JPS6119684A - Water-and oil-repellent agent having improved durability - Google Patents

Abstract

PURPOSE:To provide a water- and oil-repellent agent having excellent water- and oil-repellent effects and durability, by mixing a blocked isocyanate compd. with a specified fluorine-contg. water repellent, oil repellent agent. CONSTITUTION:A water repellent, oil repellent agent is obtd. by mixing a blocked isocyanate compd. of formula II [wherein R is a 1-8C alkyl; Q1, Q2, Q3 are each a group of formula III or IV, etc.; Y1, Y2, Y3 are each -OR<1>, a group of formula V or VI (wherein R<1>, R<2> are each a 1-4C alkyl)] such as the compd. of formula VII with a water repellent, oil repellent agent contg. polyfluoroalkyl group and active hydrogen group [e.g. a copolymer of the monomer of formula I with (meth)acrylic acid]. By adding the blocked isocyanate compd. as a crosslinking agent, the isocyanate groups are activated by heating after treatment and the strength of a water- and oil-repellent film is increased by its high reactivity to thereby increase fixation to a material to be treated, thus obtaining durable water and oil repellency.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water and oil repellent with improved durability, and more specifically, to a water and oil repellent containing a polyfluoroalkyl group and an active hydrogen group, a blocked isocyanate compound with a specific structure is added. This invention relates to a new water and oil repellent obtained by adding and mixing.

Prior Art Conventionally, homopolymers of acrylates or methacrylates containing polyfluoroalkyl groups, or these together with alkyl acrylates, maleic anhydride, vinyl chloride,
Copolymers with other vinyl monomers such as styrene are known to exhibit excellent water- and oil-repellent effects, and are widely used as water- and oil-repellent agents, primarily for textile treatment.

One of the major characteristics of this type of water and oil repellent is that it is relatively durable compared to conventional paraffin-based or ethylene urea-based water repellents, but with the recent trend towards high quality. Accordingly, further improvement in durability is desired.

Therefore, in an attempt to improve durability, a crosslinking agent such as 9, methylolmelamine resin, bifunctional aziridine compound, etc., which is obtained by copolymerizing a monomer containing a functional group with a polyfluoroalkyl group-containing monomer, was added to the water and oil repellent agent. However, it is known that methylolmelamine resin is used in combination with other resins, but the effect is not always satisfactory; on the other hand, the use of methylolmelamine resin results in a hard texture, and the use of aziridine compounds tends to cause skin disorders. Problems arise.

As another attempt, the following ProC6H50 was added to the fluororesin.
A method of using C0NI ((CH2)6NHCOOC6H5) in combination is also known (JP-A-54-128991, JP-A-54-128991;
4 = 128992, 54-181579. Same 5
4-138486 et al.). In this example, since a blocked isocyanate, in which the isocyanate groups, which are highly reactive and easily susceptible to the action of moisture, are masked with phenol, is used as the crosslinking agent, the treatment agent can be provided as an aqueous dispersion, and can be easily applied after fiber treatment. The method is to develop free iso/anate groups by heating to complete crosslinking with the fluororesin, and it can be said to be a very logical and interesting method. Unfortunately, however, the blocked incyanate compounds that have been tried so far have not been able to exhibit sufficient effects even when applied to fluorine-based water and oil repellents.

In general, in the case of fluorine-based water and oil repellents, the degree of water and oil repellency depends on the degree of orientation of perfluoro groups on the fibers, and the durability of the fluorine resin film formed on the fibers. This is due to the degree of damage or shedding caused by washing or wearing friction. In other words, the more orderly the perfluoro groups are oriented on the fiber, the better the water and oil repellency will be, and the more the perfluoro groups will be oriented on the fiber, the more excellent the water and oil repellent effect will be. It can be said to be an excellent water and oil repellent. Therefore, to improve water and oil repellency, it is important to use a compound that improves the orientation of polyfluoro groups, and to improve durability, it is important to use a highly reactive crosslinking agent to crosslink between fluororesins. It is important to complete the process and obtain a stronger film. It would be ideal if a single compound had an effect of improving orientation and also had a crosslinking effect. It seems that the blocked isocyanate compounds that have been tried in the past have placed too much emphasis on the crosslinking effect and have not given sufficient consideration to the orientational amplifier.

