JPH09183802A - Colored starch composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To readily and inexpensively obtain a colored starch composition having dense colored concentration with excellent fastness without losing shape of a starch granule before coloring and useful for coloring materials, etc., by adsorbing an anionic dye and/or a pigment onto a cation-modified starch derivative. SOLUTION: This colored starch composition is composed of (A) a cation- modified starch derivative, preferably hydrophobic-modified crosslinked cation- modified starch derivative adsorbed with (B) an anionic dye and/or an anionic pigment. Preferably, e.g. a weight ratio of (the component A)/(the component B) is used as (100/0.5)-(100/3) and the component A is obtained by reacting starch such as tapioca starch with a cationizing agent such as diethylaminoethyl chloride in a usual method.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored starch composition, and more particularly to a paint, a paint having a high coloring density and good fastness, without impairing the shape of starch particles before coloring.
The present invention relates to a colored starch composition useful for poster colors, inks and the like.

[0002]

2. Description of the Related Art Conventionally, as a method for coloring starch, a method in which a reactive dye is dyed below its gelatinization temperature (Japanese Patent Publication No. 58-35).
No. 229), a method of chemically bonding a dye capable of binding an amino group or an imino group to an aminated starch derivative (JP-A-1)
No. 266286), an unmodified starch is chemically bonded to a triazine or vinyl sulfone derivative, and an aminated starch is chemically bonded to an intramolecular charge transfer dye having a chlorosulfonyl group, a chlorocarbonyl group, a triazinyl group, or a group derived from vinylsulfone. Method (Japanese Patent Laid-Open No. 1-265898)
Has been proposed.

[0003]

In all of the above-mentioned starch coloring methods, a dye or pigment is chemically bonded to the starch, so that the chemical reaction is carried out in water or an organic solvent. For example, when the chemical reaction is performed in an aqueous medium, there is a restriction on the reaction conditions that gelatinization occurs unless the temperature is lower than the gelatinization temperature of starch. In addition, there is a restriction that only those having a substituent capable of chemical bonding can be used for chemical bonding. Further, there is a problem that the colored starch obtained by these methods becomes expensive due to the yield and the reaction cost due to the property of chemically reacting to obtain the product.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have noticed that starch and dyes / pigments have ionicity. The inventors have found that the ionic dyes and pigments are easily adsorbed at low cost to color starch by simply mixing them in water and / or an organic solvent, and the present invention has been completed. That is, the present invention provides a colored starch composition characterized by adsorbing an anionic dye and / or an anionic pigment on a cation-modified starch derivative, and a cationic dye and / or a cationic dye on an anion-modified starch derivative. The present invention provides a colored starch composition characterized by adsorbing a pigment.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is characterized in that a cation-modified starch derivative is mixed with an anionic dye and / or an anionic dye in water and / or an organic solvent and easily adsorbed at low cost. And a colored starch composition. Also provided is a colored starch composition characterized in that an anion-modified starch derivative is mixed with a cationic dye and / or a cationic pigment in water and / or an organic solvent and easily adsorbed at low cost. To do.

The starch used in the present invention is not particularly limited, and examples thereof include wheat starch, potato starch, corn starch, waxy corn starch, high amylose-containing corn starch, sweet potato starch, tapioca starch, sago starch, rice starch and the like. Is mentioned. Rice starch is advantageous when small starch particles are required, and potato starch is advantageous when large starch particles are required. In the present invention, these starches used are those which have been etherified, esterified, cross-linked, hydrophobized, acid-treated, oxidized or the like. Among these, those which have been cationized, anionized or crosslinked by an etherification reaction or an esterification reaction are preferably used.

The cation-modified starch used in the present invention is
It can be obtained by reacting the above-mentioned raw material starch with a cationizing agent (for example, diethylaminoethyl chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride, 2,3-epoxypropyltrimethylammonium chloride, etc.) by a conventional method. The degree of substitution of the cation-modified starch used in the present invention is 0.01 or more, preferably 0.02 to 0.1. When the degree of substitution is less than 0.01, the amount of dye / pigment adsorbed is small and a dark colored starch cannot be obtained. If the degree of substitution exceeds 0.1, the starch will swell in cold water, and thus a crosslinking treatment is essential.

This cross-linked cation-modified starch has the advantage that it does not become gelatinized even when the degree of substitution is high to obtain a dark colored starch, or when the temperature of mixing with a dye or pigment in water is high. The crosslinked cation-modified starch is obtained by reacting with a crosslinking agent such as formaldehyde, glyoxal, epichlorohydrin, phosphorus oxychloride, polyphosphate, diisocyanate, bisethyleneurea, adipic acid, acrolein, etc. before or after the above cationization reaction. . Crosslinking is such that the starch does not gelatinize in the colored water (so that the gelatinization start temperature is approximately 70 ° C or higher).
Do.

The anion-modified starch used in the present invention is obtained by anionizing the above-mentioned raw material starch with propane sultone, butane sultone, monochloroacetic acid, chlorosulfonic acid, maleic anhydride, succinic anhydride, orthophosphoric acid, polyphosphoric acid, metaphosphate, etc. It is obtained by reacting the agent by a conventional method. The degree of substitution of the anion-modified starch used in the present invention is 0.1.
01 or more, preferably 0.02 to 0.1. When the degree of substitution is less than 0.01, the amount of dye / pigment adsorbed is small and a dark colored starch cannot be obtained. If the degree of substitution exceeds 0.1, the starch swells in cold water, so that a crosslinking treatment is essential. As in the case of the cross-linked cation-modified starch, a cross-linking agent acts on the anion-modified starch to be used as cross-linked anion-modified starch.

The cation-modified starch and the anion-modified starch of the present invention are cross-linked in order to increase the degree of substitution to obtain a deeper color as described above or to prevent gelatinization of starch particles during coloring. Is given. Rice starch is used when a small particle size is required, and potato starch is used when a large particle size is required. Furthermore, when it is desired to prevent the sedimentation of starch particles, octenyl succinate aluminum chloride is used,
Silane coupling agent, titanate coupling agent,
The precipitation of the starch particles can be prevented by using a starch obtained by hydrophobizing the starch by reacting the starch with an aluminum-based coupling agent, a modified silicone oil, or the like, and further modifying the starch with cation or anion.

As the anionic dye used in the present invention,
Examples thereof include acid dyes, metal complex dyes, acid mordant dyes, reactive dyes, and direct dyes, and reactive dyes are preferably used because of their fastness and variety of colors. Further, an anionic fluorescent dye is also preferably used. As the cationic dye, a cationic dye or a basic dye is used. Known anionic and cationic dyes are used.

The present invention is a colored starch characterized in that a cation-modified starch derivative is mixed with an anionic dye and / or an anionic dye in water and / or an organic solvent and is easily adsorbed at low cost. A composition is provided. Also provided is a colored starch composition characterized in that an anion-modified starch derivative is mixed with a cationic dye and / or a cationic pigment in water and / or an organic solvent and easily adsorbed at low cost. To do. The colored starch composition of the present invention comprises a modified starch derivative in which a dye and / or a pigment are mixed and stirred in water and / or an organic solvent for several minutes, and the starch which is adsorbed with the dye / pigment and colored is subjected to centrifugation, filtration, sedimentation, etc. Separated from the treatment liquid by
By drying and pulverizing, a granular colored starch is obtained. Since the colored starch thus obtained has excellent fastness, it can be used in paints, paints, vostar colors and inks. The ratio of the cationic (anion) -modified starch derivative to the anionic (cationic) dye and the anionic (cationic) dye in the colored starch composition of the present invention is 100: 0.1-10, preferably 100: 0, by weight ratio. .5-
3. When the amount of the dye / pigment is less than 0.1, the coloring is light, and even if it is 10 or more, it cannot be expected that the color will be deeper, and the cost is increased, which is not preferable.

[0013]

【Example】

Example 1 Cation-modified starch (raw material: tapioca starch, nitrogen content 0.2)
5%) 50 g, and 1 g each of reactive dyes (Remazol Bryl Blue R-KN, Remazol Bryl Orange FR, Remazol Bryl Red F-3B) at room temperature in water 1
It was added to a solution dissolved in 00 g, stirred for 5 minutes, filtered, dried and pulverized to obtain a colored starch. These colored starches were bright blue, orange and red, respectively. Disperse 5 g of these colored starch in 10 g of 20% paste of oxidized starch,
R. D. S. Laboratory Coating Rod # 2
After coating on Kent paper in No. 4 and drying, a dye fastness test to sunlight of JIS L 0841 was conducted. The results were grade 4, grade 3, and grade 4, respectively.

Example 2 Crosslinked cation-modified starch (raw material: rice starch, nitrogen content 0.5)
%, 50 g of a gelatinization starting temperature of 83 ° C. are used as reactive dyes (Remazole Bryl Blue B, Remazole Bryl Green B
N, Remazol Bryl Violet 5R) 1 each
g was added to a liquid dissolved in 100 g of water at room temperature, stirred for 5 minutes, filtered, dried and pulverized to obtain a colored starch. These colored starches were bright blue, green and purple, respectively. 5 g of these colored starches are used as a 20% paste solution of oxidized starch.
g. D. S. Laboratory coating rod # 24 applied to Kent paper and dried, then JIS
A dye fastness test to light of L0841 was performed. The results were grade 4, grade 5, and grade 4, respectively.

Example 3 50 g of octenyl succinate aluminum chloride cation-modified starch (raw material: corn starch, octenyl succinate amount 0.25%, nitrogen amount 0.3%)
Was added to a solution prepared by dissolving 1 g of each of reactive dyes (Remazol Bryl Yellow 4GL, Remazol Bryl Brown GR, Remazol Gray G) in 100 g of water at room temperature, stirring for 5 minutes, filtering, drying and pulverizing to obtain a colored starch. . These colored starches were bright yellow, brown and black, respectively. 5 g of these colored starches were dispersed in 10 g of 20% paste of oxidized starch, and R. D. S. It was applied to Kent paper with a laboratory coating rod # 24, dried, and then subjected to a dye fastness test against sunlight according to JIS L 0841. The results were 6th grade, 4th grade and 3rd grade, respectively. The colored starch floats in water and can be dispersed in water by adding an appropriate amount of a surfactant so as not to precipitate.

Example 4 50 g of anion-modified starch (raw material: potato starch, carboxymethylation substitution degree 0.03) was added to a cationic dye (Dyacryl Blue AU-N, Dyacryl Red GRL-).
N, diacryl yellow AU-N) 1 g each was added to a liquid dissolved in 100 g of water at room temperature and stirred for 5 minutes.
Filtration, drying and pulverization gave a colored starch. These colored starches were bright blue, red and yellow, respectively. 5 g of these colored starches were dispersed in 10 g of 20% paste of oxidized starch, and R. D. S. Laboratory coating rod # 24 applied to Kent paper and dried, then JIS L 08
41 dye fastness tests to sunlight were performed. The results were grade 2, grade 3, and grade 2, respectively.

Example 5 Cation-modified starch (raw material: tapioca starch, nitrogen content 0.2)
50 g of 5%) was added to a solution prepared by dissolving 1.5 g each of fluorescent dyes (Kayanol Briflavin FL conc, Kayacil Rhodamine FB, Kayacil Pure Blue FGA) in 100 g of room temperature water, stirred for 5 minutes, filtered, dried and crushed. A colored starch was obtained. These colored starches were bright fluorescent colors of yellow, purple and blue, respectively.

[0018]

The colored starch composition of the present invention is simple and inexpensive to produce. Further, it is possible to provide a colored starch composition having a high coloring density and good fastness, which is useful for paints, paints, poster colors, inks, etc. without impairing the shape of starch particles before coloring.

Claims (5)

[Claims] 1. A colored starch composition comprising an anionic dye and / or an anionic pigment adsorbed on a cation-modified starch derivative. 2. A colored starch composition comprising an anionic dye and / or an anionic pigment adsorbed on a crosslinked cation-modified starch derivative. 3. A colored starch composition comprising an anionic dye and / or an anionic pigment adsorbed on a hydrophobically modified cation-modified starch derivative. 4. A colored starch composition characterized in that an anionic dye and / or an anionic dye is adsorbed on a hydrophobically modified crosslinked cation-modified starch derivative. 5. A colored starch composition, characterized in that an anion-modified starch derivative is adsorbed with a cationic dye and / or a cationic dye.