JPH08199111A - Water and oil repellent composition improved in antifouling property - Google Patents

Abstract

PURPOSE: To obtain the subject composition, excellent in both performances of water and oil repellencies and dry soil properties and further durability in the water and oil repellencies without deteriorating the touch feeling of a cloth by blending a polymer containing a polyfluoroalkyl with a specific polymer. CONSTITUTION: This composition is obtained by blending (A) 100 pts.wt. polymer containing preferably 50-80wt.% polymerization unit comprising an α,β-unsaturated monomer containing a polyfluoroalkyl [preferably an acrylate or a methacrylate of the formula (A is a bivalent organic group; Rf <1> is a straight- chain 4-6C perfluoroalkyl)] with (B) 10-60 pts.wt. polymer containing a polymerization unit comprising a fluoroolefin (preferably a 2-4C fluoroolefin such as trifluoroethylene). Furthermore, the component (A) preferably contains (meth) acrylamides, etc., as a copolymerization component. The component (B) is a copolymer of a fluoroolefin and a polymerizable compound having a side chain bound to a hydrophilic group such as acrylic acid or a hydrophilic side chain.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-dispersible fluorine-based water / oil repellent having an improved antifouling property. More specifically, the present invention relates to a water-dispersed fluorine-based water and oil repellent having excellent water and oil repellency and dry soil resistance.

[0002]

2. Description of the Related Art For the purpose of imparting water repellency and oil repellency and dry soil resistance to fibers, it is widely practiced to treat fiber cloth with a fluorine-based water and oil repellant. However, it has been pointed out that it is difficult to obtain sufficient dry soil resistance when treated with a conventional fluorine-based water and oil repellent, and various types of water and oil repellents having high dry soil resistance have been pointed out. Compositions have been proposed.

For example, (1) a composition containing a fluorine-containing urethane compound as a main component, (2) a composition in which a water / oil repellent agent and an acrylic copolymer having a high glass transition temperature are used in combination, (3)
A composition using a silicone resin in combination with a water and oil repellent has been proposed.

[0004]

However, the above-mentioned known examples have the following problems. The composition (1) has a drawback of low water and oil repellency. The combined use of the acrylic copolymer of (2) has a problem of making the texture coarse and hard. The combined use of the silicone resin of (3) has a problem that the texture of the fiber is changed (a phenomenon called so-called silicone touch) and the oil repellency of the water and oil repellent agent is lowered.

As described above, a composition which is excellent in both dry soil resistance and water / oil repellency has not been obtained yet.

[Means for Solving the Problems]

An object of the present invention is to provide a water-dispersible fluorine-based water and oil repellent composition which is excellent in dry soil resistance without deteriorating water and oil repellency.

As a result of continuous research to solve the above-mentioned problems, the present inventors have found that a water-repellent agent can be obtained by using a specific fluoroolefin polymer, which alone has no dry soil resistance, in combination with a water- and oil-repellent agent. We have found a water / oil repellent composition which is excellent in oil repellency and also exhibits excellent performance in dry soil resistance.

That is, the present invention includes a polymer containing polymerized units of an α, β-unsaturated monomer containing a polyfluoroalkyl group and a polymer containing polymerized units of a fluoroolefin. Contains α, β-
A water-dispersible fluorine-based water-repellent agent, which comprises 10 to 60 parts by weight of a polymer containing a polymer unit of a fluoroolefin with respect to 100 parts by weight of a polymer containing a polymer unit of an unsaturated monomer. An oil agent composition is provided.

Α, β-containing a polyfluoroalkyl group (hereinafter, the polyfluoroalkyl group is referred to as R _f group)
The unsaturated monomer is a compound having a structure in which the R _f group is directly or indirectly bonded to a polymerizable unsaturated group. R _f
The group has a structure in which two or more hydrogen atoms of the alkyl group are substituted with fluorine atoms. Further, the non-substituted hydrogen atom may be substituted with an atom other than the fluorine atom. As the other atom, a halogen atom is preferable, and a chlorine atom is particularly preferable.

The carbon atom of the R _f group may be replaced with an etheric oxygen atom. When the R _f group is a group containing an etheric oxygen atom, it is preferably a group containing an oxyfluoroalkylene moiety. One or two or more oxyfluoroalkylene moieties may be connected. Examples of the oxyfluoroalkylene moiety include oxyfluoromethylene and oxyfluoropropylene.

