JPH01301760A - aqueous pigment dispersion - Google Patents

Abstract

PURPOSE:To obtain the subject dispersion in a stable dispersion state suitable as a colorant in recording liquids for inks of writing utensils, jet printing, etc., by dispersing a pigment prepared by adsorbing a higher fatty acid (salt) on the surface, etc., in water using a nonionic surfactant, etc., having a high HLB value. CONSTITUTION:The objective dispersion obtained by dispersing a pigment prepared by adsorbing or binding a higher fatty acid (e.g. lauric or stearic acid) and/or a salt thereof on the surface thereof in water using a nonionic surfactant (preferably polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, etc.) and/or an anionic surfactant (preferably polyoxyethylene alkyl ether sulfate, etc.) having >=8 HLB.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to an aqueous pigment dispersion with stable dispersion and little sedimentation over time, which can be used in writing instrument inks, liquid cosmetics, diene 1 to printing, etc. The present invention relates to an aqueous pigment dispersion that can be suitably used as a colorant for recording liquids.

(Prior Art) In recent years, pigments have been widely used instead of dyes as coloring agents for writing instrument inks, liquid cosmetics, and recording liquids for jet printing because of their excellent water resistance and weather resistance.

However, unlike dyes, pigments have the property of not being soluble in water, or having very little solubility in water. Various surfactants and water-soluble resins are used alone or in combination as dispersants to make the pigments more easily wetted and to prevent the pigments from settling over time. A commonly used method is to make the material finer.

(Problems to be Solved by the Invention) However, although the conventional dispersion method described above can provide an aqueous pigment dispersion with a certain degree of dispersion stability and little sedimentation over time, it is difficult to obtain sufficient dispersion stability and prevention of sedimentation. It is difficult to say that this has been achieved, and recording liquids such as writing instrument inks, liquid cosmetics, and printing liquids that use aqueous pigment dispersions obtained by conventional dispersion methods as colorants, In some cases, problems such as clogging of the ink discharge area due to sedimentation occurred.

Therefore, the present invention can be suitably used as a coloring agent for ink for writing instruments, liquid cosmetics, recording liquid for jet printing, etc.
The purpose of the present invention is to provide an aqueous pigment dispersion with stable dispersion and little sedimentation over time.

(Means for Solving the Problems) The present invention uses a pigment having a higher fatty acid and/or a salt thereof adsorbed or bonded to the surface of a nonionic surfactant having an HLB of 8 or more and/or an anionic surfactant. The gist of the invention is an aqueous pigment dispersion characterized in that it is dispersed in water using an agent.

The present invention will be explained in detail below.

The higher fatty acid and/or its salt adsorbs or binds to the surface of the pigment, thereby once making the pigment surface lipophilic, and the nonionic surfactant and/or anionic surfactant having an HLB of 8 or more described below. It is used to improve the dispersion of the pigment in water by an agent, and specifically, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, undecylenic acid, and lanolinic acid. , isostearic acid, and their alkali metal salts and alkanolamine salts are used, and the amount used is preferably 1 to 100% by weight based on the pigment.

A nonionic surfactant and/or anionic surfactant with an HL B of 8 or more is used to micelle the pigment whose surface has been made lipophilic with the higher fatty acid and/or its salt and to stably disperse it in water. HL
Conventionally known nonionic surfactants with B of 8 or more can be used without particular limitation, but among them polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene polyoxypropylene alkylphenyl ether, polyoxyethylene Oxyethylene alkyl amines and the like are preferably used, and anionic surfactants can also be used without particular limitation, but among them, alkyl sulfates, polyoxyethylene alkyl ether sulfates,
Alkyl sulfosuccinates, N-a=3-syl amino acid salts, etc. are preferably used, and the amount used is as follows:
5 to 70% by weight, based on the pigment, is preferred.

Note that nonionic surfactants with an HLB of less than 8 are not used because they have low solubility in water and have very weak dispersion effects.

The pigment is used as a coloring agent, and conventionally known pigments can be used. Specific examples include titanium oxide, carbon black, black iron oxide, yellow iron oxide, red iron oxide, ultramarine blue, navy blue, and cobalt blue. , Chrome Green, Chrome Oxide, Hansa Yellow 10G, Hansa Yellow 5G, Hansa Yellow 3G, Hansa G, Hansa Yellow
1 Do A, Benzidine Yellow, Permanent NCG
, Tartrazine Lake, Quinoline Yellow, Sudan 1,
Permanent Orange, Indanthrene Brilliant Orange GK, Permanent Brown FG, Para Brown, Pernent Red 4R, Firelet, Brilliant Carmine BS, Pyrazolone Red, Lake Red C
, Brilliant Carmine 6B, Bordeaux 5B, Thioindigo Red B, Fast Violet-4 = B, Dioxane Violet, Alkaline Blue Lake,
Phthalocyanine blue, indigo, acid green lake, phthalocyanine clean, etc. are used.

