US2371104A

US2371104A - Rxnhxa

Info

Publication number: US2371104A
Authority: US
Publication date: 1945-03-06
Anticipated expiration: 1962-03-06

Description

.. a d p inting assistant. compositions containfrom.

must be admitted with suitableithickener, usually which is suitable for application. Inthe case of rapidly as the paste ages after being made up.

- near the boil with about an 0.1% soap solution e and again rinsed beiore the final drying .operas5 sired- Many of 11011 in an 5 Pros printing aids as one of their components im iia-a .1 2,371,1 4

o -1 STATES mes-r] orricis a 2,311,104 N,N.'-DI(AMINO) DIAMIDES or mcaanoxmo horns as ram'rmo assrs'rsu'rs Roy Herman Kienlc, Chester Albert Amish, and Alfred Louis Peiker, Bound Brook, N. 1.; assign on to American Cyanainid Company, New York, N. Y., a corporation of Maine No Drawinga Application is, 1, 1943,

- Serial 811.593.136 v This invention relates to a new type of dyeing sistant beincorporated in the actual dye paste.

ing these assistants and products printed there- I addition they are thus generally more uniformly dispersed throughout a printing-color paste made therefrom. As a result, the printing assistants usually operate more efl'ectively when tha printing-color paste is finally applied to the fabric.

Use oi printing-color pastes containing dyes," 5 particularly inprintingoperations using vat dyes, is sumciently well-knownso that the procedure has become almost standardized. The actual color-source maybe either a dye paste or a dye 7 It is only relatively recently that dye'powders powder. In hddition to the real color, a dye 10 uita le for use in makin p Printing-ch10! paste usually contains agents to prevent dryingpastes have been available. Most of the printout, settling and/or freezing. Dye powders, not ng i s Pr vi y used in dy p s being being subject to these dimculties, do not require V these agents but they usually'contain agents or not be used with dy powders, the latter beare'so processed as to promote dispersibility. ins necessarily jlimited'to the use of dry Solids In either case. the dye Paste or dye powder Nev h l is d fi thlt l m ants be incorporated in the powders at the time a gum dispersion, to form a printing-color paste 7 ply in the case of dye pastes. V vat dyes, it is also necessary to ase reds sin Dye pastes containing various liquid printing agent and usually an alkali. Because the color yield from printing-color pastes often decreases--* materials used are the alkylol am f example, triethanol amine: and/or polyhydric alc'o-' these printing-color pastes are usually prepared hols such as gly erin lycol, diethylen glycol by the fabric finishers just before they are wh and the like. Various derivatives therefrom also used. I have been tried. It a printing aid is'to be in- The printing-color pastes, however com- 'co po at d in a dye p e a s d printing a pounded, are then appliedfto textil paper or is necessary. 'Examples'oi suchsolids which have other fabric materials for decorative or protecbeen-used in the past include the hydrochlorides tive purposes. The printed pieee m dri d, aged of alkylol amines; silver salt (sodium anthrain a'steam ager, treated with an xi "agent, rinsed and dried. Usua in p ssing textiles,.the printed fabric soaped at or tain metal salts such as those oi cobalt and iron.

Unfortunately, most of these printing, aids previoi'isly used are not satisfactory as may be detion. w

In making up and applying printing-color pastes it has been foundthat a material suitable for use as a, Printing assistant is 'of advantage duce the intensification 01' color tor which they were intended. Others, such as the polyhydric alcohols, cause deterioration of the printing-color pastes so that marked variations in the strength in obtaining maximum color yield. The exa t 40 of prints therefrom are observable even after the way in which. these materials act to produce-an printing-color paste has' been allowed to stand for only a relatively short time. Many of them are satisfactory with some colors but have an ad-' verse eiifect on others, even to-the extent of visimproved color-yield in printing is not entirely understood. It is with these printing aids or assistants that the present invention'is particularly Zconcemed. 2 i 4s ibly altering the shade. None of theniar suit- Although printing aids are desirable in the printing-color pastes, the exact point at which 7 and powder compositions. q f they are added may vary. Dyepastes may con- There remains, therefore, a demandiioiisuit and printing-color pastes madetherefrorn will isfactory color intensification and will notlcause obviously contain'the printing assistant.. Where deterioration oi the dyeing or printing compoaprinting assistant is not present in the dye it may h oged at the time of making shes should b useful both with dye pastes and It is preferable, i iiii jever,

fl'heir addition at the proper point inthe manu- .iacture of the paste is not only easier, but in either liquid,,in form or extremely hydrosco'pie,

of manufacture for the same reasons which ap assistants have been 'made. Among the liquid.