Usually, the carbon number of the R _f group is preferably about 4 to 20. In addition, among carbon atoms, the number of carbon atoms to which a fluorine atom is bonded is 2 or more, preferably 4 to 18
The number is particularly preferably 6 to 16.

[0012] The number of fluorine atoms in _the R _f group, (fluorine atoms in _the R _f group) / (number of hydrogen atoms in an alkyl group having the same carbon number corresponding to _the R _f group) is 60% or more, preferably 8
The number is preferably 0% or more. Examples of the structure of the terminal portion of the R _f group include a trifluoromethyl group, a difluoromethyl group, a chlorodifluoromethyl group, and the like, but the trifluoromethyl group is preferable.

The R _f group is preferably a perfluoroalkyl group in which substantially all the hydrogen atoms of the alkyl group are substituted with fluorine atoms. The carbon number of the perfluoroalkyl group is preferably 3 or more, particularly preferably 4 to 16, and further preferably 6 to 12. The perfluoroalkyl group may have a linear or branched structure, but when it has a branched structure, the branched portion is preferably a short chain having about 1 to 3 carbon atoms. Further, the branched portion is preferably present at the terminal portion of the perfluoroalkyl group.

The α, β-unsaturated monomer containing the R _f group of the present invention is a compound having a structure in which the R _f group is directly or indirectly bonded to a polymerizable unsaturated group. The compound is selected from known compounds, and an acrylate and / or methacrylate containing an R _f group (hereinafter, the acrylate and / or methacrylate is referred to as (meth) acrylate) is preferable.

As the (meth) acrylate containing an R _f group, a compound represented by the general formula (1) is preferable. However, in the general formula (1), R ¹ represents a hydrogen atom or a methyl group, A represents a single bond or a divalent organic group, and R _f ¹ represents a C 4-16 perfluoroalkyl group.

[0016]

CH ₂ = CR ¹ COO-A-R _f ¹ (1)

As A in the general formula (1), a divalent organic group is preferable. Examples of the divalent organic group include —R ² — and —R ^{2
_{N (R 3) SO 2 -}} , - R 2 N (R 4) CO- , and the like. However, R ² represents an alkylene group and has 1 carbon atom.
~ 6 alkylene groups are preferred, and alkylene groups having 1 to 3 carbon atoms are particularly preferred. Also the alkylene group, part of hydrogen atoms may be substituted a hydroxyl group, or -OCOCH _3. R ³ and R ⁴ represent an alkyl group, preferably an alkyl group having 4 or less carbon atoms. R _f ¹ may have either a linear structure or a branched structure, but a linear structure is preferable.

Specific examples of the compound represented by the general formula (1) are shown below, but the invention is not limited thereto. In addition, R ¹ and R _f ¹ in the following formulas have the same meanings as described above.

[0019]

Embedded image CH ₂ = CR ¹ COO-CH ₂ -R _f ¹ CH ₂ = CR ¹ COO- (CH ₂ ) ₂ -R _f ¹ CH ₂ = CR ¹ COO- (CH ₂ ) ₃ -R _f ¹ CH ^{_{2 = CR 1 COO- (CH 2}} ) 2 N (CH 3) SO
^{_{2 -R f 1 CH 2 = CR}} 1 COO- (CH 2) 2 N (C 2 H 5) S
^{_{O 2 -R f 1 CH 2 =}} CR 1 COO-CH 2 CH (OH) CH 2 -R
^{_{f 1 CH 2 = CR 1 COO}} -CH (OCOCH 3) CH 2 -
R _f ¹

[0020] containing the above-described _the R _f group (meth) acrylates may be used alone, in the case of using two or more types may be used or two or more, the number of carbon atoms in _the R _f group is It is preferable to use two or more different (meth) acrylates.

Further, α, β-containing the R _f group of the present invention
The polymer containing a polymerized unit of an unsaturated monomer preferably contains a polymerized unit of another polymerizable monomer (hereinafter referred to as a comonomer). As the comonomer, a known radical-polymerizable unsaturated group-containing monomer is preferable, and various monomers can be used without particular limitation.

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.

Vinyls such as 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 comonomers may be used alone or in combination of two or more. However, when a (meth) acrylate having a functional group is used as a comonomer, it is preferably contained as a part of the comonomer, and is 1 to 10 parts by weight, preferably 2 to 5 parts by weight based on 100 parts by weight of all the comonomers. It is preferable to include about parts by weight.

In the polymer containing the polymerized units of the α, β-unsaturated monomer containing the R _f group of the present invention, the polymerized units of the α, β-unsaturated monomer containing the R _f group are The proportion is preferably 40% by weight or more, and particularly preferably 50 to 80% by weight. When the polymer contains polymerized units of comonomer, 60% by weight or more of the comonomer is preferably (meth) acrylates or (meth) acrylamides. Also, R
The molecular weight of the polymer containing the polymerized units of the α, β-unsaturated monomer containing the _f group is preferably about 1,000 to 1,000,000, and particularly preferably 3,000 to 300,000. Also,
For reasons such as dispersion stability, the particle system of the polymer is 0.
05-0.3 μm is preferable, and 0.1-0.2 μm is particularly preferable.
Is preferred.

The method for producing the polymer containing the polymerized units of the α, β-unsaturated monomer having the R _f group of the present invention is not particularly limited, and it may be solution polymerization, emulsion polymerization, suspension polymerization or the like. Known polymerization methods can be adopted. Of these, the present invention is
From the purpose of finally obtaining a water-dispersed composition,
It is efficient and preferable to carry out the polymerization by an emulsion polymerization method. Polymerization in emulsion polymerization is usually carried out by the above R _f.
A method in which the polymerizable monomer having a group and, if necessary, another polymerizable monomer are polymerized in the presence of an emulsifier in an aqueous medium using a polymerization initiator is adopted.

The emulsifier is not particularly limited, and any one of cationic, anionic, nonionic and amphoteric emulsifiers can be used. The amount of the emulsifier is 2 to 10 with respect to 100 parts by weight of the polymerizable monomer.
Parts by weight are preferred.

As the aqueous medium, water or a mixture of water and one or more water-soluble organic solvents can be selected. When the water-soluble organic solvent is contained, the dispersion stability of the polymer 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, methyl alcohol and the like. The amount of the aqueous medium is preferably about 200 to 900 parts by weight with respect to 100 parts by weight of the polymerizable monomer.

Examples of the polymerization initiator include ordinary radical polymerization initiators and ionizing radiation such as γ-rays, and it is particularly preferable to use the radical polymerization initiator represented by the following formula.

[0032]

Embedded image

[0033]

[Chemical 4]

An aqueous dispersion of a polymer containing polymerized units of an α, β-unsaturated monomer containing an R _f group can be synthesized by the above-mentioned method, or a commercially available product may be used. For example, the product name Asahi Guard Co., Ltd. from Asahi Glass Co., Ltd.
Commercially available products such as Teflon under the trade name of DuPont and Scotchguard under the trade name of 3M Co., Ltd. can be used.

On the other hand, as the polymer containing the polymerized units of fluoroolefin, a homopolymer of fluoroolefin,
Examples thereof include a copolymer of a fluoroolefin and another polymerizable compound copolymerizable with the fluoroolefin, and a copolymer of a fluoroolefin and another polymerizable compound copolymerizable with the fluoroolefin is preferable. As the fluoroolefin, a fluoroolefin having about 2 to 4 carbon atoms such as vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, pentafluoropropylene or hexafluoropropylene is preferable.

When the polymer containing the polymerized units of fluoroolefin is a copolymer of fluoroolefin and another polymerizable compound copolymerizable with fluoroolefin, the other polymerizable compound is a hydrophilic group. A polymerizable compound having a side chain bonded with or a polymerizable compound having a hydrophilic side chain is preferable.

The polymerizable compound having a side chain having a hydrophilic group bonded thereto is preferably a polymerizable compound having a side chain having a hydrophilic group bonded to the end of the side chain and a polymerizable unsaturated site. The hydrophilic _{group, -COOM, -SO 3 M, -PO} 3 M
(Here, M represents a hydrogen atom, an alkali metal, a quaternary ammonium group, or a quaternary phosphonium group.),
Alternatively, an amide group or the like is preferable.

Examples of the polymerizable compound having a side chain having a hydrophilic group bonded thereto include polyvalent carboxylic acids such as succinic acid, polyvalent sulfonic acids, acrylic acid amides, methacrylic acid amides, methacrylic acid and acrylic acid. sell.

The polymerizable compound having a hydrophilic side chain is preferably a polymerizable compound having a hydrophilic side chain and a polymerizable unsaturated site. As the hydrophilic side chain, a side chain containing an oxyalkylene moiety is preferable, a side chain containing oxyethylene, oxypropylene, oxybutylene, etc. is preferable, and a side chain containing a polyoxyethylene portion is particularly preferable.

As the polymerizable compound having a hydrophilic side chain or the polymerizable compound having a side chain to which a hydrophilic group is bound, the above-mentioned compound having a hydrophilic side chain or hydrophilic group and an ethylenically unsaturated group can be used. Of these, vinyl compounds, allyl compounds, acryloyl compounds and methacryloyl compounds are preferred.

Specific examples of the other polymerizable compound copolymerizable with the fluoroolefin are shown below, but the invention is not limited thereto. However, in the following formula, M is the same hydrogen atom as above, an alkali metal, a quaternary ammonium group, or a quaternary ammonium group.
Represents a primary phosphonium group, m is an integer of 1 to 10, and n is 1
Indicates an integer of -10.

[0042]

CH ₂ = CHOCH ₂ CH ₂ CH ₂ (OCH ₂ CH ₂ ) _n OH CH ₂ = CHCH ₂ OCH ₂ CH ₂ (OCH ₂ CH ₂ ) _n OH CH ₂ = CHCOOM CH ₂ = C (CH ₃ ) COOM CH ₂ = CHOCH ₂ CH ₂ CH ₂ (OCH ₂ CH ₂ ) _n [OCH (CH ₃ ) CH ₂ ] _m OH CH ₂ = CHOCF ₂ CF ₂ COOM CH ₂ = CHOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₃ M CH ₂ = CHOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₂ COOM CH ₂ = CHOCH ₂ CH ₂ CHOCOCH ₂ CH ₂ COOM CF ₂ = CFOCH ₂ CH ₂ CH ₂ (OCH ₂ CH ₂ ) _n [OCH (CH ₃ ) CH ₂ ] _m OH CF ₂ = CFOCF ₂ CF ₂ COOM CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₃ M CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₂ COOM CF ₂ = CFOCH ₂ CH ₂ CHOCOCH ₂ CH ₂ COOM

In the polymer containing polymerized units of fluoroolefin, the number of polymerized units based on fluoroolefin is 2
0 to 80 mol% is preferable, and 30 to 70 mol% is particularly preferable. Further, in the case of containing a polymerizable unit having a hydrophilic side chain or a polymerizable unit having a side chain to which a hydrophilic group is bonded, in a polymer containing a polymer unit of fluoroolefin, It is preferably contained at 80 mol%, particularly preferably 1 to 20 mol%. If the amount of the other polymer compound is too small, it may be difficult to disperse in water.

The polymer containing polymerized units of fluoroolefin of the present invention preferably further contains polymerized units of a monomer having a reactive group. Examples of the reactive group include a hydroxyl group, a carboxylic acid group, an amino group, an acid amide group, an active hydrogen-containing group such as a mercapto group, an epoxy group, an active halogen-containing group, and a double bond.

Examples of the monomer having a reactive group include hydroxyalkyl vinyl ethers, hydroxyalkyl allyl ethers, reaction products of hydroxyalkyl vinyl ethers with lactone compounds or dicarboxylic acid anhydrides, glycidyl vinyl ethers, glycidyl allyl ethers and phenols. Examples thereof include a reaction product, glycidyl vinyl ether, glycidyl allyl ether, aminoalkyl vinyl ether, acrylic acid amide, a reaction product of a hydroxyalkyl vinyl ether and an isocyanate alkyl (meth) acrylate, and an allyl vinyl ether.

Further, the polymer containing a polymerized unit of fluoroolefin preferably contains a polymerized unit of a polymerizable monomer other than the above polymerized units. Examples of the other polymerizable monomer include olefins, vinyl ethers, vinyl esters, allyl ethers, allyl esters,
Acrylic acid esters and methacrylic acid esters are exemplified. Of these, olefins, vinyl ethers, vinyl esters, allyl ethers, and allyl esters are preferable. The olefins have 2 carbon atoms
Those having about 10 to 10 are preferable, and as vinyl ethers, vinyl esters, allyl ethers and allyl esters, those having a linear, branched or alicyclic alkyl group having about 2 to 15 carbon atoms are preferable. .

As the other polymerizable monomer in the polymer containing polymerized units of fluoroolefin, for example, ethylene, propylene, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, vinyl pentanoate, vinyl nonanoate,
Styrene, vinyltoluene, ethylallyl ether, allyl pentanoate, butyl acrylate, butyl methacrylate, or those obtained by substituting a part or all of hydrogen bonded to carbon with a halogen atom is adopted.

As those in which a part or all of hydrogen bonded to carbon is replaced with a halogen atom, vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene fluoride, chlorotrifluoroethylene, trifluoroethylene can be mentioned. , Tetrafluoroethylene, hexafluoropropylene, pentafluoropropylene, perfluoro (propyl vinyl ether), fluoroacrylate, fluoromethacrylate and the like.

Of these, fluoroolefins having about 2 to 4 carbon atoms such as hexafluoropropylene, pentafluoropropylene, tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene and vinylidene fluoride, and fluorinated vinyl compounds. Is preferred.

In the polymer containing the fluoroolefin polymerized units, the proportion of the polymerized units of the other polymerizable monomer is 70 mol% or less in the polymer containing the fluoroolefin polymerized units. preferable.

The molecular weight of the polymer containing the polymerized units of fluoroolefin is not particularly limited, but if it is too large, it becomes difficult to disperse, which is not preferable, and if it is too small, the desired performance of the present invention may not be exhibited. Not preferable. Normally, the number average molecular weight is 1,000 to 5,000.
About 00 is preferable, and about 3000-400000 is particularly preferable.

The polymer containing polymerized units of fluoroolefin is synthesized by a known or well-known polymerization method. Among them, in the present invention, the emulsion polymerization method is preferable for the same reason as described above, and it is disclosed in JP-A-2-70706 and JP-A-3-70706.
91553, JP-A-2-225550, JP-A-5-11
It is preferable to adopt the method described in 7579 or the like.

In the present invention, the polymer containing the polymerized units of fluoroolefin is selected to have high compatibility with the polymer containing the polymerized units of the α, β-unsaturated monomer containing the R _f group. Is preferred. R synthesized as a water and oil repellent
Many polymers containing polymerized units of α, β-unsaturated monomers containing _f groups tend to be cationic and have low compatibility with anionic polymers even when they are nonionic. If the compatibility is low, the water and oil repellency may be adversely affected. On the other hand, a polymer containing polymerized units of fluoroolefin is usually anionic. Therefore,
The polymer containing a polymerized unit of fluoroolefin preferably contains a polymerized unit of a polymerizable compound having a hydrophilic side chain from the viewpoint of compatibility. However, if the amount of the polymerized units is too large, gelation may occur, which is not preferable.

In the water / oil repellent composition of the present invention, R _f
The ratio of the polymer containing the polymerized units of the α, β-unsaturated monomer containing a group and the polymer containing the polymerized units of the fluoroolefin is such that the _Rf group-containing α, β-unsaturated polymer has a solid content weight ratio. It is 10 to 60 parts by weight, and particularly preferably 20 to 40 parts by weight, based on 100 parts by weight of the polymer containing the saturated monomer polymerized units, and the ratio of the polymer containing the fluoroolefin polymerized units. If the proportion of the polymer containing the polymerized units of fluoroolefin is 10% by weight or less, the durability of dry soil resistance cannot be obtained, and if it is too large, not only the texture becomes coarse and hard but also the water and oil repellency may be deteriorated. There is. Further, the particle size of the polymer is preferably 0.05 to 0.3 μm, and particularly preferably 0.1 to 0.2 μm from the viewpoint of dispersion stability and the like.

