DE1254116B - Process for finishing textile materials - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN 4mWm PATENT OFFICE

EDITORIAL

Int. Cl .:

D 06m

German class: 8 k- 1/20

Number: 1254116

File number: C28744IVc / 8k

Filing date: December 22, 1962

Opened on: November 16, 1967

It is already known that cellulose textiles can be treated with urea-formaldehyde precondensates together with catalysts which split off acids and that the textiles can be subjected to a leaching after the precondensate has condensed out. This is intended to reduce the drop in tear strength caused by the synthetic resin treatment (German patent 969 011). It is also known from French patent specification 996 986 that cellulose textiles can be made wet-crease-resistant by treatment with dihalohydrins or the corresponding epihalohydrins in the presence of strong bases. A dry crease resistance of the cellulose textiles can be achieved by a subsequent treatment with the aminoplast-formaldehyde precondensates known for this purpose.
. A major disadvantage of this latter process is that not only must the halohydrin compounds and the strong base be applied separately, but a further operation is also necessary to achieve dry crease resistance. In addition, the effects with regard to the finishing agents applied in the second working step are not optimal.

From LJSA.-Patent 2,794,754 the common Use of polyepoxides, compounds and compounds containing methylol groups, which have a hardening effect on the epoxy groups, known on textile material, with crease and shrink-resistant fabrics can be obtained. In this case, however, either insufficient crease resistance or a insufficient whiteness of the fabric obtained, as in detail in the experimental part (see example 1) will be shown.

It has now been found that these disadvantages can be avoided and excellent finishing effects, such as, in particular, very good dry and wet crease resistance as well as iron-free effects (measured optically according to the "Monsanto wash and wear standards") while maintaining very good whiteness can achieve on the cellulose textiles, if you first soak them with an aqueous liquor, the

a) a thermosetting and / or aminoplast-formaldehyde precondensate that has a crosslinking effect on cellulose,

b) an acidic or acid-releasing catalyst and

c) a compound which has (m - n) groups of the formula in the molecule

CH ₂ X - CHOH -

Process for finishing textile materials

Applicant:

Chemical factory Pfersee G. m. B. H.,

Augsburg, Färberstr. 4th

Named as inventor:

Heinz Enders,

Günter Pusch, Stadtbergen near Augsburg

and η groups of the formula

CH ₂ - CH -

contains, where m is at least 2 and η is less than 1 and X is a halogen and whose boiling point at normal pressure is higher than 170 ^° C.

The impregnated textile material is freed of excess solution, condensed and dried at temperatures of about 120 ⁰ C and then an aqueous solution of alkali metal hydroxides or carbonates, at temperatures between 100 ° C and room temperature for a few seconds up to 24 hours allowed to act and then the textile material finished in the usual way by rinsing, acidifying and drying.

With this method, it is not only possible to save work steps, but also to be done at the same time also achieved wet and dry wrinkle strengths as well as non-iron effects that are above those that can be achieved by the known, separate treatment method with the same use of chemicals.

As thermosetting and / or cellulose-crosslinking aminoplast-formaldehyde precondensates In the context of the present invention, all formaldehyde precondensates customary for crease-proofing are used of aminoplast-forming compounds, such as urea or its derivatives, such as ethylene, Propylene, dioxyethylene urea (glyoxalmonourein), acetylene diurea, hydroxypropylene urea, as well of triazones, such as N-methyl-, N-ethyl- or N-propyltriazon, melamine or dicyandiamide, etc. into consideration. In the same way, ethers of such formaldehyde precondensates can be mixed with low molecular weight, aliphatic, monohydric alcohols can be used. These precondensates are used in amounts of 1.5

709 688/405

3 4

up to 8.5%. Based on the weight of the treated spin or suction, the excess textile material is used. Fleet removed. This is followed by drying, the duration of the drying as acidic or acid-releasing catalysts depending on the drying temperature of those based on water-soluble salts. The condensation of polyvalent metals with strong inorganic metals is then possible at temperatures above 120 ^° C., especially in the case of acids. May be mentioned as examples the 130 to 16O ⁰ C, while 10 performed to 1 minute, chlorides, nitrates or sulfates of magnesium, zinc, wherein the desirable properties already on aluminum or zirconium. Preferably chlorides will be obtained predominantly. The condensed textile or nitrates of magnesium or zinc are used. The material can now be treated directly with the aqueous solution of the strong base. It can lysators should especially 10 to 50%. based on that but also stored and at a later point in time anhydrous aminoplast-formaldehyde precondensate are subjected to this treatment,
be. The treatment with the aqueous solution of the compounds, the (m - n) can be carried temperature and 100 ⁰ C, at temperatures between room PH λτ rufvu ^J 5 groups of the formula strong base. The time ^ m ₂ A ^ ι-ιυι-ι _{the Benand} i _ung tables 24 hours at room temperature

and η groups of the formula temperature up to a few seconds at 100 ° C. be.

_, _r Alkali hydroxides or are used as strong bases

^ ² ~~, alkali carbonates into consideration. When using

^ O ²⁰ alkali carbonates should treat with the aqueous

Solution preferably via 5O ⁰ C. The cones and whose boiling point at normal pressure concentration of the strong base in the aqueous solution is higher than 17O ⁰ C, should preferably be from 2 to 22 percent by weight, in particular 5 to ethers of glycidic alcohol or glycerol monohalogen- 10 percent by weight,
hydrin with low molecular weight, polyvalent, aliphatic as Will with the aqueous solution of the strong base in table alcohols. If such polyvalent Aiko room temperature is used, the hollow, in particular divalent and trivalent textile material, impregnated with this solution, alcohols with up to 6 carbon atoms, are possible. The squeezes and then in the desired end-to-manufacture of these compounds takes place in a known state, ie in the wrinkle-free state or in one of the ways, e.g. B. by conversion of 1 mole of the desired final state corresponding folded hydric alcohol with at least 2 moles of the ent state, left the allotted time. The time, speaking epihalohydrins, possibly in opposition to those at 20 ⁰ Cz. B. 2 to 24, in particular 8 to 12 hours of suitable catalysts, removal of the amounts can be significantly reduced by increasing the treatment excess epihalohydrin and, if necessary, the temperature. Conversion of less than 1 equivalent of the used 35 z. B. the time at 90 ⁰ C only 10 seconds to 2 minutes, led Glyccrinhalogenhydrinäthergruppen in Glycid- in particular 20 to 40 seconds. Under such ether groups, through the action of strongly basic conditions, it is then possible to treat with substances such as, in particular, alkali hydroxides, al- the aqueous solution of the strong base and the ready-to-use potassium carbonates or alkali aluminates. the textile material is continuously

The connections defined above can lead to one another.

also of acetates of glycerol halohydrins or after treatment with the strong base that will

Glycid alcohol with low aliphatic aldehydes textile material rinsed in the usual way, to the full

derive such as B. the formaldehyde acetal acidified by GIy- removal of the base and finished,

ccrinhalohydrin. In the context of the method according to the invention

Furthermore, these connections can 45 but the textile material at the same time with optical also of at least tetravalent alcohols, for lightening agents, blueing dyes, soft maggots two hydroxyl groups on adjoining agents, finishing agents, etc. were treated Carbon atoms are located, derive. As the. It goes without saying that this is based on the compatible example for such compounds, the added chemicals are 1,4-dichloromethane with the pre-butanediol (2,3) called, with also less than 50 horizontal procedures to be used equipment-1 Equivalent to the «, / S-halohydrin groups in epoxy agents as well as resistance to groups can be converted. high temperatures in the presence of in particular the

The amount of these compounds to be used acidic or acid-releasing catalysts and

bears 5 to 15%> based on the weight of the goods, whereby you should pay attention to the strong bases ..

such compounds are preferably used, 55 which can additionally be used as examples of such compounds

which are water-soluble or through solubilizers, substances are dispersions of as finishing agents

such as lower alcohols or ketones, water-soluble low molecular weight polyethylenes or polyacrylic

can be made. Acid esters, as plasticizers emulsions of high

According to the process according to the invention, fatty acid amides are named,

not only woven and knitted goods, but also fleece 60.

bchandclt. traded textile materials possess excellent

For the treatment of the textile dry and wet crease resistance according to the invention and in particular materials, the three equipment components are good non-iron effects (optically measured according to the dissolved in the required amount of water, whereby the "Monsanto wash and wear standard ^"). Besides

Amount per liter of liquor from the liquor uptake of the 65, however, the textile materials show high chlorine-resistant textile material depends. With this aqueous liquor speed and an excellent soft handle. Even The textile material is now soaked, and through this is the draw and consistency caused by the finishing Measures such as B. padding or tear resistance reduction is lower than with the after

known processes produced textiles. In addition, the whiteness of the textiles remains high Dimensions received.

example 1

With the following in · specified fleets a section each (about 140 g / square meter, poplin 20 yarns per centimeter in weft and 24 yarns per centimeter in the chain) impregnated an optically brightened cotton fabric, squeezed to 65% liquor pick-up, at 120 ⁰ C dried and then condensed ^{at 145 ° C. for minutes.}

Half of the section will be

a) with a wash liquor containing 2 g of soap and per liter

Containing 2 g of sodium carbonate, washed 10 minutes at 40 ⁰ C or

b) soaked with 8% sodium hydroxide solution, squeezed off to 90% liquor uptake, ^{left to dwell for 12 hours at 20 °} C. and then washed out ao, neutralized and dried.

Test series I

1. 68 g of glycol bis (glycerol chlorohydrin ether), produced by reacting 1 mole of glycol as and 2 moles of epichlorohydrin,
64 g of a 50% strength aqueous mixture of 70% dimethylolethylene urea and 30% hexamethylolmelamine tetramethyl ether, hereinafter referred to as "resin mixture", 8 g MgCl ₂ · 6H ₂ O,
240 g of ethyl alcohol.

2. 68 g of polyepoxy compound "Polyether A" according to US Pat. No. 2,794,754,
64 g »resin mixture« as at t, 1,
8 g MgCl ₈ -6H ₂ O,
25 g [sopropanol.

3. 68 g »Polyether A« as in I, 2, "

• 64 g »resin mixture« as in I, 1,
8 g zinc fluoroborate.

Test series II

1. 150 g glycol bis (glycerol chlorohydrin ether) such as

at I, 1,
140 g »resin mixture« "as in I, 1,

18 g MgCl ₂ 6H ₂ O,
240 g of ethanol.

2. 150 g »polyether A« as in I, 2,
140 g "resin mixture" as in I, 1,

18 g MgCl ₂ 6H ₂ O, '
50 g of isopropanol.

3. 150 g »polyether A« as in I, 2,
140 g "resin mixture" as in I, 1,

18 g zinc fluoroborate,
50 g of isopropanol.

All gram data are per liter of liquor.

attempt To
treatment Crease
Avg
Chain un
dry angle,
initt off
d shot
wet Monsanto
grade Whiteness I. 1 According to the invention j a
b 110
107 116
122 cn cn . 90
90 2 comparison test < a
b 77
71 85
95 Ibis 2
Ibis 2 90
90 3 According to U.S. Patent 2,794,754 j a
b 109
103 118
117 UJ UJ 40
40 II. 1 According to the invention j a
b 126
125 138
142 4 to 5
4 to 5 85
90 2 comparison test \ a
b 77
67 VO VO
OO O to to 90
90 3 According to U.S. Patent 2,794,754 j a
b 123
118 132
134 4th
4th 30th
30th

The individual values were determined as follows:

Dry wrinkle angle according to DIN 53890

Wet crease angle according to GÜTV

Optical "wash and wear" image according to Monsanto standard

Optical whiteness according to the following scale:

Raw unbleached fabric .... Grade 0

Fabric bleached grade 50

Fabric bleached and

optically brightened grade 100

A repetition of these experiments using dimethylolurea in place of the "Resin mixture" gave practically the same results as in the table above are listed.

Example 2

A colorfully printed cotton kretonne (34 threads per centimeter in the weft and 32 threads per centimeter in the warp) is impregnated with a liquor containing 150 g of an approximately 50% aqueous solution of dimethylolethyltriazone, 12 g of Zn (NO ₃ ) _{2 per liter} · 6H ₂ O and 100 g of the product described below as well as 30 g of a 20% polyethylene emulsion and 10 g of a plasticizer based on octadecylurea. After soaking, the fabric is placed on a

Pick-up of 65%> based on the Warengcwicht, squeezed out, dried and then condensed for 2 minutes at 16O ⁰ C at 100 ⁰ C. After cooling, the fabric with an aqueous 6 ° / "aqueous KOH at 2O ⁰ C is saturated, squeezed off to a liquor pickup of about 80 ° / o. rolled up after squeezing and left rolled up for 12 hours at room temperature. To avoid migration, the roller is rotated frequently during the 12 hour dwell time. After the 12 hours have elapsed, the fabric is rinsed, acidified and dried. The cotton fabric treated in this way shows, with a loss of tensile strength of 28%, based on the starting fabric, a dry crease angle of 117 ° and a wet crease angle of 42 ° (in each case mean value from warp and weft). The usual test for chlorine retention shows that the fabric retains practically no chlorine and thus fiber damage from the bleaching and subsequent ironing does not occur.

The product used in this example with chlorohydrin or Epo.xygruppen is prepared by reacting 1 mole of glycerol with 4 moles of epichlorohydrin in the presence of 0.02 mol SnCI ₁ 6 hours was heated at reflux, the excess epichlorohydrin (about 1.8 Mol) distilled off in vacuo and the residue at about 90 ⁰ C in portions with thorough stirring with about 0.9 mol of NaOH. (in the form of flakes) and, after the reaction has subsided and cooling, the inorganic constituents are filtered off. The product has about 1.3 glycerol chlorohydrin ether and about 0.8 glycidic ether groupings per glycerol residue.

Example 3

For treating an aqueous liquor is used which contains a 60 ° / ₀ aqueous solution of Dimelhylolpropylcnharnstofi ", 14 g of anhydrous zinc chloride and 80 gl, 4-dichloro-butanediol- (2,3) to g per liter 100th is with this liquor a cotton-polyester gabardine (weighing 98 g, 26 yarns per centimeter in weft and 54 yarns per centimeter in the chain) impregnated, o squeezed off to a liquor pickup of 75 ° /, at 12O ⁰ C dried and thereafter for 6 minutes at 135 ° C condensed. The fabric is then impregnated with an aqueous 10 _^0/0 NaOH at 20 to 30 ⁰ C, o squeezed off to a liquor pickup of about 55 ° /, pleated and in this pleated shape are left for 16 hours at room temperature. After this In storage, the fabric is washed out and dried.

A fabric treated in this way does not need to be ironed or pleated again after washing, because the folds are fixed in a washable manner.

Example 4

55

A bleached, mercerized cotton poplin (weighing 128 g, 26 yarns per centimeter in weft and 46 yarns per centimeter in the chain) is impregnated with a liquor which is obtained by dissolving 130 g of an aqueous 50 ° / ₀ solution of dimethylol -dioxyethylene urea and g MgC) ₂ · 6 H ₂ O in about 300 ecm of water. A mixture of 170 g glycol bis (glycerol chlorohydrin ether) with 220 g ethyl alcohol is added to this solution with stirring and made up to 11 with water.

The poplin padded with it and squeezed off to 70% liquor pick-up is ^{dried for 5 minutes at HO 0} C with strong ventilation and then condensed at 135 ° C. for 5 minutes. It is then treated continuously in a conventional wide washing machine with a 6% sodium hydroxide solution at a temperature of 85 ° C. and a dwell time of 30 seconds, rinsed in the subsequent boxes, acidified and, if necessary, washed. Finally, wet-on-wet, a liquor containing 40 g of a 25% emulsion of polyacrylic acid ester per liter is followed by aftertreatment and drying.

Example 5

A lining made of viscose rayon is impregnated with a liquor containing 70 g of dimethylolurea and 30 g of hexamethylolmelamine, 14 g of zinc nitrate · 6H ₂ O and 140 g of butanediol- (1,4) -bis- (glycerol chlorohydrin ether) [per liter by reaction of 1 mole of butanediol (1,4) and 2 moles of epichlorohydrin] and 200 g of methyl alcohol. After soaking the fabric for a wet pickup of 85 ° / o ^aD "is crimped at 100 ⁰ C dried and then condensed for 3 minutes at 15O ⁰ C. The lining material is then g with a solution of 40 g / l KOK and 40 / l K ₂ CO ₃ padded at room temperature, squeezed off to a liquor pick-up of about 95%, rolled up after squeezing and left in this state for 12 hours at room temperature. Finally, the fabric is rinsed, acidified and dried Shrinkage with a surprisingly low loss of abrasion resistance.

Claims (2)

Patent claims: 1. Process for the finishing of textile materials, the natural and / or regenerated cellulose fibers by treatment with synthetic resins, curing catalysts and epoxy compounds as well as post-leaching, characterized that the textile materials are first impregnated with an aqueous solution that a) a thermosetting and / or aminoplast-formaldehyde precondensate that has a crosslinking effect on cellulose, b) an acidic or acid-releasing catalyst and c) a compound which has (m - n) groups of the formula in the molecule CH ₂ X - CHOH -
• and η groups of the formula
CH ₈ -CH- contains, where m is at least 2 and η is less than 1 and X is a halogen and whose boiling point at normal pressure is higher than 17O ⁰ C, the impregnated textile material freed from the excess solution, dried and ^{condensed at temperatures of over 12O 0} C, then an aqueous solution of alkali metal hydroxides or carbonates, at temperatures between 100 ⁰ C and room temperature for a few seconds to 24 hours and then in more common 9 ίο Way by rinsing, acidifying and drying low, aliphatic, polyhydric alcohols completes. derive and - if necessary with co-use- 2. The method according to claim 1, characterized by solubilizers - are water-soluble. indicates that the compounds under c) are those which differ from ethers of glycidic 5 Publications considered: alcohol and / or glycerol halohydrin with U.S. Patent No. 2,794,754. 709 688/405 11.67 © Bundesdruckerei Berlin