JP2003253152A - Water-based coloring material comprising colorant- containing resin fine particle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-based coloring material which comprises a colorant-containing resin fine particle and can be used for applications such as a coating for woodworking where high transparency is required. <P>SOLUTION: The water-based coloring material comprises a resin fine particle, which contains a colorant and has an average particle size of at most 100 nm and a maximum particle size of at most 500 nm, and a water-dispersed resin having a Tg lower than the Tg of the resin fine particle. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based paint and a water-based ink containing a colorant-containing resin fine particle and a binder resin and having a coating film with high transparency and excellent dispersion stability.

[0002]

2. Description of the Related Art In recent years, in the field of coloring materials such as paints and inks, reduction of VOC (volatile organic compound) has become a social problem, and it is desired to make it aqueous and nonsolvent. Water-based paints and water-based inks have the advantage of not being harmful to the human body because they do not use solvents, and of being free from the risk of fire, etc. Many are future issues.

Among the above-mentioned inks and paints, those using water-soluble dyes have the advantages that the number of colors is abundant, the color tone is excellent, and the demand for high-definition printed images in recent years can be met. However, on the other hand, there is a problem that bleeding, water resistance is poor, especially light fastness is greatly inferior, and those using a pigment have good water resistance and light fastness, but have a small number of colors and a color tone surface. However, the sharpness and transparency are inferior, the demand for higher definition of the printed image cannot be satisfied, and there is a problem in storage stability such as easy sedimentation.

Further, in the case of a pigment-based paint, since the pigment has a large particle size and is inferior in terms of transparency and image clarity, high transparency such as giving a desired color without hiding the wood grain is required. Its performance was not satisfactory for paint applications for wood processing. On the other hand, some researches have been conducted on resin fine particles containing a colorant as a novel coloring material. For example, Japanese Patent Laid-Open No. 2001-131213 discloses an oil-soluble dye obtained by a mini-emulsion polymerization method of a monomer. The particles are described. The average particle diameter of the colored fine particles is as small as 90 nm or less, and it is possible to realize a clear color by suppressing the scattering of visible light as much as possible. However, when the fine particles are used alone as an aqueous paint or ink. It was found that the abrasion resistance and transparency of the film (coating film) were insufficient.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and in particular, the dispersion stability and the light fastness are maintained while maintaining the color vividness which is an excellent characteristic of the colorant-containing resin fine particles. In order to provide a water-based coloring material which has extremely excellent performance and also has excellent characteristics of a film (coating film) such as transparency and abrasion resistance.

[0006]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that a liquid medium containing resin particles containing a colorant has an aqueous solution having a Tg lower than that of the resin particles. It has been found that the above problems can be solved by adding a dispersion resin, and the present invention has been solved. That is, the gist of the present invention is that the average particle size is 100 n.
colorant-containing resin fine particles having a maximum particle size of 500 nm or less and a Tg lower than the Tg of the resin fine particles.
And an aqueous dispersion resin containing a.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The water-based coloring material of the present invention has a colorant-containing resin fine particle having an average particle diameter (median diameter) of 100 nm or less so that it can be applied to applications requiring high transparency. The reason is as follows. Generally, the efficiency with which a particle scatters visible light at a wavelength λ is such that the particle diameter is λ / 2.
It is said that the maximum value is obtained in the case of particles corresponding to, and the scattered light rate is extremely small in the case of particles having a particle diameter of λ / 4 or less. Therefore, the shortest wavelength of visible light is 380
Since it is nm, in order to suppress the scattering of visible light as much as possible, it is desired that the particle diameter be 1/4 or less of 380 nm.
The presence of large particles having a size of 100 nm or more reduces the transparency of water-based coloring materials such as paints and inks, and therefore it is desirable that the amount is small, and the maximum particle size of the large particles needs to be 500 nm or less.

The average particle diameter of the colorant-containing resin fine particles is
After the fine particles are dispersed in a liquid medium, it can be measured by using a dynamic light scattering device such as "Microtrack UPA particle size distribution meter" manufactured by Honeywell. The resin type of the colorant-containing resin fine particles used in the present invention is not particularly limited as long as it can be made into the colorant-containing resin fine particles by a known method described later, but specifically, it is obtained by emulsion polymerization. Various polymers can be mentioned, and of these, vinyl polymers are preferable.

Specific examples of the monomer component constituting the vinyl polymer include styrene, α-methylstyrene,
α-Substituted styrenes such as α-ethylstyrene, m-methylstyrene, p-methylstyrene, nuclear-substituted styrenes such as 2,5-dimethylstyrene, p-chlorostyrene, p
-Vinyl aromatics such as nucleus-substituted halogenated styrenes such as bromostyrene and dibromostyrene; (meth) acrylic acid (here, "(meth) acrylic" means acryl and methacryl, and the same shall apply hereinafter. ), Crotonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, and other unsaturated carboxylic acids; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, Unsaturated carboxylic acid esters such as pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate; (meth) acrylaldehyde, (meth) acrylonitrile , (Meta)
Unsaturated carboxylic acid derivatives such as acrylamide; N-vinyl compounds such as N-vinylpyridine, N-vinylpyrrolidone; vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate; vinyl chloride, vinyl bromide, chloride Vinyl halides such as vinylidene; allyl compounds such as allyl alcohol, allyl methyl ether, allyl ethyl ether, allyl methyl ketone, allyl acetic acid, allyl phenol; N-methylol acrylamide, N-ethylol acrylamide, N-propanol acrylamide , N-methylol maleamic acid, N
-Methylol maleamic acid ester, N-methylol maleimide, N-ethylol maleimide, N- (isobutoxymethyl) acrylamide, N-methylol-p
-N-substituted unsaturated amides such as vinylbenzamide; conjugated dienes such as butadiene and isoprene; divinylbenzene, divinylnaphthalene, divinylcyclohexane,
Polyfunctional vinyl compounds such as diisopropenylbenzene;
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, Trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acryle , Dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate, Examples thereof include polyfunctional acrylates such as sorbitol hexa (meth) acrylate. The monomer components can be used alone or as a mixture of two or more kinds.

The colorant used in the present invention is not particularly limited as long as it can be contained in the resin fine particles by a known method, but a dye soluble in an organic solvent is preferable. Specifically, dyes for sublimation heat transfer, dyes for resin coloring, dyes for inks, disperse dyes, azo-based, anthraquinone-based, phthalocyanine-based,
Examples thereof include styryl dyes, indoaniline dyes, methine dyes and the like. In addition, anion dye or cationic dye is used to form a salt by using an ion pair compound or the opposite ionic dye,
An oil-soluble dye can also be used. From the viewpoint of light resistance of the dye, more preferably, a metal-containing dye is used, and specifically, Solvent Yellow 88, Solvent Yellow 89, Solvent Yellow 25, Solvent Orange 11, Solvent Orange 99, Solvent Brown 4
2, solvent brown 43, solvent brown 4
4, Solvent Red 130, Solvent Red 23
3, Solvent Red 125, Solvent Red 12
2, Solvent Red 127, Solvent Blue 67,
Solvent Blue 70, Solvent Black 28,
Solvent Black 29 and the like can be mentioned. Further, these dyes may be used as a mixture of two or more kinds.

The content of the dye in the resin fine particles can be arbitrarily selected according to the purpose and application, but if it is too small, the coloring power will be poor, so that it is preferably 10% by weight or more. The method for producing the colorant-containing resin fine particles used in the present invention is not particularly limited, and known methods such as emulsion polymerization method, miniemulsion polymerization method, phase inversion emulsification method, in-liquid drying method, and dyeing method. Can be used arbitrarily.

