JP7205375B2 - Water and oil repellent composition, method for producing the same, and article - Google Patents

Description

TECHNICAL FIELD The present invention relates to a water and oil repellent composition, a method for producing the same, and an article.

As a method for imparting water and oil repellency to the surface of an article (textiles, etc.), a water and oil repellent composition in which a copolymer having units based on a monomer having a polyfluoroalkyl group is dispersed in a liquid medium. It is known to treat articles using

The following water and oil repellent composition has been proposed as a water and oil repellent composition for obtaining articles having good water repellency, oil repellency, durability against heavy rain and good texture.
a structural unit based on the monomer (a) below, a structural unit based on the monomer (b) below, a structural unit based on the monomer (c) below and a structural unit based on the monomer (d) below A water and oil repellent composition containing a polymer and a liquid medium (Patent Document 1).
Monomer (a): (meth)acrylate having a perfluoroalkyl group having 1 to 6 carbon atoms, and the like.
Monomer (b): (meth)acrylate having no polyfluoroalkyl group and having an alkyl group having 12 or more carbon atoms.
Monomer (c): A monomer having a poly(oxyfluoroalkylene) chain in which the ratio of the number of fluorine atoms to the total number of fluorine atoms and hydrogen atoms is 70% or more.
Monomer (d): halogenated olefin.

WO2016/098823

Articles (water and oil repellent articles) treated with a water and oil repellent composition retain their water repellency even when the water and oil repellent articles continue to rub against each other or between the water and oil repellent articles and other articles. (friction durability) is required. However, the articles treated with the water and oil repellent composition described in Patent Document 1 sometimes have insufficient friction durability.

The present invention provides a water and oil repellent composition from which an article having excellent water repellent friction durability can be obtained, a method for producing the same, and an article having excellent water repellent friction durability.

The present invention is as follows.
<1> A copolymer containing a unit based on the following monomer b, a unit based on the following monomer c, and a unit based on the following monomer d, and a liquid medium,
A water and oil repellent composition, wherein the ratio of units based on the following monomer a to units based on all monomers constituting the copolymer is 1% by mass or less.
Monomer b: (meth)acrylate having no polyfluoroalkyl group and having an alkyl group having 12 or more carbon atoms.
Monomer c: A monomer having a poly(oxypolyfluoroalkylene) chain in which the ratio of the number of fluorine atoms to the total number of fluorine atoms and hydrogen atoms is 70% or more.
Monomer d: halogenated olefin.
Monomer a: A compound represented by Formula 1 below.
(ZL) _n X Formula 1.
However, Z is a perfluoroalkyl group having 1 to 6 carbon atoms or a group represented by the following formula 2, L is a divalent organic group or a single bond having no fluorine atom, n is 1 or 2, and X is any of the groups represented by the following formulas 3-1 to 3-5 when n is 1, and when n is 2, the following formulas 4-1 to Any of the groups represented by formula 4-4.
C _s F _2s+1 CH ₂ CF ₂ −(CH ₂ CF ₂ ) _t (CF ₂ CF ₂ ) _u − Formula 2.
However, s is an integer of 1-6, t is an integer of 0-3, and u is an integer of 1-3.
-CR= _CH2 Formula 3-1,
-C(O)OCR= _CH2 formula 3-2,
-OC(O)CR= _CH2 formula 3-3,
-OCH ₂ -φ-CR=CH ₂ formula 3-4,
-OCH=CH ₂ Formula 3-5.
However, R is a hydrogen atom, a methyl group or a halogen atom, and φ is a phenylene group.
-CH[-(CH ₂ ) _m CR=CH ₂ ]- formula 4-1,
—CH[—(CH ₂ ) _m C(O)OCR=CH ₂ ]— Formula 4-2,
—CH[—(CH ₂ ) _m OC(O)CR=CH ₂ ]— Formula 4-3,
-OC(O)CH=CHC(O)O- Formula 4-4.
However, R is a hydrogen atom, a methyl group or a halogen atom, and m is an integer of 0-4.
<2> the ratio of the units based on the monomer b to the units based on all the monomers constituting the copolymer is 30 to 80% by mass;
The ratio of units based on the monomer c to units based on all the monomers constituting the copolymer is 10 to 40% by mass,
The water and oil repellent composition according to <1> above, wherein the ratio of the constituent units based on the monomer d to the units based on all the monomers constituting the copolymer is 10 to 30% by mass.
<3> The water and oil repellent composition of <1> or <2>, wherein the monomer b is a (meth)acrylate having an alkyl group having 14 to 30 carbon atoms.
<4> The water and oil repellent composition according to any one of <1> to <3>, wherein the monomer b is a (meth)acrylate having an alkyl group having 16 to 24 carbon atoms.
<5> Any one of <1> to <4>, wherein the ratio of units based on the following monomer e to units based on all monomers constituting the copolymer is 10% by mass or less A water and oil repellent composition.
Monomer e: a monomer having a crosslinkable functional group.
<6> The repellent according to any one of <1> to <5>, further comprising a surfactant, wherein the liquid medium is an aqueous liquid medium, and the copolymer is emulsified in the aqueous liquid medium. Water and oil repellent composition.

<7> In the presence of a surfactant and a polymerization initiator, in a liquid medium, a monomer component containing the following monomer b, the following monomer c, and the following monomer d is polymerized and copolymerized. A method for producing a water and oil repellent composition to be combined,
A method for producing a water and oil repellent composition, wherein the ratio of the following monomer a to the entire monomer component is 1% by mass or less.
Monomer b: (meth)acrylate having no polyfluoroalkyl group and having an alkyl group having 12 or more carbon atoms.
Monomer c: A monomer having a poly(oxypolyfluoroalkylene) chain in which the ratio of the number of fluorine atoms to the total number of fluorine atoms and hydrogen atoms is 70% or more.
Monomer d: halogenated olefin.
Monomer a: A compound represented by Formula 1 below.
(ZL) _n X Formula 1.
However, Z is a perfluoroalkyl group having 1 to 6 carbon atoms or a group represented by the following formula 2, L is a divalent organic group or a single bond having no fluorine atom, n is 1 or 2, and X is any of the groups represented by the following formulas 3-1 to 3-5 when n is 1, and when n is 2, the following formulas 4-1 to Any of the groups represented by formula 4-4.
C _s F _2s+1 CH ₂ CF ₂ −(CH ₂ CF ₂ ) _t (CF ₂ CF ₂ ) _u − Formula 2.
However, s is an integer of 1-6, t is an integer of 0-3, and u is an integer of 1-3.
-CR= _CH2 Formula 3-1,
-C(O)OCR= _CH2 formula 3-2,
-OC(O)CR= _CH2 formula 3-3,
-OCH ₂ -φ-CR=CH ₂ formula 3-4,
-OCH=CH ₂ Formula 3-5.
However, R is a hydrogen atom, a methyl group or a halogen atom, and φ is a phenylene group.
-CH[-(CH ₂ ) _m CR=CH ₂ ]- formula 4-1,
—CH[—(CH ₂ ) _m C(O)OCR=CH ₂ ]— Formula 4-2,
—CH[—(CH ₂ ) _m OC(O)CR=CH ₂ ]— Formula 4-3,
-OC(O)CH=CHC(O)O- Formula 4-4.
However, R is a hydrogen atom, a methyl group or a halogen atom, and m is an integer of 0-4.
<8> The ratio of the monomer b to the total monomer component is 30 to 80% by mass,
The ratio of the monomer c to the total monomer component is 10 to 40% by mass,
The method for producing a water and oil repellent composition according to <7>, wherein the proportion of the monomer d to the total monomer components is 10 to 30% by mass.
<9> The method for producing a water and oil repellent composition according to <7> or <8>, wherein the proportion of the following monomer e with respect to the total monomer components is 10% by mass or less.
Monomer e: a monomer having a crosslinkable functional group.

<10> An article treated with the water and oil repellent composition according to any one of <1> to <6>.
<11> The article according to <10>, which is a textile product.

According to the water and oil repellent composition of the present invention, an article having excellent water repellent friction durability can be obtained.
According to the method for producing a water and oil repellent composition of the present invention, it is possible to produce a water and oil repellent composition that gives an article having excellent water repellent friction durability.
The article of the present invention is excellent in water-repellent friction durability.

In this specification, the compound represented by formula 1 is referred to as compound 1. Compounds represented by other formulas are similarly described.
In this specification, the group represented by formula 2 is referred to as group 2. Groups represented by other formulas are similarly described.
The following term definitions apply throughout the specification and claims.
"(Meth)acrylate" is a generic term for acrylate and methacrylate.
A "polyfluoroalkyl group" means a group in which some or all of the hydrogen atoms in an alkyl group have been substituted with fluorine atoms. Hereinafter, the “polyfluoroalkyl group” is also referred to as “R ^f group”.
A "perfluoroalkyl group" means a group in which all hydrogen atoms of an alkyl group have been substituted with fluorine atoms. Hereinafter, the " ^{perfluoroalkyl} group" is also referred to as "RF group".
An "oxypolyfluoroalkylene group" means a group in which some or all of the hydrogen atoms in an oxyalkylene group have been substituted with fluorine atoms.
"Oxyperfluoroalkylene group" means a group in which all hydrogen atoms of an oxyalkylene group are substituted with fluorine atoms.
The "number average molecular weight" and "mass average molecular weight" of the copolymer are values obtained in terms of polystyrene by gel permeation chromatography (GPC).
The "number average molecular weight" of the poly(oxypolyfluoroalkylene) chain of the monomer c is a value obtained by calculating the number of each oxypolyfluoroalkylene unit based on CF ₂ CH ₂ OH by ¹⁹ F-NMR. be.

