JPH11286645A - Colored particle for stipple coloration - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain colored particles for stipple coloration, having very good working suitability such as application suitability and being capable of developing a marked visual effect by using a blowing agent in an unblown state and a colorant as the essential components. SOLUTION: The colored particles for stipple coloration have a mean particle diameter of about 5-500 μm. The blowing agent in an unblown state is exemplified by heat-expandable microcapsules or a chemical blowing agent. When the heat-expandable microcapsules are used, they are colored with a colorant to obtain colored particles for stipple coloration. The colorant is not particularly limited and may be a pigment or a dye. It is desirable that the particles contain a binder selected among thermoplastic resins and thermosetting resins. The particles are obtained by spray-drying a liquid containing the two components of the blowing agent in an unblown state and the colorant as the essential components or by microencapsulating a mixture comprising the two essential components.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to colored particles for stippling, which are suitable for imparting an excellent stippling (dot) decorative effect to various objects.

[0002]

2. Description of the Related Art As one coloring method for enhancing the decorative effect of various articles such as textiles, a technique called spot coloring is known. In this method, the decoration (coloring) portion is composed of one or more kinds of innumerable small dots (dots), so that a special uniform coloring such as a marbling effect, a multicolor effect, or a three-dimensional effect cannot be obtained. It is intended to provide a simple visual effect.

Conventional methods relating to such a stippling coloring method include, for example, JP-A-2-45535, JP-A-8-3472, and JP-A-8-60025.

[0004] The above-mentioned method comprises the steps of spray-drying a mixed dispersion of an aqueous acrylonitrile polymer emulsion and a pigment having a particle diameter of 1 µ or less, to give colored polymer beads of 200 µ or less, preferably 1 to 100 µ, Is
The stippling coloring particles having an average particle diameter of 5 to 500 μm obtained by spray-drying an aqueous liquid containing at least one of a thermoplastic resin and a thermosetting resin and a pigment as an essential component. Colored beads for stippling coloring of fibers having an average particle size of 5 to 500 μm obtained by spray-drying an aqueous liquid containing the three components (A) to (C) as essential components: (A) a styrene-based polymer Granulation ingredients,
(B) a coloring component composed of pigments; and (C) a fiber adhesive component composed of an acrylic polymer.

[0005] The size of the coloring particles for stippling according to the conventional method is 200 µm or less, preferably 1 to 100 µm, and more preferably 5 to 500 µm, but in practice, it is 15 µm. 45-60 μm,
In this case, only those having a diameter of 35 to 48 μm are manufactured (see Examples), and large ones of 100 μm or more are not actually manufactured at present.

[0006]

In the stippling coloring method, individual small dots are usually formed by various granular processing colorants. Therefore, the size of the small dots is substantially equal to the size of the processing colorant. (Particle diameter).

Therefore, in order to obtain the above-mentioned visual effect due to these small points, it is necessary to use a coloring agent having a certain size (particle size). However, in order to enhance the visual effect, a larger particle size is required. When trying to use a coloring agent having
There is a problem that various work suitability typified by coating suitability is significantly deteriorated, and at present, a stippling colorant having both visual effect and work suitability has not been obtained yet.

The present invention has been made in view of such circumstances, and it is an object of the present invention to provide a stippling that has extremely good workability such as coating suitability and can exhibit a remarkable visual effect. The purpose is to provide colored particles for coloring.

[0009]

As described above, a stippling colorant having both a working effect and a visual effect has not yet been obtained, but the reason is that the working effect is improved as the coloring particles for stippling are smaller. On the contrary, the visual effect requires a certain size of particles, that is, the configuration (particle size) for improving the effect is inconsistent.

[0010] Therefore, it was a difficult technical task to obtain a stippling colorant having both a working effect and a visual effect.

The present inventors have considered that there is a means for changing the particle diameter of the colored particles before and after the application to the object to be colored, and as a means therefor, as a means, an unfoamed state is added to the colorant. If you adopt a configuration that adds a foaming agent,
Finding that the variable state can be made possible,
Finally, the present invention has been completed.

That is, the present invention is as follows.

1. Unfoamed foaming agent and colorant 2
Colored particles for stippling that contain a component as an essential component.

2. 2. The stippling coloring particles according to the above 1, wherein the unfoamed foaming agent is at least one selected from heat-expandable microcapsules and chemical foaming agents.

3. 3. The stippled coloring particles according to the above 1 or 2, wherein the unfoamed foaming agent is a heat-expandable microcapsule, and the microcapsule is colored by a coloring agent.

4. 4. The colored particles for stippling according to the above 3, wherein the heat-expandable microcapsules have a film colored by a coloring agent.

5. 5. The colored particles for stippling according to the above 1, 2, 3 or 4, wherein the colorant is at least one selected from pigments and dyes.

6. The colored particles for stippling coloring contain a binder as a granulating component.
Or the colored particles for stippling described in 5 above.

