JPS58214586A - Processing of fiber structure - 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 The present invention relates to a method for applying durable water- and oil-repellent finishing to a fiber structure.

Water-repellent finishing methods for textile products include methods using fluorine-based water repellents such as perfluoroalkyl acrylates, silicon-based water repellents, or zirconium-based water repellents, and for waterproofing methods, acrylates are used. , methacrylate, urethane, latex such as styrene-butadiene rubber, chlorosulfonated polyethylene, vinyl chloride.

The method of applying resins such as vinyl acetate is well known, and recently there has been a long-awaited emergence of products that have not only a high degree of water repellency and waterproofness, but also excellent moisture permeability and moderate air permeability.
One known example is a structure in which a porous fibrillated Teflon membrane or a porous polyethylene membrane is bonded to a fibrous structure using adhesives, etc., but these require a large amount of adhesive to obtain sufficient adhesive strength. Because it is necessary to interpose a layer, the texture of the product becomes extremely rough and hard, and it is extremely difficult to obtain durable water repellency and adequate breathability.

In order to solve the above problems, the present inventors conducted extensive research and found that after applying a specific water-repellent pre-treatment agent to a fiber structure on which a polymer film mainly composed of urethane was formed, the water-repellent The present invention was completed by discovering a method for performing the treatment.

The purpose of the present invention is to provide a fiber structure with excellent durability, water and oil repellency, and partial waterproofness, moisture permeability, and appropriate air permeability. is to provide.

The above purpose is to apply a water repellent pre-treatment agent made of aminoplast resin to a fiber structure on which a polyurethane resin film having continuous pores is formed, and then apply a water repellent agent having a perfluoroalkyl group in the side chain or ] This is achieved by applying a water repellent treatment agent whose main component is a water agent.

The polyurethane resin used in the present invention is not particularly limited and can be used as long as it is used as a normal polyurethane elastomer, but generally organic diisocyanate and polyalkylene ether glycol or hydroxyl at the terminal are used. A prepolymer is produced by reacting a polyester having a group, and a polyurethane elastomer is produced by an appropriate known method using a chain extender such as a diamine, diol, or polyol. The organic diisocyanates which are components constituting these polyurethanes include aromatic, aliphatic, and alicyclic hydrocarbon diisocyanates or mixtures thereof, specifically 1, for example, toluylene 2, 4. Diisocyanate, toluylene 2.6. diinocyanate, diphenylmethane 4.4' diinocyanate), 1.5+ ethylene diisocyanate, hexaj methylene diisocyanate, nog.
Examples include laxylylene diisocyanate.

Examples of polyalkylene ether glycol include polyethylene ether glycol.

Polypropylene ether glycol, polytetramethylene ether glycol, polyhexamethylene needle glycol, mixtures and copolymers thereof, etc., and polyesters include ethylene glycol and 1,4-butylene glycol.

Aliphatic polyalkylene glycols such as globylene glycol, tetramethylene glycol, hexamethylene glycol, alicyclic glycols such as cyclohexanediol, or aromatic glycols such as xylene diol, +L
Glycols and succinic acid, adipic acid, cepatic acid, etc.
Polymer condensates with organic acids such as terephthalic acid are used as chain extenders such as ethylene glycol, 1,4-phthalic acid, hydrazine, and ethylene diamine.

Examples include methylene di-low chloroaniline.

In addition, if necessary, triethylamine, triethylenediamine, N-methylmorpholine, N
-Ethylmorpholine, dibutyltin dilaurate,
Cobalt naphthinate or the like is used. The polyurethane thus obtained is usually applied to the invention in the form of a solution.

Suitable solvents for dissolving polyurethane include water or water-soluble or water-miscible solvents that can be extracted with water-miscible solvents, such as N,N-dimethylformamide and dimethylsulfoxide.

Tetrahydrofuran, tetramethylurea, N1N-dimethylacetamide, dioxane, butylcarbinol and the like may be used alone or in combination. These solvents may be mixed with ketones such as acetone, methyl ethyl ketone, and water in an amount of 1, for example, 20% or less, as long as they do not coagulate the polyurethane. In addition, the urethane solution contains coloring agents such as pigments and dyes, fibers, asbestos, talc, calcium carbonate, and a polymer solution whose main component is the above-mentioned polyurethane at a concentration of 50 to 15.0,000 cps.
, preferably adjusted to 100 to 100.000 cp6, and mangle quinosine roll, 70-
When applied using an appropriate method such as a cutting knife coater+, roll knife coater, Krachia coater, or rotary screen, and coagulated and regenerated in water or an aqueous solution containing a water-miscible solvent, the fiber structure has continuous pores. A polyurethane resin film is formed. At this time, the continuous pores are 0.1 to 5
μ is suitable for achieving the purpose of the present invention,
Furthermore, the above-mentioned fiber structure applied to the present invention refers to knitted fabrics, non-woven fabrics, etc. made of polyamide, polyester, polyacrylonitrile, or rayon, acetate, cotton, linen, wool, etc., or a mixture thereof. .

The water-repellent pretreatment agent applicable to the present invention includes:

Dicyandiamide / ammonium chloride / ammonia / formaldehyde, dicyandiamide / ammonium chloride / urine / formaldehyde, dicyandiamide / ammonium chloride / formaldehyde, dicyandiamide / toluidine / ammonium chloride / formaldehyde, dicyandiamide / diethylenetriamine / formaldehyde, dicyandiamide / polyalkylene polyamine / formaldehyde, Aminoplast resins such as dicyandiamide/formaldehyde, dicyandiamide/formaldehyde/methanol, dicyandiamide/detraenalbentamine, dicyandiamide/diethylenetriamine, etc. may be mentioned; Precondensates are preferably applied. Further, aminoplast resins other than the above-mentioned aminoplast resins can also be applied to the present invention, and the present invention also includes metal ion complexes such as copper complexes of the above-mentioned aminoplast resins. These water-repellent AiJ treatment agents c,
Normally 0.2~I o i/L Good 1 L< tri
1 to an aqueous solution of sFA at room temperature to 100°C, preferably 40 to 80°C for 1 second to 1 hour, preferably 5 seconds to 2
After applying it to the fiber structure for 0 minutes by an appropriate method such as dipping, excess water-repellent pretreatment agent is removed by washing with water, soaping, etc., and then hot true drying.

Dry using an appropriate method such as a pin tenter or non-touch dryer.

The fiber structure to which the water-repellent N11 treatment agent has been applied in the above manner is then treated with a water-repellent agent containing a perfluoroalkyl group in the side chain.
Alternatively, a water repellent treatment agent containing a perfluoroalkyl group-containing water repellent as a main component is applied, but these treatments damage the surface of the fibers constituting the fiber structure and the porous polymer mainly composed of polyurethane. The surface of the film and the inner wall surface of the micropores of the film have a durable and highly water-repellent surface.

It provides a high degree of water and oil repellency, waterproofness, excellent moisture permeability, and moderate air permeability.

As the paddle water agent applied to the present invention, an alkyl group (7)
Return element fi 4 to 21 perfluoroalkyl acrylate, perfluoroalkyl methacrylate, perfluoroalkylethyl azilylate, perfluoromonocarboxylic acid chromium complex salt, perfluoroalkyl acrylamide, perfluoroalkyl vinyl ether base IT or copolymers of these with ethylenically unsaturated monomers such as acrylic esters, methacrylic esters, styrene, phtadiene, bucrylamide, vinyl acetate, hydroxyalkyl acrylates, glycidyl methacrylate, acrylonitrile, etc. Examples include compounds having an alkyl group.

□ In addition, the water repellent component used in combination with these water repellents is 1, for example, the general formula % formula % (1) (wherein R1 is hydrogen or an alkyl group having 1 to 6 carbon atoms.

R2 represents an alkyl group having 11 to 20 carbon atoms. ) and the ethylenically unsaturated acid ester represented by the general formula % formula % (2) ゛ (wherein R3 is hydrogen or an alkyl group having 1 to 5 carbon atoms.

R4 represents an alkylene group having 1 to 5 carbon atoms, and R5 and R6 represent an alkyl group having 1 to 5 carbon atoms. Examples include organic acid salts of ethylenically unsaturated acid ester polymers having an active group that can partially cationize in the side chain obtained by copolymerizing with the compound represented by ().

A water repellent treatment agent that is a mixture of a polymer having an active group that can partially cationize in its side chain and the water repellent is better than a case where the water repellent is used alone.

Its water- and oil-repellent and waterproof effects are further enhanced.

These water-breaking agents or water-repellent agents can be soaked or sprayed.

Usually 0.1 to jQwt'%, preferably 0.2 to 5w in terms of solid content, is applied to the fiber Mζ structure by an appropriate method such as coating.
t administer.

Next, the fiber structure to which the water repellent or water repellent treatment agent has been applied is dried (by an appropriate means such as a non-touch dryer, hot flu dryer, pin tenter, etc.) at usually 120 to 190°C.
, preferably at 140 to 180°C for 10 seconds to 10 minutes, preferably 50 seconds to 2 minutes. When the present invention is used, compared to conventional coating water and oil repellent treatment methods, the treated fabric can be washed repeatedly. Water and oil repellency after application is significantly improved. (11 e.g.

After 4 repeated washings, the water pressure resistance of RXS L-IL192 by manual method is improved by 300 to 500B, and as the number of washings increases, the difference not only becomes noticeable, but also the difference in fabric (original fabric) without coating processing. It exhibits almost the same moisture permeability as , and maintains appropriate air permeability.

The present invention will be specifically described below with reference to Examples. Left side,
In the examples, "part" means "11 parts", and the water repellency, water pressure resistance 1 air permeability, and moisture permeability are in accordance with JISL-1079 (spray method), JI8L-1092 (method A), and JIS L-107.
Measured according to the 9-6-29 method (using a Fragiseal type air permeability measuring device) and the JISK-6528-5-5-12 method,
Washing was carried out according to the JIS L-0217-103 method.Example 1 730 parts of anhydrous geoglycerate was mixed with both ends (ρ: two-terminal gelicol having an OH group, 1.4-7' tyrene glycol and adipic acid C). molar ratio 1:1:2) 100 parts of copolymerized adipate with an average molecular weight of 2.0 OO and 4.4'
-methylene diphenyl r-socyanate) was added and reacted for 2 hours at 80°C in a nitrogen gas stream.
Cooled to 0°C.

Next, 10.9 parts of dipropylene gellicol, 0.02 parts of triethylenediamine, and 360 parts of ILN-N-dimethylformamide were added, and after the mixture was kept at 60 DEG C. for 5 hours, 05 parts of n-butanol was added to stop the chain extension reaction. When the reaction product is cooled, the solid content concentration is 50%, the viscosity is 100,
000 cps of polymer solution was obtained.

N,N-dimethylformamide was added to the polymer ffjn obtained by pressing in this way to give a solid content concentration of 26% and a viscosity of 5.
Polymer processing solution adjusted to 5,000 ops: 4:1
200 ν/ln' was applied to the #100% polyester fabric shown in the table using a reverse coater, and then 40 ν/ln' was applied using a reverse coater.
Solidify in water at ℃ for 10 minutes.

Assimilated, the water situation became dry.

The following (-dizononediamide, diethylenetriamine,
Mixture KC water with formalin and hydrochloric acid (C molar ratio 1:1:5:1) is added to make an aqueous solution of zo5A, and 1% ammonium chloride is added to the aqueous solution and mixed, and water vapor is condensed on the upper part. Polycondensation reaction 16 was carried out at 100° C. for 6 hours with stirring in a container equipped with a cooling device for refluxing, and then cooled to obtain an aqueous solution of aminoplast 4 fat. Further water was added to the obtained aqueous solution of the aminoplast resin to form an aqueous solution with a solid content of 1 Ls.
The applied polyester fabric was immersed in the aqueous solution at 80°C for 3 υ seconds, excess aminoplast 4d fat was washed away, and after drying, the fabric was immersed in a treatment solution with the following treatment agent composition to achieve a mangle pattern of 70%. Squeeze the liquid and pre-dry it at 80°C for 10 minutes, then dry it in a Hintenter for 2 minutes at 180'C. Treatment composition: Isopropyl alcohol, 1 part water.
90 parts The results are shown in Table 2 □ In addition, without aminogellast resin treatment, the treatment solution with the above treatment agent composition #) V (Atsuhi Guard AG75tl (
Asahi Glass) The results were treated in the same manner as in this example except that 5% grape-rich water mollusk solution was used as a comparative example, and the results are shown in Table 1 and Table 2.

Tables 1 and 2 show that not only the water repellency and water pressure durability are significantly improved by the present invention.

It can be seen that moderate breathability and excellent moisture permeability are maintained.

Claims (1)

[Scope of Claims] (1) After applying a water-repellent pretreatment agent made of aminoplast resin to a fiber structure on which a polyurethane resin film having continuous pores has been formed, a non-S-fluoroalkyl group is added to the side chain. 1. A method for processing a MUG structure, comprising applying a water repellent having the above-mentioned water repellent, or a water repellent treatment agent containing the water repellent as a main component. (2) The method according to claim 1, wherein the polyurethane resin film having continuous pores is obtained by wet regeneration and has continuous pores of 0.1 to 5 μm. (3) The method according to claim 1, wherein the aminoplast resin is an initial condensation product of dicyandiamide, an amine, and a formaldehyde copolymer. (4) The aminoplast resin is an initial condensation product of a dicyandiamide and formaldehyde copolymer. The method according to claim 1, which is a condensate or an initial condensate of dicyandiamide and an alkylamine. (5) The method according to claim 1, wherein the water repellent is perfluoroalkyl methacrylate (1z-) or id barfluoroalkyl acrylate. (6) Claim 1, wherein the water repellent is a copolymer of perfluoroalkyl methacrylate or haperfluoroalkyl acrylate and an ethylenically unsaturated monomer.
0(7) Method 0(8) according to Claim 6, wherein the ethylenically unsaturated monomer is an acrylic ester, a methacrylic ester, a hydroxyalkyl acrylate, a glycidyl methacrylate, acrylonitrile, or an acrylamide. Claims in which the water repellent agent is a mixture of a water repellent having a chili-fluoroalkyl group in its side chain and an ethylenically unsaturated acid ester polymer having an active group capable of partially cationizing the side chain. The method described in paragraph 1. (9) The method according to claim 8, wherein the active group that can be partially cationized is a dialkylaminoalkyloxycarbonyl group. (10) The method according to claim 8, wherein the ethylenically unsaturated acid ester polymer having an active group that can partially cationize in a side chain is a copolymer of an alkyl methacrylate and a dialkylaminoalkyl methacrylate.