<Water and oil repellent composition>
The water and oil repellent composition of the present invention contains a specific copolymer as an essential component and, if necessary, a liquid medium, a surfactant and an additive.

(Copolymer)
The copolymer includes units based on monomer b (hereinafter also referred to as “b units”), units based on monomer c (hereinafter also referred to as “c units”), and monomer d. (hereinafter also referred to as "d unit").
The copolymer may optionally contain units based on the monomer a (hereinafter also referred to as "a units").
The copolymer may optionally contain units based on the monomer e (hereinafter also referred to as "e units").
The copolymer may optionally contain units based on the monomer f (hereinafter also referred to as "f units").

Monomer b:
Monomer b is a (meth)acrylate having no ^Rf group and having an alkyl group with 12 or more carbon atoms.
The number of carbon atoms in the alkyl group is preferably 14-30, more preferably 16-24. When the number of carbon atoms in the alkyl group is at least the above lower limit, the article treated with the water and oil repellent composition has better water repellency and friction durability. When the number of carbon atoms in the alkyl group is not more than the above upper limit, the handling in the polymerization operation is facilitated, and the copolymer can be obtained with higher yield.
Monomer b is preferably lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate and behenyl (meth)acrylate, and cetyl (meth)acrylate, stearyl (meth)acrylate and behenyl (meth)acrylate. is more preferred, and stearyl (meth)acrylate and behenyl acrylate are even more preferred.

Monomer c:
Monomer c is a monomer having a poly(oxypolyfluoroalkylene) chain in which the ratio of the number of fluorine atoms to the total number of fluorine atoms and hydrogen atoms is 70% or more.
By having the c unit in the copolymer, both the water and oil repellency derived from the b unit and the film-forming properties derived from the d unit can be sufficiently exhibited.
The ratio of the number of fluorine atoms to the total number of fluorine atoms and hydrogen atoms in the poly(oxypolyfluoroalkylene) chain is preferably 75% or more, more preferably 90 to 100%.

The poly(oxypolyfluoroalkylene) chain may be a polymer chain composed of units based on at least one oxypolyfluoroalkylene group (hereinafter also referred to as "oxypolyfluoroalkylene unit"), and at least one and a unit based on at least one oxyalkylene group (hereinafter also referred to as "oxyalkylene unit").
The poly(oxypolyfluoroalkylene) chain is preferably a polymer chain composed of at least one oxypolyfluoroalkylene unit and containing no oxyalkylene unit. The polymer chain includes a poly(oxyperfluoroalkylene) chain composed of at least one oxyperfluoroalkylene group-based unit (hereinafter also referred to as "oxyperfluoroalkylene unit"), at least one oxyperfluoroalkylene unit, and Polymer chains containing oxypolyfluoroalkylene units having at least one hydrogen atom can be exemplified.
A particularly preferred poly(oxypolyfluoroalkylene) chain is a poly(oxyperfluoroalkylene) chain that is a polymer chain composed of at least one oxyperfluoroalkylene unit.

The oxypolyfluoroalkylene unit constituting the poly(oxypolyfluoroalkylene) chain preferably has 1 to 6 carbon atoms.
Specific examples of the oxypolyfluoroalkylene units include (CF ₂ O) units, (CF ₂ CF ₂ O) units, (CF ₂ CF ₂ CF ₂ O) units, (CF(CF ₃ )CF ₂ O) units, _{Oxyperfluoroalkylene} units such as _{( CF2CF2CF2CF2O} ) _units ; and _{( CF2CF2CF2CH2O} ) _units , _{( CF2CF2CF2CF2CH2O ) units} , _{( CF 2} CHFO) units and other oxypolyfluoroalkylene units having hydrogen atoms.
As the oxypolyfluoroalkylene unit having a hydrogen atom, an oxypolyfluoroalkylene unit having 1 to 4 hydrogen atoms (where the ratio of the number of hydrogen atoms to the total number of fluorine atoms and hydrogen atoms is 30% or less) is preferable.

Two or more types of oxypolyfluoroalkylene units constituting the poly(oxypolyfluoroalkylene) chain may be used.
When the poly(oxypolyfluoroalkylene) chain has two or more types of oxypolyfluoroalkylene units, the order of these bonds is not limited. For example, when having (CF ₂ CF ₂ O) units and (CF ₂ CF ₂ CF ₂ O) units, the (CF ₂ CF ₂ O) units and (CF ₂ CF ₂ CF ₂ O) units are randomly arranged. (CF ₂ CF ₂ O) units and (CF ₂ CF ₂ CF ₂ O) units may alternate, and one or more of (CF ₂ CF ₂ O) units may be and one or more blocks consisting of a plurality of (CF ₂ CF ₂ CF ₂ O) units may be connected. When having (CF ₂ O) units and other oxyperfluoroalkylene units, the (CF ₂ O) units are usually randomly arranged.

The number average molecular weight of the poly(oxypolyfluoroalkylene) chain is preferably from 100 to 20,000, more preferably from 500 to 15,000, even more preferably from 500 to 10,000.

Specific examples of poly(oxypolyfluoroalkylene) chains include the following groups. In addition, in those having two types of oxypolyfluoroalkylene units among the following, the description of the chemical formula does not mean that they are arranged in blocks, and the order of bonding is not limited as described above.
-(CF ₂ O) _f -(CF ₂ CF ₂ O) _g -,
-(CF ₂ O) _f -(CF(CF ₃ )CF ₂ O) _i -,
-(CF ₂ CF ₂ O) _g -,
-(CF ₂ CF ₂ CF ₂ O) _h -,
-(CF(CF ₃ )CF ₂ O) _i -,
-(CF ₂ CF ₂ CF ₂ CF ₂ O) _j -,
- _{( CF2CF2CF2CH2O ) k- ,}
-(CF ₂ CF ₂ O) _g -(CF ₂ CF ₂ CF ₂ CF ₂ O) _j -,
-(CF ₂ CHFO) _q -(CF ₂ CF ₂ CF ₂ CH ₂ O) _k - and the like.

The above f to k and q are the following integers so that the number average molecular weight of the poly(oxypolyfluoroalkylene) chain falls within the above range.
f is an integer of 1-100, preferably an integer of 1-80, more preferably an integer of 1-50.
g is an integer of 1-200, preferably an integer of 1-150, more preferably an integer of 1-100.
h is an integer of 1-200, preferably an integer of 1-150, more preferably an integer of 1-100.
i is an integer of 1-200, preferably an integer of 1-150, more preferably an integer of 1-100.
j is an integer of 1-200, preferably an integer of 1-150, more preferably an integer of 1-100.
k is an integer of 1-200, preferably an integer of 1-150, more preferably an integer of 1-100.
q is an integer of 1-100, preferably an integer of 1-80, more preferably an integer of 1-50.

As the poly(oxypolyfluoroalkylene) chain, the following groups are preferred.
-(CF ₂ O) _f1 -(CF ₂ CF ₂ O) _g1 - [g1/f1 molar ratio: about 1, number average molecular weight: 500-4000, f1 (CF ₂ O) and g1 (CF ₂ CF ₂ O) is randomly arranged],
—(CF ₂ O) _f2 —(CF(CF ₃ )CF ₂ O) _i1 — [i1/f2 molar ratio: 1.5-2.5, number average molecular weight: 1500-1800, f2 (CF ₂ O) and i1 (CF _{( CF3} )CF2O) are randomly arranged],
-(CF ₂ CF ₂ CF ₂ O) _h1 -,
-(CF(CF ₃ )CF ₂ O) _i2 -,
-(CF ₂ CF ₂ O) _g2 -.
However, f1 is an integer of 1 to 60, f2 is an integer of 1 to 30, g1 is an integer of 1 to 35, g2 is an integer of 1 to 15, h1 is 15 to It is an integer of 50, i1 is an integer of 1-50, and i2 is an integer of 15-50.

Compound 5 is preferred as the monomer c.
(X ¹ -) _a Y ¹ -Z ¹ -Y ² (-X ² ) _b Formula 5.
however,
X ¹ is a hydrogen atom, a fluorine atom, a hydroxyl group, or CH ₂ =CR ¹ C(O)O-, and X ² is -OC(O)CR ¹ =CH ₂ (provided that R ¹ is a hydrogen atom, a methyl group or a halogen atom).
Y ¹ is an (a+1) valent organic group or a single bond, and Y ² is a (b+1) valent organic group.
Z ¹ is a poly(oxypolyfluoroalkylene) chain in which the ratio of the number of fluorine atoms to the total number of fluorine atoms and hydrogen atoms is 70% or more.
a is an integer of 1 or more, and b is an integer of 1 or more.

a is preferably an integer of 1 to 4, more preferably 1 or 2.
b is preferably an integer of 1 to 4, more preferably 1 or 2.
The number of —OC(O)CR ¹ ═CH ₂ in compound 5 is preferably 1 to 4, more preferably 1 or 2.