Water is used as a dispersion medium.

To obtain the aqueous pigment dispersion according to the present invention, first, the pigment and the higher fatty acid and/or its salt are mixed and dispersed using a conventionally known dispersing machine such as a three-roll mill or a sand mill. Adding a nonionic surfactant and/or anionic surfactant with an HLB of 8 or more to
The pigment is mixed with the organic solvent solution of the higher fatty acid and/or its salt, and the mixture is gradually added to water with stirring to form an aqueous pigment dispersion. After dispersing the organic solvent by distillation, the nonionic surfactant and/or anionic surfactant having an HLB of 8 or more is added and mixed, and the mixture is poured into water with stirring. A method of gradually adding to an aqueous pigment dispersion,
The pigment having the higher fatty acid and/or its salt adsorbed or bonded to the surface is added to an aqueous solution in which the nonionic surfactant and/or anionic surfactant having an HLB of 8 or more is dissolved and stirred to form an aqueous solution. Examples include a method of preparing a pigment dispersion.

The aqueous pigment dispersion obtained from the above-mentioned essential components is used as a coloring agent for recording liquids such as inks for writing instruments, liquid cosmetics, and jet printing; In order to satisfy the quality characteristics required for each recording liquid for writing instruments, etc., as necessary, various complementary color inks conventionally used in the above-mentioned writing instrument inks, liquid cosmetics, jet printing recording liquids, etc. Dyes, water-soluble organic solvents such as urea, thiourea, ethylene urea and their derivatives, glycols, glycol ethers, and glycerin as anti-drying or moisturizing agents, various preservatives and anti-mold agents,
Viscosity modifiers and anti-settling aids include proteins such as gelatin, albumin and casein, water-soluble natural gums such as acacia and gum tragacanth, glucosides such as saponin, cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxymethylcellulose, Water-soluble polymers such as polyvinyl alcohol, polyvinylpyrrolidone, and polyethylene glycol, various alkalizing agents as p and H adjusters, etc. can be added as appropriate.

(Function) The aqueous pigment dispersion according to the present invention has a pigment having HLB8
Since the above-mentioned nonionic surfactants and/or anionic surfactants are dispersed in water, the pigment particles are covered with higher fatty acids and/or their salts, and furthermore, the nonionic surfactants with HLB8 or higher Since it is in a type of micelle state surrounded by an anionic surfactant and/or an anionic surfactant, it is assumed that it is stably dispersed in water and is also prevented from settling over time.

(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples. In the Examples and Comparative Examples, the term "parts" simply indicates "parts by weight."

Example 1 30.0 parts of Sicomet Black 85 (black iron oxide,
(manufactured by BASF) Oleic acid 10.0 parts Nikkor NP-105.0 parts (polyoxyethylene polyoxypropylene nonylphenyl ether, HLB16.5, manufactured by Nikko Chemicals ■) Purified water 55.0 parts In the above bone,
First, the total amount of Shicomet I Black 85 and oleic acid was thoroughly mixed to make it homogeneous, and then milled in a three-roll mill.
I ran it through 0 times. In this one, Nisocol NP
After adding the entire amount of -10 and stirring for 1 hour, it was gradually added to the entire amount of purified water with stirring to obtain a black aqueous pigment dispersion.

Example 2 Konjiyo 25, O parts (Kosei, manufactured by Daito Kasei Kogyo ■) Isostearic acid 10.0 parts Nitsukoru ○
T]? -1006,5 parts (1-1-lium di-2-ethylhexylsulfosuccinate,
(manufactured by Nikko Chemicals) Benzene 10.0 parts Purified water
4,885 parts of the above components The above-mentioned isostearic acid was dissolved in benzene, to which was added radish and stirred for 30 minutes. After further dispersion in Santomil for 1 hour, benzene was distilled off. Niracol 0TP for this thing
Purified water in which the entire amount of -100 was dissolved was added and stirred for 1 hour to obtain a blue aqueous pigment dispersion.

