JPH02298516A - Production of organic pigment-containing cellulose composite particle - Google Patents

Abstract

PURPOSE:To obtain the subject particles, having a dark color and uniform spherical shape or fine particle diameter and extensively utilizable as a colorant by producing fine organic pigment-containing viscose coagulated fine particles according to a specific method, neutralizing the resultant fine particles with an acid and then drying the neutralized particles. CONSTITUTION:The objective particles obtained by initially mixing (A) viscose with (B) fine organic pigment particles (C) water-soluble polyethylene glycol (derivative) having >=1500 number-average molecular weight and (D) metal ions capable of forming a salt of the organic pigment, providing a fine particle dispersion of the component (A) containing the component (B), further heating the above-mentioned dispersion at a temperature equal to or higher than that in producing the dispersion, forming fine coagulated viscose particles containing the component (B), subsequently separating the aforementioned fine coagulated particles from the mother liquor, neutralizing the separated fine particles with an acid and then drying the neutralized particles. Furthermore, the fine particle dispersion of the component (A) containing the component (B) is preferably produced at >=55 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing fine cellulose composite particles containing an organic pigment.

(Prior Art) Organic pigments generally have a wide variety of crystal shapes, affinities, particle sizes and shapes, etc., either intrinsically or due to the manufacturing process.

Conventionally, as a method for adjusting the size, shape, etc. of particles, a method has been used in which the particles are kneaded and dissolved with a resin or the like, solidified, and pulverized.

The above method cannot be applied to polymers that do not melt under heat, such as cellulose, and the method disclosed in JP-A No. 63-90502 has only been used to produce cellulose composite particles containing organic pigments. .

(Problems to be Solved by the Invention) An object of the present invention is to provide a method for producing microparticles of a cellulose composite consisting of regenerated cellulose (type 2 cellulose) and organic pigment microparticles.

More specifically, organic pigment particles made water-insolubilized by metal ions are difficult to be contained in a high content by the method discovered by the present inventors (Japanese Patent Laid-Open No. 63-90502), and as a coloring agent, they have a deep color. There was a turning point in manufacturing things. As a result of further research to solve these problems, the method of the present invention was discovered.

(Means and effects for solving the problems) According to the present invention, the above objects and advantages are achieved by: (1) viscose;
Organic pigment fine particles, number average molecular weight 1. , '+ O0 or more water-soluble polyethylene glycol or polyethylene glycol derivative and metal ions forming a salt of an organic pigment are mixed to form a liquid containing fine particles of hiscose containing 1 small amount of organic pigment. (2) The organic pigment fine particles in the dispersion are further heated at a temperature equal to or higher than the temperature at which the dispersion was produced. coagulated viscose'n
5 particles are produced, and then (3) the coagulated hiscose particles containing the organic pigment particles are separated from the mother liquor, acid-neutralized, washed with water, and dried. achieved by the method.

] - In the method of the present invention, ], the first step 6, step 2, organic face powder 1-Ii Atsushi particles and metal ions are added to Kaneko 1.
In the second step, a dispersion of a few particles of the histonic powder containing fine organic pigment particles is produced. i;+i
Il viscose composite fine particles were separated from the mother liquor, and ilη-
One course of cells is made of bonded fine particles.

1) Formation of Viscose Fine Particle Solution The first step is carried out by mixing viscose, N-containing pigment particles, metal ions, and a water-soluble polymer compound.

The screws to be used are, for example, as follows:
-1). Gahoon 1+IIi is 30-100
, or 35 to 90. Salt point is 3~
20, more preferably 4 to I8. Cal 1-1-
The carbon dioxide/seismic intensity is 3 to 15% by weight, more preferably 5 to 13% by weight. Alkali level L; i: 2-15%
, more preferably 4 to 13% weight.

The weight proportion of alkali (as caustic soda) to the viscose cells is 40 to 100% by weight, more preferably 50 to 90% by weight. viscose viscosity
The temperature is between 50 and 20,000 centivoise, more preferably between 80 and 18,000 centivoice at 20°C.

The pulp source for the viscose is preferably linter pulp, and may also be softwood or hardwood. The average degree of polymerization for one course of viscose cells is usually 1) 0 to 1.000.

The high molecular weight polyethylene glycol or polyethylene glycol derivative used is 1.500 or more as described above.
It has a number average molecule m of -, and preferred ones are 1. ,
It has a number average molecular weight of 500-400.000.

