JP2872859B2 - Aqueous dispersion of fluorine resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous fluororesin dispersion used for water-repellent treatment and / or oil-repellent treatment in the fiber-related industry. More specifically, the clothes are not water-repellent so that they do not get wet even if they are exposed to rain or snow. The present invention relates to an aqueous dispersion of a fluororesin that enables water- and oil-repellent treatment so that it can be easily wiped off.

[0002]

2. Description of the Related Art Conventionally, as waterproofing equipment worn during rainfall,
Rubber kappa, PVC raincoats, and woven fabrics made of resin-coated materials have been used. These processed products are satisfactory only from the viewpoint of waterproofness, but have a drawback that the inside is stuffy due to sweat when the humidity is high or when exercising due to lack of moisture permeability.
Some fabrics are treated with wax or a wax-like agent, but they have insufficient water resistance and poor washing resistance. On the other hand, in recent years, a water / oil repellent technique using a fluorine compound has been developed. This technique is divided into a method using a low molecular fluorine compound and a method using a high molecular compound. The method using a low molecular compound is easy to handle and treat, but has a problem in durability. On the other hand, the method using a high molecular compound improves durability but is still insufficient, The oil repelling treatment itself is not easy.

[0003]

[Problems to be Solved by the Invention] In order to perform water / oil repellency treatment with a fluorine-based polymer compound, the cloth is dipped, impregnated or coated with a treatment liquid by any method, and the cloth is repelled with water. -An oil-repellent layer must be formed. As the treatment liquid at this time, there are an organic solvent solution of a fluorine-based polymer compound, a non-aqueous dispersion, an aqueous dispersion, and a reactive oligomer, and it is easy to obtain an organic solvent solution, but it has a strong water repellency. It is not easy to obtain an aqueous dispersion of a fluorine-based polymer compound. However, the organic solvent solution has a problem in handling, and an aqueous dispersion is desired. Accordingly, an object of the present invention is to provide an aqueous dispersion of a fluorine-based polymer compound which has excellent water / oil repellency and is easily water / oil repellent.

[0004]

The above object is achieved by the present invention described below. That is, the present invention provides a carboxyl group-containing
Polymer and glycidyl (meth) acrylate or hydroxy
Obtained by reacting with a silalkyl (meth) acrylate
That the hydrophilic radical addition polymerizable alpha, as the resin protective colloid containing β- ethylenically unsaturated group, the resin 100 weight
Parts to 200 to 2000 parts by weight of a fluorine-based addition polymerizable monomer in an organic solvent, and then the organic solvent medium is converted to an aqueous medium.
A method for treating an article with the dispersion and a treated article.

[0005]

[Function] Using a resin containing a hydrophilic group and an addition-polymerizable α, β-ethylenically unsaturated group as a protective colloid, a fluorine-based addition-polymerizable monomer is polymerized in an organic solvent, and then the organic solvent medium is converted to an aqueous solvent. By treating the article with the aqueous fluororesin dispersion converted into a medium, an article having excellent water and oil repellency can be easily provided.

[0006]

The protective colloid used in the present invention is soluble in an organic solvent, soluble in water as it is or when neutralized, and further has a group copolymerizable with a fluorine-based addition-polymerizable monomer. For example, glycidyl (meth) acrylate is added to an acrylic resin obtained by copolymerizing acrylic acid and / or methacrylic acid and, if necessary, another hydrophilic monomer; A product obtained by reacting an alkyl (meth) acrylate; styrene / maleic acid resin, isobutylene / maleic acid resin, or a partially esterified product thereof and glycidyl (meth)
A product obtained by reacting an acrylate; a product obtained by reacting hydroxyalkyl (meth) acrylate or glycidyl (meth) acrylate with maleated polyisobutylene.

[0007] Since the protective colloid has a carboxyl group, a water-repellent treatment using the fluororesin aqueous dispersion of the present invention requires a suitable crosslinking agent such as a water-soluble epoxy crosslinking agent or a mask. It can be cross-linked with a water-soluble or water-dispersible urethane cross-linking agent. However, (meth) acrylamide or diacetone (meth) acrylamide is copolymerized in a protective colloid, and formaldehyde is reacted after polymerization. Thereby, it can be made self-crosslinkable.
The proportion of fluorine addition polymerizable monomer and the protective colloid, dollar
Containing based addition polymerizable monomer per 100 parts by weight, the protective colloid 5-50 parts by weight, preferably 10 to 30 parts by weight (protective
For 100 parts by weight of the colloid, 200 to 2000 of the monomer
Parts by weight, preferably 333 to 1000 parts by weight) .

