JPH0457970A - Moisture-permeable waterproofing of textile goods - Google Patents

Abstract

PURPOSE:To carry out the subject soft and excellent moisture-permeable waterproofing without reducing air diffusibility and moisture permeability by applying a resin solution containing porous cellulose particles including a resin-insoluble volatile solvent to a textile goods subjected to water repellency treatment, and forming a moisture-permeable resin film. CONSTITUTION:A resin-insoluble volatile solvent (preferable example: isopropyl alcohol) is included in, e.g. a spherical porous cellulose particle composed of a regenerated cellulose in advance and the resultant cellulose particles are mixed in a solution of a polymer resin preferably composed of a polyurethane resin, an acrylic copolymer, etc. The resultant resin solution containing the cellulose particles are applied to the fiber surface of a woven fabric, a nonwoven fabric, etc., composed of a natural fiber, a synthetic fiber, etc., and treated with a fluoro-based water repelling agent. After drying, heat treatment is carried out, thus readily obtain the objective soft and moisture-permeable waterproof textile goods having excellent water repellency and waterproofness without lowering air diffusibility and moisture permeability.

Description

[Detailed Description of the Invention] (Field of Industrial Application) The present invention relates to a waterproof and moisture permeable processing method for textile products, in particular a method for imparting excellent water repellency and waterproofness to textile products without reducing their breathability and moisture permeability. Moreover, it relates to a processing method that imparts a soft texture with a dry touch.

(Prior art and problems to be solved by the invention) Fluorine-based water repellents typified by perfluoroalkyl acrylate are used as a water-repellent treatment method for textile products.

Methods using silicone-based water repellents or zirconium-based water repellents are well known, and waterproofing methods include acrylic resins, polyurethane, latexes such as styrene-butadiene rubber, chlorosulfonated polyethylene, and vinyl chloride-based agents. resin.

A method using resin such as vinyl acetate resin is 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. Because it is necessary to use a large amount of adhesive, 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 regeneration film of urethane resin on a fiber structure is also known as a method for producing moisture permeable waterproof fabric, but wet regeneration requires a regeneration device and a desolvation side.

Not only does it require excessive equipment such as washing equipment, but the resulting product also needs to increase the thickness of the membrane in order to achieve a high level of waterproofness. It is extremely difficult to obtain.

The method disclosed in Japanese Patent Publication No. 62-53632 is to apply a resin solution containing porous particles mainly composed of SiO□, which contains a volatile solvent insoluble in resins and fats, to textile products and further repel them. It is characterized by a water treatment. The purpose of this invention is to industrially advantageously produce products with excellent water repellency and waterproofness without substantially reducing the air permeability and moisture permeability inherent to textile products. There is a problem in that the texture becomes a little hard due to the application of a resin liquid containing porous particles whose main component is Oz.

The purpose of the present invention is to develop an industry that can produce textile products that have extremely excellent water repellency and waterproof properties without deteriorating the texture of textile structures or substantially reducing the breathability and moisture permeability inherent in textile products. The purpose of this invention is to provide a processing method that is advantageous.

(Means and operations for solving the problems) The present invention takes the following configuration to achieve the above object.

That is, a resin liquid containing porous cellulose particles is applied to a textile product to form a moisture-permeable resin film, and the porous particles in the resin liquid contain a volatile solvent that is insoluble in the resin. This is a waterproof and moisture permeable processing method for textile products, which is characterized by treating the textile products with a water repellent agent at least before and after forming a resin film on the textile products.

Hereinafter, the constituent elements of the present invention will be explained in detail.

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 particles are not clogged with resin during the mixing, and the heating during the formation of the resin film pores. Since all of the solvent contained in the porous particles is removed, the pores of the porous particles effectively remain in the resin film, providing the product with excellent air permeability and moisture permeability in a very stable manner.

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 two or more types of fibers, interwoven or cross-knitted fabrics, leather paper, and other porous fiber-containing fabrics. Refers to quality products.

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 can be used, such as a single substance or a copolymer of , or a mixture thereof. Polymeric substances can be suitably used.

As a polyurethane resin, for example, a prepolymer is prepared by reacting an organic diisocyanate with a polyalkylene ether glycol or a polyester having a hydroxyl group at the end, and then polyurethane is produced by an appropriate known method using a chain extender such as a diamine, diol, or polyol. It is made of elastomer. The organic diisocyanates that constitute these polyurethanes include aromatic,
Aliphatic and cycloaliphatic hydrocarbon diisocyanates or mixtures thereof, in particular, for example toluylene-2,
4-diisocyanate, toluylene-26-diisocyanate, diphenylmethane-44'-diisocyanate, 1,5-naphthylene diisocyanate, hexamethylene diisocyanate.

Examples include paraxylene diisocyanate.

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, 1.4-butylene Glycols, such as aliphatic polyalkylene glycols such as propylene glycol, tetramethylene glycol, and hexamethylene glycol, alicyclic glycols such as cyclohexanediol, or aromatic glycols such as xylene diol, and glycols such as succinic acid, adipic acid, sepatic acid, and terephthalic acid. A polycondensate with an organic acid such as an acid, and ethylene glycol as a chain extender.

Examples include 1.4-butylene glycol, hydrazine, ethylenediamine, methylene di-chloroaniline, and the like. 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, dimethylsulfoxide, tetrahydrofuran, tetramethylurea, N,N-dimethylacetamide, dioxane, butyl carbinol, etc. are used alone or in combination. These solvents include ketones such as acetone and methyl ethyl ketone, and water within a range that does not coagulate the polyurethane, for example, 20
It is okay to use them in combination at less than %.

As the acrylic copolymer used in the present invention, any commonly used acrylic copolymer can be used, but for example, a hydroxyl group- or carboxyl group-containing ethylenically unsaturated monomer polymer and a crosslinking agent may be a ketone such as xylene, A solution dissolved in an organic solvent such as toluene or halogenated hydrocarbon is mainly used.

An example of an ethylenically unsaturated monomer polymer containing a hydroxyl group or a carboxyl group is - bottom% formula (1) (wherein R1 is hydrogen or an alkyl group having 1 to 2 carbon atoms, R1
is an alkyl group, an alkyl group, a halogen-substituted alkyl group,
Halogen-substituted aryl group, nitrile group or carbon number 2-1
9 represents an alkoxycarbonyl group, provided that when R3 is a nitrile group, Rq is hydrogen. ) and an ethylenically unsaturated monomer having neither a hydroxyl group nor a carboxyl group, and -bottom% formula% (2) (in the formula, R9 is hydrogen, an alkyl group or a carboxyalkyl group, and R3゜ is hydrogen or carboxyl group, R11 represents hydrogen or a hydroxyalkyl group, and n represents 0 or a positive integer. Easily obtained by scraping. Specific examples of the monomers shown here in bottom (1) include acrylonitrile and alkyl acrylate.

Alkyl methacrylate, styrene, etc. also have the general formula (2
) The monomer shown in ) is acrylic acid.

Ethylenically unsaturated acids such as methacrylic acid, itaconic acid, fumaric acid, maleic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, 3-chloro-2
-Hydroxyalkyl methacrylate, etc., and when polymerizing the monomers represented by formula (1) or (2), two or more of each of them may be used to form a ternary or more multicomponent polymer. Needless to say, yes.

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 containing silicon as the main component. It is a polymeric substance produced by a formula and is produced industrially.

P) Dehydrogenation reaction type C [ls CL CHs
CH3 (b) Dealcoholization reaction type 4 Addition reaction type silicone prepolymer is trichlorethylene, tetrachlorethylene, 1. "1.1- Halogenated hydrocarbon such as trichloroethane, benzene, toluene alone or a mixed solvent thereof with a solid content concentration of 5 to 40% and a viscosity of 3
000~50000cps, Pt, Zn, Sn
, a catalyst containing metals such as Pb is used in combination to form a resin film containing silicon as a main component on the fiber structure.

Other resins used in the present invention are not particularly limited.

The porous cellulose particles contained in such a resin and used in the present invention have a crystal structure consisting essentially of type 1 cellulose, that is, regenerated cellulose. In addition, it has a crystallinity of 5 to 35%, and is not amorphous, but is crystalline as specified by the crystallinity above, and is characterized by being truly spherical porous particles with a uniform particle size distribution. be.

Regarding the method for producing spherical cellulose particles in the present invention, JP-A No. 63-99237, JP-A No. 1-567
Although detailed in the No. 01 publication, the outline thereof will be repeated here. For example, it can be manufactured as follows.

That is, in the first step, coagulated viscose fine particles containing 10 to 100% by weight of cellulose xanthate in terms of cellulose are prepared, and in the second step, the coagulated viscose fine particles are neutralized with acid, and then the third step is carried out. The generated cellulose fine particles are separated from the mother liquor.

The coagulated viscose fine particles used in the first step are obtained by first preparing (A) an alkaline polymer aqueous solution of cellulose xanthate and the other first water-soluble polymer compound, and (B) preparing the above alkaline mixing an aqueous polymer solution and a second water-soluble anionic polymer compound to produce a fine particle dispersion of the aqueous alkaline polymer solution; (C) heating the dispersion; or heating the dispersion; The cellulose xanthate in the dispersion can be solidified as fine particles containing the first water-soluble polymer compound by mixing the cellulose xanthate with the coagulated side of the cellulose xanthate.

The first water-soluble polymer compound used in the process includes, for example, polyethylene glycol and its derivatives, and the second water-soluble polymer compound includes, for example, sodium polyacrylate, sodium polystyrene-sulfonate, etc. etc.

The particle diameter of the spherical cellulose used in the present invention is usually 5 to 30 ttm on average.

The spherical cellulose particles thus formed absorb moisture to an appropriate degree and impart lubricity to the surface of the coating film. Such lubricity suppresses the slimy feeling and creates a dry and soft feel without stickiness.

The spherical cellulose particles blended in the present invention are produced in the above manufacturing method by liberating the fine particles while encapsulating the first water-soluble polymer compound added in advance to the viscose liquid and eluting the encapsulated compound. It is characterized by having fine particles with a microporous structure, which further increases water absorption and moisture permeability. Furthermore, since the particle shape is perfectly spherical and the particle size distribution is uniform, the dispersion state is good when blended into synthetic polymers, improving fluidity and preventing particle aggregation. In addition to improvements in texture,
It is also possible to maintain the stability of luster and luster.

In the present invention, such porous cellulose particles are made to contain a specific solvent in advance and blended into the resin solution.
, preferably adjusted to 100 to 100.0OOcps, and the amount of porous particles blended is resin solid content 10
0 parts by weight, 10 to 100 parts by weight is better. If the amount is less than 10 parts by weight, the desired effect of improving the texture cannot be obtained, and if it is more than 100 parts by weight, the resin film It is not preferable because it has poor physical properties and poor flexibility in terms of feel and quality of the coated fabric.

The resin-insoluble solvent may be applied to the porous particles as long as the porous particles are wetted with the resin-insoluble solvent and the pores, that is, the cavities are filled with the solvent, and a dipping method or a spray method may be used. can. Examples of resin-insoluble solvents include water,
Methyl alcohol, ethyl alcohol, and isopropyl alcohol are preferably used, and isopropyl alcohol is particularly preferred.

Application methods such as floating knife coater, knife over roll coater, reverse roll coater/roll doctor coater, gravure roll coater, and kiss roll coater can be used to coat textile products with resin liquid. A porous resin film can be obtained.

It is necessary for textile products to be treated with a water repellent before forming a resin film, or to be treated with a water repellent after forming a resin film. Water repellents, silicone-based water repellents containing polysiloxane as a main component, water repellents having an alkyl group in the main chain or side chain, or mixtures thereof are included. However, it is not limited to these.

For example, water repellents having a barfluor group include perfluoroalkyl acrylates, perfluoroalkyl methacrylates, barfluoroalkyl ethyl acrylates, barfluoromonocarboxylic acid chromium complex salts, barfluoromonocarboxylic acid chromium complexes, and Fluoroalkyl acrylamide, barfluoroalkyl vinyl ether monomers, or their acrylic esters, methacrylic esters, styrene, butadiene, acrylamide.

Vinyl acetate, hydroxyalkyl acrylate.

Examples include compounds having a barfluoroalkyl group, such as copolymers with ethylenically unsaturated monomers such as glycidyl methacrylate and acrylonitrile.

Such water repellent agents can also be used in combination with other components, and preferred examples of such components include -
Ship bottom% formula% (In the formula, R+ is hydrogen or an alkyl group having 1 to 3 carbon atoms, R
(t represents an alkyl group having 11 to 20 carbon atoms) and the general R8 CH! = CRs / COOR, -N \ R2 (wherein R3 is hydrogen or an alkyl group having 1 to 3 carbon atoms, R4
is an alkylene group having 1 to 5 carbon atoms, and R1 and R6 are an alkyl group having 1 to 5 carbon atoms. Examples include organic acid salts of ethylenically unsaturated acid ester polymers.

The water-repellent treated side obtained by mixing the above-mentioned water repellent with a polymer having an active group that can partially cationize in its side chain has higher water repellency and waterproof properties than when the water repellent is used alone. will further increase.

These water repellents or water repellent treatment agents are applied to the fiber products by an appropriate method such as dipping, spraying, or coating, so that the solid content loss usually ranges from 0.1 to 0.1.
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, Hontflu dryer, pin tenter, etc.
Dry heat treatment is performed at 40 to 180° C. for 10 seconds to 10 minutes, preferably 30 seconds to 2 minutes.

(Example) The present invention will be specifically described below with reference to Examples.

In addition, "parts" in the examples represent "parts by weight", and the moisture permeability and water pressure resistance are in accordance with JIS-L-1099゜JIS-L-1.
092 (Method A).

<Example 1> A copolymer consisting of ethyl acrylate/butyl acrylate/acrylonitrile/2-hydroxyethyl methacrylate (weight ratio 20:68:10:2) was dissolved in tetrachlorethylene, solid content 12%, viscosity 50, 0OO
Prepare a solution of cps (measured with a BH type viscometer rotor N16.1Orpm) and add 10 parts of silicone oil and 2.4.6-) lipoxymethylaminol to 100 parts of the solution.

3.5-) 3% riazine, tetrachlorethylene solution 5
A resin solution was prepared by mixing the following parts.

Next, 50 parts of granular cellulose having an average particle diameter of 30 μm and a particle size distribution of 120 to 40 μm produced by the method shown in Example 1 of JP-A No. 63-99237 and 50 parts of isopropyl alcohol are mixed. A granular cellulose solution was prepared.

A mixture of the above resin liquid and a granular cellulose solution in the proportions shown in Table 1, and a comparative example in which a porous silica liquid (silica gel particles with a particle size of about 10 μm) was used instead of the above resin liquid alone and the granular cellulose solution. A mixture of 50 parts of porous particles with an average particle diameter of 10μ and a pore volume of 1.5 ml/g, which have a three-dimensional mesh structure due to siloxane bonds, and 50 parts of isopropyl alcohol. , were diluted by adding tetrachlorethylene to prepare a treatment liquid with a viscosity of 30,000 cps.

In advance, use fluorine-based water purifier (Asahi Guard manufactured by Asahi Glass Co., Ltd.).
100% nylon plain fabric (warp 70d/36f, weft 70d/36f, density warp 116/inch) padded with AG730) 5% solution at 30% squeezing rate and dried at 120°C for 5 minutes.

The above treatment liquid was applied to the weft (94 threads/inch, basis weight 70 g/m") using a floating knife coater, and 1
After drying at 20°C for 2 minutes, dry heat treatment was performed at 170°C for 2 minutes using a pin tenter. The results of the product physical property tests are shown in Table 2.

Table 1 The coated fabric containing granular cellulose had appropriate moisture permeability and waterproofness, had a soft and good feel, and was dry to the touch without stickiness.

<Example 2> After preparing a resin liquid and a cellulose liquid in the same manner as in Example 1, a cellulose-containing resin liquid was prepared.

The obtained cellulose-containing resin liquid was applied to a polyester plain fabric (
Warp polyester 80d/48f, weft polyester 8
0d/48f, warp density 106/inch, weft density 96
After applying it with a floating knife coater to a book/inch2 fabric weight 83 g/m t, it was dried at 120°C for 2 minutes, and then a fluorine-based water repellent (Asahi Guard manufactured by Asahi Glass Co., Ltd.) was coated with a floating knife coater.
AG-710) 3% liquid was padded with a mangle squeezing rate of 25%, dried at 120°C for 2 minutes, and then heat-treated at 170°C for 1 minute using a tenter.

At the same time, as a comparative example, the above method was carried out without mixing granular cellulose. The physical property test results of products obtained by varying the amount of resin adhesion are shown in Table 3 (Effects of the Invention) According to the present invention, excellent repellency can be achieved without reducing the air permeability and 13tW properties of textile products. It becomes possible to provide an economically efficient product that is water-based and waterproof, has a dry touch and soft texture, and provides an extremely useful method for waterproofing and breathable processing of textile products. .

Claims (1)

[Claims] (1) A moisture-permeable resin film is formed by coating a textile product with a resin solution containing porous cellulose particles, and the porous particles in the resin solution contain a volatile solvent that is insoluble in the resin. and a method for waterproofing and moisture permeable textile products, which comprises treating the textile products with a water repellent at least before and after forming a resin film.