JPH05263070A - High-flash-point water and/oil repellent and its production - Google Patents

Abstract

PURPOSE:To obtain a repellent having a high-flash-point, high water repellency, high oil repellency and good dispersion stability in water by emulsion- polymerizing a fluoroalkylated (meth)acrylate and a fluorine-free polymerizable monomer in an aqueous solution of a specified compound. CONSTITUTION:This repellent is obtained by emulsion-polymerizing a fluoroalkylated acrylate or methacrylate and a fluorine-free polymerizable monomer in an aqueous solution of a water-soluble compound soluble in at least either of the monomers and represented by the formula (wherein R1 and R2 are each H, 1-5C alkyl or acyl provided that they cannot be H simultaneously); X is H or methyl; and (n) is 1-5). The content of the acrylate or methacrylate monomer in the copolymer is suitably 40wt.% or above, especially about 50-80wt.%. The content of the fluorine-free polymerizable monomer in the copolymer is 60wt.% or below, desirably 20-50wt.%.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a water and oil repellent having a high flash point and a method for producing the same. More particularly, the present invention relates to water and oil repellents having a high flash point and a high degree of water and oil repellency, especially oil repellency, and good aqueous dispersion stability.

[0002]

2. Description of the Related Art Water and oil repellents in which a polymer of a compound such as a (meth) acrylate containing a polyfluoroalkyl group is dispersed in water have been known. It is necessary to carry out polymerization using an organic solvent for the purpose of enhancing the stability of this aqueous dispersion, but a low boiling point solvent such as acetone is used as such an organic solvent from the viewpoint of compatibility with monomers. There was no choice but to worry about fire and environmental pollution.

In order to solve this problem, it has been proposed to use saturated polyhydric alcohol instead of acetone.
(See JP-A-60-40182). However, the stability and water / oil repellency of the resulting aqueous dispersion are not sufficient. Further, the amount of the organic solvent used is as large as 60 to 100 parts by weight with respect to 100 parts by weight of the monomer, and reduction of environmental pollution is also a problem.

Further, in JP-A-55-69677, in order to increase the yield of emulsion polymerization and obtain a copolymer having a small particle size, a water-soluble organic solvent is added to the aqueous medium during the polymerization reaction. It has been proposed to add to the aqueous medium at a concentration of about 20% by weight. Examples of the organic solvent include glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether and dipropylene glycol monomethyl ether; ketones such as acetone and methyl ethyl ketone; esters such as methyl acetate and ethyl acetate. Kinds are listed. However, ketones,
Esters have a low flash point and may catch fire. Further, not all glycol ethers give an emulsion having good dispersion and a product having a high degree of water and oil repellency.

Further, Japanese Unexamined Patent Publication No. 61-276880 proposes a method of using an organic solvent having a boiling point of 150 ° C. or higher and containing oxygen. However, in this method, it was necessary to use another organic solvent (eg, ketones, esters) as a dispersion aid during emulsion polymerization.

[0006]

Means for Solving the Problems The present invention has been made to solve the above-mentioned problems, and in emulsion polymerization of a fluoroalkyl group-containing (meth) acrylate and a fluorine-free polymerizable monomer. , At least one of the above
It is characterized by using a water-soluble organic solvent that dissolves a certain monomer, that is, a specific glycol ether or glycol ester. The water and oil repellent of the present invention simultaneously satisfies a high flash point, a high degree of water and oil repellency, particularly oil repellency, and stability of an aqueous dispersion.

The gist of the present invention is to provide at least one of (A) a fluoroalkyl group-containing acrylate or methacrylate, and (B) a fluorine-free polymerizable monomer.
It is both soluble and water soluble and has the formula:

[Chemical 2] [Wherein R ₁ and R ₂ are hydrogen, an alkyl group having 1 to 5 carbon atoms or an acyl group (provided that R ₁ and R ₂ are not hydrogen at the same time), X is hydrogen or a methyl group, n is 1
Is a number from -5. ] The water-repellent and oil-repellent agent is characterized by emulsion-polymerizing components (A) and (B) in an aqueous solution of the compound represented by

The fluoroalkyl group-containing (meth) acrylate in the present invention is not limited at all, but the fluoroalkyl group preferably has 3 to 21 carbon atoms, and particularly preferably 6 to 18 carbon atoms. The preferred specific examples are as follows.

[0009]

[Chemical 3]

[0010]

[Chemical 4]

As the polymerizable monomer containing no fluorine,
Stearyl acrylate, N-methylol acrylamide, N-methylol methacrylamide, glycidyl acrylate, glycidyl methacrylate, aziridinyl acrylate, aziridinyl methacrylate, diacetone acrylamide, diacetone methacrylamide, methylol diacetone acrylamide, ethylene diacrylate, ethylene Dimethacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, 3
-Crosslinking monomers such as chloro-2-hydroxypropyl methacrylate, vinyl chloride, ethylene, vinyl acetate, acrylamide, methacrylamide, styrene, α
-Methylstyrene, p-methylstyrene, alkyl esters of acrylic acid or methacrylic acid, benzyl acrylates or methacrylates, vinyl alkyl ethers, halogenated alkyl vinyl ethers, vinyl alkyl ketones, cyclohexyl acrylates or methacrylates,
Examples thereof include maleic anhydride, butadiene, isoprene, chloroprene and the like.

The water and oil repellent of the present invention can be obtained by mixing the compound (I) at the time of emulsification and emulsion polymerization.
The medium in emulsion polymerization is usually an aqueous solvent, especially water. Specific examples of the compound (I) include dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether, pentaethylene glycol monobutyl ether, diclime and the like. Be done. Some of these compounds have already been used as a medium in emulsion polymerization, but in the present invention, they are selected according to the combination of monomers to be polymerized.

The compounds (I) can be used alone or in a mixture. Further, water-soluble ketones, esters or ethers may be used in combination, but when these are used in combination, the flash point may be lowered, so that the compound (I)
Is preferably 70% by weight or more.

Further, when the compound (I) is used, the dispersion state at the time of emulsification is dramatically improved, so that the amount of the organic solvent itself used can be greatly reduced, and there is a fear of environmental pollution. Can be reduced.

The amount of organic solvent used during the polymerization is usually 60 to 100 parts by weight of all the monomers used during the emulsion polymerization.
About 100 parts by weight is necessary. However, in the case of the present invention using the compound (I), an appropriate amount is 10 to 30 parts by weight, and a stable aqueous dispersion can be obtained with a smaller amount of solvent than usual.

In the copolymer of the present invention, the copolymerization ratio of the monomer (A) is at least 40% by weight, especially 50%.
Appropriately about 80% by weight. The amount of fluorine-free monomer is not more than 60% by weight, preferably 20 to 50% by weight, based on the copolymer. There are no particular restrictions on the surfactant and polymerization initiator used. Almost all anionic, cationic, or nonionic emulsifiers can be used as the surfactant. As the polymerization initiator, various polymerization initiators such as organic peroxides, azo compounds and persulfates, and ionizing radiation such as γ rays can be used.

The water and oil repellent of the present invention can be applied by any method depending on the type of the object to be treated. For example, a known method of coating such as dipping, coating, etc., which is applied to the surface of the object to be processed and dried, can be adopted. If necessary, it may be applied together with a suitable crosslinking agent to carry out curing. Further, the water / oil repellent of the present invention may be mixed with other polymer blenders, and other water / oil repellents or insect repellents, flame retardants, antistatic agents, dye stabilizers, anti-wrinkle agents and the like are added. Of course, it is also possible to appropriately add agents and use them together.

The article which can be treated with the water and oil repellent of the present invention includes various examples without particular limitation. Examples include textiles, glass, paper, wood, leather, fur, asbestos, bricks, cement, metals, oxides, ceramic products, plastics, painted surfaces and plasters. Textile products include natural animal and vegetable fibers such as cotton, hemp, wool and silk; various synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride and polypropylene; semi-synthetic fibers such as rayon and acetate. Inorganic fibers such as glass fiber, carbon fiber and asbestos fiber; or a mixture of these fibers. The fiber product may be in the form of fiber, thread, cloth or the like.

Next, examples of the present invention will be described more specifically, but it goes without saying that the examples do not limit the present invention. The water repellency and oil repellency shown in the following examples are shown on the following scale. That is, the water repellency is the water repellency No. by the spray method of JIS L-1005.
(See Table 1 below). For oil repellency, the test solution shown in Table 2 below is dropped on two places on the sample cloth (diameter about 4 mm).
After 30 seconds, it is judged by the permeation state (AATCC
-TM118-1966).

[0020]

[Table 1] Water repellent No. State 100 No surface adhesion and wetting 90 Surface slightly adhering and wetting 80 Surface partial wetting 70 Surface moistening 50 Surface wetness 0 Complete front and back surfaces What shows wetness

[0021]

[Table 2] Oil repellency test Solution surface tension (dyne / cm25 ° C) 8 n-heptane 20.0 7 n-octane 21.8 6 n-decane 23.5 5 n-dodecane 25.0 4 n-tetradecane 26.7 3 n-hexadecane 27.3 2 n-hexadecane 35 / Nujo165 mixed solution 29.6 1 Nujo1 31.2 0 1

Water-repellent No. and oil-repellent ones marked with + show slightly better performance.

Example 1 In this example, a typical emulsion polymerization method is described using a specific example of a terpolymer of fluoroalkyl group-containing acrylate, stearyl acrylate and N-methylol acrylamide using dipropylene glycol monomethyl ether. To do.

C _n F _{2n + 1} CH ₂ CH _{2 in a} 500 cc flask
COOCH = CH ₂ (n = 6,8,10,12,14; average 8)
100 g, stearyl acrylate 50 g, N-methylol acrylamide 1 g, pure water 200 g, dipropylene glycol monomethyl ether 30 g, acetic acid 0.3 g, polyoxyethylene alkylphenyl ether 6 g, alkyltrimethylammonium chloride 10 g were added and stirred at 50 ° C. The mixture was ultrasonically dispersed for 15 minutes. 0.75 g of azobisisobutylamidine-2 hydrochloride was added, and the reaction was carried out for 5 hours.

The solubility of water, fluoroalkyl acrylates and stearyl acrylates in organic solvents and the stability of emulsion polymerized products were investigated. Next, the polyester cloth is dipped in an aqueous dispersion having a water and oil repellent concentration of 0.06% by weight, squeezed with a mangle to make a wet pickup of 65%, and then at 80 ° C
And dried at 150 ° C. for 3 minutes. The water and oil repellency of the cloth was measured. The results are shown in Table 3.

Examples 2-7 and Comparative Examples 1-7 Using the organic solvents shown in Table 3, the same procedure as in Example 1 was repeated. The results are shown in Table 3.

[0027]

[Table 3]

In Table 3, FA is C _n F _{2n + 1} CH ₂
CH ₂ COOCH = CH ₂ (n = 6,8,10,12,14, average 8), and StA represents stearyl acrylate.
OR is oil repellent, WR is water repellent, DC-3 is JIS L-
As a result after three times of dry cleaning by the 1092-322 method, HL-3 shows a result after three times of washing by the JIS L-0217-103 method. An X of stability represents that the composite shows sedimentation after a few days. Regarding the solubility in organic solvents, those having a solubility of 50% or more at 50 ° C. were evaluated as ◯.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08F 246/00 MPY 8416-4J C08L 33/16 LJE 7921-4J C09K 3/00 112 A 9049-4H

Claims (2)

[Claims] 1. A soluble in at least one of (A) a fluoroalkyl group-containing acrylate or methacrylate, and (B) a fluorine-free polymerizable monomer,
It is also water soluble and has the formula: [Wherein R ₁ and R ₂ are hydrogen, an alkyl group having 1 to 5 carbon atoms or an acyl group (provided that R ₁ and R ₂ are not hydrogen at the same time), X is hydrogen or a methyl group, n is 1
Is a number from -5. ] The water / oil repellent agent characterized by emulsion-polymerizing the components (A) and (B) in the aqueous solution of the compound shown by these. 2. A water and oil repellent obtained by the method according to claim 1.