JPS6052231B2 - How to color textile materials - Google Patents

Abstract

Use is made of pigment dyes and, as binding agent, latexes heat-sensitised by the addition of an alkyleneurethane copolymer of formula I, the symbols in which are defined in the claim. The dyed or printed material is subjected before drying to the action of a heat-radiating source in order to coagulate the latex. Pigment migration on drying is thus avoided. <IMAGE>

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the dyeing or printing of textile materials, and in particular to the dyeing or printing of textile materials, in particular the application of all or part of a binder thereto with a pigment.
The present invention relates to a method for dyeing or printing textile materials using dispersed latexes with pigments (rral) or dyes (dyestu).

One of the advantages of printing or pigment printing on textile materials is that the dyeing can be carried out economically.

Dyeing may be accomplished simply by padding the fiber material between a pair of rollers, followed by drying and polymerization to bond the pigment and fibers. This type of dyeing method is used for dyeing fibers or mixtures of various fibers. Since no affinity is required between the pigment or dye and the fiber, the dyeing method described above allows uniform dyeing of a very wide variety of fiber mixtures and is highly reproducible. is obtained. In either case, the bond between the colorant and the fiber is influenced by the chemical affinity of the colorant with the fiber, but rather by the colorant being applied to the fiber together with the pigment as part of the printing composition. It is influenced by the binding effect provided by the binding agent used. This method does not require extensive washing of the textile material and therefore dyeing can be carried out significantly more economically than with other dyeing methods. Colorant compositions conventionally used for pigment printing textile materials consist primarily of a water-insoluble coloring substance, ie a pigment, and a binder capable of fixing the coloring substance to the textile support.

The binders are usually polymeric or copolymeric elbows, usually acrylate or alkyl methacrylate copolymers, styrene-acrylate and/or alkyl methacrylate copolymers, butadiene-acrylate, styrene-butadiene and styrene- Emulsions of butadiene-acrylate copolymers and terpolymers are used.

These various polymers make it possible to obtain latexes which disperse coloring substances and which bind this coloring substance, i.e. pigments, to textile materials which have no affinity for them, regardless of their type. .

US Patent Application No. 60104? Specification and French Patent Application No. 742766? The specification describes a novel compound that can be added to synthetic resin latex and is characterized by having heat sensitivity, in particular, the property of coagulating and activating the latex when raised to a predetermined temperature. ing.

In other words, the above patent application describes heat-sensitive latex compositions that can be activated at a given temperature. Other thermosetting latexes are also described in the above literature.

Generally, these latexes are used as binders for non-woven fabrics and, in some cases, for the production of thin-walled molded articles. For latexes containing colored substances, when using conventional latex compositions, the coloring substances usually migrate from the coated surface to the opposite surface when the temperature is increased, resulting in non-uniform coloring. Cutti
ng) becomes defective and the so-called double surface effect (DOub
It is known that phenomena such as le-Face effect) occur.

In the finished product, due to the migration of the pigment to the surface of the fiber material,
The abrasion resistance of the applied colorant becomes poor. The present invention
Pigment printing or textile printing (Impress) of textile materials
It is an object of the present invention to provide a method for dyeing textile materials, which improves the above-mentioned drawbacks in iOnprinting, improves the bond between the coloring substance and the textile material, improves the abrasion resistance, and eliminates other drawbacks. purpose.

Another object of the invention is to provide a method for dyeing textile materials which allows the migration of colorant particles to be reduced.

The object of the present invention is to provide dyeing materials containing coloring substances.
This is achieved by using nonionic or anionic heat-sensitive latexes that solidify by increasing the temperature to a predetermined value.

