JPS581232B2 - Water- and oil-repellent processing method for textile fabric with improved color fastness to rubbing - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water- and oil-repellent finishing method for dyed textile fabrics, and in particular, for pre-dyed textile fabrics, a fluoroalkyl group-containing compound having water and oil repellency is added to a functional group-containing polysiloxane. The present invention relates to a water- and oil-repellent finishing method with improved color fastness to rubbing, which is used in combination with

So-called water- and oil-repellent finishing, which attempts to repel not only water-based stains but also oil-based stains, is possible only by attaching a fluoroalkyl group-containing compound with a unique low surface energy to the base material. Nowadays, water- and oil-repellent treatments using fluoroalkyl group-containing compounds account for the majority of water-repellent treatments.

Such processing is often carried out using an organic solvent solution or an aqueous dispersion of a fluoroalkyl group-containing compound that can be used as a water and oil repellent.

Among these, in processing using an organic solvent solution, a solvent with strong dissolving power is often used because the solubility of the fluoroalkyl group-containing compound itself is low.

On the other hand, in processing with an aqueous dispersion, the compound can only be made into a stable dispersion by emulsifying it with a fairly large amount of emulsifier, so that a fairly large amount of emulsifier is deposited on the fibers.

In addition, in water- and oil-repellent finishing using such fluoroalkyl group-containing compounds, sufficient performance is exhibited only after the compounds are thermally oriented on the fibers. The process involves heating the liquid to a high temperature of 130°C or higher.

Due to these various points, when dyed fiber cloth is treated with a fluoroalkyl group-containing compound to make it water- and oil-repellent, the dye may be eluted by the above-mentioned solvents or emulsifiers, or
Currently, as a result of sublimation and embossment during baking, when the processed fabric comes into contact with other objects, the contact objects are contaminated, which means that the color fastness to rubbing is reduced. be.

However, the present inventors have conducted intensive studies on a processing method that does not have the above-mentioned drawbacks while maintaining the high water- and oil-repellent properties of fluoroalkyl group-containing compounds, and as a result, they have arrived at the present invention.

That is, the present invention is characterized in that a dyed fiber cloth is treated using a composition of a fluoroalkyl group-containing compound having water and oil repellency and a polysiloxane containing an epoxy group, a hydroxy group, an amine group, or a carboxyl group. The present invention provides a water- and oil-repellent treatment for dyed fabrics with improved color fastness to rubbing.

The fluoroalkyl group-containing compound having water and oil repellency used in the present invention refers to 3 to 20, preferably 6 to 1 fluoroalkyl group-containing compounds.
It has a fluoroalkyl group having 2 carbon atoms, is water-insoluble (less than 1% by weight at 25°C), has a main transition temperature (melting point, glass transition point, or softening point) of 20°C or higher, and has a molecular weight of about 700 to It refers to about 200,000 non-stick compounds.

Examples of such organic fluorine compounds are as follows.

(J) A homopolymer of a vinyl monomer having a fluoroalkyl group having 3 to 20 carbon atoms, and a copolymer with a vinyl monomer that does not yet contain fluorine.

Examples of vinyl monomers having a fluoroalkyl group include the following.

Examples of fluorine-free vinyl monomers include ethylene, fluoropyrene, butylene, butadiene, isoprene, chloroprene, vinyl chloride, vinylidene chloride, styrene,
Examples include esters or amides of (meth)acrylic acid with alcohols or alkyl amines (all having 20 or less carbon atoms), diacetone acrylamide, N-methylolacrylamide, acrylonitrile, acrylamide, vinyl acetate, and vinyl compounds with siloxane bonds. .

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 to a preferable range depending on the concentration of the initiator and the type and concentration of the chain transfer agent, but it is generally 3000.
The above is preferable.

(2) (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 -hydric 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.

Benzoic acid, adipic acid, sebacic acid, phthalic acid, maleic acid, trimellitic acid, ethylene glycol monomethyl ether, ethylene glycol, propylene glycol, diethylene glycol, chrycerin, polypropylene glycol, 2-ethylhexanol, stearyl alcohol, the (poly) The molecular weight of the ester is preferably 1000 or more.

3) a monohydric or polyhydric alcohol having a fluoroalkyl group having 3 to 20 carbon atoms (in some cases, a fluorine-free monohydric or polyhydric alcohol may be mixed) and a monohydric or polyhydric isocyanate; Examples (Poly)urethanes with ephenyl isocyanate, tolylene diinocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, polymethylene polyphenyl isocyanate.

The (poly)urethane preferably has a molecular weight of 700 or more.

