JPS601434B2 - Printing method for synthetic fibers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention uses a dye that is poorly soluble in water, performs pretreatment to form fine particles in a solvent that is immiscible with water, and then transforms the solution into a water-soluble dye with or without an emulsifier. The present invention relates to a method for printing hydrophobic fibers using an oil-in-water emulsion viscous steel composition of a refractory dye in water by mixing with a viscous aqueous solution of a sizing agent or with a hafe emulsion paste.

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 a colored paste is prepared using an aqueous solution of water-based glue or a herfemulsion (oil-in-water emulsion),
The dye is present in the continuous aqueous phase. On the other hand, in oil-in-water emulsion viscous steel compositions, the dye is present in the oil phase of the dispersed phase. The present inventors have discovered that when an oil-in-water emulsion sticky composition is used for printing or dyeing synthetic fibers, it is possible to obtain dyed products with extremely superior color development and vividness compared to dyeing using existing disperse dyes. I found something that can be done.

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, color development by the thermosol method is not sufficient, and attempts have been made to add strong dyes, but these are inferior in color development and white area staining during washing compared to steaming using saturated steam or superheated steam. It was difficult to put it into practical use. 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. Since the rate is high, the hot water pollution method is also extremely superior.

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 are dyeable to synthetic fibers and are resistant to 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 ionic dyes with water port properties, dyes with opposite ions are used. There are various types of structures that are made lacquer-resistant or lacquer-resistant by forming salts with other substances. Examples of dye structures include monoazo, disazo,
Anthraquinone, nitro, nitroso, methine, quinoline, benzothiazole, xanthene, acridine, triazole, azine, oxazine, triazine, lid.

Dyes commonly used for dyeing synthetic fiber materials can be used, including cyanine, styryl, naphthoquinone, berinone, 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 splitting agent, 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 ℃ include n-hexane, methylbentane, n-hebutane, methylhexane, ethylbentane, dimethylbentane, trimethylbutane, n-octane, n-nonane, n-decane , hexene, methylbenteso, ethylbutene, dimethylbutene, heptene, dimethylbentene, trimethylbutene, octene, dimethylhexene, trimethylbentene, benzene, toluene, xylene, ethylbenzene,
Isof.

Lopylbenzene, ethyltoluene, trimethylbenzene, amylbenzene, dodecylbenzene, amyltoluene, trichloromethane, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, bentachloroethane, dichloroethylene, trichlorethylene, tetrachlorethylene, trichloropropylene /Zen, Dichlorf. Chlorobenzene, chlorobutane, chlorobentane, chloromethylheptane, chlorobenzene, dichlorobenzene, frombenzene, chlorotoluene, etc. The above liquid hydrocarbons or liquid halogenated hydrocarbons may be used alone or in combination. Furthermore, various petroleum products such as petroleum ether, petroleum benzene, 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 a liquid hydrocarbon or liquid halogenated hydrocarbon is preferably one that is soluble in the liquid and well wets the dye particles, examples of which include the following.

a Fatty acid esters of sorbitan, sorbitan, and saccharose, such as solpitan monolaurate, /V remitate, 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, oleic acid, palmitic acid, margaric acid, stearic acid, etc. Monoglycerides d Polyethylene glycol alkyl ether, polyethylene glycol alkyl phenyl ether For example, lauryl ether of polyethylene glycol, stearyl Ether, oleyl ether, octyl ether, nonyl phenyl ether, polyethylene glycol acyl ester, such as lauric acid ester, suaric acid ester, oleic acid ester, etc. Phosphatide, e.g., amphoteric compounds such as lecithin, especially fatty acid ester of solpitan, polyethylene glycol and polypropylene glycol block polymers 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 (methylcellulose, hydroxyl), etc. ethyl cellulose, carboxymethyl cellulose), silica gums (nafka crystal rubber, lame gum, arabo gum) natural rubbers (tragacanth gum, gum arabic, locust bean gum) etherified locust bean gum (indalca, Maypro rubber, thickening), modified starch (British Rubber) and synthetic sizing agents (Poppal, sodium polyacrylate). These lake agents can be used alone or in combination. The pre-treatment for atomizing the dyestuff into the above-mentioned hydrocarbons involves adding a 3 to 15% dispersant to the dyestuff, and milling the dyestuff along with stainless steel balls, glass balls, sand, and porcelain balls in a ball mill or sand mill. It rotates at high speed and mechanically becomes fine particles.