[0008] The organic solvent used in the polymerization of fluorine-based addition polymerizable monomer, a polymerization temperature to dissolve the fluorine-based addition polymerizable monomer without dissolving the polymer to dissolve the protective colloid, after polymerization Those which can be easily replaced by water and have excellent polymerizability are desirable.
For example, ethyl acetate, n-propyl acetate, iso-acetate
Preferred examples include propyl, ethyl alcohol, n-propyl alcohol, and iso-propyl alcohol. The fluorine-based addition-polymerizable monomer used in the present invention is not particularly limited, but a particularly preferred one is a (meth) acrylate-based monomer having 13 to 33 fluorine atoms in the monomer. . In addition to the above, a polymerizable monomer which can be copolymerized with the above-mentioned fluorine-based addition-polymerizable monomer and / or which is not copolymerized can be mixed or separately polymerized. In this case, it is desirable that the monomer is soluble in the polymerized organic solvent and the polymer is insoluble in the organic solvent.However, even if it is soluble in the organic solvent, the stability of polymerization is not impaired. If it does not hinder the substitution, a polymer soluble in an organic solvent may be produced. Other fluorine-based addition polymerizable monomers
When polymerizable monomers are used, these monomer
At least 50% by weight of the product is a fluorine-based addition polymerizable monomer
It is.

Examples of common monomers that can be used in combination are, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate Esters, lauryl methacrylate, stearyl methacrylate, alcohols having 12 carbon atoms and 13 carbon atoms
A mixture of alcohol methacrylates, methacrylate benzyl ester, methacrylate tetrahydrofurfuryl ester, ethylene glycol monoalkyl ether methacrylate, diethylene glycol monoalkyl ether methacrylate, methacrylonitrile, methacrylamide, N- Alkoxymethyl methacrylamide, methacrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, monophthalic acid ( 2-hydroxyethyl methacrylate, mono (2-hydroxypropyl methacrylate) phthalate, methyl acrylate Ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, acrylics having 12 carbon atoms and 13 carbons A mixture of acid esters, benzyl acrylate, tetrahydrofurfuryl acrylate, acrylate of ethylene glycol monoalkyl ether, acrylate of diethylene glycol monoalkyl ether, acrylonitrile, acrylamide, N-alkoxymethylacrylamide, Acrylic acid, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, N, N-dimethyl acrylate Aminoethyl ester, acrylic acid N, N-diethylaminoethyl ester, mono phthalate (2-hydroxyethyl acrylate)
Esters, mono (2-hydroxypropyl acrylate) phthalate, diacetone acrylamide, styrene, maleic acid, monoalkyl maleate,
Fumaric acid, fumaric acid monoalkyl ester, itaconic acid, itaconic acid monoalkyl ester, vinyl acetate and the like.

Further, difunctional or trifunctional monomers such as ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate can be used, and the dry cleaning resistance of the treated article can be enhanced. However, excessive use lowers the water repellency and oil repellency of the treated article, and therefore requires careful study prior to use.
The polymerization initiator used in the present invention is not particularly limited as long as it is soluble in a polymerization solvent at a polymerization temperature, and a general one can be used as it is. The liquid obtained by polymerization is usually translucent, and the particle size of the polymer is 0.05 to 0.3 μm. The polymerization liquid is neutralized with a neutralizing agent, water is added, and the mixture is heated, and the organic solvent is distilled off to replace the organic organic solvent with water. As the neutralizing agent, ammonia, primary amine, secondary amine, tertiary amine, caustic soda, caustic potash and the like can be used, but volatile amine or ammonia is desirable from the viewpoint of water resistance. The ratio of the organic solvent to be distilled off does not necessarily have to be distilled off in the entire amount. An appropriate amount of the nonvolatile content of the obtained fluororesin aqueous dispersion is 30 to 40% by weight.

The aqueous fluorine-based resin dispersion of the present invention obtained as described above has very good performance as a water / oil repellent treatment agent by itself, but is expensive and contains no fluorine. Or contains a little fluorine, but alone has water repellency and / or
Alternatively, the cost can be reduced by mixing a normal aqueous resin emulsion having no oil repellency.
An aqueous resin emulsion for a desirable formulation is self-crosslinking, has good water resistance, good washing resistance, good friction resistance, and has good oil resistance when oil repellency is desired, and has a Tg of -50 to 100.
° C., a polymer dispersion having a particle size of 0.3 to 0.05 μm, but with respect to Tg,
Emulsion resin or stearyl (meta) having a multi-layer structure with different Tg or a structure containing a built-in inorganic substance such as fine silica.
Polymers having paraffinic crystals such as acrylates are excellent in terms of the feeling of treated articles. Aqueous resin emulsions other than those described above can also be blended.

For preparing a water-repellent treating agent using the aqueous fluorine-based resin dispersion according to the present invention, various compounding agents can be added in addition to the above-mentioned aqueous resin emulsion. For example, a cross-linking agent such as methylol melamine, a water-soluble epoxy cross-linking agent, a masked aqueous or water-soluble urethane cross-linking agent, an antifreezing agent such as ethylene glycol and diethylene glycol, and a fungicide / antibacterial agent are exemplified. In addition, a large amount of water can be added to adjust the treatment amount. In this case, it is desirable that the mixture does not contain multivalent cations such as calcium ions and magnesium ions.

[0013]

Next, the present invention will be described more specifically with reference to examples. In the text, "parts" or "%" means "parts by weight" or "% by weight".
Means Example 1 18 parts of a polymer obtained by reacting 15 parts of glycidyl methacrylate with 100 parts of a copolymer consisting of 30 parts of methacrylic acid methyl ester, 40 parts of butyl acrylate, and 30 parts of methacrylic acid, and a perfluoroalkylethyl acrylate ( 82 parts of a mixture of fluoroalkyl groups having 6 to 12 carbon atoms) and 200 parts of ethyl alcohol were polymerized at 75 ° C. using 3 parts of azobisisobutyronitrile as a polymerization initiator to obtain a nearly transparent polymerization liquid. To this, 4.5 parts of 28% aqueous ammonia and 200 parts of water were added, and the mixture was heated to distill off 200 parts of ethyl alcohol and water by azeotropy. A liquid was obtained. This is referred to as aqueous resin liquid-2. The average particle size of the resin particles was 0.26 μm. 30 parts of the above aqueous fluororesin dispersion liquid is added to 1,000 parts of water, cotton (gold) is soaked and squeezed with a mangle to reduce the water content to 78% of its own weight.
%. After drying in a drier at 100 ° C,
Perform a partial heat treatment. The water-repellent cloth was treated according to JIS L-1092-
As a result of performing a water repellency test method (spray test), the evaluation was 10
It was 0.

Example 2 70 parts of methacrylic acid methyl ester and methacrylic acid 3
18 parts of a polymer obtained by reacting 15 parts of glycidyl methacrylate with 100 parts of a polymer consisting of 0 parts, 82 parts of perfluoroalkylethyl acrylate (a mixture of fluoroalkyl groups having 6 to 12 carbon atoms), and 1 part of ethyl alcohol
When 50 parts, 50 parts of ethyl acetate, 5 parts of dimethyl phthalate and 10 parts of ethylene glycol monobutyl ether were polymerized at 75 ° C. using 3 parts of azobisisobutyronitrile as a polymerization initiator, a nearly transparent polymerization liquid was obtained. . To this, 4.5 parts of 28% aqueous ammonia and 200 parts of water were added, and heated to distill off 200 parts of ethyl alcohol, ethyl acetate and water by azeotropic distillation. An aqueous dispersion of the fluororesin of the present invention containing translucent and small amounts of ethyl alcohol and ethyl acetate, dimethyl phthalate and ethylene glycol monoethyl ether as film-forming aids was obtained. This is the aqueous resin liquid-
Let it be 2. The average particle size of the resin particles was 0.29 μm. 10 parts of the aqueous fluororesin dispersion is added to 1,000 parts of water, and a polyester cloth is immersed in the water and squeezed with a mangle to make the water content 75% of its own weight. After drying in a dryer at 100 ° C., heat treatment is performed at 150 ° C. for 10 minutes. Ketchup was applied to the water-repellent cloth and wiped off with a tissue paper one hour later. As a result, the cloth could be neatly wiped off.

Example 3 30 parts of a diethylene glycol dimethyl ether solution containing 35% of a resin obtained by reacting 36.8 parts of ethyl alcohol and 26 parts of hydroxyethyl methacrylate with 202 parts of poly (styrene / maleic anhydride), 100 parts of ethyl alcohol Parts, ethyl acetate 80 parts, methacrylate (a mixture of fluoroalkyl groups having 6 to 12 carbon atoms) 85
Part and dimethyl-2,2'-azobisisobutyrate 3
The resulting mixture was stirred at 75 ° C. for 8 hours to carry out polymerization, whereby a nearly transparent polymerization liquid was obtained. 5 parts of 28% ammonia water and 200 parts of water were added thereto, and the mixture was heated under reduced pressure to distill off 200 parts of ethyl acetate and ethyl alcohol containing water by azeotropic distillation.
The fluororesin aqueous dispersion of the present invention was obtained. This is referred to as aqueous resin liquid-3. As a result of performing the same test as in Example 1 using the aqueous resin liquid, the evaluation of water repellency was 90 to 100.

Example 4 30% of a copolymer composed of 65 parts of methacrylic acid methyl ester, 25 parts of acrylic acid and 10 parts of acrylamide
To 100 parts of an ethyl alcohol solution, 3 parts of glycidyl methacrylate and 0.03 of triethylamine were added, and 75 ° C.
For 8 hours to obtain a protective colloid solution. To 200 parts of isopropyl alcohol, 50 parts of the above-mentioned protective colloid solution, 40 parts of perfluoroalkylethyl acrylate, 45 parts of perfluoroalkylethyl methacrylate and 3 parts of azobisisobutyronitrile were added, and polymerized at 75 ° C. for 8 hours to obtain a fluororesin. Of the non-aqueous dispersion of the present invention was obtained. To this, 4.5 parts of triethylamine and 200 parts of water were added and stirred, and isopropyl alcohol 20 containing water was added.
0 parts were distilled off, and 1.8 parts of 35% formalin was added.
Stir at C for 2 hours. During this time, check the pH sometimes and check the pH>
Keep 8 The aqueous fluorine-based resin dispersion is referred to as “Aqueous resin liquid-4”. The aqueous resin liquid-4 is self-crosslinkable. 30 parts of the aqueous resin liquid-4 is mixed with 1,000 parts of water, impregnated with a test band, squeezed with a mangle so as to have a content of 70% of its own weight, dried at 100 ° C, and dried at 150 ° C for 30 minutes. Heat-treat to make test cloth. The test cloth was tested according to JIS L-1092 water repellency test (spray method).
00. Also, 9 parts of the aqueous resin liquid-4 and 21 parts of an acrylic aqueous resin dispersion for pigment printing were mixed with 1,000 parts of water, and the same test was conducted. As a result, the evaluation was 90.

[0017]

According to the present invention as described above, the fluororesin aqueous dispersion of the present invention has water and oil repellency singly, and can be mixed with various additives and compounding agents and treated as desired. Suitable performance, for example, water-repellent by treating the fabric, and also moisture-permeable, excellent waterproof clothing and waterproof sportswear; excellent oil repellency, easy to wipe off mayonnaise and ketchup Antifouling carpet; Further, by applying the aqueous fluororesin dispersion according to the present invention to a contract or a security, tampering can be prevented.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08J 7/04 C08J 7/04 Z C08L 27/12 C08L 27/12 51/06 51/06 C09K 3/00 112 C09K 3/00 112C 3 / 18 102 3/18 102 (56) References JP-A-2-269717 (JP, A) JP-A-63-10611 (JP, A) JP-A-2-58513 (JP, A) JP-A-60-203617 (JP, A)

Claims (7)

(57) [Claims] 1. A carboxyl group-containing polymer and glycidyl
(Meth) acrylate or hydroxyalkyl (meth)
A resin containing a hydrophilic group obtained by reacting with an acrylate and an addition-polymerizable α, β-ethylenically unsaturated group is used as a protective colloid , and 200 to 100 parts by weight of the resin is used.
An aqueous dispersion of a fluororesin, wherein 2,000 parts by weight of a fluorine-based addition polymerizable monomer is polymerized in an organic solvent, and then the organic solvent medium is converted to an aqueous medium. 2. The aqueous dispersion of a fluororesin according to claim 1, wherein the addition-polymerizable fluorine-based monomer is an acrylic acid or methacrylic acid ester having 13 to 33 fluorine atoms. 3. The aqueous dispersion of a fluororesin according to claim 1, wherein the organic solvent is a hydrophilic organic solvent. 4. A fluorine-containing addition polymerizable monomer,
Used together with a polymerizable monomer, these addition polymerizable
At least 50% by weight of the monomer mixture is a fluorine-based addition polymerization
The aqueous dispersion of a fluororesin according to claim 1, which is a water- soluble monomer. 5. A carboxyl group-containing polymer and glycidyl
(Meth) acrylate or hydroxyalkyl (meth)
A resin containing a hydrophilic group obtained by reacting with an acrylate and an addition-polymerizable α, β-ethylenically unsaturated group is used as a protective colloid , and 200 to 100 parts by weight of the resin is used.
A method for producing an aqueous fluororesin dispersion, comprising polymerizing 2,000 parts by weight of a fluorine-based addition-polymerizable monomer in an organic solvent, and then converting the organic solvent medium to an aqueous medium. 6. immersed <br/> article fluororesin aqueous dispersion according to claim 1, impregnated, or to apply the aqueous dispersion to the article
Method of processing an article, characterized in that that. 7. A processed article processed by the method according to claim 6 .