Example 3 Red No. 226 20.0 parts (Herringdon Pink CN, manufactured by Daito Kasei Kogyo ■) Sodium laurate 2.5 parts Myristic acid
2.5 parts Ethanol 10.0 parts Nilacol BL-212.5 parts (polyoxyethylene lauryl ether, HLB 19.
O1 (manufactured by Nikko Chemicals ■) Niracol 5EL-4, N 2.5 parts (polyoxyethylene lauryl ether sulfate sodium salt, manufactured by Nikko Chemicals ■) Purified water 60. Part ○ Among the above ingredients,
First, sodium laurate and myristic acid were dissolved in ethanol, Red No. 226 was added thereto, the solution was stirred for 30 minutes, and the solution was passed through a three-roll mill 10 times, after which the ethanol was distilled off. This one is Niracol BL-2
Purified water in which all of Niracol SEL-4N and Niracol SEL-4N were dissolved was added and stirred for 1 hour to obtain a red aqueous pigment dispersion.

Oleic acid (+i 4- MA-10030, 0 parts (carbon black, manufactured by Mitsubishi Chemical Industries, Ltd.)
10.0 parts Nitskor NP-1,0
5.0 parts (polyoxyethylene polyoxypropylene nonylphenyl ether, HLB16.5, manufactured by Nikko Chemicals ■) Sodium hydroxide 0.6 parts Purified water
54.4 parts Among the above ingredients, firstly, ShiM,
After the total amounts of A-1, OO and oleic acid were thoroughly mixed and made uniform, the mixture was passed through a three-roll mill 10 times. Add the whole amount of Niracol NP-10 to this and 1
After mixing and stirring for a period of time, this was gradually added to purified water in which the entire amount of sodium hydroxide had been dissolved in advance, with stirring, to obtain a black aqueous pigment dispersion.

Application example 1 (eyeliner) Aqueous pigment dispersion obtained in Example 1 80.0 parts Propylene glycol 10.0 parts Mechinsu M
O, 5 parts (methyl paraoxybenzoate, preservative and anti-mold agent, manufactured by Ueno Pharmaceutical ■) Peptide pA-xoo 5.0 parts (polypebutite, anti-settling agent, manufactured by ■Nitsupi) Purified urea 1.5 parts Purified water
3.0 parts of the two-legged component, purified water is added to a mixture of Metzkins M dissolved in propylene glycol and mixed uniformly, then Peptide PA-100 and purified urea are added and dissolved. The aqueous pigment dispersion obtained in Example 1 was gradually added to this solution while stirring to obtain a black eyeliner.

Application example 2 (eye shadow) 20.0 parts of the aqueous pigment dispersion obtained in Example 2 Newside sc 0.3 parts (I-lium dehydroacetate, preservative/mold-proofing agent, manufactured by Nippon Gosei Kagaku ■) Hover/ L/PVA-105 1.0 parts (polyvinyl alcohol, viscosity modifier, manufactured by Kuraray) = 12- Purified water 78.7 parts Glycerin and Newside SC dissolved in 63.7 parts of purified water among the above ingredients The aqueous pigment dispersion obtained in Example 2 was gradually added while stirring, and the mixture was stirred for 30 minutes. Then, a solution prepared by heating and dissolving Poval PVA-105 in 10 parts of purified water was added thereto, and the mixture was stirred for an additional 20 minutes. A blue eye shadow was obtained by stirring.

Application example 3 (blushing) Aqueous pigment dispersion obtained in Example 3 20.0 parts 1.3-butylene glycol 12.0 parts Phenoxyethanol 0.2 parts (preservative and fungicide, manufactured by Toho Chemical Industry ■) Peptide PA- 1002, 8 parts Purified urea 2.0 parts Kelgin LV
1.0 part (sodium alginate, viscosity modifier, made by Gosho ■) Purified water 6
2.0 parts Among the above ingredients, phenoxyethanol is dissolved in 1,3-butylene glycol, and a solution of Peptide PA-100, purified urea, and Kelgin LV dissolved in purified water is added to this and stirred to make it homogeneous. The aqueous pigment dispersion obtained in Example 3 was gradually added to this while stirring, and the mixture was further stirred for 1 hour to obtain a red blush.

A □Example 2 (writing instrument ink) Aqueous pigment dispersion obtained in Example 4 35.0 parts Ethylene glycol 15.0 parts Purified urea
3.0 parts glue HG-1,320,
4 parts (JIS Class 3 glue, anti-settling aid, manufactured by Nisopi) Gelaton BCA-30D 4.0 parts (glue decomposition product, anti-settling aid, manufactured by Sun Orient Chemical ■) Broxel X, L-22.0 parts ( 1,2-benzisothiazolin-3-one, preservative and anti-mold agent, manufactured by ICI Japan ■) Purified water 40.6 parts Among the above ingredients, Broxel XL-2 was dissolved in ethylene glycol, and purified water was added to it to homogenize. After mixing with Glue HG-
132 Gelaton BCA-30D and purified urea are added and dissolved.

