EP1141471A1

EP1141471A1 - Method for producing textile materials which contain cellulose

Info

Publication number: EP1141471A1
Application number: EP99967949A
Authority: EP
Inventors: Manfred Blauth; Friedrich Reinert; Jürgen Reichert; Klaus Bergmann
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1998-12-24
Filing date: 1999-12-16
Publication date: 2001-10-10
Anticipated expiration: 2019-12-16
Also published as: BR9916534A; WO2000039384A1; DE59913133D1; EP1141471B1; CN1331767A; ATE317924T1; CN1177094C; KR100598664B1; KR20010099872A; DE19860204A1; JP2002533585A

Abstract

The invention relates to a method for producing non-iron textile materials which contain cellulose by finishing them with an N-methylolether cross-linking agent in the presence of a magnesium chloride cross-linking catalyst. The textile materials to be finished are (a) impregnated with a finishing bath which contains the cross-linking agent in large quantities, are (b) dried to a residual moisture ranging from 3 to 10 wt.%, and are (c) condensed at a temperature ranging from 80 to 145 DEG C.

Description

Process for the production of cellulosic textile materials

description

The present invention relates to an improved process for the production of cellulose-containing textile materials by finishing with a crosslinking agent based on N-methylol ethers in the presence of a crosslinking catalyst based on magnesium chloride. In particular, non-iron textile materials can be obtained by the method according to the invention.

An important part of the textile finishing of cellulose-containing textiles is the so-called high finishing. Web-like or knitted fabrics are treated with crosslinkers. The crosslinkers are, for example, and the 1,3-bis (hydroxymethyl) -4,5-dihydroxyimidazolidinone-2, also referred to as 1,3-dimethyl-4,5-dihydroxyethylene urea ("DMDHEU"), and its derivatives with alcohols. Essential part of a

High-quality recipe is a catalyst. Magnesium chloride or mixtures of magnesium chloride with Lewis or Bronsted acids are used in many cases. Other catalysts such as zinc nitrate, zinc chloride or ammonium chloride are also common. In addition to crosslinking agents and catalysts, other aids, such as e.g. Plasticizers for use.

The most important standard method is the dry cross-linking method. The textile material is impregnated with the finishing liquor, which contains the crosslinker (typical amount for pure cotton fabric: 40 - 45 g / 1) and the crosslinking catalyst (typical amount: 12 g / 1) and squeezed off, for example, with a foulard. It is then dried at higher temperatures and crosslinked (“condensed”) either in the same step or separately in a condensation apparatus. This is usually done at condensation temperatures of 150 to 190 ° C. The condensation time is usually 15 seconds to 4 minutes; the higher the condensation temperature chosen, the shorter the condensation time. The condensation conditions must be chosen so that the reaction proceeds as completely as possible, so it must not be "over-condensed" or "under-condensed", otherwise there will be unacceptable losses in strength or insufficient easy-care effects with very high formaldehyde values. In addition to the dry crosslinking process, the wet crosslinking process has recently gained in importance, since so far only textiles, in particular cotton, with the highest finishing quality, i.e. with very high smoothness after washing and very good crease recovery with acceptable tear resistance losses, can be produced. A mineral acid (usually hydrochloric acid or sulfuric acid) serves as a catalyst in the wet crosslinking process, which may also contain salts. The textile is impregnated with this strongly acidic liquor, which can contain up to 150 g / l and more of crosslinking agent, and dried to a residual moisture content of 10 to 12% by weight. The mixture is then left at 30 to 35 ° C. for 20 to 24 h, the acid is neutralized and washed out. After drying, the usual tools for handle design are usually applied.

The wet curing process has the following disadvantages:

the strongly acidic liquors with pH 1 or below can cause enormous losses in tear strength in the finished textiles;

high levels of free formaldehyde form on the goods;

an extremely complex humidity and temperature control control is necessary;

an additional washing process to neutralize the mineral acid is necessary;

- Additional drying steps require high energy costs;

because of the intensive washing processes, large amounts of waste water are generated;

- The process is limited to goods with sufficient initial strength.

It was an object of the present invention to provide an finishing process for cellulosic textile materials which, like the moist crosslinking process, delivers the best finishing, but avoids the disadvantages thereof.

Accordingly, a process for the production of cellulose-containing textile materials by finishing with a crosslinker based on N-methylol ethers of the general formula I R ² 0

Rl 0 CH ₂ N— CR ³ (I) in the

R ^{1 represents} a C ₁ -C 8 alkyl group which may be interrupted by non-adjacent oxygen atoms and which may also carry one or more hydroxyl groups,

R ² denotes hydrogen, the group C ^ OR ¹ or a -CC ₈ -alkyl radical, which additionally carry hydroxyl groups and / or Cχ-C -alkoxy groups as substituents and is carried by non-adjacent oxygen atoms and / or Cχ-C -alkyl groups nitrogen atoms can be interrupted, and

R ^{3 is} hydrogen, a Cχ-Cιo-alkyl radical, a Cι-Cιo alkoxy radical, which can be interrupted by non-adjacent oxygen atoms, or the group (-NR ² -C ^ OR ¹ ) means

where the radicals R ² and R ^{3 are connected} to form a five- or six-membered ring and, in the case of R ³ = (-NR ² -CH ₂ OR ¹ ), two such rings are also connected via the C atoms of the radicals α to the amide nitrogen atoms R ² can be condensed into a bicyclic system,

found in the presence of a crosslinking catalyst based on magnesium chloride, which is characterized in that the textile materials to be finished

(a) with 50 to 100 wt .-%, based on the dry textile materials, a finishing liquor with 70 to 250 g / 1 of the crosslinker in the case of fabrics made of 100% cellulosic material, with 35 to 100 g / 1 of the crosslinker in In the case of knitwear made of 100% cellulosic material or impregnated with 35 to 150 g / l of the crosslinking agent in the case of mixtures of 30 to less than 100% by weight of cellulosic fibers and greater than 0 to 70% by weight of synthetic fibers,

(b) drying to a residual moisture content of 3 to 10% by weight, preferably 5 to 9% by weight, and

(c) at a temperature of 80 to 145 ° C, preferably 100 to 140 ° C, in particular 120 to 135 ° C, in the presence of the crosslinking catalyst, the crosslinking of the cellulose-containing textile materials is carried out. The drying (b) and condensation (c) steps can be carried out separately or together, ie in one reaction apparatus by heating and simultaneously removing the water vapor.

The principle of the process according to the invention can be applied both to woven fabrics and to knitted fabrics, the latter using the amounts of crosslinking agent and crosslinking catalyst to be reduced. In addition to pure cotton, the method according to the invention can also be transferred to other cellulose-containing materials. When mixed with synthetic fibers such as polyester, it is of interest due to the fiber protection and energy saving. Here too, the amount of crosslinking agent and catalyst can be reduced because of the lower proportion of cellulosic fibers.

Preferred amounts of crosslinking agent are 90 to 175 g / 1, in particular 110 to 160 g / 1 in the case of fabrics made of 100% cellulosic material, 40 to 70 g / 1, in particular 45 to 45 in the case of knitted fabrics made of 100% cellulosic material 60 g / 1, and in the case of mixtures of 30 to less than 100% by weight of cellulosic fibers and greater than 0 to 70% by weight of synthetic fibers, 45 to 120 g / 1, in particular 55 to 100 g / 1. The last-mentioned amounts of crosslinking agent are particularly suitable for polyester-cotton blends in weight percent of approximately 50:50. For all of the information above and below, the amounts of crosslinker always relate to the corresponding solids content in g per liter of equipment liquor. The crosslinkers are usually used as aqueous solutions with a solids content of 30 to 80% by weight, in particular 50 to 75% by weight.

The N-methylol ethers I to be used as crosslinkers are, by conventional reaction, usually in aqueous solution, the corresponding N-methylol compounds of the general formula II

R ² 0

H 0 CH ₂ N — CR ^{3 (} II ⁾ with alcohols of the general formula III

Rl OH ⁽ HD

easily available. The group R ¹ is ₀ alkyl group such as -CH ₂ CH ₂ OCH _3, -CH ₂ CH ₂ OCH ₂ CH ₃ or -CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ stands for an optionally interrupted by nonadjacent oxygen atoms Cι-Cι. Examples of R ¹ include: n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, 2-ethylhexyl and 2-methoxyethyl; of particular interest are the Cχ-C ₃ alkyl groups ethyl, n-propyl, iso-propyl and especially methyl. Also of interest are those alkyl groups and alkyl groups which are interrupted by oxygen atoms and which carry one, two, three or even more hydroxyl groups.

The radical R ² denotes hydrogen, the group CH ₂ OR ¹ and in particular a -CC ₈ -alkyl radical, which also carry additional hydroxyl groups and / or -CC alkoxy groups as substituents and by non-adjacent oxygen atoms and / or by Cχ-C - Nitrogen atoms carrying alkyl groups can be interrupted.

The radical R ³ is hydrogen, a Cχ-Cχ ₀ alkyl radical, one

Cι-Cιo-alkoxy radical, which can be interrupted by non-adjacent oxygen atoms, and in particular the group (-NR ² -CH ₂ OR ¹ ).

Those N-methylol ethers I in which the radicals R ² and R ³ are linked to form a five- or six-membered ring are particularly suitable for the process according to the invention. In the case of R ³ = (-NR ² -CHOR ¹ ), two such rings can also be condensed to form a bicyclic system via the C atoms of the radicals R ² which are α-amide nitrogen.

Examples of N-methylol ether I which can be used in the process according to the invention are:

Amides of Cχ-Cχ carboxylic acids, for example formic acid, acetic acid, propionic acid, butyric acid or valeric acid, which carry one or two CH ₂ OR ¹ groups on nitrogen,

Carbamates with Cχ-C ₁₀ alkyl groups in the ester radical, which can be interrupted by non-adjacent oxygen atoms, for example methyl, ethyl, n-propyl, iso-propyl, 2-methoxyethyl or n-butyl, which have two CH ₂ OR on nitrogen Carry ¹ groups,

Urea with 1 to 4 CH ₂ -OR ¹ groups on the nitrogen atoms,

cyclic ethylene ureas of the general formula Ia R ¹ - 0 CH ₂ - N ^ C ^ N CH ₂ - ^■ 0 - Rl (Ia)

X X

in which the radicals X are different or preferably the same and represent hydrogen, hydroxyl groups or Cχ-C alkoxy groups, for example methoxy or ethoxy,

cyclic propyleneureas of the general formula Ib

R ¹ - 0 CH ₂ N ^ C - N CH ₂ - 0 - R ^l (Ib)

in which Y represents CH ₂ , CHOH, C (CH ₃ ) ₂ , an O atom or an N atom bearing a Cχ-C alkyl group and Z denotes hydrogen or a Cχ-C alkoxy group, for example methoxy or ethoxy ,

bicyclic glyoxal diureas of the general formula Ic

R ¹ -0 CH ₂ N -'C ^ CH - -0- R ¹

(Ic)

R ¹ -0 CH ₂ N-ON CH ₂ -0 R ¹

II 0

bicyclic malondialdehyde diureas of the general formula Id

0

_R l - _{0 CH2} - _{N ^} - c ^ N CH ₂ - 0 R ¹

[Id)

_R l - _{0 CH2} - _N -. C _^ CH ₂ - 0 R ¹

II

0 Derivatives of 1,3-dimethylol-4,5-dihydroxyethylene-urea ("DMDHEU") in which both nitrogen atoms of the imidazolidinone ring are symmetrically or in particular asymmetrically s b-5 are particularly suitable as crosslinkers for the process according to the invention (etherified) are. Preferably, one of the two methylol groups of the DMDHEU is etherified with a methyl radical, while the other methylol group, by reaction with a polyol, selected from the group comprising ethylene glycol, diethylene glycol, 1,2- and 1,3-propylene glycol, 1,2 -, 1,3- and 1,4-butylene-10 glycol, glycerol and polyethylene glycols of the formula HO (CH ₂ CH ₂ 0) _n H with 3 <n <20, preferably diethylene glycol, is derivatized. Such asymmetrically substituted DMDHEU are described in WO-A 98/29393.

15 The crosslinking catalyst is based on magnesium chloride as the sole component or as the main component. In a preferred embodiment, a finishing liquor is used which contains 10 to 40 g / 1, in particular 20 to 30 g / 1, of the crosslinking catalyst in the case of fabrics made of 100% cellulosic material, 5 to

20 15 g / 1, in particular 8 to 13 g / 1, of the crosslinking catalyst in the case of knitwear made of 100% cellulosic material or 5 to 30 g, in particular 8 to 25 g / 1, of the crosslinking catalyst in the case of mixtures of 30 to less than 100 % By weight of cellulosic fibers and greater than 0 to 70% by weight of synthetic fibers.

25 The above quantities in g relate to magnesium chloride hexahydrate with regard to the proportions of magnesium chloride, and with other catalyst components to the solids content of commercially available form.

Practically pure magnesium chloride or mixtures of magnesium chloride and organic and / or inorganic acids such as citric acid, glycolic acid or acid-reacting inorganic salts, e.g. Sodium tetrafluoroborate, a. When using such acidic

35 gene ("accelerating") catalysts, the condensation conditions can be made milder.

In the process according to the invention, it has turned out to be particularly favorable if the finishing liquor containing the crosslinking agent and the crosslinking catalyst has a pH of 3 to 6.5, in particular 4 to 5.5, at (a).

In the process according to the invention, further additives and auxiliaries customary in textile finishing can be used, for example amino-functional polysiloxane emulsions, dispersions of anoxidized polyethylene and nonionic wetting agents. In particular, the latter aids can, if necessary, significantly increase the quality of the equipment.

The process according to the invention enables rapid and complete condensation of the crosslinking agent on the textile material at relatively low and therefore gentle temperatures. Normally, much longer condensation times are expected at the temperatures of step (c) of the process according to the invention. The condensation according to step (c) - depending on the respectively set temperature - usually takes place completely after 15 seconds to 4 minutes, in particular after 30 seconds to 3 minutes.

The cellulose-containing textile material highly refined by the process according to the invention has very high smoothness notes and very good crease recovery with unexpectedly low tear strength losses and low formaldehyde values. Such results have so far only been obtained with the wet crosslinking process, but the formaldehyde values there are very high despite washing. In the dry crosslinking process, such a high amount of crosslinker as is used in the process according to the invention and in the wet crosslinking process usually leads to the destruction of the goods because of the occurring enormous loss of tensile strength.

The process according to the invention, which ensures excellent ease of care and almost complete freedom from ironing, particularly in the case of pure cotton, is referred to as "Advanced Performance Finish" by BASF Aktiengesellschaft.

The following examples in table form are intended to explain the invention in more detail, but without restricting it. Unless otherwise stated, the percentages are percentages by weight.

Examples 1 to 5 - Upgrading Cotton Poplin Fabric

Table 1

Product Type: Cotton Poplin Fabric

After-wash 1: 3 g / 1 soda and 1 g / 1 non-ionic detergent; Wash for 5 min at 40 ° C, rinse 3 times, dry. Rinse 2: 1 g / 1 non-ionic detergent: wash for 1 min at 40 ° C, dry

1) usual dry crosslinking process

2) usual wet curing process

3) used as a 70% aqueous solution, but the amount of g relates to the solids content

4) The concentrations used in g / 1 refer to the hexahydrate

Examples 6 and 7 - high finishing of cotton knitwear

Table 2

Type of goods: knitted cotton

1) usual dry crosslinking process

4) The concentrations used in g / 1 refer to the hexahydrate

Claims

claims

1. Process for the production of cellulose-containing textile materials by finishing with a crosslinker based on N-methylol ethers of the general formula I

R ² 0

R ¹ 0 CH ₂ N-CR ^{3 (} I ⁾ in the

R ^{1 represents} a Cχ-Cχo alkyl group which may be interrupted by non-adjacent oxygen atoms and which may also carry one or more hydroxyl groups,

R ² denotes hydrogen, the group CH ₂ OR ¹ or a Cχ-C ₈ -alkyl radical, which additionally carry hydroxyl groups and / or Cχ-C-alkoxy groups as substituents and carries non-adjacent oxygen atoms and / or Cχ-C ₄ -alkyl groups Nitrogen atoms can be interrupted, and

R ³ is hydrogen, a _Cχ-C10 alkyl group, a Cι-Cι rest ₀ alkoxy, which can be interrupted by nonadjacent oxygen atoms, or the group (-NR ² -CH ₂ OR!) Means

where the radicals R ² and R ^{3 are connected} to form a five- or six-membered ring and, in the case of R ³ = (-NR ² -CH ₂ OR ¹ ), two such rings are also connected via the C atoms of the radicals R which are attached to the amide nitrogen ² can be condensed into a bicyclic system,

in the presence of a crosslinking catalyst based on magnesium chloride, characterized in that the textile materials to be finished

(a) with 50 to 100 wt .-%, based on the dry textile materials, a finishing liquor with 70 to 250 g / 1 of the crosslinker in the case of fabrics made of 100% cellulosic material, with 35 to 100 g / 1 of the crosslinker in In the case of knitwear made of 100% cellulosic material or with 35 to 150 g / l of the crosslinking agent in the case of mixtures of 30 to less than 100% by weight of cellulosic fiber sern and greater than 0 to 70% by weight of synthetic fibers impregnated,

(b) dries to a residual moisture content of 3 to 10% by weight and

(c) at a temperature of 80 to 145 ° C in the presence of the crosslinking catalyst, the crosslinking of the cellulose-containing textile materials is carried out.

2. A process for the production of cellulose-containing textile materials according to claim 1, characterized in that an equipment liquor is used in (a) which comprises 10 to 40 g / 1 of the crosslinking catalyst in the case of fabrics made of 100% cellulosic material, 5 to 15 g / 1 of the crosslinking catalyst in the case of knitwear made of 100% cellulosic material or 5 to 30 g / 1 of the crosslinking catalyst in the case of mixtures of 30 to less than 100% by weight of cellulosic fibers and greater than 0 to 70% by weight of synthetic fibers.

3. Process for the production of cellulose-containing textile materials according to claim 1 or 2, characterized in that practically pure magnesium chloride or mixtures of magnesium chloride and organic and / or inorganic acids are used as the crosslinking catalyst.

4. A process for the production of cellulose-containing textile materials according to claims 1 to 3, characterized in that the finishing liquor containing the crosslinking agent and the crosslinking catalyst has a pH of 3 to 6.5 at (a).

5. A process for the production of cellulosic textile materials according to claims 1 to 4, characterized in that a crosslinking agent based on 1, 3-dimethylol-4, 5-dihydroxyethylene urea etherified symmetrically or asymmetrically on the two methylol groups is used.