Among them, the method for producing fine particles of a colorant-containing resin by an emulsion polymerization method is one in which a monomer is emulsion polymerized in the presence of a colorant, and, for example, JP-A-9-27907.
Japanese Patent Laid-Open No. 3 (1993) discloses a method for producing resin fine particles containing a colorant, which is provided with storage stability by using a reactive emulsifier as an emulsifier and copolymerizing a monomer and the reactive emulsifier in the presence of the colorant. ing.

In the method for producing fine resin particles containing a colorant by the mini-emulsion polymerization method, an oil phase containing a monomer and a colorant is added in the presence of a surfactant so that the average particle diameter of oil droplets is 20.
After forming an O / W type emulsion having a thickness of ~ 500 nm,
To polymerize a monomer in the oil droplets, for example,
JP 2001-131213 A describes a method for producing colorant-containing resin fine particles having an average particle diameter of 90 nm or less by miniemulsion polymerization of a dye-dissolved monomer.

The method for producing colorant-containing resin fine particles by the phase inversion emulsification method is to polymerize a monomer in a colorant-containing monomer solution and then emulsify the polymer-containing solution in an aqueous medium. Japanese Patent Application Laid-Open No. 7-96163 describes a method for producing highly light-resistant colored fine particles having a particle size of 0.5 μm or less, in which an organic dye + a light stabilizer and / or an antioxidant are contained in an organic polymer compound. Has been done.

The method for producing the colorant-containing resin fine particles by the dyeing method is carried out in advance by a known polymerization method such as emulsion polymerization, miniemulsion polymerization, microemulsion polymerization, soap-free emulsion polymerization, phase inversion emulsification method and the like. A medium is produced, and then a colorant is converted therein to dye resin fine particles. For example, Japanese Patent Application No. 2001-18452.
2 discloses a resin fine particle containing a coloring agent at a high concentration of 20% by weight or more, which is obtained by dyeing a resin fine particle having a crosslinked structure with an oil-soluble dye in an aqueous medium coexisting with an organic solvent. Has been done.

Of these methods for producing colorant-containing resin fine particles, it is difficult to obtain a resin fine particle containing a colorant at a high concentration by the emulsion polymerization method, and it is difficult to obtain a system in which the particle concentration is low by the phase inversion emulsification method. The production of the colorant-containing resin fine particles by the miniemulsion polymerization method or the dyeing method is preferable because it is difficult to make the colorant-containing resin particles sufficiently small.

The colorant-containing resin fine particles used in the present invention include a conventionally known antioxidant in order to improve stability.
An ultraviolet absorber, a light stabilizer such as a hindered amine compound, or the like can be added. The aqueous dispersion resin in the present invention has a Tg lower than that of the colorant-containing resin fine particles.
And preferably has a Tg of 100 ° C. or lower,
More preferably, it is 60 ° C. or less. From the viewpoint of ease of handling and the like, those having Tg of −30 ° C. or higher, preferably 0 ° C. or higher are usually used.

As the aqueous dispersion resin having the above Tg,
For example, it is arbitrarily selected from aqueous dispersion resins generally used in the field of aqueous paints or aqueous inks, for example, resins classified into emulsion type, dispersion type (colloidal dispersion type) or slurry type. be able to. Here, the resin serves as a binder that maintains the dispersed state of the colorant-containing resin fine particles in the film (coating film) formed by the water-based paint and the water-based ink, and holds the colorant-containing resin fine particles together. At the same time, it is a main constituent that controls the properties of the film (coating film) and the performance of the film (coating film).

The emulsion type aqueous dispersion resin is obtained by stabilizing a particulate resin in water with an emulsifier, a surfactant or a protective colloid. The dispersion type aqueous dispersion resin is an emulsion of a water-soluble type aqueous dispersion resin and an emulsion. Type aqueous dispersion resin, which is an intermediate type of resin, and in which the resin is granulated in a form in which hydrophilic groups are exposed on the surface by reducing hydrophilic groups as compared with the water-soluble aqueous dispersion resin, the slurry type aqueous dispersion resin is an emulsion. A resin particle having a larger particle size than that of the water-based dispersion resin is suspended in water.

The emulsion-type, dispersion-type (colloidal dispersion-type) or slurry-type aqueous dispersion resin is preferably in the form of an aqueous dispersion having a particle size of about 0.01 μm or more. Can be used. The aqueous dispersion of the aqueous dispersion resin may contain an emulsifier, a surfactant and a protective colloid for stabilizing the dispersion.

As the above-mentioned aqueous dispersion resin, various copolymers of acrylic monomers such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and methyl methacrylate, and vinyl monomers such as styrene and vinyl acetate. Are commercially available. For example, in addition to all acrylic emulsion, acrylic / styrene, acrylic /
Vinyl acetate, acrylic / silicone, acrylic / EVA and other acrylic copolymer emulsions, vinyl acetate / ethylene copolymers, polyvinyl chloride, vinyl chloride / vinylidene chloride copolymer and other vinyl copolymer emulsions, synthetic rubber Examples include latex and the like.

Specific examples of the aqueous dispersion resin include "John Cryl Emulsion" series manufactured by Johnson Polymer Co., Ltd. Further, in addition to the emulsion polymer aqueous dispersion resins mentioned above, a polymer having a pendant carboxylic acid group is treated with an organic base such as ammonia, amine or metal hydroxide or an infinite base to give the carboxylic acid group. Anion-type water-solubilizing resin obtained by neutralizing a portion of the amino group; treating a polymer containing a primary or secondary amino group with an acid such as formic acid, acetic acid, butyric acid, etc. to neutralize the amino group portion to make it aqueous. A cationic water-based resin, or a hydroxyl group, an ether group contained in the polymer itself such as polyvinyl alcohol, polyvinyl methyl ether, polyethylene glycol, polyacrylamide, etc.
Nonionic water-based resins that are water-based with an amide group can also be used as the aqueous dispersion resin. Examples of the resin for water-based resin-based paints and water-based inks that have been hydrophilized by these methods include, for example, water-based alkyd resins, water-based urea resins, water-based phenol resins, water-based acrylic resins, water-based epoxy resins, water-based polybutadiene resins, and water-based resins. Two-component urethane resin, styrene-maleic acid resin, polyester resin and the like can be mentioned.

In addition, natural products such as rosin maleic acid resin, cellulose derivatives, casein and its derivatives, and natural product derivatives can be used as the aqueous dispersion resin. These resins may be used alone or in combination of two or more. Here, a water-soluble resin such as methyl cellulose or hydroxyethyl cellulose is usually used in an amount of 50% by weight or less with respect to the aqueous dispersion resin as an auxiliary agent for controlling the viscosity and fluidity of the coloring material and stabilizing the dispersion system. , Preferably 25% by weight or less, more preferably 1
It can also be used in combination in an amount of 0% by weight or less, particularly preferably 5% by weight or less.

The amount of the above aqueous dispersion resin to be used can be arbitrarily determined within a range that satisfies the coloring power and film physical properties required for each application such as paints and inks. It is usually used in an amount of 50% by weight or less, preferably 30% by weight or less, and more preferably 20% by weight or less with respect to the aqueous dispersion. Here, if the amount of the aqueous dispersion resin is too small, physical properties such as strength of the coating film may be affected. Therefore, the amount of the aqueous dispersion resin is usually 0.01 part by weight or more per 1 part by weight of the colorant-containing resin fine particles. , Preferably 0.05 parts by weight or more,
It is particularly preferably used in the range of 0.1 parts by weight or more.

The colorant-containing resin fine particles are usually contained in an amount of 0.5% by weight or more, preferably 1% by weight or more, more preferably 1% by weight, based on the aqueous dispersion containing the colorant-containing resin fine particles and the aqueous dispersion resin. It is used in an amount of 5% by weight or more. The aqueous colorant in the present invention is an aqueous dispersion of an aqueous dispersion resin, colorant-containing resin fine particles and additives.

The aqueous dispersion contains various additives, for example, a small amount of an organic solvent such as an alcohol solvent, an oil, a curing agent, a leveling agent, a rheology control agent, depending on each application such as an aqueous paint and an aqueous ink. A plasticizer, an emulsifier, a curing catalyst, a light stabilizer, a penetrant and the like can be optionally used. In addition, the minimum film-forming temperature of the aqueous dispersion needs to be Tg or less of the colorant-containing resin fine particles, and is preferably 50 ° C. or less, more preferably 30 ° C. or less. Further, if the minimum film-forming temperature is too low, physical properties such as stability of the coating film may be affected. Therefore, it is usually preferable to set the temperature to -30 ° C or higher.

The aqueous colorant of the present invention can be prepared by stirring and mixing an aqueous dispersion containing an aqueous dispersion resin and an aqueous dispersion of fine particles of a colorant-containing resin with various mixers.
Included in general pigment-based paint and ink manufacturing processes,
It is efficient because it does not require a kneading operation to make the pigment into fine particles and disperse it in the vehicle. Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

[0028]

EXAMPLES Synthesis Example 1 Preparation of Colorant-Containing Resin Fine Particles by Mini-Emulsion Polymerization Method "LEVENOL WZ" (Kao Corporation) was added to 55.8 g of distilled water.
Made, 26% aqueous solution of anionic surfactant) 8.52 g,
Solution A was prepared by dissolving 0.082 g of sodium hydrogen carbonate.

Methyl methacrylate 12.4 g, methacrylic acid 0.80 g, hexadecane 0.83 g, "ORAS
"OL Yellow 2RLN" (manufactured by Ciba Specialty Chemicals) 2.00 g, "ORASOL R
ed BL ”(manufactured by Ciba Specialty Chemicals) 0.43 g,“ ORASOL Blue GN ”
(Ciba Specialty Chemicals) 0.42g
Were mixed to prepare a solution B.

0.24 g of potassium persulfate was added to 2.0 of distilled water.
A solution C was prepared by dissolving in 8 g. The solution B was poured into the solution A and stirred with a stirrer for 10 minutes, and then an ultrasonic disperser (“ULTRASONIC HOMOGENI” manufactured by STM) was used.
ZER UH-600 ") for 15 minutes to prepare a monomer emulsion. The obtained monomer emulsion was transferred to a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen gas inlet tube, and after nitrogen substitution for 15 minutes, the temperature was raised to 80 to 85 ° C. to obtain solution C. Was injected, and the polymerization was terminated after 2.5 hours had elapsed. The conversion rate of the monomer was about 99%, and the average particle diameter of the obtained resin fine particles was determined by an optical Doppler particle size distribution meter (Honeywell "Micr"
otrack UPA particle size analyzer ”), the median diameter is about 50.1 nm, and the maximum particle diameter is about 410 n.
It was m. Further, when the water content of the colorant-containing resin fine particle aqueous dispersion obtained on the hot plate was evaporated and the remaining solid content was measured by DSC, Tg was about 120 ° C.

Example 1 1.0 g of the colorant-containing resin fine particle dispersion liquid of Synthesis Example 1 (particle amount: about 0.2 g) was added to "John Cryl 74J" manufactured by Johnson Polymer Co., Ltd. (Tg 22 ° C., average particle size 80 nm, nonvolatile content). 45%) 0.11 g and distilled water 0.32 g were added to prepare an aqueous ink. This ink is wire bar coater N
o. 4 was applied to Xerox 4024 paper and dried at room temperature. The spectral characteristics of this coated sample were measured by Hitachi spectrophotometer U-3500, and the light fastness was also measured according to JIS L-0843. That is, a xenon light resistance tester (“Atlas Weatherometer Ci4 manufactured by Atlas Co., Ltd.
[000 ") from the reflectance measurement results before and after 40 hours of irradiation, ΔE was converted into a concentration index of K / S (Kuberkmunk formula) to obtain the dye residual rate after irradiation, and the light fastness was evaluated. . In addition, the water-based ink was used as wire bar coater No. After being applied to a polyester film having a thickness of 200 μm at 24 and dried at room temperature, the transparency of the applied film was examined. The results are shown in Table-1.

