JPH05345810A - Dispresion of fluorine-containing water-base resin - Google Patents

Abstract

PURPOSE:To provide a fluorine-containing water-base resin dispersion having small emulsion particle diameter, exhibiting excellent safety and containing the dispersed water-base resin particles in high stability even by using only a small amount of an emulsifier. CONSTITUTION:This fluorine-containing water-base resin dispersion is produced by polymerizing a (meth)acrylic acid ester having fluoroalkyl group or copolymerizing the ester and other monomer copolymerizable therewith in the presence of an N-alkylpyrrolidone in an aqueous medium.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a water / oil repellent, weather resistance,
The present invention relates to a fluorine-containing water-based resin dispersion useful as a stain-resistant paint, etc., and particularly to a water- and oil-repellent agent comprising the fluorine-containing water-based resin dispersion capable of imparting excellent water and oil repellency to fibers, paper and the like. Is.

[0002]

2. Description of the Related Art As a water- and oil-repellent agent, a fluorine-containing aqueous resin dispersion used for paints, etc., a polymer obtained by polymerizing a (meth) acrylic acid ester having a fluoroalkyl group, or ) A fluorine-containing aqueous resin dispersion comprising a copolymer obtained by copolymerizing an acrylic ester and the like is known (Japanese Patent Publication No. 34-8838).

The polymers or copolymers constituting these fluorine-containing aqueous resin dispersions are generally produced by emulsion polymerization, but if emulsion polymerization is carried out using only water as the dispersion medium, the emulsion stability will be improved. Getting worse,
Since an emulsion with a large particle size is produced, usually, a water-soluble organic solvent is added to the aqueous dispersion medium during the polymerization reaction in order to improve the emulsion stability and obtain an emulsion with a small particle size. .. As specific examples thereof, acetone, methanol (Japanese Patent Publication No. 34-8838), polyhydric alcohols, and etherified or esterified derivatives of polyhydric alcohols (Japanese Patent Publication No. 53-4160) are known.

[0004]

However, the fluorine-containing aqueous resin dispersion produced by using a low-boiling water-soluble organic solvent such as acetone or methanol has a low flash point, and the flash, Since there is a risk of explosion, it is necessary to use equipment with explosion-proof equipment in manufacturing,
Moreover, its use is restricted due to pollution. Further, the fluorine-containing aqueous resin dispersion produced using a polyhydric alcohol or the like, the solubility of the polyhydric alcohol and the fluorine-based resin constituting the aqueous resin dispersion is not good, a small amount of emulsifier, Since it is difficult to obtain a stable emulsified dispersion, it is necessary to add a large amount of an emulsifier, but when the aqueous dispersion contains a large amount of an emulsifier, the water resistance of the fluorine-containing aqueous resin dispersion becomes poor. It had the drawback that it would end up.
The present inventors have conducted diligent studies in order to find a fluorine-containing aqueous resin dispersion in which the aqueous resin dispersion is stable even when the amount of the emulsifier used is small and the emulsion particle size is small.

[0005]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have made a monomer composed of a (meth) acrylic acid ester having a fluoroalkyl group aqueous in the presence of N-alkylpyrrolidone. The present invention has been completed by finding that an aqueous resin dispersion produced by polymerization in a medium is effective. That is, in the present invention, a (meth) acrylic acid ester having a fluoroalkyl group or the ester and another monomer copolymerizable therewith are polymerized in an aqueous medium in the presence of N-alkylpyrrolidone. The present invention relates to a fluorine-containing aqueous resin dispersion obtained as described above, and a water / oil repellent agent comprising the fluorine-containing aqueous resin dispersion.

The N-alkylpyrrolidone used in the present invention is a compound having a high boiling point and a high flash point, unlike a low-boiling point water-soluble organic solvent such as acetone or methanol, and therefore is excellent in safety. Is. N-methylpyrrolidone is used as a polymerization stabilizer for urethane type polymers, and as an application to a fluorine type compound, it is disclosed in JP-A-61-2.
In No. 49538, there is an example used in the production of a fluorine-containing polyurethane, but an application example to a polymer or a copolymer obtained by polymerizing a (meth) acrylic acid ester having a fluoroalkyl group is not known. ..

The present invention will be described in detail below. In addition, the (meth) acrylic acid ester shown below means an acrylic acid ester or a methacrylic acid ester. ○ (Meth) acrylic acid ester having a fluoroalkyl group A (meth) acrylic acid ester having a fluoroalkyl group used as an essential component for producing the polymer or copolymer constituting the fluorine-containing aqueous resin dispersion of the present invention is ,
Various conventionally known compounds can be used. For example, CH ₂ = CHCOO (CH ₂ ) ₂ (C
F ₂ ) ₈ CF ₃ , CH ₂ = CHCOO (CH ₂ ) ₂ (C
_{F 2) 6 CF (CF 3} ) CF 3, CH 2 = CHCOO
(CH ₂ ) ₃ (CF ₂ ) ₇ CF ₃ , CH ₂ = CHCOO
(CH ₂ ) ₃ (CF ₂ ) ₆ CF (CF ₃ ) CF ₃ , CH
₂ = CHCOO (CH ₂ ) ₃ (CF ₂ ) ₁₀ CF (C
F ₃ ) CF ₃ , CH ₂ = CHCOO (CH ₂ ) ₁₁ (CF
₂ ) ₇ CF ₃ , CH ₂ = C (CH ₃ ) COOCH ₂ (C
_{F 2) 4 CF 3, CH} 2 = C (CH 3) COO (C
_{H 2) 2 (CF 2)} 2 CF 3, CH 2 = C (CH 3) C
_{OO (CH 2) 2 (CF} 2) 3 CF 3, CH 2 = C (C
_{H 3) COO (CH 2)} 2 (CF 2) 4 CF 3, CH 2
_{= C (CH 3) COO (} CH 2) 2 (CF 2) 5 C
F ₃ , CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₂ (CF
₂ ) ₆ CF _{3 and} other general formulas CH ₂ ═C (R) COOR ¹ R
_f (R is hydrogen or a methyl group, R ¹ is a linear or branched alkylene group having ¹ to 11 carbon atoms, and R _f is 3 to
(Meth) acrylic acid fluoroalkyl ester represented by linear or branched perfluoroalkyl group having 15 carbon atoms, or CH ₂ ═CHCOO (C
_{H 2) 2 N (C 2} H 5) SO 2 (CF 2) 7 CF 3, C
_{H 2 = CHCOO (CH 2)} 2 N (C 3 H 7) SO
_{2 (CF 2) 7 CF 3} , CH 2 = CHCOO (CH 2)
₂ N (C ₄ H ₉ ) SO ₂ (CF ₂ ) ₇ CF ₃ , CH ₂ =
_{C (CH 3) COO (CH} 2) 2 N (CH 3) SO
General formula CH ₂ ═C (R) CO such as ₂ (CF ₂ ) ₇ CF ₃
(Meth) acrylic acid ester having a sulfonamide group represented by OR ¹ N (R ² ) SO ₂ R _f (R is hydrogen or a methyl group, R ¹ is a straight chain having ¹ to 11 carbon atoms) Or a branched alkylene group, R ² is a linear or branched alkyl group having 1 to 10 carbon atoms, and R _f is 3 to
A linear or branched perfluoroalkyl group having 15 carbon atoms can be mentioned. The (meth) acrylic acid ester having a fluoroalkyl group may be used alone or in combination of two or more.

