JPH09118877A - Water-dispersing water-and oil-repellent composition having excellent stability against impurity - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition composed of a specific fluorine- containing polymer and a mixture of surfactants, capable of exhibiting excellent water-and oil-repellency and free from the loss of water-repellent and oil- repellent functions and the decrease of emulsion stability caused by the existence of a combined supplementary agent and impurities. SOLUTION: This repellent composition is obtained by dispersing (A) a polymer consisting of a polymer unit of a polyfluoroalkyl-containing (meth)acrylate and (B) a surfactant mixture composed of surfactants consisting of a compound containing a cationic nitrogen and >=5 of oxyalkylene units in a molecule e.g. a compound of the formula [R<1> is a 6-22C alkyl, a 6-22C acyl, a 6-22C alkenyl, a 6-22C alkyl-substituted phenyl, etc.; R<2> is H, methyl, benzyl, etc.; [X<-> ] is a monovalent anion; A is oxyethylene; B is oxypropylene; (k), (m), (n) and (p) are each 0-20 and the average of the total is 5-40]} (B1 ), a nonionic surfactant (B2 ) and a cationic surfactant excluding B1 (B3 ) in an aqueous medium.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a water-dispersed water / oil repellent composition having excellent stability in a processing bath and a method for producing the same. Specifically, even when the processing bath contains a concomitant drug, or when the processing bath contains contaminants adhering to the processing cloth or the like from the pretreatment step, it has excellent dispersion stability and water repellency. The present invention relates to a water dispersion type water and oil repellent composition exhibiting oiliness.

[0002]

2. Description of the Related Art A polymer containing polymerized units of a polyfluoroalkyl group-containing polymerizable compound such as an acrylate or methacrylate containing a polyfluoroalkyl group is synthesized by emulsion polymerization, and the resulting aqueous dispersion is repelled by water. It is widely used as an oil agent (Japanese Patent Publication No.
7-40467).

[0003]

However, in conventional aqueous dispersions, the presence of an acid or an anionic substance (such as a dye fixing agent or an acid dye) in the processing bath reduces the water / oil repellency,
Problems such as emulsion particles coagulating and settling due to deterioration of dispersibility of the aqueous dispersion, resulting in deterioration of water / oil repellency, and polymer adhesion to the mangle (gum-up), resulting in uneven processing on the work cloth Was there.

[0004]

Means for Solving the Problems As a result of repeated studies to solve the above-mentioned problems, the present inventors have found that three kinds of surfactants having a specific combination are contained in a water-dispersed water- and oil-repellent agent. By including it, even if a concomitant drug such as an acid or an anionic substance or a contaminant is present, it exhibits extremely excellent dispersion stability and does not cause a decrease in water / oil repellency. It has been found that an oil composition can be provided.

That is, the present invention provides a water-dispersible repellent polymer containing a polymer (a) containing polymerized units of acrylate or methacrylate containing a polyfluoroalkyl group dispersed in an aqueous medium, and a surfactant (b). In the water / oil repellent composition, the surfactant (b) contains at least three kinds of the following surfactants (c), the following surfactants (d), and the following surfactants (e). Provided are a water-dispersed water / oil repellent composition and a method for producing the composition.

Surfactant (c): A cationic surfactant composed of a compound containing 5 or more cationic nitrogen atoms and oxyalkylene units in the molecule. Surfactant (d): a nonionic surfactant. Surfactant (e): Cationic surfactant other than (c).

First, the polymer (a) will be described. The water-dispersed water / oil repellent composition of the present invention contains a polymer (a) containing polymerized units of acrylate or methacrylate containing a polyfluoroalkyl group dispersed in an aqueous medium.

In the following, the polyfluoroalkyl group will be referred to as R ^f group. Acrylate and methacrylate are collectively referred to as (meth) acrylate, and other compounds are also referred to in the same manner. Further, the acrylate containing a polyfluoroalkyl group and the methacrylate containing a polyfluoroalkyl group are collectively referred to as an R ^f group-containing (meth) acrylate.

The R ^f group of the (meth) acrylate containing the R ^f group means a group in which two or more hydrogen atoms of an alkyl group are substituted with fluorine atoms. The R ^f group may contain a hydrogen atom substituted with a halogen atom other than a fluorine atom, and a chlorine atom is preferable as the other halogen atom.
Further, in the R ^f group, one or more carbon atoms may be substituted with an etheric oxygen atom.

The carbon number of the R ^f group is preferably 3 to 20, and particularly preferably 4 to 16. Further, the R ^f group preferably has a straight chain or branched structure, and a straight chain is preferable. In the case of a branched structure, it is preferable that the branched portion exists at the terminal portion of the R ^f group and the carbon number is short.