ouinone beta-sulfonate); anthraquinone and cerable without modification/infuse both in paste able printing-assistants which will produce a'satsition on standing. Preferably also, the assist dye powders. and inraddition'shouldbe readily ithe printing asto available or cheaply'and' easily prepared. It is,

' therefore. the object of the present invention to provide a new type of printing assistant which possesses these desirable properties.

In general the objects of the present invention are accomplished by using as a printing assistant as'naoc amides and as printing assistants in present invention. As was also pointed out, howone-or more of the dicarboxylic acid diamides represented by the general formula Nn-a Nil-R" in which Ac represents the residue of a cyclic or aliphaticdicarboxylic acid and R. and R. each represent either an aminoalkyl group in which the alkyl radicalhas from 1 to 8 carbon atoms or an aminoaryl group. Typical of the diamides of the present invention is the N,N'-di(beta-aminoethyl) succinamide which has the probable formula So far as the present invention is concerned the assistants may be added to the printing-color I pastes at any point. They may beincorporated into the thickener; into the dye pastes or powders or may be blended directly into the printing-color paste.- However, as pointed out above, it is preferable that they be incorporated in the dye paste or powder during manufacture.

The use of this new class of printing assistants a number of important advantages. These compounds are dry solids, which may be readily powdered and blended in dye powders but are also soluble or dispersible in dye paste suspensions. They have, therefore a general appli-.

cation in'both dye pastes and dye powders. They do not cause deterioration of printing-color pastes on standing. They encourage ,the production of excellent color yields even under hot ageing conditions. Their use is simple since they may be employed as powders, as suspensions in wateror. alcohol, producing excellent color yields whatever the mode of admixture.

The groups represented by R and R in the general formula y I /NH--B may be quite widely varied. As pointed out, R and R may represent substantially any aminoalkyl group in which the alkyl radical contains from'about l to 8 carbon atoms. These alkyl groups maybe either saturated or unsaturated.

Typical of the amines which may be. employed sults when convertedto dicarboxylic acid dig ever, the invention is not limited to the use of allgvlen'epolyamines. Aryldiamines such as 1-4, aminobenaene, phenylene diamine, the diamino naphthylenes and the like were found to produce excellent printing assistants when converted to dicarboxylic acid diamides. I

Theoretically the groups represented by R and B. may be different, thus forming a mixed diami'de. However, the present application is intended to include only those compounds in which R and R." represent residues of similar alkylene polyamines. Mixed diamides in which R and R differ in a manner such that one is a quinonyl group are specifically included in the copending 4 application of Keinle and Amick, two of the present inventors, for United States Letters Patent. Serial No. 493,185, filed of even date.

In preparing the compounds to be used as the printing assistants of, the present invention the dicarboxylic acid may bequite widely varied. The

compounds may be derived from either cyclic or aliphatic dicarboxylic, acids. 0f the cyclic carboxylic acids, phthalic acid is perhaps the most common and its derivatives have been found to give good results when used according to the present process. The invention however is not meant to be so limited but includes derivatives of such acids as isophthalic, te'rephthalic, polyhydrophthalic, endoallavlene acids such as endomethylene tetrahydrophthalic,

.endoethylene hexahydrophthalic and the like,

and the naphthalic acids as well as the alkyl-substituted acids derived therefrom.

Where derivatives of aliphatic dicarboxylic acids are used, the original acid or anhydride may be varied over a considerable range. If the original aliphatic acid is considered to have the generic formula coon coon or anhydride /C O 1110 o 4 in the case of the anhydrlde, 1 may have substantially any value from zero as in the case "of oxalic acid to about eight without departing from the scope of the present invention. However, where y is'greater than about 6, trouble is en- 'countered in preparing the derivatives. Above about y=8, there is a tendency for the compounds to be water-insoluble, preventing satisfactory use.

, paste or powder form. Particularly good results e The acids may be either saturated acids such as malonic, succinimglutaric, adipic, azelic, sebacic and the like or unsaturated such as maleic,

iumar ic and the like.

While the dye and printing paste compositions of the present invention are not limited to the use of any particular dyes. or dye forms, they are' especially suitable for use with vat-dyes in either may be obtained using the vnt'dye powders of high autodispersibili ty as set forth in Crossley et al., United states neissue Patent No. 21,402,

' reissued March 19, 1940; By combining the color materials of that patent into printing paste compositions oontaining the assistants of the Present invention, the full of both may be polyhydrophthalicv assures.

gained with a resultant simplicity inuse, exoek lence of shade and sharpness-of color. 1

Printing pastes made in this way have the particular advantage that the dyes remainin a highlydispersed state as individual particles rather than as dispersions oi" particle aggregates. In the presparts of. water heated over a steam bath for approximately 1% hours after the temperature reached 185'-190 F. The source of heat was ent specification and claims, where highly-dispersed dyes are referred to, reference to pastes in which the dye particles are so dispersed is intended. V

The invention will be more fully set forth in connection with the following examples which" are intended to be illustrative and not by way of limitation. All parts are bytweight unless otherwise noted.

thenremoved but stirring was continued until the temperature decreased to 120 F. at which time 1.200 parts of potassium carbonate which had been previously dissolved in 1,000 parts water was added to the cooked gum. 1,560 parts of sodiumsultoxylate formaldehyde were dissolved in 1,500 parts or w'aterat a temperature of about 140 F. and added to the common mixture with stirring until th whole was thoroughly mixed.

In the succeeding examples, test prints were made on two different fabrics. vWhere rayon is referred to, a titanium-dioxide-pigmented, allviscose-rayon flat-crepe was used. The cotton iabricreferred to is an 80 x 80 bleached, unmercerized, cotton print-cloth. Ageing 0f the prints was carried out in a steam ager which was constructed in such a manner that controlled temperatures could be used. The temperature range normally used was 100-105 C. Those ageings referred to as plant or hot ageings were carried out inthe temperature range of about 106-110 C. In the case of the cotton prints, ageing pe- 360 parts of glycerine were then added and after thorough stirring the whole was bulked to 12,000

parts. In the succeeding examplesthis mixture is reierred to as; thickener C.

I Erample 4 v A 20% aqueous slurry oi N,N'di(beta-aminoethyl) maleic acid diamide was prepared by grinding the solid and water in a ball mill until a uniform-suspensionwas obtained. Six parts of a dispersible Orange R powder (C. li.-l2l7 pre pared according to U. S. Reissue Patent 21,402 and containing 2.4 parts of real dye were pasted with 3 parts of the aqueous diamicl'e suspension and then blended-with 91'parts of thickener A to produce a homogeneous printing paste. To a riods or 3 minutes; 5 minutes orboth were used. I

'On rayon ageing periods of 5 and 10 minutes or both were-used. The shortest period which gives a satisfactory ageing is preferable.

Example 1 A paste was prepared by slurrying 2,000 parts of l'l'lv British gum (Stein Hall) in 5,000 parts pf water and the mixture was heated with continuousstir'ring until the temperature reached about 185 F. Heating wascontinued for about 1V2 hours after which-150 parts of powder'potassium carbonate and 450 parts of powdered sodium carhonate were added and the mixture stirred until the carbonates dissolved. Heating was discontinued-but stirring was continued until the temperature reached approximately 150 F. at which time 100 parts of sodium sulfoxylate were disaolvdtherein, 600 parts of glycerine were added {insane paste bulked to about 10,000 parts. Stir- I ring was continued until the paste cooled to room temperature. In the succeeding examples this paste is referred to as thickener A.