Other monomers In the present invention, the above-mentioned (meth) acrylic acid ester having a fluoroalkyl group is an essential component. However, if desired, other vinyl radical polymerizable vinyl monomers such as those shown below are used. A quantity can also be used. In the present invention, the use of a (meth) acrylic acid ester not having a fluoroalkyl group as the other radically polymerizable vinyl monomer may improve the reactivity of the (meth) acrylic acid ester having a fluoroalkyl group. It is preferable because the amount of the (meth) acrylic acid ester having a fluoroalkyl group which is high and expensive can be reduced. Specific examples of the (meth) acrylate ester having no fluoroalkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylate. Isobutyl acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (meth)
Alkyl (meth) acrylates such as octyl acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, cyclohexyl (meth) acrylate, Aromatic (meth) acrylic acid esters such as benzyl (meth) acrylate and phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate,
Examples thereof include 2-hydroxybutyl (meth) acrylate, hydroxyalkyl (meth) acrylates such as polyalkylene glycol (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and the like. It is also possible to use two or more of these in copolymerization. The copolymerization ratio of the (meth) acrylic acid ester having a fluoroalkyl group in the case of carrying out the above-mentioned copolymerization is such that the fluoroalkyl group does not (meth)
5 to 99% by weight is preferable based on the total amount of the acrylic acid ester, and if it is less than 5% by weight, it is difficult to obtain sufficient water and oil repellency. A more preferable copolymerization ratio is 2
It is 0 to 60% by weight.

Other radically polymerizable vinyl monomers include, in addition to the above-mentioned (meth) acrylic acid ester having no fluoroalkyl group, aromatic vinyls such as styrene, vinyltoluene and α-methylstyrene, ( Meta)
Unsaturated carboxylic acids such as acrylic acid and phthalic anhydride,
Unsaturated nitriles such as (meth) acrylonitrile, vinyl carboxylates such as vinyl acetate and vinyl propionate,
(Meth) acrylamides such as N-methylol (meth) acrylamide, halogenated alkenes such as vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride, trichloroethylene, vinyl groups such as γ-methacryloxypropyltrimethoxysilane It is also possible to use silanes and the like having, and in addition to the above-mentioned (meth) acrylic acid ester having no fluoroalkyl group at the time of copolymerization, one kind or two or more kinds can be used. Does not have these fluoroalkyl groups (meth)
The copolymerization ratio of the other vinyl monomers other than the acrylic ester is preferably 10% by weight or less based on the total amount of all the monomers used for the copolymerization.

N-alkylpyrrolidone N-indispensable for the fluorine-containing aqueous resin dispersion of the present invention.
Alkylpyrrolidone has the action of promoting polymerization stability and reducing the particle size of the product when it is present in the reaction system. Moreover, since it has a high boiling point (boiling point 200 ° C. in the case of N-methylpyrrolidone), it is a non-dangerous substance even if added, and it is excellent in safety. Examples of the N-alkylpyrrolidone include N-methylpyrrolidone, N-ethylpyrrolidone and N-propylpyrrolidone, and it is preferable to use N-methylpyrrolidone. The amount of N-alkylpyrrolidone added is 0.1 to 20 parts by weight based on 100 parts by weight of water in the fluorine-containing aqueous resin dispersion. If it is 0.1 parts by weight or less, the effect of adding N-methylpyrrolidone does not appear, and if it is 20 parts by weight or more, the cost becomes high, which is not practical.

Method for Producing Fluorine-Containing Aqueous Resin Dispersion The fluorine-containing aqueous resin dispersion of the present invention can be produced using a known vinyl compound emulsion polymerization technique. For example, a monomer mixture comprising a (meth) acrylic acid ester having a fluoroalkyl group, or another radically polymerizable monomer such as a (meth) acrylic acid alkyl ester having no fluoroalkyl group and N. -Alkylpyrrolidone is added to an aqueous medium to which a surfactant has been added, and the mixture is stirred to prepare an emulsion dispersion, and then the emulsion dispersion and the radical polymerization initiator aqueous solution are polymerized by previously adding water. The method of supplying in a reaction container and superposing | polymerizing is mentioned. As a method for adding the N-alkylpyrrolidone, when preparing the emulsion dispersion as described above, it may be added to and mixed with the monomer or a mixture thereof or the emulsion dispersion, or in advance in a polymerization reaction vessel together with water. You may prepare it. For the purpose of the present invention, particularly for reducing the average particle size of the produced polymer, it is preferable that N-alkylpyrrolidone is present in the polymerization system at the initiation of the polymerization.