Purpose of the Invention The present invention provides a water and oil repellent containing a polyfluoroalkyl group and an active hydrogen group (hereinafter referred to as a fluorine-based water and oil repellent).
An object of the present invention is to provide a water and oil repellent having excellent water and oil repellency and durability by adding and mixing a blocked isocyanate compound to the water and oil repellent.

Structure of the Invention The water and oil repellent of the present invention is obtained by adding and mixing a blocked isocyanate compound represented by the following general formula to a fluorine-based water and oil repellent.

CH2OC0NH-Ql-NHCOYt [However, an alkyl group such as RidC1-8 in the formula (R1 and R2 are C1
~4) represents an alkyl group. ] It is important that the fluorine-based water and oil repellent used in the present invention contains both a polyfluoroalkyl group and an active hydrogen group. Examples of such water and oil repellents include copolymers of polyfluoroalkyl group-containing polymerizable compounds and monomers having active hydrogen groups. (Of course, it may also be a polymer or copolymer of monomers containing both polyfluoroalkyl groups and active hydrogen groups.) Typical examples of alkyl group-containing materials include CF3(CF2)(CH2)20COCH=CH2, C
F3(CF2)4CH20COC(CH3)=CH2,
CF3 (CF2)6(CH2)20COC(CH13
) = CH2, CF8 (CF2) 7802N (C:17)
(CH2)20COCH=CH2, CF a (CF
2) 7(CR2) 40 COCH2CR2, CF
a (CF2) 7SO2N(CH3) (CH2)
20COC(CH3) =CH2, CF3(CF2)6
0COCH=CH2, q, F a, . F,,CF(CFz),CH2CH(OCOCHa
)OCOC(CH3)=CH2゜H(CF2)□o C
H20COCH=CH2, CF2 Cl (CF2)□
. Examples include CH20COC(CH3)diCH2, but usually the general formula CH2=C(R)Coo(R6)Rf
(However, Rf is a linear or branched polyfluoroalkyl group having 3 to 20 carbon atoms, R is a hydrogen atom or a methyl group R
5 is preferably an acrylate or methacrylate represented by a linear or branched alkylene group having 1 to 10 carbon atoms, and m represents 0 or 1. In particular, Rf has 6 to 12 carbon atoms, The number of carbon atoms is 2 to 4. It is preferable that m is 1.

In addition, as the active hydrogen group-containing monomer to be copolymerized with these polyfluoroalkyl group-containing monomers, -OR
, -NR2, -C0OH, etc. For example, CH2=C(R)Coo-(AlK-0+H (however,
R in the formula is a hydrogen atom or a methyl group, Alkle' prime number 2
~6 divalent alkylene groups, n is O or an integer from 1 to 50), CH2=C(i3)-C, ONH(A)
NHR4 (However, R3 is a hydrogen atom or a methyl group, A is a divalent alkylene group or a phenylene group, R4 is a hydrogen atom or an alkyl group), CH2=C(R)Co fence 1 (A)
Examples include OH (where R is a hydrogen atom or a methyl group, and A is a divalent alkylene group or a phenylene group).

Specific examples of active hydrogen group-containing materials include acrylic acid,
Unsaturated carboxylic acids such as methacrylic acid, itaconic acid, maleic acid, crotonic acid; alkylene oxide adducts of such unsaturated carboxylic acids such as CH2=C(CH
3) Coo(CH2CH20), ~2H, CH2=CH
C00(CH2CH20), ~2H5CH2=C(C
Ha)Coo(CH2CH20)6~8HSCH2=
C(CH3)COO(CH2CH20)7H,CH2C
(CHa)C0O(CH2CH20)9H,CH2=C
(CH3)Coo(CH2CI(O)□.OH group-containing acrylic acid such as Htanol acrylamide)
Mid; CH2= CHCONHCH2CH2N
Examples include NH group-containing acrylamides such as HCHa.

