JPH04503686A - Polyurethane terminated with alkoxysilane groups for finishing fiber materials of textile products containing polyester - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Alkoxy resin for finishing textile materials of textile products containing polyester Polyurethane with a run group at the end The present invention is a polyurethane with a run group at the end. Polyurethane terminated with alkoxysilane groups for finishing textile materials Regarding

It is possible to improve the properties of fiber materials in textile products by treating them with polynistil. is publicly known. Aims to improve the comfort of clothing made from textile materials This treatment particularly improves the hydrophilicity and antistatic properties of textile materials and provides good wind resistance. The aim is to provide the following characteristics.

European Patent No. 110267 has the following general formula: % formula % (In the formula, 80 to 97 mol% of the group is p-) unilene, 30 to 90 mol% of the group G is divalent with 3 to 6 carbon atoms optionally interrupted by 1 or 2 oxygen atoms alkane groups, 10-30 mol% of the group G have an average molecular weight of 1000-3000 divalent polyether units, 0 to 50 mol% of the group G represents ethylene units) reported a water-dispersible polynistyl consisting of ester units. this Textile products finished with these polyesters have good hydrophilic and antistatic properties. We are prepared. However, the drawback of such finishes containing polyester is their durability. In other words, it lacks resistance to washing.

The polymers reported in U.S. Pat. No. 4,617,340 include polysiloxanes and Polyols having [(CH2:h-4-○]X-chains (e.g. polyethylene reacting a mixture consisting of (recall) with a diisocyanate in the presence of a catalyst. obtained by. This reaction is preferably carried out in an organic solvent. The obtained port Rimmer imparts good hand properties and good hydrophilicity to the finished fiber material. however To improve the washing resistance of this finish, resins must be added. do not have.

In addition, German Patent No. 3723350 contains the following general formula: % formula %) (In the formula, m is 5 to 75, n is O to 10, and Sp is O to 3.) 1 mole of Nomer, 2 to 12 moles of vinyl ester, and 1 to 6 moles of N-vinylpyrrolidone. mol, and by copolymerization with 0 to 6 mol of acrylate or methacrylate Polymer compounds containing the resulting copolymers have been reported. These poly mer compounds impart permanent hydrophilicity and good hand properties to treated textiles .

The problem to be solved by the present invention is to solve the problem of the fiber material of textile products finished thereby. extremely good hydrophilic and antistatic properties, good hand properties, and the properties of these fibers. The purpose is to provide the necessary smoothness during further processing of the textile material. Finished again to ensure that the properties imparted to the fabric are retained even after repeated washing. In order to ensure that the finish provided by the present invention is highly durable, i.e. It is necessary to show high resistance to

These numerous demands placed on finishing agents for textile materials containing polyester There is no known treatment agent that can fully satisfy the above requirements. This textile finishing agent Surprisingly, the high demands placed on Filled with polyurethane.

That is, the present invention provides aliphatic and/or aromatic di- and/or triisocy Naat A, polyethylene glycol having a number average molecular weight of 500 to 6000, and OH :NC0 (73 so that the equivalent ratio is 1 = 1.5 to 1:2, B, hydrophobic diol and/or polyol and diol and/or polyol The equivalent ratio of the OH group of the ol to the NCo group still present is 1:1.1 to 1:10. and C0 general formula (■): R1 X (CHz), St (ORs-(1) (wherein R and R1 are the same or may be different <, Cl-4 is an alkyl group, and X is an amino group or a mercapto group , n is 0 or 1, q is an integer from 2 to 4) Several stages of reaction with the alkoxysilane represented by until the NCO content becomes 0% by weight Finishing textile materials for textile products containing polyester manufactured by This invention relates to a polyurethane having an alkoxysilane group at its end.

Synthesis of polyurethane with alkoxysilane groups at the end involves the steps in the above order. Therefore, it will be implemented. Theoretical content of -N=C=O groups in each stage (hereinafter simply theoretical) After reaching the desired NGO content (referred to as the desired NGO content), the reaction mixture is reacted with the next step reagent.

The expression "theoretical NGO content" means that all OH groups are -N=C=O groups (hereinafter simply Because there are no more free OH groups in the reaction product, there are no more free OH groups in the reaction product. It means something.

The alkoxysilane group-terminated polyurethane of the present invention can be prepared by a known method. [Ullmann's Encyclopedia der Technischen Hiemi] -, vol. 19, pp. 302-310 (Fuerlag Hiemie, 1980)]. place Optionally trimethylolpropane and/or dimethylolcarboxylic acid having 1 to 6 carbon atoms), 500 to 600 Polyethylene glycol having a number average molecular weight of 0 is added in the absence of a solvent to the desired in the presence of a catalyst (e.g. dibutyltin dilaurate). is reacted with triisocyanate at a temperature of 60 to 100°C. polyol component As a standard, the equivalent ratio of OH:NCO is 1:1.5 to 1:2, preferably 1:1. The ratio is 8 to 1:2. After reaching the theoretical NGO content, hydrophobic diols and/or Add the polyol to the reaction mixture at 60-100°C. At that time, hydrophobic geo The equivalent ratio of the OH groups of the alcohol and/or polyol to the NCo groups still present is 1 :1.1~1:10, better<l;! 1:1.3 to 1:5. theoretical N After reaching the GO content, the alkoxysilane represented by general formula (1) is heated at 50 to 70°C. Add at a temperature of Furthermore, relative to the NGO equivalent present, the alkoxyaminoalkyl Equimolar amounts of silane and/or alkoxymercaptoalkylsilane are used.

Note that the reaction is terminated after all existing NCo groups have reacted with the alkoxysilane. Ru. The resulting polyurethane having alkoxysilane groups at its ends was heated to room temperature, i.e. 1 It is a waxy solid and white in color at temperatures between 5 and 25°C.

Aliphatic and/or aromatic, cyclic and/or is an acyclic di- and/or triisocyanate that terminates an alkoxysilane group. Suitable for producing polyurethane with edges. such gee and/or An example of a diisocyanate is dicyclohexylmethane-4,4"-diisocyanate. 1. 6-hexane diisocyanate, 3-incyanatomethyl-3,5, 5-Trimethylcyclohexyl isocyanate (isophorone diisocyanate) , tetramethylene diisocyanate, trimethylhexamethylene diisocyanate , 1,4-fuynylene diisocyanate, diphenylmethane diisocyanate , toluene-2,4- and/or toluene-2,6-diisocyanate, 2 ．． 4. 4°-triisocyanatodiphenyl ether and/or 4',4 ″, 41′-triisocyanatotriphenylmethane.Aliphatic diisocyana Trimethylhexamethylene diisocyanate is particularly preferred. stomach.

The diisocyanate reaction is performed on polyethylene with a number average molecular weight of 500-6000. lene glycol, trimethylolpropane, and optionally 1 to 6 carbon atoms a mixture of aliphatic dimethylol carboxylic acids having 500 to 2 Polyethylene glycol, trimethylol propane with a number average molecular weight of 500 and optionally aliphatic dimethylol carbon having 1 to 6 carbon atoms. Preference is given to carrying out with a mixture of acids. Triisocyanate is 500~ Polyethylene glycol having a number average molecular weight of 6000, optionally 1 to 6 more preferably in combination with an aliphatic dimethylolcarboxylic acid having Alternatively, polyethylene glycol having a number average molecular weight of 500 to 2,500 is optionally in combination with an aliphatic dimethylolcarboxylic acid having 1 to 6 carbon atoms. It is preferable to react simultaneously. These reactions can be performed using, for example, tertiary amines, dibutyl Presence of catalysts such as tin dilaurate and/or dibutyltin diacetate It can be carried out below. Polyethylene glycol mixture containing trimethylolpropane For compounds, the trimethylolpropane content is 1 equivalent of polyethylene glycol OH. Select so that the OH equivalent of trimethylolpropane does not exceed 0.33 relative to the amount. . In polyethylene glycol mixtures containing dimethylol carboxylic acid, poly Maximum OH equivalent of dimethylolcarboxylic acid per 1 equivalent of ethylene glycol OH. Use 1 large equivalent. aliphatic dimethylolcarboxylic acids having 1 to 6 carbon atoms, For example dimethylol acetic acid, dimethylol propionate and/or dimethylol Luvaleric acid with or without polyethylene glycol and trimethylolpropane. However, polyethylene Recall, and optionally all OH groups of trimethylolpropane are NGO The aliphatic dimethylolcarboxylic acid is added to the reaction mixture only after it has reacted with the group. It is also possible to add

Equivalent ratio of OH:NGO as described above, i.e. polyethylene glycol, optionally Trimethylolpropane and optionally dimethylolcarboxylic acid OH group The equivalent ratio to NGO groups is 1:1.5 to 1:2, preferably 1:1.8 to 1: It is 2.

The hydrophobic diol and/or polyol has a number average of 400 to 2000 Polytetrahydrofuran, CI2-18 fatty acid jetanolamide with molecular weight aliphatic 08-2□ fatty acid monoglyceride and/or general formula (II) : (In the formula, X is a number from 5 to 15) It is preferable to use a polysiloxane represented by: Number of 400 to 2000 Particularly preferred are polytetrahydrofurans having a uniform molecular weight.

Polytetrahydrofuran is an industrial product, for example marketed by BASF. It's on sale. Lauric acid, myristic acid, coconut oil fatty acids and/or oleic acid It is produced by the reaction of CI2-18 fatty acids such as phosphoric acid with jetanolamine. Obtaining CI2-I8 fatty acid jetanolamide [Kirk Osmer, “Encyclopedia 22, pp. 373-376 (J. Wiley & Sons, New York, 1983), and fats and oils. , such as lauric acid, coconut oil fatty acids, stearic acid, oleic acid and/or 0, which can be produced by reaction of tallow fatty acids with glycerin, such as monoglycerides. Monoglycerides of 8-22 fatty acids [Kirk Osmer, [Encyclopecia] of Chemical Technology, Vol. 22, pp. 367-368 (John Wiley) and Sons, New York, 1983)] are also commercially available. It is a product. The polysiloxane represented by the general formula (II) is, for example, Wacker ( Wacker).

General formula (1) [where the groups R and R1 may be the same or different, methyl or or ethyl, X is an amino group, n is 0 or 1, q is 2 or 3] The indicated alkoxysilanes, such as aminopropyltriethoxysilane and/or or aminopropyltrimethoxysilane has an alkoxysilane group at the end It is particularly suitable for the production of polyurethane. Alkoxysilane is an industrial product For example, there is a guide from Dynamit Nobel. It is commercially available under the trade name Dynasilan.

The polyurethanes of the invention are used in the form of aqueous dispersions. To produce this dispersion melts polyurethane with alkoxysilane groups at its ends at 60 to 100°C. , then injected into an alkaline aqueous solution at 5 to 60°C with stirring, or Mix with alkaline aqueous solution at ~60°C. The viscosity of the molten polyurethane is Well, the melting temperature should not exceed a value of 50000 mPa,s. alkalinity As an aqueous solution, preferably sodium hydroxide or potassium hydroxide solution is used. Ru. The polyurethane content of the aqueous dispersion obtained is between 5 and 30% by weight, preferably 1 It is 0 to 20% by weight. The pH value of the dispersion is 10 or more.

Application of the polyurethane according to the invention can be carried out by the bagging or absorption method in known procedures. It will be done. In a preferred embodiment, the fiber material of the textile product containing polyester 5 to 150 g of aqueous polyurethane dispersion per liter, preferably 30 g Apply an aqueous dip containing ~75 g by padding at a temperature of 5 to 50 °C. . When squeezed at a temperature of 5-50℃ and dried at a temperature of 80-200℃, the fiber material becomes porous. The urethane content is between 2.0 and 7.5 g per kg of fiber material.

The fiber material of textile products containing polyester is the polyester fiber itself. or contain natural fibers such as cotton, wool, and/or lace. John stable and/or e.g. polyamide, polyethylene and/or may be mixed with synthetic fibers such as polyacrylonitrile. textile fiber Materials include flock, sliver, knitting thread, woven thread, sewing thread, stockinette products (knitted fabric) ), woven or non-woven fabrics, preferably knitted yarns, woven yarns, sewing threads, Exists as knitted or woven fabric. Having the alkoxysilane group of the present invention at the end Polyurethane works extremely well on textile materials, including polyester, that are finished with it. Hydrophilic properties with excellent sewing ability and extremely good wash resistance, and antistatic properties with wash resistance. It provides very good texture (feel) properties.

Polywaxes 1550 (polyethylene glycol, Number average molecular weight 1600, moisture content 0.06% by weight, manufactured by Hiemische Bell Chemische Werke Hols) 72g5t 0.45 g of limethylolpropane and 0.02 g of benzoyl chloride in a 3-necked flask. The mixture was mixed in a tank under nitrogen atmosphere. Trimethylhexamethylene diisocyanate 2 After adding 1 g, the mixture was heated to 60°C. After 1 hour, 4.5% by weight theory 50 g of polytetrahydrofuran (number average molecular weight 2000) was added.

After stirring for 2 hours at 70° C., the theoretical NGO content reached 1.5% by weight.

Then, 11.1 g of aminopropyltriethoxysilane was gradually added. 50℃ After stirring for 1 hour at , the NCO content reached a value of 0% by weight.

Upon cooling to 22° C., the product was obtained as a white waxy solid.

Polywax 1550 (moisture content 0.06% by weight) 64g, ) Rimethylolp 0.45 g of lopane and 0.02 g of benzoyl chloride were placed in a 3-necked flask under nitrogen atmosphere. Mixed under air. 21g of trimethylhexamethylene diisocyanate was added. Afterwards, the mixture was heated to 60°C. After 1 hour, a theoretical NCO content of 5.4% by weight Reached. Then 0.67 g of dimethylolpropionic acid was added. 2 at 70℃ After stirring for an hour, the theoretical NGO content reached 4.9% by weight. Polytetrahydrofura After adding 50 g of N (number average molecular weight 2000), the mixture was stirred at 70°C for 2 hours, A theoretical NCO content of 1.5% by weight was obtained.

Then, 11.1 g of aminopropyltriethoxysilane was gradually added. 50℃ After stirring for 1 hour at , the NCO content reached a value of 0% by weight.

Upon cooling to 22° C., the product was obtained as a white waxy solid.

Example 3 Polyurethane with alkoxysilane group at the end (1) Polyurethane (1) 125g was melted at 85°C. The melt was then charged with potassium hydroxide at a temperature of 5°C. 875 g of a 0.25% by weight aqueous solution of M. Added in between. A homogeneous aqueous dispersion was obtained.

100 g of polyurethane QI) was melted at 85°C. The melt was then heated to a temperature of 25°C. 900g of a 0.25% by weight aqueous solution of potassium hydroxide at 60 Or, p, m, Added over 10 minutes with stirring. A homogeneous aqueous dispersion formed.

Zario Performed per liter of pre-washed and air-dried polyester knitted fabric. 20 in an aqueous dip containing 60 g of the aqueous dispersion prepared in Example 3 or Example 4. Processed by padding at a temperature of °C.

The squeezing effect in the padding machine was 75%. Then, heat the knitted fabric at 140℃ for 3 minutes. Dry. The amount of active substance applied per kg of polyester knitted fabric is For dispersions containing urethane (I), 5,6 g1 polyurethane (II) In the case of a dispersion containing , the amount was 4.5 g.

Polyester treated with the alkoxysilane group-terminated polyurethane of the present invention Test results for le knitted fabric To measure durability, the knitted fabric was washed with a mild detergent [Feta®, Henkel KGaA] and washed 5 times at 40°C. The washing machine program is and wear' and rotary drying.

In the table, durability is shown in the column of "5 washes".

A. Measurement of thread smoothness (sewing ability) Pfaff 483 equipped with a penetration force recorder to measure sewing ability. The needle penetration force was measured on a type industrial sewing machine at a speed of 4000 stitches per minute.

The table below shows the average value (sewing needle thickness: 8ON+++) obtained from 50 penetrations. Ta.

Determining the water absorption of finished knitted polyester fabrics according to DIN 53924j: did. For testing, a small piece of knitted fabric was placed in a container and one end of it was immersed in water. 15 seconds and after 120 seconds, the height of the rising liquid is measured according to the present invention to measure the antistatic property. The electrical surface resistance of the finished polyester knitted fabric was measured by Siemens (Si measured with an electrode (measurement conditions = 20°C/65% relative air humidity) [Maha et al. Mahall, “Textilve Edelung” 15, pp. 80-85 (1980)].

Electrical resistance evaluation lXl0'~lXl0'' ohm = very good 1x10s~lX109 ohm Good condition '1x10@~1x1010 ohm = pretty good lXl0''~5X1 0” ohm = Sufficient > 5X10” ohm = Insufficient Aqueous dispersion containing polyurethane (I) or containing polyurethane (II) Knitted polyester fabrics treated with any of the aqueous dispersions that The untreated polyester knitted fabric had a smooth and flat texture. Shows standard polyester feel.

international search report international search report PCT/EP 90100260

Claims (17)

[Claims] 1. Aliphatic and/or aromatic di- and/or triisocyanates A. polyethylene glycol having a number average molecular weight of 500 to 6000, and OH :NCO equivalent ratio is 1:1.5 to 1:2, B. Hydrophobic diol and/or polyol and diol and/or polyol The equivalent ratio of the OH group of the ol to the NCO group still present is 1:1.1 to 1:10. and C. General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R and R1 are the same or different. may be a C1-4 alkyl group, and X is an amino group or a mercapto group, n is 0 or 1, q is an integer from 2 to 4) Several stages of reaction with the alkoxysilane represented by until the NCO content becomes 0% by weight Finishing processing of textile materials for textile products containing polyester manufactured by A polyurethane with an alkoxysilane group at the end for the purpose of 2. Claim 1, wherein the OH:NCO equivalent ratio in stage A is from 1:1.8 to 1:2. Polyurethane with alkoxysilane groups at its ends. 3. or one of claims 1 and 2, wherein the equivalent ratio of stage B is from 1:1.3 to 1:5. A polyurethane having an alkoxysilane group at its terminal as described in both. 4. Polyurethane is obtained by reaction of aliphatic diisocyanates It has an alkoxysilane group according to one or more of claims 1 to 3 at its terminal. Polyurethane. 5. A claim in which the polyethylene glycol has a number average molecular weight of 500 to 2,500. A polyurethane having an alkoxysilane group at a terminal according to one or more of items 1 to 4. Letang. 6. Polyurethane contains polyethylene glycol, trimethylolpropane, and and optionally aliphatic dimethylolcarboxylic acids having 1 to 6 carbon atoms. Claims 1 to 3 are obtained by reacting a mixture of Polyurethane having an alkoxysilane group at its terminal according to one or more of item 5. hmm. 7. Hydrophobic diol and/or polyol has a number average content of 400 to 2000 Polytetrahydrofuran, C12-18 fatty acid diethanolamide with molecular weight , C8-22 fatty acid monoglyceride and/or general formula (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, x is a number from 5 to 15) The polysiloxane according to one or more of claims 1 to 6, which is a polysiloxane represented by A polyurethane with terminal lukoxysilane groups. 8. Hydrophobic diol and/or polyol has a number average content of 400 to 2000 One or more of claims 1 to 7, which is polytetrahydrofuran having a molecular weight. A polyurethane having an alkoxysilane group at its terminal as described in . 9. In general formula (I), the groups R and R1 may be the same or different and may be methyl or is ethyl, X is an amino group, n is 0 or 1, and q is 2 to 3, Polyurethane having an alkoxysilane group at the end according to one or more of item 8 hmm. 10. Aliphatic and/or aromatic di- and/or triisocyanates A. polyethylene glycol having a number average molecular weight of 500 to 6000, and OH :NCO equivalent ratio is 1:1.5 to 1:2, B. Hydrophobic diol and/or polyol and diol and/or polyol The equivalent ratio of the OH group of the ol to the NCO group still present is 1:1.1 to 1:10. and C. General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R and R1 are the same or different. may be a C1-4 alkyl group, and X is an amino group or a mercapto group, n is 0 or 1, q is an integer from 2 to 4) Several stages of reaction with the alkoxysilane represented by until the NCO content becomes 0% by weight Polyurethane with terminal alkoxysilane groups manufactured by Use for finishing textile materials in textile products containing esters. 11. Claim 10, wherein the OH:NCO equivalent ratio in step A is 1:1.8 to 1:2. Use of listed. 12. or one of claims 10 to 11, wherein the equivalent ratio of step B is from 1:1.3 to 1:5. is used as described in both. 13. One or more of claims 10 to 12 in which an aliphatic diisocyanate is used. Uses as described above. 14. Use polyethylene glycol with a number average molecular weight of 500 to 2500 14. Use according to one or more of claims 10 to 13. 15. Polyurethane with alkoxysilane groups at the ends is polyethylene glyco trimethylolpropane, and optionally having 1 to 6 carbon atoms obtained by reaction of a mixture of aliphatic dimethylol carboxylic acids with diisocyanates. 15. Use according to one or more of claims 10 to 14. 16. Polytetrahydrofuran with number average molecular weight of 400 to 2000, C1 2-18 fatty acid diethanolamide, aliphatic C8-22 fatty acid monoglyceride and/or general formula (II): ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ( In the formula, x is a number from 5 to 15) A polysiloxane having a number average molecular weight of preferably 400 to 2000 using polytetrahydrofuran as hydrophobic diol and/or polyol. 16. Use according to one or more of claims 10 to 15. 17. General formula (I) (wherein the groups R and R1 may be the same or different, thyl or ethyl, X is an amino group, n is 0 or 1, and q is an integer of 2 to 3. or one of claims 10 to 16, which uses an alkoxysilane represented by Uses as described above.