As the emulsifier used in the production of the fluorine-containing aqueous resin dispersion of the present invention, various kinds of commonly used anionic, cationic and nonionic surfactants can be used. Representative anionic emulsifiers include alkylbenzene sulfonic acid alkali metal salts, alkylnaphthalene sulfonic acid alkali metal salts, dialkyl sulfosuccinic acid alkali metal salts, alkyl sulfate alkali metal salts, polyoxyethylene alkyl ether sulfate alkali metal salts, and the like. .. Typical cationic emulsifiers are dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyltetradecylammonium chloride, trimethyloctadecylammonium chloride, (tridecylmethylbenzyl) trimethylammonium chloride, benzyldodecyldimethyl. Examples thereof include ammonium chloride and N-[(2-dimethylamino) ethyl] -oleamide hydrochloride. Typical nonionic emulsifiers include polyoxyethylene sorbitan monoalkylate, polyethylene glycol distearate, polyoxyethylene cetyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene polyoxypropylene block copolymer and the like. The nonionic emulsifier can be used in combination with an anionic emulsifier or a cationic emulsifier. The preferred amount of the emulsifier is 0.1 to 10 parts by weight per 100 parts by weight of the total amount of the monomers used,
It is more preferably 0.1 to 5 parts. The amount of the surfactant used is preferably smaller so as not to impair the water resistance of the resulting aqueous resin dispersion.

As the radical polymerization initiator, any of those generally used for radical polymerization can be used, and an appropriate one may be selected according to the polymerization method. For example, inorganic radical polymerization initiators include ammonium persulfate and hydrogen peroxide, and organic polymerization initiators include
Peroxyketals such as 2,2-bis (tert-butylperoxy) octane, hydroperoxides such as cumene hydroperoxide, dialkyl peroxides such as tert-butylcumyl peroxide, diacyl peroxides such as benzoyl peroxide, Peroxydicarbonate, peroxyester, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), azobis-4-cyanovaleric acid, azobis (2,4-dimethyl) Valeronitrile), Azobis (4
-Methoxy-2,4-dimethylvaleronitrile), dimethyl-2,2'-azobisisobutyrate, azobis-
Examples thereof include azo compounds represented by 1-cyclohexacarbonitrile and the like.

In order to adjust the molecular weight and viscosity, mercaptoacetic acid, mercaptopropionic acid, 2-propanethiol, 1-butanethiol, 2-methyl-2-propanethiol, 2-mercaptoethanol, ethylmercaptoacetate, thiophenol, Chain transfer agents such as 2-naphthalene thiol, dodecyl mercaptan, and thioglycerol can be used as necessary.

The polymerization temperature is generally preferably about 50 to 150 ° C, more preferably 60 to 100 ° C. The polymerization time can be variously selected according to the monomer to be used and the purpose, but it is preferably 3 to 100 hours, more preferably 5 to 10 hours.

Water- and oil-repellent agent The fluorine-containing aqueous resin dispersion of the present invention can be used as a coating material, a water- and oil-repellent agent, etc., but can impart excellent water and oil repellency to fibers, papers and the like. It is useful as a water and oil repellent. When used as a water / oil repellent, the treatable article can be used for various articles. For example, textile fabric, glass, paper, wood, leather, fur, brick, cement,
Metals, metal oxides, nitrification products, plastics, painted surfaces and blasters. Specific examples of fiber woven fabrics include
Animal fibers such as cotton, hemp, wool and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene and polytetrafluoroethylene, semi-synthetic fibers such as rayon and acetate, glass fibers, Alternatively, it can be applied to these mixed fibers.

[0017]

EXAMPLES The present invention will be described more specifically with reference to examples. In addition, "part" in each example means a "weight part."

Method for Producing Fluorine-Containing Aqueous Resin Dispersion Example 1 CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₂ (CF ₂ ) _n
CF ₃ (n = 2 to 5; n = 2: 5%, n = 3: 60%,
(n = 4: 25%, n = 5: 10%) to a mixed solution of 50 parts and 50 parts of methyl methacrylate, 1 part of N-methylpyrrolidone.
0 part was dissolved and the resulting liquid was emulsified and dispersed in 43 parts deionized water using 2 parts sodium lauryl sulfate as an emulsifier. The average particle size of the obtained emulsified dispersion is 0.1.
It was less than μm. To a 1 L flask equipped with a stirrer, a thermometer, and a condenser, 97 parts of deionized water was added, the internal temperature was kept at 80 ± 1 ° C. while blowing nitrogen gas, and then 10 parts by weight of a 10 wt% aqueous solution of ammonium persulfate and the above were stirred. 155 parts of the emulsion dispersion of the monomer mixture was added dropwise from the dropping funnel over 5 hours. After the dropping was completed, the reaction was continued for another 2 hours. The polymer was stable without separation or blocking. As a result of filtering the obtained resin dispersion with a 200-mesh net, the grid amount was 0.1 part or less. When the molecular weight of the obtained resin was measured by gel permeation chromatography, the polystyrene-reduced number average molecular weight was 162,000 and the weight average molecular weight was 8
It was 78,000. Further, the average particle size of the resin dispersion is measured by a laser diffraction particle size distribution measuring device LA- manufactured by Horiba, Ltd.
When measured by 500, it was 0.1 μm or less.

Example 2 CH ₂ = CHCOO (CH ₂ ) ₂ N (C ₄ H ₉ ) SO ₂
(CF ₂ ) ₇ CF ₃ Mixture of 30 parts, butyl methacrylate 70 parts, N-methylpyrrolidone 15 parts, polyoxyethylene octyl phenyl ether 3 as emulsifier
Parts, in the same manner as in Example 1, using deionized water 3
Emulsified and dispersed in 8 parts. The average particle size of the obtained emulsified dispersion was 0.1 μm or less. The obtained emulsified dispersion was polymerized in the same manner as in Example 1.
During the polymerization, separation and blocking did not occur and it was stable. As a result of filtering the obtained resin dispersion through a 200-mesh net, the grid amount was 0.1 part or less. When the molecular weight and average particle diameter of the obtained resin were measured in the same manner as in Example 1, the number average molecular weight was 156,000, the weight average molecular weight was 98,000, and the average particle diameter was 0.1 μm. It was below.

Example 3 CH ₂ = CHCOO (CH ₂ ) ₂ N (C ₄ H ₉ ) SO ₂
(CF ₂ ) ₇ CF ₃ 30 parts, butyl methacrylate 20
Part, stearyl methacrylate 49 parts, acrylic acid 1 part mixed solution, N-methylpyrrolidone 10 parts, trimethyltetradecyl ammonium chloride 2 as an emulsifier
Parts, in the same manner as in Example 1, using deionized water 3
Emulsified and dispersed in 8 parts. The average particle size of the obtained emulsified dispersion was 0.1 μm or less. The obtained emulsified dispersion was polymerized in the same manner as in Example 1.
During the polymerization, separation and blocking did not occur and it was stable. As a result of filtering the obtained resin dispersion through a 200-mesh net, the grid amount was 0.1 part or less. When the molecular weight and average particle diameter of the obtained resin were measured in the same manner as in Example 1, the number average molecular weight was 199,000, the weight average molecular weight was 100,000, and the average particle diameter of the dispersed resin was It was 0.1 μm or less.

Comparative Example 1 Emulsification and dispersion were carried out in the same manner as in Example 1 except that N-methylpyrrolidone was not added. However, emulsion dispersion was not carried out and a stable emulsion dispersion could not be obtained. By increasing the amount of sodium lauryl sulfate from 2 parts to 20 parts,
An emulsion dispersion could be obtained. The average particle size of the obtained emulsified dispersion was 2.22 μm. The obtained emulsified dispersion was polymerized in the same manner as in Example 1. Some grid was generated during the polymerization, but neither separation nor blocking occurred. The obtained resin dispersion is added to 200
As a result of filtering with a mesh net, the grid amount is 1.5
It was a department. When the molecular weight and average particle diameter of the obtained resin were measured by the same methods as in Example 1, the number average molecular weight was 1
It was 79,000, the weight average molecular weight was 912,000, and the average particle size of the dispersed resin was 0.43 μm.

Comparative Example 2 Emulsification and dispersion were carried out in the same manner as in Example 1 except that the same amount of butyl cellosolve was used instead of adding N-methylpyrrolidone, but a stable emulsion dispersion was obtained without emulsion dispersion. I couldn't.

Comparative Example 3 Emulsification and dispersion were carried out in the same manner as in Example 2 except that N-methylpyrrolidone was not added, but no stable emulsified dispersion could be obtained without emulsification and dispersion. An emulsion dispersion could be obtained by increasing the amount of polyoxyethylene octyl phenyl ether from 3 parts to 35 parts.
The average particle size of the obtained emulsified dispersion was 2.18 μm. The obtained emulsified dispersion was polymerized in the same manner as in Example 1. Some grid was generated during the polymerization, but neither separation nor blocking occurred. The resulting resin dispersion was filtered through a 200 mesh net,
The grid amount was 1.8 parts. When the molecular weight and average particle diameter of the obtained resin were measured by the same method as in Example 1, the number average molecular weight was 161,000 and the weight average molecular weight was 8
59,000 and the average particle size of the dispersed resin is 0.41μ
It was m.

Water / Oil Repellency Test Water repellency and oil repellency were tested by the following methods. The water repellency is according to the test method of "JISL-1005".
It was represented by "Water repellency No. by JISL-1005 spray" (see Table 1 below).

[0025]

[Table 1]

Oil repellency was tested according to the following test method using a test solution whose composition is shown in Table 2 below (product kit method). A test solution having a predetermined kit number is dropped from a height of 2.5 cm above the sample piece, and after 15 seconds, the oil drop is wiped off and the trace thereof is observed. If a trace of penetration of the test solution is found, the test is rejected, the display is less than the kit No. used, and the test solution is tested one rank lower. If no trace is found, the test is performed again with a test solution one rank higher, and the adjacent kit numbers with and without the trace are noted.

[0027]

[Table 2]

The water and oil repellency tests were conducted on the resin dispersion liquids produced in Examples 1 to 3 and Comparative Examples 1 and 2. The test piece was prepared by immersing each test base material in each resin dispersion liquid for 2 seconds,
It was manufactured by squeezing the base material between two rubber rollers to make the wet pickup 90% and drying at 100 ° C. for 3 minutes. The results are shown in Table 3. The resin dispersions having comparatively large average particle diameters as in Comparative Examples 1 and 3 have poor water- and oil-repellency, because they have poor penetrability into each substrate.

[0029]

[Table 3]

[0030]

The fluorine-containing aqueous resin dispersion of the present invention comprises
It has a small amount of emulsifier, excellent stability, and a small particle size. Moreover, N-alkylpyrrolidone has a high boiling point,
Since it has a high flash point, it has excellent safety and is particularly suitable as a water and oil repellent.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08J 3/03 CEY 9268-4F C09K 3/18 102 8318-4H D06M 15/356 D21H 19/20 / / C08L 33/14 LJG 7921-4J

Claims (2)

[Claims] 1. A (meth) acrylic acid ester having a fluoroalkyl group or the ester and another monomer copolymerizable therewith are polymerized in the presence of N-alkylpyrrolidone in an aqueous medium. The resulting fluorine-containing aqueous resin dispersion. 2. A water and oil repellent agent comprising the fluorine-containing aqueous resin dispersion according to claim 1.