JP2515988B2 - Water and oil repellent - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to a water- and oil-repellent agent containing a fluorine-containing copolymer, and more specifically, a fluorine-containing copolymer which does not yellow even when heated. The present invention relates to a water / oil repellent containing a polymer.

Technical Background of the Invention and Problems Thereof In order to impart water repellency or oil repellency to fibers such as cotton, it has been widely practiced to treat the fibers with a fluorocopolymer. As a fluorine-containing copolymer for imparting water and oil repellency to such fibers, a copolymer of (a) a fluoroalkyl (meth) acrylate and (b) vinyl chloride or vinylidene chloride has been conventionally used. It has been used mainly. (B) Vinyl chloride or vinylidene chloride has been used as a monomer to be copolymerized with (a) a fluoroalkyl (meth) acrylate.
(B) Vinyl chloride or vinylidene chloride does not adversely affect the water / oil repellency of the (a) fluoroalkyl (meth) acrylate when copolymerized with the (a) fluoroalkyl (meth) acrylate. This is because b) vinyl chloride and vinylidene chloride are inexpensive, and the copolymer obtained by copolymerizing the above (a) and (b) has good affinity with fibers.

However, the water- and oil-repellent agent containing a fluorine-containing copolymer obtained by copolymerizing (a) a fluoroalkyl (meth) acrylate with (b) vinyl chloride or vinylidene chloride has the following problems. . That is, when the fiber was treated with the water and oil repellent agent containing the fluorine-containing copolymer and then the fiber was heated, the fiber sometimes turned yellow.
It is presumed that this is because the vinylidene chloride and vinyl chloride components in the copolymer are heated to cause a dehydrochlorination reaction and the fluorine-containing copolymer turns yellow. And such a yellowing phenomenon, the higher the concentration of the fluorine-containing copolymer in the water and oil repellent for treating the fiber, the higher the curing temperature at the time of curing the treated fiber, and It becomes noticeable as the curing time increases.

Moreover, recently, there is an increasing tendency to treat fibers with a water- and oil-repellent agent containing a high concentration of a fluorine-containing copolymer, which is called a high-grade finish, and thus the yellowing phenomenon of the fibers as described above is noticeable. It is like this.

An object of the present invention is to solve the problems associated with the prior art as described above, in which the fiber is treated with a water / oil repellent containing a fluorine-containing copolymer in a high concentration. Even if the treated fiber is cured at a high temperature for a long time, it is an object of the invention to provide a water and oil repellent agent which does not cause yellowing of the fiber.

SUMMARY OF THE INVENTION A first water and oil repellent according to the present invention comprises (i) a fluoroalkyl group-containing monomer represented by the following formula [I], and (ii) (meth) acrylic acid represented by the following formula [II]. It is characterized by containing a fluorine-containing copolymer having an ester as a copolymerization unit.

(In the formula, R ₃ is hydrogen or a lower alkyl group, and n is 6 to
12 is an integer, and m is an integer of 1 to 4. ) (In the formula, R ₁ and R ₂ may be the same or different and each is hydrogen or a lower alkyl group, and n is 1
It is an integer of ~ 20. The second water- and oil-repellent agent according to the present invention is (i) a fluoroalkyl group-containing monomer represented by the above formula [I], and (ii) a (meth) acrylic acid ester represented by the above formula [II]. And (iii) a fluorinated copolymer having benzyl (meth) acrylate as a copolymerized unit.

The water and oil repellent according to the present invention comprises (i) a fluoroalkyl group-containing monomer, (ii) a (meth) acrylic acid ester, and optionally (iii) benzyl (meth) acrylate as a third comonomer. Since it contains a fluorinated copolymer having as a copolymerized unit, even if the fiber is treated with a water / oil repellent containing a high concentration of this fluorinated copolymer, Even when cured at a temperature for a long time, the fluorine-containing copolymer does not turn yellow, and therefore the fibers do not turn yellow, and the water-repellent and oil-repellent properties are excellent.

DETAILED DESCRIPTION OF THE INVENTION The water and oil repellent according to the present invention will be described in more detail below.

The water and oil repellent according to the present invention comprises (i) a fluoroalkyl group-containing monomer represented by the above formula [I], (ii) a (meth) acrylic acid ester represented by the above formula [II], and optionally ( iii) It contains a fluorinated copolymer having benzyl methacrylate as a constituent unit.

The fluoroalkyl group-containing monomer (i) is preferably present in the fluorocopolymer in an amount of 40% by weight or more, and preferably 50 to 70% by weight.

Further, (ii) the (meth) acrylic acid ester represented by the above formula [II] as a constitutional unit of the fluorocopolymer may be present in the fluorocopolymer in an amount of 3 to 50% by weight. desirable. In this fluorine-containing copolymer (i
i) When the amount of (meth) acrylic acid ester is less than 3 mol%, the affinity for fibers such as cotton is decreased, which is not preferable. On the other hand, when it exceeds 50 mol%, the resulting fluorine-containing copolymer is It is not preferable because the chemical stability decreases.

In the (ii) (meth) acrylic acid ester represented by the above general formula [II], n is an integer of 1 to 20 as described above, but when n exceeds 20, fibers such as cotton are It is not preferable because the affinity is lowered, and in consideration of the emulsion stability during production of the fluorocopolymer, n is preferably 10 or less.

As a constitutional unit of the fluorine-containing copolymer according to the present invention, (iii) benzyl (meth) acrylate, which is optionally used, has the general formula (Wherein R ₄ is hydrogen or a lower alkyl group).

Such benzyl (meth) acrylate is present in the fluorocopolymer according to the present invention in an amount of 0 to 50% by weight.

Next, the method for producing the above-mentioned fluorine-containing copolymer will be described. This fluorine-containing copolymer can be produced by an emulsion polymerization method or a solution polymerization method.

In the emulsion polymerization method, the above copolymer monomer,
Water and an organic solvent are added to a surfactant, a chain transfer agent, etc. so that the solid content concentration becomes 20 to 30% by weight, and these mixtures are emulsified by using a stirring device such as a colloid mill. Then, the obtained emulsion was transferred to a reaction vessel equipped with a stirrer, the system was replaced with nitrogen, and then a polymerization initiator was charged into the system and heated to a temperature of 40 to 70 ° C to carry out the polymerization reaction. A fluorocopolymer is obtained.

Further, in the solution polymerization method, to the above-mentioned copolymerization monomer, polymerization initiator, etc., an organic solvent is added so that the solid content concentration becomes 20 to 30% by weight, and the obtained product is transferred to a reaction vessel with a stirrer, After substituting the system with nitrogen, the system is heated to a temperature of 40 to 70 ° C. to cause a polymerization reaction to obtain a fluorocopolymer.

Emulgen 950 (manufactured by Kao Soap) or the like is used as the surfactant used in the emulsion polymerization method, and n-dodecyl mercaptan or the like is used as the chain transfer agent.

As the organic solvent, acetone or the like is used,
As the polymerization initiator, V-50 (manufactured by Wako Pure Chemical Industries, Ltd.) or the like is used.

As the organic solvent used in the solution polymerization method, 1,1,2-
Trichloro-1,2,2-trifluoroethane or the like is used, and as the polymerization initiator, Pacadox P-16 is used.
(Made by Kayaku Nouri) and the like are used.

The fluorine-containing copolymer thus obtained has the constitutional units (i) and (ii) and optionally (iii)
Are arranged randomly.

By diluting the emulsion or solution containing the fluorocopolymer thus obtained with water or an organic solvent, the water / oil repellent according to the present invention can be obtained.

The performance test of the water and oil repellent obtained as described above,
This is done as follows.

The fluorine-containing copolymer obtained by the emulsion polymerization method is diluted with water so that the solid content concentration becomes 0.5% by weight, and the cotton kanakin No. 3 fabric is sufficiently dipped in the obtained liquid and squeezed to 80 Dry with warm air for 10 minutes at ℃
Cure at 3 ° C for 3 minutes to obtain a water / oil repellent test cloth.

On the other hand, the fluorine-containing copolymer obtained by the solution polymerization method is obtained by diluting with 1,1,2-trichloro-1,2,2-trifluoroethane so that the solid content concentration becomes 0.5% by weight. Soak the cotton kanakin No. 3 cloth in the solution and squeeze it to 80
Dry with warm air at ℃ for 10 minutes to make a water and oil repellent test cloth.

Regarding the water / oil repellent test cloth thus obtained, JI
Water repellency is tested by the S.L-1092 spray method and oil repellency is tested by the Nujol-n-heptane method.

Further, in the following examples, the color change test of the fibers is performed as follows.

The fluorine-containing copolymer obtained by the emulsion polymerization method is diluted with water so that the solid content concentration becomes 10% by weight,
Cotton kanakin No. 3 fabric was thoroughly dipped in the obtained liquid, squeezed, dried with warm air at 80 ° C, and further cured at 170 ° C for 30 minutes to determine the whiteness of the fiber, the color tone and the reflectance. It is evaluated by measuring.

On the other hand, the fluorine-containing copolymer obtained by the solution polymerization method was obtained by diluting it with 1,1,2-trichloro-1,2,2-trifluoroethane until the solid content concentration became 10% by weight. Dip cotton kanakin No. 3 cloth in the liquid sufficiently and squeeze it to 80 ℃
Dry with warm air at 37 ° C., cure for an additional 30 minutes at 170 ° C., and evaluate the whiteness of the fiber by measuring the shade and reflectance.

 The evaluation of color tone is as follows.

A: No discoloration B: Slightly reduced whiteness C: A slight yellowing is visible.

D: Yellowing Measurement of reflectance It is examined how much the reflectance decreases when the reflectance of the cotton Kanakin No. 3 fabric which has not been treated with the water and oil repellent agent is set to 100%. When this value is 90% or less, it looks slightly yellowish with the naked eye.

The water- and oil-repellent agent according to the present invention does not cause yellowing of treated fibers or decrease in whiteness and reflectance even when containing a fluorine-containing copolymer at a high concentration. . Further, the water and oil repellent according to the present invention does not cause yellowing of the treated fiber or decrease in whiteness and the reflectance also decreases even when the treated fiber is cured at a high temperature for a long time. do not do. This is the above formula [II] in the fluorine-containing copolymer.
It is considered that this is probably because the (meth) acrylic acid ester represented by

Moreover, the fiber treated with the water / oil repellent according to the present invention exhibits excellent water repellency and oil repellency. For example, in the fluorine-containing copolymer, (meth) represented by the above formula [II]
By including an acrylate ester as a constitutional unit, (i) a fluoroalkyl group-containing monomer and (ii)
i) The water repellency and especially the oil repellency are improved as compared with the water and oil repellent agent containing a fluorine-containing copolymer containing benzyl (meth) acrylate as a constituent unit.

EFFECTS OF THE INVENTION The water and oil repellent according to the present invention comprises (i) a fluoroalkyl group-containing monomer, (ii) a (meth) acrylic acid ester, and optionally (iii) benzyl (meth) as a third comonomer. Since it contains a fluorine-containing copolymer having acrylate as a copolymerized unit, it can be treated even if the fiber is treated with a water- and oil-repellent agent containing this fluorine-containing copolymer in a high concentration. Even when the fiber is cured at a high temperature for a long time, the fluorine-containing copolymer does not yellow, and therefore the fiber does not yellow, and in addition, it has excellent water repellency and oil repellency.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 56 g of perfluorooctylethyl acrylate (FAA)
(70% by weight of the constitutional unit of the fluorine-containing copolymer), CH ₂ = CHC
OO (C ₂ H ₄ O) C ₆ H ₅ (NK ester AMP-10G manufactured by Shin Nakamura Chemical) 1
6 g (20% by weight of the constitutional unit of the fluorine-containing copolymer), benzyl methacrylate 8 g (10% of the constitutional unit of the fluorine-containing copolymer)
% By weight), 6 g of N-methylol acrylamide, [CH ₂ =
_{C (CH 3) COOCH 2 CH} 2 N (CH 3) 3] + Cl - 0.2g, n- dodecyl mercaptan 0.32 g, Emulgen 9506G, acetone 30g
After a colloid mill treatment was performed on a mixture of water and 152 g of water, the mixture was charged into a flask, and N ₂ gas replacement was performed for 30 minutes while stirring. The temperature was raised during N ₂ gas replacement, but was set to 40 ° C. after 30 minutes. Then, an aqueous solution prepared by dissolving 2 g of an azo radical initiator (Wako Pure Chemicals V-50) in 50 g of water was added to the reaction system, and a copolymerization reaction was carried out at 70 ° C for 4 hours to obtain a solid content concentration of 25% by weight. A fluorine-containing copolymer emulsion of was obtained.

This fluorine-containing copolymer emulsion has a solid content of
Dilute with water to 0.5% by weight, soak the cotton kanakin No. 3 dough in the obtained solution, squeeze it, dry with warm air at 80 ° C for 10 minutes, and further cure it at 150 ° C for 3 minutes. A water- and oil-repellent test cloth was made by ringing.

Regarding the water / oil repellent test cloth thus obtained, JI
Water repellency was tested by the S.L-1092 spray method, and oil repellency was tested by Nujol-n-heptane.

 Table 1 shows the results.

 Further, the color change test of the fiber was conducted as follows.

The fluorine-containing copolymer obtained as described above is diluted with water so that the solid content concentration becomes 10% by weight, and the cotton kanakin No. 3 dough is sufficiently dipped in the obtained liquid and squeezed, 80 ° C
It was dried with warm air at 37 ° C., and further cured at 170 ° C. for 30 minutes, and the whiteness of the fiber was evaluated by measuring the color tone and the reflectance.

A: No discoloration B: Slightly reduced whiteness C: A slight yellowing is visible.

D: Yellowing Measurement of reflectance It was examined how much the reflectance was reduced when the reflectance of the cotton kanakin No. 3 fabric which was not treated with the water and oil repellent was set to 100%. When this value is 90% or less, it looks slightly yellowish with the naked eye.

 Table 1 shows the results.

In Example 1, when producing the fluorine-containing copolymer, in place of _{CH 2 = CHCOO (C 2 H} 4 O) C 6 H 5, CH 2 = CHCOO
A fluorine-containing copolymer emulsion was produced in the same manner as in Example 1 except that (C ₂ H ₄ O) ₆ C ₆ H ₅ was used, and the water and oil repellency and discoloration test were conducted.

 Table 1 shows the results.

Example 3 In Example 1, in the production of the fluorine-containing copolymer, CH ₂ ═CHCOO instead of CH ₂ ═CHCOO (C ₂ H ₄ O) C ₆ H _5.
A fluorine-containing copolymer emulsion was produced in the same manner as in Example 1 except that (C ₂ H ₄ O) ₂ C ₆ H ₅ was used, and the water / oil repellency and discoloration test were conducted.

 Table 1 shows the results.

Example 4 In Example 1, in the production of the fluorine-containing copolymer, CH ₂ ═CHCOO instead of CH ₂ ═CHCOO (C ₂ H ₄ O) C ₆ H _5.
(C ₂ H ₄ O) ₂ C ₆ H ₅ was used in the same manner as in Example 1 except that the amount was 25% by weight and the amount of benzyl methacrylate was 5% by weight. Was manufactured and subjected to water and oil repellency and discoloration tests.

 Table 1 shows the results.

Example 5 In Example 1, in producing the fluorine-containing copolymer, CH ₂ ═CHCOO (C ₂ H ₄ O) C ₆ H ₅ instead of CH ₂ ═CHCOO.
(C ₂ H ₄ O) ₂ C ₆ H ₅ was used in the same manner as in Example 1 except that 24 g was used and no amount of benzyl methacrylate was used.
A fluorine-containing copolymer emulsion was produced and subjected to water / oil repellency and discoloration tests.

 Table 1 shows the results.

Example 6 56 g of perfluorooctylethyl acrylate (FAA)
(70% by weight), CH ₂ = CHCOO (C ₂ H ₄ O) ₂ C ₆ H ₅ (NK ester AMP-20G manufactured by Shin Nakamura Chemical) 12 g (15% by weight), benzyl methacrylate 12 g (15% by weight), parka Docks P-16
(Made by Kayaku Nouri) 1 g and 1,1,2-trichloro-1,2,2
-A mixture of 185 g of trifluoroethane was charged into a flask, and nitrogen substitution was carried out for 30 minutes while stirring. Thereafter, this mixture was heated to 70 ° C. and subjected to a copolymerization reaction for 24 hours to obtain an aqueous solution of a fluorine-containing copolymer having a solid content concentration of 30% by weight.

This fluorinated copolymer solution was diluted with 1,1,2-trichloro-1,2,2-trifluoroethane so that the solid concentration was 0.5% by weight, and the resulting solution was coated with cotton kanakin No. 3 fabric. After sufficiently immersing, it was squeezed and dried with warm air at 80 ° C. for 10 minutes to obtain a water / oil repellent test cloth.

Using the obtained water / oil repellent test cloth, water repellency and oil repellency were evaluated in the same manner as in Example 1.

Further, the obtained fluorine-containing copolymer, solid concentration of 10
Dilute with 1,1,2-trichloro-1,2,2-trifluoroethane until the weight% is reached, fully immerse the cotton kanakin No. 3 dough in the resulting solution, squeeze, and warm at 80 ° C. Air dried and further cured at 170 ° C. for 30 minutes and the whiteness of the fiber was evaluated by measuring the shade and reflectance.

 Table 1 shows the results.

Comparative Example 1 In the same manner as in Example 1 except that CH ₂ ═CHCOO (C ₂ H ₄ O) C ₆ H ₅ and 24 g of vinylidene chloride (VDC) were used instead of benzyl methacrylate, A fluorine-containing copolymer emulsion was produced and subjected to water / oil repellency and discoloration tests.

 Table 1 shows the results.

Comparative Example 2 In Example 1, except that CH ₂ ═CHCOO (C ₂ H ₄ O) C ₆ H ₅ 16 g and benzyl methacrylate 8 g were replaced with vinylidene chloride (VDC) 20 g and benzyl methacrylate 4 g, A fluorine-containing copolymer emulsion was produced in the same manner as in Example 1, and the water and oil repellency and discoloration tests were conducted.

 Table 1 shows the results.

Comparative Example 2 In Example 1, 12 g of vinylidene chloride (VDC) and 12 g of benzyl methacrylate were used instead of 16 g of CH ₂ = CHCOO (C ₂ H ₄ O) C ₆ H ₅ and 8 g of benzyl methacrylate, A fluorine-containing copolymer emulsion was produced in the same manner as in Example 1, and the water and oil repellency and discoloration tests were conducted.

 Table 1 shows the results.

Comparative Example 4 In Example 1, except that CH ₂ ═CHCOO (C ₂ H ₄ O) C ₆ H ₅ 16 g and benzyl methacrylate 8 g were used instead of vinylidene chloride (VDC) 4 g and benzyl methacrylate 20 g, A fluorine-containing copolymer emulsion was produced in the same manner as in Example 1, and the water and oil repellency and discoloration tests were conducted.

 Table 1 shows the results.

Comparative Example 5 In the same manner as in Example 1 except that CH ₂ ═CHCOO (C ₂ H ₄ O) C ₆ H ₅ and 24 g of benzyl methacrylate were used instead of benzyl methacrylate in Example 1,
A fluorine-containing copolymer emulsion was produced and subjected to water / oil repellency and discoloration tests.

 Table 1 shows the results.

Comparative Example 6 In Example 1, instead of CH ₂ ═CHCOO (C ₂ H ₄ O) C ₆ H ₅ , and benzyl methacrylate, vinyl chloride (V
A fluorocopolymer emulsion was prepared in the same manner as in Example 1 except that 24 g of C) was used, and the water and oil repellency and discoloration tests were conducted.

 Table 1 shows the results.

Comparative Example 7 Example 1 was repeated except that CH ₂ = CHCOO (C ₂ H ₄ O) C ₆ H ₅ and 24 g of (N-methylol acrylamide) (NMAM) were used in place of benzyl methacrylate in Example 1. A fluorine-containing copolymer emulsion was prepared in the same manner as above, and the water / oil repellency and discoloration test were conducted.

 Table 1 shows the results.

Comparative Example 8 Instead of 12 g of CH ₂ ═CHCOO (C ₂ H ₄ O) C ₆ H _{5 and} 12 g of benzyl methacrylate in Example 6, 15 g of vinylidene chloride (VDC) and 15 g of benzyl methacrylate were used.
A fluorine-containing copolymer emulsion was produced in the same manner as in Example 6 except that was used, and the water / oil repellency and discoloration test were conducted.

 Table 1 shows the results.

Claims (7)

(57) [Claims] 1. A fluorine-containing copolymer having (i) a fluoroalkyl group-containing monomer represented by the following formula [I] and (ii) a (meth) acrylic acid ester represented by the following formula [II] as copolymerized units. A water and oil repellent comprising a polymer: (In the formula, R ₃ is hydrogen or a lower alkyl group, and n is 6 to
12 is an integer, and m is an integer of 1 to 4. ) (In the formula, R ₁ and R ₂ may be the same or different and each is hydrogen or a lower alkyl group, and n is 1
It is an integer of ~ 20. ) 2. The water- and oil-repellent agent according to claim 1, wherein the fluoroalkyl group-containing monomer is present in the fluorocopolymer in an amount of 40% by weight or more. 3. The water and oil repellent agent according to claim 1, wherein the (meth) acrylic acid ester is present in the fluorocopolymer in an amount of 40% by weight or more. 4. A fluoroalkyl group-containing monomer represented by the following formula [I], (ii) a (meth) acrylic acid ester represented by the following formula [II], and (iii) benzyl (meth) acrylate. A water- and oil-repellent agent comprising a fluorine-containing copolymer having and as a copolymerized unit: (In the formula, R ₃ is hydrogen or a lower alkyl group, and n is 6 to
12 is an integer, and m is an integer of 1 to 4. ) (In the formula, R ₁ and R ₂ may be the same or different and each is hydrogen or a lower alkyl group, and n is 1
It is an integer of ~ 20. ) 5. The water and oil repellent according to claim 4, wherein the fluoroalkyl group-containing monomer is present in the fluorocopolymer in an amount of 40% by weight or more. 6. The water and oil repellent according to claim 4, wherein the (meth) acrylic acid ester is present in the fluorocopolymer in an amount of 40% by weight or more. 7. The water and oil repellent according to claim 4, wherein the benzyl (meth) acrylate is present in the fluorine-containing copolymer in an amount of 0 to 50% by weight.