JPS6247993B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for water-repellent and waterproofing textile products. A waterproofing method in which a synthetic resin solution is applied and dried on a textile product to form a continuous film on the surface is well known. Textile products that have been subjected to such waterproofing are usually treated with a water-repellent finish to further impart water-repellent properties. Not only is this method a complicated two-step process, but depending on the combination of waterproofing synthetic resin and water-repellent agent used, waterproofing and water-repellent finishing cannot be performed in succession. It had the disadvantage of poor productivity because it required more than two days to process. In order to solve this problem, attempts have been made to provide water repellency as well as waterproofing by mixing a water repellent agent into a synthetic resin solution for waterproofing, applying the mixture, and drying the solution. However, wax-based and fluorine-based resins that have been conventionally used as water-repellent agents have drawbacks such as not being compatible with waterproof synthetic resins, resulting in a hard texture, and lack of water repellency on the back side of the synthetic resin coating. be. On the other hand, organopolysiloxanes have traditionally been widely used to provide water repellency, give a slimy feel, and soften the texture. ; Dibutyltin acetate, dibutyltin dilaurate, dibutyltin oxide; Alkyl titanates such as butyl titanate; Naphthenic acid salts of zinc, tin, zirconium, iron, lead, cobalt, etc.; Used in combination with catalysts such as zinc zirconium salts of formic acid or acetic acid It has been. However, when organopolysiloxane is used as a waterproofing water repellent in the same bath, the above-mentioned conventional catalysts may not be compatible with the waterproofing synthetic resin solution, or even if they are compatible, the pot life of the synthetic resin compound solution may be extremely short. Either it is short or it does not show any water repellent effect, etc.
Favorable results were not obtained. The present inventors have completed the present invention as a result of extensive research into processing agents and catalysts that do not have the drawbacks of conventional methods for blending organopolysiloxane into a waterproofing synthetic resin solution and applying water-repellent and waterproof finishing. It is ivy. That is, the present invention provides a water-repellent waterproofing method in which organopolysiloxane is blended into a waterproofing synthetic resin solvent solution, applied onto a textile product, and dried to impart waterproofness and water repellency at the same time in one step.
As a catalyst for the above-mentioned organopolysiloxane, a dialkyltin dichloride whose alkyl group has 1 to 10 carbon atoms is added to the above-mentioned organopolysiloxane.
It relates to a processing method characterized by using 0.01 to 50% by weight. In the processing method of the present invention, the compatibility between the catalyst and the synthetic resin solution is good, the pot life of the compounded liquid is long, and furthermore, by coating and drying on the textile product, it provides waterproofness to the textile product and at the same time Excellent water repellency can be imparted not only to the coated surface but also to the coated back surface. The waterproofing synthetic resin referred to in the present invention may be any resin as long as it forms a continuous film on textile products, but vinyl resins and urthane resins are commonly used. Examples of vinyl resins include acrylic acid, methacrylic acid, acrylic acid alkyl esters, methacrylic acid alkyl esters, acrylonitrile, styrene, vinyl acetate, vinyl chloride, vinylidene chloride, vinylpyrrolidone, acrylamides, ethylene, propylene, butadiene, etc. Examples include homopolymers or copolymers of monomers having a polymerizable carbon-carbon unsaturated bond in the molecule, and modified vinyl polymers such as chlorosulfonated polyethylene and chlorinated polyethylene.
Urethane resin is obtained by reacting a compound having one or more hydroxyl groups at the end or a compound having one or more amino groups with a compound having one or more isocyanate groups at the end, and contains a urethane group or urea group in the molecule. Refers to a polymer having a group. Of course, such synthetic resins can be used alone or in combination, and also include those modified for some purpose. The organic solvent referred to in the present invention may be any solvent as long as it dissolves the waterproof synthetic resin well, such as hydrocarbons such as toluene, xylene, and turpentine, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, Examples include esters such as butyl acetate, ethers such as dioxane and tetrahydrofuran, hydrogen chloride such as 1,1,1-trichloroethane and trichlene, dimethylformamide, and N-methylpyrrolidone. The organopolysiloxane referred to in the present invention may be any organopolysiloxane as long as it is compatible with the waterproof synthetic resin and exhibits a water-repellent effect, but generally the following general formula (),
() or those indicated by () are used. In the formula, R ₁ is methyl, phenyl, methoxy, or hydroxy group, R ₂ is A, methyl or phenyl group, and R ₃ is methyl or phenyl group. A is an alkyl group having 1 to 7 carbon atoms or a hydrodiene having a functional group such as epoxy, hydroxy, alkoxy, amino, or carboxy at the end. 1, m, and n are positive integers representing repeating units, and 1 and m+n are such numbers as to give the organopolysiloxane a viscosity of 10 to 100,000 centistokes. In this case, the concentration of the functional group is such that its equivalent weight is 40 to 10,000. In the present invention, the amount of organopolysiloxane mixed in the waterproof synthetic resin is 1 to 1 in solid content ratio.
100% by weight is preferred. If it is less than this, the desired water-repellent effect cannot be obtained, while if it exceeds 100%, it not only impairs economic efficiency but also impairs the adhesion between the waterproof synthetic resin and the textile product, which is undesirable. In the dialkyltin dichloride according to the present invention, as long as the alkyl group has 1 to 10 carbon atoms, the alkyl group may be linear, branched, or cyclic, and other atoms may be present between the carbon atoms. It doesn't matter if someone intervenes. When the number of carbon atoms in the alkyl group is 11 or more, the effect is weak and impractical. The blending amount of dialkyltin dichloride in organopolysiloxane is preferably 0.01 to 50% by weight in terms of solid content; if it is less than this, no water repellent effect can be obtained, and on the other hand, 50% by weight.
If it exceeds this, it is unfavorable in terms of co-usability with a crosslinking agent and economical efficiency. Of course, in addition to the alkyltin dichloride, other organopolysiloxane catalysts may be used in combination as long as there are no problems with the pot life of the compounded liquid or the compatibility with the synthetic resin. In the water-repellent and waterproofing solution of the present invention, cross-linking agents for forming a strong film, diluting solvents for viscosity adjustment, softeners, anti-blocking agents, pigments, and dyes may impair the effects of the present invention. There is nothing wrong with mixing it to the extent that it does not. Furthermore, there are no restrictions on the method of applying the liquid mixture onto the textile product or the method of drying it. Generally, roll coating or doctor knife coating is used, and drying must be sufficient to evaporate the organic solvent in the compounded solution and, in some cases, to promote crosslinking of the synthetic resin. However, from an economical point of view, the temperature is generally 50 to 200°C without damaging textile products. The textile products referred to in the present invention include woven fabrics, knitted fabrics, felts, nonwoven fabrics, paper, etc. made of natural fibers, synthetic fibers, and artificial fibers alone or in combination, as well as products made from these materials. Examples of the present invention are shown below. All parts herein are parts by weight. Water pressure resistance was measured using a chopper type water pressure tester according to JIS-L-1004, and water repellency was measured using JIS-L-1004.
-Measured by spray method according to L-1004. Examples 1 to 5, Comparative Examples 1 to 3 Butyl acrylate 83 parts, acrylonitrile 15
1 part of acrylic acid, and 1 part of β-hydroxyethyl methacrylate were reacted in toluene to obtain a synthetic resin solution A having a resin concentration of 20% and a viscosity of 30,000 cps (25°C). On the other hand, 1 mole of trimethylolpropane and 3 moles of 2.6-tolylene diisocyanate were subjected to an addition reaction in ethyl acetate to obtain a crosslinking agent with a resin concentration of 75%. These synthetic resin solutions, methylhydrodiene polysiloxane and alkyl dichloride were mixed as shown in Table 1, coated on 70 denier nylon taffeta with a doctor knife, and heated at 80°C for 30 seconds.
It was further dried at 160°C for 20 seconds, and after aging for 3 days indoors at 20°C and 65% relative humidity, the physical properties were measured.
As comparative examples, the results are shown in Table 1, including examples in which no catalyst was used at all and examples in which only other catalysts were used.

[Table] Examples 6 to 9, Comparative Example 4 ≪1・4- having a hydroxyl group at the end with a molecular weight of 2000
A polyester diol of butanediol and adipic acid≫ is reacted with ethylene glycol and methylene bis-4,4'-diphenyl isocyanate in dimethylformamide to achieve a resin concentration of
Urethane resin solution B with a viscosity of 30% and a viscosity of 50,000 cps (25°C) was obtained. Various organopolysiloxanes and alkyltin dichlorides were blended with this as shown in Table 2, and the mixture was applied onto a Tetron single-line blended fabric using a doctor knife, dried at 120°C for 1 minute, and aged under the same conditions as in the previous example. , the physical properties were measured. As a comparative example, an example in which no catalyst was used is also shown.

[Table] Example 10 Ethylene-vinyl acetate copolymer was dissolved in toluene, resin solid content was 12%, viscosity was
Synthetic resin C of 30,000 cps (25°C) was obtained. 4 parts of methylhydrodiene polysiloxane to 100 parts of this resin.
1 part, 4 parts of silanol-modified dimethylpolysiloxane, and 4 parts of dimethylpolysiloxane, 0.002 part of dibutyltin dichloride was added, coated on Tetron taffeta with a doctor knife, and heated at 100°C.
Dry for 1 minute. After aging under the same conditions as in Example 1, physical properties were measured. As a result, the coating amount was 3.0 g/m ² (solid content), the water pressure was 450 mm H ₂ O, and the water repellency was 90 on the coated side and 90 on the non-coated side.
It was 90.

Claims (1)

[Claims] 1 In a water-repellent waterproofing method in which organopolysiloxane is blended into an organic solvent solution of a synthetic resin and applied onto a textile product and dried, it imparts waterproofness and water repellency at the same time in one step. A processing method characterized in that 0.01 to 50% by weight of dialkyltin dichloride having an alkyl group having 1 to 10 carbon atoms is used as a catalyst for the siloxane, based on the organopolysiloxane.