For example, as a single polyethylene glycol compound, only the hydroxyl group at one end of polyethylene glycol has 1 to 1 carbon atoms.
A water-soluble compound blocked by an alkyl group of 18, a phenyl group substituted with an alkyl group having 1 to 1B carbon atoms, or an asol group having 2 to 18 carbon atoms, or a Δ-13-A' type block compound. Polymers (where A and A' are the same or different and represent polyethyloxy 1-blocks, and B represents polypropyleneoxy 1-blocks) are preferably used. More specifically, examples include polyethylene glycol monomethyl ether, polyethylene glycol monolauryl needle, polyconytylene glycol monocetylcotyl; polyethylene glycol monomethyl phenylconite, polyethylene glycol monononyl phenyl ether root, polyethylene glycol monolaure. 1; and poly-1-thiethylene
Examples include cypropylene bronocoupolyoisoethylenebutylene 1) and the like.

Among polyethylene glycol and its derivatives, polyethylene glycol is more preferred, with a number average molecular weight of 6
．． O O O ~ 2 0 0. 0 0 0 is more preferable, and the number average molecular weight is 8.000 to 1 0 0,
Particularly preferred is one with a number average molecular weight of 10
．． 000 to 30,000 is particularly preferred.

The polyethylene glycol diluent is preferably 1.500
It has a number average molecular weight of ~16.000.

The pigments applicable to the present invention include Red No. 202 and Red No. 2 when considering the application of colorants in the food and cosmetic fields.
No. 03, Red No. 204, Red No. 205, Red No. 206,
Red No. 207, Red No. 208, Red No. 219, Red No. 22
No. 0, red No. 221, red No. 228, orange 203
issue.

Daicolor No. 204, Yellow No. 205, etc. are preferred, but printing ink, paint, plastic, fiber.

All pigments that form salts with metal ions can be used for coloring rubber. Of course, a mixture of two or more of these pigments can also be used (for example, "New Edition Dye Handbook").
, edited by the Organic Synthetic Chemistry Society, Marukubi ■, 1970). The organic pigment is preferably in the form of fine particles, and the particle size is preferably 1/20 or less of the target particle size of the cellulose composite particles to be produced.

dilute caustic soda if the particle size of the organic pigment is large)
It can also be used in the form of a gel or dissolved in water.

According to the method of the present invention, viscose, organic pigment fine particles, metal ions, and water-soluble polymer compound are mixed first, but it is preferable to mix viscose and organic pigment fine particles in advance.

The metal ion used is the same as the metal ion constituting the organic pigment, and Aj2'' and Ba'' are usually used, and 2 to 10% by weight/viscose is preferred. 2% by weight
When the amount is less than 1, the pigment is partially dissolved and the pigment content in the composite particles is reduced. On the other hand, if the amount is more than 10 wt%/viscose, viscose tends to become unstable (it may be difficult to form a fine particle dispersion of viscose. If the usage amount is 10 wt%/viscose or more) may be partially added to the anionic polymer compound.

For mixing, any means can be used as long as a fine particle dispersion of viscose is produced. For example, mechanical stirring using stirring blades, baffles, etc., ultrasonic stirring, or mixing using a static mixer can be carried out alone or in combination.

The water-soluble high molecular weight polyethylene glycol or its derivative is preferably used as an aqueous solution, more preferably the concentration of the polyethylene glycol or its derivative is from 0.5 to
60% by weight, particularly preferably 5-55% by weight, especially 10% by weight
It is used as a ~40% by weight aqueous solution.

Viscose and polyethylene glycol or polyethylene glycol derivative means 1 part of polyethylene glycol or polyethylene glycol derivative per 1 part by weight of cellulose.
It is used in an amount of up to 30 parts by weight, more preferably 2 to 28 parts by weight, particularly preferably 4 to 24 parts by weight, especially 8 to 16 parts by weight, and is used in Mixing-I.

The organic pigment fine particles are 0.05 to 7 parts per 1 part by weight of cellulose.
used in parts by weight, more preferably 0.1 to 5 parts by weight,
mixed.

Although there is no particular restriction on the temperature during mixing, it is desirable that the mixing be carried out at a temperature lower than the temperature at which a viscose fine particle dispersion containing organic pigment fine particles is produced. The viscose microparticle dispersion containing organic pigment microparticles is produced at a temperature of 55°C or higher.

At temperatures below 55° C., it is not possible to obtain a microparticle dispersion of viscose containing underlying organic pigment microparticles capable of providing the desired microscopic cellulose particles.

According to the method of the present invention, the viscose fine particle dispersion produced in the first step is then solidified in the second step to produce solidified viscose fine particles containing organic pigment fine particles. The coagulation reaction described above is desirably carried out while applying a mixing operation to the produced dispersion. Further, the coagulation reaction is carried out at a temperature equal to or higher than the temperature at which the dispersion is produced. Coagulation by heating is preferably carried out at a temperature of 60°C to 90°C.

According to the method of the present invention, it is then separated from the mother liquor in the third step, 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 by selecting appropriate manufacturing conditions, the average particle diameter can be reduced to 1.
From slightly larger particles of 00 to 300 It m, it is possible to obtain particles of a cellulose composite having an average particle size of 5 to 20 μm and as small as one particle.

(Effects of the Invention) According to the present invention, it is possible to produce particles of a cellulose composite having a dark color, uniform particle formation, or a minute particle size. The particles obtained can also be used as colorants in a wide range of industrial fields.

(Example) In the following, the present invention will be further described with reference to Examples.

Example 1 Industrial His': 60 g of 1-su (viscosity', +!l OO centivoise, cell 1 course stiffness 9.2% by weight, alkali concentration 58% by weight), 5.5 g of pigment (red No. 202) 10 g of a 30% by weight aqueous solution of calcium chloride was mixed at room temperature. This mixture and an aqueous solution of polyethylene glycol (
Molecule M20,000, polymer concentration 30%) 240g and 50
Put the 0mff flask into the /& temperature of 30°C, and stir (Mol) I': LL R-5]
Yama [manufactured by Wagakusha, rotating blade 7 m)] 000r
pm stirring for 10 minutes, and further raised the temperature to 62"C to produce a dispersion of several particles of viscose containing pigment.
-After the water has cooled down, continue stirring and cook for 6 hours at night.
Raise the temperature from °C to 80 °C in 15 minutes, 80 °C130
Minutes 1) t↑, ~ to coagulate the fine particles of tahiscose containing the pigment. Then ζ, ], after separating the coagulated fine hiscose particles containing it from the liquid II through a type 4 glass filter. , l Wash thoroughly with Qwt% calcium chloride aqueous solution, and then with a large excess of water/7]
After neutralization with 2% hydrochloric acid and washing with water, the mixture was dried at 80 DEG C. for 13 hours to obtain small particles containing pigment.

The obtained cellulose microparticles containing 70% by weight of cellulose were spherical with a particle size of 2 A II m.

Example 2 After mixing 60 g of the hiscose used in Example 1 and 16.8 g of Face*-1 (Red No. 204) at room temperature, 20 g of a 30 wt% barium hydroxide aqueous solution was added while further mixing.
g was added.

This mixture was mixed with 20% of the pigment described above in the same manner as in Example.
Spherical pigment-containing cell I'l]-s particles having an average particle diameter of 42 μm and containing 0% by weight of 1 cose were obtained.

Example 3 Viscose containing the pigment used in Example 1 (Pigment 5
0% by weight/cellulose) 60g and polyethylene glycol aqueous solution (molecular weight 20,000, polymer concentration 40%) 240g
g in a laboratory stirrer at 40 Org at a liquid temperature of 30'C.
pm stirring for 10 minutes, and further heated to a temperature of 62°C to produce pigment-containing viscose microparticles, followed by the same method as in Example 1 to obtain pigment-containing cellulose microparticles. . The fine particles were in the shape of an Fy with a ladle diameter of 70 μrn.

Claims (1)

[Claims] 1. (1) Viscose, organic pigment fine particles, water-soluble polyethylene glycol or polyethylene glycol derivative having a number average molecular weight of 1,500 or more, and a metal ion that forms an organic pigment salt are mixed. (2) further heating the dispersion at a temperature equal to or higher than the temperature at which the dispersion was produced; (3) Separating the coagulated viscose particles containing the organic pigment particles from the mother liquor, acid-neutralizing them, washing with water, and drying them. Method for producing pigment-containing cellulose composite particles.