[0011] The number of fluorine atoms in the R ^f groups, when expressed as a percentage of the number of hydrogen atoms of the corresponding alkyl group ^the R ^f group and the same number of carbon atoms is preferably 60% or more, 80%
The above is more preferable. Further, the R ^f group is preferably a group in which all the hydrogen atoms of the alkyl group are substituted with fluorine atoms (hereinafter referred to as a perfluoroalkyl group) or an R ^f group containing a perfluoroalkyl group.

The (meth) acrylate containing an R ^f group is preferably a compound represented by the formula (10). However,
In the formula (10), R ^f1 represents a linear or branched polyfluoroalkyl group having 4 to 16 carbon atoms, and preferably a perfluoroalkyl group. Further, in the formula (10), a fluorine atom is preferably bonded to the carbon atom bonded to R ⁶ of the R ^f1 group. R ⁶ represents a divalent linking group, preferably a linear or branched alkylene group having 1 to 10 carbon atoms, and particularly preferably those described in specific examples. R ⁷ represents a hydrogen atom or a methyl group.

[0013]

Embedded image R ^f1 —R ⁶ —OCOCR ⁷ ═CH ₂ (10)

Specific examples of the (meth) acrylate containing an R ^f group are shown below, but the invention is not limited thereto.

[0015]

[Chemical formula 4] CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₃ OCOCH = CH ₂ CF ₂ H (CF ₂ ) ₇ (CH ₂ ) ₃ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₆ CH ₂ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₄ CH ₂ OCOC (CH ₃ ) = CH ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₆ (CH ₂ ) ₂ OCOCH = CH ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₁₀ (CH ₂ ) ₃ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₆ (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂

[0016]

[Chemical Formula 5] (CF ₃ ) ₂ CF (CF ₂ ) ₄ (CH ₂ ) ₂ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ ) ₂ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₃ OCOCH = CH ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH (OH) CH ₂ OCOCH = CH ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH (OCOCH ₃ ) OCOC (CH ₃ ) = CH ₂

The polymer (a) of the present invention contains one or more of the above R ^f group-containing (meth) acrylates.
When two or more kinds are contained, it is preferably a (meth) acrylate in which the R ^f group has different carbon numbers.

The polymer (a) may be a polymer consisting only of polymerized units of the above R ^f group-containing (meth) acrylate, but other polymerizability other than the R ^f group-containing (meth) acrylate. It is preferably a copolymer containing polymerized units of monomers. The other polymerizable monomer is not particularly limited as long as it is a compound copolymerizable with the (meth) acrylate containing an R ^f group. Preferred examples of other polymerizable compounds include the following compounds.

N-methylol (meth) acrylamide,
(Meth) acrylamide, glycidyl (meth) acrylate, aziridinyl (meth) acrylate, diacetone (meth) acrylamide, methylolated diacetone (meth) acrylamide, ethylene glycol di (meth) acrylate, hydroxyalkyl (meth) acrylate, 3-fluoro- 2-Hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, one-terminal methylethylketone oxime blocked isophorone diisocyanate / hydroxyethyl (meth) acrylate reaction product, one-terminal methylethylketone oxime blocked tolylene diene A polymerizable monomer having a crosslinkable group such as an isocyanate / hydroxyethyl (meth) acrylate reaction product.

Vinyl chloride, ethylene, vinyl acetate, vinyl fluoride, styrene, α-methylstyrene, alkyl (meth) acrylate, benzyl (meth) acrylate, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, cyclohexyl (meth ) Acrylate, maleic anhydride, butadiene,
Isoprene, chloroprene, etc.

When the polymer (a) is a copolymer containing a polymerized unit of another polymerizable monomer, the other polymerizable monomer may contain one kind or two or more kinds. .

When the polymer (a) of the present invention is a copolymer containing a polymerized unit of the R ^f group-containing (meth) acrylate and a polymerized unit of another polymerizable monomer, the polymer (a) in the copolymer is The polymerized unit of (meth) acrylate containing an R ^f group is preferably 40% by weight or more in the polymer, and particularly preferably about 50 to 80% by weight. Further, when a monomer having a crosslinkable group is contained as the other polymerizable monomer, the amount of the monomer may be small, and usually 0.01 to 10% by weight in the copolymer. Degree is preferred, especially 0.1
It is preferably about 5% by weight.