The latex may be composed in whole or in part of the materials described in the aforementioned US patent application. In particular, the heat-sensitive latex used in the present invention is Latex 1 (1)
0.05 to 5 parts per part of the formula: where R represents an aliphatic group and/or an aromatic group optionally substituted by biuret, urethane or isocyanate groups; R'' is the number of carbon atoms represents 1 to 8 alkyl groups;
(CnH2TlO square, represents the residue of a copolymer of ethylene glycol and propylene glycol; p is at least 5; x is O or 1; y is "always greater than 2; the sum of x and y is alkylene-urethane copolymers (always greater than 2).Latices that can be used in the heat-sensitive systems of the present invention include: conjugated diolefins such as butadiene, methylbutadiene, isoprene and their congeners A homopolymer of the above diolefin and vinyl and acrylic monomers copolymerizable therewith, such as styrene, methyl methacrylate, vinyl acetate, acrylonitrile, acrylic ester, acrylic acid, methacrylic acid, vinyl chloride and vinylidene chloride. copolymers of the conjugated diolefin and isoolefins such as isobutylene; homopolymers and copolymers of ethylene monomers; copolymers of the vinyl monomers and acrylic monomers; It is a copolymer with an olefin that can be copolymerized with an ethylene monomer such as propylene; vinyl acetate,
Homopolymers or copolymers of vinyl monomers such as vinyl chloride; acrylic monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate, acrylic acid, methacrylic acid, acrylamide, N - Homopolymers and copolymers of methylol acrylamide and glycidyl methacrylate; copolymers of vinyl-acrylic monomers, such as copolymers of vinyl acetate and the above-mentioned acrylic monomers, vinyl chloride or vinylidene chloride and the above-mentioned acrylic monomer, and a copolymer of styrene and the above-mentioned acrylic monomer.

Other homopolymers, copolymers and terpolymers containing monomers such as those described above may also be used.

The proportion of alkylene-urethane copolymer to the binder used is from 2 to 8% by weight, preferably from 5 to 3% by weight. Detailed descriptions of the invention for alkylene-urethane copolymers having the formula are found in the aforementioned US and French patent applications.

The latex contains additives or auxiliaries necessary to promote the curing or condensation of the polymer and improve the stability of the latex and the mechanical strength and chemical stability of the resulting polymer. may contain additives for

For example, ammonium salts (eg, ammonium chloride, diammonium phosphate) may be used in the textile industry to promote the condensation of acrylic polymers with reactive groups of the N-methylol type. In the latex system according to the invention, such additives can be used without problems. The solids content of the natural or synthetic latex system according to the invention is between 25 and 75
% by weight, preferably 40-5% saliva.

The heat-sensitive composition according to the invention can be prepared simply by using the amount of copolymer necessary to obtain the desired solidification temperature.
It can be adjusted by adding an alkyl oxide copolymer to the latex.

This coagulation temperature can be adjusted for a particular latex by changing the proportion of urethane-alkylene oxide copolymer added, but is usually between 30 and 80'C. In order to obtain the best results in the storage stability of the treatment bath and its use, it is preferred to adjust the coagulation temperature to 35-55°C. Examples of the present invention and production examples of alkylene-urethane copolymers are shown below.

Example 1 A pre-hydrophylized and bleached woven cotton fabric was impregnated with a composition consisting of the following components: 591e post-coloring substance, i.e. pigment, 40y1
The binder described below, the heat-transferring aid described below 20vIe, the excess liquid from the aqueous impregnation bath is removed by passing between a pair of pressure rollers, and the woven fabric is impregnated with the impregnation bath. 80% of the weight of the liquid was retained.

The woven fabric is then irradiated by passing it through a tunnel equipped with an infrared heating device having a spectrum with a maximum irradiation value of 2.3 to 3.4 manometers (Wavelength). Rapid pre-drying in seconds.

After finally drying this woven fabric at a temperature of 100°C, it was heat treated at 150°C for 4 minutes in heated air. Pigment:
Hellzallne Blue R
) is a colored pigment commercially available from BASF under the trade name.

Binder: 40% solids thermosetting aqueous emulsion consisting of ethyl acrylate-butyl acrylate-methyl acrylamide copolymer.

Heat-sensitive auxiliary agent: an aqueous solution containing 3% by weight of the alkylene-urethane copolymer obtained in Production Example A described later. After carrying out the above treatment, it was observed that the blue colorant was completely and effectively bound to the fabric.

When the test was conducted without the use of a heat-sensitive aid, it was found that the hue was unclear, the coloring was irregular, and colorant migration had occurred. EXAMPLE The same procedure as in Example 1 was repeated using the following materials: Woven fabric: Polyester-viscose woven fabric Colorant: 5yIe Helizaline Red R (trade name of BASF) Bindery 45% solids aqueous emulsion heat-sensitive aid consisting of ethyl acrylate-acrylonitrile copolymer: Same as Example 1.

After treatment, the woven fabric exhibited a deep red color, there was no migration of the colorant, and the colorant remained firmly bound even after repeated washing.

The abrasion resistance of the colorant of the sample without the heat sensitive aid was poor. EXAMPLE The experiment was carried out under the same conditions as in Example 1.

The fabric was passed through an infrared preheating device, then folded in half to make the heating conditions particularly harsh, increasing the possibility of colorant migration, and then dried at 100°C.

After treatment, the fabric was opened and it was found that the two surfaces were identical, so no colorant had migrated.
When the same test was performed without the heat-sensitizing aid, when the fabric was opened, it was found that the density on the inside had decreased, indicating that the colorant had migrated to the opposite surface. EXAMPLE A cotton woven fabric was impregnated with a composition consisting of the following ingredients in a bath.

5y1e colorant; 30y1e binder; 15y1' heat sensitive auxiliary; Colorant: aqueous dispersion of Helizalin (BASF product) Binding auxiliary: butadiene-acrylonitrile copolymer 45
% aqueous emulsion heat-sensitive aid containing: 30% aqueous solution of polysiloxane commercially available from BASF under the trade name Coaguland WS.

After impregnating in the same manner as in the example, the cloth was layered and
It was dried at 0°C. No colorant migration was observed in the sample after treatment.

Example The same method as in Example was repeated, except that a solution containing 5yIe of the alkylene-urethane copolymer prepared in Production Example C below was used as the heat-sensitive auxiliary agent.

After processing in the same manner as in the example, the colorant is more effectively and permanently bonded to the fabric than in the example, and there is no migration of the stain and no unevenness of the stain. It was not recognized. In place of the binder of Example 40V1', 25
The thermosetting binder of vIe was used in the form of an aqueous emulsion containing 4% ethyl acrylate-to-acrylonitrile copolymer and the thermosetting binder used in Example 1 of 15y1e. A procedure similar to Example 1 was repeated.

After treatment, no colorant migration was observed in the fabric.

Samples were prepared under identical conditions using a 40yIe non-thermosetting emulsion, ie an emulsion without thermosetting latex.

This sample had an unclear hue and was unevenly colored. A manufacturing example of the heat-sensitive auxiliary agent used in the above examples is shown below. Production Example A In a 2e flask equipped with a stirrer, thermometer and reflux condenser, add 500y of toluene and a molecular weight of about 10.000.
100 y of monobutyl ether of ethylene glycol-propylene glycol copolymer (weight ratio 50/50) was charged.

Traces of water were first removed by azeotropic distillation of water-toluene and then 2.5 g of phenyl polyisocyanate (PAP) was removed.
(commercially available under the trade name I)) was added. The reaction mixture was heated at 100-110°C for 3 hours and then at 170°C.
Distillation was performed under a vacuum of 40 Hg to remove toluene. The heat-sensitive compound (4) thus obtained has a high viscosity,
It is a clear yellow oil with a cloud point of 44°C, soluble in cold water. Preparation Example B Preparation Example A was repeated using an excess of phenyl polyisocyanate to monobutyl ether of polyethylene glycol/polypropylene glycol copolymer (50/50 weight ratio).

The product (B) with isocyanate groups in the free, ie active state, is thus capable of reacting with water.

A clear yellow oil was obtained which was highly viscous and soluble in cold water and had a cloud point of 20°C. Production Example C In a 2' flask equipped with a stirrer, thermometer and reflux condenser, 500y of toluene and polyethylene glycol-polypropylene glycol (with a molecular weight of about 8000) were added.
weight ratio 50/50) copolymer monobutyl ether 10
0y was charged.

After removing water by azeotropic distillation, 3.5 y of a 75% solution of polyisocyanate obtained by condensing hexamethylene diisocyanate and water was charged.

