JPH07173772A - Water-dispersible type fluorine-based water-repellent and oil-repellent agent and production thereof - Google Patents

Abstract

PURPOSE:To obtain a water-dispersing fluorine-based water-repellent and oil- repellent agent having high color fastness to washing and soft handle. CONSTITUTION:The characteristic of this water-repellent and oil-repellent agent is to include 100 pts.wt. of a polymer containing a polymerization unit of polymerizable monomer containing a polyfluoroalkyl group and a polymerization unit of other polymerizable monomer and 1-20 pts.wt. of glycols.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-dispersible fluorine-based water / oil repellent having a high dyeing fastness and a soft texture and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, as a water-dispersible fluorine-based water and oil repellent, a polymerizable monomer containing a polyfluoroalkyl group and another polymerizable monomer are emulsion-copolymerized in a specific ratio. It has been reported that water-dispersed water and oil repellents are useful. These water and oil repellents, when producing a polymer,
In order to improve the compatibility of the polymerizable monomer containing a polyfluoroalkyl group with an aqueous medium and the compatibility with other monomers, an organic solvent having a low boiling point such as acetone or ethyl acetate is contained. It is obtained by emulsion polymerization in an aqueous solution. In this case, the organic solvent should be at least 5 parts with respect to 100 parts by weight of the monomer for the purpose of increasing the polymerization yield.
It was customary to include 0 parts by weight.

However, since an organic solvent remains in such a fluorine-based water and oil repellent agent, it is difficult for the dyed color to transfer when the cloth is treated, that is, the dyeing fastness is low. That was a problem.

On the other hand, in order to raise the flash point of products in recent years,
Commercially available fluorine-based water and oil repellents obtained by emulsion polymerization of dipropylene glycol monomethyl ether, dipropylene glycol, etc., which are high boiling point organic solvents, in an amount of at least 30 parts by weight based on 100 parts by weight of monomers. Came to be. The high-boiling organic solvent not only has the problem of further lowering the dyeing fastness due to a larger residual amount, but also when the water- and oil-repellent treatment is applied, the organic solvent fixes the fibers of the cloth, There is also a problem in that the texture of the cloth becomes stiff as it has an effect such as when it is formed. Thus, up to now, there is no known method for safely obtaining a water / oil repellent having satisfactory performance.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems that the prior art had. That is, even when treated with water and oil repellency, the dyeing fastness is high,
Provided are a water-dispersible fluorine-based water and oil repellent agent which can give a processed cloth having a soft texture, and a method for producing a water-dispersed fluorine-based water and oil repellent agent.

[0006]

The present invention provides a polymer containing polymerized units of a polymerizable monomer containing a polyfluoroalkyl group and a polymerized unit of another polymerizable monomer, and 100% of the polymer. Provided is a water-dispersible fluorine-based water / oil repellent characterized by containing 1 to 20 parts by weight of glycols with respect to parts by weight. Further, the present invention, when emulsion-polymerizing a polymerizable monomer containing a polyfluoroalkyl group and another polymerizable monomer in an aqueous medium, relative to 100 parts by weight of the total amount of the polymerizable monomer. Also provided is a method for producing a water-dispersible fluorine-based water and oil repellent characterized by including 1 to 20 parts by weight of an organic solvent in an aqueous medium and performing emulsion polymerization.

In the present invention, the polymerizable monomer containing a polyfluoroalkyl group is a compound containing a polyfluoroalkyl group and a carbon-carbon double bond.

The polyfluoroalkyl group (hereinafter, the polyfluoroalkyl group is referred to as Rf group) means a group in which two or more hydrogen atoms of the alkyl group are substituted with fluorine atoms. The Rf group may have either a linear structure or a branched structure. Rf group has about 1 to 20 carbon atoms,
It is preferably 4 to 16.

The proportion of fluorine atoms in the Rf group is preferably such that 80% or more of the hydrogen atoms in the alkyl group are replaced by fluorine atoms, and particularly when all of the hydrogen atoms are replaced by fluorine atoms (ie, perfluoro). (When it is an alkyl group) is preferable. As the perfluoroalkyl group, a linear structure is preferable, and particularly C _n F _{2n + 1-} (provided that
n is an integer of 4 to 16 and is preferably an integer of 6 to 12).

Part or all of the non-substituted hydrogen atoms of the Rf group may be substituted with an atom other than a fluorine atom, for example, a chlorine atom. Further, it may have a structure in which one or more oxygen atoms are present between the carbon-carbon bonds of the Rf group, that is, a structure having an oxypolyfluoroalkylene moiety.

The polyfluoroalkyl group-containing polymerizable monomer of the present invention has a structure containing the above Rf group and a carbon-carbon double bond. The Rf group and the carbon-carbon double bond may be either a direct bond or an indirect bond via a polyvalent organic bonding group.

The polyvalent organic bonding group is not particularly limited, but a divalent organic bonding group is usually preferable,
Particularly, an organic bonding group containing an ester bond portion is preferable. For _{example, -COO (CH 2) a -} , - COO (CH 2) b
^{N (R 1) CO -,} - CHR 2 (CH 2) c -, - CO
_{O (CH 2) d N (} R 3) SO 2 -, - COOCH (C
_{H 2 Cl) (CH 2)} e O (CH 2) f NR 4 SO 2 -
(Here, a to f are integers of 1 or more, preferably 1 to 4 and R ^{1 to} R ⁴ have a carbon number of 1 or more, preferably 1 to 4
Is an alkyl group. ) Etc. are preferable.

Specific examples of the polyfluoroalkyl group-containing polymerizable monomer of the present invention are shown below, but the invention is not limited thereto. In the chemical formula below, R
⁵ is a hydrogen atom or a methyl group, Rf is a polyfluoroalkyl group, and φ is a phenylene group.

[0014]

[Chemical Formula 1] CH ₂ = C (R ⁵ ) COOCH ₂ CH ₂ Rf CH ₂ = C (R ⁵ ) COOCH ₂ CH ₂ N (C ₃ H ₇ ) CORf CH ₂ = C (R ⁵ ) COOCH (CH ₃ ) CH ₂ Rf CH ₂ = C (R ⁵ ) COOCH ₂ CH ₂ N (CH ₃ ) SO ₂ Rf CH ₂ = C (R ⁵ ) COOCH ₂ CH ₂ N (CH ₃ ) CORf

[0015]

CH ₂ = C (R ⁵ ) COOCH ₂ CH ₂ N (C ₃ H ₇ ) SO ₂ Rf CH ₂ = C (R ⁵ ) COOCH ₂ CH ₂ N (C ₂ H ₅ ) CORf CH ₂ = C (R ⁵ ) COOCH ₂ CH ₂ N (C ₃ H ₇ ) SO ₂ Rf CH ₂ = C (R ⁵ ) COOCH (CH ₂ Cl) CH ₂ OCH ₂ CH ₂ N (CH ₃ ) SO ₂ Rf CH ₂ = CHRf ^{_{CH 2 = C (R 5)}} COOCH 2 CH 2 φCH 2 OCH 2 CH 2 CH 2 Rf

As the above-mentioned polymerizable monomer containing a polyfluoroalkyl group, one kind or two or more kinds of different compounds can be used. Further, in the usual case, they are used as compounds having different carbon numbers of polyfluoroalkyl groups.

In the present invention, the above-mentioned polymerizable monomer containing a polyfluoroalkyl group and another polymerizable monomer are emulsion polymerized in an aqueous medium.

The other polymerizable monomer is not particularly limited, and a known or well-known compound having a polymerizable unsaturated bond can be adopted. (Hereinafter, acrylate and methacrylate are collectively referred to as (meth) acrylate, and their meanings are shown. The same applies to other compounds.)

Specific examples of other polymerizable monomers include, for example, (meth) acrylic acid esters such as 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, and polyoxyalkylene. (Meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth)
Acrylate, benzyl (meth) acrylate, isocyanate ethyl (meth) acrylate, aziridinyl (meth) acrylate and the like.

As the (meth) acrylates having a hydroxyl group, compounds which are monoesters or polyesters of polyhydric alcohol and (meth) acrylic acid and which have at least one hydroxyl group. For example, monoesters of diols, which are dihydric alcohols, and (meth) acrylic acid are mentioned, and monoesters of alkylene diols and (meth) acrylic acid are particularly preferable. For example, hydroxyalkyl (meth) acrylate and the like.

Other copolymerizable monomers include ethylene, butadiene, isoprene, chloroprene, vinyl acetate, vinyl halides such as vinyl chloride and vinyl fluoride,
Styrene, α-methylstyrene, p-methylstyrene,
Acrylic acid, methacrylic acid, (meth) acrylamide,
Examples thereof include diacetone (meth) acrylamide, methylolated (meth) acrylamide, N-methylol (meth) acrylamide, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, maleic anhydride, and N-vinylcarbazole.

The above-mentioned other polymerizable monomers may be used alone or in combination of two or more. Among these, vinyl chloride or stearyl acrylate is preferable as the polymerizable monomer of the present invention because of the advantages such as higher water and oil repellency.

The ratio of the polymerizable monomer containing a polyfluoroalkyl group and the other polymerizable monomer is such that the polyfluoroalkyl group is contained in 100 parts by weight of the total amount of the polymerizable monomers. The polymerizable monomer is preferably about 30 to 95 parts by weight, and particularly preferably 50 to 80 parts by weight.

The water-dispersible fluorine-based water and oil repellent of the present invention is
1 to 20 parts by weight of glycols is contained with respect to 100 parts by weight of a polymer containing polymerized units of a polymerizable monomer containing a polyfluoroalkyl group and polymerized units of other polymerizable monomers. It is a feature.

The glycols are not particularly limited,
Usual glycols, alkyl ethers of glycols and the like can be mentioned. Preferably, 1,4-butanediol, 1,6-hexanediol, ethylene glycol,
Preferred are propylene glycol, diethylene glycol, dipropylene glycol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and the like. Moreover, 1 type (s) or 2 or more types can be used for glycols.

In the water-dispersible fluorine-based water and oil repellent agent of the present invention, a method for producing a polymer containing polymerized units of a polymerizable monomer containing a polyfluoroalkyl group and polymerized units of another polymerizable monomer As the above, an emulsion polymerization method is preferable.

As an emulsion polymerization method, a usual method is used, and the above-mentioned both polymerizable monomers are added in the presence of an emulsifier in an aqueous medium containing an organic solvent in a specific ratio with a polymerization initiator. And a method of polymerizing.

In the present invention, the organic solvent is contained in an aqueous medium in an amount of 1 to 20 parts by weight, preferably 5 to 18 parts by weight, and more preferably 100 parts by weight of the total amount of the above-mentioned polymerizable monomers. It is characterized by including 5 to 15 parts by weight and emulsion-polymerizing.

The organic solvent is not particularly limited,
Usually, acetone, ethyl acetate, methyl isobutyl ketone, methyl ethyl ketone, methyl alcohol, isopropyl alcohol, ethyl alcohol, butyl acetate,
Examples include glycerin and the above glycols.
These organic solvents may be used alone or in combination of two or more. Preferred organic solvents include the above glycols,
And a mixture of the glycols and other organic solvents is preferable.

The amount of the aqueous medium in the emulsion polymerization is usually about 100 to 300 parts by weight, preferably 150 to 250 parts by weight, based on 100 parts by weight of the total of the polymerizable monomers.

The emulsifier is not particularly limited, and various anionic, cationic, amphoteric or nonionic emulsifiers can be used. The amount of the emulsifier is usually about 2 to 15 parts by weight, preferably 5 to 8 parts by weight, based on 100 parts by weight of the polymerizable monomer.

The polymerization initiator is not particularly limited, but preferable examples are shown below.

[0033]

[Chemical 3]

[0034]

[Chemical 4]

The above polymerization initiators may be used either individually or in combination of two or more. The amount of the polymerization initiator is usually 0.1 to 100 parts by weight of the total amount of the polymerizable monomers.
About 3 parts by weight, preferably 0.5 to 1 part by weight.

Further, in the present invention, it is preferable to emulsify the polymerization reaction system before starting the emulsion polymerization, that is, before adding the polymerization initiator. That is, by preliminarily emulsifying to improve the compatibility between the polymerizable monomers and the medium, the polymerization yield can be improved even if the amount of the organic solvent in the aqueous medium is reduced. Furthermore, various inconveniences caused by the residual organic solvent can be avoided.

This effect is particularly advantageous when glycols are used. This is because when a large amount of glycols is used, it is difficult to remove them after the polymerization reaction. On the other hand, reducing the amount of the organic solvent has a drawback of decreasing the polymerization yield. However, by emulsifying the polymerization reaction system in advance, the polymerization yield does not decrease even when the amount of the organic solvent is reduced, and the amount of the solvent remaining in the water / oil repellent agent can also be reduced.

The method of emulsification is not particularly limited, but in general, it is carried out by passing it through a homogenizer under high pressure conditions. The pressure of the homogenizer is preferably about 50 to 600 Kg / cm ² .
The temperature is preferably about 20 to 80 ° C.

The polymer produced by the above method is prepared into an emulsion according to a conventional method. The emulsion is usually prepared so that the sum of the polymer and the emulsifier is about 30 to 40% by weight in the emulsion. The emulsion thus prepared is used by appropriately diluting it as needed.

The water and oil repellent composition of the present invention can be applied to an article to be treated by any method depending on the type of the article to be treated and the form of preparation. For example, a coating method such as dip coating is applied to the surface of the object to be treated and dried. If necessary, curing may be performed.

Further, the water / oil repellent composition of the present invention may contain other additive components. For example, other water repellents, oil repellents, cross-linking agents, insect repellents, flame retardants, antistatic agents, anti-wrinkle agents and the like can be appropriately added and used in combination.

The article that can be treated with the water / oil repellent composition of the present invention is not particularly limited. For example, fiber woven fabrics, fiber knits, leathers, and furs. Textile fibers, as fiber textiles,
Natural animal and plant fibers such as cotton, hemp, wool and silk, polyamide,
Examples thereof include synthetic fibers such as polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, and woven or knitted fabrics of these mixed fibers.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

[0044]

[Examples] The water repellency, oil repellency, dyeing fastness, and texture shown in the following examples were evaluated by the following evaluation tests.

[Evaluation method of water repellency] JIS-L1092
The water repellency number by the spray method of Table 1 shows the water repellency numbers.

[Evaluation method of oil repellency] A few drops (diameter about 4 mm) of the test solution shown in Table 2 were placed at two places on the test cloth, and the state of permeation after 30 seconds was used for determination (AATCC-TM118).
-1966).

The evaluation results obtained by adding + (-) marks to the water-repellent number and the oil-repellent number have a slightly better (bad) meaning than the state in which each evaluation is represented by a number.

[0048]

[Table 1]

[0049]

[Table 2]

[Dyeing fastness evaluation method] JIS-L08
49. A test cloth was cut into a size of 22 cm × 3 cm, which was processed with a water / oil repellent agent. this,
It was fixed to a friction tester (JIS-L0281 friction tester II type). Further, a dry white cotton cloth was put on the tip of the friction element of the friction tester, and 10 cm on the fixed test cloth was reciprocated 100 times at 30 times / minute. The degree of coloring of the white cotton cloth for rubbing was judged by comparing with the grace scale for staining described in JIS-L0805. Grace scale for pollution is 1
It consists of color chart No. 5, and the larger the number on the color chart, the lighter the color (higher the fastness).

[Evaluation method of texture] A difference from the unprocessed cloth was judged by a sensory test by 5 testers. The criteria are shown in Table 3.

[0052]

[Table 3]

The meanings of the abbreviations used in the following examples are shown in Table 4.

[0054]

[Table 4]

Example 1 60 parts by weight of FA, 37 parts by weight of StA, and G in a glass autoclave (internal volume of 1 liter) equipped with a thermocouple type thermometer and a current type stirrer.
Add 3 parts by weight of MA, 5 parts by weight of polyoxyethylene lauryl ether, 1 part by weight of stearyl trimethyl ammonium chloride, 10 parts by weight of dipropylene glycol and 175 parts by weight of water, and apply a pressure of 400 Kg / cm.
² , treated with a homogenizer at a temperature of 30 ° C. to obtain a milky white emulsion. Furthermore, as a polymerization initiator 2,
0.5 parts by weight of 2'-azobis (N, N'-dimethyleneisobutyramidine) (manufactured by Wako Pure Chemical Industries, Ltd./trade name VA-061) and 0.3 parts by weight of sulfuric acid were added, After performing nitrogen substitution for about 60 minutes while stirring, raise the temperature to 60 ° C.,
Polymerization was initiated. The mixture was heated and stirred at 60 ° C for 15 hours and then cooled to obtain an emulsion having a solid content concentration of 35% by weight. The conversion rate of FA by gas chromatography is 99.8.
%, And the yield of the stable emulsion emulsion was 97% based on all the monomers. The amount of dipropylene glycol in the emulsion was 3.9% by weight.

Example 2 60 parts by weight of FA, 15 parts by weight of DOM, and 5 parts by weight of monomer A were placed in a glass autoclave (internal volume of 1 liter) equipped with a thermocouple type thermometer and a current type agitator. , 5 parts by weight of surfactant B, 1 part by weight of imidazolinium betaine-type amphoteric surfactant (manufactured by Nikko Chemical / AM-101), 175 parts by weight of water, 10 parts by weight of dipropylene glycol are added, and the pressure is applied. 400
The mixture was treated with a homogenizer at Kg / cm ² and a temperature of 30 ° C. to obtain a milky white emulsion. Furthermore, as a polymerization initiator, 2,2′-azobis (N, N′-dimethyleneisobutyramidine) hydrochloride (Wako Pure Chemical Industries, Ltd./V
A-044) 0.5 part by weight is added, and the mixture is stirred to about 2
After performing nitrogen substitution for 0 minutes, add 20 parts by weight of VC,
The temperature was raised to 60 ° C. to start polymerization. The mixture was heated and stirred at 60 ° C for 15 hours and then cooled to obtain an emulsion having a solid content concentration of 35% by weight. The conversion rate of FA by gas chromatography was 99.8%, and the yield of stable emulsion emulsion was 98% based on all the monomers. The amount of dipropylene glycol in the emulsion was 4.6% by weight.

Example 3 As shown in Table 5, emulsion polymerization was carried out in the same manner as in Example 1 except that the monomers were changed.
An emulsion having a solid content concentration of 35% by weight was obtained. The conversion rate of FA by gas chromatography was 99.8%, and the yield of the stable emulsion emulsion was 97% based on all the monomers. The amount of dipropylene glycol in the emulsion was 3.8% by weight.

Example 4 As shown in Table 5, emulsion polymerization was carried out in the same manner as in Example 1 except that the monomers were changed.
An emulsion having a solid content concentration of 35% by weight was obtained. The conversion rate of FA by gas chromatography was 99.8%, and the yield of stable emulsion emulsion was 98% based on all the monomers. The amount of dipropylene glycol in the emulsion was 4.3% by weight.

[Comparative Example 1] The polymerizable monomers of Example 1 are shown in Table 5, the amount of water was 150 parts by weight and the amount of dipropylene glycol was 50 parts by weight to carry out a polymerization reaction.
An emulsion having a solid content concentration of 33% by weight was obtained. Also,
The amount of dipropylene glycol in the emulsion was 19% by weight.

[Comparative Example 2] The polymerizable monomers of Example 1 are shown in Table 5, the amount of water was 150 parts by weight and the amount of dipropylene glycol was 50 parts by weight to carry out a polymerization reaction.
An emulsion having a solid content concentration of 33% by weight was obtained. Also,
The amount of dipropylene glycol in the emulsion was 17% by weight.

[0061]

[Table 5]

A latex stock solution was prepared by adjusting the solid content concentration of the emulsions obtained in the above Examples and Comparative Examples to 20% by weight, and the latex stock solution was diluted with water (the ratio of the stock solution to water was 1.5%). % By weight) was used as a latex treatment liquid. Using this latex treatment liquid, water and oil repellency performance was measured.

[Measurement of water / oil repellency] A polyester cloth was dipped in the above-mentioned latex treatment liquid, and the cloth was squeezed between two rubber rollers to obtain a wet pickup of 30% by weight. Next, it was dried at 110 ° C. for 90 seconds and further heat-treated at 170 ° C. for 60 seconds. Performance after 5 washes is J
After repeating 5 times by IS-L-0217-103 method, what was dried at 100 degreeC for 3 minutes was used. Table 6 shows the results of evaluating the water / oil repellency, the fastness, and the texture of the obtained test cloth.

[0064]

[Table 6]

[0065]

The cloth treated with the water-dispersible fluorine-based water and oil repellent of the present invention has excellent dyeing fastness and soft hand. Further, according to the production method of the present invention, it is possible to produce a water / oil repellent composition having a high yield and excellent durability even when emulsion polymerization is performed with a reduced amount of an organic solvent. In addition, the method of the present invention is a method that is extremely safe in terms of work since it can greatly reduce the amount of the organic solvent, and is also a very excellent method in terms of environmental impact.

Claims (5)

[Claims] 1. A polymer containing polymerized units of a polymerizable monomer containing a polyfluoroalkyl group and a polymerized unit of another polymerizable monomer, and a glycol based on 100 parts by weight of the polymer. A water-dispersed fluorine-based water and oil repellent, which comprises 1 to 20 parts by weight. 2. When emulsion-polymerizing a polyfluoroalkyl group-containing polymerizable monomer and another polymerizable monomer in an aqueous medium, 100 parts by weight of the total amount of the polymerizable monomer is used. A method for producing a water-dispersible fluorine-based water and oil repellent, which comprises emulsifying and polymerizing 1 to 20 parts by weight of an organic solvent in an aqueous medium. 3. The method according to claim 2, wherein the polymerizable monomer containing a polyfluoroalkyl group is a polymerizable monomer containing a polyfluoroalkyl group having 4 to 16 carbon atoms. 4. The method according to claim 2 or 3, wherein the other polymerizable monomer is vinyl chloride or stearyl acrylate. 5. The production method according to claim 2, wherein the polymerization reaction system is emulsified and then emulsion polymerization is performed.