JPS636676B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a water- and oil-repellent finishing method, particularly to a water- and oil-repellent finishing method for textile products that improves the deterioration of water- and oil-repellent performance after dry cleaning and washing. Currently, the mainstream of water and oil repellent finishing is a processing method in which a fluoroalkyl group-containing compound with a unique low surface energy is attached to textile products to repel not only water-based stains but also oil-based stains. It's on. Such processing methods are often carried out using an organic solvent solution or an aqueous dispersion of a fluoroalkyl group-containing compound that can serve as a water and oil repellent, but this compound may be washed off from the treated textile product, or If it is dissolved out, water and oil repellency will not be maintained. Particularly when dry cleaning textile products, dry cleaning solvents have recently been improved from kerosene to perchloroethylene, which has a strong dissolving power, and then to Freon (chlorofluoroethane), which is a water- and oil-repellent agent that can be used at the same time as cleaning dirt. Also, after dry cleaning, there is almost no water or oil repellency, and there is no dirt repellency. As a result of intensive research in order to improve this drawback, the present inventor has found that a textile product treated by blending a polyfunctional isocyanate with a fluoroalkyl group-containing compound that can be used as a water and oil repellent has significantly improved this drawback, and at the same time The present invention was completed based on the discovery that the various characteristics of the process were not impaired in any way. That is, the present invention provides water- and oil-repellent treatment of textile products with a fluoroalkyl group-containing compound having water and oil repellency, in which a polyfunctional isocyanate is added to 100 parts by weight (hereinafter simply referred to as "parts") of the fluoroalkyl group-containing compound. It relates to a water- and oil-repellent processing method for textile products, characterized by blending 5 to 300 parts of. The fluoroalkyl group-containing compound having water and oil repellency used in the present invention has a fluoroalkyl group having 3 to 20 carbon atoms, preferably 6 to 12 carbon atoms, and is water-insoluble (1 at 25°C). It is a non-adhesive compound having a main transition temperature, that is, a melting point, a glass transition point, or a softening point of 20° C. or higher, and a molecular weight of about 700 to about 200,000. Examples of such organic fluorine compounds are as follows. (1) A homopolymer of a vinyl monomer having a fluoroalkyl group having 3 to 20 carbon atoms or a copolymer with a vinyl monomer that does not contain fluorine. Examples of vinyl monomers having a fluoroalkyl group include the following. C ₇ F ₁₅ CH ₂ OCOCH=CH ₂ C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOCH=CH ₂ C ₈ F ₁₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOC (CH ₃ )= _CH2 C ₇ F ₁₅ CON (C ₂ H ₅ ) CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ OCH = CH ₂ C ₈ F ₁₇ (CH ₂ ) ₁₁ OCOC (CH ₃ ) = CH ₂ (CF ₃ ) ₂ CFO (CH ₂ ) ₅ OCOCH=CH ₂ C ₈ F ₁₇ SO ₂ N (CH ₂ CH ₂ OCOCH=CH ₂ ) ₂ C ₈ F ₁₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₁₀ COOCH ₂ CH=CH ₂ C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) CH ₂ CH ₂ OCOCH=CHCOOC ₄ H ₉ C ₆ F ₁₃ SO ₂ N(CH ₃ )CH ₂ CH ₂ OCOCH=CH ₂ C ₈ F ₁₇ SO ₂ NHCH ₂ CH ₂ SO ₂ CH=CH ₂ Fluorine Examples of vinyl monomers that do not include ethylene, propylene, butylene, butadiene, isoprene, chloroprene, vinyl chloride, vinylidene chloride, styrene, alcohols or alkyl amines of (meth)acrylic acid (all have 20 carbon atoms or less) Examples include esters or amides of , diacetone acrylamide, N-methylol acrylamide, acrylonitrile, acrylamide, vinyl acetate, and vinyl compounds having a siloxane bond. Any of the monomers can also be used in combination. These homopolymers or copolymers can be produced by known methods of vinyl polymerization, and for example, solution polymerization and emulsion polymerization using a radical initiator are common. The molecular weight of the polymer can be adjusted within a preferred range by adjusting the concentration of the initiator and the type and concentration of the chain transfer agent, but is generally preferably 3000 or more. (2) A (poly)ester of a monohydric or polyhydric alcohol containing a fluoroalkyl group having 3 to 20 carbon atoms and an optionally fluorinated monohydric or polyhydric carboxylic acid. A (poly)ester of an optionally fluorinated monohydric or polyhydric alcohol and a monohydric or polyhydric carboxylic acid having a fluoroalkyl group having 3 to 20 carbon atoms. Examples of components used in this case are listed below. C ₉ F ₁₉ CH ₂ CH ₂ OH C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OH C ₈ F ₁₇ SO ₂ N (CH ₂ CH ₂ OH) ₂ C ₈ F ₁₇ SO ₂ N( C ₂ H ₅ )CH ₂ CH(OH)CH ₂ OH C ₇ F ₁₅ COOH C ₈ F ₁₇ SO ₂ N(C ₃ H ₇ )CH ₂ COOH Benzoic acid, adipic acid, sebacic acid, phthalic acid, maleic acid, trimellitic acid ethylene glycol monomethyl ether, ethylene glycol, propylene glycol, diethylene glycol, glycerin, polypropylene glycol, 2-ethylhexanol, stearyl alcohol, the (poly)ester has a molecular weight is preferably 1000 or more. (3) Monohydric or polyhydric alcohol having a fluoroalkyl group having 3 to 20 carbon atoms (in some cases, fluorine-free monohydric or polyhydric alcohol may be mixed) and monohydric or polyhydric isocyanate. , such as phenyl isocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate,
(Poly)urethane with polymethylene polyphenyl isocyanate. The (poly)urethane preferably has a molecular weight of 700 or more. (4) Epoxy compounds having a fluoroalkyl group having 3 to 20 carbon atoms, e.g. Homopolymers of and preferably copolymers with fluorine-free epoxy compounds such as propylene oxide and epichlorohydrin. The molecular weight of such a polymer is preferably 3000 or more. Therefore, the fluoroalkyl group-containing compound used in the present invention is prepared by making a diluted solution (solution or dispersion) with a concentration of 0.5% by weight, and adding 100% of polyester
Soak processed yarn fabric and wet pick up 100%
Squeeze until the diluent has adhered to the same weight as the fabric.
After drying at 170℃ for 3 minutes, the treated fabric was
When measured by AATCC Test Method 118-1966 method, it should have an oil repellency of 3 or more, that is, n-hexadecane does not penetrate into the fabric, and the organic fluorine compound should
It should exhibit water repellency of 50 or higher when measured using the AATCC Test Method 22-1971 spray method, meaning that water does not bleed onto the back side of the fabric. Next, the polyfunctional isocyanate used in the present invention may be any organic compound containing two or more isocyanate functional groups in the molecule, examples of which include 2,4-, 2,6-tolylene diisocyanate, Trimethylolpropane tolylene diisocyanate adduct, trimethylolethane tolylene diisocyanate adduct, glycerin tolylene diisocyanate adduct, triphenylmethane triisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, 4,4'-
These include dicyclohexylmethane diisocyanate and mixtures thereof. Furthermore, isocyanate-functional group-terminated prepolymers which have been prepolymerized with a polyol and an excess of polyisocyanate are also preferably used. The isocyanate functionality of the compound may be intact or stabilized. Stabilizers include phenols, ε-caprolactam, malonic acid diethyl ester, methyl ethyl ketoxime, sodium bisulfite, and imidazoles, which are stabilized to the extent that they dissociate upon heating and regenerate active isocyanate groups. Polyfunctional isocyanates are often blended in the form of organic solvent solutions or aqueous dispersions. The blending ratio of the fluoroalkyl group-containing compound having water and oil repellency and the polyfunctional isocyanate is
The latter 5 to 300 copies per 100 copies is appropriate. This is because if the amount is more than 300 parts, the water and oil repellency will be insufficient, and if it is less than 5 parts, the dry cleaning resistance will be poor. The polyfunctional isocyanate may be added to the water and oil repellent in advance, or may be added to the processing bath during processing. In addition to polyfunctional isocyanates, antistatic agents, aminoplast resins, and acrylic polymers are used to soften, prevent static, improve water and oil repellency, and improve durability against home washing. , natural wax, silicone resin, etc. may be added to the extent that the effects of the present invention are not impaired. The water and oil repellent finishing of the present invention can be carried out by spraying, coating, etc. in addition to the dipping method. Target textile products include cotton, silk,
Natural fiber fabrics such as wool, linen, rayon, synthetic fiber fabrics such as nylon, vinylon, polyester, acrylic, cloth, cloth products, knitted fabrics, non-woven fabrics, clothing, leather, synthetic leather, leather products, paper, paper products, etc. Can be mentioned. Textile products treated with this method have improved durability after dry cleaning, but not only that, but also improved durability after washing with water at home and improved texture after processing. There are also some surprising effects, such as making it more firm. Examples and comparative examples will be given to explain the present invention in more detail. Examples 1 _to 4, Comparative Example 1 _C8F17SO2N ( _{CH3 ) CH2CH2OCOC} as a _fluoroalkyl group-containing compound having water and oil repellency
(CH ₃ ) = 70 parts of CH ₂ and stearyl methacrylate
30 parts of 1,1,1-trichloroethane was dissolved in 896 parts of 1,1,1-trichloroethane, 1 part of azobisisobutyronitrile as a polymerization initiator and 3 parts of lauryl mercaptan as a polymerization modifier were added, and the mixture was stirred at 80°C for 4 hours. Copolymer solution with a molecular weight of approximately 20,000 (polymer concentration 10%, F
-1) was obtained. Table 1 for this drug, polyfunctional isocyanate and 1,1,1-trichloroethane
Table 1 shows the results of preparing a processing bath and processing it into nylon taffeta. From this result as well, the dry cleaning resistance performance of using polyisocyanate in combination is clear. Test method Processing method: Immersion squeezing Squeezing ratio: 90% (Table-1), 100 (Table-2) Drying conditions: (Table-1) 160℃ x 1 minute (Table-2) 100℃ x 2 minutes (pre-drying ) 160℃ x 2 minutes (curing) Water repellency: AATCC Test: Method 22-1971
Spray rating method oil repellency: AATCC Test Method 118-1966
Hydrocarbon resistance method dry cleaning conditions: Mix the processed fabric with 30 times its weight of perchloren and stir in a rounder meter at room temperature for 30 minutes. After air drying at 140℃
Iron for 20 seconds. 3-time dry cleaning means that the above operation is repeated three times.

