JPS5821665B2 - Emulsion emulsion - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention uses a dye that is poorly soluble in water, performs a pretreatment to form fine particles in a solvent that is immiscible with water, and then converts the solution into a water-soluble sizing agent containing or not containing an emulsifier. The present invention relates to a method for producing an oil-in-water emulsion viscous composition of a dye that is hardly soluble in water by mixing with a viscous aqueous solution of a dye or a half emulsion paste, wherein the dye is present in the oil phase of the dispersed phase. This is a novel composition that

Conventionally, dyes that have the ability to dye synthetic fibers and are poorly soluble in water are used as disperse-type dyes that are dispersed in water, so a water-soluble dispersant is added to commercially available disperse dyes.

Therefore, when colored glue is prepared using an aqueous solution or half emulsion (oil-in-water emulsion) of water-soluble glue,
The dye is present in the continuous aqueous phase.

In contrast, in the composition of the present invention, the dye is present in the oil phase of the dispersed phase.

The present inventors have discovered that when the composition of the present invention is used for printing or dyeing synthetic fibers, dyed products with extremely superior color development and vividness can be obtained compared to dyeing using existing disperse dyes. .

Conventionally, the color development methods for textile printing and continuous dyeing are saturated steam,
Steaming using superheated steam, thermosol method using dry heated air, etc. are used.

However, the color development by the thermosol method is not sufficient, and attempts have been made to add strong dyes, etc., but this method is inferior to steaming using saturated steam or superheated steam in terms of color development and white water contamination during washing, so it has not been put to practical use. was difficult.

The method of the present invention is significantly superior to those using existing disperse dyes, especially in terms of color development by thermosol method and superheated steam steaming, and it is possible to obtain practical densities without using dyeing agents, and to fix the dye. Because of its high rate, it is also extremely resistant to contamination of hot water.

Furthermore, dye bleeding during steaming with saturated steam or superheated steam is also superior to conventional methods.

Next, the method of the present invention will be explained in detail.

The dyes that can dye synthetic fibers and are poorly soluble in water used in the present invention include dyes with various structures that do not have a water-soluble group in the dye molecule, and in the case of water-soluble ionic dyes, counterionic substances. There are various structures that are made poorly soluble or insoluble by forming salts with.

Examples of dye structures include monoazo, disazo, anthraquinone, nitro, nitroso, methine, quinoline, benzothiazole, xanthine, acridine, triazole, azine, oxazine, triazine, phthalocyanine,
Dyes commonly used for dyeing synthetic fiber materials can be used, including styryl, naphthoquinone, perinone, quinophthalone, and the like.

However, since the above-mentioned dyes are generally used after being dispersed in water, the commercially available ones are disperse dyes containing a water-soluble dispersant, but the dyes used in the present invention are raw dyes.

A boiling point of 50 to 250 that does not mix with the water used in the method of the present invention
Examples of liquid hydrocarbons and liquid halogenated hydrocarbons at a temperature of , hexene, methylpentene, ethylbutene, dimethylbutene.

Heptene, dimethylpentene, trimethylbutane, octene, dimethylhexene, trimethylpentene, benzene, toluene, xylene, ethylbenzene, isopropylbenzene, ethyltoluene, trimethylbenzene, amylbenzene, dodecylbenzene, amyltoluene, trichloromethane, tetrachloromethane, dichloroethane , trichloroethane, tetrachloroethane, pentachloroethane, dichloroethylene, trichlorethylene, tetrachloroethane, trichloropropane, dichloropropane, chlorobutane, chlorbencune, chloromethylhebutane, benzene, dichlorobenzene, bromobenzene, Chlortoluene etc.

Liquid hydrocarbons or liquid halogenated hydrocarbons may be used alone or in mixtures.

Furthermore, various petroleum products such as petroleum ether, petroleum benzine, ligroin, gasoline, kerosene, light oil, and heavy oil are used, and industrial gasoline No. 4 and No. 5, kerosene, and light oil are particularly preferred.

