JPS6045679A - Waterproof processing of fiber product - 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 provides a waterproofing method for textile products, in particular, a method for waterproofing textile products, which provides excellent water repellency and waterproofing without reducing the breathability and moisture permeability of textile products.
This relates to the processing method used.

Addition of water repellency to textile products] As a method, fluorine-based water repellents typified by perfluoroalkyl acrylates9. Methods using silicone-based water repellents or zirconium-based water repellents are well known, and waterproofing methods include acrylic resins, polyurethane, latexes such as nuthylene-butadiene rubber, chlorosulfonated polyethylene, and chlorinated polyethylene. Methods using resins such as vinyl resins and vinyl acetate resins are known.

Furthermore, recently there has been a strong demand for products with excellent moisture permeability and appropriate air permeability.For example, products with porous fibrillated Teflon membranes or porous polyethylene bonded to the surface of fabric using adhesives are known. Since it is necessary to interpose a multi-prong adhesive between the parts, the texture of the product becomes extremely rough and hard, and it is difficult to obtain durable water repellency and adequate breathability. In addition, a method of forming a wet recycled urethane resin film on a fiber structure is known as a manufacturing method for moisture permeable waterproof fabric, but wet recycling requires excessive equipment such as recycling equipment, solvent removal, and water washing equipment. In addition, in order to obtain a high degree of waterproofness in the obtained product, it is necessary to increase the thickness of the membrane, and in this case, it is extremely difficult to obtain excellent moisture permeability and appropriate air permeability.

Therefore, the present inventors have developed a new method that provides fiber structures with excellent moisture permeability, waterproofness, water repellency, and appropriate air permeability without deteriorating their texture. First, JP-A-58-4
The method proposed in Publication No. 873 is characterized in that a water repellent having a perfluoroalkyl group in the side chain is applied to a fiber structure on which a polyurethane resin film containing porous particles mainly composed of H1SiO2 is formed. Although almost satisfactory performance is obtained in terms of moisture permeability and water repellency, further improvements are required in waterproofness, texture, and moisture permeability, and there is a strong need to improve productivity. ing.

In order to meet these demands, the present inventors have conducted intensive research based on extensive experiments, and have further improved and developed the previously proposed method, using various resins to achieve more stable performance. They discovered that a good product could be obtained and completed the present invention.

An object of the present invention is to provide an industrially advantageous addition method that can produce textile products with extremely excellent water repellency and waterproof properties without substantially reducing the air permeability and moisture permeability inherent to textile products. It is in.

That is, in the method of the present invention, a moisture-permeable film is formed by applying a resin solution containing porous particles mainly composed of SiO□ to a textile product, and the porous particles in the resin solution are insoluble in the resin. It is characterized in that it contains a volatile solvent, and that the textile product is treated with a water repellent at least one of before and after forming the resin film.

In the present invention, since the porous particles are pre-contained with a resin-insoluble solvent and mixed into the resin liquid, the pores of the porous nuclei are not clogged with resin during the mixing, and the porous particles can be heated to form the resin film. Since all the solvent contained in the hexagrams is removed, the pores of the porous particles are formed in the resin film. However, it remains effectively and can provide the product with extremely stable and excellent air permeability and moisture permeability (=J).

In the present invention, textile products include knitted fabrics, woven fabrics, non-woven fabrics made of natural fibers or synthetic fibers alone, blended fabrics made of one or more types of fibers, interwoven or interwoven fabrics, leather, paper, and other fibers. Refers to porous products that contain

The resins used in the present invention are not particularly limited, and include polyurethane, acrylic copolymers, silicone-based polymers, vinyl chloride-based polymers, chlorosulfonated polyethylene, etc. Any elastomer that is normally used for coating processing, such as a single substance or a copolymer of , or a mixture thereof, can be used; Polymeric substances that can be used suitably.

As the polyurethane resin, for example, organic diisocyanate-1
・Produce a prepolymer by reacting polyalkylene ether glyco-7 or a polyester having a hydroxyl group at the end, and prepare a polyurethane elastomer by an appropriate known method using a chain extender such as a diamine, diol, or polyol. It was made into Nutmer. The organic diisocyanates that constitute these polyurethanes include aromatic, aliphatic, and alicyclic hydrocarbon diisocyanates, or mixtures thereof, specifically, for example, toluylene-
Examples include 2,4-diisocyanate, toluylene-2,6-diisocyanate, diphenylmethane-1,4'-diisocyanate-1,1,5-naphthylene diisocyanate, hexamethylene diisocyanate, paraxylene diisocyanate, and the like.

Examples of polyalkylene ether glycols include polyethylene ether glycol, polypropylene ether glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, and mixtures and copolymers thereof; examples of polyesters include ethylene glycol/L', 1.4 butylene glycol,
Aliphatic polyalkylene glycols such as propylene glycol, tetramethylene glycol, and hexamethylene glycol, alicyclic glycols such as cyclohexanediol, or polycondensates with xylene organic acids are used as chain extenders, such as ethylene glycol, l, 4- Butylene glycol, hydrazine, ethylene diamine, methylene diamine 0
-・Chloroaniline, etc. can be mentioned. If necessary, triethylamine, triethylenediamine, N-methylmorpholine, N-ethylmorpholine laurate, cobalt naphthinate, etc. are used as a polymerization reaction catalyst.

The polyurethane thus obtained is usually applied to the invention in the form of a solution. The solvent for dissolving polyurethane is water,
4 or water-miscible solvents are suitable, such as N,N-dimethylformamide, dimethylnulphogenide, tetrahydrofuran, tetramethylurea, N,N- dimethylacetamide,
Dioxane, butyl carbinol, etc. may be used alone or in combination.These solvents may include ketones such as acetone, methyl ethyl ketone, and water within a range that does not coagulate the polyurethane, for example, 20% or less. do not have.

Any commonly used Aku IJ/shi copolymer can be used in the present invention, but for example, if a hydroxyl group- or carboxyl group-containing ethylenically unsaturated monomer polymer and a crosslinking agent are combined with a ketone etc., xylene, toluene,
A solution dissolved in an organic solvent such as a halogenated hydrocarbon. Liquid is mainly used.

An example of an ethylenically unsaturated monomer polymer containing a hydroxyl group or a carboxyl group is the general formula % (in the formula, 1<7 is hydrogen or an alkyl having 1 to 2 carbon atoms).
, (, 1 (, represents an alkyl group, an aryl group, a halogen-substituted alkyl group, a halogen-substituted aryl group, a nitrile, or an alkoxycarbonyl group having 2 to 19 carbon atoms. However, 1<3 is 2. J + (When R7 is hydrogen. 1<9 is hydrogen, alkyl group or carboxyalkyl percentage ``10 is hydrogen or carboxyl J, (, I-<
11 represents hydrogen or a hydroxyalkyl atom, and 1] represents O or a positive integer. ) It can be obtained very easily by polymerizing ethylenically unsaturated monomers having a hydroxyl group or a carboxyl group as shown in the following by a known appropriate method. Specific examples of the monomer represented by general formula (1) include acrylonitrile, a) V-kyl acrylate, alkyl methacrylate,
Ethylenically unsaturated acids such as nutylene acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate-1,
, 3-chloro)V-2-hydroxyalkyl methacrylate, etc., and these monomers represented by the formula (1) or (2) can be used to form ternary or It does not go so far as to say that it is okay to use a multi-component polymer of more than that.

Dehydrogenation, dealcoholization, and addition reaction products of silicone prepolymers having hydrogen, alkyl groups, and hydroxyl groups at the terminals are generally used as polymeric substances whose main component is silicon, but these are generally expressed by the following formula. It is a polymeric substance produced industrially.

(6) Dehydrogenation reaction type (b) Dealcoholization reaction type 1 1 1 1 (c) I/j addition reaction type 1 1 1 1 Silicon preformanitrichlorethylene, tetrachlorethylene, 1,1.1-1- A halogenated hydrocarbon such as lychloroethane, a single solvent such as benzene or l-luene, or a mixed solvent thereof, with a solid content concentration of 5 to 40% and a viscosity of 3.
000~50000 cps, P[, Zn, S
A resin film containing silicon as a main component is formed on the fiber structure by using a catalyst containing metals such as n and Pb.

The resin slag used in the pond water invention is not particularly limited.

The porous particles contained in such resins are mainly composed of SiO2, and usually have an average particle diameter of 2 to 50μ and a final volume of pores in the resin of 0.2 to 5 wl/ g is used. It is also preferable to have hydroxyl groups on the surface of the particles.
Preferred examples of the r-element include those having a highly porous network structure in which silica gel particles on the order of millimicrons are three-dimensionally connected through silogysan bonds.

In the present invention, such porous particles are made to contain a specific solvent in advance and blended into the resin solution, and at this time, the resin solution viscosity is 50 to 150.000 cps, preferably Vi10゛0 to lOo, o.

The amount of porous particles to be mixed is preferably 0.5 to 150 parts by weight, preferably 11 to 100 parts by weight, per 100 parts by weight of the resin solid content. If the amount is less than 0.5 parts by weight, the porosity is meaningless, and if it is more than 150 parts by weight, the physical properties of the resin film will be poor.

The resin-insoluble solvent may be applied to the porous particles by moistening the porous particles with the resin-insoluble solvent and filling the pores, that is, the cavities, with the solvent, and a dipping method or a spray method may be used. can. Examples of resin-insoluble solvents include water,
The use of methyl alcohol, ethyl alcohol and isopropyl alcohol is preferred, with isopropyl alcohol being particularly preferred.

Application of the resin liquid to textile products can be achieved by a thin film coating method using a munchle-killing roll, float ink knife coater, roll knife coater, Clavia coater, rotary screen, etc. After spreading, it is dried and becomes porous. A resin film can be obtained.

It is necessary that the textile product be treated with a water repellent before the resin film is formed, or that it be water repellent treated after the resin film is formed. or mixtures thereof. However, it is not limited to these.

For example, a water repellent having a perfluoro group has 1, a perfluoroalkyl group having 4 to 21 carbon atoms and an alkyl group having 4 to 21 carbon atoms.
Gil ali lit, perfluo
17/Rekyl methacrylate, perfluoroalkifurethyl acrylate, chromium perfluoromonocarboxylate J11. 'j I'aj+, perfluoroalkyl acrylic @mer or their acrylic acid ester, methacrylic ester, nutylene, butadiene,
Compounds having a perfluoroalkyl group, such as copolymers with ethylenically unsaturated monomers such as acrylamide, vinyl acetate, hydroxyalkyl acrylate, glycidyl methacrylate, and acrylonitrile, can be mentioned.

Such a water repellent can also be used in combination with other components, and those preferably used as such components include, for example, the general formula % (where R1 is hydrogen or an alkyl group having a prime number of 1 to 3, R
2 represents an alkyl group having 11 to 20 carbon atoms. ) is an ethylenically unsaturated acid ester represented by R, a general formula group, R is an alkyl group having 1 to 5 carbon atoms, R5 and R6
represents 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 ().

These (water repellent treatment agents) are a mixture of a polymer having an active method capable of partially cationizing the III chain and the water repellent,
Compared to the case where a water repellent is used alone, its water repellency and waterproof properties are further increased.

These water repellents or water repellent treatment agents are applied to the fiber products by an appropriate method such as dipping, spraying, coating, etc., usually in a range of 0.1 to 0.1 in terms of solid content.
10% by weight, preferably 0.2-5% by weight.

Next, the textile product to which the water repellent has been applied is dried by an appropriate means such as a non-touch dryer, hot flue dryer, pin tenter, etc., and then usually at 120 to 190"C, preferably 140 to 180"C for 10 seconds to 10 minutes. , preferably 3
Dry heat treatment is performed for 0 seconds to 2 minutes.

According to the present invention, the previously proposed JP-A-56-1Q26
It is possible to obtain a product that has improved waterproofness and moisture permeability compared to the method described in 'i'2, and is also more economical.

The present invention will be specifically explained below with reference to Examples.