(4) an epoxy compound having a fluoroalkyl group having 3 to 20 carbon atoms, such as a homopolymer and preferably propylene oxide;
Copolymer with fluorine-free epoxy compounds such as 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 preparing a diluted solution (solution or dispersion) with a concentration of 0.5% by weight, dipping a 100% polyester textured yarn fabric in this, and picking up the fluoroalkyl group-containing compound by wet-to-weight pickup. After squeezing to 100% (equal weight of the diluent attached to the fabric) and drying at 170°C for 3 minutes, the treated fabric was tested in the AATCC Test.
When measured using Method 118-1966, 3
In other words, the organic fluorine compound should have such oil repellency that n-hexadecane does not penetrate into the fabric, and the organic fluorine compound should be able to pass through the AATCC TestMet.
hod2 2-] 9 7 ] It should exhibit water repellency of 50 or more when measured by a spray method, that is, water does not ooze out to the back side of the fabric.

On the other hand, the epoxy group, hydroxy group used in the present invention,
Polysiloxane having an amino group or a carboxyl group is defined by the following general formulas: , R3 is a methyl group or phenyl group, A is an alkylene group having 1 to 5 carbon atoms or a carbon number 6 to or carboxy group.

Furthermore, d, m, and n are positive integers representing the number of repeating units, and l or m+n is 10 to 100,000, respectively.
The number of repeating units that should give the polysiloxane a viscosity of centistokes, and 30 to 10
It shall mean a number that simultaneously satisfies the functional group equivalent of 000.

etc.

Among these, those having characteristically functional groups in their side chains are recommended.

Although it is currently unclear why only this particular compound among the many polysiloxanes satisfies the purpose of the present invention, when placed under thermal conditions, It is presumed that this is the result of the specific polysiloxane flowing to the fiber surface or a certain position of the fluoroalkyl-containing compound, and then being oriented via the functional group in question to regulate the flow.

Even when compared with dimethylpolysiloxane, which is a typical example of non-functional polysiloxane, it is found that only such specific compounds reduce the water repellency and oil repellency of the fluoroalkyl group-containing compound used in combination with dimethylpolysiloxane. This can be inferred from the fact that there is a tendency for there to be very few cases.

In carrying out the method of the present invention, it is appropriate that the mixing ratio of each of the above-mentioned fluoroalkyl group-containing compounds and polysiloxane is in the range of 10:1 to 1:5 by weight. If the amount of the polysiloxane is too small, the dyeing abrasion fastness will not be improved, and on the other hand, if the amount of the fluoroalkyl group-containing compound is too small, the water and oil repellency, especially the oil repellency, will deteriorate, which is disadvantageous.

The treatment referred to in the present invention may be any treatment as long as it exhibits better performance using a composition containing the above-mentioned fluoroalkyl group-containing compound and polysiloxane, but generally, the treatment It is a method of uniformly dissolving it in an organic solvent and spraying it on a dyed fiber cloth, or immersing the dyed cloth in this and then drying it.
Alternatively, the composition may be co-emulsified, or both emulsified dispersions of the above-mentioned fluoroalkyl group-containing compound and polysiloxane may be blended, and depending on the case, the dyed fiber cloth may be immersed after being diluted with water, followed by drying. There is.

Of course, in this case, there are also other purposes such as improving the wrinkle resistance of the dyed fabric, improving the durability of water and oil repellency, giving it a rigid or flexible texture, or preventing the accumulation of static electricity. For this purpose, the composition includes aminoplast resin, acrylic resin, dimethylpolysiloxane, natural wax,
There is no problem in adding a phosphate, a surfactant, or a catalyst for each of these agents, as long as the effects of the present invention are not impaired.

As the dyed fiber cloth to which the method of the present invention can be applied, there are no restrictions on its material or weave structure, and any cloth that is commonly used for this type of water- and oil-repellent finishing can be used. can do.

Thus, the processed fabric obtained by the method of the present invention generally has a soft texture, the color fastness to rubbing is not impaired in the slightest, and it has excellent not only water repellency but also oil repellency. It is.

Next, the present invention will be specifically described in detail with reference to Examples, in which all parts and percentages are based on weight unless otherwise specified.

In addition, in this example, the water repellency test was performed using AATCC Test Method 2 2 -]
9 7] based on the spray method and the evaluation criteria as shown in Table 1. On the other hand, the 8 oil repellency test was rated as AA.
TCC Test Method] 8 -] 9
6.6, and based on the evaluation criteria as shown in Table 2.

Oil repellency is determined by dropping designated standard reagents starting from the lowest judgment grade (diameter 5 dragons), and after 30 seconds, judging the corresponding grade based on the penetration state of the droplets.

Judgment Standard reagent grade 0 1 Nujol 2 Nujol/n-hexatecane = 6 5/3 5 3 n-hexadecane 4 n-tetradecane 5 n-dodecane 6 n-decane 7 n-octane 8 n-heptane Furthermore, color fastness to rubbing uses a Gakushin type friction tester,
After rubbing 200 times back and forth using a cotton cloth as a friction cloth under a load of 500 g, it is judged on a gray scale for contamination (6 levels from grade 20 to grade 5).

Evaluation of color fastness to rubbing Grade 5 No coloring.

Grade 4: Slightly colored.

Grade 3: Coloring.

Grade 2: Significantly colored.

Grade 1: Vividly colored.

Grade O: Quite intensely colored.