The poly(oxypolyfluoroalkylene) chain in Z ¹ is as described above, and preferred embodiments are also the same.

Poly(oxyperfluoroalkylene) wherein Z ¹ is the above -(CF ₂ O) _f1 -(CF ₂ CF ₂ O) _g1 -, -(CF ₂ O) _f2 -(CF(CF ₃ )CF ₂ O) _i1 -, etc. ) chains are commercially available. Compound 5 is preferably a commercially available compound described below or a compound derived from the commercially available compound.
Examples of commercially available compounds include the following compounds. The following d represents an integer of 1-30.
_HCF2OZ1 ^- _CF2H ,
_{HOCH2CF2OZ1 -} ^CF2CH2OH _{, _}
HO(CH ₂ CH ₂ O) _d CH ₂ CF ₂ O-Z ¹ -CF ₂ CH ₂ (OCH ₂ CH ₂ ) _d OH,
^HOCH2CH _{( OH} ) _{CH2OCH2CF2OZ1 - CF2CH2OCH2CH ( OH} ) _CH2OH ,
_{HOCH2CH (} OH) _{OCH2CF2OZ1 -} ^CF2CH2OCH ₍ OH) _CH2OH ,
HOOC(CH ₂ CH ₂ O) _d CH ₂ CF ₂ O-Z ¹ -CF ₂ CH ₂ (OCH ₂ CH ₂ ) _d COOH.
Compound 5 is preferably a derivative of the above diol or tetraol, more preferably a derivative of the above diol.

When Y ¹ is a divalent organic group, the following groups may be mentioned.
_-CF2O- ,
—(CH ₂ ) _c (CF ₂ ) _e O—,
- _{( CH2CH2O ) dCH2CF2O- ,
-CH2CH ( OH} ) _CH2OCH2CF2O- ,
—(CH ₂ ) _c —NHC(O)O—Y ¹¹ —,
—(CH ₂ ) _c —OC(O)NH—Q—NHC(O)O—Y ¹¹ — and the like.
However, c and e are each independently an integer of 1 to 10, and when two or more c are present in the same group, the values of c may be the same or different. Y ¹¹ is -(CH ₂ ) _c CF ₂ O-, -(CH ₂ CH ₂ O) _d CH ₂ CF ₂ O-, -CH ₂ CH(OH)CH ₂ OCH ₂ CF ₂ O- or -CH ₂ CH(OH)OCH ₂ CF ₂ O—, and Q is a divalent group other than the isocyanate group of the diisocyanate represented by OCN-Q-NCO.
In each of the above groups, one terminal atom of Y ¹ is bonded to X ¹ and the other terminal atom (--O--) is bonded to Z ¹ . The bonding portion between Y ¹ and X ¹ and the bonding portion between Y ¹ and Z ¹ do not form a continuous bond of oxygen atoms. Therefore, the terminal atom of Z ¹ that bonds to Y ¹ is not an oxygen atom (--O--).
Diisocyanates represented by OCN-Q-NCO include aromatic diisocyanates, aliphatic diisocyanates and alicyclic diisocyanates. Specific examples of diisocyanates include tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate and norbornene diisocyanate.

When Y ¹ is a trivalent or higher organic group, for example, among the above divalent organic groups, Y ¹¹ is —CH ₂ CH(OH)CH ₂ OCH ₂ CF ₂ O——(CH ₂ ) _c —NHC(O)O—Y ¹¹ — or —(CH ₂ ) _c —OC(O)NH—Q—NHC(O)O—Y ¹¹ —, where the OH in Y ¹¹ is replaced by O—CONH—(CH ₂ ) ) _c --substituted group. Also, some of the isocyanate groups of a polyisocyanate having 3 or more isocyanate groups were substituted with -NHC(O)O-(CH ₂ ) _c -, and the rest were substituted with -NHC(O)O-Y ¹¹ -. Structural groups are included. Examples of polyisocyanates having 3 or more isocyanate groups include nurate-modified and burette-modified diisocyanates.
Specific examples of trivalent Y ¹ include the following groups (8-1) to (8-4).
In groups (8-1) to (8-4), Y ¹² is —(CH ₂ ) _c CF ₂ O—, —(CH ₂ CH ₂ O) _d CH ₂ CF ₂ O—, Q, c , d are as described above. —O— at the end of Y ¹¹ does not bond to an oxygen atom. X ¹ is bonded to each of two -(CH ₂ ) _c - among the terminals of groups (8-1) to (8-4), and Z ¹ is bonded to -Y ¹² - or -O- .

When X ¹ is a hydrogen atom or a fluorine atom, Y ¹ is preferably a single bond or -CF ₂ O-.
When X ¹ is CH ₂ =CR ¹ C(O)O-, (X ¹ -) _a Y ¹ - is
_CH2 = ^CR1C (O)O- _{( CH2} ) _cCF2O- ,
_{CH2 =} ^CR1C ₍ O)O _- CH2CH(OH) _CH2OCH2CF2O- ,
_CH2 = ^CR1C ₍ O)O _{- CH2CH} (OC(O)CR1 _{= CH2} ) ^CH2OCH2CF2O- ,
_{CH2 =} ^CR1C (O)O _- CH2CH(OH) _OCH2CF2O- ,
_CH2 = ^CR1C (O)O _{- CH2CH} (OC(O)CR1 _{= CH2} ) ^OCH2CF2O- ,
_CH2 = ^CR1C (O)O-( _CH2 ) _c -NHC(O)O- ^Y11- ,
CH ₂ ═CR ¹ C(O)O—(CH ₂ ) _c —OC(O)NH—Q—NHC(O)O—Y ¹¹ —,
a group in which two X ¹ are bonded to any one of groups (8-1) to (8-4),
is preferred.
(X ¹ —) _a Y ¹ — is particularly CH ₂ ═CR ¹ C(O)O—(CH ₂ ) _c CF ₂ O—, CH ₂ ═CR ¹ C(O)O—(CH ₂ ) _c —OC(O)NH—Q—NHC(O)O—Y ¹¹ — (where Q is the residue of hexamethylene diisocyanate or the residue of diphenylmethane diisocyanate), and groups (8-1) to (8- A group in which two CH ₂ ═CR ¹ C(O)O— are bonded to any one of 4) is preferred.

When Y ² is a divalent organic group, examples of Y ² include the following groups.
_-CF2- ,
—(CF ₂ ) _e (CH ₂ ) _c —,
_{-CF2CH2 ( OCH2CH2 )d- ,}
-CF _{( CF3} )CH2-,
_{-CF2CH2OCH2CH ( OH} ) _CH2- ,
—Y ²¹ —OC(O)NH—(CH ₂ ) _c —,
—Y ²¹ —OC(O)NH—Q—NHC(O)O—(CH ₂ ) _c — and the like.
provided that c, e, d, and Q are as described above, and Y ²¹ is —CF ₂ (CH ₂ ) _c —, —CF ₂ CH ₂ (OCH ₂ CH ₂ ) _d —, —CF ₂ CH ₂ OCH ₂ CH(OH)CH ₂ - or -CF ₂ CH ₂ OCH(OH)CH ₂ -.
In each of the above groups, ^one terminal atom of ^Y2 is bonded to X2 and the ^other terminal atom is bonded to Z1. The bonding portion between Y ² and X ² and the bonding portion between Y ² and Z ¹ do not form a continuous bond of oxygen atoms.

When Y ² is a trivalent or higher organic group, for example, among the divalent organic groups described above, Y ²¹ is -CF ₂ CH ₂ OCH ₂ CH(OH)CH ₂ - -Y ²¹ -OC(O )NH—(CH ₂ ) _c — or —Y ²¹ —OC(O)NH—Q—NHC(O)O—(CH ₂ ) _c —, the OH in Y ²¹ is replaced by O—CONH—(CH ₂ ) A group having a _c -substituted structure may be mentioned. Also, some of the isocyanate groups of the polyisocyanate having 3 or more isocyanate groups were substituted with -NHC(O)O-(CH ₂ ) _c -, and the rest were substituted with -NHC(O)O-Y ²¹ -. Structural groups are included.
Specific examples of trivalent Y ² include the following groups (9-1) to (9-4).
In groups (9-1) to (9-4), Y ²² is —CF ₂ (CH ₂ ) _c — or CF ₂ CH ₂ (OCH ₂ CH ₂ ) _d —, and Q, c, and d are As mentioned above. X ² is bonded to each of two —(CH ₂ ) _c — among the terminals of groups (9-1) to (9-4), and Z ¹ is bonded to —Y ²² — or —CF ₂ —. do.

As Y ² (−X ² ) _b ,
^-CF2 ( _CH2 ) _c -OC(O)CR1 _{= CH2} ,
_{-CF2CH2OCH2CH} (OH) _{CH2 -} OC(O) ^CR1 _{= CH2} ,
^{-CF2CH2OCH2CH} (OC(O)CR1 _{= CH2} ) _{CH2 -} OC(O) ^CR1 _{= CH2} ,
^-CF2CH2OCH (OH) _{CH2 -} OC(O)CR1 _{= CH2} ,
^-CF2CH2OCH (OC(O)CR1= _CH2 ) _{CH2 -} OC(O) ^CR1 _{= CH2} ,
-Y ²¹ -OC(O)NH-(CH ₂ ) _c -OC(O)CR ¹ =CH ₂ ,
—Y ²¹ —OC(O)NH—Q—NHC(O)O—(CH ₂ ) _c —OC(O)CR ¹ =CH ₂ ,
a group in which two —OC(O)CR ¹ ═CH ₂ are bonded to any one of groups (9-1) to (9-4),
is preferred.
—Y ² (—X ² ) _b is particularly —CF ₂ (CH ₂ ) _c —OC(O)CR ¹ =CH ₂ , —Y ²¹ —OC(O)NH—(CH ₂ ) _c —OC (O) CR ¹ ═CH ₂ , —Y ²¹ —OC(O)NH—Q—NHC(O)O—(CH ₂ ) _c — (where Q is a hexamethylene diisocyanate or diphenylmethane diisocyanate residue), and , two -OC(O)CR ¹ =CH ₂ are bonded to any of the groups (9-1) to (9-4) to which two -OC(O)CR ¹ =CH ₂ are bonded preferable.

Compound 5 includes the following compounds.
_{CH2 =} ^CR1C ₍ O)O _{- CH2CF2O} -[( _CF2O )f-( ^CF2CF2O ) _g ] _{-CF2CH2 -} OC(O)CR1 _{= CH2} ,
_{CH2 =} ^CR1C (O)O _{- CH2CF2O} -[( _CF2O )f-(CF( _CF3 ) _CF2O ) _i ] _{-CF2CH2 -} OC(O) ^CR1 = _CH2 ,
_{CH2 =} ^CR1C ₍ O)O _- CH2CF2O-( ^CF2CF2CF2O ) _{h - CF2CH2 -} OC(O)CR1 _{= CH2} ,
_{CH2 =} ^CR1C (O)O _{- CH2CF2O-} (CF( _CF3 )CF2O) _i - ^CF2CH2 _- OC(O)CR1 _{= CH2} ,
_{CH2 =} ^CR1C ₍ O)O _- CH2CF2O-(CF2CF2O) _g ^- _{CF2CH2 -} OC(O)CR1 _{= CH2} ,
_{CH2 =} ^CR1C ₍ O)O _{- CH2CF2O} -[( _CF2CHFO ) _q- ( ^{CF2CF2CF2CH2O} ) _k ]-OC ₍ O)CR1 _{= CH2} ,
_{CH2 =} ^CR1C _{( O} ) _{O - CH2CF2CF2CF2O} -[ _{( CF2CF2O} ) _{g- ( CF2CF2CF2CF2O} ) _{j ] -CF2CF2CF} ^2CH2 _- OC(O)CR1 _{= CH2} ,
G—CH ₂ CF ₂ O—[(CF ₂ O) _f —(CF ₂ CF ₂ O) _g ]—CF ₂ CH ₂ —G,
G—CH ₂ CF ₂ O—[(CF ₂ O) _f —(CF(CF ₃ )CF ₂ O) _i ]—CF ₂ CH ₂ —G,
_{G - CH2CF2CF2O- ( CF2CF2CF2O} ) _{h - CF2CF2CH2 - G} ,
G—CH ₂ CF ₂ O—(CF(CF ₃ )CF ₂ O) _i —CF ₂ CH ₂ —G,
G—CH ₂ CF ₂ O—(CF ₂ CF ₂ O) _g —CF ₂ CH ₂ —G,
_{G - CH2CF2CF2O} -[ _{( CF2CF2O} ) _{g- ( CF2CF2CF2CH2O )k ] -CF2CF2CH2 - G ,}
G _{- CH2CF2O} -[ _{( CF2CF2O} ) _{g- ( CF2CF2CF2CF2O} ) _{j ] -CF2CH2 - G} ,
F—[(CF ₂ O) _f —(CF ₂ CF ₂ O) _g ]—CF ₂ CH ₂ —OC(O)CR ¹ =CH ₂ ,
F—[(CF ₂ O) _f —(CF(CF ₃ )CF ₂ O) _i ]—CF ₂ CH ₂ —OC(O)CR ¹ =CH ₂ ,
F—(CF ₂ CF ₂ CF ₂ O) _h —CF ₂ CF ₂ CH ₂ —OC(O)CR ¹ =CH ₂ ,
F—(CF(CF ₃ )CF ₂ O) _i —CF ₂ CH ₂ —OC(O)CR ¹ =CH ₂ ,
F—(CF(CF ₃ )CF ₂ O) _i —CF(CF ₃ )CH ₂ —OC(O)CR ¹ =CH ₂ ,
F—CF ₂ O—(CF ₂ CF ₂ O) _g —CF ₂ CH ₂ —OC(O)CR ¹ =CH ₂ ,
F-[ _{( CF2CHFO} ) _{q- ( CF2CF2CF2CH2O} ) _k ] _{-CF2CF2CF2CH2 -} ^OC ₍ O) _{CR1 = CH2} ,
F-[ _{( CF2CF2O} ) _{g- ( CF2CF2CF2CF2O} ) _j ] _{-CF2CF2CF2CH2 -} ^OC ₍ O) _{CR1 = CH2 ,
HOCH2} -[( _CF2O )f-( ^CF2CF2O ) _g ] _{-CF2CH2 -} OC ₍ O) _{CR1 = CH2} ,
HOCH ₂ —[(CF ₂ O) _f —(CF(CF ₃ )CF ₂ O) _i ]—CF ₂ CH ₂ —OC(O)CR ¹ =CH ₂ and the like.

R ¹ , f, g, h, i, j, k, and q are as described above.
f and g in [(CF ₂ O) _f -(CF ₂ CF ₂ O) _g ] are preferably f1 and g1 described above, respectively.
f and i in [(CF ₂ O) _f -(CF(CF ₃ )CF ₂ O) _i ] are preferably f2 and i1 described above, respectively.
G is a monofunctional or bifunctional urethane (meth)acrylate structure.
Monofunctional urethane (meth)acrylate structures include, for example, CH ₂ ═CR ¹ C(O)O—C(O)NH—, CH ₂ ═CR ¹ C(O)O—(CH ₂ ) _c OC( O)NH—, CH ₂ ═CR ¹ C(O)O—Q—OC(O)NH— and the like. Examples of bifunctional urethane (meth)acrylate structures include -CF ₂ CH ₂ OCH ₂ CH{-OC(O)NH-(CH ₂ ) _c OC(O)CR ¹ =CH ₂ }CH ₂ -OC( O)NH—(CH ₂ ) _c OC(O)CR ¹ =CH ₂ and the like. c is as described above.

As compound 5, compound 5-1 and compound 5-2 are preferable.
FZ ³ -Y ³ -OC(O)CR ¹ =CH ₂ Formula 5-1.
X ⁴ -Y ⁴ -Z ³ -Y ³ -X ³ formula 5-2.
with the proviso that Z ³ is -(CF ₂ O) _f -(CF ₂ CF ₂ O) _g -, -(CF ₂ O) _f -(CF(CF ₃ )CF ₂ O) _i -, -(CF ₂ CF ₂ CF ₂ O) _h — or —(CF(CF ₃ )CF ₂ O) _i —.
Y ³ represents -(CF ₂ ) _c (CH ₂ ) _c - or -CF(CF ₃ )CH ₂ -.
X ³ and X ⁴ are each independently CH ₂ ═CR ¹ C(O)O—, CH ₂ ═CR ¹ C(O)O—C(O)NH—, CH ₂ ═CR ¹ C(O)O —(CH ₂ ) _c OC(O)NH— or CH ₂ ═CR ¹ C(O)O—Q—OC(O)NH—.
Y ⁴ represents -CF ₂ - or (CF ₂ ) _e (CH ₂ ) _c -.
R ¹ , Q, c, e, f, g, h and i have the same meanings as above. When two or more cs are present in the same molecule, the values of c may be the same or different.

As compound 5, the following compounds are more preferable.
_{CH2 =} ^CR1C ₍ O)O _{- CH2CF2O} -[( _CF2O )f1-( ^CF2CF2O ) _g1 ] _{-CF2CH2 -} OC(O)CR1 _{= CH2} ,
_{CH2 =} ^CR1C (O)O _{- CH2CF2O} -[( _CF2O ) ^f2- (CF( _CF3 ) _CF2O ) _i1 ] _{-CF2CH2 -} OC(O)CR1= _CH2 ,
_{CH2 =} ^CR1C ₍ O)O _- CH2CF2O-( ^CF2CF2CF2O ) _{h1 - CF2CF2CH2 -} OC(O) _{CR1 = CH2} ,
_{CH2 =} ^CR1C (O)O _{- CH2CF2O-} (CF( _CF3 )CF2O) _i2 - ^CF2CH2 _- OC(O)CR1 _{= CH2} ,
_{CH2 =} ^CR1C ₍ O)O _- CH2CF2O-(CF2CF2O) _g2 ^- _{CF2CH2 -} OC(O)CR1 _{= CH2} ,
G _{- CH2CF2O} -[( _CF2O ) _{f1- ( CF2CF2O} ) _g1 ] _{-CF2CH2 -} G,
G—CH ