Low temperature pigment binder compositions for textile fabrics

*1

-I -, 3 Ό95 320

United States Patent Omce Patented June 2S, 1963

095 320

LOW TEMPERATURE FIGMENT BINDER COMPOSITIONS FOR TEXTILE FABRIC^

Georae J. Leitoer, PeekskSl, N.Y., assignor to Geigy Chemical Corporation, New York, N.Y., a corporation | No*DrSg. F'^{!cd Oct}· ^N°· ^64,263

Claims. (CI. 117—119.6)

This invention relates to an improved composition for use in the printing and padding of textile fabrics, m particular synthetic textile fabrics or mixtures of natural and synthetic fabrics. The novel compositions of the invention are employed in the formation of print pastes . and padding liquors for the coloring of textile fabrics. Tjhe invention also relates to· a method of using said compositions. ., ,., __

It is an object of the invention to provide a binder component for a finished print paste or padding liquor, which binder component permits the curing of the printed or padded fabric at generally lower temperatures than heretofore practiced. Prior binder components have required curing of the colored fabric at higher temperatures for longer periods of time than the binder components according to the present invention. For example, in the past it has been common to subject the printed fabric to a temperature of about 300° F. to about 350° F. for from 2 to 10 minutes. Often the process of curing, at such temperatures requires special handling of the 'textile goods and added operations. According to^; the present invention, however, the printed goods are dried and cured on hot cans in the same operation at from about 180° F. to about 250° F. for from about 0.5 to about 5 minutes. The prior method requires separate drying and curing steps and higher temperatures, as well as more time to accomplish the curing of the print. Thus, the use of the low temperature pigment binder compositions of the present invention results in a saving of valuable time, heat energy and manpower. Other advantages of the invention will appear from the specification and examples which follow hereinafter.

The low temperature cure according to the present invention has been devised to solve a problem raised by the advent of the many heat-sensitive synthetic fabrics and blends of synthetic with natural fabrics. The curing , of colored fabrics which are at least partially synthetic at temperatures of 300° F. to 350° F. for periods in excess of 2 to 3 minutes, may result in some cases in shrinkage of up to 15% of the original dimensions of the fabric. High temperatures, such as those above 300° F. often cause considerable distortion of the printed design, particularly in blended fabrics. This heat sensitivity is characteristic of such diverse synthetics as the polyamides, polyesters, polyacrylics, and also some of the acetate fabrics. In addition, it is known that application of high temperatures to various fabrics causes loss of tensile strength with resultant reduction of durability in articles of clothing or other consumer goods manufactured with the aforesaid heat-treated fabrics.

The binder component of the invention is composed of two elements: a hard latex and a soft latex. An additional agent which is required for the successful operation of the invention in the finished print paste is a latent acid catalyst. The inventive concept, thus, extends to a binder composed of from 10 to 90% by weight of a component, e.g. a hard latex, as defined hereinbelow, and from 90 to 10% of a soft latex consisting essentially of from 2 to 10% of methacrylic acid, from 60 to 85% of butadiene, and from 38 to 5% of either acrylonitrile or styrene, said soft latex being a polymerization product having the composition by weight indicated. The binder component, when used in combination with the latent acid catalysts defined below, is successful in forming print pastes and padding liquors which produce textile colored fabrics which are wash- and rub-fast, as well as resistant to dry cleaning solvent and to dry and wet crocking.

One or more latent acid catalysts may be employed in the compositions of the invention. Any suitable latent acid catalyst may be used, i.e. any catalyst may be used whose basic element is volatile on heating and may be removed to leave an acid catalytic element. Thus, tor example, ammonium nitrate, ammonium thiocyanate, ammonium sulfate, ammonium chloride, and diammonium hydrogen phosphate are all useful. Amine salts of mineral acids are also employable, as are the morpholine and/or pyridine salts thereof, etc..

The latent acid catalyst is used in an amount ot rrom about 2 to about'10% by weight, based upon the. quantity of binder component used in the finished coloring ρθ¹¹¹ position. On the basis of the total weight of the finished print paste or padding liquor, from about 0.025 to about 2% by weight of latent acid catalyst is used.

' The hard latex element of the binder component comprises several types of latex which lend themselves to setting at lower temperatures when combined with the soft latex defined above, and when in the presence of the acid catalyst above mentioned. In one aspect of the ²⁵ invention, the hard latex is a water-insoluble linear polymer of a mixture comprising (i) from about 1% to about 25% by weight of a monomer of the formula

Ri

CHi=C(R)C0N

Rz wherein

R is either hydrogen or lower alkyl, preferably methyl, ³⁵ R_t and R₂ are each independently either hydrogen or alkyl, preferably alkyl having from 1 to 10 carbon atoms, and (ii) 99% to 75% by weight of at least one alkyl ester of acrylic and/or methacrylic acid, the alkyl group of said ester containing from 1 to 8 carbon atoms. The aforesaid water-insoluble linear polymer is preferably mixed with an auxiliary crosslinking agent. The crosslinking agent is dissolved in an aqueous composition or in a clear extender in which the pigment is dispersed to⁴⁵ gether with the water-insoluble linear polymer defined above. The ratio between the weights of the linear polymer and the crosslinking agent is in the range of 6:1 to 1:6, preferably 5:2 to 2:5.

The auxiliary crosslinking agent is a bivalent or bifunctional organic compound, such as one having one or more reactive carbonyl groups, as e.g. formaldehyde, glyoxal, propanediol, etc. Low molecular weight condensation polymers are also useful. Monomeric reaction products of an aldehyde, e.g. formaldehyde, with urea, ⁵⁵ thiourea or biuret, or homologues or derivatives thereof, may be used. Thus, the following may be used as auxiliary crosslinking agents: aldehyde condensates with N,Nethyleneurea, Ν,Ν^Λ - ethyleneurea, N,N^Z - dimethylurea, N,N' - diethylurea, N,N' - dimethoxymethylurea, N,N-di⁶⁰ methoxymethylurea, Ν,Ν'-diethoxyethylurea, tetramethoxymethylurea, tetraethoxyethylurea; formaldehyde condensates with triazines, e.g. to yield melamines, also N,Ndimethylmelamine, alcohol-modified melamine-formaldehyde thermosetting resin condensates, e.g. of methyl and ⁶⁵ ethyl alcohols, such as dimethoxymethyl monomethylolmelamine. Other crosslinking agents may be formed from reaction of formaldehyde with mixtures of triazines with urea, biuret or other urea derivatives.

In another aspect of the invention, the hard latex com ponent may be replaced by the crosslinking agent alone, as defined above.

3,095,320

In still another aspect of the invention, the hard latex comprises an integrated chemical composition having been copolymerized in a free radical emulsion polymerization from the following monomers:

Ethyl acrylate (I)

Methyl methacrylate (II) Styrene (III)

Preferred proportions of said composition are from about 65% to about 75% ethyl acrylate, from about 10% to about 15% methyl methacrylate and from about 15% to about 10% styrene. A particularly preferred composition comprises about 67% (I), about 12.5% (II) and about 12.5% (III) plus other agents, such as minnamounts of wetting agents and alkali to adjust pH, as well as small amounts of copolymers of (I), (II) or (III) with: ’

Methacrylic acid (IV) and/or Methacrylamide (V)

The proportions of copolymers formed from (IV) and (V) may be from about 0.5% to about 10%, preferably about 4%. (All foregoing percentages by weight are based on the total composition.) Not more than abount 2% to about 4% by weight (on total composition) of other materials (such as wetting agents, alkali) is contemplated. . These materials are inert for the purposes of this invention and do not play a significant role therein Examples of wetting agents are e.g. the alkaryl sodium .sulfonates, ethylene oxide condensates with octyl or nomd phenols, etc. ^J

The invention is illustrated, but not limited, by the examples which follow. In the examples, unless otherwise noted, parts are by weight and temperature is in degrees Fahrenheit.

Example 1 . This, example illustrates various components useful m making the compositions for printing and padding textile fabrics according to the invention, the employment of some of which is further illustrated in Examples 2 through 7.

„ ⁴

Part D—Low temperature curing binder:

(a) Hard Polymers— (1)8 parts methacrylamide, 32 parts of methyl methacrylate and 60 parts of ethyl acrylate witn 17 parts of dimethoxymethyl monomethylol melamine.

(2) 10 parts N,N-dimethylacrylainide, 90 parts of n-butyl acrylate and 20 parts of dimethyl-N,N'-ethyleneurea.

