DE2504398A1 - AUXILIARY CARRIAGE FOR TRANSFER PRINTING - Google Patents

Description

■ ^: ■■■■■■■. ^.: 25Ö4J9 $ '

Bayer Aktiengesellschaft

Zeö patents, trademarks and licenses

509 Leverkusen, Bayisrwerk

Auxiliary carrier for transfer printing

The invention relates to auxiliary carriers for dyeing or printing synthetic fiber materials using the ■ heat transfer printing process, which are characterized in that they are printed with printing inks, which sublimable carbonic oil base extracts cationic dyes of the formula

AC- (L = L) _n -ED (I)

wherein

A, B and D stand for an aryl or heteryl radical, B also stands for hydrogen or together with A can form the remaining members of a heterocyclic ring system,

E for a direct bond or an N-alkyl group stands,

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Denotes alkyl, aralkyl, cycloalkyl or aryl, for a methine group optionally substituted by alkyl, cyano or alkoxycarbonyl or stands for an N atom, which means the numbers 0 or 1,

as well as substances which react alkaline under the transfer printing conditions.

Particularly suitable color bases of the formula I are those of the formulas

a)

"where Z ^ i and

Y ₃ and

mean.

H or C ₁ -C ₄

Amino, C 1 -C ₄ -alkylamino, C2-C 4 -dialkylamino or

C ₁ -C ₄ alkoxy

X, or H

H, methyl or chlorine

C ₁ -C ₄ alkyl, benzyl or phenyl

(Very particularly preferred are those with Y ₁ = OCH ^; Y ₄ = H and Y ₃ = Cl or

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b)

worxn

T ₁ methyl, ethyl, n-propyl, η-butyl or cyanoethyl

T ₂ methyl or ethyl

T ₃ T ₂ or H and

T ^ H, Br or Cl mean and

X _{1 has} the meaning mentioned.

c)

T /

T--

worm

and

have the meaning mentioned and

H or CN

H, CH ₃ , OCH ₃ , NO ₂ , Cl, COOCH ₃ or COOC ₂ H ^ and

1 or 2 mean.

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worm

T ₁ methyl, ethyl, n-propyl, η-butyl or cyanoethyl

T ₂ methyl or ethyl ■

T ₅ T ₂ or H and

T ^ H, Br or Cl mean and

X _{1 has} the meaning mentioned.

c) -

T--

and X _{1 have} the meaning given and H or CN

H, CH ₃ , OCH ₃ , NO ₂ , Cl, COOCH ₃ or COOC ₂ H ₅ and 1 or 2 mean.

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d) (TJ

6'm

where ■ .. · - '■■ ---., -

X ₁ , Tg and m have the meanings mentioned and U _{1 is} hydrogen, C ₁ -C ^ -alkyl, C ₁ -C ^ -AIkOXy or

C2-C, - alkylcarbonylamino.

The color bases and their use in transfer printing are known (cf. DOS 2 325 928 = BE-PS 814 779 and DOS 2 325 154 = BE-PS 815 108)

Such compounds can be used as substances with an alkaline reaction into consideration that show the required alkaline reaction under normal conditions, as well as those that only at elevated temperatures, i.e. at temperatures of 50 to 200 C, cause an alkaline reaction through decomposition *

Examples are:

Alkali and alkaline earth hydroxides, alkali and alkaline earth carbonates and hydrogen carbonates, alkali and alkaline earth salts of weak acids, especially carboxylic acids such as formic acid and acetic acid, Alkali and alkaline earth alcoholates, as well as alkaline earth and " Aluminum oxides. .

Preferred alkaline reacting agents are sodium methylate and ethylate (in the case of anhydrous printing inks) and NaOH, KOH, soda, KpCO ₃ and calcium oxide in the case of aqueous printing inks.

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Of course, the printing pastes to be used contain the usual binders and thickeners as well as solvents, which, however, should not have any anionic groups and do not decompose under the transfer printing conditions »

Synthetic » semi-synthetic and natural resins. In principle, all of the paint and printing inks can be used? but also in the textile industry use common binders and thickeners, provided they meet the above conditions.

The following are preferred:

Polyvinyl alcohols, polyvinyl acetates, locust bean gum and their derivatives, guar flours and derivatives, cellulose esters and cellulose ethers or mixtures of such thickeners and binders. The solvents used are those in which the the above-mentioned thickeners and binders dissolve or swell.