Alternatively, it may be mechanically made into fine particles using a loin mill. The amount of the dispersant used is preferably 4 to 10 t% per skin. The dye is made into fine particles until it exhibits a particle size of 5 or less, but the average particle size is preferably 1 or less. Stainless steel balls, glass balls, sand, porcelain balls used after wet grinding in a ball mill, sand mill, etc., separated by mechanical methods, and 3.
In the material kneaded by this roll, the dye is uniformly dispersed in the form of fine particles in the hydrocarbon.

The dispersion of the dye in the hydrocarbon can be adjusted to high concentrations by the method described above. When mixing the water-soluble sizing agent with the viscous steel aqueous solution, add a non-volatile acid such as tartaric acid in advance to adjust the pH to 4-5.
5. Viscosity 4000-1000 ratio. p. (Measured with a high viscosity rotor viscometer 2500 rotor No. 5 20 v.p.m.) The water-soluble sizing agent solution adjusted to 20 v.p.m. was vigorously stirred in a homomixer while the above dye dispersion was gradually added, and the addition was completed. After that, an oil-in-water emulsion viscous composition containing a dye in the oil phase and uniformly and finely dispersed is obtained by further 30 to 12 hours of immersion.

Further, by adding a lagoonal emulsifier to the lagoon solution in an amount of 0.1 to 1% based on the weight of the composition, an emulsion composition with even better stability can be obtained.

Also, when mixing with Hafemulsion glue, the viscosity is 50% by the usual method.
00-800 ratio. p. The above-mentioned dispersion was gradually added while mixing the Herfemulsion prepared in a homomixer.
After the addition is complete, if 30 to 12 quartz sand is added vigorously, an o/w emulsion composition with excellent stability can be obtained.

In this case, the amount of hydrocarbon or halogenated hydrocarbon as oil phase is preferably from 5 to 3 t% based on the weight of the composition. The water-soluble emulsifier used in this case is generally used for preparing o/w emulsions. L. B. 8
~18 surfactants, such as polyoxyethylene lauryl ether, cetyl ether, stearyl ether, oleyl ether, octyl phenyl ether, nonyl phenyl ether, polyoxyethylene sorbitan monolaurate, sorbitan monostearate, so/ These include floc polymers of sorbitan monooleate, sorbitane dioleate, polyethylene glycol, and polypropylene glycol.

The dye color tone and concentration may be adjusted during the dispersion process, but after the dispersion is completed, liquid hydrocarbons or liquid halogenated hydrocarbons may be added to dilute the dye. It can also be adjusted by mixing it with emulsion glue.

In this case, the total weight of the dye dispersion and liquid hydrocarbon or liquid halogenated hydrocarbon is preferably 20% or less of the total weight of the color class. Furthermore, an o/we emulsion may be prepared by dissolving a water-dispersible emulsifier in water and 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 o/w emulsion clay rice compositions and conventional ha-femulsions is that in the former, the dye is contained in the oil phase, which is the dispersed phase, whereas in the latter, the dye is contained in the water phase, which is the continuous phase. It is contained in the phase.

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

The o/w emulsion sticky composition of the present invention can be used for hydrophobic fibers such as polyester, polyamide, triacetate, acetate, their blends, weaves, and knits, and their blends, weaves, and knits with natural fibers. Ru.

The dye fixation rate when using the O/W emulsion adhesive column composition is 90% or more, whereas the dye fixation rate when using a commercially available dye with the same structure and conventional Mizugata color paste is 90% or more. is generally about 30 to 40%.

The salient features of the use of o/we emulsion column compositions are as follows.

{1} Extremely excellent color development.

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

'2) Less bleeding during dye color development. The edges of the image appear sharp.

{3} Excellent resistance to hot water staining during washing with water after color development and during reducing washing.

{41 The water fastness of the dyed product is excellent.

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

Reference example 1 Kayalon Polyester Yellow 9R-
SE 200gr (Dye Raw Material in Commercially Available Dyes) Sorbitan Monooleate Logr Industrial Gasoline No. 4 79 Female R was placed in a ball mill, rotated with a stainless steel ball (3/16 inch in diameter), and processed for 1 feeding period.

The stainless steel bulbs are then separated in a furnace to obtain a composition in which the dye is finely dispersed in a liquid hydrocarbon (this one).
The average particle diameter was 5A or more. Viscosity 1000 ratio adjusted to PH5 with tartaric acid. p. While mixing 990g of etherified locust bean gum aqueous solution with a homomixer,
Add the above dispersion composition logr and add 8000v. p.
m. When treated for 1 minute, dye-containing oil droplets are dispersed in the form of fine particles in a water-soluble sizing agent solution with a viscosity of 1100. p. o/w
An emulsion sticky steel composition was obtained.

