JPS6160112B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel non-aqueous emulsion type water and oil repellent. Research on imparting water-repellent and water-repellent properties to fibers has been conducted for a long time. Among these, so-called fluorine-based water repellents having a fluoroalkyl group have not only water repellency but also the property of repelling oil and oil stains, and have recently attracted attention as water and oil repellents. This fluorine-based water and oil repellent is used as an aqueous emulsion or an organic solvent solution. However, although water-based emulsions do not pose fire hazards or toxicity concerns, it is difficult to dispose of used water-based emulsions, the emulsifier used in combination may have a negative effect on effectiveness, and the processing process requires a curing step. On the other hand, while organic solvent solutions do not have the drawbacks of water-based emulsions, they always pose a risk of fire and toxicity, and the processed fabric becomes stiffer than unprocessed fabric, resulting in poor texture. The disadvantage is that it gets worse. As a result of intensive research into fluorine-based water and oil repellents that do not have such drawbacks, the present inventors have surprisingly found that a specific fluorine-based polymer can be stably dispersed in a specific liquid organic fluorine compound. This non-aqueous emulsion is not only nonflammable and has low toxicity, but when used as a water and oil repellent, air drying is sufficient without curing, and it does not deteriorate the texture of the processed fabric. The inventors discovered that the number of cases is extremely small and completed the present invention. That is, the present invention relates to general formula (A)

[Formula] [In the formula, Rf is a perfluoroalkyl group represented by ClF _2l+1 (l = 4 to 16), Q ₁ is -(CH ₂ )- _n ,

【formula】

【formula】

[Formula] (where m = an integer of 1 to 10; R ₂ is H, or an alkyl group having 1 to 18 carbon atoms, or an OH-containing alkyl group), and Q ₂ is -O- or

[Formula], and R ₁ is H or CH ₃ . ] Monomer (A) represented by and general formula (B)

[In the formula, R ₁ is H or CH ₃ . n=2~10 n=2m+1-p-q Integer of p≧0 Integer of q≧1]

A copolymer with the monomer (B) represented by R ₂
However, the homopolymer of the monomer (A) which is an OH-containing alkyl group has 2% by weight or more of hydroxyl groups, and (C) benzotrifluoride, m-xylene hexafluoride, hexafluorobenzene, perfluorobenzene, etc. One or more liquid fluorine-based solvents selected from decalin, perfluorohexane, perfluoromethylcyclohexane, perfluorotributylamine, perfluorobutyltetrahydrofuran, and chlorofluoroethane solvents (R-112, R-121, R-131) The present invention provides a non-aqueous emulsion type water and oil repellent characterized by being dispersed in compound (C). The monomer (A) of the present invention is represented by the above general formula (A), and the perfluoroalkyl group of the monomer (A) is a group in which hydrogen of an alkyl group is substituted with fluorine; may be linear, branched, cyclic, or a combination thereof, and preferably has 4 to 16 carbon atoms, particularly 4 to 12 carbon atoms. Specific examples of the monomer (A) having both a perfluoroalkyl group and a hydroxyl group and a polymerizable unsaturated bond include the following. Examples of the monomer (A) having a perfluoroalkyl group and a polymerizable unsaturated bond include the following. Monomer (B) is represented by the general formula (B), and specific examples include 2-hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxybropyl (meth)acrylate, 2-hydroxy Propyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, trimethylolpropane (meth)acrylate

[Formula] can be given. The non-aqueous emulsion type water and oil repellent of the present invention is produced by polymerization using a liquid fluorine compound as a reaction medium, since the copolymer is substantially insoluble in organic solvents. The reaction temperature is usually 50 to 150°C, and the molecular weight is adjusted using known methods such as polymerization inhibitors, polymerization initiators, and polymerization regulators. (Co)polymers range from low molecular weight polymers with a molecular weight of about 1,000 to high molecular weight polymers of about 500,000, but from the viewpoint of water and oil repellency, those with a molecular weight of 4,000 to 100,000 are preferable. In addition, in order to obtain a stable non-aqueous emulsion, the (co)polymer concentration should be 50% by weight or less, preferably 40% by weight or less, whereas considering the economical efficiency of use, it should be 1% by weight or more, preferably is 10% by weight
It should be more than that. The fluorine atom content and the amount of hydroxyl groups in the (co)polymer as well as their ratio are important. The fluorine atom content in (co)polymers is usually 10
~70% by weight. If it is less than 10% by weight, it is difficult to recognize water and oil repellency, and conversely, if it is more than 70% by weight, it is difficult to manufacture. In addition, the hydroxyl group content in the (co)polymer is usually 2 to 10% by weight, and if it is less than 2% by weight, it is difficult to form a stable non-aqueous emulsion.
On the other hand, if it exceeds 10% by weight, it is difficult to recognize water and oil repellency.
The ratio of fluorine atom content/hydroxyl group content is 2 to 700, preferably 5 to 50. The liquid fluorine-based compound (C) is benzotrifluoride, m-xylene hexafluoride, hexafluorobenzene, perfluorodecalin, perfluorohexane, perfluoromethylcyclohexane, perfluorotributylamine, perfluorobutyltetrahydrofuran, chlorofluoro Ethane solvent (R-112, R-121, R-131)
One or more fluorine-based compounds selected from
These are (co)polymer production reaction temperatures of 50 to 150℃.
It is liquid in the vicinity. Of course, since the liquid fluorine-based compound (C) is a dispersion medium, it must not dissolve more than 0.1% by weight of the (co)polymer at room temperature. Depending on the intended use, other suitable liquids, crosslinking agents, antistatic agents, etc. may be added to the obtained non-aqueous emulsion type water and oil repellent to an extent that the emulsion is not destroyed. The reason why the non-aqueous emulsion type water and oil repellent of the present invention is stable is not known in detail, but it is probably because the perfluoroalkyl groups selectively face outward (toward the liquid organic fluorine compound) and the hydroxyl groups face inward. It is presumed that the fluorine-based (co)polymer becomes spherical by stabilizing it by forming intermolecular and intramolecular hydrogen bonds, and exists stably as an emulsion. The nonaqueous emulsion type water and oil repellent of the present invention can be applied to fibers, paper, glass fibers, leather, etc. to make them water and oil repellent. In that case, the non-aqueous emulsion type water and oil repellent of the present invention is
It is stable without any auxiliary agents, can be handled without the risk of fire or toxicity, does not require a curing step during processing, and does not significantly impair the texture of processed fabrics. Next, the present invention will be explained in more detail with reference to Examples. Synthesis Example 1 In a 200 ml four-necked flask, 70 g of benzotrifluoride, 21 g of the monomer of -1 mentioned above, and 3-
Add 9 g of chloro-2-hydroxypropyl methacrylate, add 0.6 g of azobisisobutyronitrile as a catalyst, and 0.2 g of dodecyl mercaptan as a polymerization modifier, attach a thermometer, condenser, and nitrogen gas inlet tube, and heat to 80 ml while stirring. As the reaction progressed, a translucent stable emulsion was obtained. This emulsion is mechanically stable, with benzotrifluoride and R-113 to infinity, and tetrahydrofuran, methyl ethyl ketone and ethyl acetate to the order of 10 times.
Carbon tetrachloride, barchloroethylene, 1・1・1−
It was possible to dilute about 5 times with trichlorethylene and toluene. On the other hand, the aggregated emulsion was insoluble in all solvents. Moreover, the hydroxyl group content of this copolymer was 2.9% by weight. Synthesis Example 2 Polymerization was carried out under the same conditions as in Synthesis Example 1 except that 2-hydroxyethyl methacrylate was used instead of 3-chloro-2-hydroxypropyl methacrylate. A water emulsion was obtained. This emulsion contains benzotrifluoride,
R-113, fluorine-based liquid such as perfluorohexane to infinity, tetrahydrofuran, methyl ethyl ketone and dimethyl formamide to about 10 times, ethyl acetate, perchloroethylene, 1.1.
19. It was possible to dilute about 5 times with trichloroethylene, carbon tetrachloride, and toluene. On the other hand, the aggregated emulsion was insoluble in all solvents. Moreover, the hydroxyl group content of this copolymer was 3.9% by weight. Comparative synthesis example 1 70g of benzotrifluoride, -1 described above
21 g of monomer and 9 g of 2-chloroethyl vinyl ether were placed in a 200 ml four-necked flask, and 0.6 g of azobisisobutyronitrile was added as a catalyst.
and dodecyl mercabutane 0.2 as polymerization modifier
A thermometer, a condenser, and a nitrogen gas inlet tube were attached, and the temperature was raised to 80° C. with stirring. A uniform transparent solution was obtained without forming an emulsion. This solution was coagulated with methanol to obtain not only benzotrifluoride but also ethyl acetate,
Dissolved in 1,1,1-trichloroethane and methyl ethyl ketone. Comparative Synthesis Example 2 When polymerization was carried out under the same conditions as in Comparative Synthesis Example 1, except that n-stearyl methacrylate was used instead of 2-chloroethyl vinyl ether, no emulsion was obtained, but a uniform, transparent emulsion was obtained. A solution was obtained. This solution was coagulated with methanol and dissolved not only in benzotrifluoride but also in 1,1,1-trichloroethane, ethyl acetate, methyl ethyl ketone, toluene, and verchloroethylene. Comparative Synthesis Example 3 When polymerization was carried out under the same conditions as in Synthesis Example 1 except that n-propyl methacrylate was used instead of 2-hydroxypropyl methacrylate, an emulsion was not obtained but a uniform transparent solution was obtained. Obtained. The functional group content of this polymer was 0%. This solution was coagulated with methanol and dissolved in tetrahydrofuran, methyl ethyl ketone, and ethyl acetate. Comparative Synthesis Example 4 Among the conditions of Synthesis Example 1, 9g of 3-chloro-2-hydroxypropyl methacrylate was set to 3g, and n
- When polymerization was carried out under exactly the same conditions except that 6 g of propyl methacrylate was used, no emulsion was obtained but a homogeneous transparent solution was obtained. The functional group content of this polymer was 10% by weight. This solution was coagulated with methanol and dissolved in tetrahydrofuran, methyl ethyl ketone, and ethyl acetate. Example 1 The non-aqueous emulsions of Synthesis Examples 1 and 2 and the non-aqueous solutions of Comparative Synthesis Examples 1 to 4 were each diluted with benzotrifluoride to a polymer concentration of 0.5% by weight, and a cloth was immersed once in this treatment bath. Squeeze to 60% and air dry or cure (after air drying, 160%
℃ for 2 minutes) to make it water and oil repellent. The water repellency and oil repellency of the processed and unprocessed fabrics were measured by the AATCC method, and the bending resistance was measured by the handrometer method (slit width 1 cm).The results are shown below.

【table】

[Table] The bottom row is based on Quring. ”
As a result, it can be seen that the non-aqueous emulsion type water and oil repellent of the present invention can be softer than untreated cloth in some cases. Synthesis Example 3 80 g of perfluorodecalin and 20 g of monomer 1 mentioned above were placed in a 200 ml four-necked flask.
Furthermore, 0.5 g of benzoyl peroxide and 0.2 g of dodecyl mercaptan were added, and a thermometer and a nitrogen gas inlet tube were attached, and the mixture was heated to 80° C. and stirred. As the reaction progressed, a bluish non-aqueous emulsion was produced. The hydroxyl group content of this polymer was 2.6% by weight. Synthesis Example 4 80 g of perfluorotributylamine, 13 g of the above monomer -3 and 7 g of 3-chloro-2-hydroxypropyl methacrylate were mixed into 200 ml of 4
Add 0.4 g of azopisisobutylnitrile and 0.8 g of dodecyl mercaptan to a necked flask, attach a thermometer and nitrogen gas inlet tube, and heat to 75°C.
The mixture was heated and stirred. As the reaction progressed, a stable nonaqueous emulsion with a slightly yellowish color was produced. The hydroxyl group content of this copolymer is 3.3
It was in weight%. Synthesis example 5 m-xylylene hexafluoride 50g, 1.
30g of 1,1-trichloroethane, -5 mentioned above
Put 16 g of the monomer and 4 g of 2-hydroxyethyl methacrylate into a 200 ml four-necked flask,
Furthermore, 0.5 g of benzoyl peroxide and 0.3 g of dodecyl mercaptan were added, and a thermometer and a nitrogen gas introduction tube were attached, and the mixture was heated to 80° C. and stirred. As the reaction progressed, a bluish, translucent non-aqueous emulsion was produced. The hydroxyl group content of this copolymer was 2.6% by weight. Synthesis Example 6 Polymerization was carried out under the same conditions as in Synthesis Example 1 except that monomer -6 was used instead of monomer -1, and a non-aqueous emulsion with a bluish tint was obtained. The hydroxyl group content of this copolymer was 2.9% by weight. Synthesis Example 7 Polymerization was carried out under the same conditions as in Synthesis Example 2, except that monomer -4 was used instead of monomer -1, and a non-aqueous emulsion with a bluish tinge was obtained. The hydroxyl group content of this copolymer was 3.9%. Example 2 The nonaqueous emulsions obtained in Synthesis Examples 3, 4, 6, and 7 were diluted with R-113, and the nonaqueous emulsions obtained in Synthesis Example 5 were diluted with perfluorobutyltetrahydrofuran to a polymer concentration of 0.5% by weight, respectively. Using this treatment bath, nylon taffeta was treated to be water and oil repellent in the same manner as in Example 1. The water repellency and oil repellency of processed and unprocessed fabrics were examined using the AATCC method, and the results are shown below.

[Table] There was no change in the texture of any of the processed fabrics. The results in Tables 1 and 2 also show that the non-aqueous emulsion type water and oil repellent of the present invention does not require "curing".

Claims (1)

[Claims] 1 General formula (A) [Formula] [In the formula, Rf is a perfluoroalkyl group represented by ClF _2l+1 (l = 4 to 16), and Q ₁ is -(CH ₂ ) _-n , [Formula] [Formula] [Formula] (However, m = an integer of 1 to 10; R ₂ is H, or an alkyl group having a carbon number of 1 to 18 or an OH-containing alkyl group.) Q ₂ is -O- or [Formula], and R ₁ is H or CH ₃ . ] A monomer (A) represented by the general formula (B) [Formula] In the formula, R ₁ is H or CH ₃ . Copolymer with monomer (B) represented by m=2~10 n=2m+1-pq p≧0 integer q≧1 integer, or R ₂
However, the homopolymer of the monomer (A) which is an OH-containing alkyl group has 2% by weight or more of hydroxyl groups, and (C) benzotrifluoride, m-xylene hexafluoride, hexafluorobenzene, perfluorobenzene, etc. One or more liquid fluorine selected from decalin, perfluorohexane, perfluoromethylcyclohexane, perfluorotriptylamine, perfluorobutyltetrahydrofuran, and chlorofluoroethane solvents (R-112, R-121, R-131) A non-aqueous emulsion type water and oil repellent characterized by being dispersed in a system compound (C). 2. The nonaqueous emulsion type water and oil repellent according to claim 1, wherein the (co)polymer has a molecular weight of 1,000 to 500,000. 3. The nonaqueous emulsion type water and oil repellent agent according to claim 1 or 2, wherein the (co)polymer contains 10 to 70% by weight of fluorine atoms and 2 to 10% by weight of hydroxyl groups. . 4. Claim 1, wherein the (co)polymer has a fluorine atom/hydroxyl group weight ratio of 2 to 700.
The non-aqueous emulsion type water and oil repellent according to item 1 or 2. 5. Claim 3, wherein the (co)polymer has a weight ratio of fluorine atoms/hydroxyl groups of 2 to 700.
The non-aqueous emulsion type water and oil repellent described in 2. 6. The nonaqueous emulsion type water and oil repellent according to claim 1, 2, or 5, wherein the concentration of the (co)polymer is 1 to 50% by weight. 7. The nonaqueous emulsion type water and oil repellent according to claim 3, wherein the concentration of the (co)polymer is 1 to 50% by weight. 8. The nonaqueous emulsion type water and oil repellent according to claim 4, wherein the concentration of the (co)polymer is 1 to 50% by weight.