[7] 7. The stippled coloring particles according to the above item 6, wherein the binder is at least one selected from a thermoplastic resin and a thermosetting resin.

8. Unfoamed foaming agent and colorant 2
The above-mentioned 1, 2, wherein the liquid containing the component as an essential component is granulated by spray drying.
8. The method for producing colored particles for stippling according to 3, 4, 5.6 or 7.

9. 9. The method for producing stippled colored particles according to the above item 8, wherein the liquid material contains a binder as a granulating component.

10. The above 1, 2, 3, wherein a mixture comprising two components of an unfoamed foaming agent and a colorant is granulated by microencapsulation.
The method for producing colored particles for stippling according to 4, 5, 6, or 7.

11. (1) The liquid containing microcapsules containing a foaming agent and a coloring agent in an unfoamed state is granulated by spray drying.
The method for producing colored particles for stippling according to 2, 3, 4, 5, 6, or 7.

12. 12. The method for producing stippled colored particles according to the above item 11, wherein the liquid material contains a binder as a granulating component.

13. 8. A coloring composition comprising the stippling coloring particles according to the above 1, 2, 3, 4, 5, 6, or 7.

14. 14. The coloring composition comprising the stippling coloring particles according to the above 13, wherein the coloring composition is an ink or a paint.

15. 15. A stippling coloring method comprising applying a coloring composition containing the stippling coloring particles according to the above 13 or 14 to an object to be colored, and then foaming an unfoamed foaming agent constituting the coloring particles. .

The term "unexpanded foaming agent" as used in the present invention means a foaming agent whose volume is increased by heating or the like before it expands its volume.

In the case of the heat-expandable microcapsules, pre-foamed microcapsules, that is, those in an initial foamed state that does not reach a completely foamed state, are also included in the "unfoamed foaming agent" of the present invention.

The present invention is particularly characterized in that it has developed coloring particles for stippling coloring which comprise two components of a foaming agent and a colorant in an unfoamed state as essential components.

The colored particles for stippling of the present invention have an average particle diameter of 5 to 500 μm. When the average particle size is less than 5 μm, the visual effect as pointillism coloring is poor, while when it exceeds 500 μm, the tactile sensation, texture,
It is not preferable because it deteriorates or lowers the fastness to friction and the like and also deteriorates the workability such as coating suitability.

The above-mentioned particle diameters are the particle diameters before the foaming agent in the unfoamed state expands. If the foaming agent expands after the colored particles are applied to the material to be colored, the volume of the foaming agent will be increased. Increases about 1.5 to 100 times.

That is, the size of the stippled coloring particles of the present invention is a size (5 to 500 μm) that does not cause any problem in operation when applied to a material to be colored, but after application. , Fired by heating, etc., and become large enough to contribute to visual effects.

Therefore, the coloring particles for stippling that have been newly developed in the present invention have a relatively small particle size when applied to an object to be colored, and after being applied, have a particle size by heating or the like. The present invention is, for the first time, extremely suitable for workability, and is capable of exhibiting a remarkable visual effect. Is very good.

The present invention is also valuable in that, for the first time, large colored particles contributing to a noticeable visual effect are obtained.

Hereinafter, the present invention will be described in more detail.

[1] Constituents of the colored particles for stippling coloring of the present invention The constituents of the colored particles for stippling coloring of the present invention include the following components (A) to (D). Components A) and (B) are essential components.

(A) Foaming Component In the present invention, an unfoamed foaming agent is used. Examples of the foaming agent include heat-expandable microcapsules and chemical foaming agents. The present invention is not limited only to these.

Hereinafter, the heat-expandable microcapsules and the chemical foaming agent will be described.

As the thermally expandable microcapsules, for example, the following can be used.

Acrylic esters, methacrylic esters, acrylonitrile, vinylidene chloride, butadiene,
Ethylene, butane, pentane, isopentane, neopentane, hexane, heptane and other hydrocarbon-based hydrocarbons are contained in fine particles coated with a thermoplastic resin composed of a homopolymer or copolymer such as styrene or urethane or a crosslinked thermoplastic resin. Those that contain volatile swelling components. The particle size is about 1 to 50 μm, and it is preferable that the volume is increased by about 5 to 100 times when heated to a temperature higher than the boiling point of the expansion component.

The chemical foaming agent is not particularly limited as long as it is a compound capable of decomposing upon heating to generate gas components such as carbon dioxide gas and nitrogen gas.

For example, azodicarbonamide, N, N '
Organic blowing agents such as dinitrosopentamethylenetetramine, p-toluenesulfonylhydrazide, 4,4'-oxybis (benzenesulfonylhydrazide), hydrazodicarbonamide, sodium hydrogencarbonate, ammonium carbonate, sodium thiosulfate, sodium pyrophosphate; Inorganic foaming agents such as magnesium oxalate and silicon oxyhydride are exemplified.

In the present invention, these foaming agents can be used alone or in combination of two or more, depending on the mode.

(B) Colorant As the colorant, pigments and dyes are widely used and are not particularly limited.

For example, Hansa yellow, benzidine yellow, benzidine orange, pyrazolone orange, quinacridone red, various azo red organic pigments, dioxazine violet, anthraquinone yellow, phthalocyanine blue, indanthrene blue, phthalocyanine green, aniline black, etc. General organic pigments; fluorescent organic pigments obtained by coloring a resin with a fluorescent cationic dye or disperse dye; chrome yellow, cadmium yellow, chrome orange, red stalk, cadmium red, cobalt purple, ultramarine, navy blue, viridian, emerald green, etc. General chromatic inorganic pigments; black inorganic pigments such as carbon black and iron black; white inorganic pigments such as barium carbonate, talc, zinc oxide and titanium oxide; zinc sulfide, calcium sulfide, zinc silicate, zinc cadmium sulfide and the like. Activators such as copper, silver, manganese, bismuth, mesotrium, tritium, etc .; and fluorescent pigments comprising a sintered mixture of a metal oxide such as strontium aluminate, calcium aluminate and a rare earth element such as europium or dysprosium. Metal powder pigments such as gold powder, silver powder, bronze powder, copper powder, and aluminum powder; mica; I. O. , Glass spheres or the like or further nickel, cobalt, copper, gold,
Metallic luster pigments, pearl pigments, or reflective pigments coated with silver, aluminum, palladium, titanium oxide, iron oxide, etc .; thermochromic dyes, photochromic dyes,
Microcapsules containing electrochromic dyes, ultraviolet light-emitting dyes or compositions thereof, solid solution fine particles, reversible color changing pigments such as matrix fine particles, quasi-reversible color changing pigments or irreversible color changing pigments; and disperse dyes, naphthol dyes, sulfur dyes And general dyes such as oil color, mordant dye, vat dye, reactive dye, acid dye and direct dye.

In the present invention, these colorants can be used alone or in combination of two or more, depending on the mode.

(C) Binder In order to increase the granulation strength, it is preferable to add a binder. As the binder, any kind of thermoplastic resin or thermosetting resin can be used.

For example, polyethylene, polystyrene, polypropylene, polyester, polyamide, vinyl chloride, vinylidene chloride, vinyl acetate,
Acrylic ester, methacrylic ester, acrylonitrile, acrylamide, urethane, phenoxy, butadiene, polycarbonate, EVA
System, ethylene-vinyl chloride copolymer system, EVA-vinyl chloride graft polymerization system, AAS system, AES system, AS system, AB
S, ACS, MBS, chlorinated vinyl chloride, chlorinated polyethylene, chlorinated polypropylene, Teflon, polyacetal, thermoplastic polyimide, polyetherimide, polyether, polyetheretherketone , Polyphenylene ether, polyphenylene sulfide, polymethylpentene, polyparamethylstyrene, polyethylene oxide, polyvinylformal, polyamideimide, fluorine, ketone, cumarone, vinyl propionate , Ionomer type, cellulose type, various liquid crystal polymer type, natural rubber type, natural paste type, epoxy type, phenol type, melamine type, guanamine type, urea type, urethane type, alkyd type,
Xylene, silicone, polyimide, crosslinkable acrylic, maleic acid, diallyl phthalate, DFK
And various homopolymers, such as vinyl esters, unsaturated polyesters, polyoxybenzoyls, and furans, or copolymers or modified polymers thereof.

One or more thermoplastic resins and thermosetting resins constituting these binders are used.

The mixing ratio of the binder may be set arbitrarily according to the desired granulation strength and the like, and is not particularly limited.

(D) Additive In the present invention, various additives can be added as needed.

For example, surfactants, polymer protective colloids, fats and oils, waxes, catalysts, electrolytes, plasticizers, resin crosslinking agents, wetting agents, softeners, ultraviolet absorbers, antioxidants, antistatic agents, preservatives, Deodorant, repellent, insect repellent, antibacterial, insecticide, fungicide, adsorbent, titanium oxide photocatalyst, rust inhibitor,
pH adjuster, viscosity adjuster, flame retardant, filler, extender,
Examples include a fluorescent whitening agent, a drying regulator, an antifoaming agent, a water repellent, a fragrance, and various other stabilizers.

[2] Granulation method The colored particles for stippling according to the present invention contain the two components (A) and (B), ie, an unfoamed foaming agent and a colorant as essential components. The granulation method is not particularly limited as long as it is granulated into a particulate shape.
Hereinafter, a suitable granulation method will be described.

(1) Preparation of Liquid Material Prior to granulation, first, at least the essential two components described above, that is, at least the unfoamed foaming agent of component (A) and the coloring agent of component (B) are contained. A liquid material is prepared.

This liquid can be usually prepared by uniformly dispersing or dissolving the above two essential components in water or an organic solvent. The mixing ratio may be arbitrarily set according to, for example, the conditions of the spray drying described later or the target particle diameter of the colored particles of the present invention, and is not particularly limited, but is usually 100 parts by weight of water or an organic solvent. It is sufficient to use 0.5 to 30 parts by weight of an unfoamed foaming agent and 0.001 to 30 parts by weight of a coloring agent with respect to parts.

As described above, the liquid medium constituting the liquid material can be arbitrarily selected from water, an organic solvent, or the like, and is not particularly limited.
From the viewpoint of safety measures such as explosion, it is preferable to use an aqueous medium mainly composed of water (including a mixture of an aqueous organic solvent such as alcohol and glycol).

Further, the binder of the component (C) can be added to this liquid in order to increase the granulation strength and the like. In this case, the compounding ratio of the component (C) can be usually 1 to 60 parts by weight based on 100 parts by weight of water or the organic solvent.

Further, the additive of the component (D) can be added to the liquid as needed.

(2) Granulation Granulation is preferably performed by a spray drying method or a microencapsulation method. Hereinafter, the spray drying method and the microencapsulation method will be described.

(A) Spray drying method The liquid prepared as in the above (1) is charged into a spray dryer (hereinafter referred to as a spray dryer) at a constant speed to perform spray drying. The volatile particles (mainly, a liquid medium) are volatilized to give a granular material, whereby the colored particles for stippling of the present invention can be obtained.

As the spray drier, any of a disk rotating type, a pressurizing nozzle type, a two-fluid nozzle type and the like may be used, but in particular, a disk rotating type suitable for obtaining a uniform particle size. It is preferable to use those of the formula.

Other conditions may be set in accordance with a conventional method except that the spray drying is performed at a temperature not higher than the temperature at which the foaming agent foams (expands the volume to a completely foamed state). For example, the disk rotation speed, the nozzle injection amount, the feed speed of the liquid material, and the like may be appropriately adjusted according to the properties of the liquid material to be used so that a granular material having a target particle diameter is obtained.

(B) Microencapsulation method A mixture comprising the foaming agent in the unfoamed state of the component (A) and the colorant of the component (B) is used directly or in a liquid medium as described in the above (1). In the state of a liquid dispersed or dissolved in water, the particles are granulated by an ordinary microencapsulation method, whereby the colored particles for stippling of the present invention can be obtained.

Examples of the microencapsulation method include a coacervation method, an interfacial polymerization method, an in situ (in-situ) polymerization method, a liquid curing coating method, an air suspension coating method, and a spray drying method. These can be used alone or in combination of two or more. The shape of the microcapsules obtained by each of these methods may be a core / wall structure or a solid solution structure, and these may be further microencapsulated to form a multi-layer structure. It may be. In addition, these microcapsules may be in the form of mononuclear primary particles or in the form of secondary agglomerates in which they are aggregated to form multiple nuclei. sell.

As the wall film material or matrix material forming the microcapsules, various thermoplastic resins and / or thermosetting resins as exemplified as the binder of the component (C) can be usually used. .

These wall membrane materials or matrix materials can be colored by the colorant of the component (B). In this case, microcapsules containing only the unfoamed foaming agent as a core material are used. Shape.

On the other hand, when heat-expandable microcapsules are used as the unfoamed foaming agent, the microcapsules can be colored with a coloring agent to obtain the stippled colored particles of the present invention.

The method of coloring the microcapsules in this case includes a method of encapsulating the colorant in the microcapsules together with the volatile expanding component, and a method of coloring the film of the microcapsules with the coloring agent.

As a method of coloring the film of the microcapsule, a method is used in which a colorant is present together with the microencapsulation and the colorant is incorporated into the film simultaneously with the formation of the film, or the film is formed after the formation of the microcapsule. Is colored by the coloring agent.

As a coloring method using a coloring agent after the formation of the microcapsules, a method such as a dyeing method by an ordinary method or an exhaustion method by ion adsorption can be used.

(C) A composite method of (a) and (b) A microcapsule containing two components of the unfoamed foaming agent of the component (A) and the coloring agent of the component (B), or the microcapsule and the (C) The liquid material containing at least the binder of the component (1) can be granulated by the spray drying method of the above (A) to obtain the colored particles for stippling coloring of the present invention.

The colored particles for stippling of the present invention obtained by each of the above-mentioned granulation methods can be used in accordance with the type of the granulation method.
It can be obtained in various forms. For example, it may be obtained in a powdery state or in a state of being dispersed in a liquid medium.

When the colored particles of the present invention can be obtained in a state of being dispersed in the liquid medium, the colored particles of the present invention can be separated from the liquid medium by means of filtration or centrifugal separation or the like for practical use. Although it can be used, it can be used in actual use in a dispersed state.

[3] Stippling Coloring Method The coloring particles for stippling coloring of the present invention obtained by each of the above-mentioned methods may be used alone or in combination of two or more to form a coloring composition of a normal formulation, that is, a printing ink or a textile printing. Various aqueous or oily inks such as pastes, paints, spray colorants, coating agents and the like, or aqueous or oily paints are prepared into coloring compositions.

The coloring composition is adhered to a material to be colored by means such as printing, printing, transfer, coating, painting, dipping, spraying, or brushing.

Next, the uncolored foaming agent constituting the colored particles is foamed by applying a treatment such as heating to the colored object to be colored. As a result, a unique marbling effect,
A coloring matter having extremely excellent visual effects such as a colorful effect, a three-dimensional effect, and a washing effect can be obtained.

The object to be colored, which is the object of application of the coloring composition containing the coloring for stippling of the present invention, is not limited at all, and can be applied to an extremely wide range.
Various materials such as plastic, wood, glass, metal, and ceramics can be used.

It is, of course, also possible to apply the colored particles for stippling coloring of the present invention once to a transfer medium such as a transfer sheet or ink ribbon, and then to the above-mentioned object to be colored via the medium.

[0080]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In the following examples, “parts” and “%” mean “parts by weight” and “% by weight”, respectively.

[0081]

Example 1 Foaming (thermal expansion) as an unfoamed foaming agent
10 parts of thermally expandable microcapsules (Microsphere F-84D manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) having a temperature of about 160 ° C. and an organic blue pigment (phthalocyanine blue having an average particle diameter of about 0.4 μm, 25% concentration) as a colorant 40 parts of an aqueous dispersion) was uniformly dispersed in 70 parts of water to prepare an aqueous liquid.

Next, the aqueous liquid was sprayed at a temperature of 140 ° C. and a disk rotation speed of 14,000 rpm.
Injection into a type 8 spray dryer (manufactured by Okawara Kakoki Co., Ltd.) at a feed rate of 1.0 liter / hour, spray drying, and 20 parts of blue colored stippling coloring particles of the present invention having an average particle diameter of 40 μm. I got

An aqueous printing paste was prepared by mixing 10 parts of the coloring particles, 90 parts of an acrylate resin emulsion (a printing binder 350R manufactured by Matsui Dyeing Chemical Industry Co., Ltd.) and 2 parts of an epoxy-based crosslinking agent. The paste was applied to a cotton T
After imprinting on the shirt, preliminary drying was performed at 130 ° C. for 1 minute. Thereafter, a further heat treatment was performed at 180 ° C. for 2 minutes to foam the foaming agent. As a result, a blue stipple-colored pattern having a very visual effect was formed on the cotton T-shirt.

[0084]

Example 2 10 parts of the thermally expandable microcapsules used in Example 1 as an unfoamed foaming agent, and an organic red pigment (quinacridone red having an average particle size of about 0.2 μm dispersed at a concentration of 30% as a colorant) 30 parts of an aqueous dispersion), 60 parts of a 1: 2: 2 copolymer of methyl acrylate-ethyl acrylate-acrylonitrile (aqueous emulsion having a solid content of 45%) as a binder, and carbon dioxide as a filler as another additive. Calcium 10 parts, antifoam silicone oil
An aqueous liquid was prepared by uniformly dispersing 0.1 part in a liquid medium consisting of 60 parts of water and 5 parts of ethylene glycol.

Next, the aqueous liquid was subjected to spray drying at a temperature of 145 ° C. and a disk rotation speed of 12,000 rpm.
Inject into the 8 type spray drier (described above) at a feed rate of 1.0 liter / hour, spray dry, and average particle size
At 50 μm, 60 parts of red colored particles for stippling coloring of the present invention were obtained.

10 parts of the colored particles, an acrylate resin emulsion (the binder for printing 3 used in Example 1)
50R) 90 parts of an epoxy-based cross-linking agent and 2 parts of an epoxy-based crosslinking agent were mixed to prepare an aqueous printing paste, and the paste was printed on a cotton T-shirt using a 100-mesh character pattern screen plate. Pre-drying for 1 minute was performed. Thereafter, a further heat treatment was performed at 180 ° C. for 2 minutes to foam the foaming agent. As a result, a red stippling coloring pattern having a very visual effect was formed on the cotton T-shirt.

As a comparative example, an aqueous liquid was prepared in the same manner except that 10 parts of the above-mentioned heat-expandable microcapsules were not used, and spray-dried using the same under the same conditions as above. Thereby, colored particles were obtained.

The obtained colored particles had the same average particle diameter of 50 μm as described above. Using this, an aqueous printing paste having the same formulation as described above was prepared, and cotton T under the same conditions as described above. As a result of printing on a shirt, the obtained colored pattern was almost uniformly colored as compared with the above-described pointillized colored pattern rich in visual effect, and had no expected visual effect at all. .

Then, when the stippled colored pattern according to the present invention obtained above and the colored pattern according to the comparative example were compared by a micrograph, the size (measured as an average diameter) of the stippled colored portion in the former was about 120 μm. Whereas that of the latter was about 50 μm.

[0090]

Example 3 The procedure was the same except that 10 parts of the thermally expandable microcapsules used in Example 2 were replaced with 10 parts of azodicarbonamide, a chemical blowing agent having a foaming temperature of about 200 ° C. After preparing the aqueous liquid by spraying, spray drying was performed under the same conditions as above to obtain colored particles for stippling coloring of the present invention. The obtained colored particles had an average particle size of 50 μm.

Subsequently, 0.5 part of the colored particles, 50 parts of vinyl chloride resin, 50 parts of diisononyl phthalate, and 50 parts of lead stearate
A vinyl chloride plastisol ink consisting of 2 parts and 5 parts of dibasic lead phosphite was prepared. Next, using the vinyl chloride plastisol ink, a PVC foamed wallpaper provided with a foam layer (one coated with a normal formulation of a vinyl chloride plastisol ink containing a foaming agent) on a flame-retardant paper as a backing paper. After printing any pattern on the foam layer, 200
Heat treatment was performed at 3 ° C. for 3 minutes to obtain a PVC foam wallpaper having a stippled coloring pattern with a very rich visual effect.

[0092]

Example 4 Foaming (thermal expansion) as an unfoamed foaming agent
10 parts of heat-expandable microcapsules (Microsphere F-94D, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) having a temperature of about 220 ° C. and 1 part of an organic green dye (CI Solvent Green 3) as a coloring agent are diisononyl phthalate 30. After uniformly dispersing in the part, epoxy resin (Epicoat 828: manufactured by Yuka Shell Epoxy) 5
Was added to obtain a homogeneous solution. 35 parts of this solution at 60 ° C
% Gelatin aqueous solution and stirred, with an average particle size of 5
It was emulsified and dispersed uniformly so as to form 0 μm oil droplets. continue,
3 parts of a curing agent for epoxy resin (Epicure U: manufactured by Yuka Shell Epoxy Co., Ltd.) were added, and the liquid temperature was raised to 90 ° C. while stirring was continued, and the mixture was reacted at that temperature for 1 hour. Thereafter, the mixture was cooled, and the formed granules were washed with water, separated by filtration, and air-dried to obtain microcapsule-like colored particles for stippling coloring having an average particle diameter of 50 µm.

Next, the colored particles 2 thus obtained
Part, polyurethane resin (Chris Bon S-125: manufactured by Dainippon Ink), 50 parts of methyl isobutyl ketone, 10 parts of isophorone and 1 part of a silicone defoamer to prepare an oil-based ink, and the surface is peeled off. On the release-treated surface of the treated polyester film, an alphabet pattern opposite to the actual pattern was printed by an ordinary silk screen method using an 80 mesh screen plate to form a stippled pattern pattern layer.

After the layer was dried, 5 parts of Superflex E-2000 (trade name of an aqueous solution of a polyurethane resin, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 5 parts of Daiamide 450P-1 (a hot melt made of a polyamide resin) Adhesive product name: 30 parts by Daicel Chemical Co., Ltd., carboxymethylcellulose 5
Part and the ink composition consisting of 60 parts of water, using a 50 mesh screen plate of the same pattern type as above, and overprinted,
An adhesive layer was formed. Next, this was dried to obtain a thermal transfer sheet.

The obtained thermal transfer sheet was placed on the white cotton knit with its adhesive layer side in contact with the white cotton knit as the article to be transferred. After applying heat and pressure of 500 g / cm ² at ℃ (corresponding to the temperature at which the unfoamed foaming agent can foam (volume expansion)), the polyester film was immediately peeled off. On top, a green stippled colored alphabet pattern with excellent visual effect was transferred and formed.

As comparative examples, microcapsule-shaped colored particles were obtained in the same manner except that 10 parts of the above-mentioned heat-expandable microcapsules were not used, and the same thermal transfer sheet as above was obtained using these particles. Obtained.

When this thermal transfer sheet was transferred onto a white cotton knit under the same conditions as described above, the resulting alphabet pattern was almost uniformly colored, and the expected visual effect (particularly the three-dimensional appearance) was obtained. ) At all.

[0098] Then, when the stippled colored alphabet pattern according to the present invention obtained above and the colored alphabet pattern according to the comparative example were compared by a micrograph, the size (measured as an average diameter) of the stippled colored portion in the former was determined. 125
μm, whereas that of the latter was 40 μm.

[0099]

Example 5 10 parts of the microcapsule-shaped pointed coloring particles of the present invention obtained in Example 4, 80% of a 40% aqueous emulsion of a urethane resin as a binder (Suncur 861 manufactured by Suncore) and carbonic acid as a filler An aqueous liquid was prepared by uniformly dispersing 20 parts of calcium in 70 parts of water as a liquid medium. Next, this aqueous liquid was introduced into an L-8 type spray dryer (manufactured by Okawara Kakoki Co., Ltd.) set at a spray drying temperature of 170 ° C. and a disk rotation speed of 10,000 rpm at a feed rate of 0.9 liter / hour, and sprayed. Drying was performed to obtain 65 parts of green coloring particles for stippling of the present invention having an average particle diameter of 100 μm.

Subsequently, 3 parts of the obtained colored particles, 40 parts of Dianal SE-5248 (thermosetting acrylic resin solution: manufactured by Mitsubishi Rayon Co., Ltd.), and Super Beckamine G-821-60 (melamine resin: Dai Nippon Ink) 10 parts, ethylene glycol monobutyl ether 30 parts, homogenol L-100
3 parts, Adetol XL-297 (Anti-settling agent, manufactured by Hoechst)
After preparing an oil paint consisting of 0.5 part and 0.1 part of Tinuvin 326 (ultraviolet absorber: manufactured by Ciba Geigy), this oil paint was previously colored brown by a spray gun type spray electrostatic coating method. And then heat-treated at 150 ° C. for 10 minutes.

Further, Dianal SE-5248 (supra) 60
Parts, Super Beckamine G-821-60 (supra) 15 parts, xylene 10 parts and ethylene glycol monobutyl ether 1
A 5-part transparent oil-based paint is applied on the miniature car in the same manner as described above to form a transparent protective glossy layer, and then 230 ° C. (a temperature at which the unfoamed foaming agent can foam). For 10 minutes to obtain a die-cast miniature car having a stippled coloring pattern. Such a green stippling pattern was extremely rich in visual effect, and together with the brown color of the base, a military diorama-like miniature car could be obtained.

[0102]

Example 6 The foaming temperature was about 15 as an unfoamed foaming agent.
10 parts of a heat-expandable microcapsule (Matsumoto Yushi Seiyaku Co., Ltd .: Microsphere F-50D) at 0 ° C. was mixed with 1% of a cationic polymer (acrylamide and 2-methacryloxyethyltrimethylammonium chloride in a 3: 2 copolymer ratio). Combined) Add to 100 parts of aqueous solution with stirring, adjust the liquid temperature to 60 ° C,
After the treatment for 0 minutes, the wall film of the microcapsules was subjected to cationization treatment by filtration and air drying.

Subsequently, glow pink MIB as a coloring agent
(Water dispersion containing 50% of pink daylight fluorescent pigment: manufactured by Matsui Dyeing Chemical Industry Co., Ltd.) 5 parts of the above-mentioned cationized heat-expandable microcapsules are stirred in 100 parts of an aqueous dispersion containing 10 parts. The solution is treated for 10 minutes at a liquid temperature of 70 ° C., and the surface thereof is colored in a fluorescent pink color by ion exhaustion dyeing. Microcapsules were obtained.

Next, an acrylate resin emulsion (ethyl acrylate:
After adding 20 parts of a 50% emulsion of a 2: 1: 1 copolymer of butyl acrylate: 2-ethylhexyl acrylate), it was filled into a padding bath in a roll padder. Subsequently, the nylon knitted fabric is passed through a padding bath in this roll padder and dewatered with a mangle so as to have a squeezing ratio of 100%. Was dried in a non-touch method to obtain a nylon knitted fabric which was spot-colored in a fluorescent pink color with a full visual effect.

[0105]

Example 7 The same as the aqueous dispersion finally filled in the padding bath in Example 6 (that is, the aqueous dispersion containing the stippled coloring particles of the present invention and an acrylate resin emulsion as a binder). To 100 parts of the aqueous dispersion of the composition, a thermosensitive reversible color changing pigment (microcapsulated thermochromic composition that becomes blue on the low temperature side and colorless on the high temperature side around 35 ° C.) Aqueous dispersion containing 50% concentration: trade name, Chromicolor Aqualight Ink Turkis Blue AQ-27, manufactured by Matsui Dyeing Chemical Industry Co., Ltd.), and aqueous dispersion was prepared by uniformly dispersing. . Next, the aqueous liquid was fed into an L-8 type spray drier (described above) set at a spray drying temperature of 125 ° C. and a disk rotation speed of 15,000 rpm.
The mixture was charged at a rate of 1.0 liter / hour and spray-dried to obtain colored particles for stippling of the present invention having an average particle diameter of 45 μm.

After preparing the aqueous gravure ink of the usual formulation containing the obtained colored particles for stippling, the gravure ink is used to prepare an aqueous foam wallpaper having a foam layer provided on a flame-retardant paper by an aqueous coating agent. A pattern was printed on the foamed layer and heat-treated at 160 ° C. (temperature at which the thermally expandable microcapsules foamed) for 1 minute to obtain a foamed wallpaper having a stippled colored pattern. This stippling coloring pattern has an excellent visual effect and exhibits a fluorescent purple color at a temperature of 35 ° C or less, but at a temperature of 35 ° C or more, it reversibly changes to a fluorescent pink color. It was excellent.

[0107]

Example 8 As an unfoamed foaming agent, 10 parts of azodicarbonamide (chemical foaming agent) having a foaming (thermal expansion) temperature of 200 ° C. and heat-expandable microcapsules having the same foaming temperature of 200 ° C. (Matsumoto Yushi Seiyaku Co., Ltd.) Made: Microsphere F-110
D) 10 parts, 5 parts of aluminum powder as a colorant, and 10 parts of a blue pigment (phthalocyanine blue), and an acrylate-based copolymer resin (1: 10: 1 of methacrylic acid-methyl acrylate-acrylonitrile-ethyl acrylate) as a binder
0: 2 copolymer), 60 parts of a 50% emulsion and 10 parts of a 10% aqueous solution of methylated methylolmelamine prepolymer, 5 parts of calcium carbonate as a filler, 5 parts of zinc stearate as an auxiliary for a chemical foaming agent, 0.1 part of silicone oil as a foaming agent was added to 130 parts of water, and the mixture was uniformly dispersed to prepare an aqueous liquid.

Next, this aqueous liquid was subjected to spray drying at a temperature of 170 ° C. and a disk rotation speed of 15,000 rpm.
It is charged at a feed rate of 1.0 liter / hour into an 8 type spray drier (described above), spray-dried, and has a mean metallic particle diameter of about 50 μm and a blue metallic luster color of the present invention. Got a part.

10 parts of the colored particles and 90 parts of a urethane emulsion binder (AR binder GS: manufactured by Matsui Dyeing Chemical Industry Co., Ltd.) were mixed to form an aqueous coating agent, which was uniformly coated on wood free paper. Heat treatment was performed for 1 minute at ℃ (the temperature at which the foaming agent foams) to obtain a stipple-colored wrapping paper having a blue metallic luster color, which was extremely rich in visual effect.

Further, when the above-described coloring means was applied using the red colored particles obtained in Example 2 in addition to the above colored particles, the wrapping paper exhibited a purple metallic luster as a whole. Also, when observed in close proximity, it was possible to observe in a mixed state of blue metallic glossy dots and red dots, which was extremely excellent in various effects.

[0111]

The color particles for stippling coloring newly developed in the present invention have a relatively small particle size when applied to a material to be colored, and after being applied, have a particle size by heating or the like. The present invention is, for the first time, extremely suitable for workability, and is capable of exhibiting a remarkable visual effect. Is very good.

The present invention is also valuable in that, for the first time, it is possible to obtain large colored particles contributing to a noticeable visual effect.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI D06P 5/00 D06P 5/00 D21H 19/36 C09C 3/10 // C09C 3/10 D21H 1/22

Claims (15)

[Claims] 1. Coloring particles for stippling, comprising two components, an unfoamed foaming agent and a coloring agent, as essential components. 2. The stippled coloring particles according to claim 1, wherein the unfoamed foaming agent is at least one selected from heat-expandable microcapsules and a chemical foaming agent. 3. The stippled coloring particles according to claim 1, wherein the unfoamed foaming agent is a heat-expandable microcapsule, and the microcapsule is colored by a coloring agent. 4. The colored particles for stippling according to claim 3, wherein the film of the heat-expandable microcapsule is colored by a coloring agent. 5. The stippling coloring particles according to claim 1, wherein the coloring agent is at least one selected from pigments and dyes. 6. The stippled coloring particles according to claim 1, wherein the stippling coloring particles contain a binder as a granulating component. 7. The stippled coloring particles according to claim 6, wherein the binder is at least one selected from a thermoplastic resin and a thermosetting resin. 8. A liquid material containing two components of an unfoamed foaming agent and a colorant as essential components, and granulated by spray drying.
The method for producing colored particles for stippling according to 4, 5, 6, or 7. 9. The method according to claim 8, wherein the liquid material contains a binder as a granulation component. 10. A mixture comprising two components of an unfoamed foaming agent and a coloring agent, wherein the mixture is granulated by microencapsulation.
8. The method for producing colored particles for stippling according to 5, 6 or 7. 11. A liquid material containing microcapsules containing a foaming agent and a colorant in an unfoamed state is granulated by spray drying.
7. The method for producing colored particles for stippling according to 3, 4, 5, 6, or 7. 12. The method for producing stippled colored particles according to claim 11, wherein the liquid material contains a binder as a granulating component. 13. The method of claim 1, 2, 3, 4, 5, 6, or 7.
A coloring composition comprising the stippled coloring particles described in the above. 14. The coloring composition according to claim 13, wherein the coloring composition is an ink or a paint. 15. Applying a coloring composition containing the stippling coloring particles according to claim 13 to a material to be colored, and then bubbling an unfoamed foaming agent constituting the coloring particles. Characteristic stippling coloring method.