Reference example 2 Kayalon Polyester Turq・Blue
GL-S400gr (Dye raw material in commercially available dyes) Light oil 58g Sorbitan monooleate logr Glycerin monostearate A mixture of 8gr was treated with 27KHz sound waves at 4000 for 5 minutes, then placed in a sand mill and rotated at high speed for 60 Perform decentralization processing for 1 minute.

Separation of the sand yielded a very finely dispersed composition. 20 gr of polyoxyethylene lauryl lenal (J.L.B.15.7) and polyoxyethylene sorbitan monooleate (J.L.B.11.0) in water 310
) 20gr dissolved in a homomixer,
A mixture of 10 scales of the above-mentioned dispersion composition and 64 liters of industrial gasoline was gradually added, and after the addition was completed, the mixture was held for another 1 minute.

Viscosity 600, with which the dye is uniformly dispersed in the oil droplets of the dispersed phase.
ratio. p. A stable o/w emulsion was obtained. Furthermore, 700 gr of the o/w emulsion was mixed with a homomixer and the viscosity was adjusted to 3000. p. When 300 gr of a sodium alginate aqueous solution adjusted to pH 5 was added and stirred for 1 minute, a good o/w type emulsion viscous steel composition was obtained. Reference example 3 Kayal.

nPolyesterBI Melon T-S 300
gr (Dye raw material in commercially available dyes) Sorbitan monooleate 1 female r Kerosene
69 female r was treated with a kneader for 20 minutes, and then passed through three rolls three times, resulting in a dispersion 1.
Mix 5gr and kerosene over 1r.

This has a viscosity of 1000. p. An aqueous solution of a 1:1 mixture of British gum "etherified locust bean gum" with a pH of 4.5 was gradually added to an aqueous solution of 970 ml while stirring for 1 minute, and the viscosity was 1200 ml containing dye in the oil droplets. ratio.
p. An o/w emulsion viscous maple composition was obtained. Reference Example 4 An o/w type emulsion viscous steel composition was obtained in the same manner as in Example 3 except that light oil, industrial gasoline No. 4 and No. 5, and heavy oil were used in place of the kerosene used in Reference Example 3, respectively.

Reference example 5 Kayalon Polyester B1us EBL-
E 150gr (Dye raw material in commercially available dyes) Lecithin 3gr Sorbitan monooleate 5gr Polyethylene glycol nonyl phenyl eneal
2 gr
Industrial gasoline No. 4 84 female r was placed in a ball mill, and 100 gr of the resulting dispersion was subjected to atomization treatment according to the method of Reference Example 1 and mixed with industrial gasoline No. 4 56 kg.

Add this to 300g of water polyoxyethylene sorbitane dioleate (J.L.B.11.2) log, polyoxyethylene nonyl phenyl ether (J.L.B.13)
．． 3) Gradually add to the solution of 30 mochi while leaving a lees.

The emulsion 100 mochi prepared in this way has a viscosity of 1
000 ratio. p. PH5 sodium alginate aqueous solution 900
Add it to gr with a homo mixer and add it to 500 yen. p.
m. I lost my respects for another minute. An o/w type emulsion steel composition with excellent stability was obtained. Reference Example 6 Instead of the dispersant used in Reference Example 5, a block polymer of sorbitan sesquioleate, distearate, trioleate, oxyethylene-oxypropylene (M.W.
3000, days. death. B4.5) oleate ester alone or as a mixture at 1% (wt) based on the weight of the composition
When used and treated by the method of Example 5, it has excellent stability.
/w type emulsion clayey rice composition was obtained.

Reference example 7 Kayalon Polyester Red Group L-S
150gr (Dye raw material in commercially available dyes) Sorbitan monooleate 4gr Sorbitan sesquioleate 4gr Perkleen
Put 84 r into a ball mill and turn 6 with a stainless steel ball (3/16 inch diameter). p.
When the stainless steel bulbs were separated, a liquid dispersion of the dye was obtained.

Viscosity 1000 ratio adjusted to pH5 with citric acid. p. Sodium alginate etherified locust bean gum 1:2
While mixing 990g of the aqueous solution of the mixture with a homomixer, 1 female of the above dispersion was added and 800g of the aqueous solution was mixed. p. m. de1
A highly stable o/w emulsion viscous steel composition was obtained when treated for 1 minute. Reference Example 8 When the same process as in Reference Example 7 was carried out using tetrachloroethane, trichloroethylene, and chlorobenzene instead of perchlorene used in Reference Example 7, a stable o/w emulsion clay rice composition was obtained in the same machine. Obtained.

In place of the dyes used in Reference Examples 1 to 8 above, similar o/w emulsion compositions were obtained by treating in the same manner the dyes having the following color indexes, singly or in combination.

Reference Example 22 Contains etherified locust pea gum and sodium alginate in a ratio of 1:1, and further contains lwt relative to the weight of printing paste
% polyoxyethylene oleyl ether (J.LB.
Viscosity 900 ratio containing 12.0). p. While heating 960 g of the printing paste adjusted to pH 5 with a homomixer, a mixture of 16 gr of the dye dispersion of Example 14, 20 gr of the dispersion of Example 19, and 20 gr of the dispersion of Example 20 was gradually added.
After addition, add 800 nails for 1 minute. p. m. I worshiped the candles.

Viscosity 1200 ratio containing dye in oil droplets as dispersed phase.
p. A black o/w type emulsion viscous steel composition was obtained. Example 1 The o/we emulsion composition prepared in Reference Example 1 was printed on a polyester textured yarn fabric, intermediately dried for 80,005 minutes, and subjected to dry heat treatment in a 200q06 inkstone sand bath.

Next, water washing, wound washing, and reduction washing were performed using conventional methods. A yellow print with extremely excellent color development was obtained. The fixation rate of the dyed product according to this method was 92%, but the fixation rate of a dyed product dyed by the same method using a commercially available dye of the same structure was 32%. Example 2 The o/w type emulsion composition prepared in Reference Example 2 was printed on a polyester jersey, intermediately dried for 100005 minutes, then steamed with superheated steam for 180005 minutes, and washed with water, scratched, and reduced.

A vivid turquoise blue print with excellent color development was obtained. The fixation rate of dyeing by this method was 98%, but the fixation rate of dyeing by the same method using a commercially available dye with the same structure was 80%. Example 3 The o/w emulsion composition prepared in Reference Example 5 was printed on a polyester processed yarn fabric, intermediately dried for 80,005 minutes, and then steamed with superheated steam for 180,005 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 by this method was 90%, but the fixation rate of dyeing by the same method using a commercially available dye made by the same manufacturer was 25%. Example 4 Reference Example 3 The o/w emulsion composition prepared in B was printed on a triacetate filament fabric, and subjected to intermediate drying for 80,003 minutes and dry heat treatment for 1,800,060 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 by this method was 95%, but the fixation rate of dyeing by the same method using a commercially available dye made by the same manufacturer was 30%. Example 5 The o/w emulsion composition of Reference Example 16 was printed on a nylon filament fabric, subjected to intermediate drying for 80,003 minutes, and then steamed for 1,000,020 minutes.

When soaping was carried out after color development, a scarlet dyed product with extremely excellent color development was obtained. Example 6 The o/w emulsion composition prepared in Reference Example 22 was printed on a polyester jersey, intermediately dried for 100,005 minutes, and then subjected to dry heat treatment for 200,001 minutes.

After reduction washing and drying using a conventional method, a deep black print with excellent color development was obtained. The fixation rate of dyeing by this method was 93%, but the fixation rate of dyeing by the same method using a commercially available dye made by the same manufacturer was 20%.
Example 7 In place of the color development method used in Examples 1, 2, and 3, steaming between the two powders using saturated steam at 130° C. similarly produced a print with excellent color development.

Example 8 Using the O/W type emulsion composition prepared in Reference Example 2, a rotary screen was printed on a polyester processed yarn fabric using a printing machine, and 200009 inkstone sand was printed without intermediate drying.
Dry heat treatment was performed, followed by water washing, wound washing, and reduction washing using conventional methods.

Claims (1)

[Claims] 1. Dyeing synthetic fibers and sparingly soluble dyes in liquid hydrocarbons or liquid halogenated hydrocarbons with a boiling point of 50 to 250°C that do not mix with water using a nonionic activator or an amphoteric activator. An oil-in-water emulsion consistency obtained by pre-treatment to form an oil-in-water emulsion and then mixing the solution with a viscous aqueous solution of a water-soluble sizing agent with or without an emulsifier or by mixing with a half-emulsion paste. A synthetic fiber printing method characterized by using a composition.