JPS6071781A - Printing of fiber base material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the printing of cellulose or cellulose/polyamide fiber substrates.

Cotton cloth is directly printed with dye, the dye is fixed on the fiber by heat, soaped at 40-50℃ to remove unfixed dye and residual sizing agent from the printing paste, and finally the printed material is cationically fixed. It is known that post-treatment with a chemical agent is used. Although this improves the fastness properties of the print, this effect is often temporary and does not survive repeated washing.

Now, if a fixing agent F) as described in U.S. Pat. It has been found that long-term improvements in properties can be obtained.

Furthermore, the fixing agent F) can also be used as a pretreatment agent, in which case also a final washing step after fixing the dye is unnecessary.

Therefore, the present invention provides a method for printing a fiber base material consisting of cellulose alone or a mixture of cellulose and a natural or synthetic polyamide, which method comprises a) printing the base material with an anionic dye, a basic printing with a printing paste containing a dye or a cationic dye and a synthetic thickening agent, b)
c) treating the substrate with a fixing agent F) before or after steps a) and b); and d) thermally curing the fixing agent F), The fixing agent F) is (A) the reaction product of a monofunctional or polyfunctional primary or secondary amine in free base or salt form with cyanamide, dicyanodiamide, guanidine or biguanidine, bonded to a nitrogen atom; and (B) an N-methylol derivative of urea, melamine, guanamine, doriazinone, uron, carbamate or acid amide in aqueous solution; and C) for crosslinking of the N-methylol derivative. It is characterized by containing a water-soluble product obtained by reaction with a catalyst.

In step a), the printing paste preferably comprises a dye, such as a direct dye, a reactive dye, an acid dye, a pigment, a sulfur dye or a vat dye or a developer dye formed by diazo coupling on the fiber. . More preferably, the dyes are direct dyes, especially 1:1 or 1:2 metal complex dyes, reactive dyes, especially those containing mono-, di- or trihalopyrimidyl or mono- or dihalotriazinyl reactive groups, or Acidic dyes containing up to 4 acid groups, for example -3o, H groups. Particular preference is given to direct dyes.

The printing paste preferably comprises a polymer containing carboxylic acid groups in salt form, for example a synthetic thickening agent such as polyacrylic acid, polymethacrylic acid or a copolymer of hydrolyzed ethylene and maleic anhydride in salt form. . The amount of synthetic sizing agent used is suitably between 1 and 20, preferably between 3 and 1
0.0 of the weight of the glue, giving a viscosity of o Pascal/sec.
It is 2-5%, preferably 0.5-2%. The printing paste is
It may also contain conventional additives such as urea, solvents, antifoaming agents, carriers, etc.

Step b) Smell (, fixation is done by the usual method - B) For example,
5 to 40 minutes at 102°C with saturated hot air, preferably 1
0 to 20 minutes or 30 minutes at 150 to 200℃ with hot air
sec to 5 minutes, preferably 1 to 3 minutes or by heating steam at 150 to 200°C for 1 to 15 minutes, preferably 5 to 1
This can be done for 0 minutes.

However, by using synthetic adhesives, the fixing time can be reduced to about half of these values, even for dark colors, for example.
With saturated steam at 102°C, it can be reduced to less than 10 minutes.

Preferably steps C) and d) are carried out after steps a) and b). That is, the fixing agent F) is used as a post-treatment agent. In this case, it is not necessary to wash the substrate between fixing step b) and post-treatment step C). This provides considerable advantages over conventional printing processes that require time-consuming washing steps. Furthermore, the use of synthetic glues leaves less residue on the component after drying without cleaning than common natural glues such as alginate or carob, so the hand of the finished product is not adversely affected. I won't accept it.

The fixing agent F) is preferably prepared by reacting diethylenetriamine with dicyanodiamide and further treating this product with catalyst C.
) in the presence of dimethylol dihydroxyethylene urea.

In the preparation of F) diethylenetriamine and dicyanodiamide are preferably reacted in a molar ratio of 1:1,
The catalyst is preferably an aluminum, magnesium or zinc nitrate, sulphate, chloride or dihydrogen orthophosphate, more preferably magnesium chloride. The adhesive may be prepared and applied as described in US Pat. No. 4,410,652, the preferred method of application being padding at room temperature. An appropriate amount is, for example, for a 1/1 standard density print padded with 70 to 100% of the dry weight of the material, padding liquid I.
30-200 g F/I), preferably 70-130 g/j for cotton! , and 100-200 g/A' for regenerated cellulose.

Thermal curing step d) is also carried out as described in US Pat. No. 4,410,652, e.g. by drying at 70-120°C;
It is then crosslinked at 130-180°C for 30 seconds to 8 minutes, or alternatively at 120-200°C, preferably 140-200°C.
At 180°C for 5 seconds to 8 minutes, more preferably at 170°C for 3
This is carried out by simultaneously performing drying and crosslinking for 0 seconds to 1 minute.

Selection of suitable direct and reactive dyes is similarly carried out as described in US Pat. No. 4,410,652.

Alternatively, the fixing agent 1i) can be applied as a n1j treatment agent to an undyed substrate, dried, cured with P4, printed, and finally fixed in the process by fixing the printed dye. It can be used by carrying out steps c), d), a) and b) in this order, or by carrying out steps c), a>, b) and d) in this order. In the latter process sequence, the fixing agent F) is applied to the undyed substrate, which is then printed, if desired after an intermediate drying step.

Finally, heat is applied to fix the dye and heat cure the fixing agent.

This may be done in two separate steps). for example,
Steam at 102°C, then heat treat at 180°C in G). (or it may be done in a single step).

For example, it is heated at 150 to 200°C in hot air.

The process order is c), a), b), d) or c
), d), a), and b), the final cleaning step after the final fixing step can be omitted.

A printed substrate is obtained which has good hand and fastness properties, such as wash and sweat fastness.

When applying fixative F) as a post-treatment agent, it has surprisingly been found that the dye does not leach into the padding liquid or contaminate the padding rollers, even without an intermediate cleaning step.

The following examples are intended to further illustrate the invention:
Parts and percentages are by weight.

Example 1 Step a) A cotton cloth with a satin weave was printed in a conventional manner using a printing paste having the following composition.

20 parts of C, ■, Direct Yellow 98,300 parts of water, 100 parts of urea, 550 parts of polyacrylic acid in sodium or ammonia salt form (30 parts of polyethylene glycol (MW approx. 8% solution of a commercially available synthetic sizing agent) 300),
1000 parts of a solubilizing mixture consisting of benzyl alcohol, hexylene glycol, monoethanolamine and water Total step b) Fixation was carried out with saturated steam at 102° C. for 10 minutes.

Step C) After fixing, the unwashed cloth is used in accordance with U.S. Patent 4,410,65
2 Example 1 product 100 g/j! The material was padded with a liquid containing 20% of the total pinkness, and the pink-up was reduced to 60%.

Step d) The treated fabric was dried on a tenter at 80°C and then heat treated at 180°C for 30 seconds to 1 minute.

The yellow print obtained had excellent wet fastness properties, for example fastness to washing and alkaline sweat.

Also, the yellow color did not bleed through during the padding process (Step C).

Example 2 Step a) A fabric consisting of 80% cotton and 20% nylon 6 was printed in a conventional manner with a printing paste consisting of:

0.1 of 10 parts. 77310 parts of Direct Blue 100 parts of water 30 parts of urea 550 parts of the solubilized mixture of Example 1 1000 parts of the synthetic sizing solution of Example 1 Step b) Fixation was carried out with hot air at 180° C. for 90 seconds.

Steps c), d) The prints were padded and cured as described in Example 1 without intermediate washing steps.

A deep blue print was obtained which had good wet fastness properties.

Example 3 Example 2 was repeated using a regenerated cellulose substrate. Equally good results were obtained.

Example 4 A mercerized sateen-weave cotton fabric was flant screen printed in four color patterns using four different printing pastes, including:

1) 20 parts (:, 1. Dairef 1-Yellow 982)
10 parts C, 1, Direct Blue 773) 15 parts (7
) C, 1, Dairef I, IJ: LJ-93 and C1■, 1:l mixture of Dairef 1 to Blue 77 (olive-green) 4) 120 parts of stabilized diazonium salt and naphthlate ll, llt+oner) Glues 1)-3) contained 550 parts of the size solution of Example 1, 30 parts of the solubilized mixture of Example 1 and water for a total of 1000 parts. Glue 4) 600 parts of the glue solution of Example 1;
It contained 10 parts of neutral chromate solution, 30 parts of the solubilizing mixture of Example 1, and water for a total of 100 parts. Upon fixation, the diazonium salt was liberated and camped with naphthol to form a chromium complex azo dye. Fixation and post-treatment were carried out as in Example I. Good wet fastness properties such as water, wet iron, wash and sweat fastness were obtained.

Example 5 Process C) The mercerized cotton fabric was
,410,652 of the product of Example 1 120 g/7! The material was padded with water, squeezed to 8o% of the dry weight, and dried.

Step d) The dried fabric was heat cured on a tenter at 180'C for 30 seconds.

Step a) 1) 20 parts of each C. 1. Direct I~
Yellow 162 and 2) 10 parts of C.I. 1. Two color prints were made on the treated fabric using two printing pastes as described in Example 1, including Direct Blue 77.

Step b) The print was then dried and steamed at 102° C. for 10 minutes.

The final prints showed good wet fastness properties even without a washing step after dye fixation.

Example 6 A substrate that has been dried but not cured after step C) is imprinted (a), the imprint is fixed by steaming for 10 minutes at 102° C. (b), and finally Example 5 was repeated except that the print was cured at 180° C. for 30 seconds (“1 culm d”). Similarly good results were obtained.

Examples 7-12 Example 1 was repeated using each of the dyes listed below.

C, 1, Direct reso l-83 C, 1, Direct Hioresotho 66 C, 1, Direct Blue 251 C, 1, direct blank 118 C, 1, Dairef (Green 69 C, 1, Direct Brown 240 Good results were obtained.

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Claims (1)

[Claims] 1. When printing a fiber base material consisting only of cellulose or consisting of cellulose and natural or synthetic polyamide, a) the base material contains an anionic dye, a basic dye, or a cationic dye and a synthetic sizing agent; A step of printing by printing i〃1, b) a step of fixing the dye by heat, C) a step of treating the substrate with a fixing agent F) before or after steps a) and b), and d) a fixing agent F), wherein the fixing agent F) comprises (A) a 3u free base or a salt form of a monofunctional or polyfunctional primary or secondary amine and cyanamide, disylinodiamide,
A reaction product with guanidine or biguanidine,
a product containing a reactive hydrogen atom bonded to a nitrogen atom, and (I3) an N-methylol derivative of urea, melamine, guanamine, doriazinone, uron, carbamate or acid amide in aqueous solution; and C) an N-methylol compound. A process characterized in that it comprises a water-soluble product reacted with a catalyst for crosslinking. 2. The method of claim 1, wherein steps C) and d) are carried out after steps a) and b). 3. The method according to claim 2, wherein no intermediate cleaning step is carried out between steps b) and C). 4. The method according to claim 1, wherein the steps are carried out in the order of c), d), a) and b). 5. The method according to claim 1, wherein the steps are carried out in the order of C), a), b) and d). 6. A process according to any one of claims 1 to 5, wherein in step a) the printing paste comprises a direct dye, a reactive dye or an acid dye containing up to 4 acid groups. 7. The method according to claim 6, wherein the printing paste contains a 1:1 or 1:2 metal complex direct dye. 8. The method according to any one of claims 1 to 7, wherein the synthetic sizing agent is a polymer containing carbonic acid groups in salt form. 9. In step b), the fixation is performed by saturated steam at 102
9. A method according to any one of claims 1 to 8, which is carried out at <RTIgt;C for</RTI> less than 10 minutes. 10. According to claims 1 to 9, the fixing agent F) is the product of reacting diethylenetriamine with dicyanodiamide and further reacting this product with dimethylol dihydroxyethylene urea in the presence of catalyst C). Any method described. 11. Claims in which the fixing agent F) is the product of reacting diethylenetriamine and dicyanodiamide in a molar ratio of 1:1 and further reacting this product with dimethyloldihydroxyethyleneurea in the presence of magnesium chloride. The method according to paragraph 1O.