The polymer (a) of the present invention is dispersed in an aqueous medium. Examples of the aqueous medium include water, or water containing a water-soluble organic solvent. Examples of the water-soluble organic solvent include ketones, esters, glycols, glycol ethers, alcohols and the like. When the aqueous medium contains a water-soluble organic solvent, the water-soluble organic solvent is added in an amount of 5 to 100 parts by weight of water.
It is preferable to contain about 50 parts by weight.

The water-dispersed water / oil repellent composition of the present invention is characterized by containing a specific surfactant (b) in addition to the above aqueous medium and the polymer (a). The specific surfactant (b) includes three specific surfactants [surfactant (c), surfactant (d), and surfactant (e)].
Is a surfactant containing.

Surfactant (c): A cationic surfactant composed of a compound having 5 or more cationic nitrogen atoms and oxyalkylene units in the molecule. The surfactant (d) is a nonionic surfactant (hereinafter referred to as the nonionic surfactant (d)). The surfactant (e) is a cationic surfactant other than (c) (hereinafter referred to as the cationic surfactant (e)).

First, the surfactant (c) will be described. The surfactant (c) is a cationic surfactant composed of a compound containing 5 or more cationic nitrogen atoms and oxyalkylene units in the molecule. The surfactant is a component that exhibits excellent dispersion stability in the emulsion even when a concomitant drug such as an acid or an anionic substance or a contaminant coexists in the processing bath.

The oxyalkylene unit in the surfactant (c) molecule is preferably oxyethylene or oxypropylene. The oxyalkylene unit may be only one kind or two or more kinds. The surfactant (c) is a compound containing 5 or more oxyalkylene units in the molecule, and the oxyalkylene units are present in the molecule as a polyoxyalkylene chain in which 2 or more are connected. preferable. The polyoxyalkylene chain may be either a polyoxyalkylene chain in which two or more oxyalkylene units are linked, or a polyoxyalkylene chain in which two or more oxyalkylene units are linked in two or more. Good. When two or more oxyalkylene units are connected in series of two or more, each of the oxyalkylene units may be connected in either a block form or a random form. Furthermore, it is preferable that 1 to 3 polyoxyalkylene chains are present in the molecule, especially 1 to
Two is preferable. Further, the surfactant (c) may contain one kind or two or more kinds.

Specific examples of the surfactant (c) of the present invention are as follows. In the formula below, when oxyethylene units and propylene units are linked,
It may be either block-shaped or random.

[0029]

[Chemical 6]

However, in the specific examples of the surfactant (c), R ^{1 to} R ³ , [X] ⁻ , A, B, Q, k, m, n,
p and q to v have the following meanings. R ¹ : an alkyl group having 6 to 22 carbon atoms, an alkenyl group having 6 to 22 carbon atoms, an acyl group having 6 to 22 carbon atoms, a phenyl group to which an alkyl group (having 6 to 22 carbon atoms) is bonded, or an alkenyl group ( A phenyl group having 6 to 22 carbon atoms bonded. R ² and R ³ may be the same or different and each is a hydrogen atom, a methyl group, an ethyl group or a benzyl group.

[X] ⁻ : Indicates a monovalent anion, which is a chlorine ion, HSO ₄ ⁻ , NO ₃ ⁻ , CH ₃ COO ⁻ , CH ₃ CH
₂ COO ⁻ , HCOO ⁻ , C ₂ H ₅ SO ₄ ^{− and the} like are preferable. A: oxyethylene group. B: oxypropylene group _{[-CH 2 CH (CH 3)} O-
Or _{-CH (CH 3) CH 2 O-} ]. When the oxypropylene group is bonded to a nitrogen atom, a nitrogen atom and-
It is preferable that they are bound by CH ₂ or —CH. _{Q :-( CH 2) k - (} k represents a divalent linking group represented by integers) from 0 to 5.. When Q is 0, it indicates a single bond, and the nitrogen atom and the nitrogen atom are directly bonded.

K, m, n, p: each is an integer of 0 to 20, and the average value of k + m + n + p is 5 to 40.
k, m, n and p represent the number of oxyethylene units or oxypropylene units. The number of oxyethylene units and / or oxypropylene units in the readily available surfactant (c) is usually k, m, n,
And p are different in two or more different combinations, and even in that case, the average value of k + m + n + p is 5 to 40, and preferably 10 to 35. Further, when both m and n are 0, it means that the nitrogen atom and the hydrogen atom are directly bonded. The same meaning is shown in other cases.

Q, r, s, t, u, v: 0 to 0, respectively
It represents an integer of 20, and the average value of q + r + s + t + u + v is 5 to 40. q, r, s, t, u and v represent the number of oxyethylene units or oxypropylene units.
The number of oxyethylene units and / or oxypropylene units in the readily available surfactant (c) is usually two or more different combinations of q, r, s, t, u, and v, and In some cases, q + r + s
The average value of + t + u + v is 5 to 40, preferably 10 to 35. When both q and r are 0, it means that the nitrogen atom and the hydrogen atom are directly bonded. The same meaning is shown in other cases.

Further, when the surfactant (c) is one of the above formulas (1) to (4), the readily available surfactant (c) is usually a mixture of two or more kinds. Yes, R ¹
And mixtures having different carbon numbers. For example, R ¹ is a mixed group of an alkyl group and an alkenyl group having an alkyl group as a main component (coconut oil alkyl group), a mixed group of an alkyl group and an alkenyl group (beef tallow alkyl group),
Most of them are groups having an alkyl group (hardened beef tallow alkyl group) and the like.

In the above surfactant (c) molecule,
If the proportion of oxyethylene groups or oxypropylene groups is low, there is a possibility that sufficient processing bath stability, which is the main object of the present invention, may not be obtained, while if it is too high, hydrophilicity increases and sufficient repellency is not obtained. It may not be possible to obtain water.

Among the surfactants (c), the surfactants represented by the formula (1) are commercially available, and examples thereof include the following. Polyoxyethylene coconut oil alkylmonomethylammonium chloride (average number of oxyethylene groups: 15) [trade name: Esoguard C / 25 (manufactured by Lion Akzo)]. Polyoxyethylene lauryl monomethylammonium chloride (average number of oxyethylene groups: 7) [trade name: Cation L-207 (manufactured by NOF Corporation)].

The surfactant represented by the formula (1) is
By the reaction of a surfactant represented by the following formula (5) with a mineral acid such as hydrochloric acid, sulfuric acid and nitric acid, an organic acid such as formic acid, acetic acid and propionic acid, methyl chloride, benzyl chloride, diethyl sulfuric acid and dimethyl sulfuric acid. Can also be synthesized. In addition, R ¹ , A, B, k, m, n, and p in the formula (5) have the same meanings as described above.

[0038]

Embedded image

Surfactants represented by the formula (5) are commercially available, and examples thereof include the following. Polyoxyethylene stearylamine (average number of oxyethylene groups is 15) [Brand name: Nymeen S-215 (manufactured by NOF CORPORATION)]. The structure of Nymeen S-215 is shown in Formula (6). In the formula (6), a is an integer of 0 to 15 and b is 0 to 1.
It is an integer of 5, the average value of a + b is 15, and R represents a stearyl group.

[0040]

Embedded image

Polyoxyethylene coconut oil alkylamine (average number of oxyethylene groups: 15) [trade name: Esomin C / 25 (manufactured by Lion Akzo)]. Polyoxyethylene oleylamine (Average number of oxyethylene groups is 1
0) [Product name: Esomin O / 20 (manufactured by Lion Akzo)]. Polyoxyethylene polyoxypropylene coconut oil alkylamine (average number of oxyethyleneoxypropylene groups is 16) [Product name: Esopropomin C / 18-18 (manufactured by Lion Akzo)].

Further, among the surfactants (c), the surfactant represented by the formula (2) includes hydrochloric acid, sulfuric acid, nitric acid, etc. with respect to 1 equivalent of the surfactant represented by the formula (7). Mineral acid, formic acid,
It can be synthesized by reacting 2 equivalents of an organic acid such as acetic acid or propionic acid, methyl chloride, benzyl chloride, diethylsulfate, dimethylsulfate and the like. However, R ¹ , A, B, and q to v in the formula (7) have the same meanings as described above.

[0043]

[Chemical 9]

Among the surfactants (c), the surfactants represented by the formulas (3) and (4) are the same as the above formula (7).
With respect to 1 equivalent of the surfactant represented by, hydrochloric acid, sulfuric acid,
Mineral acids such as nitric acid, organic acids such as formic acid, acetic acid and propionic acid,
It can be synthesized by reacting 1 equivalent of methyl chloride, benzyl chloride, diethyl sulfate, dimethyl sulfate and the like.

Next, the nonionic surfactant (d) will be described. As the nonionic surfactant (d),
Known or known nonionic surfactants can be adopted,
Among the nonionic surfactants described in the Surfactant Handbook, nonionic surfactants classified into polyethylene glycol type and polyhydric alcohol fatty acid (partial) ester type are preferable. The nonionic surfactant (d) may contain one kind or two or more kinds.

