JPS59217776A - Aqueous pigment composition - Google Patents

Abstract

PURPOSE:The titled composition, containing a specific titanium oxide based mixed pigment and a copolymer of an unsaturated compound monomer and an unsaturated carboxylic acid monomer in a specific proportion, having a high hiding power and improved storage stability, light and chemical resistance, and useful for aqueous printing ink, etc. CONSTITUTION:An aqueous pigment composition obtained by incorporating (A) a mixed pigment obtained by mixing (i) 100pts.wt. titanium oxide with (ii) 5- 100pts.wt. aluminum silicate based pigment with (B) a copolymer of (i) an unsaturated compound monomer having a carbon-carbon double bond, e.g. an acrylic acid ester, and (ii) an unsaturated carboxylic acid monomer, e.g. maleic anhydride, having 30-500 acid value at (20:1)-(1:2) weight ratio between the components (A) and (B). EFFECT:Matte color after use. USE:An aqueous ink for writing utensils, poster colors, water colors for watercolor paintings, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aqueous pigment composition suitable for aqueous inks for writing instruments, poster colors, watercolor paints, aqueous printing inks, and the like. More specifically, the present invention has the advantages of high hiding power during use, good storage stability, a matte color after use, and excellent light resistance, water resistance, and chemical resistance. The present invention relates to an aqueous pigment composition shown in FIG.

In general, writing ink must have the following properties: to flow smoothly from the core material of the writing instrument, not to clog, not to dry easily in the core material, and not to solidify within the writing instrument due to changes over time. Furthermore, it must be harmless to the human body, non-flammable, have little odor, and the characters formed after use must be light-resistant, water-resistant, and chemical-resistant.
Desirable properties include being clear, being able to be recoated, not penetrating too much into the base material, and not setting off.

However, the oil-based writing that is usually used
.

In addition to containing a flammable substance that is harmful to the human body and has a strong odor, ink for writing tools has the disadvantage that the characters formed by writing lack sharpness and cannot be overcoated.

On the other hand, water-based inks for writing instruments solve the above-mentioned problems of oil-based inks, but the characters that are shaped by writing become unclear, and the light resistance and
It inevitably lacks water resistance and chemical resistance, or becomes difficult to recoat. This problem can be solved to some extent by using pigments instead of dyes as coloring agents, but pigments! When stored for a long period of time, the pigments in the water-based ink tend to aggregate, resulting in clogging of the core material of the writing instrument and precipitation of the pigment in the container, resulting in the inability to write properly. This causes problems such as not being able to obtain the color tone and clarity of the image.

For this reason, various proposals have been made to solve these problems in water-based inks that use pigments as coloring agents. For example, a method in which a pigment is dispersed in an aqueous medium containing a hydrophilic organic solvent using a polymer containing an alkyl ester of acrylic acid or meth-3-acrylic acid as a main component (Japanese Patent Publication No. 55-λ6434); A method of adding short asbestos fibers to the ink (Japanese Patent Publication No. 52-40256), a method of centrifuging water-based ink to remove coarse particles that tend to settle (
Japanese Unexamined Patent Publication No. 5,616,1466) and the like have been proposed.

By the way, in order to make the characters etc. formed after writing clear and to make it possible to apply multiple coats, it is important to use a pigment with hiding power as a coloring agent. Titanium oxide is the most effective. Therefore, as a water-based ink using a pigment as a coloring agent, it is desirable to use titanium oxide or titanium oxide and an organic pigment as a coloring agent, and it is possible to easily obtain an intermediate color by using such a water-based ink. There is also the advantage of being able to do so.

However, in all of the above-mentioned methods proposed so far, it has been difficult to obtain a low-viscosity, high-concentration aqueous pigment composition when titanium oxide or titanium oxide and an organic pigment are used as colorants.

41 In view of these circumstances, the present inventors have conducted intensive research to provide an aqueous pigment composition that satisfies each property required as a pigment for writing instruments, and have found that titanium oxide and aluminum silicate This objective can be achieved by using a pigment composition consisting of an aqueous dispersion containing a pigment based on pigments, or a mixed pigment consisting of a titanium oxide, aluminum silicate pigment, and an organic pigment, and a specific resin in a predetermined ratio. Based on this finding, the present invention has been completed.

That is, 1. the present invention comprises (A) a mixed pigment containing 5 to 100 parts by weight of an aluminum silicate pigment and optionally 100 parts by weight or less of an organic pigment per 100 parts by weight of titanium oxide; 1; and (B) a carbon-carbon double pigment. A copolymer of an unsaturated compound monomer having a bond and an unsaturated carboxylic acid monomer having an acid value of 30 to 500 is prepared in a weight ratio of component (A) to component (13) of 20: The aluminum silicate pigment used in the composition of the present invention is protected in the aqueous pigment dispersion. In order to exhibit the function of Colloid-5-et al. 21 with a low viscosity, for example, the viscosity is 100 centipoise (hereinafter referred to as cps) or less, preferably 5
To reduce changes over time in a dispersion system during storage of an aqueous pigment composition containing titanium oxide with a low viscosity such as Q cps or less, or a titanium oxide and an organic pigment as a coloring agent, and give it a matte appearance. By imparting the above-mentioned matte tone, the cursive writing has a clear color tone and a good texture, and has the advantage that the eyes do not get tired even when looking at it for a long time.

Therefore, aluminum silicate pigments and titanium oxide,
Alternatively, an aqueous pigment composition using a mixed pigment that is a combination of these and an organic pigment as a coloring agent has a high hiding power, a matte appearance, and even at low viscosity, there is extremely little change in the dispersion system over time during storage. It will be later.

The titanium oxide used in component (A) of the composition of the present invention may be either rutile type or anatase type, but rutile type is preferable from the viewpoint of high hiding power. Furthermore, aluminum silicate pigment is a mixture whose main components are silicon dioxide and aluminum oxide. double) -6
- Although the effects of the present invention can be expected to some extent even when silicon oxide is used alone, the effects of the present invention are greater when a mixture of silicon dioxide and aluminum oxide is used. The mixing ratio of the two is appropriately selected depending on the purpose of use.

Examples of organic pigments used in component (A) include azo pigments such as azo lake, insoluble azo pigments, condensed azo pigments, and chelate azo pigments; phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, and thioincy pigments. , polycyclic pigments such as isoindolinone pigments and quinophthalone pigments; dye lakes such as basic dye lakes and acidic dye lakes; nitro pigments; nitroso pigments; aniline black; and daylight fluorescent pigments. . Preferred among these are azo pigments, polycyclic pigments, dye lakes, and daylight fluorescent pigments, and among the azo pigments are insoluble azo pigments and azo lakes, and among the polycyclic pigments are phthalocyanine pigments, Particular preference is given to quinacridone pigments, dioxazine pigments and anthraquinone pigments. These pigments may be used alone or in combination of two or more.

Next, specific examples of these pigments are shown in the table, but the pigments that can be used in the present invention are not limited to these examples.

The mixing ratio of each pigment in the mixed pigment used as component (A) of the composition of the present invention is 5 to 100 parts by weight, preferably 1 part by weight of aluminum silicate pigment per 100 parts by weight of titanium oxide.
0 to 50 parts by weight, if an organic pigment is used, the amount is 10
The amount is selected within the range of 0 parts by weight or less, preferably 60 parts by weight or less. If the amount of aluminum silicate is less than this, the storage stability will be lowered and a matte tone will not be obtained, and if it is more than this, the viscosity of the aqueous pigment composition will increase and its suitability will decrease. On the other hand, even if the amount of organic pigment is greater than the above, the color density does not change and the ink properties tend to be impaired.

The copolymer used as component (B) of the composition of the present invention has both the function of dispersing the above-mentioned mixed pigment and the function of adhering the pigment to the base material, and has a carbon-carbon double bond. It is obtained by copolymerization of an unsaturated compound monomer with an unsaturated carboxylic acid monomer. Examples of the unsaturated compound monomer having a carbon-carbon double bond include esterhestyrene unsaturated carboxylates such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate; Examples include aromatic vinyl compounds such as vinyltoluene, chlorinated vinyl compounds such as vinyl chloride and vinylidene chloride, nitrile compounds such as acrylonitrile, organic vinyl acids such as vinyl acetate and vinyl noropionate, and natural organic compounds such as rosin. be able to. Among these, acrylic esters, methacrylic esters, styrene and rosin are preferably used.

On the other hand, unsaturated carboxylic acid monomers include, for example, monobasic lower unsaturated carboxylic acids such as acrylic acid and methacrylic acid, dibasic unsaturated carboxylic acids such as maleic acid, maleic anhydride, itaconic acid, and fumaric acid, and maleic acid. Examples include dibasic unsaturated carboxylic acid monoesters such as acid monoalkyl esters and fumaric acid monoalkyl esters. Particularly preferred among these are maleic anhydride and itaconic acid.

This copolymer of an unsaturated compound monomer and an unsaturated carboxylic acid monomer can be prepared, for example, by mixing the above-mentioned monomer components in a predetermined ratio, and then using a peroxide catalyst or an azo compound catalyst according to a conventional method. It can be produced by copolymerization.

This copolymer may be either a random copolymer or a block copolymer, or may be obtained by graft polymerizing an unsaturated carboxylic acid to a polymer or copolymer of an unsaturated compound monomer having a carbon-carbon double bond. It may also be something you have.

Although the ratio of each monomer component in the copolymer used as component (B) of the composition of the present invention can be arbitrarily selected, it is necessary that the acid value of the produced copolymer be in the range of 30 to 500. be.

If this acid value is less than 30, the solubility of the resin in an aqueous solution is poor, while if it exceeds 500, it will adversely affect the physical properties of the coating film such as water resistance.
It is in the range of 200. Moreover, this copolymer may be used alone or in combination of two or more types.

In the present invention, when using the resin, it is preferable to dissolve it in an alkaline aqueous solution. The alkaline substance used in this alkaline aqueous solution is preferably an inorganic alkali substance such as sodium hydroxide, potassium hydroxide, or ammonia, or an organic amine such as monoethanolamine, jetanolamine, monoisozolopanolamine, or morpholine. It is desirable to use these to adjust the pH of the composition to a range of 7.5 to 11.0.

The blending ratio of the mixed pigment and resin in the composition of the present invention is as follows:
20:1 to 1:2, preferably 10:1 by weight
Mixed pigment with a blending amount of resin ranging from 1:1 to 1:1
If the amount is less than 5 parts by weight, the ability to disperse the mixed pigment and the ability to adhere the pigment to the substrate will be poor;
If the amount exceeds 0.00 parts by weight, the ability to adhere the pigment to the base material will not improve, and it will not become matte, which is impractical.

In the composition of the present invention, it is preferable to use a surfactant in order to promote the dispersion effect of the mixed pigment. As this surfactant, an anionic surfactant, a nonionic surfactant, or both can be used.

Among these, nonionic surfactants are H, L, B, 8~
18 is preferable, and HlL, B, is preferably 11 to
7-ionic surfactants in the range of 16 are preferred.

The amount of this surfactant to be blended is desirably 20% by weight or more based on the mixed pigment. If this amount exceeds 20 Ichikawa, the water resistance of the coating film will be poor.

Further, in the composition of the present invention, it is preferable to use alcohol in order to adjust the drying rate of the composition. These alcohols include those that perform a quick-drying function and those that perform a slow-drying function. Examples of alcohols that perform a quick-drying function include hamethyl alcohol, ethyl alcohol, isozologyl alcohol, and phthyl alcohol. Examples include monohydric alcohols. On the other hand, those having a slow-drying function include, for example, polyhydric alcohols such as ethylene glycol, diethylene glycol, and diethylene glycol, and alkyl ethers of polyhydric alcohols such as ethylene glycol monoethyl ether and ethylene glycol monoethyl ether. Each of these alcohols may be used alone or in combination of two or more, and the blending amount is 5% relative to the amount of water used.
It is desirable that the amount is 0% by weight or less.

Further, the amount of water used in the composition of the present invention is usually 25% by weight or more based on the mixed pigment.

The composition of the present invention is prepared by kneading and grinding each component with water using, for example, a sand mill, an attriday mill, a ball mill, a three-roll mill, a colloid mill, or the like.

The aqueous pigment composition of the present invention has a large hiding power when used, has a matte appearance, and has good dispersion stability during storage, and has excellent physical properties such as light resistance, water resistance, and chemical resistance. In addition, it has the characteristics of less odor and less penetration into the base material compared to oil-based inks, and can be used as is or semi-finished products for water-based inks for writing instruments, poster colors, water-based inks for water paints, etc. It can be used as

The invention will be explained in further detail by the following examples.

In addition, all parts and parts in the examples represent parts by weight and weight %.

Moreover, each characteristic was evaluated as follows.

Concealability: Mitsubishi felt-tip pen water-based W-50012c
The glossiness t was evaluated in comparison with Lotus and was measured using a Nigelosmeter (1 to ioo Chiro o0 mirror gloss meter, manufactured by Toyo Seiki Seisakusho Co., Ltd.).

Storage stability: Evaluated by measuring the viscosity after standing in a constant temperature bath at 50° C. for 6 months using a B-type viscometer (manufactured by Akira Tokyo Keiki).

Water resistance: After writing on imitation paper and allowing it to stand for 2 minutes, it was immersed in water for 5 seconds and the bleeding of the drawn lines was examined.

Light resistance: Discoloration and fading was examined using a Ford 0 meter for 100 hours.

15-Example 1 Titanium JR-602 (Rutile type titanium oxide, Teikoku Kako (
100 copies of Optiwhite P (810251,
0 to 52.4 inches, A120342.1 to 44.3 inches, made by Varghese) ioL Cyan Blue MS Paste (C
1 ■ Pigment Blue 15, manufactured by Mikuni Shiki (I)) 8 parts (
(excluding pigment (2 parts)), Hicoat PL-200 (acid value 85, manufactured by Toyo Kagaku @)) 60 parts (resin content 21 parts), ethyl alcohol 20 parts, ethylene glycol 5 parts, and Emulgen A
-90 (nonionic surfactant, HLB 14.5,
After adding 6 parts of Kao Soap (manufactured by I) and adding water to make a total of 300 parts, and dispersing it in a sand mill for about 1 hour, the pH was 8.5, the viscosity was 25 cps, and the pigment content was 37.
．． A 0% light blue, pastel-like aqueous pigment composition with excellent hiding properties was obtained.

The storage stability of this composition at low viscosity was investigated,
In addition, the felt was packed in a water-based signboard and actual writing was performed to examine the concealability, glossiness, water resistance, and light resistance.

As a result, the storage stability, water resistance, and light resistance were all good, the hiding power was sufficient, and the gloss was 2.

Example 2 100 parts of titanium JR-602, Ozochi White P15
parts, Hyros 5M-27 (styrene maleic acid resin, acid value 200-250, manufactured by Seiko Kagaku Co., Ltd.) 15 parts, 25 thiammonia water 6 parts, ethyl alcohol 20 parts, ethylene glycol 5 parts, and Emuln A-907 parts , water was added to make a total of 300 parts, and the mixture was dispersed in a sand mill for about 1 hour, resulting in a white aqueous pigment with excellent hiding properties, pH 8.5, viscosity 2 BCp, and 33.0 cm outside the pigment. A composition was obtained.

As a result of examining various properties of this composition, it was found that this composition had sufficient hiding power and was excellent in physical properties such as storage stability with a gloss level of 2%, water resistance, and light resistance.

Example 3 Titanium JR-500 (rutile type titanium oxide, Teikoku Kako ■
) to 100 parts of aluminum silicate #5o (5
to251.0-52.4 section, A/2C) 342.1
~44.3cm, manufactured by Baders) 25 parts, Hump Yellow GLN paste (c, ■ Pigment Yellow 74, manufactured by Mikuni Shiki ■) 150 parts (50 parts excluding pigment), No Iros AW-
36 (water-soluble acrylic resin, acid value 50-70, manufactured by Seiko Kagaku@)) 60 parts, 25% ammonia water 20 parts, isopropyl alcohol 60 parts, ethylene glycol 15 parts, and Neugen PA-130T (nonionic surfactant, H
LB 13 (manufactured by Daiichi Kogyo Seiyaku@)) was added, water was added to make a total of 800 parts, and the mixture was dispersed in a paint shaker (manufactured by Rhett Dell Co., Ltd.) for about 1 hour. , PH8, (S, viscosity 24 cps, pigment-free 2
A 2.0% yellow, pastel-like aqueous pigment composition with excellent hiding properties was obtained.

As a result of examining various properties of this composition, it was found that this composition had sufficient hiding power and was excellent in various physical properties such as storage stability with a gloss level of 2%, water resistance, and light resistance.

Example 4 100 parts of titanium, rR-500, 1 part of aluminum silicon
8- Kate: #30 25 parts, Brilliant First Scarlet FBT (0, I 1: Gment Red 22
, manufactured by Mikuni Shiki ■) 5 parts, Malquido-32 (rosin maleic acid, acid value 120-13o, manufactured by Kagaku Kagaku (Ha)) 6 parts
Add 0 parts, 20 parts of 25 thiammonia water, 15 parts of diethylene glycol and 15 parts of Neuden PA-130T,
After adding water to a total of 500 parts and dispersing with a three-roll mill, 60 parts of isozorobyl alcohol
and 240 parts of water were mixed and stirred for 30 minutes, resulting in a pH of 8.4, a viscosity of 24 cpe, and a pigment content of 21.9.
% of a pastel-like aqueous pigment composition with excellent hiding properties was obtained.

As a result of examining various properties of this composition, it was found that this composition had sufficient hiding power and was excellent in various physical properties such as storage stability with a gloss level of 2, water resistance, and light resistance.

Example 5 Optiwhite P20 to 100 parts of titanium JR-602
part, cyan green 2G8 paste (C0 ■ Pigment Green 5, manufactured by Mikuni Shiki ■) 80 parts (face 19 - ingredients 30 parts), Hump Yellow GLN paste 30 parts (excluding pigment 10 parts), Hyros AV-3650 parts, 25 parts Add 14 parts of aqueous ammonia, 50 parts of n-propyl alcohol, 101 ethylene glycol, and 12 parts of Emalden A-90 (nonionic surfactant, HLB14.5, manufactured by Kao Soap@) to make the total amount 700 parts. When water was added to the solution and dispersed in a sand mill for about an hour, the pH
A green, pastel-like aqueous pigment composition with excellent hiding properties and a viscosity of 26 cps and 22.4% of pigment content was obtained.

As a result of examining various properties of this composition, it was found that the hiding power was sufficient, the gloss was 2.0, and the storage stability, water resistance, and light resistance were excellent.

Example 6 100 parts of titanium JR-602, Optihoy) P15
15 parts of Sumitomo First Violet RL (C, Pigment Violet 23, manufactured by Sumitomo Chemical (C)),
Hyros 5M-2740 parts, 25% ammonia water 12L
30 parts of isozorobyl alcohol, 8 parts of ethylene glycol
Part, Nonipol 140 (nonionic surfactant, HLB
14.8, manufactured by Sanyo Chemical @)) 8 parts and Calibon L
-400 (Anionic surfactant, Sanyo Chemical (Yanagi))
When I added 2 parts and further added water to make a total of 500 parts and dispersed it in a sand mill for about 1 hour, the pH was 8.
9. A purple aqueous pigment composition with a viscosity of 24 cps and a pigment content of 26 cm and excellent hiding properties was obtained.

As a result of examining various properties of this composition, it was found that this composition had sufficient hiding power and was excellent in various physical properties such as storage stability with a gloss level of 2%, water resistance, and light resistance.

Example 7 To 100 parts of the aqueous pigment composition prepared in Example 1, 0.2 parts of Rheosic 250H (sodium polyacrylate, Nippon Tsumugi Co., Ltd.) was added as a thickener and mixed and stirred for 30 minutes. A light blue, clear poster color ink having a pH of 8.5 and a viscosity of 2,000 QpB was obtained.

Example Day 0.5 parts of Rheosic 250H was added to 100 parts of the aqueous pigment composition prepared in Example 6 and mixed and stirred for 30 minutes, resulting in a pH of 8.6 and a viscosity of 10. A yellow, bright, high viscosity screen ink of ODD cps was obtained.

Patent applicant: Mikuni Shiki Co., Ltd. (1 other person) Agent Isomorphic Akira

Claims (1)

[Scope of Claims] 1(A) A mixed pigment containing 100 parts by weight of titanium oxide and 5 to 100 parts by weight of an aluminum silicate pigment, and (B
) A copolymer of an unsaturated compound monomer having a carbon-carbon double bond and an unsaturated carboxylic acid monomer, with an acid value of 3
0 to 500 in a weight ratio of component (A) to component (B) of 20:1 to 1:2. 2 (A) A mixed pigment containing 100 parts by weight of titanium oxide, 5 to 100 parts by weight of an aluminum silicate pigment, and 100 parts by weight or less of an organic pigment, and (B) an unsaturated compound monomer having a carbon-carbon double bond. A copolymer with an unsaturated carboxylic acid monomer having an acid value of 30 to 500 in a proportion where the weight ratio of component (A) to component (B) is 20:1 to 1:2. An aqueous pigment composition comprising an aqueous dispersion containing.