(3) 15 parts of acrylamide, 30 parts of methyl methacrylate and 55 parts of ethyl acrylate with 40 parts N,N'-dimethoxymethylurea.

(4) 3 parts of N-methyl methacrylamide, 17 parts of methyl methacrylate and 80 parts of ethyl acrylate with 30 parts of dimethoxymethyl monomethylol melamine.

(5) Soft polymers— (1) 7 parts of methacrylic acid, 73 parts of butadiene and 20 parts of acrylonitrile.

(2) 8 parts of methacrylic acid, 62 parts of butadiene and 30 parts of styrene.

(3) 10 parts of methacrylic acid, 80 parts of butadiene and 10 parts of acrylonitrile.

(4) 3 parts of methacrylic acid, 77 parts of butadiene and 20 parts of styrene.

(5) 5 parts of methacrylic acid, 85 parts of butadiene and 10 parts of acrylonitrile.

(6) 8 parts of methacrylic acid, 72 parts of butadiene ^an^ ^2d Parts of acrylonitrile.

(c) Some especially advantageous crosslinking agents— (1) N,N,-dimethyl melamine.

(2) Dimethoxymethyl monomethylol melamine.

piethoxymethyl monomethylol melamine.

(4) N,N'-dimethylurea.

(5) N,N-dimethoxymethylurca.

Example 2

A print paste is made with:

Part A—Color concentrate: Phthalocyanine Blue Pigment___________

Water__________________

Sodium lauryl sulfate_______________

Sodium diisopropyl naphthalene sulfonate ~~~

Casein ______________________

Methyl cellulose, 15 cps.

Solvent soluble butylated melamine formaldehyde ________________________

Anti-foam agent_____ xyioi___________________Ξ-ΞΞΞΞΞΞΞΞΞΞ”^-

Mineral, spirits___________________ ~

Parts 15.0 57.6

2.8

2.4

1.5

1.5 parte of phthalocyanine blue color concentrate (example 1, Part A), parts of stabilized 40% aqueous emulsion binder combination containing 50% of hard polymer (Example 1, Part D, _a-l) and 50% of soft polymer (Example 1, Part D, b-1), parte of printing extender (Example ’1, Part C) parts of 50% solution of ammonium nitrate

7.5

0.2

7.5

4.0

100.0

Part B—Extender concentrate:

Water_____________________

Casein_______________________2~~2

Sodium lauryl sulfate________________

Ammonium lauryl sulfate__________ΞΞΞΞΞΞ

Solvent soluble butylated melamine formaldehyde _____________________

Methyl cellulose, 4000 cps. __ΖΖΞ_Ζ_ΖΖΞΞΞ~

Ammonium hydroxide_______________2_~~

Solvent __________

30.0

1.5

10.0

7.5

GO

12.0

14.0

2.0

23.0

G5

100.0

Part C—Printing extender: Extender concentrate (Part B) Water____________________

Mineral spirits ____________2

2.0

43.0

55.0

100 parts _n TL”^ad/t°^{n COtton}’ fabric (nylon), COrton bteST ⁽°^c'Z^{rOn) and cotton and ac}Dlic fabric (Orlon blend) and dry-cured on hot cans for approxi“^at'^{ly2 tes ai} 200 to 230°. The prints obtained

-ve high brilliancy, good handle and very good fastness lAATCcV^Ν°· ^{3 Wash Test)}’ ^{dry cIeanin}S (AATCc7^ei M^MX^thiZ^{d) and} '^{Wet and dry} crocking (AATCC Test Method).

Example 3

A print paste is prepared with:

parts of color concentrate (Example 1, Part A) ^{15 a stab}.^{iHzed 43 %} solids aqueous emulsion binder containing 35% of hard polymer (Example 1, Part D, a-3) and 65% soft polymer (Example 1, Part D, b-2) parts of printing extender (Example 1, Part C) parts of a 50% solution of ammonium thiocyanate parts

100.0

100

Prints are made on Dacron batiste, nylon shear, and a cotton acetate blend. They are dry-cured on a bank of hot cans at 180° to 210° for approximately 3 minutes.

3,096,320

Fabric blends of cotton and silk, and Dacron -and cotton are padded with this liquor to a pick-up of 50% and dry-cured at 220° for 2 minutes. Wash fastness and crock fastness test results are very good.