JPH02300243A - Organic pigment-containing cellulosic composite particle and its production - Google Patents

Abstract

PURPOSE:To obtain the title deeply colored and uniform particles by heating a dispersion containing a viscose, organic pigment particles, a water-soluble anionic polymeric compound and a specified metal ion to coagulate the viscose, neutralizing the product with an acid, washing it with water and drying it. CONSTITUTION:1 pt.wt. viscose of a gamma value of 30-100, a salt point of 3-20, a cellulose concentration of 3-15wt.%, an alkali concentration of 2-15wt.% and a viscosity of 50-20000cP at 20 deg.C, 0.05-3 pts.wt. organic pigment particles of a particle diameter <=1/20 of that of the purpose particle, 0.3-100 pts.wt. water-soluble anionic polymeric compound of a number-average MW >=5000 (e.g. polysodium acrylate), 2-10wt.% metallic ion which can form a salt of the organic pigment (e.g. CaCl2), and water at 0-40 deg.C to obtain a viscose particle dispersion containing the organic pigment particles. This dispersion is heated to a temperature above the b.p. of CS2 to coagulate the viscose, and the coagulated viscose is separated, neutralized with an acid, washed with water, and dried to obtain fine cellulose composite particles of a mean particle diameter <=300mum containing the organic pigment.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to microcellulose particles containing an organic 1111 material and a method for producing the same.

(Prior Art) Organic pigments generally vary widely depending on their crystal form, affinity, particle size, nature or production process.

The method used to make particles uniform in size and shape is to knead and melt them with resin, etc., solidify, and then crush. The above method is not practical for polyols that do not melt by heat, such as cell 1 course, and the method disclosed in JP-A No. 63-90502 is sometimes used to prepare cellulose composite particles containing organic f1rIsit. only.

(Problems to be Solved by the Invention) An object of the present invention is to provide microparticles of a cellulose composite consisting of regenerated cellulose or type II cellulose and organic pigment microparticles, and a method for producing the same. More specifically, organic an n made water insolubilized by metal ions
The i-particles can be obtained by the method described above (Japanese Patent Laid-open No. 63-90502, No. 63-92GO3) discovered by the present inventors.
(No. Publication), it contains a high content of tekasumi, and as a coloring agent;
There was a problem in manufacturing colored products.

In order to solve these problems, the method of the present invention has been discovered.

(One step and action for solving the problem) The present invention includes:
These are organic pigment-containing cellulose composite particles with an average particle size of 300 μm or less. Preferably, the n#I material is cellulose 1
It is a cellulose composite particle containing 0.02 to 7 parts by weight per part by weight, and if it is less than 0.02 part by weight, it is insufficient as a coloring material, while if the content exceeds 1 part by 7rIL, the morphology of the particles deteriorates. Agglomeration of particles may occur;
Undesirable.

The production and removal of the pigment-containing composite particles of the present invention are as follows: (1) Mixing viscose, organic pigment fine particles, a water-soluble anionic polymer compound, and a metal ion that forms an organic pigment salt. to produce a microparticle dispersion of viscose containing particles imitating the material, 2. coagulate the viscose in the dispersion by heating the dispersion, and then 3. The special feature is to separate the coagulated viscose fine particles containing fine particles from the mother liquor, neutralize with acid, wash with water, or dry.

According to the method of the present invention, the first step forms a viscose fine particle dispersion containing organic pigment fine particles and metal ions, and the second step forms coagulated viscose fine particles containing organic pigment fine particles. and in a third step separating the coagulated viscose composite particles from the mother liquor,
Composite fine particles of regenerated cellulose.

The first step of producing a viscose fine particle dispersion is carried out by mixing viscose, organic pigment fine particles, metal ions, and a water-soluble anionic polymer compound.

The viscose used has, for example, the following properties. Gamma number is 30-100, more preferably 35-90
It is. The salt point is 3-20, more preferably 4-18. The cellulose concentration is 3 to 15% by weight, more preferably 5 to 131% by weight. The alkali concentration is between 2 and 15% by weight, more preferably between 4 and 13% by weight. The weight proportion of alkali (as caustic soda) to cellulose in viscose is 40-100% by weight, more preferably 50-90% AT. The viscosity of viscose is 20℃
50 to 20,000 centivoices, more preferably 80 to 18,000 centivoices.

The viscose bulb source is preferably linter pulp, and may also be softwood or hardwood. The average degree of polymerization of viscose as cellulose is usually 110 to 1.000.

The water-soluble anionic polymer compound used has, for example, a sulfonic acid group, a phosphonic acid group, or a carboxylic acid group as an anionic group. These anionic groups are in the form of free acids, and C may also be in the form of salts.

A water-soluble polymer compound having sulfone 61 as an anionic group has the sulfonic acid group, for example, vinylsulfonic acid, styrenesulfonic acid, methyls-y-lenesulfonic acid, furylsulfonic acid, methacrylsulfonic acid, allylamide methylpropane. It can be derived from monohedra such as sulfonic acids or their salts.

Similarly, water-soluble polymeric compounds having anionic groups as well as sponic acid groups can be derived from monomers such as styrene sulfonic acid, vinylphosphonic acid, or salts thereof.

Further, the water-soluble polymer compound having a carboxylic acid group as an anionic group can be derived from a monomer such as acrylic acid, methacrylic acid, styrene carboxylic acid, maleic acid, itaconic acid, or a salt thereof.

For example, a water-soluble polymer compound having a carboxylic acid group can be prepared by polymerizing sodium acrylate alone or by rH-polymerizing it with another copolymerizable monomer, such as methyl acrylate, according to a method known per se. It is supplied as a homopoly7- or copolymer containing polymerized units of sodium acrylate. Furthermore, for example, a water-soluble polymer compound having a sulfonic acid group can be produced by sulfonating a suylene homopolymer. When the sulfonic acid group is derived from a monomer other than styrene sulfonic acid and phosphonic acid J
, (, The same applies to the case where each of the carboxylic acid groups is derived from the iam body as described above.

The water-soluble anionic polymer compound has anion P[7!
It preferably contains at least 20 mole % of polymerized units of monomers as described above having a . Such preferred polymeric compounds include copolymers and homopolymers.

The water-soluble anionic polymer compound preferably has a number of at least 5,000, more preferably 10,000 to 3,000,000.
It has an average molecular weight.

The water-soluble anionic polymer compound in the present invention includes:
In addition to the vinyl type polymers mentioned above, other examples include carboxymethyl cellulose, sulfoethyl cellulose, and salts thereof such as Na salts.

The RN materials that can be applied to the present invention include Red No. 202, Red No. 203, Red No. 204, Red No. 205, Red No. 206, Red No. 207, Red No. No. 208, red No. 219 5 red 2
No. 20, Red No. 221, Red No. 228, 9 Daidai 20
No. 3.

Daidai No. 204, Yellow No. 205, etc. are preferred, but any pigment that forms salts with metal ions can be used for coloring printing inks, paints, plastics, textiles, and rubber. Of course, a mixture of two or more of these pigments can also be used (see, for example, "New Edition Dye Handbook", edited by the Organic Synthetic Chemistry Association, Marukubi III, 1970). The organic pigment is preferably in the form of fine particles, and the particle size is The particle diameter is preferably 1/20 or less of the target particle diameter of the cellulose composite particles to be produced.

When the particle size of the organic pigment is large, it can be dissolved in dilute caustic soda or the like or used in the form of a gel.

1. According to the method of the present invention, viscose and f1 aircraft head F'l
? The gold metal ion particles and the water-soluble anionic polymer compound are first mixed, and it is preferable that the viscose and the percussion pigment fine particles be mixed in a Y/m ratio.

The metal ion used is the same as the metal ion A constituting the organic pigment, and Δ13i, B, and 11+ are usually used, and the content thereof is preferably 2 to 1N%/viscose. . If it is less than 2% by weight, the pigment will be partially dissolved and the fTl content of the pigment in the composite particles will decrease. When the amount is more than 10% by weight/viscose, viscose becomes unstable and it may be difficult to produce a bis:1-su fine particle dispersion. If the amount used exceeds 10% by weight of viscose, a part of it may be added to the anionic polymer compound, and the mixing should be carried out in ml of viscose: 4T-if a dispersion is produced. Any means can be used.

For example, mechanical interference caused by stirring blades, obstructive slopes, etc.
Mixing using mrfit↑ or a state-of-the-art mixer can be carried out alone or in combination.

The water-soluble anionic polymer compound is preferably water-soluble, and more preferably the cough polymer compound has a degree of 0.5.
It is used as an aqueous solution of 25% by weight, particularly preferably 2 to 22% by weight.

Viscose and water-soluble anionic polymer compounds are cellulose! 0.3 ml of the polymer compound per small portion
It is used in an amount of 1 part by weight, 45 parts by weight, particularly preferably 1 to 20 parts by weight, and 1 part by weight.

U machine pigment fine particles are 0.05 to 3 per tonne of cellulose.
1 to 2 parts by weight, preferably 1 to 2 parts by weight, are used and mixed.

The mixing is advantageously carried out at a temperature below the boiling point of the carbon disulfide contained in the viscose, more preferably in the range from 0 to 40°C.

According to the method of the present invention, the viscose fine particle dispersion containing organic pigment fine particles produced in Step 1I is then coagulated in the second step.

Solidification occurs at temperatures above the boiling point of carbon disulfide contained in bis21-sulphide.
It can be carried out conveniently at a temperature of, for example, 50°C to 90'C.

According to the method of the present invention, in the 31st step, it is separated from the mother liquor, treated with an acid necessary for neutralization, washed with water, and dried.

Thus, according to the present invention, it is possible to obtain microparticles of a cellulose composite containing organic pigment microparticles, and the average particle diameter can be adjusted to 100 to 300μI by selecting appropriate seedling conditions.
The average particle size is 5 to 20 μm, starting from the slightly larger n.
The particles of microscopic cellulose particles are t? ) can be done.

(Effects of the Invention) According to the present invention, it is possible to produce particles of Cell I:+-su composite having four colors, uniform grain formation, or a minute particle diameter. In addition, the obtained liquid can be used as a coloring agent and used in a wide range of industrial fields.

(Example) The present invention will be explained in detail with reference to Examples below.

Example 1 60 g of industrial viscose (viscosity 5.900 centivoise, cell L7-su (12 degrees 9.2% by weight, alkaline concentration 5.8% by weight)), 5.5 g of pigment (red No. 202) and lucium chloride 10 g of a 30% aqueous solution was combined at room temperature. This mixture was combined with a water-cooled solution of sodium polyacrylate (min.
50,000 stars, polymer) 1 degree 12ffl19.6) Put 240g in a 500ml flask? (Moto Lab Stirrer (MODIEI, 1, R-5113) at 30℃
, manufactured by Yamato Scientific Co., Ltd., rotating blade 7crn) i 000 r
Stirring was carried out for IO minutes to form a fine particle dispersion of bis=1-se containing 1'111 Fl, and then the solution was heated to 30°C with continued stirring. to 7
The temperature was heated to 0°C for 15 minutes and maintained at 70°C for 30 minutes to solidify the fine particles of viscose containing the r)n material.Then, it was passed through an IGd type glass filter and removed from the mother liquor. After the coagulated viscose fine particles containing the RN material were separated, they were treated with an aqueous solution of 50゛Cl2g/β salt jhycalcium, and neutralized with 2g/1 of a sulfuric acid water solution, followed by a large excess. Washed with water and dried at 80°C for 3 hours to form cellulose fine particles containing RN material fa7-
I got it.

The obtained cellulose fine particles containing 91% of pigment and cellulose were LH-shaped particles with a diameter of 62 μm.

Example 2 nr- was obtained by the h method similar to Example 1, using pigment No. 204 instead of the pigment used in Example 1.
Contains 5 layers of cellulose and has a particle size of 70. c+m
Met.

Claims (1)

[Scope of Claims] 1. Micro cellulose composite particles containing an organic pigment and having an average particle size of 300 μm or less. 2. The particles according to claim 1, which contain an organic pigment in an amount of 0.02 to 7 parts by weight per 1 part by weight of cellulose. 3 (1) Viscose, organic pigment fine particles, a water-soluble anionic polymer compound, and a metal ion that produces an organic pigment salt are mixed to produce a viscose fine particle dispersion containing organic pigment fine particles. (2) The viscose in the dispersion is coagulated by heating the dispersion, and (3) the coagulated viscose fine particles containing the organic pigment fine particles are separated from the mother liquor, acid neutralized, washed with water, and then dried. A method for producing organic pigment-containing cellulose particles, characterized by: