JPH06287548A - Production of water-dispersible fluorine-based water-and oil-repellent composition - Google Patents

Abstract

PURPOSE:To produce the subject compsn. which has high water repellency and dispersion stability and exhibits excellent compatibility when mixed with an anionic additive. CONSTITUTION:A polyfluoroalkylated alpha,beta-unsatd. monomer and a radical- polymerizable unsatd. monomer are copolymerized in an emulsion by using a peroxysulfate as a radical polymn. initiator and a polyoxyalkylene monoalkyl ether as an emulsifier.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a water-dispersible fluorine-based water / oil repellent composition.

[0002]

2. Description of the Related Art In recent years, water-repellent and oil-repellent finishing of clothes has been actively carried out, and various water-dispersed fluorine-based water- and oil-repellent compositions have been proposed. When water-repellent and oil-repellent treatment is carried out with these water-dispersed fluorine-based water and oil-repellent compositions, the water- and oil-repellent compositions are rarely used alone, and in many cases, antistatic agents and softeners are used. The one to which a concomitant agent such as the above is added is used.

[0003]

Most of these concomitant agents are anionic, but conventional water-dispersed water- and oil-repellent compositions, when an anionic concomitant agent is added, form a phase with the concomitant agent. Solubility was not sufficient, and satisfactory dispersion stability and water repellency could not be obtained.

An object of the present invention is to solve the above problems found in the prior art.

[0005]

The present invention is directed to an α, β-unsaturated monomer containing a polyfluoroalkyl group (hereinafter referred to as an Rf group) and a radical-polymerizable unsaturated monomer (hereinafter referred to as a comonomer). A peroxosulfate radical polymerization initiator,
A method for producing a water-dispersed fluorine-based water- and oil-repellent composition, which comprises emulsion-polymerizing a polyoxyalkylene monoalkyl ether as an emulsifier.

The water-dispersible fluorine-based water and oil repellent composition of the present invention comprises a copolymer of an Rf group-containing α, β-unsaturated monomer and a comonomer dispersed in water.

The Rf group-containing α, β-unsaturated monomer has a structure in which the Rf group is directly or indirectly bonded to a polymerizable unsaturated group.

As the Rf group, a group having a structure in which a hydrogen atom of a hydrocarbon group is substituted with a fluorine atom is usually selected. Examples of the hydrocarbon group include a linear or branched alkyl group or alkenyl group, and an oxygen-containing hydrocarbon group obtained by substituting a part of carbon atoms of the hydrocarbon group with an etheric oxygen atom. Good.

The Rf group usually has 4 to 20 carbon atoms. Among these carbon atoms, the number of carbon atoms to which the fluorine atom is bonded is 2 or more, preferably 4 to 18, particularly preferably 6 to 16.

The Rf group is a group containing two or more fluorine atoms, but usually 6 of the atoms bonded to the carbon atom is used.
A group in which 0% or more, preferably 80% or more is a fluorine atom is preferable. Further, the carbon atom of the Rf group may be bonded with another atom other than a fluorine atom and a hydrogen atom. As the other atom, a halogen atom is preferable, and a chlorine atom is particularly preferable.

When the Rf group is an oxygen-containing hydrocarbon group, a group containing an oxyfluoroalkylene moiety is preferred. It may also be a group containing a structure in which two or more oxyfluoroalkylene moieties are connected. Examples of the oxyfluoroalkylene moiety include oxyfluoromethylene and oxyfluoropropylene.

Examples of the structure of the terminal portion of the Rf group include a trifluoromethyl group, a difluoromethyl group, a chlorodifluoromethyl group and the like, and a preferable structure is the trifluoromethyl group.

The most preferred Rf group is a perfluoroalkyl group having a structure in which all hydrogen atoms are replaced by fluorine atoms. The perfluoroalkyl group preferably has a linear structure. The carbon number of the perfluoroalkyl group is 3
1 or more, preferably 4 to 16 and more preferably 6 to
12 is good.

The Rf group is directly or indirectly bonded to the polymerizable unsaturated group via a divalent bonding group. Rf
The α, β-unsaturated group-containing monomer is not particularly limited as long as it is a known monomer having an Rf group and a polymerizable unsaturated group, and acrylates or methacrylates containing an Rf group are preferable. In the following description, acrylate and methacrylate are generically referred to as (meth) acrylate, which means both. The same applies to (meth) acrylamide and the like.

Suitable Rf group-containing (meth) acrylates can be represented by Formula 1. However, in Chemical formula ¹ , R ¹ is hydrogen or a methyl group, A is a divalent bonding group,
Rf 'represents a perfluoroalkyl group having 4 to 16 carbon atoms.

[0016]

Embedded image CH ₂ = CR ¹ COO-A-Rf ′

As -A- in Chemical formula 1, -R ^2- , -R ^{2
_{N (R 3) SO 2 -}} , - R 2 N (R 3) CO- , and the like. Here, R ² represents an alkylene group and has 1 carbon atom.
-6, preferably 1-3 alkylene groups are preferred. Further, it may have a structure in which a hydroxyl group, —OCOCH ₃ or the like is bonded to the alkylene group. R ³ represents an alkyl group, preferably an alkyl group having 4 or less carbon atoms. Rf ′ may have either a linear structure or a branched structure.

Examples of Rf group-containing (meth) acrylates are shown in Chemical formula 2, but are not limited to these examples. Note that Rf 'in Chemical formula 2 is as described above.

[0019]

CH ₂ ═CR ¹ COOCH ₂ Rf ′, CH ₂ ═CR ¹ COOC ₂ H ₄ Rf ′, CH ₂ ═CR ¹ COOC ₃ H ₆ Rf ′, CH ₂ ═CR ¹ COOC ₂ H ₄ N (CH ₃ ) SO ₂ R
^{_{f ', CH 2 = CR 1}} COOC 2 H 4 N (C 2 H 5) SO 2 R
f ′, CH ₂ = CR ¹ COOCH ₂ CH (OH) CH ₂ R
^{_{f ', CH 2 = CR 1}} COOCH (OCOCH 3) CH 2 R
f '.

The above-mentioned Rf group-containing (meth) acrylates may be contained alone or in combination of two or more. When two or more kinds are used, it is preferable to include (meth) acrylates having different carbon numbers of Rf groups.

The comonomer in the present invention is not particularly limited as long as it is a known monomer having a radical-polymerizable unsaturated group, and various monomers can be used.

Examples thereof include (meth) acrylates, vinyls, olefins, (meth) acrylonitriles, (meth) acrylamides, and unsaturated carboxylic acid esters. Further, as the (meth) acrylates, there are (meth) acrylates having a functional group such as an amino group, an epoxy group and a hydroxyl group, and a (meth) having a long chain hydrocarbon group.
Acrylates and the like are also included. The long-chain hydrocarbon group is a hydrocarbon group having 8 or more carbon atoms, preferably 2-ethylhexyl group, stearyl group and the like.

The following are examples of comonomers, but the present invention is not limited to these examples.

(Meth) acrylate, ethylene di (meth) acrylate, cyclohexyl (meth) acrylate, polyoxypropylene diol mono- or di (meth) acrylate, (meth) acrylate having an organopolysiloxane residue, glycidyl (meth) acrylate, Aziridinyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate, (meth) acrylic acid alkyl ester.

Vinyl chloride, vinyl acetate, vinyl fluoride,
Vinyl alkyl ketone, halogenated alkyl vinyl ether, ethylene, styrene, α-methylstyrene, butadiene, isoprene, chloroprene, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, diacetone (meth) acrylamide.

Of these comonomers, it is preferable to use (meth) acrylates, (meth) acrylamides, and vinyls.

The above-mentioned comonomers may be used either individually or in combination of two or more. When using a comonomer having a structure in which functional groups are bonded, it is preferable to include it as a part of the comonomer, and 1 to 10 parts by weight, preferably 2 to 5 parts by weight or so with respect to 100 parts by weight of all the monomers. It is preferable to include it.

In the copolymerization of the Rf group-containing α, β-unsaturated monomer and the comonomer, the proportion of the Rf group-containing α, β-unsaturated monomer is 40% by weight or more, particularly 50 to 80% by weight. The case of copolymerization in% is preferable. In addition, 60 of comonomer
Weight% or more is (meth) acrylates or (meth)
Acrylamides are preferred.

In the present invention, the Rf group-containing α, β-
The copolymerization of the unsaturated monomer and the comonomer is carried out by the emulsion polymerization method. In the present invention, it is important to carry out emulsion polymerization by incorporating a specific polymerization initiator and a specific emulsifier.

Peroxosulfate is used as the polymerization initiator. Peroxosulfates include peroxomonosulfate,
Both peroxodisulfates are included, but since peroxomonosulfate is unstable, peroxodisulfate which is relatively stable is usually used. Peroxodisulfate can be represented by the general formula M ₂ S ₂ O ₈ . M of these
Is K or NH ₄ , ammonium peroxosulfate, potassium peroxosulfate and the like are preferable.

The amount of peroxosulfate used is not particularly limited, but if it is too small, a stable emulsion dispersion cannot be obtained, and if it is too large, sufficient water / oil repellency cannot be obtained. 0.01 to 3 parts by weight,
It is particularly preferable to use 0.1 to 1 part by weight.

As the emulsifier, polyoxyalkylene monoalkyl ether is used. The polyoxyalkylene monoalkyl ether has a structure in which a polyoxyalkylene portion in which two or more alkylene oxides are linked to a hydroxyl group of an aliphatic alcohol is ether-bonded and a terminal portion is a hydroxyl group.

The aliphatic alcohol is preferably a higher aliphatic alcohol having 8 or more carbon atoms, particularly preferably 10 to 18 carbon atoms.

The higher aliphatic alcohol is preferably a higher aliphatic secondary alcohol. Specific examples of the higher aliphatic secondary alcohol are shown in Chemical formula 3, but the present invention is not limited thereto. As the higher aliphatic secondary alcohol, one kind or two or more kinds can be used.

[0035]

[Chemical formula 3] sec-C ₁₁ H ₂₃ OH, sec-C ₁₂ H ₂₅ OH, sec-C
₁₃ H ₂₇ OH, sec-C ₁₄ H ₂₉ OH, sec-C ₁₅ H ₃₁ OH, se
c-C ₁₆ H ₃₃ OH, sec-C ₁₇ H ₃₅ OH, sec-C ₁₈ H ₃₇ O
H.

The alkylene oxide has 1 carbon atom.
~ 4 alkylene oxides. Of these, ethylene oxide and propylene oxide are preferable,
Ethylene oxide is particularly preferable.

One kind or two or more kinds of alkylene oxides can be added, but it is preferable to add one kind. Ethylene oxide is preferred when adding one of the alkylene oxides. When adding two or more kinds, a combination of ethylene oxide and propylene oxide is preferable. In this case, two or more kinds of alkylene oxides can be added randomly or in blocks.

The amount of alkylene oxide added to the higher aliphatic alcohol is preferably 6 to 30 moles of alkylene oxide per mole of higher aliphatic alcohol. Especially when adding only ethylene oxide,
6 moles of ethylene oxide per mole of higher aliphatic alcohol
It is preferable to add ˜20 mol.

Of these polyoxyalkylene monoalkyl ethers, alkylene oxide adducts of higher aliphatic secondary alcohols, which are particularly highly biodegradable, are preferred. Particularly preferably, 6 to 30 mol of alkylene oxide is added to 1 mol of higher aliphatic secondary alcohol.

In the present invention, other emulsifiers may be used in combination with the polyoxyalkylene monoalkyl ether. Even when another emulsifier is used in combination, it is preferable to select a nonionic emulsifier having high biodegradability.

The amount of the above-mentioned emulsifier is such that the Rf group-containing α, β-
There is no particular limitation as long as it is an effective amount that can stably emulsify and disperse the copolymer of the unsaturated monomer and the comonomer.
In a usual case, 20 parts by weight or less, preferably 0.1 to 5 parts by weight is used with respect to 100 parts by weight of all monomers of the Rf group-containing α, β-unsaturated monomer and comonomer.

As a medium for emulsion polymerization, water or one containing two or more water-soluble organic solvents can be selected. By including the water-soluble organic solvent, the dispersion stability of the composition can be further enhanced. Examples of the water-soluble organic solvent include acetone, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methyl ethyl ketone, isopropyl alcohol and methyl alcohol. When adding a water-soluble organic solvent, it is 5-1 per 100 parts by weight of all monomers.
It is preferable to use 00 parts by weight, preferably 10 to 70 parts by weight.

The average particle diameter of the copolymer of the Rf group-containing α, β-unsaturated monomer and the comonomer of the present invention is 0.2 μm.
In the following, it is particularly preferably 0.02 to 1.5 μm in terms of dispersion stability.

In the water-dispersible fluorine-based water and oil repellent composition of the present invention, the concentration of the copolymer of the Rf group-containing α, β-unsaturated monomer and the comonomer is 50% by weight or less. It is adjusted with water etc. But this proportion is
It can be appropriately changed depending on the purpose and treatment method. In the usual case, it is further diluted with water or the like 10 to 100 times before use. For example, when the composition of the present invention is applied to a fiber woven fabric or a fiber knitted product, the proportion of the copolymer is usually adjusted to about 0.2 to 2% by weight before use.

The water-dispersible fluorine-based water / oil repellent composition of the present invention can be applied by any method depending on the kind of the material to be treated and the form of adjustment. For example, a known method of coating such as a dip coating method and the like can be adopted in which it is adhered to the surface of the object to be processed and dried. If necessary, a suitable crosslinking agent may be added for curing.

Further, the water-dispersible fluorine-based water and oil repellent composition of the present invention contains other water repellent, oil repellent, insect repellent, flame retardant, antistatic agent, dye stabilizer, anti-wrinkle agent and other additives. Can be appropriately contained.

The object to be treated with the water-dispersible fluorine-based water / oil repellent composition of the present invention is not particularly limited, and various examples can be given. Examples include, but are not limited to, textile products, glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and metal oxides, ceramic products, plastics, and the like.

In particular, the water-dispersible fluorine-based water / oil repellent composition of the present invention is suitable for treating textiles. Textile products include knitted fabrics and nonwoven fabrics of various fibers. As the fiber, 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, and glass. Inorganic fibers such as fibers, carbon fibers, asbestos fibers, and mixed fibers thereof can be used.

[0049]

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the description is not intended to limit the present invention. The meanings of the abbreviations used in the description of the examples and comparative examples are shown in Table 1.

[0050]

[Table 1]

Example 1 120 g (60 parts by weight) FA, 76 g FA in a glass autoclave (internal volume 1 liter) equipped with a thermocouple type thermometer and a current type agitator.
(36 parts by weight) StA, 8 g (4 parts by weight) HEA,
Add 3 g (1.5 parts by weight) of emulsifier A, 120 g (60 parts by weight) acetone, 350 g (175 parts by weight) water, and 1 g (0.5 parts by weight) potassium peroxosulfate and stir about After performing nitrogen substitution for 20 minutes, 60
The temperature was raised to 0 ° C. to initiate polymerization. The mixture was heated and stirred at 60 ° C. for 15 hours and then cooled to obtain an emulsion having a nonvolatile component concentration (hereinafter referred to as solid content concentration) of 31% by weight. When carried out several times under the same conditions, the conversion rate of the copolymerization reaction by gas chromatography was 99.0 to 99.8% (based on FA). The yield of the stable emulsion emulsion was 95 to 99% based on all the monomers.

[Examples 2 to 4, Comparative Examples 1 to 5] Example 1
Emulsion polymerization was carried out by changing the monomer, the emulsifier, and the polymerization initiator in the same manner as in. Table 2 shows the monomers, emulsifiers, and polymerization initiators used.

[0053]

[Table 2]

[Evaluation Method of Water Repellency] The emulsions obtained in Examples and Comparative Examples were diluted with water to obtain a solid content of 1.
The water repellent performance was tested by adjusting to 5% by weight. The test was conducted on a nylon taffeta cloth, and the test cloth was dipped in a diluted emulsion-polymerized emulsion, and the test cloth was squeezed between two rubber rollers to obtain a wet pickup of 30% by weight. Then, it is dried at 110 ° C. for 90 seconds and further 17
It heat-processed at 0 degreeC for 60 second, and used for the test. Water repellency is JIS
The result of the test by the spray method of L1092 is shown by the water repellency number shown in Table 3.

[0055]

[Table 3]

[Evaluation Method of Particle Size] The particle size is the average particle size (unit: μ) of the copolymer measured by observation with an electron microscope.
m) is shown.

[Mechanical Stability Evaluation Method] The emulsions obtained in Examples and Comparative Examples were diluted with tap water having a pH of 6 to adjust the solid content concentration to 0.5% by weight, and the homogenization was performed at 2500 rpm with a homomixer. The resulting scum was filtered through a polyester black doskin cloth. The case where there was no scum was rated as 5, and the case where scum generation was remarkable was defined as 1 and was evaluated in 5 levels.

[Method for evaluating anion combined use] The emulsions obtained in Examples and Comparative Examples were diluted with tap water containing 2% by weight of anionic oil agent by the same procedure as for mechanical stability, Stir and filter. The diluted emulsion thus obtained was placed in a 100 cm ³ glass bottle and stored at 45 ° C for 3 months, and then the appearance was visually observed and the presence or absence of sediment was observed. The results are summarized in Table 4.

[0059]

[Table 4]

[0060]

According to the method of the present invention, a water-dispersible fluorine-based water / oil repellent composition having excellent compatibility with an anionic concomitant agent and excellent water repellency can be produced. The water-dispersed fluorine-based water / oil repellent composition produced according to the present invention has excellent mechanical stability and dispersion stability. In the water-dispersible fluorine-based water and oil repellent composition of the present invention, since an emulsifier with high biodegradability is used, it has little influence on environmental pollution.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location D06M 13/17 15/277

Claims (3)

[Claims] 1. A polyfluoroalkyl group-containing α, β-unsaturated monomer and a radically polymerizable unsaturated monomer, a peroxosulfate as a radical polymerization initiator, and a polyoxyalkylene monoalkyl ether as an emulsifier. A process for producing a water-dispersible fluorine-based water / oil repellent composition, which comprises emulsion polymerization. 2. The method according to claim 1, wherein the polyoxyalkylene monoalkyl ether is obtained by adding an alkylene oxide to a higher aliphatic secondary alcohol. 3. The polyoxyalkylene monoalkyl ether is obtained by adding 6 to 30 mol of alkylene oxide to 1 mol of a higher aliphatic secondary alcohol.
Manufacturing method.