Example 2 An aqueous ink was prepared and coated in the same manner as in Example 1 except that the amount of "John Krill 74J" manufactured by Johnson Polymer Co., Ltd. was 0.22 g and the amount of distilled water was 0.21 g. The spectral characteristics and the like were evaluated. The results are shown in Table-1. Example 3 An aqueous ink was prepared in the same manner as in Example 1 except that the amount of "John Krill 74J" manufactured by Johnson Polymer Co., Ltd. was 0.43 g and no distilled water was used, and evaluation of coating, spectral characteristics, etc. Was done. The results are shown in Table-1.

Comparative Example 1 An aqueous ink was prepared in the same manner as in Example 1 except that "John Cryl 74J" manufactured by Johnson Polymer Co., Ltd. was not used, and the amount of distilled water was 0.43 g, coating, spectral characteristics, etc. Was evaluated. The results are shown in Table-1. Comparative Example 2 Lightfastness comparison with a commercially available wood stain A dye-based oil stain (“Oil stain cheek color” manufactured by Nippe Home Products) was evaluated in the same manner as in Example 1 to evaluate spectral characteristics and the like. Table of these results
Shown in 1.

Comparative Example 3 Comparison of light fastness with a commercially available wood stain In the same manner as in Example 1, a pigment-based water-based stain (“Pourstein Oak (9)” manufactured by Wako Shin Paint Co., Ltd.) was evaluated for spectral characteristics and the like. . The results are shown in Table-1.

[0035]

[Table 1]

From the above results, the water-based coloring material of the present invention has high transparency and excellent light fastness comparable to that of a pigment-based water stain, and is stable without sedimentation even after 3 days. It can be seen that it has excellent dispersion stability such that it is dispersed in.

[0037]

EFFECTS OF THE INVENTION According to the present invention, a film (coating film) having extremely excellent performance particularly in dispersion stability and light fastness while maintaining the vividness of color and having transparency, abrasion resistance and the like. ) An aqueous coloring material having excellent physical properties is provided. .

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Toshifumi Shiratani             1000 Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa             Within Mitsubishi Chemical Corporation (72) Inventor Kimiya Takeshita             1000 Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa             Within Mitsubishi Chemical Corporation (72) Inventor Munehiro Sakamoto             1000 Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa             Within Mitsubishi Chemical Corporation F-term (reference) 4J038 CC012 CC021 CC022 CC082                       CC092 CD002 CD021 CE022                       CF031 CF032 CG012 CG141                       CG142 CG172 CH031 CH032                       CH041 CH042 CH082 CH172                       CK032 DA061 DA141 DB001                       DD001 DG001 GA02 GA03                       GA08 GA12 KA08 MA02 MA08                       MA10 MA13 NA25                 4J039 AD02 AD04 AD09 AD10 AD12                       AD23 BE01 BE02 CA05 EA44

Claims (4)

[Claims] 1. A colorant is contained, and the average particle size is 100 n.
An aqueous coloring material comprising resin fine particles having a maximum particle diameter of 500 nm or less and an aqueous dispersion resin having a Tg lower than the Tg of the resin fine particles. 2. The water-based coloring material according to claim 1, wherein the coloring agent is a pigment or an oil-soluble dye. 3. The content of the colorant in the fine particles is 10% by weight.
It is above, The water-based coloring material in any one of Claim 1 or 2. 4. The Tg of the aqueous dispersion resin is −30 to 100 ° C.
It is the following, The water-based coloring material in any one of Claims 1-3.