Example 2'- 2,100 parts of Be-2 Blfitish gum, 200 parts of j typioca ilou'r and 500 parts of cornstarch were. I

added to 2,500 partsof' water and heatedover a' steam bath for approximately 1 /2 hours after the temperature reached about 185 F. The source second 6 parts oi the same Orange R powder,.

3 parts of water were added and then 91 parts of thickener A. This was the control sample. Each or these pastes were printed on cotton and rayon.

After drying in ahot air-dryeathe prints were aged in a steam ager, oxidized', rinsed and soaped in a 1s% soap solution for 5 minutes at the boil, again rinsed and'ironed dry. The prints made from the pastes containing the reaction product of ethylene diamine and maleic anhydride gave better color yields than those made from the pastes containing water only.

Example 5 The procedure of Example 4 was followed ex- I-actly except .that .sLN' di(gamma-aminopropyl) maleic acid diamide was used as the printing ussistant in place of MN dimminoethyl) maleic of heat was then removed but stirring was conq tinned until the temperature decreased to F. at which time 2,100 parts of potassiumcarbonate whichhad been previously dissolved iii hot water was added to the. cooked sum. 1,100 parts or sodium sulfo wlatedormaldehyde were added to the common mixture at a temperature of about 1".. Subsequently, 1,400 parts of glycerine were added and after thorough stirring the whole acid dian ide. The prints ohtained from the paste containing =the printing assistant save much stronger andsuperior results than those prints made from the pastes containing water only. P

1 5 Example 6 The procedure of Example. 4 was again followed-except using N,N' di(para-aminophenyl) V maleic acid diamide as the printing t.

Both the control sample and the one containing the printing assistant were printed on cotton and rayon. The prints obtained from the paste containing the printing assistant gave better color yields than those made from the pastes contain;

, ing water only.

Example 7 I The procodure'oi Example 4= was repeatedusing N.N' di(be'ta-aminoethyl) succinamide. fiihe prints obtained from the pastes containing the reaction product of ethylene diamine and sucwas bulked to about 10,000 parts. The mixture was cooled and stirred continuously until the mass .reached room. temperature. In the succeeding -examples this mixture is referred to as thickener B. I

Eromple 3 720 parts or 134 British gum and 720 pa'rts' of gum (Stein Hall) were add d to. 5.600"

cinic anhydr ide gave very markedly stronger and superior ts tharf those prints made from the control paste.

- Example 8 2o partsof -Vat Yellow ac powder (0. 1. i 1118, prepared according to 1 U. S.

hatent 21,402, and about 2 .parts siie color'was first slurried with 3 parts at deilnitely superior to control sample.

the aqueous diamide suspension of Example 4 and then blended with 77 parts or thickener B. A control sample was prepared without the printing assistant. Both samples or the paste were printed on rayon. After the finishing operations, the color of the prints obtained from the paste containing the assistant was very that obtained from the control sample.

Example 9 The, procedure of Example 8 was duplicated except'that thickener A was used in place of thickener B. Again the prints made from the paste containing the reaction product of ethylene diamine and maleic anhydride were very decidedly superior to, those obtained from the Example 10 A sample of wet presscake of Orange .8

"(C. I.1217) was dispersed with the sodium salt of disulio-dinaphthyl methane and adjusted with water to contain about 12% real dye. Then 10 parts of this colorwere mixed with 0.3 part of N,N' di(beta-aminoethyl) succinamide and stirred until the mixture .was homogeneous and thoroughly wet, after which 90 parts of thickener those obtained from the control sample.

Mample 11 The procedure of Example 10 was duplicated except that the N,N' di(beta-aminoethyl) adipic acid diamide was used as the printing assistant. Prints made from the paste containing the N,N'

di(beta-aminoethyl) adipic acid diamide were much stronger in color yield than those obtained from the pastecontaining water only.