Examples of the nonionic surfactant (d) include polyethylene glycol esters, polyoxyethylene alkyl ethers, polyoxyethylene propylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters,
Examples thereof include polyoxyethylene glycerin esters, sorbitan esters, glycerin esters, polyoxyethylene fatty acid esters and the like. In particular, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, and polyoxyethylene propylene alkyl ethers are preferable because of their high stability.

Further, the cationic surfactant (e) will be described. The cationic surfactant (e) is a cationic surfactant other than the above-mentioned surfactant (c),
Among known or well-known cationic surfactants described in the Surfactant Handbook, surfactants classified into quaternary ammonium salt type or amine salt type are preferable,
Particularly, an alkylammonium salt or an alkylamine salt is preferable. The cationic surfactant (e) may also be incorporated alone or in combination of two or more. Furthermore, from the viewpoint that the cationic surfactant does not adversely affect the water / oil repellency after processed into fibers, the alkylammonium salt represented by the formula (8) is an alkylamine salt. Is preferably represented by the formula (9).

[0048]

Embedded image [R ⁴ —N ⁺ (CH ₃ ) ₂ R ⁵ ]. [X ¹ ] ^- (8) R ⁴ —N (CH ₃ ) R ⁵ salt (9)

However, in equations (8) and (9),
R ⁴ , R ⁵ , and [X ¹ ] ⁻ have the following meanings. R ^4: an alkyl group having 6 to 22 carbon atoms, an alkenyl group having 6 to 22 carbon atoms, an alkyl phenyl group (the carbon number is 6 to 22) is bonded or alkenyl group (carbon number, 6
22) represents a phenyl group to which is bonded and has 12 to 22 carbon atoms.
And an alkenyl group having 12 to 22 carbon atoms are preferred. R ⁵ : hydrogen atom, alkyl group having 1 to 22 carbon atoms, alkenyl group having 2 to 22 carbon atoms, alkyl group (having 6 to 2 carbon atoms)
2) bonded phenyl group, alkenyl group (having 6 to 6 carbon atoms)
22) represents a phenyl group bonded to benzyl group, or a benzyl group bonded to an alkenyl group (having 6 to 22 carbon atoms), a hydrogen atom, a methyl group, an ethyl group, a benzyl group, an alkyl group having 12 to 22 carbon atoms. , Or 12 to 22 carbon atoms
Alkenyl groups are preferred.

[X ¹ ] ⁻ : Indicates a monovalent anion, which is a chlorine ion, HSO ₄ ⁻ , NO ₃ ⁻ , CH ₃ COO ⁻ , CH ₃ C
H ₂ COO ⁻ , HCOO ⁻ , C ₂ H ₅ SO ₄ ^{− and the} like are preferable.

The amount ratio of the surfactants (c), (d) and (e) in the specific surfactant (b) of the present invention preferably has the following relationship when expressed by weight ratio. . (D) / (c) = 99/1 to 1/99. (E) / [(c) + (d)] = 1/99 to 40/60.

In the water-dispersed water / oil repellent composition of the present invention, it is important that the surfactant contains at least three kinds of the above-mentioned surfactants. For example, the nonionic surfactant (d) alone does not have sufficient stability in a processing bath in the presence of contaminants, which causes a problem of polymer adhesion (gum-up) to mangles. On the other hand, although the surfactant (c) alone improves the stability to impurities, it has a problem that the water and oil repellency becomes insufficient. Therefore, it is necessary to use (d) and (c) together as the surfactant.
The ratio between (d) and (c) is (d) / (c) = 99/1.
It is preferable to use them by mixing them at an arbitrary ratio between 1/99 and (d) / (c) = 95 / 5-40 / 60.

Further, in the present invention, it is important to use the component (e) together in order to achieve both good dispersion stability and high water / oil repellency. However, if the proportion of the component (e) becomes too high, the dispersion stability will decrease,
The range of (e) / [(c) + (d)] = 1/99 to 40/60 is preferable, and 5/95 to 35/65 is particularly preferable.

The total amount of the surfactant (b) is the polymer (a).
3 to 15 parts by weight is preferable with respect to 100 parts by weight, and particularly,
5 to 13 parts by weight is preferable. If the amount of the surfactant (b) is small, the stability of the emulsion is not sufficient, and if it is large, the water and oil repellency may decrease.

The water-dispersed water / oil repellent composition of the present invention may contain a surfactant other than the above-mentioned surfactant (b). Examples of other surfactants include amphoteric surfactants and polymer surfactants other than the above surfactants (c) to (e). For example, betaine acetate, imidazolinium betaine, amine oxides, Examples thereof include polyoxyethylene alkyl ether acetate, polyoxyethylene alkyl ether sulfate, polyvinyl alcohol and the like.

