JP2000282015A - Water / oil repellent composition and method for producing the same - Google Patents

Abstract

(57) [Problem] To provide a water / oil repellent composition exhibiting durability against strong friction and heavy rain. A polymer particle containing two or more kinds of specific copolymers having different fluorine contents or one or more kinds of the copolymer and one or more other polymers in one particle, a surfactant, And aqueous media. The specific copolymer is a (meth) acrylate having a polyfluoroalkyl group and 100 mL of water.
A copolymer with a polymerizable monomer having a hydroxyl group and having a solubility of 10 g or less at 25 ° C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a water / oil repellent composition and a method for producing the same. The fiber or fiber product treated with the water / oil repellent composition of the present invention exhibits excellent water / oil repellency, excellent heavy rain durability and excellent friction durability.

[0002]

2. Description of the Related Art (Meth) having a polyfluoroalkyl group (hereinafter, a polyfluoroalkyl group is referred to as an ^Rf group).
The fibers are treated with a water- and oil-repellent agent containing, as an active ingredient, a copolymer containing polymerized units of acrylate and other polymerized units to facilitate water and oil repellency and to facilitate removal of dirt by washing or the like. (JP-A-53-134789 and JP-A-59-2).
04980, 62-7782).

[0003] Textile products treated with a water- and oil-repellent agent are widely used in everyday clothing, sports clothing, interior goods, outdoor goods, travel goods, and the like. Sufficient properties and durability (washing resistance, dry cleaning resistance, rub resistance) are required. In particular, sports clothing and outdoor equipment are required to have the above-mentioned durability against washing and heavy rain.

In order to enhance the durability, a melamine resin, a glyoxal resin,
Alternatively, a composition using a urea resin in combination has been proposed. Further, a water / oil repellent composition containing as an active ingredient polymer particles composed of a polymer having water repellency and a polymer having adhesive properties has been proposed (Japanese Patent Publication No. 7-53862, Japanese Patent Application Laid-Open No. 7-278442). ).

[0005]

In a conventional water / oil repellent composition, it is intended to improve durability by including a polymerized unit having a hydroxyl group in a polymer. Polymers containing polymerized units of monomers, N-
A conventional water / oil repellent composition using a polymer containing a polymerized unit such as methylol (meth) acrylamide has a problem that it does not exhibit sufficient durability when subjected to heavy rain or strong friction.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems. The present inventors have found that a water / oil repellent composition containing a polymer particle (A) containing a specific copolymer as an active ingredient can exhibit excellent downpour durability and friction resistance. .

That is, the present invention provides the following polymer particles (A), surfactant (B), and aqueous medium (C)
The present invention provides a water / oil repellent composition comprising: Polymer particles (A): two or more of the following copolymers (A ¹ ) having different fluorine contents or ^{one of the following} copolymers (A ¹ )
Polymer particles containing, in one particle, at least one kind and at least one kind of the following polymer (A ² ). Copolymer (A ¹ ): a polymerized unit of (meth) acrylate (a ¹ ) having a polyfluoroalkyl group and water 100
a copolymer having a solubility in mL of not more than 10 g at 25 ° C. and containing polymerized units of a polymerizable monomer (a ² ) having a hydroxyl group. Polymer (A ² ): A polymer other than copolymer (A ¹ ). Aqueous medium (C): a medium comprising only water or a medium comprising water and a water-soluble solvent.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the present specification, acrylate and methacrylate are collectively referred to as (meth) acrylate. The same applies to notations such as (meth) acrylamide. In this specification, a homopolymer, a copolymer, a graft polymer, and the like are collectively referred to as a “polymer”.

The R ^f group is a group in which two or more hydrogen atoms of an alkyl group have been substituted with fluorine atoms. The ^Rf group preferably has 2 to 20 carbon atoms, particularly preferably 6 to 16 carbon atoms. R
^{The f} group may have a linear structure or a branched structure,
A linear structure is particularly preferred. In the case of a branched structure, the branched portion exists at the terminal portion of the R ^f group, and has 1 to 1 carbon atoms.
It is preferably about 4 short chains.

The R ^f group may contain a halogen atom other than a fluorine atom. Other halogen atoms include
A chlorine atom is preferred. An etheric oxygen atom or a thioetheric sulfur atom may be inserted between carbon-carbon bonds in the R ^f group. The structure of the terminal portion of the R ^f group includes -CF ₂ CF ₃ , -CF (CF ₃ ) ₂ , -CF ₂
H, -CFH _2, -CF ₂ Cl and the like, -CF ₂ C
F ₃ is preferred.

[0011] The number of fluorine atoms in the R ^f groups, [(R ^f number of fluorine atoms in the group) / (R ^f number of hydrogen atoms contained in the alkyl group corresponding same carbon number and group)] × 100 When expressed in (%), it is preferably at least 60%, particularly preferably at least 80%. Further, the R ^f group is preferably a group in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms (that is, a perfluoroalkyl group), or a group having a perfluoroalkyl group at a terminal portion.

The carbon number of the perfluoroalkyl group is from 2 to
20 is preferable, and especially 4-16 is preferable. If the number of carbon atoms in the perfluoroalkyl group is small, the water repellency and oil repellency tend to decrease, and if the number of carbon atoms in the perfluoroalkyl group is large, it may be difficult to handle (meth) acrylate having an ^Rf group. .

Specific examples of the R ^f group include the following groups. _{C 4 F 9 - [F (} CF 2) 4 -, (CF 3) 2 CFC
F ₂ —, (CF ₃ ) ₃ C—, or CF ₃ CF ₂ (CF ₃ ) C
One] structural isomers groups such F-, C ₅ F ₁₁ - [e.g. _{F (CF 2) 5 -]} , C 6 F 13 - [ e.g. F (C
_{F 2) 6 -], C} 7 F 15 - [ e.g. _{F (CF 2) 7 -]} ,
C ₈ F ₁₇ - [e.g. _{F (CF 2) 8 -]} , C 9 F 19 - [ e.g. _{F (CF 2) 9 -]} , C 10 F 21 - [ e.g. F (C
_{F 2) 10 -], C} 12 F 2 5 - [ e.g. F (CF _{2)
12 -], C 14 F 29} - [ e.g. _{F (CF 2) 14 -]} , C
₁₆ F ₃₃ - [e.g. _{F (CF 2) 16 -]} , Cl (CF 2)
_t −, H (CF ₂ ) _t − (where t is an integer of 4 to 16), (CF ₃ ) ₂ CF (CF ₂ ) _k − (where k is 1 to
13 integers).

