JPS6018355B2 - How to treat synthetic fiber yarn - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for treating synthetic fiber yarns comprising applying to the fibers a sizing agent consisting of a 5-4% strength by weight aqueous solution of a water-soluble polyurethane.

The current trend in the textile industry is to weave yarns of "synthetic" fibers that have only a twist imparted by the frame spinning the continuous filaments, i.e. 10-19 twists/skin.

However, low tension yarns do not have sufficient binding properties and therefore it is not possible to weave such yarns with great strength, so a very high I is required for a good weaving operation.
It is necessary to use performance paste. Of course, these glues need to be removed with water before dyeing. Various products have been proposed for gluing synthetic fiber yarns, such as those based on acrylic or vinyl polymers, but these products are not suitable for application to green polyesters such as polyethylene terephthalates. unsuitable or highly unsuitable, and the performance of these products remains limited).

Other products that have been proposed include water column sulfonated aliphatic polyester or aromatic polyester types. Examples include polyesters obtained from isophthalic acid, sodium dimethylisophthalate-sulfonate and diethylene glycol, or polyesters obtained from isophthalic acid, sodium dimethylisophthalate-sulfonate, adipic acid and diethylene glycol, or isophthalic acid. , polyesters obtained from unsaturated acids (maleic and itaconic acids), diethylene glycol and isomeric sodium bisulfite. Commercial products of this type are not always completely satisfactory.

When using them, various types of difficulties are usually encountered, either from an application point of view or from a production technology point of view. Thus, the mechanical properties of the polymers are insufficient if the shelf life of their aqueous solutions is relatively short and the number average molecular weight of the polymers does not reach very high values. However, significant technical difficulties are encountered when attempting to obtain polymers with high number average molecular weights. That is, it is necessary to carry out the condensation under high reduced pressure for a considerable period of time. Another difficulty encountered especially in the case of acrylic polymers lies in the fact that these products contaminate the loom to some extent. The inventor has found and devised a means to avoid the above-mentioned drawbacks.

The present invention has a molecular weight between 500 and 3000, an acid value of 209 KOH/ta or less, and a sulfur content of 0.
A sulfonated anionic polyester containing 8 to 2% by weight and at least one diisocyanate are combined in a molar ratio of NCO/OH+COO of less than 1 to 130% by weight.
It has as its main ingredient a novel water-soluble polyurethane obtained by reaction at temperatures between 0 and 230°C.

More precisely, this polyurethane is prepared in particular in a first step by combining a dibasic acid or one of the gesters with a diol, a dibasic acid having a sulfonic acid group as anionic component, or its ester, an anionic dibasic acid and a non-anionic dibasic acid. in the presence of - such that a sulfur amount of between 0.8% and 2% by weight is introduced relative to the anionic dibasic acid;
It is then obtained by condensation in the presence of a common polyesterification catalyst.

More specifically, this operation is performed when the polyester is 20 female K.
OH/ta or less, more preferably 5 female KOH/ta or less and an acid value of 0. between % and 2% by weight, preferably 1.2% by weight
and 1.8% by weight. The value of the molar ratio NCO/OH+COO is selected according to the desired final molecular weight of the polyurethane.

The value of this ratio is defined by the weight percentage of the diisocyanate introduced. The reaction between the diisocyanate and the polyester is carried out in a solid medium or in a molten medium. Preferably, this reaction is carried out in a molten medium. The polyurethane according to the invention, whether in particular powder, granule or flake form, is spontaneously soluble in any concentration even in cold water, forming a clear solution.

Still another object of the present invention is that the polyurethane content is 40% by weight.
The water-soluble polyurethane is in an aqueous solution, which can be highly concentrated.

The invention further relates to the application of aqueous solutions of polyurethane for gluing weaving warp threads.

The invention also relates to the application of an aqueous solution of the polyurethane for joining flesh and grain splits in leather.

The following may be mentioned as starting materials for carrying out the method of the invention, but this is by way of illustration and is not meant to be limiting.

'1' acids succinic acid, adipic acid, suberic acid and sebacic acid, maleic acid, fumaric acid and itaconic acid, and orthophthalic acid, isophthalic acid and terephthalic acid, dibasic acids with several aromatic nuclei, al-alif Saturated or unsaturated aliphatic dibasic acids and aromatic dibasic acids, such as attic dibasic acids, anhydrides of these acids, and gestates of those acids, such as methyl, ethyl, propyl and butyl gestates. .

'2, Diol ethylene glycol, diethylene glycol and higher homologs, dipropylene glycol and higher homologues, 1.4
- Aliphatic glycols such as butanediol, 1,6-hexanediol, neobentyl glycol, and cyclohexanediol and dicyclohexanediol -
Cycloaliphatic glycols like propane.

Components containing '3' anionic groups Dialkyl sulfoisophthalate and sodium dibasic acid sulfonate such as dialkyl sulfoisophthalate and dialkyl sulfosuccinate, such as sodium dimethyl isophthalate-5-sulfonate or sodium dimethyl succinate sulfonate. or their esters.

■Diisocyanate hexamethylene diisocyanate, tetramethyl hexamethylene diisocyanate, isophorone diisocyanate, m- and p-phenylene diisocyanate, toluene-2.4- and -2,6-diisocyanate (same as toluylene-2,4- and -2,6-diisocyanate), dicyclohexylmethane-diisocyanate, 4,4'-diphenylmethane-diisocyanate and naphthalene-diisocyanate aliphatic, like nat;
Cycloaliphatic, unsaturated cycloaliphatic, aryl or alkylaryl diisocyanates.

The selection between these various components is made according to the chemical nature of the surface to be treated with the polymer and according to the desired properties of the polymer itself.

Examples for carrying out the invention are provided below, but these examples are intended to be illustrative and not limiting.

In the examples, parts, percentages and ratios are to be understood as being by weight unless otherwise specified. Example
1 A Production of anionic polyester First, a polyester is produced by condensing adipic acid, sodium dimethylisophthalate-5-sulfonate, and diethylene glycol at a molar ratio of 0.8/0.146/1.18. .

To carry out this condensation reaction, 1247 parts of adipic acid, 432 parts of sodium dimethylisophthalate-5-sulfonate,
1200 parts of diethylene glycol and 0.4 parts of the catalyst, namely tetraisopropyl orthotitanate, are placed in a reaction vessel equipped with a stirring device, a thermometer and a distillation device. This cocondensation is carried out in the same manner as ordinary polyesterification.

The final conditions are a temperature of 220 qo and a pressure of 40 side Hg.
A polyester is obtained which exhibits the following properties: Acid value (la)
oKOH' Tahidroxyl Number (10H) of 0.8 60.5M9KOH/TaiSou Content 1.88% Number Average Molecular Weight 1835B Preparation of Polyurethane To prepare a water-soluble polyurethane in accordance with the present invention, the operations subsequently taken are as follows: It is.

92 parts of toluene diisocyanate are slowly added over a period of 2 hours to 100 ml of polyester prepared according to the method detailed in Section A and heated to a temperature of 200 qo.

This base corresponds to a proportion of 9.2% by weight. The temperature is 200
Hold at pm C. The mixture becomes very sticky. The reaction is continued for 1/hour after the addition of toluene diisoanate is complete. After cooling to ambient temperature, the product is in the form of a highly elastic solid. This product dissolves very easily in cold water and gives clear solutions of low viscosity for polymer concentrations up to 40%. The polymer obtained in this B-stage has the following characteristic values.

Number average molecular weight (Mh): 85000
Toluene diisocyanate introduced into the reaction: 9.2
% Glass transition temperature (Tg): 800
This information regarding the 0 properties is reproduced in summary table form along with information regarding the products of the examples shown below.

Example 2 The following is prepared under virtually the same conditions as Example 1.

A Anionic polyester component Molar part 100% 0.46 671-
6 dimethyl isophthalate ○14 414.4-
5-Sodium sulfonate adipic acid 0.
4 584 diethylene glycol 1.12
1187.2 This polyester has an acid number la2 and an OH number 10 days of 44.6.

B Anionic polyester from polyurethane A 100 parts Toluene diisocyanate 71.5 parts Mn12
000 and a Tg of 5° C. is obtained.

Examples 3-5 Polyurethanes were prepared according to the method described in Example 1 by varying the relative proportions of isophthalic acid and adipic acid in the polyester and by varying the proportion of toluene diisocyanate used in the polyurethane forming reaction. Manufacture.

The properties of these polymers are summarized in a summary table for comparison.

Example 6 / This example describes the preparation of polyurethane with sodium dimethylsuccinatesulfonate as the anionic component.

A. Preparation of anionic polyester A polyester with a molar ratio of 0.854/0.146/1.13 is prepared.

1411 parts of isophthalic acid, 372 parts of sodium dimethyl succinate sulfonate, 12 parts of diethylene glycol
1 part and 0.4 parts of catalyst are placed in the container shown in Example 1.

Cocondensation is carried out in a conventional manner. Finally, the temperature is 190 qo and the pressure is 15 Hg. This polyester has an acid value of 16 and a hydroxyl value of I. 6. B. Production of soluble polyurethane Toluene-diisocyanate 11 base was added to polyester 100 base produced in A above, and heated to 19 °C in a container.
Heating to 0°C was then continued as described in Example 1 B.

The resulting polyurethane polymer has a glass transition point of 400 and a Mhl of 1400.

Table abbreviations: IA: Isophthalic acid DMSIP: Sodium dimethyl isophthalate sulfonate DMSS: Sodium dimethyl succinate sulfonate AA: DEG adipic acid: Diethylene glycol Mn: Number average molecular weight Example 7 Practically the same conditions as Example 1 The following items are manufactured below.

The final conditions for A anionic polyester condensation are a temperature of 220°C and a pressure of 20 Hg.
It is.

Acid value (la) 0.5 9KOH/
Hydroxyl value (10H) 29.9 imitation KOH/
Anionic polyester from polyurethane A
100 parts toluene diisocyanate (80/20 mixture of 2-4 and 2-6 isomers) 39.
The 6-part polyurethane - the polymer obtained in this B stage - dissolves very easily in water, even cold water.

This polyurethane has the following characteristic values. Glass transition temperature (Tg): 170 number average molecular weight (
Mm): 19650 Example 8 A water-bathable polyurethane polymer is prepared by reacting 100 parts of the polyester described in Example 7(A-) with 38.8 parts of diphenylmethane diisocyanate.

This polyurethane has the following characteristic values. Glass transition temperature (Tg): 14℃ number average molecular weight (
Mn): 17800 Some application examples are shown below.

Example 9 A 5% strength by weight solution of the polyurethane of Example 4 is prepared.

Polyester yarn is glued with this solution using an industrial drum gluer.

This yarn is made into a yarn of 2Z 76 decitex strands with 180 twists. After gluing, which was carried out without the use of aliphatic auxiliaries, a yarn with a coverage of 3% by weight was obtained. The glued yarn is machined on a regular loom with a thread count of 210/min and a width of 1.60 with an arc of 35 wefts/arc.
Used for weaving into skin taffeta tissue.

The web of yarn behind the weave is found to be very easily undone and released.

After weaving 1,500 lengths of fabric, it was found that no rods were soiled and there was no glue on any part of the loom. This polymer can be removed without problems by conventional methods before dyeing the fabric. Example
10 Prepare a 6% by weight solution of the polyurethane of Example 5.

Polyester warp yarns are glued with this solution.

This yarn is untwisted 72 decitex Nostrand 2
Two semi-pine yarns. The amount of glue is 3%. This glued yarn is used for weaving as in Example 9, except that the warp is a 70 strand polyester-viscose yarn.

Claims (1)

[Claims] 1 The molecular weight is between 500 and 3000, and the acid value is 2.
0mgKOH/g or less, and sulfur content of 0.8 to 2
% by weight of a sulfonated anionic polyester and at least one diisocyanate.
130°C and 230°C at a molar ratio of O/OH + COOH of 1 or less
A method for treating synthetic fiber yarns, which comprises applying to the fibers a sizing agent consisting of an aqueous solution with a concentration of 5 to 40% by weight of a water-soluble polyurethane obtained by reaction at temperatures between