In the examples, "part" means 1 part by weight, and the air permeability, moisture permeability, water pressure resistance, and water repellency are in accordance with JIS f)-1.
0'79-6-29 method (using 7 Lassie TV 3J4i air permeability measuring device), JISK
-6328-5-3-1 2 method, J Is-L-1o9
z (method A) and JIS-L~1079 (7. play method).

Example [l] A copolymer consisting of ethyl acrylate/butyl acrylate-1/acrylonitrile/2-hydroxyl 4-/l/methacrylate (weight ratio 20:68:10:2) was dissolved in tetrachlorethylene, and the solid content 12%, viscosity 50,000 cps (measured with BIT type viscometer rotor No. 6, 10 rpm), and 100 parts of the solution were mixed with 10 parts of silicone oil and 2.
4.

A resin liquid was prepared by mixing 30% of 6-dributoxymethylamino-1,3.5-triazine and 5 parts of a tetrachlorethylene solution.

Next, silica gel particles with a particle size of about 10 mμ have an average particle size of 1, which has a three-dimensional network structure due to siloxane bonds.
A porous silica liquid was prepared by mixing 50 parts of porous powder with a diameter of 0μ and an axial pore volume of 1.5 gt19 and 150 parts of isopropyl alcohol/l. A mixture, and as a comparative example, the resin liquid alone and the resin liquid directly mixed with 12.5 parts of the porous powder were diluted by adding tetrachlorethylene, respectively.
A treatment solution with a viscosity of 30,000 cps was prepared. Fluorine-based water repellent (Asahi Guard AG7 manufactured by Asahi Glass Co., Ltd.)
30) Pad a 5% solution at a squeezing rate of 30%,
Low iron 100% plain woven fabric dried at 20°C for 5 minutes (warp 70'/36", weft 70"/36f, density warp 11)
6 lines/inch, latitude 94 lines/inch, date 7ofl1wl
) was coated with the treatment solution using a floating knife coater, dried at 120°C for 2 minutes, and coated with a pin tenter for 1 minute.
Dry heat treatment was performed at 70″C for 12 minutes.

The results of the physical property tests of the product are shown in Table 2.

Table 1 *,) Comparative example *2) The number in parentheses indicates the amount of silica.

Table 2* Comparative Example Example [2] A copolymer consisting of ethyl acrylate/2-hydroxyethyl methacrylate (weight ratio 95:5) was dissolved in tetrachlorethylene KM to give a solid content of 10% and a viscosity of 55. ,000 cps (B11 type viscometer rotor No.
, a , l Orpm) was prepared, and for 100 parts of the solution, 10 parts of silicone oil and 2.4.6 parts of silicone oil were added.
-Dryptoxyamino-1,3.5-triazine 30%
5 parts of tetrachlorethylene solution was added, and further Example (
84 parts of the porous silica liquid shown in 1) was added, and then tetrachlorethylene was added to adjust the viscosity to 32,000 cps. t) The resulting silica-containing resin liquid was applied to a polyester plain weave fabric (warp polyester 80'/4 B', weft polyester 8 o/a, 8', warp density 10).
6 lines, 7 inches, latitude density 96 lines, 7 inches, date 83g
/7)? ), after applying with knife coater, 120”
Dry for 2 minutes at C for 2 minutes, and then apply a 3% solution of fluorine water repellent (Asahi Guard AG710 manufactured by Asahi Glass Co., Ltd.) to a mangle squeezing rate of 25.
%, dried at 120"G for 2 minutes, and then heat-treated at 170°C for 1 minute using a Tenku. At the same time, as a comparative example, the above method was carried out without mixing the porous silica liquid. Tree Fm f Table 3 shows the results of physical property tests of products obtained by changing the J shield foot.

Table 3* Comparative Example Example [3] 50 parts of anhydrous hydrochloride, tetramethylene glycol having OH groups at both ends, 1,4-butylene glycol and adipic acid (molar ratio 0.4:1) .6: 2) Copolymerized adipate 10 with a different average molecular filx7°O
0 parts and 39.5 parts of hexano)ethylene diisocyanate were added, and the mixture was allowed to react at 80°C for 3 hours in a nitrogen gas stream, and then cooled to 30°C.