The water-dispersible fluorine-based water / oil repellent of the present invention contains a polymer containing polymerized units of the α, β-unsaturated monomer containing the R _f group and a polymerized unit of fluoroolefin. The total amount of the polymer is 10 to 40% by weight in terms of solid content concentration.
It is preferably about the same. The solid content concentration can be appropriately changed depending on the form of the water and oil repellent agent, the type of the treated material, and the like. Usually, it is used by diluting it to a concentration suitable for the intended use. Further, the water-dispersible fluorine-based water and oil repellent of the present invention may contain components other than the above components. Other components include, for example, other water repellents and oil repellents, or additives such as cross-linking agents, insect repellents, flame retardants, antistatic agents, dye stabilizers and anti-wrinkle agents.

Any method can be applied to the article to be treated with the composition of the present invention depending on the type and the preparation form. For example, by a known coating method such as a dip coating method, it is attached to the surface of the object to be processed and dried,
A method of heat treatment is adopted. Further, the composition of the present invention may contain a polymer other than the above, and other water repellent or oil repellent, or a cross-linking agent, insect repellent, flame retardant, antistatic agent, dye stabilizer, It is also possible to appropriately contain additives such as anti-wrinkle agents.

As the object to be treated in the present invention,
Various examples can be given without particular limitation. For example, as examples of fiber woven fabrics and knitted fabrics, cotton, hemp, wool,
Natural animal and vegetable fibers such as silk, 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, Alternatively, a woven or knitted fabric of these mixed fibers may be used.

[0058]

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but this description does not limit the present invention. The water repellency, oil repellency, and dry soil resistance are shown on the following scale.

[Evaluation method of water and oil repellency] Water repellency is JIS
-Water repellency number by spray method of L1092 (Table 1
The oil repellency was determined by placing a few drops (diameter about 4 mm) of the test solution shown in Table 2 in two places on the test cloth, and determining the permeation state after 30 seconds (AATCC-TM118).
-1966). The water-repellent number and the oil-repellent number with + (-) indicate that the properties are slightly good (bad).

[0060]

[Table 1]

[0061]

[Table 2]

[Evaluation Method of Dry Soil Resistance] The dry soil resistance is 5 g of black clay powder (prepared by a ball mill) containing 8% of water in a polyethylene bag, and a test cloth (1
After placing 10 pieces of 0 cm square) and 10 rubber balls, the pieces were inflated with nitrogen gas and shaken for 5 minutes. After removing soil dirt adhering to the test cloth with a vacuum cleaner, the L value was measured with a color difference meter. Difference from uncontaminated cloth △
Shown as L.

[Synthesis Examples 1 and 2] Ethyl vinyl ether (EVE), cyclohexyl vinyl ether (CHVE), hydroxybutyl vinyl ether (HBVE), EOVE [CH] having the composition shown in Table 3 were placed in a stainless steel autoclave equipped with a stirrer having an internal volume of 200 ml. ₂ = CHO (CH ₂ ) ₄ (OCH ₂ CH ₂ )
_n OH (number average molecular weight 500)], ion-exchanged water (66.
1% by weight), emulsifier (polyoxyethylene glycol monolauryl ether 1.32% by weight), potassium carbonate (K ₂ CO ₃ ) (0.35% by weight), sodium bisulfite (NaHSO ₃ ) (0.02% by weight) ) And ammonium persulfate (APS) (0.08 wt%) were charged, the mixture was cooled with ice, and nitrogen gas was degassed by pressurizing it to 3.5 kg / cm ² . After repeating this pressure deaeration twice,
After degassing to 0 mmHg to remove dissolved air, chlorotrifluoroethylene (CTFE) or tetrafluoroethylene (TFE) was charged and the reaction was carried out at 30 ° C. for 12 hours.

[0064]

[Table 3]

[Synthesis Examples 3 and 4] Perfluoroalkyl ethyl acrylate (FA) having the composition shown in Table 4, cyclohexyl vinyl ether (CHVE), hydroxybutyl vinyl ether (HBVE), and chlorinated in an autoclave made of glass and having a stirrer and having an internal volume of 1000 ml. Vinyl (VC
l), dioctyl maleate (DOM), 2-hydroxyethyl acrylate (2HEA), octadecyl acrylate (C18A), ion-exchanged water (300 parts by weight), acetone (100 parts by weight), emulsifier (polyoxyethylene glycol monolaurel ether) 16 parts by weight), azo polymerization initiator (1 part by weight, Wako Pure Chemical V-5
0) was charged and replaced with nitrogen gas. Then, in Synthesis Example 3, vinyl chloride (VCl) was introduced under pressure, the temperature was raised to 60 ° C. with stirring, and the reaction was carried out for 15 hours.

FA: CH ₂ = CHCOOCH ₂ CH ₂ (CF ₂ CF ₂ ) _n CF ₂ CF ₃ is a mixture of compounds in which n is 1 to 5, respectively. The weight ratio of each compound is (n = 1):
(N = 2): (n = 3): (n = 4): (n = 5) =
It is 5: 60: 20: 10: 5.

[0067]

[Table 4]

[Examples 1 to 4] Water and oil repellency and dry soil resistance were evaluated by using polyester tropical cloth and cotton broad cloth as test cloths. The test cloth was dipped in a bath prepared from the latex prepared in Synthesis Example in terms of solid content weight ratio as shown in Table 5. The bath ratio (solid content weight: bath weight) was 1:20, the bath temperature was 25 ° C., and the bath pH was 6.
Next, squeeze the test cloth between the two rubber rollers,
The wet pickup was 60% by weight. Then 1
What was dried at 10 ° C. for 90 seconds and further heat-treated at 170 ° C. for 60 seconds was used for evaluation. The evaluation results are shown in Table 6.

[Comparative Examples 1 to 3] Evaluations were performed in the same manner as in Examples 1 to 4 using a bath having a solid content weight ratio shown in Table 5. The results are shown in Table 6.

[Reference Example] Evaluation was carried out in the same manner as in Examples 1 to 4 using an unprocessed test cloth. The results are shown in Table 5.

[0071]

[Table 5]

[0072]

[Table 6]

[0073]

The water-dispersed water / oil repellent composition of the present invention comprises:
The composition is excellent in both water and oil repellency and dry soil resistance. In addition, the cloth treated with the composition does not impair the texture and is excellent in water and oil repellency and durability.

Claims (7)

[Claims] 1. α, β containing a polyfluoroalkyl group
A polymer containing a polymer unit of an unsaturated monomer and a polymer containing a polymer unit of a fluoroolefin, and a polymer containing a polymer unit of an α, β-unsaturated monomer containing a polyfluoroalkyl group. A water-dispersible fluorine-based water / oil repellent composition comprising 10 to 60 parts by weight of a polymer containing polymerized units of fluoroolefin, relative to 100 parts by weight. 2. The aqueous dispersion according to claim 1, wherein the polymer containing a polymer unit of an α, β-unsaturated monomer having a polyfluoroalkyl group is a polymer containing a polymer unit of another polymerizable monomer. Fluorine-based water and oil repellent composition. 3. α, β containing a polyfluoroalkyl group
The polymer containing a polymerized unit of an unsaturated monomer is a polymer containing 40% by weight or more of a polymerized unit of an α, β-unsaturated monomer containing a polyfluoroalkyl group.
The water-dispersible fluorine-based water and oil repellent composition of. 4. α, β containing a polyfluoroalkyl group
A polymer containing polymer units of an unsaturated monomer is a polymer containing polymer units of acrylate and / or methacrylate containing a polyfluoroalkyl group.
The water-dispersible fluorine-based water and oil repellent composition according to any one of 3 above. 5. The water-dispersible fluorine-based water and oil repellent according to claim 1, wherein the polymer containing fluoroolefin polymer units is a polymer containing 20 to 80 mol% of fluoroolefin polymer units. Composition. 6. A polymer containing a fluoroolefin polymerized unit comprises a polymerized unit of a fluoroolefin and a polymerized unit of a polymerizable compound having a hydrophilic group or a polymerized unit of a polymerizable compound having a hydrophilic side chain. The water-dispersible fluorine-based water and oil repellent composition according to claim 1, which is a united body. 7. A polymer containing a polymerized unit of a fluoroolefin is a polymerized unit of a fluoroolefin, a polymerized unit of a polymerizable compound having a hydrophilic group or a polymerized unit of a polymerizable compound having a hydrophilic side chain, and other units. The water-dispersible fluorine-based water and oil repellent composition according to claim 1, which is a polymer containing polymerized units of a polymerizable monomer.