US3617182A

US3617182A - Process for finishing cellulosic textile materials with etherified melamines

Info

Publication number: US3617182A
Application number: US31054A
Authority: US
Inventors: Michael Thomas Beachem; Frederic Houghton Megson
Original assignee: American Cyanamid Co
Current assignee: Wyeth Holdings LLC
Priority date: 1967-03-13
Filing date: 1970-04-06
Publication date: 1971-11-02
Anticipated expiration: 1988-11-02
Also published as: US3519626A

Abstract

This invention relates to new amino-methylolated melamines and to their use on cellulosic textile materials that have been dyed with direct dyes. The new amino-methylolated melamines impart crease-resistance to such materials and dyed materials so finished have improved light-fastness.

Description

United States Patent [72] Inventors Michael Thomas Beachem [50] Field of Search or 8/1163, l7 Somerset; 74, I162 Frederic Houghton Megson, Martinsville, both of NJ. [56] References Cited [21] Appl. No. 31,054 UNITED STATES PATENTS [22) Filed Apr-6,1970 3,519,626 7/1970 Beachem etal. 8/1163 x Division of Ser. No. 622,415, Mar. 13, 1967. I I 5 patented N9 2 1971 Primary Exammer-George F. Lesmes [73] Assignee American Cyanamid Company Amman! Cannon Stamford, Conn. At orney-John E. Hanrahan [54] PROCESS FOR FINISHING CELLULOSIC TEXTILE ETHERIFIED MELAMINES ABSTRACT: This invention relates to new amino-methylog lated melamines and to their use on celluloslc textile materials [52] U.S.Cl r 8/74, that have been dyed with direct dyes. The n w i /1 /1163, 8/17. /21 methylolated melamines impart crease-resistance to such [5 l] lint. Cl 006m 13/38, materials and dyed materials so finished have improved lightfastness.

PROCESS FOR FINISHING CELLULOSIC TEXTILE MATERIALS WITI-I ETHERIFIED MELAMINES This is a division of application Ser. No. 622,4l5, filed Mar.

wherein "alltyl" is a lower-alkyl group (one to four C atoms) and each of R and R is hydrogen alkyl of up to 18 C atoms. phenyl or phenyl-(lower-alkyl), any of the phenyl or said R groups, especially when R is aryl, having up to two inert radicals, such as lower-alkyl and lower-alkoxy.

The use of aminoplast resins to impart crease-resistance to cellulosics is well-knownv These resins perform their function economically and efficiently without adversely affecting many of the other desirable properties of cellulosics, such as for example. fabric hand, soil resistance or fabric durability. However, aminoplast resins do, in some cases, have an adverse effect on color stability of dyed cellulosics. Thus, it is wellknown that aminoplast crease-preventing finishes can cause accelerated fading of many direct dyes, i.e., the lightfastness of cellulosic textile material dyed with direct dyes is often reduced when the dyed material is after-treated with an aminoplast resin or reactant, such as a urea formaldehyde or a melamine-formaldehyde condensate. Commercial resins which have been shown to cause fading of certain direct dyes include hexa(methoxymethyl)melamine. polymethylolurea with slight degree of methylation, blends of partially methylated hexamethyloltnelamine and urea-formaldehyde reaction products, and methylated trimethylolmelamine.

In view of the widespread use of both direct dyes and aminoplast resins on cellulosics, it is extremely undesirable to have the use of the resin for its purpose, restrict the functioning of the dye for its purpose. It is therefore an object of the present invention to provide a means of treating direct dyed cellulosics with aminoplast resins whereby crease-resistance is imparted to the' cellulosic with no substantial reduction in lightfastness other than normally encountered. it is a further object to provide cellulosics which have been direct dyed and have improved lightfastness while also exhibiting good creaseresistance by virtue of treatment with a particular aminoplast resin textile improving agent. Other objects will be apparent from the ensuing description of this invention.

1t has now been discovered in accordance with this invention that methylolated melamines of Formula I impart creaseresistant properties to cellulosic textile materials without adversely afi'ecting the lightfastness of such material dyed with direct dyes. This is a surprising discovery since cellulosics dyed with direct dyes are normally adversely afiected as to lightfastness when after-treated with aminoplast textile finishes.

The textile finishing aminoplast resins used in this invention are applied to direct-dyed cellulosic textile materials by standard procedures, as by dipping, padding. spraying, etc., and the finishes are converted to an insoluble state by heating the treated fabrics in the presence of a catalyst. The dyed materials thus treated exhibit crease-resistant and wrinkle-recovery properties, and a lightfastness equal to, or even better than the untreated, dyed material.

The compounds of Formula 1 can be made by reacting an N- halomethylmelamine of Formula 11 with a compound of Formula 111 as follows:

CH X

H Compounds HX Formula I wherein X is chlorine or bromine and alkyl" and R and R are as defined above for Formula l. The compounds of Formula 11 and a process for their manufacture are disclosed and claimed in U.S. Pat. No. 3,317,529 issued May 2. 1967 to Beachem et a1. 7

Representative N-halomethylmelamines of Formula 11 which can be used in this invention include N-chloromethyl- N,N',N',N",N"-pentakis(methoxymethyl)-2.3,6-triamino-striazine, N-bromomethyl-N.N'.N.N",N"-pentakis(methoxymethyl)-2,4,6-triamino-s-triazine, N-bromomethyl-N.N'.N'. N",N'"pentakis(ethoxymethyl)-2,4,6-triamino-s-triazine, N- chloromethyl-N.N'.N',N",N"-pentakis(butoxymethyl)-2.4.6- triamino-s-triazine, etc.

Representative compounds of Formula 111 include diphen ylamine, di-p-tolylamine, di-m-tolylamine. bis(pethylphenyl)amine. p-methyldiphenylamine. and bis(p-methoxybiphenylyl)amine.

The reaction of compounds of Formula 11 with compounds of Formula 111 is carried out with or without a solvent, although it is preferable to --use a solvent. particularly when both reactants are solids. It is also advantageous to use an acid acceptor such as an alkali metal carbonate or bicarbonate to take up the hydrogen halide which is formed by the reaction The reaction is conveniently carried out at room temperature. although any temperature between the freezing and boiling points of the reaction mixture may be used Equimolar amounts of reactants can be advantageously used although an excess of either can be present without adverse effect The cellulosic textile materials include fibers. threads. yarns, knitted and woven cloth as well as nonwoven fabrics and felted materials. These cellulosic materials will normally contain at least 50 percent cellulosic fibers. such as cotton. viscose. cuprammonium rayons, linen, hemp. ute. and ramie. either alone or mixed with themselves or other fibers.

The cellulosic textile materials will be dyed with the class of azo dyes known as direct dyes and so classified in the Color Index, second edition. Such dyes are characterized as anionic dyes having affinity for cellulosic fibers when applied from an aqueous dyebath containing an electrolyte They are mainly azo dyes containing sulfonic acid groups as the sodium salts Representative direct dyes are Direct Yellow 6 1C 1 4.001 direct Yellow 1 1 (Cl 40000), Direct Orange 26 (C 1 29.150). Direct Red 1 (Cl. 22.310). Direct Red 11 (Cl 29.100). Direct,Blue 2 (Cl 22,590) and Direct Green I (30.280).

The dyed materials are treated with the textile finishes of this invention using aqueous or organic solvent solutions or dispersions which can be applied by spraying. dipping or padding according to well-known procedures Between 0.5 percent and 40 percent solutions or dispersions are normally used. The amount of finish on the textile material can be varied, usually between 0.5 percent and 40 percent based on the weight of the textile material, with amounts between 2.5 percent and 15 percent preferably being used for practical crease-resistant and wrinkle-recovery properties. The treated fabrics are dried and then heated. preferably in the presence of a catalyst, to effect insolubility of the precondensate on the fabric (cross-linking. etc.). Curing temperatures between 275 and 400 F. for periods of about 20 minutes to 30 seconds are normally used. Suitable catalysts include those normally used for melamine-formaldehyde condensates and their etherates. These include the metal salts such as magnesium chloride, zinc nitrate and zinc chloride, ammonium salts such as ammonium sulfate, ammonium chloride, and organic amine hydrochlorides. ln the case of magnesium chloride, the amount is between about 4.5 percent and 24 percent, preferably between 9 percent and 15 percent, of the anhydrous salt based on the weight of the precondensate.

The treated dyed fabric obtained by this invention will be found to have good wrinkle recovery and crease resistance nonnally required for commercial cellulosics. In addition, advantageously, they will be found to possess lightfastness not previously attained with aminoplast resin-treated direct-dyed cellulosics.

The following examples are presented to further illustrate this invention.

EXAMPLE 1 I YC I HQM c To a solution of 25.4 parts (0.15 mole) of diphenylamine in 80 parts of acetone containing 82.9 parts (0.60 mole) of potassium carbonate there is added a solution of 138.4 parts (0.30 mole) of Nchloromethyl-MN',N',N",N"-pentakis(methoxymethyl)-2,4,6triamino-s-triazine in 80 parts of acetone. After a reaction period of about 15 hours, the reaction mixture is filtered, and the acetone is removed by distillation. A solution of the residue in benzene is washed with water. The benzene is removed by distillation and the residue is extracted with ether. The residue from the evaporation of the ether, a viscous liquid, is N-(diphenylaminomethyl)- N,N',N',N",N"-pentakis(methoxymenthyl)-2,4,6-triamino-striazine.

EXAJIPLE 2 CHQO CH;

To a solution of 0.l mole of di(p-tolyl)amine in 80 parts of acetone containing 82.9 parts (0.60 mole) of potassium carbonate there is added a solution of 138.4 parts (0.30 mole) of N-chloromethyl-N,N,N',N",N"-pentakis(methoxymethyl)- l,4,6-triaminos-triazine in 80 parts of acetone. After a reaction period of about hours, the reaction mixture is filtered and the acetone is removed by distillation. A solution of the residue in benzene is washed with water. The benzene is removed by distillation and the residue is extracted with ether. The residue from the evaporation of the ether, a viscous liquid, is N-(di-p-tolylaminomethyl)-N,N',N',N",N-pentakis(methoxymethyl)-2,4,6-triamino-s-triazine.

EXAMPLE 3 N(CH3OC1H5)3 To a solution of 25.4 parts (0. l 5 mole) of diphenylamine in 80 parts of acetone containing 82.9 parts (0.60 mole) of potassium carbonate there is added a solution of 0.30 mole of N-chloromethyl-N,N',N,N",N"-pentakis(ethoxymethyl)- 2,3,6-triamino-s-triazine in 80 parts of acetone. After a reaction period of about 15 hours, the reaction mixture is filtered,

and the acetone is removed by distillation. A solution of the residue in benzene is washed with water. The benzene is removed by distillation and the residue is extracted with ether. The residue from the evaporation of the ether, a viscous liquid, is N-(diphenylaminomethyl)-N,N,N',N",N"-pentakis(ethoxymethyl)-2.4,6-triamino-s-triazine.

EXAMPLE4 N(CH OCHa)i C s x /CH,OCH3 rcmocu, ,r-:-C C.\'

N CH NICuHACBHP-(DH) To a solution of 0.l5 mole of di(biphenylyl)amine in parts of acetone containing 82.9 parts (0.60 mole) of potassium carbonate there is added a solution of 1384 parts (0.30 mole) of N-chloromethyl-N,N',N',N",N"-pentakis(methoxymethyl)-2,4,6-triaminos-triazine in 80 parts of acetone. After a reaction period of about 15 hours, the reaction mixture is filtered, and the acetone is removed by distillation. A solution of the residue in benzene is washed with water. The benzene is removed by distillation and the residue is extracted with ether. The residue from the evaporation of the ether, a viscous liquid, is N-[di(biphenylyl)aminomethyl]-N,N' ,N',N"N"pentakis(methoxymethyl)-2,4,6-triamino-striazine.

EXAMPLE 5 .\'(CH;OCH:):

C i N (Cato CHmN-(J C-N CH OCH;

To a solution of 0. l 5 mole of di(p-ethylphenyl)amine in 80 parts of acetone containing 82.9 parts (0.60 mole) of potassium carbonate there is added a solution of l38.4 pans (0.30 mole) of N-chlor0methyl-N,N',N',N",N"-pentakis(methoxymethyl)-2,4,S-triamino-s-triazine in 80 parts of acetone After a reaction period of about l5 hours. the reaction mixture is filtered, and the acetone is removed by distillation. A solution of the residue in benzene is washed with water The benzene is removed by distillation and the residue is extracted with ether. The residue from the evaporation of the ether, a viscous liquid, is X-[di(p-ethylphenyl)aminomethyl]-N,N ',N '.N",N"- pentakis(methoxymethyl)-2,4,fi-triamino-s-triazine.

EXAMPLE 6 Pad baths are prepared containing 6.25 percent precondensate solids and I2 percent magnesium chloride based on the precondensate solids in the bath.

Pad Bath A N-( Diphenylaminomethyl)N,N ',N',N",N" -pentakis(methoxy-methyl)-2,4,6-triamino-s-triazine in acetone.

Pad Bath B N,N,N',N',N",N"-Hexakis(methoxymethyl)-2.4.6- triamino-s-triazine in water.

The pad baths are applied to a sample of 80x80 cotton percale dyed with Direct Red 8l (Cl 28160] at 5 percent 0 w.f. of precondensate solids by standard padding procedure using 80 percent wet pickup. The treated fabrics are dried for 2 minutes at 225- F., and the finishes are cured by heating the fabrics at 350 F for L5 minutes. Also. a sample of the dyed, but untreated, fabric is rinsed in water and dried. A portion of each of the fabrics of each color is washed in a home-style washing machine at llO-l l5 F. with water containing 0.25 percent of a commercial anionic surface active agent and 0.25

percent of sodium carbonate. The washed fabrics are dried.

Samples of the treated fabrics, both washed and unwashed,

are exposed in a Fade-Ometer for 60 hours. The degrees of I fading of the exposed samples of fabric is measured as follows:

Spectrophotometric curves of the unexposed portion of dyed fabric and the exposed portion of dyed fabric are recorded for 21 wavelengths over the complete visual range. The spectrophotometric data are converted to colorimetric data by means ofa digital computer. Numerical expressions of color in terms of 3-dimensional color coordinates are thus obtained. The two sets of colorimetric data, i.e., one set for unexposed fabric and one set for the exposed fabric, are then converted into a single color difference (in NBS units) by the system of Wyszecki, J. Opt. Soc. Am, 53, 1318 (I963). The evaluation of the colorimetric data can be done by computer.

The single number color difference thus obtained can be considered in this instance to be strength ratio figures between exposed and unexposed fabric, negative numbers indicating loss in strength, i.e. fading. The larger the color difference number, the greater the difference in the visual appearance between the two samples.

It is generally accepted that a color difference of 0.2 NBS unit is the minimum detectable amount which an experienced person can detect between two samples. The color difference for an acceptable commercial match is probably between 1.0 and 2.0 NBS units as discussed in the monograph by Judd, Color in Business, Science and Industry," Wiley, New York, 1952.

The results of the fading measurements are shown in table 1, Finishes A and B, corresponding to Pad Baths A and B, respectively.

It can be seen that Finish A is superior to Finish B in re sistance to light-fading and is generally equipment to the untreated dyed fabric.

We claim:

I. A process which comprises impregnating a cellulosic textile material bearing a direct dye with a solution of an amino methylolmelamine of the formula:

wherein alkyl" is an alkyl radical of l-4 C atoms and R and R" are individually either alkyl of up to l8 C atoms. phenyl. (lower-alkoxy) phenyl or hydrogen and heating the impregnated textile material in the presence of a catalyst to cure the finish to a substantially insoluble state.

2. The process of claim 1 wherein the mcthylolmelamine is the compound CH OCH:

3. The process of claim 1 wherein the catalyst is magnesium chloride.

4. The process of claim 1 wherein the textile material is cotton.

5. The textile material produced by the process of claim 1 V i n Patent No. 3,617,182 Dated November 2, 1971 Inventor(s) Michael Thomas Beachem and Frederic Houghton Megson It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 22, kindly insert a comma after the word "hydrogen".

Column 3, line 52, "1,4,6- should read 2, +,6-

Column 3, line 7%, "2,3,6-" should read 2,4,6-

Column 4, line #3, "2, +,5-" should read 2,4,6-

Column I, line 49, "X-[di(p-" should read N-[di(p- Column 6, line 21, "R" should read R' Signed and sealed this 9th day of May 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTI'SCHALK Attesting Officer Commissioner of Patents ORM PDQ-1950 (10-59) USCOMM-DC suave-ps9 a U 5 GOVERNMENT PRINTING OFFICE I569 0 3G6'33l

Claims

2. The process of claim 1 wherein the methylolmelamine is the compound
3. The process of claim 1 wherein the catalyst is magnesium chloride.
4. The process of claim 1 wherein the textile material is cotton.
5. The textile material produced by the process of claim 1.