Next, 10.91 parts of ethylene glycol and 0.01 part of N-ethylmorpholine were added together with 300 parts of N-dimethylformamide, and after holding at 60°C for 5 hours,
0.5 part of +1-butanol was added to stop the chain extension reaction. When the reaction product is reduced to 6%, the solid content is 30% and the viscosity is 1.
A 20.000 cps polymer solution was obtained.

To this polymer solution, 5i02 porous 48 particles having different pore volumes were mixed with methyl alcohol of the same type in advance so that the solid content of 5102 was 25 parts per 100 parts of resin solid content, and methyl ethyl !・
Process and dilute the mixture to a viscosity of 30,000 cp.
sK adjusted.

The treatment solution thus obtained was applied to a 100% polyester fabric (warp 15074B', false twisted yarn, weft 150/48
' False twisting, 2 yarns combined and twisted, warp density 143 yarns/inch, weft yarn density 72 yarns/inch, mesh = i 2 s 29
/door) using a reverse coater to coat 1oof/yt
It was applied at a ratio of f and dried at 120''C for 5 minutes.

Next, a fluorine-based water repellent (3M's Scotchgard I)
C453) The above fabric was immersed in a 4% solution, squeezed with a mangle to a squeezing rate of 80%, dried at 80"C for 10 minutes, and then dried at 17"C.
Dry heat treatment was performed at 0″C for 2 minutes.

Table 4 shows the results of the physical property test of the product. For comparison, 5
I02 Instead of porous particles, the average particle diameter is 0.5'! Table 4 also shows the results of the same treatment as in m1 except that + calcium carbonate was used.

Table 4* Comparative Examples [4] Dimethylpolysiloxane prepolymer with hydrogen and hydroxyl groups at the ends (average degree of polymerization 4o).

O) was dissolved in tetrachlorethylene, solid content 16%,
A polymer solution with a viscosity of 40,000 cps was prepared.

Next, add 0 part of 5102 porous particles (particle size 4/1, total pore volume 0.44 ml/!) I to the same amount of isopropyl alcohol. Mix and stir the polymer m R*
and further 0.5 part of diptyltin dilaure-1.
was added to prepare a treatment solution.

Polyester plain fabric (warp polyester 80/48, weft The above treatment solution was applied to polyester 80d7481 (warp density 106 threads/inch, weft density 96 threads/inch, date s3+7/m) using a knife coater, dried at 120"C for 2 molecules lJl, and then heat treated at 170°C for 1 minute. Table 5 shows the results of the physical property test of the product. In addition, as a comparative example, Table 5 shows the results of performing the same treatment as above without adding 5I02 porous particles.

Table 5 ・1chi Comparative example

Claims (6)

[Claims] (1) A moisture-permeable resin film is formed by applying a resin liquid containing porous particles mainly composed of 5IO2 to textile products, and the porous particles in the resin liquid absorb volatile solvents that are insoluble in the resin. 1. A method for waterproofing textile products, characterized in that the textile product is treated with a water repellent at least one of before and after the formation of a resin film. (2) Porous particles have an average particle diameter of 2 to 50μ and a pore volume of 0
．． Claim No. (1) having 2 to 5 ml/9
) Method described in section. (3) The method according to claim 11 or (2), wherein the porous particles are contained in the resin film at a ratio of 0.5 to 150 parts by weight per 100 parts by weight of the resin solid content. (4) The resin used is a simple substance or copolymer of polyurethane, acrylic copolymer, silicone-based polymer material, vinyl chloride-based polymer material, polysulfonated polyethylene, or The method according to any one of claims (1) to (3), which is a mixture thereof. (5) A water repellent having a perfluoro group. Claims 11 to 4 are silicon-based water repellents having a main component of polysiloxane, water repellents having alkyl/I/groups in the main chain or side chain, or mixtures thereof.
The method described in any of the paragraphs. (6) Claims 1II to 11, wherein the solvent contained in the porous particles is isopropyl alcohol, ethyl alcohol, methyl alcohol, water, or a mixture thereof. (The method described in any of Section 51.