When the R ^f group is a group in which an etheric oxygen atom or a thioetheric sulfur atom is inserted between carbon-carbon bonds, the following groups may be mentioned. _{F (CF 2) 5 OCF (} CF 3) -, F [CF (C
_{F 3) CF 2 O] r} CF (CF 3) CF 2 CF 2 -, F [CF
(CF ₃ ) CF ₂ O] _r CF (CF ₃ ) —, F [CF (CF
_{3) CF 2 O] u CF} 2 CF 2 -, F (CF 2 CF 2 CF 2 O)
_{v CF 2 CF 2 -, F} (CF 2 CF 2 O) w CF 2 CF 2 -, F
_{(CF 2) 5 SCF (CF} 3) -, F [CF (CF 3) CF
_{2 S] r CF (CF 3} ) CF 2 CF 2 -, F [CF (CF 3)
CF ₂ S] _r CF (CF ₃ ) —, F [CF (CF ₃ ) CF _{2
S] u CF 2 CF 2 -} , F (CF 2 CF 2 CF 2 S) v CF 2 C
F _2- , F (CF ₂ CF ₂ S) _w CF ₂ CF _2- (r is 1 to 5
U is an integer of 2 to 6, v is an integer of 1 to 6, w is 1
-9) and the like.

The water and oil repellent composition of the present invention comprises polymer particles (A), a surfactant (B) and an aqueous medium (C) as essential components. The polymer particles (A) include two or more copolymers (A ¹ ) having different fluorine contents or ^{one of the} copolymers (A ¹ ).
Polymer particles containing at least one species and one or more polymers (A ² ) in one particle.

The copolymer (A ¹ ) is composed of a polymerized unit of (meth) acrylate (a ¹ ) having an R ^f group and 100 mL of water.
Is a copolymer having a solubility of 10 g or less at 25 ° C. and a polymerizable unit of a polymerizable monomer (a ² ) having a hydroxyl group. The polymer (A ² ) is a copolymer (A ¹ )
Other polymers. The (meth) acrylate (a ¹ ) having an R ^f group in the polymer particles (A) refers to a compound in which the R ^f group is present in an alcohol residue portion of the (meth) acrylate.

[0017] As has R ^f group (meth) acrylate (a ^1), a compound represented by the following formula a ¹¹ is preferred. However, R ^f and R ^f group in the formula a ^11, Q is a divalent organic radical, R represents a hydrogen atom or a methyl group. R ^f -Q-OCOCR = CH ₂ Formula a ¹¹ R ^f in the formula a ¹¹ is preferably an R ^f group containing no etheric oxygen atom or thioetheric sulfur atom, particularly preferably a perfluoroalkyl group, particularly preferably a straight-chain alkyl group. A perfluoroalkyl group having a chain structure is preferred. The linear perfluoroalkyl group is represented by-(CF ₂ ) _n F (where n is an integer of 2 to 20, preferably 4 to 16 and particularly preferably 6 to 12). Are preferred.

[0018] Q in the formula a ¹¹ is, - (CH _{2)
p + q -, - (CH} 2) p CONR a (CH 2) q -, - (CH
_{^{2) p OCONR a (CH 2}} ) q -, - (CH 2) p SO 2 NR
^a (CH ₂ ) _q -,-(CH ₂ ) _p NHCONH (CH ₂ ) _{q
-, - (CH 2) p} CH (OH) (CH 2) q -, - (CH
^{_{2) p CH (OCOR a)}} (CH 2) q - and the like are preferable. Here, Ra represents ^a hydrogen atom or an alkyl group. Also,
p and q each independently represent an integer of 0 or more;
It is an integer of 22.

Furthermore Q in the formula a ¹¹ is, - (CH _{2)
p + q -, - (CH} 2) p CONR a (CH 2) q -, or -
(CH ₂ ) _p SO ₂ NR ^a (CH ₂ ) _q- , q is an integer of 2 or more, and p + q is preferably 2 to 6, and p + q is preferably 2 to 6. − (CH ₂ ) _{p + q}
- (i.e., an ethylene group-hexamethylene group) compound when it is (equation a ¹¹⁾ is particularly preferred. Also, the expression a ¹¹
It is preferable that a fluorine atom is bonded to the carbon atom of R ^f bonded to Q in the above. (Meta) having R ^f group
Examples of the acrylate (a ¹ ) include the following compounds. However, R in the following compounds represents a hydrogen atom or a methyl group.

F (CF ₂ ) ₅ CH ₂ OCOCR = CH ₂ , F (CF ₂ ) ₆ CH ₂ CH ₂ OCOC
R = CH ₂ , H (CF ₂ ) ₆ CH ₂ OCOCR = CH ₂ , H (CF ₂ ) ₈ CH ₂ OCOCR = CH ₂ , H
(CF ₂ ) ₁₀ CH ₂ OCOCR = CH ₂ , H (CF ₂ ) ₈ CH ₂ CH ₂ OCOCR = CH ₂ , F (C
F ₂ ) ₈ CH ₂ CH ₂ CH ₂ OCOCR = CH ₂ , F (CF ₂ ) ₈ CH ₂ CH ₂ OCOCR = CH ₂ , F
(CF ₂ ) ₁₀ CH ₂ CH ₂ OCOCR = CH ₂ , F (CF ₂ ) ₁₂ CH ₂ CH ₂ OCOCR = CH ₂ , F
(CF ₂ ) ₁₄ CH ₂ CH ₂ OCOCR = CH ₂ , F (CF ₂ ) ₁₆ CH ₂ CH ₂ OCOCR = CH ₂ ,
(CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH ₂ OCOCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH
₂ OCOCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH ₂ OCOCR = CH ₂ , F (CF ₂ ) ₈
SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOCR = CH ₂ , F (CF ₂ ) ₈ (CH ₂ ) ₄ OCOCR = C
H ₂ , F (CF ₂ ) ₈ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOCR = CH ₂ , F (CF ₂ ) ₈ SO ₂ N (C
₂ H ₅ ) CH ₂ CH ₂ OCOCR = CH ₂ , F (CF ₂ ) ₈ CONHCH ₂ CH ₂ OCOCR = CH ₂ ,
(CF ₃ ) ₂ CF (CF ₂ ) ₅ (CH ₂ ) ₃ OCOCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ CH ₂ CH
(OCOCH ₃ ) OCOCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ CH ₂ CH (OH) CH ₂ OCOCR
= CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₇ CH ₂ CH (OH) CH ₂ OCOCR = CH ₂ , F (CF ₂ ) ₉
CH ₂ CH ₂ OCOCR = CH ₂ , F (CF ₂ ) ₉ CONHCH ₂ CH ₂ OCOCR = CH ₂ .

In the copolymer (A ¹ ) of the present invention,
One or more polymerized units of a (meth) acrylate having an R ^f group may be contained. When two or more (meth) acrylate polymerized units having an R ^f group are contained,
It is preferably a polymerized unit of a (meth) acrylate having an R ^f group having a different number of carbon atoms.

In the present invention, the copolymer (A)¹) Is R^fBase
(Meth) acrylate having (a) ¹) And polymerized units
The amount dissolved in 100 mL of water is 1 at 25 ° C.
0 g or less of polymerizable monomer having a hydroxyl group
(A^Two) Is essential. In addition, the following
Of the compound in 100 mL of water at 25 ° C
The amount is called solubility. Polymerizable monomer (a^Two) Has a solubility of
It is preferably from 0 to 5 g. The solubility is 0
"Does not substantially dissolve in water."

The polymerizable monomer (a ² ) having a solubility of 10 g or less is preferably selected from known or well-known polymerizable monomers. Further, the polymerizable monomer (a ² )
Is preferably a polymerizable monomer having one or two polymerizable unsaturated groups, and particularly preferably a polymerizable monomer having one polymerizable unsaturated group. The hydroxyl group in the polymerizable monomer (a ² ) is preferably a hydroxyl group bonded to a carbon atom.
The polymerizable monomer (a ² ) has a residue obtained by removing a hydroxyl group from two carboxyl groups of vinyl group, acryloyl group, methacryloyl group, or maleic acid, and is a hydroxyalkyl group or a hydroxy halogen group. Polymerizable compounds having an alkylated alkyl group are preferred.

[0024] As the polymerizable monomer in the present invention (a ²⁾ is a compound represented by the following formula a ^21, a compound represented by the following formula a ^22, and selected from the compounds represented by the following formula a ²³ A polymerizable monomer having a solubility of 10 g or less, or 3
-Chloro-2-hydroxypropyl (meth) acrylate is preferred.

[0025]

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However, the symbols in the formulas a ²¹ to a ²³ have the following meanings. ^{R 1, R 2, R 3} , R 4, R 5, R 6, R 7, R 8, R 9: each independently, a hydrogen atom or a methyl group. n: an integer of 2 to 6. m: an integer from 1 to 20. x, y, z: each independently an integer of 0 to 30. However,
x, y and z do not become 0 at the same time. a, b, c: each independently an integer of 0 to 30. However,
a, b, and c do not become 0 at the same time. p: an integer of 3 to 6.

[0027] In formula a ^21, m is preferably 2 to 10, n is preferably 3 to 5. A compound represented by the formula a ^21, solubility Specific examples of the compound is less than 10 g, the following compounds may be mentioned.

[0028]

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The oxyalkylene moieties in formula a ^22, means that it is linked to form blocks. In the formula a ²² is preferably one or both of x and z is 0. Also, x in the formula a ²² is preferably 0 to 10,
y is preferably 2 to 20, and z is preferably 0 to 10. Also, (x + y + z) is preferably 3 to 20. Among the compounds represented by the formula a ^22, solubility Specific examples of the compound is less than 10 g, the following compounds may be mentioned.

[0030]

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The oxyalkylene moieties in formula a ^23, means that it is linked to form blocks. In the formula a ^23, it is desirable that at least one of a or c is 0. Further, a is preferably 0 in formula a ^22, b is preferably from 2 to 20, c is preferably 0 to 10 is. Further, (a + b + c) is preferably 3 to 20. A compound represented by the formula a ^23, solubility 10g
Specific examples of the following compounds include the following compounds.

[0032]

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Further, as the polymerizable monomer (a ² ),
3-Chloro-2-hydroxypropyl (meth) acrylate or the following compounds are particularly preferred.

[0034]

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Furthermore, during the copolymer (A ^1), polymerized units and the polymerizable monomer of the polymerizable monomer (a ¹⁾ with (a ^2), the polymerizable monomer (a ¹⁾ and It may contain a polymerized unit of a polymerizable monomer (a ³ ) other than the polymerizable monomer (a ² ).

As the polymerizable monomer (a ³ ), ethylene, vinylidene chloride, vinyl chloride, vinylidene fluoride,
Vinyl acetate, styrene, α-methylstyrene, p-methylstyrene, glycidyl (meth) acrylate, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, diacetone (meth) acrylamide, methylolated diacetone (meth) acrylamide, N-methylol (meth) acrylamide (solubility is more than 10 g), vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, butadiene, isoprene, chloroprene, aziridinylethyl (meth) acrylate, benzyl (meth) acrylate, aziridinyl ( (Meth) acrylate, polyoxyethylene mono (meth) acrylate having a solubility of more than 10 g, methylpolyoxyalkylene (meth) acrylate, 2-ethylhexylpoly Kishiarukiren (meth)
Acrylate, polyoxyalkylene di (meth) acrylate, (meth) acrylate having polysiloxane, triallyl cyanurate, allyl glycidyl ether, allyl acetate, N-vinylcarbazole, maleimide, N-methylmaleimide, (2-dimethylamino) Ethyl (meth) acrylate, (meth) acrylate having an alkyl group having 8 to 20 carbon atoms, cycloalkyl (meth) acrylate, hydroxyethyl (meth) acrylate (solubility is more than 10 g), glycerol (meth) acrylate (solubility is 10 g Super) and the like.

Among these, as the polymerizable monomer (a ³ ), vinyl chloride and a (meth) acrylate having an alkyl group having 8 to 20 carbon atoms are preferable.
Stearyl (meth) acrylate, dioctyl maleate, or 2-ethylhexyl (meth) acrylate is preferred.

The copolymer (A)¹)) (A)¹)
Of the polymerized unit of the copolymer (A ¹5-95 quality inside)
% Of the polymerizable monomer (a^Two)% Of polymerized units
When the copolymer (A¹2) to 60% by mass is preferred.
And a polymerizable monomer (a^Three) Is included in the copolymer
Body (A¹)) Is preferably 0.1 to 50% by mass.

The polymer particles (A) in the present invention contain two or more polymers in one particle, and the polymers are two or more of copolymers (A ¹ ) having different fluorine contents, or ,
It comprises one or more copolymers (A ¹ ) and one or more polymers (A ² ). When the polymer particles (A) are composed of two or more copolymers (A ¹ ) having different fluorine contents, the difference between the fluorine contents is preferably at most 10 to 80, particularly preferably 20 to 50. Preferably it is. In addition, a fluorine content value means the value which represented the fluorine content in a polymer by mass%.

In the case where the polymer particles (A) are composed of at least one kind of the copolymer (A ¹ ) and at least one kind of the polymer (A ² ), the polymer (A ² ) It is a polymer other than A ¹ ). Polymer (A ²⁾ is a homopolymer of having ^the R ^f group (meth) acrylate (a ^1), having ^the R ^f group (meth)
Acrylate copolymer obtained by polymerizing two or more kinds of (a ^1), having ^the R ^f group (meth) acrylate at least one polymerizable monomer (a ¹⁾ with one or more (a ³⁾ Copolymer,
Alternatively, the polymer is preferably a polymer obtained by polymerizing at least one kind of the polymerizable monomer (a ³ ).

The polymer particles (A) in the present invention are polymer particles containing two or more kinds of polymers, and the polymer in the particles is obtained by simply blending two or more kinds of polymer particles. Unlike these, two or more polymers are micro-mixed and formed by, for example, a seed polymerization method or the like, and each polymer cannot be separated by a normal separation method. That is, the polymer particles (A) are different from the secondary particles formed by aggregation of two or more kinds of polymers. That is, in the polymer particles (A), the individual particles are not aggregated with other particles, and are formed as particles that exist alone, that is, as primary particle-like polymer particles.

