JP2004339463A - Colorant for clay, and aqueous hardenable colored clay using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prevent a colorant from being eluted into water, when it is included in an aqueous hardenable colored synthetic clay. <P>SOLUTION: The colorant for clay is obtained by the followings: a pigment, an oil-soluble dye fine powder or a process color prepared by processing them, is blended with a resin, the resultant blend is melt-kneaded by heating, and after the obtained kneaded product is cooled and pulverized into colored fine resin particles, the particles are classified so as to obtain those having diameters of ≥1.15 μm, or are homogeneously kneaded with a water-insoluble high boiling point non-volatile liquid, or with a semi-solid. The safe and chromatic colored aqueous hardenable colored clay, is obtained by using the colorant, fully satisfying an elution test in water according to the self-regulation standard by The Japan Toy Association, (ST mark authorization standard). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a technique for coloring modeling clay used for handicrafts, school teaching materials, toys, and the like, and is particularly effective when applied to prevent water from dissolving a colorant.

  BACKGROUND ART Conventionally, various synthetic clays, including natural clays, have been used as modeling clays used for handicrafts, school teaching materials, toys, and the like. Among them, water-based curable synthetic clays are preferably used because they harden sufficiently in a dried state after shaping and have good shape retention after shaping.

  As a coloring method of such an aqueous setting type clay, a method of dyeing a non-colored (white) so-called achromatic clay, or a method of using an aqueous dispersion of a coloring agent has been adopted (for example, Patent Document 1, 2, 3, 4, 5).

  In addition, a synthetic resin powder is mixed in the presence of water with an aqueous emulsion of an organic or inorganic pigment and a self-crosslinkable acrylic resin as a crosslinker, and the resulting synthetic resin gel is dried and pulverized to obtain a pigment-coloring composition. A method for producing a colored clay without color transfer using a resin powder has also been proposed (for example, see Patent Document 6).

On the other hand, the Food Sanitation Law was enacted in 1948 with regard to plastic clay used for handicrafts, school teaching materials, toys, etc., including water-curable colored synthetic clay. Therefore, efforts are being made to conform to the self-regulation standards (ST mark recognition standards) of the Japan Toy Association, which was established with the intent.
JP-B-47-16421 (page 1, right column, lines 7 to 29) JP-B-48-19379 (page 1, right column, lines 8 to 18) JP-B-54-3184 (page 1, right column, line 36 to page 2, left column, line 13) JP-A-54-153826 (page 11, lower left column, lines 11 to 15) JP 2001-202004 A (paragraph number [0011]) JP-A-1-285982 (page 3, line 7 to page 4, line 1)

  However, there is no water-based curable colored clay currently on the market that has the “ST mark” labeling that has been approved for safety and health by the Japan Toy Association voluntary regulation standards (ST mark certification standards). Colored (white) uncolored water-based curable colored synthetic clay, and chromatic colors, even if water elution is observed, there are products that have obtained the ST mark using legal food dyes because they are safe because they are safe. However, as the color density increases, the color shifts to the hands violently in the work, making it unsuitable for molding.At any color density, chromatic aqueous curing with no color elution at all No mold-colored synthetic clay compositions are known.

  In other words, the current water-based curable colored synthetic clay composition clears the restriction that the color in the voluntary regulation standard (ST mark certification standard) determined by the Japan Toy Association must not be eluted in water. In fact, it is not possible to receive ST mark certification easily.

  As described above, a raw inorganic pigment or an organic pigment, or a processed pigment obtained by easily dispersing the raw inorganic pigment or the organic pigment with a powder dispersing aid, or a water-dispersed processing colorant thereof, as described above, is used for coloring the aqueous curable colored synthetic clay. However, since the water-soluble dye used for the dyeing technique or the legal food color is used, a clear color elution to water is clearly observed.

  On the other hand, as a method for eliminating water elution of such a color, a non-aqueous colored piece having a large particle size is uniformly kneaded with an achromatic (white) non-colored water-based curable synthetic clay, which is commercially available. In such commodities, the particle size of the non-aqueous colored pieces is large, a uniform colored state cannot be obtained in the clay, and a so-called different-color dotted pattern in which the colored portions are dotted with the ground color of the clay results.

  Further, as described in Patent Document 6, it is considered that the dissolution property of the pigment into water is suppressed by the inclusion of the pigment by a transparent resin that is microscopically bound in a network. The present inventors considered that the conditions described in the gazette alone were not enough to satisfy the gist of the sex test, and that other conditions were necessary.

  As described above, the conventional or current water-based curable colored synthetic clay composition has a problem of water elution of the used colorant, or a problem of safety and hygiene of a dyeing aid when a dyeing method is used. However, when the processing colorant used has no water elution property, problems such as insufficient uniform coloring property have not been solved.

  An object of the present invention is to prevent a water-eluting property of a colorant in a water-based curable colored clay.

  The present inventors have conducted intensive studies in view of the above problems and found the following solution.

  In the present invention, a pigment obtained by dispersing a pigment in a water-insoluble medium, or a colored substance obtained by dissolving and dispersing an oil-soluble dye in a water-insoluble medium, in the form of fine powder, or fine particles, or liquid, Alternatively, by forming the pigment or oil-soluble dye in a semi-solid state, the dissolution of the pigment or oil-soluble dye into water is suppressed, and a clay colorant that can be mixed with clay is obtained.

  In addition, when used in the form of fine powder or fine particles, the particle size falls within the specified range to achieve uniform colorability and self-regulation standards (ST mark certification standards) determined by the Japan Toy Association. The requirement that a certain color "must not elute in water" could be satisfied.

  That is, the present invention is a colorant used for coloring clay, wherein the colorant is obtained by mixing a fine powder of either a pigment or an oil-soluble dye with a resin, heat-melting and kneading, and then heating and melting the mixture. It is characterized in that it is fine particles of a colored resin obtained by cooling and kneading the kneaded material.

  In the above configuration, the fine powder or fine particles of the colored resin have a particle size of 500 microns or less and are used in a water dissolution test according to a voluntary regulation standard (ST mark certification standard) determined by the Japan Toy Association. The size of the filter paper is larger than that of the filter paper. In this configuration, the particle size larger than the mesh of the filter paper is at least 1.15 microns.

  Another invention is a coloring agent used for coloring clay, wherein the coloring agent is a water-insoluble high-boiling nonvolatile liquid or a water-insoluble semi-solid containing fine powder of a pigment. I do.

  In any one of the above structures, the fine particles of the pigment or the oil-soluble dye are contained in the clay colorant in an amount of 0.05% by weight or more and 70% by weight or less.

  In any one of the above configurations, the pigment or oil-soluble dye contained in the colorant for clay is selected from a product on a self-regulation standard coloring material positive list defined by the Sanitation Council such as polyolefin. And

  However, this does not apply even if there is no data on the safety and hygiene of various types of colorants to be used, even if they are not described in the positive list of self-regulation color materials of the Polyolefin Sanitation Council.

  Another aspect of the present invention is a water-based curable colored clay, wherein the clay colorant having any one of the above structures is mixed with the water-based curable clay.

  According to the present invention, it is possible to prevent the water-eluting property of the clay colorant in the water-based curable colored synthetic clay.

  At the same time, by regulating the particle size of the colorant for clay, a safe chromatic water system that can sufficiently satisfy the water dissolution test defined by the voluntary regulation standard of the Japan Toy Association (ST mark certification standard). A curable colored clay can be provided.

  Hereinafter, embodiments of the present invention will be described in detail. The present invention provides a colored substance obtained by dispersing a pigment in a water-insoluble medium, or dissolving and dispersing an oil-soluble dye in a water-insoluble medium, in the form of fine particles, liquid, or semi-solid. It is a colorant for clay that is mixed with water-based curable clay.

  Another aspect of the present invention is a water-based curable colored clay produced using such a coloring agent for clay, which has a color defined by a voluntary regulation standard (ST mark certification standard) determined by the Japan Toy Association. Do not dissolve in water. "

(Embodiment 1)
In the present embodiment, a pigment obtained by dispersing a pigment in a water-insoluble medium or dissolving and dispersing an oil-soluble dye in a water-insoluble medium is used in the form of fine particles mixed with an aqueous curable clay. A coloring agent for clay and a water-based curable coloring clay using the coloring agent will be described.

  That is, the clay colorant described in the present embodiment is obtained by selecting a fine powder of either a pigment or an oil-soluble dye, a resin as a water-insoluble medium, mixing with the resin, and heat-melting and kneading. These are fine particles of a colored resin obtained by pulverizing the heated, melt-kneaded colored product in a state cooled to a pulverizable temperature.

  As the pigment, any of an inorganic pigment and an organic pigment can be used. The fine powder of these pigments or oil-soluble dyes may be used directly as they are, or the fine powder may be easily dispersed with a dispersing aid, a surfactant or the like to obtain a dry color, a wet color, if necessary. Can be used as a process color obtained by processing a paste color, a liquid color, or the like.

  In particular, when considering the safety and health based on the coloring of the water-based curable colored clay, the pigment or oil-soluble dye to be contained in the colorant should be selected from the products listed in the Self-Regulatory Standard Coloring Material Positive List determined by the Hygiene Council such as Polyolefin. What is necessary is just to make it select.

  In addition, if there is data without any problem in safety and health, it may be used even if it is not described in the self-regulation standard color material positive list of the Polyolefin and Other Health Council.

  In addition, as a dispersant or a dispersing agent for dispersing a pigment or an oil-soluble dye in a resin, fatty acids and derivatives thereof, metal salts of fatty acids, amide-based, paraffin-based or wax-based lubricants, nonionic (amphoteric, Nonionic or anionic surfactants, and plasticizers, vegetable oils, mineral oils, synthetic oils, and in some cases, greases, oily high-boiling nonvolatile liquids insoluble in water such as glycerin, or semisolids. .

  As the resin, any of a thermoplastic resin, a rubber, and a thermosetting resin can be used.

  For example, as the thermoplastic resin, polyolefin-based or polystyrene-based resin, polymethacrylic, polymethylpentene, polybutene, polybutadiene, polyvinylidene chloride, polyamide, polyethylene terephthalate, polycarbonate, poval, polyacetal, polyphenylene ether, polyacrylonitrile, fluorine Resin, polybutylene terephthalate, polymethacryl styrene, polyallylsulfone, polyarylate, hydroxybenzoic acid polyester, polyetherimide, polyethylene naphthol, polycyclohexylene dimethylene terephthalate, polyester carbonate, polyvinyl chloride, polyvinyl butyral, maleic acid , Rosin, glue, petroleum, terpene, polyvinyl acetate, polyvinyl formal, poly Various resins such as vinyl chloride, chlorinated polyether, impact-resistant acrylic, polyacrylic α-methylstyrene, ethylcellulose, cellulose acetate, propylcellulose, cellulose acetate / butyrate, cellulose nitrate, polyurethane, coumarone, indene, and modifications thereof. It may be selected from copolymer derivatives and the like.

  It is not necessary to limit the polymerization method of such a resin. For example, a resin obtained by a suspension polymerization method or the like and a resin formed by solidification of an emulsion are naturally included in the category of the resin according to the present invention.

  Examples of the rubber include natural rubber, synthetic natural rubber, chlorinated polyethylene, epichlorohydrin, nitrile, nitrile isoprene, isoprene, urethane, polysulfide rubber, silicone rubber, fluorine rubber, acrylic rubber, butadiene, styrene butadiene, butyl, and ethylene propylene. , Ethylene-vinyl acetate copolymer, chloroprene, chlorosulfonated polyethylene, and other rubbers, and modified derivatives thereof.

  Examples of the thermosetting resin include phenol resins, formaldehyde resins, urea resins, melamine formaldehyde resins, epoxy resins, furan resins, xylene resins, unsaturated polyester (alkyd) resins, silicone resins, diallyl phthalate resins, and the like. What is necessary is just to select from these modified derivatives.

  In addition, a resin having a three-dimensional structure obtained by cross-linking polymerization in the production of a thermoplastic resin, a resin obtained by a suspension polymerization method or the like, or an emulsion type, a two-part mixed type, and a polymerization agent were used in combination with a cross-linking agent. Resins and the like are also included in the category of the thermosetting resin.

  As the crosslinking agent, for example, diamines such as ethylenediamine and cyclic aliphatic polyamine, polyamines, liquid polyamide resin, phenol novolak resin, anhydride, phenol resin, etherified esterified amino resin and the like can be used.

  Such a resin and the fine powder of the pigment or the oil-soluble dye described above are uniformly heated and kneaded or uniformly mixed and thermoformed, and a resin containing the pigment or the oil-soluble dye at a high concentration is pulverized at a crushable temperature ( If cooled to room temperature, for example, and then finely pulverized, the obtained fine-particle colored resin becomes a colorant for clay called a processing colorant (master batch powder). In the case of fine pulverization, pulverization cost is required, but freeze pulverization may be employed.

  However, when an oil-soluble dye is used, it causes bleeding or migration. Therefore, the above-mentioned oil-soluble dye is used for a crystalline thermoplastic resin, rubber, or a high-boiling nonvolatile liquid and a semi-solid described in Embodiment 2. do not do.

  The fine-particle clay colorant described in the present embodiment is a machine for uniformly dispersing a raw pigment or an oil-soluble dye in a resin or rubber by strong mechanical kneading and mechanical pulverization (including freezing pulverization). It will be manufactured by a conventional means.

  That is, a thermoplastic resin or rubber, or a thermosetting resin, an inorganic pigment, an organic pigment, or an oil-soluble dye, or these pigments, a process color obtained by processing the oil-soluble dye, a ball mill, a tumbler, Mechanically and uniformly mixed with a Despar, Supermixer, Hensel type mixer, etc.

  In such mixing, the fine powder of the pigment or the oil-soluble dye may be mixed so as to be 0.05% by weight or more and 70% by weight or less of the colorant for clay.

  In the configuration of the aqueous curable colored clay of the present invention, the coloring agent for the clay is mixed with the aqueous curable clay in a predetermined amount to create a colored state. , A certain degree of density is required.

  On the other hand, the colorant for clay of the present invention is prepared by mixing a pigment or an oil-soluble dye into a resin so as to prevent the pigment or the oil-soluble dye from being eluted into water. Somewhat must be secured.

  That is, if the amount is less than 0.05% by weight, the coloring property of the water-based curable clay obtained by mixing the coloring agent for clay of the present invention may not be sufficiently ensured. There is a possibility that the pigment or oil-soluble dye used in the colorant for clay is eluted with water. Therefore, from such a viewpoint, it is preferable to set the content to 0.05% by weight or more and 70% by weight or less. More preferably, it should be 1% by weight or more and 50% by weight or less.

  After uniform mixing in this way, for example, heat and knead with a Banbury mixer, a twin-screw extruder, a single-screw extruder, a pressure-type kneader, an open-type kneader, two rolls, three rolls, and the like, and then to room temperature. If it is cooled, if it has a tendency to block, uniformly mix an appropriate amount of an anti-blocking agent (external lubricant), treat it with a pulverizer (freezing and pulverization if necessary), and then dry to obtain the desired fine particles. Is obtained.

  With the clay colorant having the above structure, the color does not elute in water. However, the present inventors have noticed that such a treatment alone is not enough to clear the water dissolution test of the voluntary regulation standard (ST mark certification standard) determined by the Japan Toy Association. That is, in the dissolution test, it is required that the filtrate filtered through a filter paper having a predetermined mesh has no color.

Incidentally, the water dissolution test of the self-regulation standard (ST mark certification standard) defined by the Japan Toy Association is defined as follows. That is, 2 ml of warm water at 40 ° C. was added per 1 cm ² of the surface area, and the sample was immersed for 10 minutes while maintaining the temperature at 40 ° C., and then filtered through Advantech No. 5C filter paper. Is determined.

  Certainly, even if the clay colorant of the present invention is used, unlike the conventional product, the phenomenon that the color is eluted in water can be prevented, but the fine particles of the clay colorant dispersed in the filtrate pass through the filter paper together with the filtrate. It is possible. The present inventors have sought to more strictly prevent such a colorant from passing through the filter paper.

  Therefore, the present inventors have proposed that the particle size of the colorant for clay be larger than the size of the filter paper used in the test. In this way, no coloring phenomenon occurs in the water passing through the filter paper.

  That is, at the time of fine pulverization, the particle size of the colorant for clay produced by the fine pulverization is determined by a filter paper used for a water dissolution test according to the voluntary regulation standard (ST mark certification standard) determined by the Japan Toy Association. The particle size was set so as not to pass through.

  According to the current standard, since the size of the filter paper is set to 1 micron, the particle size of the colored resin should be larger than 1 micron. It has been found that setting the particle size to 1.15 microns or more is sufficient to prevent the clay colorant from mixing with the filtrate passing through the filter paper.

  On the other hand, when the coloring agent for clay is mixed with the water-based curable clay, if the particles of the coloring resin, which is the coloring agent for clay, are coarse, the resin particles in the clay are conspicuous, and the appearance of the coloring is sufficiently uniform. May not be possible. Therefore, as a result of the experiment, it was found that the range in which the uniformity of the coloring can be obtained should be 500 microns or less.

  Therefore, if the color resin finely pulverized in the above manner is further classified so that the particle size falls within a range of 1.15 μm or more and 500 μm or less, the self-regulation standard (Japan Toy Association) A colorant for a clay which satisfies the standard of the water dissolution test (ST mark certification standard) and which can be used for a water-based curable colored clay that ensures uniform coloring is obtained.

  Further, the aqueous curable colored clay of the present invention can be produced by mixing the above-described colorant for clay with the aqueous curable clay. As the water-curable clay, those having various features have been marketed or devised. As typical examples, three water-curable synthetic clays whose compositions are shown in Table 1 can be mentioned. Can be.

  The water-based curable synthetic clay shown as composition 1 shown in Table 1 is composed of 10 parts by weight of a water-soluble resin, 30 parts by weight of starch, 10 parts by weight of a fiber material, 5 parts by weight of a filler, and 51 parts by weight of water. Consists of

  More specifically, a copolymer of a hydrophobic resin and Poval (registered trademark HV polymer) is used as a water-soluble resin as a sizing agent. As the starch, for example, any starchy substance such as wheat flour can be used. Above all, corn starch is preferred in order to obtain the fineness of the clay and the whiteness of the skin.

  As the fiber material, for example, pulp is used. For example, talc is used as the filler. In addition to inorganic powder such as talc, in order to reduce the weight of the entire clay, a porous body such as a shirasu balloon or a foamed spherical fine particle such as expanded polystyrene may be used.

  In the water-based curable synthetic clay having such a composition, the specific gravity is reduced by replacing the filler with an inorganic non-foamed material such as talc by a shirasu balloon or a foamed fine spherical (or pulverized product) resin, thereby reducing the specific gravity after molding. A water-based hardening synthetic clay with a fine skin texture and moderate softness and a white skin color.

  It is not necessary to limit the mixing ratio of the water-based curable synthetic clay to the mixing ratio shown in Table 1, and the mixing ratio can be appropriately adjusted as needed within the following range. That is, the amount of the water-soluble resin is 1 to 20 parts by weight, preferably 0.2 to 3 parts by weight of polyethylene oxide, 4 to 60 parts by weight of starch, 1 to 20 parts by weight of the fiber material, the remainder being water, or the rest being water and What is necessary is just to make it a porous material.

  For example, a mixing ratio such as 10 parts by weight of a water-soluble resin, 25 parts by weight of starch, 10 parts by weight of a fiber material, 5 parts by weight of a shirasu balloon, and 50 parts by weight of water is exemplified. Alternatively, a mixing ratio such as 10 parts by weight of a water-soluble resin, 25 parts by weight of starch, 10 parts by weight of a fiber material, and 5 parts by weight of a fine spherical foamed resin is also a preferred example.

  The water-based curable synthetic clay shown as composition 2 shown in Table 1 was composed of 11.2 parts by weight of a water-soluble resin, 2 parts by weight of starch, 8 parts by weight of a fiber material, 16 parts by weight of a microsphere hollow resin, and glycerin. 5 parts by weight, 5 parts by weight of machine oil, and 44.8 parts by weight of water.

  More specifically, carboxymethyl cellulose (abbreviated as CMC) and polyvinyl alcohol (abbreviated as PVA) may be used as the water-soluble resin. As such CMC, the degree of etherification is 1.0 or more, and the viscosity of a 1% aqueous solution at 25 ° C. is 700 mPa.s. s. As PVA, a partially saponified polyvinyl acetate having a saponification degree of 88 mol% was used. In addition, 1.2 parts by weight of PVA was used.

  Gelatinized starch was used as the starch. Powder pulp was used as the fiber material. The microsphere hollow resin is a lightweight micromaterial of a hollow microsphere in which gas is included in particles. Generally, the outer shell is a vinylidene chloride-acrylonitrile copolymer having a particle size of 20 to 150 microns and a bulk density of 0.02.

  The water-based curable synthetic clay having such a composition is lightweight, has a white color, has appropriate hardness and easiness of elongation, has appropriate fragility, and is less sticky.

  The resin forming the outer shell may be a vinyl acetate-acrylonitrile copolymer resin, a methyl methacrylate-acrylonitrile copolymer resin, or the like. Further, the ratio between CMC and PVA can be appropriately adjusted in a weight ratio of 10: 0.5 to 10: 3.

  The water-based curable synthetic clay shown as composition 3 in Table 1 contains 10 parts by weight of polyvinyl alcohol (abbreviated as PVA), 1 part by weight of polyethylene oxide (abbreviated as PEO), and 6 parts by weight of a vinyl acetate resin emulsion as a water-soluble resin. , 14 parts by weight of micro spherical hollow resin, 4 parts by weight of fiber material, 3 parts by weight of nonionic surfactant, and 62 parts by weight of water.

  More specifically, PVA was a partially saponified polyvinyl acetate having a saponification degree of 88 mol% and a 3% aqueous solution having a viscosity at 20 ° C. of 850 mPa · s. As the PEO, a ring-opened polymer of ethylene oxide having an average molecular weight of 700,000 was used. As the vinyl acetate resin emulsion, Polysol S-6 manufactured by Showa Kogaku Co., Ltd. was used (the amount used is indicated by the solid content).

  Powder pulp was used as the fiber material. As the nonionic surfactant, a polyoxyethylene alkyl ether having an HLB of 10.0 to 18.9 was used. Microsphere F-50E manufactured by Matsumoto Yushi Co., Ltd. was used as the micro hollow spherical resin (the amount used is indicated by the solid content).

  It is not necessary to limit the mixing ratio of the water-based curable synthetic clay to the mixing ratio shown in Table 1, and the mixing ratio can be appropriately adjusted as needed.

  For example, 5 to 10 parts by weight of PVA, 0.5 to 1.5 parts by weight of PEO, 1.5 to 7 parts by weight of a vinyl acetate resin emulsion, 0.5 to 4 parts by weight of a fiber material, 5 to 15 parts by weight of fine spherical hollow resin, The blending ratio may be appropriately adjusted as necessary, using 2 to 8 parts by weight of the nonionic surfactant and the remainder as water or water and a humectant such as liquid paraffin, sorbitol, and glycols.

  The water-based curable synthetic clay having such a composition is excellent in deformation durability during curing, good in workability and feel, and lightweight.

  In this way, by mixing the required amount of the clay colorant described above with the achromatic water-based curable synthetic clay having the above composition, a chromatic water-based curable synthetic clay composition can be produced. The mixing amount of the clay colorant may be an appropriate amount so that the required color strength is produced in the water-based curable colored synthetic clay.

  Note that any method may be adopted as a method of polymerizing the resin used in the present embodiment. For example, when an emulsion type (one-pack type) is used as the resin base material, the emulsion, the above-described process color, and if necessary, other additives exemplified by a nonionic surfactant, a crosslinking agent, and the like are mixed. After uniformly mixing with a machine, the mixture is heat-molded and solidified, and then mechanically pulverized to obtain a desired fine powdery colorant for clay.

  Alternatively, when a two-liquid mixture type is used as the resin base material, the above-mentioned process color and other additives such as a nonionic surfactant are uniformly mixed with the larger amount of the solution using a mixer. Thereafter, the remaining solution and a polymerization initiator (curing agent) are added, and the mixture is further homogeneously mixed. Thereafter, the mixture is solidified by heat molding, and then mechanically pulverized to obtain a desired fine particle colorant for clay.

  When a cross-linking agent is contained in the solution, the resin has a three-dimensional network structure, and thus becomes a clay colorant using a thermosetting resin.

(Embodiment 2)
In the present embodiment, a liquid or semi-solid colored substance obtained by dispersing a pigment in a water-insoluble medium or kneading with a water-insoluble medium is used for mixing and using a water-based curable clay. A coloring agent and a water-based curable colored clay using the coloring agent will be described.

  In the first embodiment, the use form of the clay colorant is solid, but in the present embodiment, the colorant is provided as a liquid or a semi-solid.

  That is, when the same fine powder of an inorganic pigment or an organic pigment as described in the first embodiment is easily dispersed with a surfactant or the like and processed into a paste color or a liquid color, a paste color medium or A liquid clay coloring agent can be obtained by uniformly kneading and dispersing a water-insoluble high-boiling nonvolatile liquid in a liquid coloring medium.

  Alternatively, if a semi-solid such as grease or solid wax is selected as the paste coloring medium or the liquid coloring medium, a so-called semi-solid colorant for clay can be obtained.

  That is, the raw pigment is insoluble in water in a high-boiling non-volatile liquid, or semi-solid, if necessary, using a dispersing aid and a surfactant together, and premixed with a Leica machine or open-type kneader. What is necessary is just to knead and disperse mechanically uniformly with three rolls.

  The water-based curable colored clay can be manufactured by mixing the clay-based colorant having such a configuration with the water-based curable synthetic clay in the same manner as in the first embodiment. In particular, in the water-based curable colored synthetic clay of the present embodiment, since the clay colorant is formed in a liquid state or a semi-solid state, relatively uniform coloring can be obtained as compared with fine powder or fine particles. The time required for kneading can be shortened, and a water-based curable synthetic clay having a smooth touch can be easily produced.

  The pigment may be blended so as to be 0.05% by weight or more and 70% by weight or less based on the colorant for clay. More preferably, the content is 1% by weight or more and 50% by weight or less. Since the form of the colorant for the clay is liquid, paste-like, and semi-solid, the particle diameter is hard to specifically determine its range, but since it is dispersed with the particle size of the pigment before being used as the colorant for the clay, The coloring power is superior to that of the first embodiment.

  Hereinafter, the present invention described in the above embodiment will be more specifically shown by representative examples, and the effectiveness of the present invention will be verified by comparing the present invention with comparative examples.

  The clay colorant described in the first embodiment is the clay colorant described in the first embodiment, and a resin is selected by using a fine powder of a pigment or an oil-soluble dye as a water-insoluble medium. These are fine particles of a colored resin obtained by pulverizing the heat-melt-kneaded colored material obtained by mixing with this resin and heat-melting and kneading, while cooling to a crushable temperature.

  Such a colorant for clay was produced as follows. That is, 100 parts by weight of a low-density polyethylene having a melt flow rate of 30 g / mm, a Vicat softening point of 83 ° C., a melting point of 105 ° C., and an average particle diameter of 190 μm, and a color index number pigment yellow 83 (manufactured by Sanyo Dyeing Co., Ltd. 50 parts by weight of a yellow organic pigment (trade name: Pigment yellow IRC) and 10 parts by weight of a zinc stearate powder as a pigment dispersing aid with respect to the pigment were uniformly mixed by a Hensell type mixer.

  Thereafter, the mixture was kneaded with a pressure kneader at a resin temperature of 130 ° C. until the resin became uniform. After kneading, the mixture was pulverized while gradually cooling to obtain a coarsely pulverized processed colorant.

  The coarsely pulverized product thus obtained was further finely pulverized by a powerful refrigeration pulverizer (refrigerant, liquid nitrogen). At the time of pulverization, 1 part by weight of the fine zinc stearate powder was externally lubricated in order to prevent reaggregation. The resulting mixture was further classified to obtain a fine colorant for clay having a particle size of 10 to 50 microns.

  10 parts by weight of the yellow colorant for clay is kneaded with the three types of water-based curable clays of Compositions 1, 2, and 3 described in the first embodiment with respect to the total amount shown in Table 1, and then water-cured. Mold-colored synthetic clay was produced.

  Each of the water-based curable colored synthetic clays thus obtained was subjected to a water dissolution test according to the voluntary regulation standard (ST mark certification standard) defined by the Japan Toy Association described in the first embodiment, and the results were obtained. Are shown in Table 2. No coloring was observed in the filtrate, and no water-eluting property of the clay colorant was observed.

  The water dissolution test was performed as follows. The aqueous curable colored synthetic clay according to the present invention in the form of a plate having a size of 50 mm x 50 mm x 1 mm is put into a beaker, 50 ml of warm water at 40 ° C is added and immersed, and a dissolution test at 40 ° C for 10 minutes on a water bath. Was done. Thereafter, the mixture was filtered through Advantech No. 5C filter paper, and evaluated by visual colorimetry.

  The clay colorant described in the second embodiment is the clay colorant described in the first embodiment, and a resin is used as a non-water-soluble medium by using a fine powder of a pigment or an oil-soluble dye. Colored resin fine particles are obtained by mixing with this resin, heating and melting and kneading, and then pulverizing the heat-melt-kneaded colored product obtained by cooling to a temperature at which pulverization is possible.

  Such a colorant for clay was produced as follows. That is, 100 parts by weight of a spherical polymethyl methacrylate having a molecular weight of 80 to 1,000,000, a glass transition point of 130 ° C., a melting point of 150 ° C., and an average particle diameter of 20 μm, and a color index number pigment blue 15-3 (manufactured by Sanyo Dyeing Co., Ltd.) , Cyanine Blue KRO), and 30 parts by weight of an ethylene bis-stearamide powder as a pigment dispersing aid and 10 parts by weight of the pigment were uniformly mixed with a Hensel type mixer.

  After uniform mixing, the mixture was kneaded with a pressure type kneader at a resin temperature of 170 ° C. until uniform, and then gradually cooled and pulverized to obtain a coarse pulverized processing colorant.

  The coarsely pulverized material thus obtained was finely pulverized by a powerful refrigeration pulverizer (refrigerant, liquid nitrogen). At the time of pulverization, 1 part by weight of the ethylene bisstearomide fine powder was externally lubricated in order to prevent reaggregation. It was further classified to obtain a clay colorant having a particle size of 10 to 50 microns.

  10 parts by weight of the blue colorant for clay is kneaded with the three types of water-based curable clays of compositions 1, 2, and 3 described in the first embodiment with respect to the total amount shown in Table 1, and then water-cured. Mold-colored synthetic clay was produced.

  Each of the water-based curable colored synthetic clays thus obtained was subjected to a water dissolution test according to the voluntary regulation standard (ST mark certification standard) defined by the Japan Toy Association described in the first embodiment, and the results were obtained. Are shown in Table 2. No coloring was observed in the filtrate, and no water-eluting property of the clay colorant was observed.

  The clay colorant described in the third embodiment is the clay colorant described in the first embodiment, and a resin is selected by using a fine powder of either a pigment or an oil-soluble dye as a water-insoluble medium. Colored resin fine particles are obtained by mixing with this resin, heating and melting and kneading, and then pulverizing the heat-melt-kneaded colored product obtained by cooling to a temperature at which pulverization is possible.

  Such a colorant for clay was produced as follows. That is, a water-based emulsion paint styrene methyl methacrylate copolymer (polystyrene content 90%, polymethyl methacrylate 10%) used as a clear top, having a solid content of 45% and a viscosity of 3000 mPa · s / 30 ° C. 100 parts by weight of melt flowrete, 100 parts by weight, 15 parts by weight of a yellow inorganic pigment of Color Index Number Pigment Yellow 53 (manufactured by Ishihara Sangyo Co., Ltd., Tipaque Yellow TY-70S), and polyoxyethylene as a nonionic surfactant 2 parts by weight of lauryl ether (HLB = 10.5) and 5 parts by weight of ethylenebisstearamide were uniformly kneaded in an open kneader at room temperature with respect to the pigment. Thereafter, the mixture was heated to 180 ° C. to evaporate water to complete the polymerization, and then gradually cooled and pulverized to obtain a coarsely pulverized processed colorant.

  The coarsely pulverized product thus obtained was pulverized and classified in the same manner as in Example 2 to produce a yellow colorant for clay having a particle size of 10 to 50 microns. During the pulverization, 1 part by weight of ethylene bis stearamide was externally lubricated to prevent reaggregation.

  10 parts by weight of the yellow colorant for clay is kneaded with the three types of water-based curable clays of Compositions 1, 2, and 3 described in the first embodiment with respect to the total amount shown in Table 1, and then water-cured. Mold-colored synthetic clay was produced.

  Each of the water-based curable colored synthetic clays thus obtained was subjected to a water dissolution test according to the voluntary regulation standard (ST mark certification standard) defined by the Japan Toy Association described in the first embodiment, and the results were obtained. Are shown in Table 2. No coloring was observed in the filtrate, and no water-eluting property of the clay colorant was observed.

  The clay colorant described in the fourth embodiment is the clay colorant described in the first embodiment, and a resin is selected by using a fine powder of either a pigment or an oil-soluble dye as a water-insoluble medium. Colored resin fine particles obtained by mixing with this resin, heat-softening and melting, and pulverizing the heat-softened and melted colored product obtained by cooling to a crushable temperature.