Examples 1 to 3 and Comparative Examples 1 and 2 First, as water- and oil-repellent main agents, 85 parts, 10 parts of 2-ethylhexyl methacrylate, and 5 parts of N-methylolacrylamide were combined with 2 parts of octadecyldimethylamine acetate and A dispersion obtained by emulsion polymerization with 5 parts of polyethylene oxide nonyl phenyl ether (HLB20) (polymer concentration 20%; hereinafter, this is referred to as [
It is abbreviated as dispersion liquid (F-1) 1.

)It was used. On the other hand, as the functional group-containing polysiloxane, epoxy-modified polysiloxane (10000est
, epoxy equivalent: 1000) was dispersed with a nonionic emulsifier to a polymer concentration of 20% (hereinafter, this will be abbreviated as "dispersion (S-1)j").

)It was used.

Next, both of these were blended as specified in Table 3 and diluted with water to a total of 100 parts to prepare a blended bath.

Table 3 Processing fabric: Brown polyester/cotton blend dyed with disperse dyes and reactive dyes (65/35) Fabric processing method: 1 dip, 1 squeezing, 90% wet pickup, pre-drying at 120℃ x 3 minutes curing 160°C for 3 minutes Examples 4 to 10 and Comparative Example 3 As a water and oil repellent main agent without washing? 3H7 C F So NCH CH OH 2 moles 817222 Tolylene diisocyanate A solution of 10 parts of the urethane obtained by adding 1 mole in 10 parts of methyl isobutyl ketone was added with 0.3 parts of octadecyldimethylamine hydrochloride. The emulsified dispersion liquid (resin concentration 20%) and the dispersion liquid obtained in Examples 1 to 3 (F-1)
(resin concentration 20%; hereinafter, this will be abbreviated as "dispersion F-2").

) was also used. On the other hand, as the functional group-containing polysiloxane, amine-modified polysiloxane (20000 cst,
(amine equivalent: 800) was dispersed with a nonionic emulsifier at a polymer concentration of 20% (hereinafter referred to as "dispersion liquid (S)").
It is abbreviated as -2Ll.

) and diol-modified polysiloxane (6000cst,
Hydroxy equivalent: 4000) was dispersed with a nonionic emulsifier at a polymer concentration of 20% (hereinafter, this was abbreviated as [dispersion (S-:NJ).

)It was used. Table 4 Processed fabric: Dark blue polyester/cotton blend dyed with disperse dyes and vat dyes (65/35) Fabric processing conditions: Same as in Table 3 Examples 11 to 15 and comparative examples 4 to 7 In each example, CF3\CF(CF2)8CH2CH20COCH=CH2C is used as the water- and oil-repellent main agent.
F3 73, 100 parts of a copolymer consisting of 25% ethyl acrylate and 2% diacetone acrylamide was added to C18
An emulsion polymer obtained by emulsifying 9 parts of H37(OCH2CH2)2oOH and 1 part of octadecyldimethylamine hydrochloride (polymer concentration 20%, hereinafter abbreviated as "dispersion (F-4) J").

) was also used.

On the other hand, the functional group-containing polysiloxane was obtained by dispersing epoxy-modified polysiloxane (8000 cst, epoxy equivalent: 2000) with a nonionic emulsifier to a polymer concentration of 20% (hereinafter referred to as " It is abbreviated as dispersion liquid (S-4).

) was also used. Table 5 Processed fabric: 100% brick color dyed with several types of disperse dyes
Polyester processed yarn Amundsen cloth Processing method: 1 dip, 1 squeeze, 7 wet pickups
0 stage pre-drying 100°C x 2 minutes Curing 180°C x 2 minutes Examples 16 and 17 and Comparative Examples 8 and 9 16 parts and 4 parts of benzyl methacrylate in 80 parts of 1,1.1-trichloroethane, Using 1 part of azobisisobutyronitrile as a catalyst, conduct radical copolymerization at 80°C to obtain a solution (F-4) with a polymer concentration of 20q/).
I got it.

In addition, 20 parts of the epoxy-modified polysiloxane used to obtain the dispersion liquid (S-1) in Examples 1 to 3 was added to 80 parts of the epoxy-modified polysiloxane.
1,1,1-trichloroethane (polymer concentration 20φ, hereinafter abbreviated as "Solution (S-5) J").

)It was used.

Both were mixed as shown in Table 6, and diluted with ]-4-lichloroethane to a total of 100 parts to prepare a mixed bath.

Table 6 Processed cloth: Same as in Table 5 Processing method: 1 time dipping, 1 time squeezing 100% wet pickup Drying/curing 140℃ x 2 minutes

Claims (1)

[Claims] 1 A fluoroalkyl group-containing compound having water and oil repellency and a polysiloxane containing an epoxy group, hydroxy group, amino group or carboxyl group are mixed so that the weight ratio of the former to the latter is 10:1 to 1:5. 1. A method for water- and oil-repellent processing of dyed fiber cloth with improved dyeing abrasion fastness, characterized by treating the dyed fiber cloth with a composition comprising: