Resist printing on hydrophobic fiber materials

Details Resist printing on hydrophobic fiber materials Resist printing on hydrophobic fiber materials

2000-12-15

2003-09-09

Einsmann, Margaret (Department: 1751)

Bleaching and dyeing; fluid treatment and chemical modification

Process of printing permanently on substrate, other than...

Resist or reserve

C008S478000, C008S485000, C008S922000, C008S576000, C008S606000

Reexamination Certificate

active

06616711

ABSTRACT:

The present invention relates to a special process for printing hydrophobic fibre materials with disperse dyes by the resist printing process.
The resist printing process with disperse dyes is known for hydrophobic fibre materials. However, these materials, especially polyester fibre materials, are usually printed by the so-called discharge resist process in which the predyed or preprinted base dye is destroyed locally by treatment with a strongly alkaline assistant and by printing these areas with one or several other dyes which must by discharge resistant. Treatment with the discharge agent is, however, ecologically and economically disadvantageous; thus, for example, the treated fibre material may be attacked and damaged by the action of strong alkali. There is therefore a need for a simpler resist printing process, which is gentle on the fibre, for printing hydrophobic fibre materials, especially polyester fibre materials.
Surprisingly, it has now been found that the hydrophobic fibre material can be printed in a manner which is gentle on the fibre by the process of this invention, the resulting print having good allround fastness properties and, in particular, very good fastness to hot light.
Accordingly, this application relates to a process for printing hydrophobic fibre materials with disperse dyes, which process comprises
1) dyeing or printing the fibre materials overall with a disperse dye, and
2) printing the fibre materials in areas with a printing paste, which comprises
as component (A), at least one cationic assistant,
as component (B), at least one polyethylene glycol,
as component (C), at least one nonionogenic detergent
and, optionally,
as component (D), at least one disperse dye,
it being possible for steps 1) and 2) to be carried out in any sequence and for step 2) to be carried out repeatedly without using any dye, or using different dyes, and, if necessary, drying the fibre material thus treated and then fixing the dye on the fibre material by heat treatment.
Disperse dyes suitable for steps 1) and 2) of the novel process are, for example, those dyes which are described in Colour Index, 3
rd
edition (3
rd
Revision 1987 including additions and amendments up to No. 85) under “Disperse Dyes”. These dyes include, for example, car-boxylic acid- and/or sulfonic acid group-free nitro, amino, aminoketone, ketoninime, methine, polymethine, diphenylamine, quinoline, benzimidazole, xanthene, oxazine or coumarine dyes and, in particular, anthraquinone and azo dyes, such as mono- or disazo dyes.
Dyes which are preferably used for the novel process are those of formulae
wherein
R
1
is hydroxy or amino,
R
2
is hydrogen; phenyl which is unsubstituted or substituted by C
1
-C
4
alkyl, C
1
-C
4
alkoxy, hydroxy-C
1
-C
4
alkyl or C
1
-C
4
sulfo,
R
3
is hydrogen, hydroxy, amino or nitro,
R
4
is hydrogen, hydroxy, amino or nitro,
R
5
is hydrogen, halogen or C
1
-C
4
alkoxy, and
R
6
is hydrogen, halogen or —O—(CH
2
)
2
—O—COOR
7
, wherein R
7
is C
1
-C
4
alkyl or phenyl,
 wherein
R
8
and R
9
are each independently of the other hydrogen, —(CH
2
)
2
—O—(CH
2
)
2
—OX or —(CH
2
)
3
—O—(CH
2
)
4
—OX, wherein X is hydrogen or —COCH
3
,
 wherein
Rio is amino which is mono- or disubstituted by —(CH
2
)
2
—O—COCH
3
, —(CH
2
)
2
—CN, —CH(CH
3
)—COOCH
3
or —CH
2
—C(OH)CH
3
,
R
11
is hydrogen, C
1
-C
4
alkyl or halogen,
R
12
is hydrogen or NHCOR
15
, wherein R
15
is C
1
-C
3
alkyl,
R
13
is hydrogen or halogen, and
R
14
is halogen, nitro or cyano,
wherein R
16
is methyl, ethyl or —(CH
2
)
2
—O—C
1
-C
2
alkyl, and
The amounts in which the disperse dyes are used in the dye baths or printing pastes can vary, depending on the desired tinctorial strength; advantageous amounts having been found to be usually from 0.01 to 15% by weight, preferably from 0.1 to 10% by weight, based on the total sum of the dyes per 1 litre of the liquor, or from 0.01 to 400 g, preferably from 0.2 to 300 g, more preferably from 0.5 to 200 g, of the dyes per kg of printing paste.
If the hydrophobic fibre material is dyed in step 1), a continuous dyeing process is usually used, for example the padding process. If appropriate, the dyed material is dried before further treatment, for example for 1 to 5 minutes at 80 to 1 40° C.
In addition to the dye, the dye liquor can contain other customary additives, for example acid donors, such as aliphatic amine chlorides or magnesium chloride, the aqueous solutions of inorganic salts, such as of alkali chlorides or alkali sulfates, alkali hydroxides, urea, thickeners, such as alginate thickeners, water-soluble cellulose alkyl ether, and also levelling agents, antifoams and/or deaerators, penetration accelerators, migration inhibitors, UV ab-sorters and wetting agents.
The printing paste which may optionally be used in step 1) is a printing paste customarily used in printing technology, which comprises, in addition to the dye, the conventional assistants, for example thickeners of natural or synthetic origin, for example commercially available alginate thickeners, starch ethers or carob seed grain ether, in particular sodium alginate, by themselves or in admixture with modified cellulose, preferably with 20 to 25% by weight of carboxymethylcellulose.
In the above printing paste, it is preferred to use synthetic thickeners, for example those based on poly(meth)acrylic acids, poly(meth)acrylamides, and their co- or terpolymers. If desired, the printing paste can also contain acid donors, such as butyrolactone or sodium hydrogenphosphate, preservatives, sequestrants, emulsifiers, water-insoluble solvents, oxidants, UV absorbers or deaerators.
The material printed in step 1) may optionally be dried before further treatment, for example for 1 to 5 minutes at 80 to 140° C.
Suitable components (A) in the printing paste used in step 2) are in particular organic poly-mer compounds containing quaternised amines; salts of nitrogen-containing organic polymer compounds, or aminoxides of formula
wherein
R is an aliphatic radical containing 8 to 24 carbon atoms, and
R
1
and R
2
are each independently of the other an aliphatic radical which is unsubstituted or substituted by hydroxy, C
1
-C
4
alkoxy, halogen, sulfo or acyl containing 1 to 24 carbon atoms, or a radical —(CH
2
CH
2
O)
k
W, wherein k is a number from 2 to 80, and W is C
1
-C
4
alkyl, acyl, phenyl, naphthyl, benzyl or, preferably, hydrogen.
R defined as aliphatic radical containing 8 to 24 carbon atoms is, for example, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, heptadecyl, octadecyl, eicosyl or docosyl. R
1
and R
2
defined as aliphatic radical containing 1 to 24 carbon atoms is, for example, a C
1
-C
24
alkyl radical, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, heptadecyl, octadecyl, eicosyl or docosyl.
Of these compounds, the organic polymer compounds based on the polymono- and polydi-allylamines merit particular mention, for example polydiallyl ammonium hydrochloride or polydiallyldimethyl ammonium chloride, and also ethoxylated and/or propoxylated fatty amines which are quaternised, for example, with methyl chloride, dimethyl sulfate or benzyl chloride, such as dodecylamine which is reacted with 17 ethylene oxide units and quater-nised with methyl chloride.
The printing paste contains 1 to 70, preferably 1 to 40, more preferably 1 to 30 g of the catio-nic assistant per 1 kg of the printing paste.
A suitable component (B) for use in the printing paste used in step 2) is advantageously a polyethylene glycol having a molecular weight in the range from 200 to 9000, preferably from 200 to 2500.
The printing paste usually comprises 5 to 140, preferably 5 to 60 g, of a polyethylene glycol per 1 kg of printing paste.
Component (C) in the printing paste used in step 2) is, for example, fatty acid polyglycol esters which are optionally end-capped, fatty acid esters of polyvalent alcohols, for example diethylene glycol or glycerol, naturally occurring and optionally par

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