JPS62177070A - Coloring solution - Google Patents

Abstract

PURPOSE:A coloring solution, containing titanium oxide having the surface treated with a silane coupling agent, color pigment, phosphoric acid ester based surfactant, resin and organic solvent as essential components without separation and settling of the pigment and useful for writing utensils, coating tools, manicures, etc. CONSTITUTION:A coloring solution containing (A) titanium oxide having the surface treated with a silane coupling agent, preferably a compound expressed by formula I (x is 1-4; R1 is 1-18C alkyl, phenyl, alkylphenyl or benzyl; R2 is 1-8C alkyl or phenyl) and/or titanate coupling agent, (B) coloring pigment, (C) a phosphoric acid ester based surfactant, preferably a compound expressed by formula II (n is 1-8; x is 1-3; R1 is 4-30C alkyl, alkenyl, alkylaryl, etc.; R2 is H or methyl; M is H, NH4, alkanolamine, etc.), (D) a resin and (E) an organic solvent capable of dissolving the resin (D).

Description

DETAILED DESCRIPTION OF THE INVENTION FIELD OF INDUSTRIAL APPLICATION This invention relates to colored liquids. More specifically, the present invention relates to a colored liquid in which a pigment is dispersed in a medium, and which has improved dispersion stability and is useful for writing tools, applicators, and cosmetic tools such as nail polish.

BACKGROUND OF THE INVENTION Several attempts have been made to stably disperse white pigments such as titanium dioxide in a medium. for example,
Japanese Patent Publication No. 55-7871 describes an ink for writing instruments containing a reaction product of titanium dioxide and a silane coupling agent. However, in the combination system of titanium dioxide and colored pigment, separation and sedimentation of the pigment are suppressed, and the pen tip or application member (equipped with capillary gaps)
Almost no effective embankment plan has been disclosed that satisfies dispersion stability and redispersibility by stirring, etc. to suppress clogging and ensure stable outflow.

Problems to be Solved by the Invention As a coloring liquid with a relatively low viscosity (approximately 1 oocps or less at 25°C) that uses titanium dioxide and a color pigment in combination,
A writing instrument that suppresses separation and sedimentation of titanium dioxide, improves dispersion stability and redispersibility over time, and suppresses clogging when passing through the pen tip or application member, allowing liquid to flow out stably over a long period of time. To provide a coloring liquid useful for applicators and cosmetic tools.

Means for Solving the Problems The colored liquid of the present invention comprises titanium oxide surface-treated with a silane coupling agent and/or a titanate coupling agent;
Contains as essential components a colored pigment, a phosphate ester surfactant, a resin, and an organic solvent that dissolves the resin,
A requirement is a configuration in which the above-mentioned components are dispersed.

In the above configuration, the untreated titanium oxide may be either rutile type or anatase type, but I! i! The rutile type is more desirable in terms of shielding power. Titanium oxide is generally surface-treated with silica or alumina, but it is also effective to use titanium oxide that has been surface-treated with barium sulfate, which has the property of enhancing the gloss of the coating film. The surface of titanium oxide is usually hydrophilic, so when it is applied to a non-aqueous solvent, it has conventionally been treated with a lipophilic resin, polymer, or metal salt of fatty acid. However, the dispersion stability was insufficient.

As a result of various studies on the surface treatment of titanium oxide particles, the present inventors found that the application of titanium oxide surface-treated with a silane coupling agent and/or a titanate coupling agent is effective as a coloring liquid for the purpose of the present invention. I discovered that. That is, as a silane coupling agent, the following general formula (1) % formula % (1) (wherein, and a benzyl group, R2 represents an alkyl group having 1 to 8 carbon atoms or a phenyl group, respectively), a silane having 1 to 4 alkoxy groups, and a silane having 1 to 4 phenoxy groups. It is selected from silane or a combination of an alkoxy group and a phenoxy group, and is used in an amount of 0.1 to 5.0% by weight (hereinafter expressed as %) based on the above titanium oxide, but a more preferable range is: 0,
5 to 1.5%.

Next, the titanate coupling agent will be described. The hydrophilic group of the coupling agent is selected from a monoalkoxy type, a chelate type such as an oxyacid residue, a glycol residue, a coordinate type bonded with a phosphite ester, etc. 10% is used, more preferably in the range of 1.0 to 5.0%. Note that the coupling agent is used as a surface treatment for titanium oxide, and the desired performance can also be obtained by post-adding it to a solvent. Furthermore, the particle size of titanium oxide is
From the viewpoint of hiding effect, the range is 0.05 to 0.5 μm, more preferably 0.15 to 0.4 μm.

Surface-treated titanium oxide can be obtained by adding the above-mentioned coupling agent to the above-mentioned titanium oxide and stirring for 30 minutes or more in a crusher or ball mill (dry method), or by adding the same weight of water and the coupling agent as the titanium oxide. Stir at high speed for 15 minutes with a disperser (
! After drying, completely dry in a constant temperature bath at 120°C.
It can be obtained by a method such as subsequent pulverization (wet method). The surface-treated titanium oxide mentioned above is 0 in the ink composition.
．． It can be blended in a range of 1 to 50%, more preferably 0.5 to 40%.

As the phosphate ester surfactant, the following general formula (2) is used.
Compounds that satisfy the following are effective.

(In the formula, n is a number from 1 to 8, X is a number from 1° to 3, R1
is an alkyl group having 4 to 30 carbon atoms, alkenyl group, alkylaryl group, aryl group, acrylic acid residue or methacrylic acid residue, R2 is hydrogen or methyl group, M is hydrogen, ammonium, alkanolamine, alkali metal or Each represents an alkaline earth metal. ) The phosphoric acid ester surfactant is blended in an amount of 0.1 to 10%, more preferably 0.5 to 5% of the total amount in the coloring liquid composition.

In addition to titanium oxide, the coloring agent blended in the coloring liquid of the present invention includes ultramarine blue, h+i blue, Bengara, carbon blank, etc.
Examples include organic pigments such as pigments, azo pigments, phthalocyanine pigments, thioindigo pigments, threne pigments, and quinacryline pigments, and fluorescent pigments of resin solid solution type of fluorescent dyes. In addition, if necessary, oil-soluble dyes obtained by treating basic dyes with resin acids, amine salts of acidic dyes, and solvent dyes such as salt products made of acidic dyes and basic dyes may also be used. It is possible. These colorants are used in the coloring liquid in an amount of 0.05 to 10%, more preferably 0.1 to 5%.

Examples of resins include ketone resin, polyacrylic ester resin, methacrylic ester resin, maleic M resin, esterified rosin, phenol resin, amino resin, polyamide resin, aliphatic or aromatic hydrocarbon resin, terpene resin, coumaron resin. , natural resins such as dammar, shellac, cellulose derivatives, vinyl chloride-vinyl acetate copolymers, styrene-maleic acid copolymers, vinyl polymers such as polyvinyl butyral, polyvinyl acetate, polyvinyl alkyl ethers, and modified alkyl ethers. Examples include resin. A portion of the above resin may be used as a coloring agent, or may be used as a surface treatment resin for pigments. It is effective to mix the amount of fat in the colored liquid in the range of 1 to 50%, more preferably 3 to 30%.

The organic solvent may be one that dissolves the resin and additives, and has a boiling point of 70 to 200 from the viewpoint of drying the colored liquid.
Solvents in the °C range are preferred. Aromatic hydrocarbons such as doluol and quidylol, esters such as ethyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, glycol ethers and glycol acetates such as methoxypropanol and butoxetanol are used. In addition, aliphatic hydrocarbons, alicyclic hydrocarbons, aliphatic alcohols, etc. can be used as diluting solvents.

Effect By adsorbing silane and/or titanate coupling agent on the surface of titanium oxide, it improves the affinity of inorganic pigments to existing substances such as other colorants and solvents, making them easier to disperse in the low viscosity range. , contributes to dispersion stabilization. It is presumed that the alkoxy group in the structure of the silane coupling agent orients the alkyl group outward on the surface of titanium oxide and chemically adsorbs it, thereby making the titanium oxide particles more compatible with the organic solvent. Any type of ditanate coupling agent (monoalkoxy type, chelate type, coordinate type, etc.) is adsorbed on the surface of titanium oxide and improves its affinity for the medium, similar to the silane coupling agent.

By using the above two types of coupling agents alone or in combination,
By promoting lipophilicization of the titanium oxide surface, a good dispersion can be obtained in a combined system of titanium oxide and an organic pigment. However, the main object of the present invention is a pen tip or an application member (liquid deriving body with capillary gaps such as a bundle such as a fiber bundle, a plastic porous body with continuous pores, or a plastic molded body having through holes in the axial direction). It is insufficient in terms of suppressing the separation of titanium oxide and coloring pigments and facilitating redispersibility.

The present inventors have found that if the dispersion system is intentionally changed into a slightly agglomerated system by blending a phosphate ester surfactant in the coloring liquid in addition to the coupling agent, the pen It was discovered that the coloring liquid of the present invention has remarkable effects in terms of suppressing the separation of pigments in the tip and coating member and redispersing them, and has completed the coloring liquid of the present invention. To explain this point, by adding a phosphoric acid ester surfactant to a mixed dispersion system of surface-treated titanium oxide and a color pigment to cause slight aggregation, the bulking effect and relative Synergistic effects such as a reduction in the specific gravity of the pigment and an increase in the repulsion between particles in the liquid are obtained, thereby preventing a decrease in hiding performance due to separation of the pigment in the liquid extractor having capillary gaps, and the method itself is long-lasting. Even after a long period of time, it can be easily redispersed by slight stirring or vibration.

Examples Colored liquids for Examples (1-5) and Comparative Example (1-5) were prepared as follows. Note that all parts in the following formulations are parts by weight.

(1) Preparation of surface-treated titanium oxide A predetermined amount of titanium oxide and a camping agent were mixed and stirred using a crusher for 1 hour to obtain the surface-treated titanium oxide shown in Table 1.

(2) Preparation of white paste After melting the resin and, if necessary, a surfactant in a solvent, add surface-treated titanium oxide (see Table 1), and add glass beads (1,0 ~2.Ova+)
Dispersion was prepared using a paint conditioner for 1 hour. tK-2-'! "=v) Table-1 Composition of surface-treated titanium oxide Explanation in the (Note) column of Table-3 Composition of (Note 1)
Composition of (Note 2) [Pigment Yellow #48 (C , 1,77160) 25.0 parts, n-butyl polyacrylate 37°0 parts, nonionic surfactant 1.0 parts, mineral turpentine 37.0 parts]. Banbury mixer for quantitative determination
Alternatively, the chips obtained by dispersing or kneading with a 3-wood roll are stirred with a solvent for 5 hours using a disper.

(Note 3) 60% luene solution of soybean oil alkyd resin (manufactured by Arayo Kagaku Kogyo ■), (Note 4) Terpene phenol resin (manufactured by Yasuyu Kogyo ■), (Note 5) Phosphate ester polyoxyethylene lauryl ether , (Note 6) Phosphate ester polyoxyethylene lauryl ether monoethanolamine salt (manufactured by Daiichi Kogyo ■), (Note 7) Phosphate ester polyoxyethylene dodecyl phenyl ether (Toho Chemical Industry type) Handwriting in Table 4 above As shown in the comparison table of hiding performance, the coloring liquid of the present invention is a system containing only titanium oxide surface-treated with a coupling agent (no phosphate ester surfactant coexisted) or a system containing no phosphate ester surfactant. However, compared to a system that does not use titanium oxide and is surface treated with a coupling agent, it not only shows better concealment of initial handwriting, but also shows that when the pen body is impregnated with a colored liquid, The three components of titanium oxide, colorant, and vehicle always maintain a predetermined ratio in the pen body even after being stored for a long time. It is now possible to suppress the separation and sedimentation of pigments in the pen body or application member, which was considered a weak point, and is effective as a coloring liquid for writing instruments, applicators, cosmetics, etc.

Claims (1)

[Claims] 1 Contains as essential components titanium oxide surface-treated with a silane coupling agent and/or titanate coupling agent, a colored pigment, a phosphoric acid ester surfactant, a resin, and an organic solvent that dissolves the resin. A colored liquid made by 2. The colored liquid according to claim 1, wherein the silane coupling agent is a compound represented by the following general formula (1). (R_1)_4_-_XSi(OR_2)_X...(1
) (wherein, X is a number of 1 to 4, R_1 is a number of carbon atoms of 1 to 1
R_2 represents an alkyl group having 1 to 8 carbon atoms or a phenyl group, respectively. ) 3. The colored liquid according to claim 1, wherein the phosphoric acid ester surfactant is a compound represented by the following general formula (2). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(2) (In the formula, n is a number from 1 to 8, x is a number from 1 to 3, R_1
is an alkyl group having 4 to 30 carbon atoms, alkenyl group, alkylaryl group, aryl group, acrylic acid residue or methacrylic acid residue, R_2 is hydrogen or methyl group, M is hydrogen, ammonium, alkanolamine, alkali metal or Each represents an alkaline earth metal. )