【table】

[Table] Examples 5 to 7, Comparative Examples 3 and 4 C ₈ F ₁₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOCH as a fluoroalkyl group-containing compound having water and oil repellency
= 85 parts of CH ₂ , 10 parts of 2-ethylhexyl methacrylate, 5 parts of N-methylolacrylamide,
A dispersion (polymer concentration 20%, referred to as F-2) obtained by emulsion polymerization with 2 parts of octadecyldimethylamine acetate and 5 parts of polyethylene oxide nonyl phenyl ether [HLB20] was used. As a polyfunctional isocyanate, 1,6-hexanediol adipate (number average molecular weight 3000)
A dispersion (active ingredient concentration 20%, referred to as P-1) in which 100 parts of an isocyanate functional group-terminated prepolymer called tolylene diisocyanate adduct (isocyanate groups are blocked with methyl ethyl ketoxime) is emulsified with 5 parts of octadecyldimethylamine acetate is prepared. used. Using both together, polyester/
Table 2 shows the results of processing into a cotton (65/35) blend (poplin).

[Table] Example 8 C ₈ F ₁₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOCH=CH ₂
70 parts and 30 parts of stearyl acrylate in 1,
After dissolving in 900 parts of 1,1-trichloroethane, 1.0 part of azobisisobutyronitrile and 3 parts of lauryl mercaptan were added, and a polymerization reaction was carried out with stirring at 80°C for 4 hours to obtain a molecular weight of approximately 20000
A solution of copolymer (polymer concentration 10%; F-3
) was obtained. Next, a processing bath was prepared with the composition shown in Table 3, and processed into nylon taffeta in the same manner as in Examples 1 to 4. The results are summarized in the same table. The various performance evaluation tests were conducted in the following manner. Test method The drying conditions were 160℃ for 1 minute, and all other water repellency, oil repellency, and dry cleaning conditions were the same as in Examples 1 to 4. Only the washing resistance test was performed as follows. I used a method like this. Washing conditions: 40℃ bath containing 0.1% neutral detergent
The test piece was placed in a bath with a bath ratio of 1:30 and washed for 5 minutes, then dehydrated for 4 minutes, dried, and then ironed at 140℃ for 20 seconds. The washing resistance was tested by repeating this cycle 5 times in total.

【table】

【table】

[Table] As is clear from the results, the processed fiber products obtained according to the method of the present invention have excellent durability, and have improved not only dry cleaning resistance but also washing resistance. It is known that

Claims (1)

[Claims] 1. When performing water and oil repellent treatment on textile products with a fluoroalkyl group-containing compound having water and oil repellency, 5 to 300 parts by weight of a polyfunctional isocyanate is blended to 100 parts by weight of the fluoroalkyl group-containing compound. Water and oil repellent processing method for textile products.