring material can be manufactured by applying the dispersion liquid onto a base resin film using a bar coater, an applicator, etc., drying it, and peeling it off from the base resin film.

Another method is to knead a mixture containing a water-soluble polymer, colored resin particles, and an extender using a kneader or the like, extrude the kneaded product, and, if necessary, perform calendering, rolling, etc. , it is possible to produce a uniform sheet-like coloring material.

<Water-soluble sheet color material set>
The water-soluble coloring material set according to the present invention includes:
a first water-soluble sheet coloring material comprising a water-soluble polymer, a first coloring agent, and an extender;
A water-soluble polymer, a second colorant, and a second water-soluble sheet coloring material comprising an extender, the first coloring agent being colored resin particles, and the second coloring agent being colored resin. The coloring agent is different from the particles. Here, the second colorant may be colored resin particles different from the first colorant, or may be a colorant other than colored resin particles.
Here, the colorant that is not the colored resin particles is not particularly limited, and any conventionally known pigments or dyes can be used, but pigments are preferred. Pigments are not particularly limited and include, for example, inorganic, organic, and processed pigments, but specific examples include carbon black, aniline black, ultramarine blue, yellow lead, titanium oxide, iron oxide, and phthalocyanine pigments. , azo pigments, quinacridone pigments, quinophthalone pigments, styrene pigments, triphenylmethane pigments, perinone pigments, perylene pigments, dioxazine pigments, and the like. Among these, by selecting colored resin particles, especially fluorescent colored resin particles, as the first coloring agent, and selecting a white pigment such as titanium oxide as a coloring agent other than colored resin particles as the second coloring agent, it is possible to use This method is effective because it is easy to form pastel-like handwriting with a pale color desired by the person, and the handwriting has excellent coloring and hiding properties even on black paper.
Moreover, the first water-soluble sheet-like coloring material and the second water-soluble sheet-like coloring material each contain a water-soluble polymer. These may be the same or different in the first water-soluble sheet-like coloring material and the second water-soluble sheet-like coloring material. From the viewpoint of compatibility and ease of production when mixing the first water-soluble sheet coloring material and the second water-soluble sheet coloring material, it is common to use the same water-soluble polymer; It is also possible to adopt different materials in consideration of compatibility and stability with resin particles and the like.
By using the first and second water-soluble sheet-like coloring materials in combination, a paint having a new color can be formed.
Furthermore, three or more sheet-like coloring materials can be combined.

<Paint set>
The paint set according to the present invention includes the sheet-like coloring material according to the present invention or the sheet-like coloring material set according to the present invention, and a brush. Additionally, water containers, pallets, etc. can be combined. The paint set according to the present invention can be used not only for drawing but also for calligraphy and painting.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

<Example 1>
(1a) Manufacture of coloring composition for producing sheet-like coloring material - 45 parts by mass of 20% by mass aqueous solution of polyvinyl alcohol (polyvinyl alcohol degree of polymerization 500, degree of saponification 87.0-89.0 mol%)
・Colored resin particle dispersion 43.0 parts by mass ("Lumicol NKW-2317H", Nippon Fluoro Chemical Co., Ltd., SA resin particles dyed with fluorescent dyes Basic Violet 11:1, Basic Red 1:1 and Basic Yellow 40) (average particle size 0.4 μm, 45% by mass water dispersion)
・Kaolin 10.0 parts by mass ("ASP-600", hydrated kaolin, BASF)
・Glycerin 1.0 parts by mass ・Surfactant 1.0 parts by mass (acetylene glycol surfactant "Dynol 604", Nissin Chemical Industry Co., Ltd.)
-Water 3.0 parts by mass The above formulation was stirred and mixed at room temperature for 1 hour to obtain a coloring composition for producing a sheet-like coloring material.
(1b) Production of sheet-like coloring material The colorant composition obtained in (1a) above was applied onto a 100 μm polypropylene film using a bar coater, dried at 50°C for 12 hours, and then coated on the polypropylene film. A film-like product in which the composition was formed into a film was obtained. By peeling this film-like material from the polypropylene film, a fluorescent pink sheet-like coloring material was obtained.

表中、
・ポリビニルアルコール水溶液：ポリビニルアルコール２０質量％水溶液、ポリビニルアルコール 重合度５００、ケン化度８７．０～８９．０モル％、
・プルラン水溶液：プルラン１０質量％水溶液、プルラン 質量平均分子量約４０万、
・着色樹脂粒子分散体Ａ：ＳＡ樹脂粒子が蛍光染料（ベーシックバイオレット１１：１とベーシックレッド１：１とベーシックイエロー４０）で染着されたもの、平均粒子径０．４μｍ、４５％水分散体、ルミコールシリーズ、日本蛍光化学株式会社製、
・着色樹脂粒子分散体Ｂ：ＳＡ樹脂粒子が蛍光染料（ベーシックイエロー４０とディスパーズイエロー８２）で染着されたもの、平均粒子径０．４μｍ、４５％水分散体、ルミコールシリーズ、日本蛍光化学株式会社製、
・青色顔料分散体：ピグメントブルー１５ ２５質量％水分散体、１０質量％ジエチレングリコール含有、
・カオリン：「ＡＳＰ－６００」、含水カオリン、ＢＡＳＦ社、
・界面活性剤：アセチレングリコール系界面活性剤「ダイノール６０４」、日信化学工業株式会社。 <Examples 2 and 3 and Comparative Examples 1 and 2>
(a) Production of a coloring composition for producing a sheet-like coloring material A coloring composition for producing a sheet-like coloring material was produced in the same manner as in Example 1, except that the formulations shown in Table 1 below were used. A sheet-like coloring material was obtained in the same manner as in Example 1 using the obtained colored composition. Composition numbers in the table indicate parts by mass.

In the table,
・Polyvinyl alcohol aqueous solution: polyvinyl alcohol 20% by mass aqueous solution, polyvinyl alcohol polymerization degree 500, saponification degree 87.0 to 89.0 mol%,
- Pullulan aqueous solution: pullulan 10% by mass aqueous solution, pullulan mass average molecular weight approximately 400,000,
・Colored resin particle dispersion A: SA resin particles dyed with fluorescent dyes (Basic Violet 11:1, Basic Red 1:1, and Basic Yellow 40), average particle size 0.4 μm, 45% aqueous dispersion , Lumicol series, manufactured by Nippon Fluorescent Chemical Co., Ltd.
・Colored resin particle dispersion B: SA resin particles dyed with fluorescent dyes (Basic Yellow 40 and Disperse Yellow 82), average particle size 0.4 μm, 45% water dispersion, Lumicol series, Nippon Fluorescent Manufactured by Kagaku Co., Ltd.
・Blue pigment dispersion: Pigment Blue 15 25% by mass aqueous dispersion, containing 10% by mass of diethylene glycol,
・Kaolin: "ASP-600", hydrated kaolin, BASF,
・Surfactant: Acetylene glycol surfactant "Dynol 604", Nissin Chemical Industry Co., Ltd.

When the state of the film of the obtained sheet-like coloring material was evaluated by palpation, the film formability was good in all cases. Moreover, when these sheet-like coloring materials were brought into contact with water, they quickly became uniform.
The film thickness of the obtained sheet-like coloring material was measured. The film thickness was measured using a microgauge. The results obtained are shown in Table 1.

The sheet-like coloring materials of Examples 2 to 5 have a more suppressed surface stickiness than the sheet-like coloring material of Example 1, and are easy to tear without stretching when torn by hand, making them easier to handle. It was even better.

The sheet-like coloring materials of all Examples have thicker film thickness, higher film strength, and moderate self-supporting properties than the sheet-like coloring material of Comparative Example 1. When the coloring material is manufactured, damage is less likely to occur when it is peeled off from the polypropylene film, and manufacturing is easy. On the other hand, they were also easy to tear by hand or cut using scissors or the like. When dissolved in water, the dissolution rate was even faster.
Among the Examples, the sheet coloring material of Example 4 was better than the sheet coloring material of Example 5, and the sheet coloring material of Examples 1 to 3 was better than the sheet coloring material of Example 4. The film was thicker, had higher strength, and had appropriate self-supporting properties.

A brush dipped in water at room temperature was brought into contact with the obtained sheet-like coloring material and rubbed to form a uniform liquid paint. A brush was soaked in each paint and drawn on white or black paper. Visual evaluation of the color development when drawing showed that the sheet-like coloring materials of Examples 1 to 5 had high color development when drawing on white paper and black paper, and had good hiding properties on black paper. it was high. The sheet-like coloring material of Example 4 is better than the sheet-like coloring material of Example 5, and the sheet-like coloring material of Examples 1 to 3 is better than the sheet-like coloring material of Examples 1 to 3. The concealability was higher.
The sheet-like coloring material of Comparative Example 1 had high color development when drawing on white paper and black paper, but the hiding property on black paper was lower than that of the example. The sheet-like coloring material of Comparative Example 2 had high coloring property on white paper, but had low coloring property on black paper, and its hiding property was lower than that of Comparative Example 1.

Claims (8)

water-soluble polymer,
A water-soluble sheet-like coloring material comprising colored resin particles and an extender,
A water-soluble sheet-like coloring material, wherein the colored resin particles are a combination of a fluorescent colorant and styrene-acrylonitrile resin particles . The water-soluble sheet coloring material according to claim 1, wherein the water-soluble polymer is selected from the group consisting of nonionic chain polymers and polysaccharides. The water-soluble sheet coloring material according to claim 2, wherein the water-soluble polymer is a combination of a nonionic chain polymer and a polysaccharide. The sheet-like coloring material according to any one of claims 1 to 3 , wherein the extender is selected from the group consisting of kaolin, talc, mica, clay, bentonite, calcium carbonate, barium sulfate, and aluminum hydroxide. . The water-soluble sheet coloring material according to any one of claims 1 to 4 , further comprising a polyhydric alcohol. The water-soluble sheet coloring material according to any one of claims 1 to 5 , having an average film thickness of 5 to 300 μm. water-soluble polymer,
a first coloring agent, and a first water-soluble sheet coloring material containing a substance;
water-soluble polymer,
a second coloring agent; and a second water-soluble sheet coloring material containing an extender, the first coloring agent being colored resin particles, and the second coloring agent being the colored resin particles. A water-soluble sheet-like coloring material set , wherein the colored resin particles are a combination of a fluorescent coloring agent and styrene-acrylonitrile resin particles . A paint set comprising the water-soluble sheet-like coloring material according to any one of claims 1 to 6 and a brush.