In addition to water, suitable solvents are neutral ones, i.e. with Organic solvents that do not react chemically with the dye-forming agents, e.g. hydrocarbons such as benzene, toluene, Xylene; Chlorinated hydrocarbons such as chlorobenzene, ethylene chloride, tri- and tetrachlorethylene; Alcohols like. Methanol, ethanol, Isopropanol, butanol, benzyl alcohol; Glycols; Ketones such as methyl ethyl ketone, cyclohexanone, as well as various ethers and esters. They are used in pure form or as mixtures. Preferred solvents are the hydrocarbons mentioned, of which in turn toluene, as well as ethanol and glycol.

The inks can be according to the different in paper printing and coating applied to the subcarrier using conventional methods.

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such as roller, rotary and flat film printing or copper rotogravure, flexographic, screen and offset printing, Mankann die Apply printing inks also by means of a Strelchräkel or with a foulard, as well as with spray guns or brushes.

Sometimes it is also of advantage if, in addition to the basic dyes mentioned, sublimable dyes are included in the color pastes Disperse dyes such as e.g.

Disperse Yellow 3 and 54

Disperse Red 4, 11 and 15 ■ ''

Disperse Violet 1 and 4

Disperse Blue 14

incorporated, because this results in the sometimes moderate lightfastness can improve a bit of dyeing with purely basic dyes.

The proportion of disperse dyes in the total dye content of the printing inks is 1 to 90 % *

The addition of disperse dyes offers, in addition to the increased light fastness, the advantage that one with voluminous Woven or knitted - such as plush material - can achieve a better print through. Another more general one Advantage of adding disperse dyes to the alkaline ones Printing pastes in which the dye bases are almost colorless consists in the fact that the more strongly colored disperse dyes give the printing inks so much color that " flawless processing on the paper printing machines becomes possible. It is only through the color of the pastes that the printer is given the opportunity to continuously produce the perfect one To control the printing process.

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Paper is preferably used as an auxiliary carrier, its Quality is determined by the type of printing ink and the printing process. In addition, cellophane is also suitable, Cellulose textiles, metal foils (especially aluminum foils) and the like.

The transfer printing from the auxiliary carrier to the substrate takes place in a manner known per se at 160 to 230.degree. (see e.g. ER-PS

1 223 330 and 1 334 829) Suitable substrates are above all Common textile materials that can be dyed with basic dyes, such as those made from polyacrylonitrile, from copolymers of acrylonitrile with other vinyl compounds such as vinyl chloride, Vinylidene chloride, vinyl fluoride, vinyl acetate, vinyl pyridine, Vinyl imidazole, vinyl alcohol, acrylic and methacrylic acid esters and amides, such as dicyanethylene, from acid-modified polyamide fibers. Acid modified aromatic polyesters are, for example, polycondensation products from sulfoterephthalic acid and ethylene glycol, i.e. polyethylene glycol terephthalates containing sulfonic acid groups (type DACRON 64 of

E. I. Du Pont de Nemours and Company), as described in the Belgian U.S. Patent 549,179 and U.S. Patent

2,893,816.

There are also other types of fiber, e.g. tannin Cotton, leather and the like are suitable.

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example 1

In a solution consisting of

100 parts of ethylene glycol 820 parts of ethanol denate. 40 parts of ethyl cellulose N 22 40 parts of sodium methylate

1000 parts
60 parts of the dye of the formula A are

CH

entered and the mixture on a ball or belt mill homogenized or brought into solution.

♦ -

This paste is then coated with a hand squeegee a paper with a square meter weight between 60 and 90 g and a Cobb value also between 60 and 90.

It is dried. This paper gives a strong red print having good wet and light fastness properties with a thermal transfer on a polyacrylonitrile (PAC) at 20Q ⁰ C and 30 seconds. Even if the paper is stored for several weeks before transferring; an equally deep and deeply colored print is then obtained under the conditions described above.

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Example 2

60 g of a dye of the formula B

20 parts of p-oxydiphenyl polyglycol ether 370 parts of water

50 parts of sodium hydroxide solution 38 Be

Parts

are rubbed in a ball mill and then entered 1000 parts of a thickening that is made from a 10 96igen There is swelling of a locust bean gum in ¥ water. The printing paste obtained in this way is used to print an auxiliary carrier, e.g. a cotton nettle according to one of the methods used in textile printing customary methods, dries and carries out the thermal transfer as described in Example 1.

! fen is given a clear shade of blue on a PAC fabric good light and wet fastness properties, even if the cotton auxiliary carrier has been stored for a few weeks.

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Example 5

A mixture of

30 parts of chlorinated rubber solution (52 % in toluene) 5 parts of solvent-free, medium-oil alkyd resin 3 parts of dibutyl phthalate,

48 parts of toluene and 10 parts of dye of the formula C

CH ₃

C-CH = N-N - // \> N ^ \

I OCH, CH, CH ₃ ^D

4 parts of sodium methylate 100 parts

is homogenized in a ball mill and then printed on an aluminum foil using the gravure printing process and dried.

The transfer is as described in Example 1 on a polyacrylonitrile fabric listed.

A yellow impression with good fastness properties is obtained.

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Example 4
In a mixture of
60 parts of dye of the formula D.

60 parts Disperse Blue 14

10 parts of a non-ionic emulsifier, for example a reaction product of nonylphenol and 10 moles of ethylene oxide, 20 parts of ethyl cellulose N 20
50 parts of ethylene glycol
760 parts of ethanol
40 parts of sodium methylate

is ground in a ball or funnel mill, and the printing ink thus obtained is printed on paper using a gravure printing machine , and dried.

A transfer printing is carried out on a high-pile polyacrylonitrile fabric according to Example 1. A clear turquoise-blue color is obtained Print with good lightfastness and a good print through through the high-pile fabric. Similar good results is obtained even if the printed and dried paper has been stored for several weeks and months.

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Example 5

The procedure described in Example 4, but used as Dyes a red dye of the formula E.

CH = CH J / YS-ßK

and a disperse dye of the Disperse Red 15 type

or Disperse Red 11

or Disperse Red 4

After a transfer printing as in Example 1, clear and clear brilliant red prints on PAC of a better lightfastness than if one were without the addition of one of the disperse dyes is working.

These papers can also be stored well and give a print of the same color yield when printed after prolonged storage and brilliance.

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Claims (9)

Claims; 1) auxiliary carrier for heat transfer printing, characterized in that that these are printed with printing inks, which sublimable carbinol base derivatives of cationic dyes the formula B.
AC- (L = L) _n -ED (I) worm A, B and D stand for an aryl or heteryl radical, also denote hydrogen or, together with A, the remaining members of a heterocyclic Can form a ring system, E for a direct bond or an N-alkyl group stands, X is alkyl, aralkyl, cycloalkyl or Aryl means L represents a methine group which is optionally substituted by alkyl, cyano or alkoxycarbonyl or there is an N atom, η means the numbers 0 or 1, as well as substances which react alkaline under the transfer printing conditions. 2) auxiliary carrier according to claim 1, characterized in that the printing inks also contain disperse dyes. Le A 16 216 - 13 - 609832 / 080§ 3) auxiliary carrier according to claim 1, characterized in that the printing inks are water-free and have an alkaline reaction Substances contain alkali alcoholates. 4) auxiliary carrier according to claim 3, characterized in that the printing inks contain sodium methylate. 5) auxiliary carrier according to claim 1, characterized in that the printing inks dye bases of the formulas wherein
Z "and and mean, H or C 1 -C 4 alkyl Amino, C ₁ -C ₄ alkylamino, or C 1 -C 4 alkoxy Y ₁ or H H, methyl or chlorine C 1 -C 4 alkyl, benzyl or phenyl -C ^ dialkylamino Le A 16 216 - 14. - 609832/0809 wherein Methyl, ethyl, n-propyl, η-butyl or cyanoethyl Methyl or ethyl Tp or H and H, Br or Cl mean and has the meaning mentioned, wherein T ₄ and have the meaning mentioned and H or CN H, CH ₃ , OCH ₃ , NO ₂ , Cl, COOCH ₃ or COOC ₂ H ₅ 1 or 2 mean or where X, and m have the meaning mentioned and for hydrogen, C ₁ -C ₄ -A ^ yI, C ₁ -C ₄ -AIkOXy or C ₂ -C ₅ -Alkylcarbonylamino contains. Le A 16 - 15 609832/0808 49 ■ ': V.; ^: ; ■ 6) Process tin dyeing or printing of synthetic, preferably acid-modified fiber materials according to your Heat transfer printing principle, characterized in that one Auxiliary carrier according to claim 1 used. 7) Synthetic fiber materials printed using auxiliary carriers according to claim 1 according to the heat transfer printing principle. 8) Polyacrylonitrile fibers printed using auxiliary carriers according to claim 1 according to the goods transfer printing principle. 9) Printing inks for printing auxiliary carriers for heat transfer printing, characterized in that they have the composition specified in claim 1. Le A 16 216 - 16 - 603332 / 08-0.8