JP3484708B2 - Water / oil repellent composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel water-dispersible fluorine-based water / oil repellent composition having little environmental pollution and high performance.

[0002]

2. Description of the Related Art In recent years, water-dispersible fluorine-based water and oil repellents for clothes and the like have been actively used, and the disposal of residual liquid after processing has become a big problem. Conventionally, in order to achieve high performance and stability of a water-dispersed water / oil repellent composition, as a surfactant for emulsifying and dispersing the water / oil repellent, a nonionic surfactant having an aromatic ring, particularly an alkylphenol Ethylene oxide adducts were often used. Nonionic surfactants having an aromatic ring have low biodegradability and pose a problem of polluting rivers. Further, when it is treated as industrial waste, biodegradation takes time, resulting in high treatment cost, and there is a strong demand for its improvement.

[0003]

However, fluorine-containing surfactants such as polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, and polyoxyethylene sorbitan fatty acid ester, which are generally known as highly biodegradable surfactants, are used. When used as a water-dispersing surfactant for water- and oil-repellent agents, the dispersion stability becomes low and the water- and oil-repellency becomes insufficient, so that a satisfactory water-dispersion type water- and oil-repellent agent has not been obtained yet.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a composition which uses a highly biodegradable surfactant and provides high water / oil repellency and dispersion stability. is there.

[0005] A water dispersion type fluorine-containing water- and oil-repellent composition fluorine-containing water- and oil-repellent is dispersed in water by a surfactant consisting of an alkylene oxide adduct of a higher aliphatic secondary alcohol, a fluorine-based A water and oil repellent agent is prepared by emulsion polymerization.
The surfactant is used as a polymerization emulsifier at the time of production.
Water-dispersed fluorine-based water repellent characterized by being used as
Oil agent composition .

[0006] In the present invention, as the higher aliphatic secondary alcohol, secondary aliphatic alcohols of 10 to 18 carbon atoms is used alone or in a mixture. Especially, carbon number 1
1 to 14 aliphatic secondary alcohols are preferred. This higher aliphatic secondary alcohol is produced, for example, by an oxidation method using paraffin as a raw material. Specifically, the following higher aliphatic secondary alcohols and mixtures of two or more thereof are used.

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, sec-C ₁₆ H ₃₃ OH, sec
_{-C 17 H 35 OH, sec-} C 18 H 37 OH.

As the alkylene oxide, usually ethylene oxide alone or a combination of ethylene oxide as a main component and other alkylene oxides is used. Preferably, ethylene oxide alone or a combination of ethylene oxide and a small amount of propylene oxide is used. When two or more alkylene oxides are added to the higher aliphatic secondary alcohol, they can be added randomly or in a block.
In particular, ethylene oxide alone is preferably used as the alkylene oxide.

[0009] addition amount of the alkylene oxide relative to the higher aliphatic secondary alcohol is Ru alkylene oxide 6-30 mole der to higher aliphatic secondary alcohols mole.
In particular, when ethylene oxide alone is used as the alkylene oxide, the amount of ethylene oxide is preferably 6 to 20 mol per 1 mol of the higher aliphatic secondary alcohol.

In the present invention, as the surfactant for dispersing the fluorine-based water and oil repellent agent in water, other surfactants may be used in combination with the alkylene oxide adduct of the higher aliphatic secondary alcohol. As the other surfactant, a surfactant other than this compound, particularly another nonionic surfactant having high biodegradability is preferable.

The above-mentioned specific surfactant in the present invention is
The fluorine-containing water- and oil-repellent is surfactant for dispersing in water, use the surfactant as the polymerization emulsifier at the time of manufacturing by emulsion polymerization of a full Tsu-containing system water- and oil-repellent
It

The amount of this specific surfactant in the water-dispersible fluorine-based water / oil repellent composition is an effective amount capable of stably dispersing the fluorine-based water / oil repellent agent in water, or other surface active agents. When the agents are used in combination, there is no particular limitation as long as the effective amount is less than that. However, it is usually 20% by weight or less, preferably 0.1 to 10% by weight, based on the fluorine-based water and oil repellent.

As the fluorine-based water and oil repellent, a polymer having a polyfluoroorganic group which imparts water and oil repellency is preferable. However, the present invention is not limited to this, and various polyfluoroorganic group-containing compounds having a polyfluoroorganic group that imparts water / oil repellency may be used. Hereinafter, the fluorine-based water and oil repellent agent of the present invention will be described by taking a polymer type fluorine-based water and oil repellent agent as an example.

The polyfluoroorganic group which imparts water / oil repellency is a hydrocarbon group such as an alkyl group or an alkenyl group, or an oxygen-containing hydrocarbon group formed by substituting a part of carbon atoms with an etheric oxygen atom. A group in which a hydrogen atom in an organic group is replaced with a fluorine atom. The number of carbon atoms to which a fluorine atom is bonded is 2 or more, preferably 4 to 18, particularly 6 to 16, and the ratio of the number of substituted fluorine atoms to the hydrogen atoms of the unsubstituted organic group (substitution rate) is 60% or more,
Particularly, 80% or more is preferable. Further, the total carbon number of the polyfluoro organic group is preferably 4 to 20. This polyfluoro organic group is bonded to a functional group such as a polymerizable unsaturated group described later directly or through a bonding group.

The most terminal carbon moiety of the polyfluoroorganic group is preferably a trifluoromethyl group, a difluoromethyl group or a chlorodifluoromethyl group, and when the most terminal is branched, it is preferably a perfluoroisopropyl group. A particularly preferred terminal end is a trifluoromethyl group. Further, a part of carbon atoms of this polyfluoro organic group may be substituted with an etheric oxygen atom. Particularly, those having a perfluorooxyalkylene group are preferable.

Further, the polyfluoroorganic group is preferably a polyfluoroalkyl group, and particularly preferably a linear polyfluoroalkyl group. Furthermore, it has 3 carbon atoms at the end.
As described above, a linear perfluoroalkyl group having 4 to 16, preferably a polyfluoroalkyl group having the perfluoroalkyl group portion is preferable. Especially carbon number 6 to 1
Most preferred is a straight chain perfluoroalkyl group of 6.

As the polyfluoroorganic group-containing polymer capable of exhibiting high water / oil repellency, a polymer or copolymer of a polyfluoroorganic group-containing monomer, particularly a polyfluoroalkyl group-containing acrylate or methacrylate polymer or another copolymer thereof is used. Copolymers with a sex comonomer are suitable. In the following, acrylate and methacrylate are collectively referred to as (meth) acrylate, and the same applies to (meth) acrylamide and the like. As the (meth) acrylate containing a polyfluoroalkyl group, two or more kinds may be used in combination, and usually a mixture of two or more kinds of (meth) acrylate containing a polyfluoroalkyl group having different carbon numbers of the polyfluoroalkyl group is used. It

This polyfluoroalkyl group-containing (meth)
As the acrylate, a fluorine-containing monomer represented by the following formula (1) is preferable. As this fluorine-containing monomer, a compound well known as a fluorine-containing monomer containing a polyfluoroalkyl group is suitable.

CH ₂ = CRCOO-A-R ^f (1) (wherein R is a hydrogen atom or a methyl group, A is a divalent bonding group, and R ^f is a perfluoroalkyl group having 6 to 16 carbon atoms) Represents)

The divalent linking group A includes --R ^2- , --R
_{^{2 N (R 3) SO 2}} -, - R 2 N (R 3) CO-, other divalent linking groups are suitable. R ² represents an alkylene group, particularly an alkylene group having 2 to 6 carbon atoms, and R ³
Is an alkyl group, particularly an alkyl group having 4 or less carbon atoms (hereinafter,
Lower alkyl group). R ^f has 6 to 16 carbon atoms
The above perfluoroalkyl group is preferably a straight chain or branched perfluoroalkyl group having a branch at the end. The following compounds are illustrated as preferable fluorine-containing monomers.

CH ₂ = CHCOOC ₂ H ₄ C _n F _{2n + 1} CH ₂ = CHCOOCH ₂ C _n F _{2n + 1} CH ₂ = CHCOOC ₃ H ₆ C _n F _{2n + 1} CH ₂ = C (CH ₃ ) C00C ₂ H ₄ C _n F _{2n + 1} CH ₂ = C (CH ₃ ) C00CH ₂ C _n F _{2n + 1} CH ₂ = C (CH ₃ ) C00C ₃ H ₆ C _n F _{2n + 1} CH ₂ = CHCOOC ₂ H ₄ N (CH ₃ ) SO ₂ C _n F _{2n + 1}

CH ₂ = CHCOOC ₂ H ₄ N (C ₃ H ₇ ) SO ₂ C _n F _{2n + 1} CH ₂ = C (CH ₃ ) COOC ₂ H ₄ N (C ₂ H ₅ ) SO ₂ C _n F _{2n +1} CH ₂ = CHCOOC ₂ H ₄ C _n F _2n-1 (CF ₃ ) ₂ CH ₂ = CHCOOC ₃ H ₆ C _n F _2n-1 (CF ₃ ) ₂ CH ₂ = C (CH ₃ ) C00C ₂ H ₄ C _n F _2n-1 (CF ₃ ) ₂ CH ₂ = CHCOOCH ₂ CH (OH) CH ₂ C _n F _2n-1 (CF ₃ ) ₂ CH ₂ = CHCOOCH (OCOCH ₃ ) CH ₂ C _n F _2n-1 ( CF ₃ ) ₂

Various monomers may be used as the copolymerizable monomer (hereinafter referred to as a copolymerizable comonomer) capable of copolymerizing with the polyfluoro organic group-containing monomer. Two or more of these copolymerizable comonomers can be used in combination. Examples of copolymerizable comonomers include (meth) acrylates, vinyl halides, olefins, (meth) acrylonitriles, (meth) acrylamides, unsaturated polycarboxylic acid esters, and other widely used monomers. There is. Preferably, (meth) acrylates, (meth) acrylamides, vinyl chloride, and monomers having various functional groups such as hydroxyl groups, amino groups, epoxy groups, and polymerizable unsaturated groups of these and other than these And monomers having a long-chain hydrocarbon group having 8 or more carbon atoms (2-ethylhexyl group, stearyl group, etc.). In particular, it is preferable to use a monomer having a functional group as described above in a relatively small amount as a part of the copolymerizable comonomer.

Specific examples of copolymerizable comonomers include, but are not limited to, the following monomers.

N-methylol (meth) acrylamide,
Glycidyl (meth) acrylate, aziridinyl (meth) acrylate, diacetone (meth) acrylamide, methylolated diacetone acrylamide, ethylene di (meth) acrylate, hydroxyalkyl (meth)
Acrylate, 3-chloro-2-hydroxypropyl methacrylate, mono (or di) methacrylate of polyoxypropylene diol, and (meth) acrylate having an organopolysiloxane residue.

Vinyl chloride, ethylene, vinyl acetate, vinyl fluoride, (meth) acrylamide, styrene, α-methylstyrene, alkyl ester of (meth) acrylic acid, benzyl (meth) acrylate, vinyl alkyl ether, halogenated alkyl vinyl ether. , Vinyl alkyl ketone, cyclohexyl (meth) acrylate,
Maleic anhydride, butadiene, isoprene, chloroprene.

In the copolymer of the polyfluoro organic group-containing monomer and the copolymerizable comonomer, the polyfluoro organic group-containing monomer is 40% by weight or more, and particularly 50 to 80% by weight, based on the total amount of both monomers. Polymers obtained by polymerizing the mixture are preferred. The copolymerizable comonomer used is preferably 60% by weight or more of (meth) acrylates or (meth) acrylamides. Further, it is appropriate to use the monomer having a functional group in an amount of usually 1 to 10% by weight, particularly 2 to 5% by weight, based on all the monomers.

[0028] The polymerization of the monomer is Ru Oh by emulsion polymerization. In the case of emulsion polymerization, a direct water dispersion type fluorine-based water / oil repellent composition can be obtained. The emulsion obtained by emulsion polymerization can be blended with a compounding agent or diluted with water or the like, if necessary. Further, it is preferable to carry out emulsion polymerization in an aqueous medium containing a water-soluble solvent in order to further enhance dispersion stability. There is no particular limitation on the polymerization initiator used in the emulsion polymerization, such as an organic peroxide as a polymerization initiator, an azo compound, various polymerization initiators such as persulfate, and further ionizing radiation such as γ rays. Can be adopted.

From the viewpoint of dispersion stability, the average particle size of the fluorine-based water and oil repellent polymer obtained by emulsion polymerization is preferably small. The average particle size of the polymer obtained by emulsion polymerization using the surfactant of the present invention is preferably 0.2 μm or less, and particularly preferably 0.02 to 1.5 μm. Emulsion polymerization using the surfactant of the present invention Thus, a polymer having this average particle diameter can be easily obtained.

The amount of the fluorine-based water / oil repellent agent in the water-dispersed fluorine-based water / oil repellent agent obtained by emulsion polymerization is usually 50% by weight or less, but not limited to this. When treating an object to be treated, it is usually diluted with water or the like.

The water-dispersed water / oil repellent composition of the present invention can be applied to an object to be treated by any method depending on its type. For example, a known method of coating such as a dip coating method may be used in which it is attached to the surface of the object to be processed and dried. Also, if necessary, apply with a suitable crosslinking agent,
Curing may be performed. Further, the water / oil repellent composition of the present invention may be mixed with another polymer as a blender, and other water / oil repellent or insect repellent, flame retardant, antistatic agent, dye stabilizer, anti-wrinkle agent may be mixed. Additives such as agents may be appropriately added and used in combination.

The object to be treated with the water / oil repellent composition of the present invention includes various examples without any particular limitation. Examples include textile products, glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and their oxides, ceramic products, plastics, and the like. It is particularly suitable for treating textile products, and the textile products include knitted fabrics and nonwoven fabrics of various fibers. As the fibers, natural animal and vegetable fibers such as cotton, hemp, wool and silk, polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride,
Examples thereof include various synthetic fibers such as polypropylene, semi-synthetic fibers such as rayon and acetate, inorganic fibers such as glass fibers and carbon fibers, or mixed fibers thereof.

The present invention will be specifically described below with reference to Examples (Examples 1 to 4) and Comparative Examples (Examples 5 to 8), but the present invention is not limited to these Examples.

[0034]

EXAMPLES [Evaluation of Water Repellency] Regarding the water repellency shown in Examples and Comparative Examples, the water repellency N according to the spray method of JIS L-1092 is used.
o. (Table 1 below), each No. Attached to-is the N
o. Lower than.

[0035]

[Table 1]

The abbreviations of the raw materials used in the following examples are as follows. Further, the biodegradability of the surfactant is shown in [] after the chemical formula of each surfactant. The biodegradability of the surfactant is the result of testing in accordance with JIS K-3364 (shaking culture method) at an initial sample concentration of 30 PPM.

FA: CH ₂ = CHCOOCH ₂ CH ₂ C
_{k F 2k + 1 [k =} 6~12, average _{9], FMA: CH 2 =} C (CH 3) COOCH 2 CH 2 C k
F _{2k + 1} [k = 6 to 12, average 9], EHMA: 2-ethylhexyl methacrylate, DAAA: diacetone acrylamide, HEA: 2-hydroxyethyl acrylate, StA: stearyl acrylate, VCl: vinyl chloride, NMAM: N- Methylol acrylamide.

Polymerization initiator A: Azobis (dimethyleneisobutylamidine) [Wako Pure Chemical Industries, Ltd., trade name "VA"
-061 "], polymerization initiator B: 2,2'-azobis (2-amidinopropane) dihydrochloride [Wako Pure Chemical Industries, Ltd., trade name" V-5 "
0 ”].

Surfactant A: sec-C ₁₂ H ₂₅ O (C ₂
H ₄ O) ₁₅ H [99%], surfactant B: sec-C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₁₂ H
[99%], surfactant C: sec-C ₁₆ H ₃₃ O (C ₂ H ₄ O) ₁₂ H
[99%], surfactant D: sec-C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₁₀ H
[99%], surfactant _{E: n-C 9 H 19} C 6 H 4 O (C 2 H 4 O)
₂₀ H [68.5%], surfactant F: n-C ₁₆ H ₃₃ O (C ₂ H ₄ O) ₃₀ H [9
9%, Surfactant _{G: n-C 18 H 37} O (C 2 H 4 O) 20 H [9
9%, Surfactant _{H: n-C 12 H 25} O (C 2 H 4 O) 20 H [9
9%].

[Example 1] 120 g of FA was placed in a glass autoclave (internal volume of 1 liter) equipped with a thermocouple type thermometer and a current type agitator.
(60 parts by weight), EHMA 76 g (36 parts by weight), DA
AA 8 g (4 parts by weight), surfactant A 10 g, stearyl trimethyl ammonium chloride 2 g, acetone 12
0 g (60 parts by weight), 350 g (175 parts by weight) of water, and 1 g of the polymerization initiator A were added, nitrogen substitution was performed for about 20 minutes while stirring, and then the temperature was raised to 60 ° C. to start the polymerization. It was The mixture was heated and stirred at 60 ° C. for 15 hours and then cooled to obtain an emulsion having a solid content concentration of 31% by weight. The conversion rate of the copolymerization reaction by gas chromatography is 99.0-9.
It was 9.8% (relative to FA). The yield of the stable emulsion emulsion was 95 to 99% with respect to all the monomers.

[Examples 2 to 8] Emulsion polymerization was carried out in the same manner as in Example 1 except that the monomer, surfactant and polymerization initiator were changed. The type and ratio (molar ratio) of the monomers used, the surfactant, and the polymerization initiator are shown in Table 2 including Example 1.

[0042]

[Table 2]

[Performance Test] The emulsions obtained in Examples 1 to 8 were diluted with water to prepare a treatment liquid having a solid content concentration of 1.5% by weight, and the water repellency was measured using the treatment liquid. That is, a test cloth made of nylon taffeta cloth was dipped in the treatment liquid, the cloth was squeezed between two rubber rollers, and the wet pickup was set to 30% by weight. Then, it was dried at 110 ° C. for 90 seconds and further heat-treated at 170 ° C. for 60 seconds. The initial water repellency represents the water repellency of the obtained test cloth. Water repellent HL-5, which represents washing durability, is JI
It is the result of having carried out the water repellency test after repeating washing 5 times by SL-0217 103 method and drying at 100 degreeC for 3 minutes. The results are shown in Table 3.

The particle size is the average particle size measured by observation with an electron microscope. Furthermore, mechanical stability was obtained by diluting the emulsions obtained in Examples 1 to 8 with tap water having a pH of 6 to obtain an emulsion having a solid content of 0.5% by weight, and stirring the emulsion with a homomixer at 2500 rpm for 10 minutes. The generated scum was filtered through a polyester black doskin cloth. The case where there is no scum is 5 and the case where scum is remarkable is 1
Is the result of evaluation in 5 stages. The storage stability at 45 ° C. indicates the result of observing the appearance by visually observing the precipitate after the 0.5% by weight solid content diluted emulsion was stored in a 100 cm ³ glass bottle for 3 months. The results are shown in Table 3.

In Table 3, the type of treatment liquid is indicated by the example number of the composition produced.

[0046]

[Table 3]

[0047]

EFFECTS OF THE INVENTION According to the present invention, by using a nonionic surfactant having a specific structure that is highly biodegradable and does not adversely affect the water / oil repellency and stability, it has not been possible to achieve high levels. It is possible to provide an excellent water-dispersible fluorine-based water and oil repellent which not only achieves durability but also causes little environmental pollution.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ identification code FI D06M 13/17 D06M 13/17 15/277 15/277 (58) Fields investigated (Int.Cl. ⁷ , DB name) C09K 3 / 18 D06M 13/17 D06M 15/277 C08F 2/22-2/30 C08L 33/14 C08L 71/02

Claims (2)

(57) [Claims] 1. An alkylene oxide is added in an amount of 6 to 30 moles to 1 mole of a higher aliphatic secondary alcohol having 10 to 18 carbon atoms.
A water-dispersible fluorine-based water / oil repellent composition comprising a fluorine-based water / oil repellent agent dispersed in water by a surfactant comprising an alkylene oxide adduct, the fluorine-based water / oil repellent agent being produced by emulsion polymerization. A water-dispersible fluorine-based water and oil repellent composition, wherein the surfactant is used as an emulsifying agent for polymerization at the time. 2. The water / oil repellent composition according to claim 1, wherein the alkylene oxide comprises ethylene oxide alone or a combination of ethylene oxide as a main component and other alkylene oxides .