Such a colorant for clay was produced as follows. That is, to 100 parts by weight of powdery urea resin (RIKEN UP, registered trademark), 15 parts by weight of color furnace carbon black of Color Index Number Pigment Black 10 (Carbon ^# 45, manufactured by Mitsubishi Chemical Corporation) are uniformly mixed with a Hensel type mixer. Mixed. Thereafter, thermoforming was performed at a compression molding temperature of 170 ° C. and a compression molding pressure of 140 to 500 kg / cm ² , and after cooling, a plate-like molded product that was easily crushed was obtained.

  The thus obtained molded product is finely pulverized by a powerful refrigeration pulverizer (refrigerant, liquid nitrogen). In the fine pulverization, 1 part by weight of ethylene bis stearamide fine powder is used in order to prevent reaggregation. Was externally lubricated. It was further classified to produce a clay colorant having a particle size of 10 to 50 microns.

  20 parts by weight of such a black colorant for clay is kneaded with the three types of water-curable clays of compositions 1, 2, and 3 described in the first embodiment, and 20 parts by weight of the total amount shown in Table 1 is kneaded. Mold-colored synthetic clay was produced.

  Each of the water-based curable colored synthetic clays thus obtained was subjected to a water dissolution test according to the voluntary regulation standard (ST mark certification standard) defined by the Japan Toy Association described in the first embodiment, and the results were obtained. Are shown in Table 2. No coloring was observed in the filtrate, and no water-eluting property of the colorant for clay was observed.

  The clay colorant described in the fifth embodiment is the clay colorant described in the first embodiment, and a resin is selected from a fine powder of a pigment or an oil-soluble dye and a water-insoluble medium. Colored resin fine particles are obtained by mixing with this resin, heating and melting and kneading, and then pulverizing the heat-melt-kneaded colored product obtained by cooling to a temperature at which pulverization is possible.

  Such a colorant for clay was produced as follows. That is, 20 parts by weight of a green organic pigment of Color Index Number Pigment Green 36 (manufactured by BASF, Heliogen Green 8GA) and 20 parts by weight of rosin with respect to 100 parts by weight of granular styrene-butadiene synthetic rubber (Tafprene (registered trademark)) Were uniformly mixed with a Hensel type mixer. Thereafter, the mixture was kneaded with a pressure kneader at a temperature of 130 ° C. until uniform, and then gradually cooled and pulverized to obtain a coarse pulverized processed colorant.

  The coarsely pulverized material thus obtained is finely pulverized by a powerful refrigeration pulverizer (refrigerant, liquid nitrogen), and in the case of fine pulverization, 1 part by weight of magnesium stearate fine powder is added to prevent reaggregation. External lubrication. It was further classified to obtain a clay colorant having a particle size of 10 to 50 microns.

  15 parts by weight of the green colorant for clay is kneaded with the three types of water-based curable clays of compositions 1, 2, and 3 described in the first embodiment with respect to the total amount shown in Table 1, and then water-cured. Mold-colored synthetic clay was produced.

  Each of the water-based curable colored synthetic clays thus obtained was subjected to a water dissolution test according to the voluntary regulation standard (ST mark certification standard) defined by the Japan Toy Association described in the first embodiment, and the results were obtained. Are shown in Table 2. No coloring was observed in the filtrate, and no water-eluting property of the clay colorant was observed.

  The clay colorant of the sixth embodiment is the clay colorant described in the second embodiment, and is obtained by dispersing a pigment in a water-insoluble high-boiling nonvolatile liquid or a water-insoluble semi-solid. Liquid or semi-solid clay colorant.

  Such a colorant for clay was produced as follows. That is, 50 parts by weight of liquid paraffin, 35 parts by weight of a red organic pigment of Color Index Number Pigment Red 149 (manufactured by Hoechst, PV Fast Red B), and sorbitan monooleate (HLB = 4.3) as a pigment dispersion aid 3 parts by weight of the nonionic surfactant with respect to the pigment were uniformly mixed with an open kneader, and then uniformly dispersed and kneaded with three rolls to obtain a paste (liquid) colorant for clay.

  5 parts by weight of the red colorant for clay is kneaded with the three types of water-curable clays of Compositions 1, 2 and 3 described in the first embodiment with respect to the total amount shown in Table 1, and then water-cured. Mold-colored synthetic clay was produced.

  Each of the water-based curable colored synthetic clays thus obtained was subjected to a water dissolution test according to the voluntary regulation standard (ST mark certification standard) defined by the Japan Toy Association described in the first embodiment, and the results were obtained. Are shown in Table 2. No coloring was observed in the filtrate, and no water-eluting property of the clay colorant was observed.

(Comparative Example 1)
In Comparative Example 1, for comparison with the clay colorants according to the present invention in Examples 1 to 6, the case where the clay colorant is a water dispersion of a pigment is shown.

  That is, 80 parts by weight of water, 17 parts by weight of a red organic pigment of Color Index Number Pigment Red 238 (manufactured by Sanyo Dyestuffs Co., Permanent Carmine F5B), 2 parts by weight of polyoxyethylene lauryl ether (HLB = 10.5), and dialkyl sulfo succinate One part by weight of sodium phosphate (solid content 70%) was uniformly dispersed and mixed by a ball mill to obtain an aqueous dispersion of a red organic pigment as a colorant for clay.

  15 parts by weight of the red colorant is added to the three types of water-based curable clays of Compositions 1, 2, and 3 described in the first embodiment, and 15 parts by weight based on the total amount shown in Table 1, and the mixture is subjected to an open kneader. By uniformly kneading, a water-based curable colored synthetic clay uniformly colored was produced.

  Each of the water-based curable colored synthetic clays thus obtained was subjected to a water dissolution test according to the voluntary regulation standard (ST mark certification standard) defined by the Japan Toy Association described in the first embodiment, and the results were obtained. Are shown in Table 2. The filtrate was colored, and the water dissolution property of the colorant was clearly observed.

(Comparative Example 2)
Similar to Comparative Example 1, Comparative Example 2 also shows a case where the clay colorant is an aqueous dispersion of a pigment.

  That is, 80 parts by weight of water, 15 parts by weight of a yellow organic pigment of Color Index Number Pigment Yellow 151 (Symuler Fast Yellow 4GO, manufactured by Dainippon Ink and Chemicals, Inc.), and 3 parts by weight of polyoxyethylene lauryl ether (HLB = 10.5) And 2 parts by weight of sodium dialkyl sulfosuccinate (solid content 70%) were uniformly dispersed and mixed by a ball mill to obtain an aqueous dispersion of a yellow organic pigment.

  20 parts by weight of the yellow colorant is added to the three types of water-based curable clays of Compositions 1, 2, and 3 described in Embodiment 1 with respect to the total amount shown in Table 1, and the mixture is mixed with an open kneader. By uniformly kneading, a water-based curable colored synthetic clay uniformly colored was produced.

  Each of the water-based curable colored synthetic clays thus obtained was subjected to a water dissolution test according to the voluntary regulation standard (ST mark certification standard) defined by the Japan Toy Association described in the first embodiment, and the results were obtained. Are shown in Table 2. The filtrate was colored, and the water dissolution property of the colorant was clearly observed.

(Comparative Example 3)
Similarly to Comparative Example 1, Comparative Example 3 shows a case where the clay colorant is a water dispersion of a pigment.

  That is, 80 parts by weight of water, 15 parts by weight of a blue organic pigment of color index number pigment blue 15-3, 3 parts by weight of polyoxyethylene lauryl ether (HLB = 10.5), sodium dialkyl sulfosuccinate (solid content 70%) 2) Parts by weight were uniformly dispersed and mixed in a ball mill to obtain an aqueous dispersion of a blue organic pigment.

  The blue colorant was added to the three types of water-based curable clays of Compositions 1, 2, and 3 described in the first embodiment, and 20 parts by weight based on the total amount shown in Table 1 was added. By uniformly kneading, a water-based curable colored synthetic clay uniformly colored was produced.

  Each of the water-based curable colored synthetic clays thus obtained was subjected to a water dissolution test according to the voluntary regulation standard (ST mark certification standard) defined by the Japan Toy Association described in the first embodiment, and the results were obtained. Are shown in Table 2. The filtrate was colored, and the water dissolution property of the colorant was clearly observed.

(Comparative Examples 4 to 8)
In Comparative Examples 4 to 8, the total amount shown in Table 1 was added to the three types of water-based curable clays of Compositions 1, 2, and 3 described in Embodiment 1 using the pigment itself as a colorant for clay. In the following mixing amount, the mixture was uniformly kneaded with an open-type kneader to produce a water-based curable synthetic clay that was substantially uniformly colored.

  In Comparative Example 4, 2.5 parts by weight of the pigment red 238 as a red organic pigment, in Comparative Example 5, 2.5 parts by weight of the pigment yellow 83 as a yellow organic pigment, and in Comparative Example 6, the pigment blue 15 as a blue organic pigment. -3, 2.5 parts by weight, in Comparative Example 7, 4 parts by weight of Pigment Red 101 to 102 (Tokoro Kabushiki Kaisha 140M) as a red inorganic pigment, and in Comparative Example 8, the above-mentioned Pigment Yellow 53 as a yellow inorganic pigment. A water-based curable colored clay was prepared using 4 parts by weight.

  Each of the water-based curable colored synthetic clays thus obtained was subjected to a water dissolution test according to the voluntary regulation standard (ST mark certification standard) defined by the Japan Toy Association described in the first embodiment, and the results were obtained. Are shown in Table 2. In all of Comparative Examples 4 to 8, the filtrate was colored, and the water-eluting property of the colorant was clearly observed.

  The present invention is not limited to the above-described embodiments and examples, and may be changed as needed without departing from the gist thereof.

  For example, the case where the clay colorant of the present invention is used to color the water-curable synthetic clay exemplified in Table 1 above is shown. However, it may be naturally mixed with other synthetic clays and natural clays. .

  INDUSTRIAL APPLICABILITY The present invention can be applied to a coloring technology for preventing water from dissolving a colorant in a modeling clay used for handicrafts, school teaching materials, toys, and the like.

Claims (7)

A coloring agent used for coloring clay,
The colorant is a fine particle of a colored resin obtained by mixing a fine powder of either a pigment or an oil-soluble dye with a resin, heat-melting and kneading, and cooling and pulverizing the obtained hot-melt kneaded material. A colorant for clay characterized by the following. The colorant for clay according to claim 1,
The fine particles of the colored resin have a particle size of 500 microns or less, and are larger than the size of the filter paper used in the water dissolution test of the voluntary regulation standard (ST mark certification standard) determined by the Japan Toy Association. A coloring agent for clay, which is: The clay colorant according to claim 2,
The colorant for clay, wherein the particle size larger than the size of the filter paper is 1.15 microns or more. A coloring agent used for coloring clay,
A colorant for clay, wherein the colorant is a water-insoluble high-boiling nonvolatile liquid containing a fine powder of a pigment or a water-insoluble semi-solid. The colorant for clay according to any one of claims 1 to 4,
A colorant for clay, wherein the fine powder of the pigment or the oil-soluble dye is contained in an amount of 0.05% by weight or more and 70% by weight or less in the colorant for clay. The colorant for clay according to any one of claims 1 to 5,
The pigment or oil-soluble dye contained in the clay colorant is selected from the items on a positive list of self-regulation standard color materials defined by the Hygiene Council of Polyolefin and the like.   A water-based curable colored clay, wherein the clay colorant according to any one of claims 1 to 6 is mixed with the water-based curable clay.