This polyisocyanate is DESMO
It is commercially available under the trade name DUR)N. 2 of the reaction mixture
After refluxing for an hour, the solvent was removed at 170° C. under reduced pressure of 40 wnHg. Yellow transparent oily heat sensitive compound (C)
was gotten. Product (C) was soluble in cold water and had a cloud point of 44°C. Production Example D To a 2e flask equipped with a stirrer, thermometer and reflux condenser, 500y of toluene and a molecular weight of 10.000
Monobutyl ether of polyethylene glycol/polypropylene glycol (weight ratio 50/50) copolymer 1
00y was charged.

After removing water by azeotropic distillation, 5.7 f of a 75% ethyl acetate solution of polyisocyanate obtained by condensing toluene diisocyanate and trimethylolpropane was introduced. This polyisocyanate is Desmodyur L
It is commercially available under the trade name. The reaction mixture was refluxed for 3 hours, then the toluene was removed at 170° C. under reduced pressure of 40° Hg. The thermotransferable compound (F) thus obtained was a very viscous, cold water soluble, yellow oil with a cloud point of 47C. Production Example E Into a 2F flask equipped with a stirrer, a thermometer, and a reflux condenser, 500y of toluene and 70y of monobutyl ether of polyethylene glycol/polypropylene glycol (weight ratio 50/50) copolymer with a molecular weight of 10.000 were added.
and polyethylene glycol nonylphenyl ether having a molecular weight of 1524.

After removing traces of water by azeotropic distillation, 7.2 y of a solution of Desmodyur N was added. This solution contains 75% by weight of a mixture of ethyl glycol acetate and xylene polyisocyanate. The reaction mixture was refluxed for 3 hours,
Then, toluene was removed under reduced pressure of 40 wnHg at 170°C. The heat-sensitive compound (F) thus obtained was a very viscous, cold-waterable, yellow oil with a cloud point of 41°C. Production Example F Monobutyl ether of polyethylene glycol-polypropylene glycol copolymer (weight ratio 50/50) with a molecular weight of 10.000, PLURON
The same method as in the above production example was repeated using polyethylene glycol-polypropylene glycol copolymer 30V with a molecular weight of 1830, commercially available under the trade name IC), and the polyisocyanate 9.5y used in Production Example E. .

The heat-sensitive compound (F) thus obtained is a very viscous,
It was a white substance with a cloud point of 45°C, soluble in cold water. Comparative Example Except for using a 3% aqueous solution of the alkylene urethane copolymer of the present invention containing 50 moles of residues of an ethylene glycol-propylene glycol copolymer with a molar ratio of ethylene oxide doripropylene oxide = 50:50. , the same method as in Example 1 was carried out.

After being treated in the same manner as in Example 1, the fabric was colored a pure blue, no migration of the colored substance was observed, and the colored substance was firmly bound to the fabric.

When the dyeing bath was heated to 60°C, coagulation of the latex was clearly observed. On the other hand, the same method as above was repeated using an alkylene-urethane copolymer containing only residues of ethylene oxide polymer.

The hue of the fabric obtained was very non-uniform, indicating that considerable migration of the colored substances occurred during dyeing.

Claims (1)

[Scope of Claims] 1 A fiber material in the form of latex and with the formula: ▲ Numerical formula, chemical formula, table, etc. ▼ [wherein R is an aliphatic group optionally substituted with biuret, urethane or isocyanate group and/or represents an aromatic group;
R' represents an alkyl group having 1 to 8 carbon atoms; ▲Numerical formula,
There are chemical formulas, tables, etc. ▼▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ represents the residue of a copolymer of ethylene glycol and propylene glycol; p is at least 5;
Colorant in a binder containing a heat-sensitive auxiliary consisting of an alkylene-urethane copolymer, wherein x is 0 or 1; y is always greater than 2; the sum of x and y is always greater than 2. and heating the treated textile material to a temperature sufficient to activate the latex and bind the colorant to the textile material. 2 Claim 1 in which the alkylene-urethane copolymer is used in an amount of 2 to 8% by weight based on the weight of the latex.
The method described in section. 3. The method of claim 2, wherein the alkylene-urethane copolymer is used in an amount of 5 to 30% by weight based on the weight of the latex. 4. After contacting the fibrous material with a composition containing a colorant, latex, and heat-sensitive aid, radiation heating is performed to coagulate the heat-sensitive latex and prevent migration of the colorant, and then the fibrous material is 4. The method according to claim 3, for drying.