. Example 12 The procedure of Example 10 was also repeated except (that N,N' di(beta-aminoethyl) phthalic acid was used as the printing assistant. A control sample was also prepared from the Orange R. presscake but no printing assistant was added. Each oi these pastes were printed on rayon and cotton. Prints obtained from the V .Example13 Another set of comparativepastes was prepared according to the procedure of Example 10 using N,N' di(beta-aminoethyl) iumaramide in one paste as the printing assistant. Prints obtained from the paste containing the iumaramide had much better color value than those obtained from the control sample.

Example 14 methyl 2,2 bis-thio-naphthene indigo) presscake were deflocculated with the sodium salt of disulfo-dinaphthyl methane, then passed through a Mikr'o colloid mill to give a smooth uniform suspension. This product was called.

Vat Pink FF deflocculatedlpresscake. Aiter desoo'parts or Vat Pink F1" (633' dichloro 4,4 a1- v weighed quantity was entered in a ball mill.

Enough water was added to this mass to reduce the dye content to approximately 15%, and the mix was ground for 24 hours. This 15% Pink FF- water paste was called the blank. Another portion of Vat Pink FF deilocculated presscake containing approximately parts of dye was ground in a ball mill with 6 parts oiprinting essis'tant of Example 4 (N,N" di(beta-aminoethyl) maleic acid amide). The dye content of this mixture was reduced by adding water and the mix was ground for approximately 24 hours.

Both samples were then analyzed for extracted solids. The emciency factor was determined by ciency factor of 1.28.

Example 15 The procedure of Example 14 was duplicated using N,N' di(beta-aminoethyl) succinamide. In this case the efliciency factor was 1.2.

Example 16 10 parts 01 Dark Blue 150 dispersed powder (0. I.1099) prepared according to United States- Reissue Patent 21,402 and containing about 3.7 parts of real dye were blended with 0.3 part of the printing assistant of Example 14 and 90 parts of thickener C. After intimate mixing. prints were made of this paste and also of the control sample prepared in the same way except that no printing assistant was added. Prints on both cotton and rayon obtained from the paste containing the maleic acid diamide were stronger than those obtained from the blank. This was true especially when the samples were aged under plant ageing condition at 106l10 F.

We claim:

l. A color composition comprising a vat dye and at least one substance represented by the in which Ac represents the residue of a dicarpaste containing the printing assistant were suu perior to those obtained from the control sample.

which dye and at leastone solid, powderable substance represented by the formula boxylic acid selected from the group consisting of the phthalic acids, naphthalic acids and the saturated and unsaturated aliphatic dicarboxylic acids of from 2 to 10 carbon atoms and R, represents a radical selected from the group consisting of the aminoalkyl radicals of irom ul to 8 carbon atoms and the aminoaryl radicals. I

4. A dye composition comprising a vat dye powformula R-NH-Ac-NH-R in which Ac re'presentsthe residue 'of a Clienttermining the dye content of this material, a boxylic acid selected troni the group consisting inwhi'ch Ac represents the residue of a dicarder. of high autodispersibility and at least one powdered substance represented by the generalof the phthalic acids, naphthaiic acids and the saturated and unsaturated aliphatic dicarboxylic, acids of from 2 to 10 carbon atoms and R. repre-; sents a radical selected from the group consistingof the aminoallwl radicals of from 1 to 8 carbon atoms and the aminoaryl radicals.

5. A printing paste composition comprising avat dye, a thickener and at least-one substance represented by the general formula R-NHAclNH-R in which Ac represents the residue of a dican.

boxylic acid selected from the group consisting of the phthalic acids, naphthalic acids and the" saturated and unsaturated aliphatic dicarboxylic' acids of from; to 10 carbon atoms and R repre- X cents a radical selected from the group consisting or the aminoalkyl radicals of from 1 to 8 carbon atoms and the aminoaryl radicals. A

B. A printing paste composition comprising a 20 highly-dispersed vat dye, a-thickener and a Print ing assistant comprising at least one substance represented by the general formula in which Ac represents the residue of a dicarboxylic acid ected from thevgroup consisting of the phthalic acids, naphthalic acids and the saturated and' unsaturated aliphatic dicarboxylic acids of from 2 to 10 carbon atoms and R represents a radical selected from. the group consisting of the aminoalkyl radicals of from 1 to 8 carbon