The water / oil repellent composition of the present invention may contain particles formed by agglomeration of two or more polymers in addition to the polymer particles (A). In order for the water / oil repellent composition to exhibit sufficient performance, the ratio of the number of polymer particles (A) to the total number of polymer particles contained in the water / oil repellent composition must be 50% or more. It is preferably at least 70%, particularly preferably at least 70%.
It is preferably from 0 to 100%.

The polymer particles (A) and the polymer particles other than the polymer particles (A) formed by agglomeration of two or more kinds of polymers can be distinguished by observation with a dispersion type transmission electron microscope.
In addition, in an electron micrograph, since the polymer particles (A) may be adjacent to each other while being in contact with each other,
When the ratio of the number of the polymer particles (A) to the total number of the polymer particles is determined, it is preferable to determine the average value of the ratio in several photographs.

Further, the polymer particles (A) are polymer particles composed of two kinds of polymers (hereinafter also referred to as a first polymer and a second polymer), that is, the following copolymers having different fluorine contents. Two types of the polymer (A ¹ ) or the following copolymer (A ¹ )
And polymer (A ² ) in one particle. When the polymer particles (A) are particles composed of two kinds of polymers, the difference between the fluorine contents of the polymers is preferably from 10 to 80, particularly preferably 2 to 80.
It is preferably from 0 to 50.

The polymer particles (A) of the present invention, the copolymer (A ¹⁾ of the surface or inside of the particles, the polymer particles formed different copolymers of fluorine content of (A ¹⁾ by a polymerization reaction, on or inside of the particles of the copolymer (a ^1), the polymer particles to form a polymer (a ²⁾ by a polymerization reaction or polymer on the surface or inside of the particles of (a ^2),, co by the polymerization reaction It is preferable that the polymer particles form the polymer (A ¹ ).

The polymer particles (A) are preferably synthesized by a seed emulsion polymerization method. That is, in the present invention, a particulate first polymer is produced by an emulsion polymerization method in the presence of an aqueous medium and a surfactant, and then polymerized on the surface or inside of the first polymer particles. It is preferred to produce by forming a second polymer by reaction,
In particular, a particulate copolymer (A ¹ ) or polymer (A ² ) is produced, and then a copolymerization reaction is carried out on the surface or inside of the copolymer (A ¹ ) or polymer (A ² ) particles. It is preferred to produce it by forming the polymer (A ¹ ). The aqueous medium and the surfactant in the method may be the same as or different from the aqueous medium (C) and the surfactant (B) described below, and are preferably the same.

In the case where the polymer particles (A) are composed of two kinds of polymers, a core-shell type in which the first polymer and the second polymer are phase-separated in a layered form is preferable in terms of performance, The separation form may be a sea-island structure, a structure in which one polymer is localized, or a structure in which the polymers are entangled.

The water / oil repellent composition of the present invention contains a surfactant (B). As the surfactant (B), it is preferable that a nonionic surfactant and / or a cationic surfactant are essential. As the nonionic surfactant,
Nonionic surfactants selected from the following surfactants (b ¹ ) to (b ⁶ ) are preferred, and the following surfactant (b ⁷ ) is preferred as the cationic surfactant.

The surfactant (b ¹ ) is a nonionic surfactant comprising a polyoxyalkylene monoalkyl ether, a polyoxyalkylene monoalkenyl ether, or a polyoxyalkylene monoalkapolyenyl ether.

An alkyl group in the surfactant (b ¹ ),
The alkenyl group or alkapolyenyl group preferably has 4 to 26 carbon atoms. Further, the alkyl group, alkenyl group, or alkapolyenyl group may have a linear structure or a branched structure, respectively. In the case of a branched structure, a secondary alkyl group, a secondary alkenyl group, or a secondary alkapolyenyl group is preferred. Specific examples of the alkyl, alkenyl, or alkapolyenyl groups include octyl, dodecyl, tetradecyl, hexadecyl, octadecyl, behenyl (docosyl), and oleyl (9-octadecenyl). No.

The surfactant (b ¹ ) is preferably a polyoxyalkylene monoalkyl ether or a polyoxyalkylene monoalkenyl ether. The polyoxyalkylene portion of the surfactant (b ¹ ) is preferably composed of one or two oxyalkylene groups, and when composed of two types, it is preferred that their connection is a block. The polyoxyalkylene portion preferably comprises a portion in which two or more oxyethylene groups and / or oxypropylene groups are linked.

[0052] The surfactant (b ^1), a compound represented by the following formula b ¹¹ are preferred. However, R ¹⁰ in the following formula b ¹¹ represents an alkyl group having 8 or more carbon atoms or an alkenyl group having 8 or more carbon atoms, s represents an integer of 5 to 50, and g represents 0 to 2
Indicates an integer of 0. When g and s are 2 or more,
Is connected becomes blocky The oxyethylene group and oxypropylene group in the formula b ^11.

[0053]

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R ¹⁰ in the formula b ¹¹ may have either a straight-chain structure or a branched structure. s is preferably an integer of 10 to 30, and g is preferably an integer of 0 to 10. s is 4 or less,
Alternatively, if g is 21 or more, it becomes hardly soluble in water and does not dissolve uniformly in the aqueous medium (C), so that the effect of improving permeability may decrease. When s is 51 or more, hydrophilicity is increased, and there is a possibility that water repellency is reduced.

Specific examples of the compound (formula b ¹¹ ) include the following compounds. Where s and g are
Has the same meaning as described above, and the preferred embodiment is also the same. Further, the oxyethylene group and the oxypropylene group are connected in a block shape.

[0056]

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The surfactant (b ² ) has at least one carbon-carbon triple bond and at least one hydroxyl group in the molecule,
And a nonionic surfactant comprising a compound exhibiting surface activity.

The surfactant (b ² ) is preferably a nonionic surfactant comprising a compound having one carbon-carbon triple bond and one or two hydroxyl groups in the molecule. Further, the nonionic surfactant may have a polyoxyalkylene moiety as a partial structure. As the polyoxyalkylene portion, a polyoxyethylene portion, a polyoxypropylene portion, a portion in which oxyethylene groups and oxypropylene groups are connected in a random shape, or a portion in which polyoxyethylene and polyoxypropylene are connected in a block shape, Is mentioned. Surfactant (b
² ) As specific examples of the following formulas b ²¹ , b ²² and b ²³
Or a compound represented by the following formula b ²⁴ are preferred.

[0059]

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However, A ¹ , A ² and A ³ in the formulas b ²¹ to b ²⁴ each independently represent an alkylene group, m and n each represent an integer of 0 or more, and (m + n) represents 1 or more. Is an integer. k represents an integer of 1 or more. When m, n or k is 2 or more, A ¹ , A ² and A ³ may each consist of only one kind of alkylene group or may consist of two or more kinds of alkylene groups. .

R ^{11 to} R ¹⁶ each independently represent a hydrogen atom or an alkyl group. The alkyl group has 1 to 12 carbon atoms.
Is preferable, and an alkyl group having 6 to 12 carbon atoms is particularly preferable. Specific examples of these groups include a methyl group, an ethyl group, a propyl group, a butyl group and an isobutyl group. Further, the oxyalkylene portion preferably comprises an oxyethylene portion, an oxypropylene portion, or both an oxyethylene portion and an oxypropylene portion. The number of oxyalkylene groups of the surfactant (b ²⁾ in a preferred 1-50 is.

Further, as the surfactant (b ² ), a nonionic surfactant represented by the following formula b ²⁵ is preferable. However, x and y in formula b ²⁵ represents 0 or respective integers. The nonionic surfactant (formula b ²⁵ ) may be used alone or in combination of two or more.

[0063]

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The nonionic surfactant (formula b ²⁵ ) includes a nonionic surfactant in which the average of the sum of x and y is 10, and a nonionic surfactant in which x is 0 and y is 0 Or a nonionic surfactant in which the average of the sum of x and y is 1.3.

The surfactant (b ³ ) comprises a polyoxyethylene portion in which two or more oxyethylenes are continuously connected,
It is a nonionic surfactant comprising a compound in which two or more oxyalkylenes having 3 or more carbon atoms are continuously linked and both terminals are hydroxyl groups. The oxyalkylene having 3 or more carbon atoms in the surfactant (b ³ ) is preferably oxytetramethylene and / or oxypropylene.

[0066] As the surfactant (b ^3), a nonionic surfactant made of a compound represented by the following formula b ³¹ or the formula b ³² are preferred. Note the h in the formula b ³¹ and the formula b ³² 0
An integer of ~ 200, r is an integer of 2 ~ 100, t is 0 ~ 20
It represents an integer of 0. When h is 0, t is an integer of 2 or more. When t is 0, h is an integer of 2 or more. Further, -C ₃ H ₆ in the formula b ³¹ - moiety, -CH (CH ₃₎ C
Regardless of H ₂ — or —CH ₂ CH (CH ₃ ) —, —CH (CH ₃ ) CH ₂ — and —CH ₂ CH (CH ₃ ) —
And may be mixed. Further, each polyoxyalkylene moiety in the following formula is connected in a block shape.

[0067]

Embedded image

Further, as the surfactant (b ³ ), a nonionic surfactant comprising any of the following compounds is preferable.

[0069]

Embedded image

[0070] Surfactant (b ⁴⁾ is a nonionic surfactant having an amine oxide moiety in its molecule, a nonionic surfactant made of a compound represented by the following formula b ⁴¹ are preferred.

[0071]

Embedded image

R ¹⁷ , R ¹⁸ and R ¹⁹ in the formula b ⁴¹ are
Each independently represents a monovalent hydrocarbon group. Surfactants having an amine oxide moiety (N → O) in the molecule are sometimes classified as cationic surfactants, but are treated as nonionic surfactants in the present invention. The surfactant may be one kind or two or more kinds.

As the surfactant (b ⁴ ), particularly, the following formula b
^The nonionic surfactant represented by ⁴² is preferable because it improves the dispersion stability of the polymer particles (A). (R ²⁰ ) (CH ₃ ) ₂ N (→ O) Formula b ⁴² R ²⁰ in the formula b ⁴² represents an alkyl group having 6 to 22 carbon atoms, an alkenyl group having 6 to 22 carbon atoms, an alkyl group ( 6 to 2 carbon atoms
A phenyl group to which 2) is bonded or a phenyl group to which an alkenyl group (having 6 to 22 carbon atoms) is bonded;
An alkyl group having 22 or an alkenyl group having 8 to 22 carbon atoms is preferable.

Specific examples of the nonionic surfactant (formula b ⁴² ) include the following compounds. [H (CH ₂ ) ₁₂ ] (CH ₃ ) ₂ N (→ O), [H (C
H ₂ ) ₁₄ ] (CH ₃ ) ₂ N (→ O), [H (CH ₂ ) ₁₆ ]
(CH ₃ ) ₂ N (→ O), [H (CH ₂ ) ₁₈ ] (CH ₃ ) ₂
N (→ O).

The surfactant (b ⁵ ) is a condensate of polyoxyethylene mono (substituted phenyl) ether or a nonionic surfactant composed of polyoxyethylene mono (substituted phenyl) ether. As the substituted phenyl group in the surfactant (b ⁵ ), a phenyl group substituted with a monovalent hydrocarbon group is preferable, and a phenyl group substituted with an alkyl group, an alkenyl group or a styryl group is more preferable.

As the surfactant (b ⁵ ), a condensate of polyoxyethylene mono (alkylphenyl) ether,
A condensate of polyoxyethylene mono (alkenylphenyl) ether, polyoxyethylene mono (alkylphenyl) ether, polyoxyethylene mono (alkenylphenyl) ether, or polyoxyethylene mono [(alkyl) (styryl) phenyl] ether is preferable. .

Polyoxyethylene mono (substituted phenyl)
Specific examples of the condensate of ether or polyoxyethylene mono (substituted phenyl) ether include formaldehyde condensate of polyoxyethylene mono (nonylphenyl) ether and polyoxyethylene mono (nonylphenyl)
Ether, polyoxyethylene mono (octylphenyl) ether, polyoxyethylene mono (oleylphenyl) ether, polyoxyethylene mono [(nonyl)
(Styryl) phenyl] ether, polyoxyethylene mono [(oleyl) (styryl) phenyl] ether and the like.

The surfactant (b ⁶ ) is a nonionic surfactant comprising a fatty acid ester of a polyol. Examples of the polyol in the surfactant (b ⁶ ) include polyethylene glycol, decaglycerin, and ethers of polyethylene glycol and a polyol (other than polyethylene glycol).

As the surfactant (b ⁶ ), 1: 1 (molar ratio) ester of octadecanoic acid and polyethylene glycol, 1: 4 (molar ratio) ester of ether of sorbitol and polyethylene glycol and oleic acid A 1: 1 (molar ratio) ester of polyoxyethylene glycol and sorbitan with octadecanoic acid, a 1: 1 (molar ratio) ester of polyethylene glycol and sorbitan with oleic acid, and dodecanoic acid 1: 1 (molar ratio) ester with sorbitan, (1 or 2): 1 (molar ratio) ester of oleic acid and decaglycerin, (1 or 2): 1 (molar ratio) of octadecanoic acid and decaglycerin Esters are mentioned.

[0080] As the surfactant (b ^7), cationic surfactant represented by the following formula b ⁷¹ are preferred.

[0081]

Embedded image

Where the formula b⁷¹The symbols in the table indicate the following
You. R^{twenty two}, R^{twenty three}, R^{twenty four}, R^{twenty five}: Even if they are the same
May be different, a hydrogen atom, an alkyl having 1 to 22 carbon atoms.
A kill group, an alkenyl group having 1 to 22 carbon atoms, or a terminal
A polyoxyalkylene group which is a hydroxyl group; Where R^{twenty two},
R^{twenty three}, R^{twenty four}And R ^{twenty five}Do not become hydrogen atoms at the same time. [X^Ten]^-: 1-valent anion.

[0083] formula R ²² in ^{b 71, R 23, R 24} , R 25 are each, when it is alkyl group having 1 to 22 carbon atoms, (preferably 6 to 22 carbon atoms) long chain alkyl groups Required It is preferred that When there is an alkyl group other than the long-chain alkyl group, a methyl group or an ethyl group is preferable.

[0084] formula R ²² in ^{b 71, R 23, R 24} , R 25 are, in each case an alkenyl group having 1 to 22 carbon atoms,
A long chain (preferably having 6 to 22 carbon atoms) alkenyl group is preferred. R ^22, R ²³ in the formula b ^71, R ^24, R ²⁵ is, if the terminal is respectively a polyoxyalkylene group is a hydroxyl group, a polyoxyethylene group. [X ¹⁰ ] ^-is 1
It is a valent anion, and is preferably a chloride ion, an ethyl sulfate ion or an acetate ion.

[0085] As the cationic surfactant of the formula b ⁷¹ is (tetra -N-substituted) ammonium salts, (mono -
N-substituted or di-N-substituted) oxyethylene ammonium salts are preferred, for example, mono (long chain alkyl) amine hydrochloride, mono (long chain alkyl) dimethylamine hydrochloride, mono (long chain alkyl) dimethylamine acetate, mono ( Long-chain alkenyl) dimethylamine hydrochloride, mono (long-chain alkyl) dimethylamine-ethyl sulfate, mono (long-chain alkyl) trimethylammonium chloride, di (long-chain alkyl) monomethylamine hydrochloride, di (long-chain alkyl) dimethyl Examples thereof include ammonium chloride, mono (long-chain alkyl) amine hydrochloride, mono (long-chain alkyl) monomethyldi (polyoxyethylene) ammonium chloride, and mono (long-chain alkyl) monomethylmono (polyoxyethylene) ammonium chloride.

[0086] Further, specific examples of the cationic surfactant of the formula b ^71, monostearyl trimethyl ammonium chloride, monostearyl dimethyl monoethyl ammonium ethyl sulfate, mono (long chain alkyl) monomethyl (Monopoli oxyethylene ) Ammonium chloride, di (tallow alkyl) dimethylammonium chloride, dimethylcoconutamine acetate and the like.

The surfactant (B) in the water / oil repellent composition of the present invention is preferably only the surfactants (b ¹ ) to (b ⁷ ). Further, as the surfactant (B), surfactants (b ¹ ), (b ² ), (b ³ ), (b ⁴ ),
(B ⁶ ) or (b ⁷ ) is preferred. When a surfactant other than the surfactants (b ¹ ) to (b ⁷ ) is used,
It is preferable to select a surfactant having a structure that does not contain an aromatic group in its structure.

Surfactants other than the surfactants (b ¹ ) to (b ⁷ ) include alkyl sulfonic acids and salts thereof, alkyl carboxylic acids and salts thereof, and sodium (polyoxyethylene having a terminal alkoxy) sodium sulfonate. And the like, and an amphoteric surfactant such as a betaine type, a choline type, an ethanolamine type, or a phosphate type. The amount of the surfactant (B) is determined based on the amount of the polymer particles (A)
Is preferably 20% by mass or less, more preferably 3 to 10% by mass.

The water / oil repellent of the present invention contains an aqueous medium (C). The aqueous medium is a medium composed of only water or water and a water-soluble solvent. When the aqueous medium is a medium comprising water and a water-soluble solvent, the amount of the water-soluble solvent is 2 to 30 with respect to water.
0 mass% is preferable, and especially 5 to 120 mass% is preferable.

The water-soluble solvent is preferably a glycol-based solvent or a glycol ether-based solvent. Ethylene glycol, diethylene glycol, triethylene glycol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether , Diethylene glycol dibutyl ether, propylene glycol, dipropylene glycol, tripropylene glycol, propylene glycol monomethyl ether, propylene glycol dimethyl ether, dipropylene glycol monomethyl ether, propylene glycol dimethyl ether, and the like are preferable, particularly from the viewpoint of water and oil repellency. Propylene glycol monomethyl ether or tripropylene glycol.

The aqueous medium (C) is (1) water only, (2)
When the solvent is water and a glycol-based solvent, or (3) water and a glycol ether-based solvent, the dispersibility of the polymer particles (A) in the water- and oil-repellent composition is improved, and the performance such as water repellency is improved. There is an advantage of improving.

The water / oil repellent composition of the present invention contains
Components other than the above (hereinafter, referred to as other components) may be included. Other components include a blocked product of a polyisocyanate compound or a modified product thereof, or a melamine resin. As the polyisocyanate compound, isophorone diisocyanate, hexamethylene diisocyanate and the like are preferable, and as the modified product, a burette modified product of a polyisocyanate compound, an isocyanurate modified product of a polyisocyanate compound, a carbodiimide modified product of a polyisocyanate compound, and the like are preferable. The melamine resin can be selected from various melamines from trimethylol melamine to hexamethylol melamine.

Further, as other components, other water / oil repellents,
Insect repellents, flame retardants, antistatic agents, dyes, stabilizers, anti-wrinkle agents and the like may be used. These components can be appropriately changed according to the processing purpose of the water / oil repellent and the object to be processed.

The concentration of the polymer particles (A) in the water / oil repellent composition of the present invention is 2 to 60% by mass in the water / oil repellent composition.
Is preferable, and it is particularly preferable to be 5 to 50% by mass. In the treatment, the composition may be diluted. When diluting, it is preferable to dilute with water, and it is preferable that the concentration of the polymer particles (A) in the water / oil repellent composition at the time of dilution is 0.2 to 16% by mass.

The water / oil repellent composition of the present invention is preferably used for treating fibers or textile products. As the treatment method, any method can be adopted depending on the type of the object to be treated, the preparation form of the composition, and the like. For example, a method in which the fiber is adhered to the surface of a fiber or a fiber product and dried by a coating method such as dip coating is employed. If necessary, the composition may be applied together with a suitable crosslinking agent to perform curing.

The water and oil repellent composition of the present invention imparts excellent downpour resistance and friction durability to the fiber or textile product to be treated. The fibers treated with the water / oil repellent composition of the present invention include animal and plant natural fibers such as cotton, hemp, wool, and silk, and synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene. , Rayon, and semi-synthetic fibers such as acetate. In addition, as a fiber product treated with the water / oil repellent composition of the present invention, one or two types of the fiber may be used.
Fiber products and the like obtained using more than one kind are included.

[0097]

EXAMPLES [Treatment method] A nylon cloth was immersed in a latex treatment liquid described later, and the cloth was squeezed between two rubber rollers to obtain a wet pickup of 80%. Next 11
After drying at 0 ° C. for 90 seconds, a heat treatment was further performed at 170 ° C. for 60 seconds to obtain a test cloth. The test cloth was subjected to a water / oil repellency test, a washing durability test, a heavy rain durability test, and a friction durability test. + (-) Attached to a number showing water repellency or oil repellency indicates that the performance is slightly better (bad) than the performance indicated by that number.

[Evaluation of Water Repellency] A spray test according to JIS-L1092 was conducted, and the water repellency numbers shown in Table 1 were used.

[0099]

[Table 1]

[Evaluation of oil repellency] AATCC-TM118
The results are shown in Table 2.

[0101]

[Table 2]

[Washing Durability Test Method] An automatic reversing spiral electric washing machine (manufactured by Toshiba Corporation; same performance as VH-1150) was used for 45 tests.
× 45cm test cloth (fabric after processing) 800g and 40
0.2% by mass weak alkaline detergent at ± 2 ° C (JIS-
K3371 Weakly alkaline.
Washed for 25 minutes under strong conditions. Then use a centrifugal dehydrator for about 30
After dehydration for 2 seconds, rinsing was performed for 10 minutes while overflowing normal temperature water. Thereafter, the sample was again dehydrated for about 30 seconds, rinsed under the same conditions for 10 minutes, and then dehydrated for about 30 seconds. By performing the above operation five times, one set is obtained,
The test was repeated 20 times, and the test cloth was washed 20 times. This test cloth was evaluated.

[Heavy rain durability test method] JIS-L1092
According to the method described in the method (C), the rainfall conditions were a rainfall amount of 200 cc / min, a rainfall temperature of 20 ° C. and a rainfall time of 20 minutes, and the water repellency of the surface was determined by the water repellency number shown in Table 1. Hereinafter, it is also called a Bundesmann test method.

[Friction Durability Test Method] A test cloth was rubbed with a pilling tester equipped with a wet cotton cloth for 5 minutes at a pressing pressure of 750 g. Next, evaluation was made by the Bundesmann test method.

[Production Example 1: Synthesis Example of First Polymer] Perfluoroalkylethyl acrylate [C _m F _{2m + 1} CH ₂
CH ₂ OCOCH ＝ CH ₂ : m is 6, 8, 10, 12, 1
The average is 9 for a mixture of 4, 16] (hereinafter referred to as FA) 2,720 g, n-dodecyl mercaptan 50.
g, 140 g of a polyoxyalkylene secondary alkyl ether as a nonionic surfactant, 14 g of an alkyldimethylamine acetate, 280 g of dipropylene glycol monomethyl ether, and 4200 g of water were pre-dispersed with a homogenizer, followed by a high-pressure homogenizer (emulsion manufactured by Menton Goulin Co., Ltd.). It was treated with 400 kg / cm ² using a machine) to give an emulsion. 7000 g of the emulsion was placed in a 10 L autoclave, and 36 g of azobisisobutyronitrile was added.
It was replaced with nitrogen. After the temperature was raised to 60 ° C., polymerization was performed for 8 hours to obtain a dispersion of the first polymer having a solid content of 38.8%.

The abbreviations used in the following are:
The following compounds are meant. CeA: cetyl acrylate, CHPMA: 3-chloro-2-hydroxypropyl methacrylate (solubility: 3 g), PCEA: CH ₂ ＣC (CH ₃ ) COOCH ₂ CH ₂ O ｛C
O (CH ₂ ) ₅ O｝ ₁₀ H (solubility is 1 g or less), PPGMA: CH ₂ ＣC (CH ₃ ) COO ｛CH ₂ CH
(CH ₃ ) O｝ ₉ H (solubility is 1 g or less), CHMA: cyclohexyl methacrylate, GMA: glycidyl methacrylate, PEGMA: CH ₂ ＣC (CH ₃ ) COO (CH ₂ CH)
₂ O) ₂₃ H (solubility> 10 g), HEA: hydroxyethyl acrylate (solubility: 10 g)
g).

[Production Examples 2 to 7] A dispersion of a first polymer was obtained in the same manner as in Production Example 1, except that 100 parts by mass of the monomers having the compositions shown in Table 3 were used.

[0108]

[Table 3]

Example 1 A dispersion of the first polymer 5 prepared in Production Example 1 was placed in a 10 L stainless steel autoclave.
000 g (solids concentration 38.8%), FA 350 g, C
175 g of HMA and 58 g of PCEA were charged. Further, dipropylene glycol monomethyl ether 250
g and 360 g of water were added to make the total solid content 40% by mass. After stirring the mixture, 2,2′-azobis [2-
(2-imidazolin-2-yl) propane], and the mixture was purged with nitrogen, reacted at 60 ° C. for 15 hours, and cooled to obtain a dispersion. The solid concentration in the dispersion is 37.8
%Met.

The dispersion was observed with a transmission electron microscope (magnification:
(1 × 10 ⁵ times), and a photographic image of characteristic fine particles in which the two polymers were composited was obtained. In addition, a photographic image of the different fine particles aggregated was obtained. The number of characteristic fine particles in which the two polymers were composited was counted in 10 photographic images, and the average was calculated with respect to the total number of particles. The result was 85%.

Furthermore, the solid content concentration of the obtained dispersion was adjusted to 2
It was diluted with ion-exchanged water so as to be 0% to obtain a latex stock solution. Melamine resin (Sumitec Resin M-3, manufactured by Sumitomo Chemical Co., Ltd.) was added to 10 parts by mass of the latex stock solution.
3 parts by mass, catalyst (Sumitex accelerator ACX,
Latex treatment liquid 1 was obtained by adding 0.3 parts by mass of Sumitomo Chemical Co., Ltd.) and 89.4 parts by mass of water. Test cloths treated with the latex treatment liquid 1 were prepared and subjected to various evaluation tests. Table 6 shows the results.

Example 2 In addition to the melamine resin and catalyst of Example 1, a blocked isocyanate compound (isocyanurate-modified isophorone diisocyanate) was added.
A latex treatment liquid 2 was obtained in the same manner as in Example 1 except that 3 parts by mass was added and the amount of water was 89.1 parts by mass. A test cloth treated with the latex treatment liquid 2 was prepared and subjected to various evaluation tests. Table 6 shows the results.

Examples 3 to 10 Dispersions were prepared in the same manner as in Example 1 except that the polymers shown in Table 4 were used as the first polymers and the polymerizable monomers shown in Table 4 were charged. I got When each dispersion was observed with a transmission electron microscope in the same manner as in Example 1, a photographic image of characteristic fine particles in which two polymers were composited was obtained in all the dispersions, and the ratio of the fine particles was 80%. % Or more. Next, latex treatment liquids 3 to 10 were obtained in the same manner as in Example 1. Evaluation was performed using the latex processing liquids 3 to 10. Table 6 shows the results.

[0114]

[Table 4]

[Examples 11 to 13] Comparative latex test liquids 11 to 13 were obtained in the same manner as in Example 1 using the first polymer and the polymerizable monomer shown in Table 5. Test cloths treated with the comparative latex test liquids 11 to 13 were prepared and evaluated. Table 6 shows the results.

[Example 14] The dispersion obtained in Production Example 1 was combined with the dispersion obtained in Production Example 7 so that the solid content contained in the dispersion obtained in Production Example 1 was 15. 4% by mass,
What was diluted with ion-exchanged water so that the solid content concentration contained in the dispersion liquid obtained in Production Example 7 was 4.6% by mass was used as the comparative latex stock solution 14. A test cloth treated with the comparative latex test liquid 14 was prepared and evaluated. Table 6 shows the results.

[0117]

[Table 5]

[0118]

[Table 6]

[0119]

The water / oil repellent composition of the present invention comprises polymer particles containing a specific copolymer (A ¹ ) as essential components, so that the fibers and fiber products treated with the composition can be used. ,
Provides excellent water and oil repellency. The fiber or fiber product according to the present invention continuously exhibits excellent water and oil repellency even when subjected to strong friction even after washing. Therefore, the textile product treated with the composition of the present invention can exhibit sufficiently excellent heavy rain durability and friction durability even in sportswear and the like.

Continued on the front page (72) Inventor Toyotsu Shimada 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture Inside Asahi Glass Co., Ltd.

Claims (11)

[Claims] 1. A water / oil repellent composition comprising the following polymer particles (A), a surfactant (B), and the following aqueous medium (C). Polymer particles (A): two or more of the following copolymers (A ¹ ) having different fluorine contents or ^{one of the following} copolymers (A ¹ )
Polymer particles containing, in one particle, at least one kind and at least one kind of the following polymer (A ² ). Copolymer (A ¹ ): a polymerized unit of (meth) acrylate (a ¹ ) having a polyfluoroalkyl group and water 100
a copolymer having a solubility in mL of not more than 10 g at 25 ° C. and containing polymerized units of a polymerizable monomer (a ² ) having a hydroxyl group. Polymer (A ² ): A polymer other than copolymer (A ¹ ). Aqueous medium (C): a medium comprising only water or a medium comprising water and a water-soluble solvent. 2. The water / oil repellent composition according to claim 1, wherein the ratio of the polymer particles (A) to the total number of polymer particles contained in the water / oil repellent composition is 50% or more. 3. The polymer particles (A) are two kinds of copolymers (A ¹ ) having different fluorine contents or ^{one of the} copolymers (A ¹ ).
The water / oil repellent composition according to claim 1 or 2, which is a polymer particle containing a seed and one kind of the polymer (A ² ) in one particle. 4. The polymer particles (A), wherein the polymer particles (A ¹ ) having different fluorine contents are formed on the surface or inside of the particles of the copolymer (A ¹ ) by a polymerization reaction. on or inside of the particles of the polymer (a ^1), the polymer particles to form a polymer (a ²⁾ by a polymerization reaction or polymer on the surface or inside of the particles of (a ^2),, copolycondensation by the polymerization reaction A polymer particle having formed a united body (A ¹ ),
4. The water / oil repellent composition according to 2 or 3. 5. The polymerizable monomer (a ^2), a compound represented by the following formula a ^21, a compound represented by the following formula a ^22, and the formula a
5. A polymerizable monomer selected from the compounds represented by formula ( ²³⁾ and having a solubility in 100 mL of water of 10 g or less at 25 ° C., or 3-chloro-2-hydroxypropyl (meth) acrylate. The water / oil repellent composition according to any one of the above. Embedded image However, the symbols in the formula a ²¹ ~ formula a ²³ have the following meanings. ^{R 1, R 2, R 3} , R 4, R 5, R 6, R 7, R 8, R 9: each independently, a hydrogen atom or a methyl group. n: an integer of 2 to 6. m: an integer from 1 to 20. x, y, and z: each independently an integer of 0 to 30. However, x, y, and z do not become 0 at the same time. a, b and c: each independently an integer of 0 to 30. However, a, b, and c do not become 0 at the same time. p: an integer of 3 to 6. 6. The water / oil repellent composition according to claim 1, wherein the surfactant (B) essentially comprises a nonionic surfactant and / or a cationic surfactant. 7. A surfactant (B) comprising the following surfactant (b)
¹)-(B⁷) Is one or more surfactants selected from
The water / oil repellent composition according to claim 1. Surfactant (b¹): Polyoxyalkylene monoalkyl
Ether, polyoxyalkylene monoalkenyl ether
Ter or polyoxyalkylene monoalkalipolyene
Nonionic surfactant composed of ruether. Surfactant (b^Two): One or more carbon-carbon atoms in the molecule
It has a heavy bond and one or more hydroxyl groups, and has a surface activity
A nonionic surfactant comprising the compound shown below. Surfactant (b^Three): Two or more oxyethylenes are continuous
And a polyoxyethylene moiety connected with
Polyoxy in which two or more oxyalkylenes are continuously connected
Linked to a silalkylene moiety, and both ends are hydroxyl groups
A nonionic surfactant comprising a certain compound. Surfactant (b^Four): Amine oxide moiety in the molecule
Nonionic surfactant. Surfactant (b^Five): Polyoxyethylene mono (substituted
Condensate of phenyl) ether or polyoxyethylene
Nonionic surfactant consisting of no (substituted phenyl) ether
Sex agent. Surfactant (b⁶): From fatty acid ester of polyol
Nonionic surfactant. Surfactant (b⁷): The following formula b⁷¹Cationic interface consisting of
Activator. Embedded imageWhere b⁷¹The symbols in the table have the following meanings. R^{twenty two}, R
^{twenty three}, R^{twenty four}, R^{twenty five}: Different even if they are the same
A hydrogen atom, an alkyl group having 1 to 22 carbon atoms,
The alkenyl group of numbers 1 to 22, or the terminal is a hydroxyl group
Polyoxyalkylene group. Where R^{twenty two}, R^{twenty three}, R^{twenty four}You
And R ^{twenty five}Do not become hydrogen atoms at the same time. [X^Ten]^-: 1-valent anion. 8. An aqueous medium (C) comprising: (1) water only;
The water / oil repellent composition according to any one of claims 1 to 7, which is water and a glycol solvent, or (3) water and a glycol ether solvent. 9. The water / oil repellent composition according to claim 1, which is for treating fibers. 10. A fiber or fiber product treated with the water / oil repellent composition according to claim 1. 11. In the presence of an aqueous medium and a surfactant,
A particulate copolymer (A ¹ ) or polymer (A ² ) is produced by an emulsion polymerization method, and then polymerized on the surface or inside of the copolymer (A ¹ ) or polymer (A ² ) particles. method for producing a water and oil repellent composition according to claim 3, characterized in that to form a copolymer (a ¹⁾ by the reaction.