The dispersant used in the pre-treatment to finely particulate the dye into liquid hydrocarbon or liquid halogenated hydrocarbon is preferably one that is soluble in vaginal fluid and can well wet the dye particles, such as the following.

a) Fatty acid esters of sorbitol, sorbitan, and saccharose, such as sorbitan monolaurate, palmitate, stearate, monooleate, sesquioleate, distearate, trioleate, and their oxyethylated products b) High-molecular polypropylene oxide, and polypropylene oxide and polyethylene oxide block polymer C) glycerides of higher fatty acids, such as lauric acid,
Monoglycerides such as oleic acid, palmitic acid, margaric acid, stearic acid, etc. d) Polyethylene glycol alkyl ether, polyethylene glycol alkyl phenyl ether.

For example, polyethylene glycol lauryl ether, stearyl ether, oleyl ether, octyl ether, nonylphenyl ether e) Polyethylene glycol acyl ester, such as lauric acid ester, stearic acid ester, oleic acid ester, etc. f) Metal salts of higher fatty acids, such as calcium stearate , aluminum oleate, magnesium palmitate, etc.g) Phosphatides Amphoteric compounds such as lecithin, in particular fatty acid esters of sorbitan, block polymers of polyethylene glycol and polypropylene glycol, and lecithin are preferred.

The above active agents may be used alone or in combination.

The water-soluble sizing agents used in the present invention are those commonly used for printing fiber woven and knitted materials, such as starches (wheat flour, rice flour), seaweed (sodium alginate), cellulose derivatives (methyl cellulose, hydroxyethyl cellulose). , carboxymethyl cellulose), natural rubbers (nafka crystal rubber, lame gum, arabo gum) natural rubbers (tragacanth gum, gum arabic, locust bean gum)
Examples include etherified locust bean rubber (Indal Riki, Maypro Rubber, Thickening), processed starches (British Rubber), and synthetic sizing agents (Poval, sodium polyacrylate).

These adhesives can be used alone or in combination.

The pre-treatment for atomizing the dye into the above-mentioned hydrocarbons involves adding a dispersant of 3 to 5% by weight to the dye, and using a ball mill,
In a sand mill, stainless steel balls, glass balls, sand, and porcelain balls are rotated at high speed to mechanically form fine particles.

Alternatively, it may be mechanically made into fine particles using a roll mill.

The amount of the dispersant used is preferably 4 to 100 wt.

The dye is made into fine particles until it exhibits a particle size of at least 5 μm or less, but the average particle size is preferably 1 μm or less.

In the case of wet-pulverized stainless steel balls, glass balls, sand, or porcelain made by mechanical methods after wet grinding in a ball mill, sand mill, etc., or those kneaded with three rolls, the dye is mixed into the hydrocarbons as fine particles. Evenly distributed.

The dispersion of the dye in the hydrocarbon can be adjusted to high concentrations by the method described above.

When mixing a water-soluble sizing agent with a viscous aqueous solution, add a non-volatile acid such as tartaric acid in advance to adjust the pH to 4-5.5 and the viscosity to 4000-1.
A water-soluble sizing solution adjusted to 0000 c, p (measured using a high viscosity rotational viscometer, 25° C., rotor A5, 20 r, p, m) was vigorously stirred with a homomixer while gradually adding the above dye dispersion. and after addition, add 30 to 1
When vigorously stirred for 20 seconds, an oil-in-water emulsion viscous composition containing the dye in the oil phase and uniformly and finely dispersed is obtained.

Further, by adding a water-soluble emulsifier to the water-soluble sizing agent solution in an amount of 1 to 1% based on the weight of the composition, an emulsion composition with even better stability can be obtained.

Also, when mixing with half emulsion glue, the viscosity is 50% by the usual method.
While stirring the half emulsion adjusted to 00 to 8000 c, p with a homomixer, gradually add the above dispersion, and after the addition is complete, stir vigorously for an additional 30 to 120 seconds to obtain the 0/W type, which also has excellent stability. An engineered multimulsion composition is obtained.

In this case preferably hydrocarbons or /'%0 as oil phase
The amount of hydrogenated hydrocarbon is 5 to 30w based on the weight of the composition.
I am in charge of T.

The water-soluble emulsifier used in this case is generally O/W.
H, L, B used for W emulsion adjustment.

8 to 18 surfactants, such as polyoxyethylene lauryl ether, cetyl ether, stearyl ether, oleyl ether, octylphenyl ether,
These include block polymers of nonylphenyl ether, polyoxyethylene sorbicun monolaurate, sorbitan monostearate, sorbitan monooleate, sorbitan dioleate, polyethylene glycol, and polypropylene glycol.

The dye color tone and concentration may be adjusted in the dispersion step, but after the dispersion is completed, liquid hydrocarbons or liquid/\logenated hydrocarbons may be added to dilute the dye, or an aqueous solution of a water-soluble sizing agent or It can also be adjusted by mixing it with half emulsion glue.

In this case, the dye dispersion and liquid hydrocarbon or liquid/
'% The total weight of logenated hydrocarbons is 20% of the total weight of colored paste
The following are preferred.

Furthermore, a 0/W emulsion may be prepared by dissolving a water-soluble emulsifier in water, gradually adding the dye dispersion while stirring vigorously, and then mixing with the water-soluble sizing agent solution.

That is, they can be mixed at various stages as described above.

The viscosity of the colored glue can be adjusted appropriately depending on the type and amount of the glue used.

The essential difference between the O/W type emulsion viscous composition obtained by the present invention and conventional half emulsions is that in the former, the dye is contained in the oil phase, which is a dispersed phase, whereas in the latter, the dye is contained in a continuous oil phase. It is contained in the aqueous phase.

Furthermore, especially when a dye dispersion is mixed with an aqueous water-soluble sizing agent solution, the amount of oil used is significantly smaller than in conventional half emulsions.

The 0/W engineered marsillon viscous composition of the present invention is used for hydrophobic fibers such as polyester, polyamide, triacetate, acetate, blends, weaves, and knits thereof, and products of blends, weaves, and knits of these and natural fibers. be done.

The dye fixation rate when using the 0/W engineered multimulsion composition of the present invention is 90% or more, whereas the dye fixation rate when using a commercially available dye with the same structure and a conventional water-soluble color paste. is generally about 30 to 40.

The remarkable features of using the O/W engineered multilayer composition of the present invention are as follows.

(1) Extremely excellent color development.

Vivid and deep colors can be obtained, and dye efficiency is high.

(2) There is less bleeding during color development of the dye.

The edges of the image appear sharp.

(3) Excellent resistance to hot water staining during washing with water after color development and during reduction washing.

(4) The dyed product has excellent water fastness.

The method of the present invention will be specifically explained below using Examples.

Example I Kayalon Polyester Yellow
5R-8E200 gr (Dye raw material in commercially available dyes) Sorbitan monooleate 10 gr Industrial gasoline No. 4 790 gr was placed in a ball mill, rotated with a stainless steel ball (3/16 inch diameter), and treated for 20 hours.

The stainless steel spheres were then separated by filtration to obtain a composition in which the dye was finely dispersed in the liquid hydrocarbon, and the average particle size of this was 5 μm or less.

Viscosity 10000C, P adjusted to PH5 with tartaric acid.

While stirring 990 gr of an aqueous solution of etherified locust bean gum with a homomixer, 10 gr of the above dispersion composition was added.
was added and treated at 8000 r, p, m for 1 minute,
A viscous O/W multi-mulsion composition having a viscosity of 11,000 c, p, in which dye-containing oil droplets were dispersed in a water-soluble sizing agent solution in the form of fine particles, was obtained.

Example 2 Kayalon Poyester Turq, Bl
ue GL-800gr (Dye raw material in commercially available dyes) Light oil 582gr Sorbitan monooleate 10gr Glycerin monostearate A mixture of 8gr was treated with 27KHz ultrasonic waves at 40℃ for 5 minutes, then placed in a sand mill and rotated at high speed. Dispersion treatment is performed for 180 minutes.

Separation of the sand yielded a very finely dispersed composition.

Polyoxyethylene lauryl ether (
H,L,B, 15.7) 20gr and polyoxyethylene sorbitan monooleate (H,L,B.

A mixture of 10 gr of the above-mentioned dispersion composition and 640 gr of industrial gasoline was gradually added to the solution in which 20 gr of 11.0) was dissolved using a homomixer, and the mixture was further stirred for 1 minute after the addition was completed.

Viscosity 600, with which the dye is uniformly dispersed in the oil droplets of the dispersed phase.
A stable 0/W type emulsion with 0 c,p was obtained.

Furthermore, while stirring 700 gr of the 0/W emulsion with a homomixer, it was given a viscosity of 30000 c, p, PH5.
300 g of a sodium alginate aqueous solution adjusted to 300 g was added and stirred for 1 minute to obtain a good 0/W type engineered multilayer viscous composition.

Example 3 Kayalon Polyester Blue T-
8300gr (Dye raw material in commercially available dyes) Sorbitan monooleate 10gr light
After treating 690 gr of oil in a kneader for 20 minutes, it was passed through three rolls three times, and the resulting dispersion was 15 gr and 15 gr of kerosene.
Mix.

This was gradually added while stirring to 970 gr of an aqueous solution of a 1:1 mixture of pritish gum with a viscosity of 10,000 c, p, and a pH of 4.5, and etherified locust bean gum in a ratio of 1:1.
Stirred for an additional minute.

Viscosity 12000c,p,0/ containing dye in oil droplets
A W-type engineered mulchion viscous composition was obtained.

Example 4 Light oil and industrial gasoline 4 were used instead of kerosene used in Example 3.
Similarly, using the method of Example 3 using No.
/W type emulsion viscous composition was obtained.

Example 5 Kayalon Polyester Blue EB
L-E50gr (Dye raw material in commercially available dyes) Lecithin 3gr Sorbitan monooleate 5gr Polypolylene glycol nonylphenyl ether gr Industrial gasoline No. 4 840gr was placed in a ball mill and micronized using the method of Example 1. 100 gr of the dispersion was added to industrial gasoline No. 4 560
Mix with gr.

This was mixed with 10 g of polyoxyethylene sorbicune dioleate (H, L, B, 11.2) in 300 g of water.
r, polyoxyethylene nonylphenyl ether (H
, L, B, 13°3) is gradually added to the solution containing 30 g while stirring.

100 gr of the emulsion prepared in this way was added to 900 gr of a sodium alginate aqueous solution with a viscosity of 10,000 c, p, and pH 5 while stirring with a homomixer.
The mixture was further stirred for 1 minute at 00 r, P, m.

A highly stable O/W type emulsion viscous composition was obtained.

Example 6 Sorbitanthes-+t was used instead of the dispersant used in Example 5.
oleate, distearate, trioleate, oxyethylene-oxypropylene block polymers (M, W
, 300s H, L, B 4.5) oleic acid ester alone or as a mixture at 1% (
wt) and treated according to the method of Example 5, an O/W type engineered mulsion viscous composition with excellent stability was obtained.

Example 7 Kayalon Polyester Red 2BL
-8150gr (Dye raw material in commercially available dyes) Sorbitan monooleate 4gr sorbicun sesquioleate 4gr perkleen
Put 842 gr into a ball mill and make 6 Or with a stainless steel ball (3/16 inch diameter).
After treatment with p and m for 20 hours and separating the stainless steel spheres, a liquid dispersion of the dye was obtained.

Viscosity 10000c, p adjusted to pH5 with citric acid.

While stirring 990 gr of an aqueous solution of a 1:2 mixture of sodium alginate and etherified locust bean gum in a homomixer, 10 gr of the above dispersion was added and the mixture was heated to 8000 r.
, p, m for 1 minute, a highly stable O/W-type emulsion viscous composition was obtained.

Example 8 When the same treatment as in Example 7 was carried out using tetrachloroethane, trichloroethylene, and chlorobenzene in place of the perchlorene used in Example 7, a similarly stable O/W type emulsion viscous composition was obtained. was gotten.

Similar O/W emulsion compositions were obtained by replacing the dyes used in Examples 1 to 8 above with dyes having the following color indexes, singly or in combination, and treating in the same manner.

Example 22 Contains etherified locust bean gum and sodium alginate in a ratio of 1=1, and further contains iwt relative to the weight of printing paste
% of polyoxyethylene oleyl ether (H, L, B
, 12.0) with a viscosity of 9000 c, p, pH 5, 960 gr was added to this while stirring with a homomixer, 16 gr of the dispersion of the dye of Example 14, 4 gr of the dispersion of Example 19, and the dispersion of Example 20. Gradually add 20 gr of the mixture and heat at 8000 r, p, m for another 1 minute after the addition is complete.
A black O/W type emulsion viscous composition having a viscosity of 12,000 c, p and containing a dye in oil droplets as a dispersed phase was obtained.

Dyeing Example 1 The O/W emulsion composition prepared in Example 1 was printed on a polyester processed yarn fabric, and intermediately dried at 80°C for 5 minutes.
Dry heat treatment was performed at 200°C for 60 seconds.

Next, washing with water, washing with hot water, and reduction washing were carried out using conventional methods.

A yellow print with extremely excellent color development was obtained.

The fixation rate of dyed products using this method is 92%, but the fixation rate of dyed products dyed by the same method using a commercially available dye with the same structure is 32%.
It was 0;b.

Dyeing Example 2 The 0/W type engineered multilayer composition prepared in Example 2 was printed on a polyester jersey, dried at 100°C for 5 minutes, then steamed at 180°C for 5 minutes with superheated steam, washed with water, washed with hot water, and reduced. Washed.

A vivid turquoise blue print with excellent color development was obtained.

The fixation rate of dyeing using this method is 98%, but the fixation rate of dyeing using the same method using a commercially available dye with the same structure is 80%.
He was in charge.

Dyeing Example 3 The O/W type engineered multi-colour composition prepared in Example 5 was printed on a polyester processed yarn fabric, intermediately dried at 80°C for 5 minutes, and then steamed with superheated steam at 180°C for 5 minutes.

After post-treatment and drying in a conventional manner, a vivid blue print with excellent color development was obtained.

The fixation rate of dyeing using this method is 90%, but the fixation rate of dyeing using the same method using a commercially available dye with the same structure is 25%.
He was in charge.

Dyeing Example 4 The O/W type emulsion composition prepared in Example 3 was printed on a triacetate filament fabric, intermediately dried for 8033 minutes, and then subjected to dry heat treatment at 180° C. for 60 seconds.

Then, after post-treatment and drying in a conventional manner, a blue printed material with good color development was obtained.

The fixation rate of dyeing using this method is 95%, but the fixation rate of dyeing using the same method using a commercially available dye with the same structure is 30%.
He was in charge.

Dyeing Example 5 The 0/W molded multicolor composition of Example 16 was printed on a nylon filament fabric, intermediately dried at 80°C for 3 minutes, and then steamed at 100°C for 20 minutes.

After color development, saw pinking was performed, and a scarlet dyed product with extremely excellent color development was obtained.

Dyeing Example 6 The 0/W type engineered resin composition prepared in Example 22 was printed on a polyester jersey, intermediately dried at 100°C for 5 minutes, and then subjected to dry heat treatment at 200°C for 1 minute.

After reduction washing and drying using a conventional method, a deep black print with excellent color development was obtained.

The fixation rate of dyeing using this method is 93%, but the fixation rate of dyeing using the same method using a commercially available dye with the same structure is 20%.
It was a;b.

Dyeing Example 7 In place of the coloring method used in Dyeing Example 1.2.3, steaming was carried out at 130° C. for 20 minutes with saturated steam, and a print with excellent coloring was obtained in the same manner.

Dyeing Example 8 Using the 0/W type technical mullillon composition prepared in Example 2, plain printing was performed on a polyester processed yarn fabric using a rotary screen printing machine, dry heat treatment was performed at 200°C for 90 seconds without intermediate drying, and then dry heat treatment was performed using a conventional method. Washing with water, hot water, and reduction cleaning were performed.

A uniform bright turquoise blue plain dyed product with excellent color development was obtained.

Claims (1)

[Claims] 1. Perform pre-treatment to micronize a dye that has dyeability on synthetic fibers and is poorly soluble in water into a liquid hydrocarbon or liquid halogenated hydrocarbon with a boiling point of 50°C to 250°C that does not mix with water,
An oil-in-water emulsion viscous composition of a poorly water-soluble dye is then mixed with a viscous aqueous solution of a water-soluble thickening agent containing or not containing an emulsifier, or mixed with a half-emulsion glue. How things are made.