The aqueous pigment dispersion obtained in Example 4 was gradually added to this solution with stirring to obtain a black writing instrument ink.

Comparative Example 1 (Eyeliner) Oleic acid was removed in Example 1, purified water was added accordingly, and all components were passed through a three-roll mill 10 times to obtain a black aqueous pigment dispersion.

The black aqueous pigment dispersion was prepared in Example 1 in Application Example 1.
Application example 1 except that it was used instead of the aqueous pigment dispersion obtained in
A black eyeliner was obtained in the same manner as above.

Comparative Example 2 (Eye Shadow) Nilacol 5S-10 (pigment surface lipophilic agent, sorbitan monostearate 1~, HLB4.7, manufactured by Nikko Chemicals ■) was used instead of isostearic acid in the components of Example 2. A blue aqueous pigment dispersion was obtained in the same manner as in Example 2 except for this.

The blue aqueous pigment dispersion was prepared in Example 2 in Application Example 2.
Application example 2 except that it was used instead of the aqueous pigment dispersion obtained in
A blue eye shadow was obtained in the same manner.

Calendar λ (cheek blush) Red No. 226 2060 copies SMA-10
00 6.0 parts (styrene-maleic anhydride copolymer, manufactured by Arco Chemical) Purified water 74.0 parts Among the above components,
Red No. 226, SMA-1000, and 20 parts of purified water were mixed, passed through a three-roll mill 10 times, and gradually added to the remaining purified water with stirring to obtain a red aqueous pigment dispersion. Ta.

The red aqueous pigment dispersion was prepared in Example 3 in Application Example 3.
Application example 3 except that it was used instead of the aqueous pigment dispersion obtained in
A red blush was obtained in the same manner.

Comparative Example 4 (Ink for Writing Instruments) In Example 4, oleic acid was removed, purified water was added accordingly, and all components were passed through a three-roll mill 10 times to obtain a black aqueous pigment dispersion.

The black aqueous pigment dispersion was prepared in Example 4 in Application Example 4.
Application example 4 except that it was used instead of the aqueous pigment dispersion obtained in
A black writing instrument ink was obtained in the same manner as above.

(Effects) Application examples 1 to 3 above. Each of the cosmetics obtained in Comparative Examples 1 to 3 was filled into an applicator equipped with a prototype urethane nib having continuous pores or a nib made of bundled nylon filamen I- as an applicator. 4. The ink for writing instruments obtained in Comparative Example 4 was filled into a commercially available brush pen (Pentel Fude Pen, manufactured by Pentel ■) equipped with a urethane nib having continuous pores to prepare a test sample, and a quality test was conducted. . (
However, Application Example 1.2 and Comparative Example 1.2 were filled with an applicator equipped with a urethane pen tip, and Application Example 3 and Comparative Example 3 were filled with an applicator equipped with a pen tip with a bundle of nylon filaments 1 to 1. . ) The results are shown in Table 1.

Table 1 ■Dispersion stability test
The condition of agglomeration of the pigment particles was observed.

O: No aggregation Δ: Slight aggregation ×: Aggregation ■ Time-lapse sedimentation test *2: Each cosmetic was placed in a test tube with a lid, and after being left at room temperature for 6 months, the state of sedimentation was observed.

O: No sedimentation △: Slight sedimentation ×: Much sedimentation ■ Time-lapse clogging test *3: Samples filled with each cosmetic and writing instrument ink were left at room temperature for one month with the pen tip facing downward. , perform the application (writing), and apply the application (
I observed the traces of the brush strokes.

○: Good application (brush) marks without clogging △: Slight clogging occurs, and the application (brush) marks at the beginning of writing are slightly faded, but it becomes a good application (brush) mark ×: Application with clogging (Brush) As long as the marks are blurred, as explained in detail by taking cosmetics and ink for writing instruments as an example, the aqueous pigment dispersion according to the present invention has stable dispersion and does not easily settle over time, so it can be used for writing instruments. An aqueous pigment dispersion that can be suitably used as a coloring agent in recording liquids such as inks, liquid cosmetics, and jet printing without causing problems such as clogging at the ink ejection part due to sedimentation over time. It is.

Patent applicant: Pentel Co., Ltd.

Claims (1)

[Claims] A pigment having higher fatty acids and/or salts thereof adsorbed or bonded to the surface thereof is dispersed in water using a nonionic surfactant and/or anionic surfactant with an HLB of 8 or more. Aqueous pigment dispersion.