The method of obtaining the polymer (a) of the present invention is not particularly limited, but a method of synthesizing the polymer by an emulsion polymerization method is efficient and preferable. Further, the polymer (a)
The method of synthesizing by an emulsion polymerization method, a method of naturally dispersing by stirring at the time of polymerization, also, before adding the polymerization initiator of the emulsion polymerization, emulsified by a homomixer or a high-pressure emulsification device, then The method of dispersing by initiating polymerization is preferred. That is,
When the polymer (a) of the present invention is obtained by an emulsion polymerization method, a (meth) acrylate containing an R ^f group and, if necessary, another polymerizable monomer are added to the specific surfactant (b). A method of synthesizing by emulsion polymerization in the presence is preferable.

As the polymerization medium at the time of emulsion polymerization, it is preferable to use the same one as the water-based medium of the water / oil repellent composition of the present invention, and it is preferable to use only water or a water containing a water-soluble organic solvent. Can be mentioned. Examples of the water-soluble organic solvent include ketones, esters, glycols, glycol ethers, alcohols and the like.

The emulsion polymerization is usually carried out by allowing a polymerization initiation source to act. The polymerization initiation source is not particularly limited, and a normal polymerization initiator such as an organic peroxide, an azo compound, a persulfate, or ionizing radiation such as γ-rays can be used.

The polymer (a) containing the polymerized units of (meth) acrylate containing R _f groups dispersed in an aqueous medium is preferably dispersed in the form of particles. It is preferably about 03 to 0.25 μm.

The water-dispersed water / oil repellent composition of the present invention is diluted to an arbitrary concentration according to the purpose and application and applied to the object to be treated. As the method of applying the object to be processed, any method can be adopted depending on the type of the object to be processed. For example, a known method of coating such as dip coating may be applied to the surface of the object to be processed and dried. If necessary, it may be applied together with an appropriate crosslinking agent to carry out curing.

The water-dispersed water / oil repellent composition of the present invention exhibits excellent stability even when used in combination with other compounds. Therefore, if necessary, other polymer blenders and other oleophobic agents may be used. Additives such as water repellents, oil repellents, insect repellents, flame retardants, antistatic agents, dye stabilizers and anti-wrinkle agents can be used in combination.
Even when other compounds are used together, excellent water / oil repellency and stability as a dispersion type composition are exhibited.

The article which can be treated with the water and oil repellent of the present invention includes various examples without particular limitation. For example, textile, glass, paper, wood, leather, fur, asbestos, brick,
Cement, metals and oxides, ceramic products, plastics, etc.

As the fiber woven fabric, 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, rayon,
Examples of the woven fabric include semi-synthetic fibers such as acetate, glass fibers, carbon fibers, inorganic fibers such as asbestos fibers, and mixed fibers thereof.

[0064]

The mechanism by which the water-dispersed water- and oil-repellent composition of the present invention exhibits excellent stability is not always clear, but in the composition of the present invention, the usual stabilization of the nonionic surfactant (d) is performed. In addition to the effect, the surfactant (c) having a cationic nitrogen atom and a polyoxyalkylene chain acts on the coexisting acid or anionic substance, whereby the coexisting substance reacts with other compounds. It is believed to prevent the formation of compounds insoluble in the aqueous medium from the composition. Even if an insoluble compound is produced, it is considered that the stability of the composition is improved by the solubilizing action of the hydrophilic polyoxyalkylene chain in the surfactant (c). On the other hand, the surfactant (c) having such a hydrophilic portion may adversely affect the water and oil repellency, but the adverse effect is that the surfactant (e) having a hydrophobic group such as a long chain alkyl group (e) is used. ) Is assumed to be reduced by the hydrophobic effect of

[0065]

EXAMPLES Next, the present invention will be specifically described with reference to Examples (Examples 1 to 6) and Comparative Examples (Examples 7 to 9), but the present invention is not limited to these. The water repellency shown in the following examples is represented by the water repellency number by the spray method of JIS L1092 (see Table 1 below), and the oil repellency is shown by the test solution shown in Table 2 below on the sample cloth with a few drops (two drops). The diameter was set to about 4 mm) and the state of permeation after 30 seconds was evaluated (AATCC-TM118-1966).