Copolymer type fluorine-based water and oil repellents include other chemicals such as ethylene, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride, acrylamide, methacrylamide, styrene, α-methylstyrene, p-methylstyrene, alkyl ether of acrylic acid or methacrylic acid, benzyl acrylate or methacrylate, vinyl alkyl ketone μ, halogenated alkyl vinyl ether,
Vinyl alkyl ketone, chlorohexyl acrylate or methacrylate, maleic anhydride, getadiene, isoprene, chloroprene, CH2=C(R') , X is an integer of 1 to 50, and R/, Rf is a hydrogen atom or a methyl group) may be further copolymerized.

In addition, fluorine-based repellents containing active hydrogen groups (-OH) and polyfluoroalkyl groups can also be produced by copolymerizing vinyl acetate or the like with polyfluoroalkyl group-containing polymers and hydrolyzing the resulting copolymer. It can also be used as a water and oil repellent.

Furthermore, as a fluorine-based water and oil repellent, RfCONH-(Aβ-0)-H Rf5O2N(R7)-CAlk-0)-HlR
f(R6) 0-(Aβ-0)-Hm
H (However, Rf in the formula has 3 to 3 carbon atoms.
20 linear or branched polyfluoroalkyl groups, R7
is hydrogen or a lower alkyl group, R6 is a linear or branched alkylene group having 1 to 10 carbon atoms, m is 0 or 1, and n is 0 to
An integer of 50, A11c is an alkylene group having 2 to 6 carbon atoms), there is polyfluorocarbon in the molecule! Compounds containing both a syl group and an active hydrogen group may also be employed.

The fluorine-based water and oil repellent is prepared and used in any form such as an emulsion, a solvent solution, or an aerosol.

Next, as the Glock German cyanate compound added to the fluorine-based water and oil repellent, any of the compounds represented by the above formula (1) can be used. It is produced by reacting and masking the free isocyanate groups with alcohol, phenol, oxime, lactam, etc.

The use of trimethylolpropane as the starting material for the trial alcohol works most effectively in improving the orientation of the polyfluoroalkyl group of the fluorine-based water and oil repellent used in combination, and is excellent in the water and oil repellent of the present invention. It is known that it exhibits water and oil repellency.

As the diisocyanate compound, it is preferable to use toluylene diisocyanate and hexamethylene diisocyanate, and as a masking agent, it is preferable to use one that protects the isocyanate group stably at around room temperature and that can be easily removed by heat treatment, and the use of phenol and oxime is preferable. However, it is particularly desirable to use oximes in consideration of the adverse effects on the working environment.

Examples include blocked isocyanates used in the present invention.

The blending ratio of the fluorine water and oil repellent to the blocked isocyanate compound in the present invention is not particularly limited, but is generally used in a weight ratio of 45:55 to 99:1. A particularly preferred range is 65:35 to 95:5,
The most commonly used range is 80:20 to 90:10.

Articles that can be treated with the water and oil repellent of the present invention are mainly fibers.
Although it is a product, it is not necessarily limited to this.
Application to paper, leather, etc. is also possible. Examples of textile products include yarns, woven fabrics, knitted fabrics, non-woven fabrics, and processed products thereof, made of natural fibers, synthetic fibers, semi-synthetic fibers, and inorganic fibers singly or of two or more types. The water and oil repellent of the present invention exhibits outstanding durability effects on cellulose fiber products (including blended products, interwoven fabrics, and interwoven fabrics) that have 10H groups that easily react with groups.

Next, examples of the present invention will be described in more detail, but it goes without saying that this description does not limit the present invention. The water repellency and oil repellency shown in the following examples are shown on the following scale. That is, the water repellency is J I
5-L-100Fy7) Water repellency is expressed by spraying dust (see Table 1 below), and oil repellency is expressed by spraying a few drops of the test solution shown in Table 2 below on the sample cloth (approximately 1 inch in diameter).
(Parrot) and judge based on the penetration state after 30 seconds (AAT
CC-TM 118-1966).

Table 1 also shows the durability of the treated fabric with pallast fabric.
Then, put it in an electric washing machine, wash it at 50°C for 10 minutes with 60f of detergent (Super Zabu: brand name), and air dry it for 10 minutes.
Judgment is made by measuring water and oil repellency.

In addition, all the compounding ratios of each component in Examples are shown by weight ratio.

Example [1] 52.2 I of 2,4-toluylene diisocyanate was placed in a four-loop flask with an internal volume of 500 m2 equipped with a dropping funnel, temperature needle, cooling tube, and stirring blade and set on a water bath.
C0,8mo/I/), trimethylolpropane 13.4
1 (0.1 mol) and 200 f of methyl ethyl ketone were added, and while stirring, the temperature of the liquid was raised to 7°C, and the temperature was maintained at the same temperature.
time and then 2-butanone oxime 26.1F (
0.8Mo)V) was added dropwise through the dropping funnel over a period of 91 hours, and stirring was continued for an additional hour after the addition was completed.

After distilling off the solvent methyl ethyl ketone from the reaction mixture using a vacuum evaporator, the residue was vacuum-dried. A yellowish white solid of 7FI was obtained. This solid was analyzed by gas chromatography and infrared absorption spectroscopy, and the yield was 92.5% based on isocyanate.
5% (the above compound is referred to as TPDt).

Rf CH2CH20COCH2CH2 (R
f is C6H13, C3F17. Cl0F21 and Cl
1/3/2/1 mixture of compounds that are 2F2)), butyl methacrylate and N-methylol acrylamide 70
1.1 containing a comonomer consisting of /28/2 at a concentration of 2%
．． 1-t') Chloroethane solution (hereinafter referred to as solution A) 7
In a solution consisting of 0 parts and 80 parts of a methyl ethyl ketone solution (hereinafter referred to as solution B) containing the above-mentioned TPDO at a concentration of 2%,
About 1 piece of cotton broadcloth (dated about L20f/mf) using the scouring method
After immersion for 0 seconds, it was squeezed with a mangle (squeezing rate 55%).

Then, after drying at 100°C for 3 minutes, curing was performed at 170°C for 3 minutes. The water and oil repellency of the obtained product was measured. Regarding the durability test, water and oil repellency were measured after washing 5 times. The results are shown in Table 1.

Comparative example [1] Pheno-/V 18.8f (0.2mo)v), 2.4-
) Louis V'J diisocyanate 17.4 g (0.1 mol) and methyl ethyl ketone 200 y were charged into a four-bottle flask with an internal volume of 500 ω, and after reacting at 70'C for 4 hours, methyl ethyl ketone was distilled under reduced pressure and further vacuum dried. By doing this, 3417 was obtained as a yellowish white solid. As a result of analysis by gas chromatography and infrared absorption spectrum, the selectivity of the target product 06H50CONT(-Qo-CH2XNHCOOC6H3 (hereinafter referred to as TDIP) was 96%, and the yield based on 2,4-toluylene diisocyanate was It was 94%.

Processing was carried out in exactly the same manner as in Example 1, except that a solution consisting of 70 parts of the above solution A and 30 parts of methyl ethyl ketone (referred to as methyl ethyl ketone) containing the above TDIP at a concentration of 2% was used as the processing liquid. The results of measuring the water and oil repellency of the product are also listed in Table 1.

The product of Example [1] produced by the method of the present invention exhibited superior water and oil repellency both initially and after washing, compared to the comparative example using a difunctional blocked isocyanate.

Table 1 Example [2].

AP St,able (manufactured by Nippon Polyurethane Industries Co., Ltd., 3 mol of toluylene diisocyanate) and 1 mole of trimethylolpropane reactant masked with phenol (blocked German cyanate) 1
5 parts, 15 parts of methyl ethyl ketone, and 1.5 parts of lauryl alcohol ethylene oxide adduct.
Stir and dissolve at C for 30 minutes. Next, add 270 ml of water under strong stirring.
F! was added dropwise using a dropping funnel over a period of 1 hour. After the addition was completed, stirring was continued for another 30 minutes to obtain a milky white hydrogen dispersion (solid content concentration 5%, hereinafter referred to as dispersion).

On the other hand, as a water and oil repellent containing a polyfluoroalkyl group and an active hydrogen group, Rf CH2 similar to Example [1]
CH2 0COCH = CI (280 parts, 2-ethylhexyl methacrylate) 15 parts and (jN-methylol acrylamide 5 parts m 2 parts octadecyldimethylamine acetic acid 1 part and nonylphenol ethylene oxide adduct 5 parts) An aqueous dispersion (polymer concentration 20%, hereinafter referred to as dispersion E) was obtained by emulsion polymerization in the presence of the polymer.

After immersing refined polyester/cotton (65/85) broad (approx. 120 g β) in a solution consisting of 7 parts of Dispersion D, 87 parts of Dispersion, and 86 parts of water for about 8 seconds, the water and oil repellency was measured. . Regarding the durability test, the water and oil repellency was measured after washing 5 times. The results are shown in Table 2.

Comparative Example [2] The same method as in Example [2] was carried out, except that a solution consisting of 87 parts of the dispersion and 93 parts of water was used as the treatment liquid.

Table 2 shows the water and oil repellency of the products.

From this, it is clear that the product of Example [2] according to the present invention exhibits extremely superior durable water and oil repellent effects compared to the comparative example that does not use a crosslinking agent.

Table 2 Example (a), [4] Squeezing with 3 parts of Dispersion D, 3 parts of Dispersion E, and 94 parts of water (Drawing ratio: Polyester V785%, Nylon: 40%), then 2 parts at 110°C. After drying for 1 minute, curing was performed at 170°C for 2 minutes. Table 3 shows the results of measuring the water and oil repellency of the obtained cloth before and after washing.

In all of the examples in Table 3, excellent durable water repellent finishing was possible.

Effects of the Invention In the present invention, a trifunctional block ananate compound having a specific structure is added as a crosslinking agent to a water- and oil-repellent agent containing a polyfluoroargyl group and an active hydrogen group. The isocyanate group of the crosslinking agent is activated by heating, and its high reactivity increases the strength of the water- and oil-repellent coating film and improves its adhesion to the object being treated, resulting in durable water- and oil-repellency. It is.

Furthermore, the orientation of the polyfluoroalkyl groups in the water and oil repellent is maintained well due to the specific steric structure of the crosslinking agent, and extremely excellent water and oil repellency effects can be obtained.

Claims (3)

[Claims] (1) A water and oil repellent obtained by adding and mixing a blocked isocyanate compound to a water and oil repellent containing a polyfluoroalkyl group and an active hydrogen group, the blocked isocyanate compound having the general formula ▲ mathematical formula, chemical formula , tables, etc. ▼ (However, R in the formula is an alkyl group consisting of C_1_-_8 Q_1, Q_2, Q_3 respectively ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ or -(CH_2)-
_1_~_6, Y_1, Y_2, Y_3 are each -O
R_1, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼ or -O-▲ Numerical formulas, chemical formulas,
A water and oil repellent with excellent durability characterized by using a compound represented by <R_1 and R_2 represent an alkyl group consisting of C_1_ to_4>. (2) The water repellent according to claim 1, wherein the weight ratio of the water and oil repellent containing a polyfluoroalkyl group and an active hydrogen group to the blocked isocyanate compound is 45:55 to 99:1. Oil repellent. (3) The blocked isocyanate compound is a compound represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R_1R_2 represents an alkyl group consisting of C_1_ to_4) The water and oil repellent described in item 2.