[0066]

[Table 1]

[0067]

[Table 2]

Example 1 A 1 liter glass autoclave was charged with perfluoroalkylethyl acrylate [C _n
F _{2n + 1} CH ₂ CH ₂ OCOCH = CH ₂ and n is 6
The average value of the mixture of 16 to 16] (154 g), stearyl acrylate (95 g), (2-hydroxyethyl)
Acrylate (7.7 g), stearyl mercaptan (0.77 g), (polyoxyethylene) octyl phenyl ether (18.5 g), stearyl trimethyl ammonium chloride (2.7 g), RN ⁺ (CH ₂ P)
_{h) [(C 2 H 4} O) 15 H] 2 Cl - [R is a tallow alkyl group, Ph represents a phenyl group. ] (5.3g),
Ion-exchanged water (307.6 g), dipropylene glycol monomethyl ether (DPGMME) (141 g),
Azobis (dimethyleneisobutyramidine) hydrochloride (0.
After adding 5 g), the autoclave was purged with nitrogen. The temperature was raised to 60 ° C. with stirring and polymerization was carried out for 6 hours to obtain a milky white emulsion having a solid content concentration of 38% and a particle diameter of 0.08 μm.

[Examples 2 to 6] Polymerization monomers and surfactants shown in Table 3 were used in the amounts shown in Table 3 to carry out polymerization in the same manner as in Example 1 to obtain emulsions. The abbreviations in Tables 3 and 4 are as follows.

FA: C _n F _{2n + 1} CH ₂ CH ₂ OCOCH
= CH ₂ and n is a mixture of 6 to 16. StA: Stearyl acrylate. HEA: (2-hydroxyethyl) acrylate. GMA: glycidyl methacrylate. VCl: vinyl chloride. DOM: Dioctyl malate. DMAA: dimethyl acrylamide. PEPA: polyoxyethylene polyoxypropylene methacrylate. HE6P: one-terminal methyl ethyl ketone oxime blocked isophorone diisocyanate / 2-hydroxyethyl methacrylate reaction product. EDMA: ethylene glycol dimethacrylate. CHMA: cyclohexyl methacrylate. NMAM: N-methylol acrylamide.

TBzPOEC: Polyoxyethylene tallow alkylbenzylammonium chloride represented by the following formula (10). However, in the formula (10), R is a beef tallow alkyl group, Ph is a phenyl group, and a is 0 to 30.
Is an integer of 0 to 30, and a + b = 30. SMPOEC: polyoxyethylene stearyl methyl ammonium chloride represented by the following formula (11), R
Is a stearyl group, c is an integer of 0 to 15, d is an integer of 0 to 15, and c + d = 15. POE / OPE: Polyoxyethylene (octylphenyl) ether, a compound containing 20 oxyethylene units. POEL: Polyoxyethylene lauryl ether, a compound containing 15 oxyethylene units. STMAC: Stearyl trimethyl ammonium chloride. DTDMAC: Di (tallow alkyl) dimethylammonium chloride.

[0072]

[Chemical 11]

[0073]

[Chemical 12]

[0074]

[Table 3]

[Examples 7 to 9] Polymerization monomers and surfactants shown in Table 4 were used to carry out polymerization in the same manner as in Example 1 to obtain emulsions of Examples 7 to 9.

[0076]

[Table 4]

[Evaluation of Water / Oil Repellent Performance] The emulsion obtained by the above method was adjusted to a solid content concentration of 20% by weight with water to prepare a stock solution. The water- and oil-repellent performance was measured using a treatment solution diluted to give a ratio of the stock solution to water of 2% by weight. Further, 0.05% by weight of a dye fixing agent for nylon (hereinafter referred to as a fixing agent; manufactured by Meisei Chemical Industry Co., Ltd./trade name: DIMAFIX ES) was added to the treatment liquid to give water and oil repellency in the presence of an anionic substance. The performance and condition of the treatment bath were investigated.

The evaluation of the water / oil repellency was carried out on the nylon taffeta cloth which was subjected to the water / oil repellency treatment by the following method. A test cloth is dipped in the treatment liquid prepared above, and the cloth is squeezed between two rubber rollers to make a wet pickup 60.
It was set to% by weight. Then, a cloth which was dried at 110 ° C. for 90 seconds and further heat-treated at 170 ° C. for 60 seconds was obtained, and this cloth was evaluated.

Regarding the state of the treatment bath, the treatment bath after addition of the fixing agent was visually observed. ○ indicates that sedimentation does not occur, △ indicates that white turbidity is observed, and × indicates that sediment is observed. Table 5 shows the results.

[0080]

[Table 5]

[0081]

The water-dispersed water / oil repellent composition of the present invention comprises:
Shows excellent water and oil repellency. Further, even if there is a co-use aid or a contaminant, the water / oil repellent composition is excellent in practical use because the water / oil repellency and emulsion stability are not deteriorated.

Claims (7)

[Claims] 1. A polymer (a) containing polymerized units of acrylate or methacrylate containing a polyfluoroalkyl group dispersed in an aqueous medium, and a surfactant (b).
In a water-dispersed water and oil repellent composition containing, the surfactant (b) is selected from at least three kinds of the following surfactants (c), the following surfactants (d), and the following surfactants (e). A water-dispersed water- and oil-repellent composition. Surfactant (c): a cationic surfactant composed of a compound containing 5 or more cationic nitrogen atoms and oxyalkylene units in the molecule. Surfactant (d): a nonionic surfactant. Surfactant (e): Cationic surfactant other than (c). 2. The surfactant (b) is contained in a total amount of 3 to 15 parts by weight based on 100 parts by weight of the polymer (a).
The water-dispersed water and oil repellent composition of. 3. The water-dispersed water / oil repellent composition according to claim 1, wherein the weight ratio of the surfactant (c), the surfactant (d) and the surfactant (e) is within the following range. Stuff. Surfactant (d) / surfactant (c) = 99/1 to 1 /
99. Surfactant (e) / [surfactant (c) + surfactant (d)] = 1/99 to 40/60. 4. A polymer (a) is synthesized by emulsion-polymerizing a polymerizable monomer containing an acrylate or a methacrylate containing a polyfluoroalkyl group in an aqueous medium in the presence of a surfactant (b). The water-dispersed water- and oil-repellent composition according to any one of claims 1 to 3, which is a polymer obtained from the above. 5. The water-dispersible water-repellent agent according to claim 1, wherein the surfactant (c) is at least one selected from the surfactants represented by formulas (1) to (4). Oil repellent composition.
However, R ^{1 to} R ³ , [X] ⁻ , A, B, Q, k, m,
n, p, and q to v have the following meanings. R ¹ : an alkyl group having 6 to 22 carbon atoms, an alkenyl group having 6 to 22 carbon atoms, an acyl group having 6 to 22 carbon atoms, a phenyl group to which an alkyl group (having 6 to 22 carbon atoms) is bonded, or an alkenyl group ( A phenyl group having 6 to 22 carbon atoms bonded. R ² and R ³ may be the same or different and each is a hydrogen atom, a methyl group, an ethyl group or a benzyl group. [X] ⁻ : A monovalent anion. A: oxyethylene group. B: Oxypropylene group. _{Q :-( CH 2) k - (} k is a divalent linking group represented by an integer from 1 to 5). k, m, n, p: each is an integer of 0 to 20, k
The average value of + m + n + p is 5 to 40. q, r, s, t, u, v: each is an integer of 0 to 20, and the average value of q + r + s + t + u + v is 5 to 40. Embedded image 6. The surfactant (e) is at least one selected from the surfactants represented by formula (8) or formula (9).
The water-dispersed water / oil repellent composition according to claim 1, which is a seed. Embedded image [R ⁴ —N ⁺ (CH ₃ ) ₂ R ⁵ ]. [X ¹ ] ^- (8) R ⁴ —N (CH ₃ ) R ⁵ salt (9) where R ⁴ , R ⁵ , and [X ^{1] -} represents the following meanings. R ^4: an alkyl group having 6 to 22 carbon atoms, 6 carbon atoms
~ 22 alkenyl group, alkyl group (having 6 to 2 carbon atoms
A phenyl group to which 2) is bonded or an alkenyl group (having 6 to 22 carbon atoms) is bonded to a phenyl group. R ⁵ : hydrogen atom, alkyl group having 1 to 22 carbon atoms, alkenyl group having 2 to 22 carbon atoms, alkyl group (having 6 to 2 carbon atoms)
2) bonded phenyl group, alkenyl group (having 6 to 6 carbon atoms)
22) is a phenyl group, a benzyl group, or an alkenyl group (having 6 to 22 carbon atoms) is a benzyl group. [X ¹ ] ^- : a monovalent anion. 7. A polymerizable monomer containing an acrylate or a methacrylate containing a polyfluoroalkyl group is added to the following surfactant (c), the following surfactant (d), and the following surfactant in an aqueous medium. A method for producing a water-dispersed water- and oil-repellent composition, which comprises emulsion-polymerizing in the presence of (e). Surfactant (c): a cationic surfactant composed of a compound containing 5 or more cationic nitrogen atoms and oxyalkylene units in the molecule. Surfactant (d): a nonionic surfactant. Surfactant (e): Cationic surfactant other than (c).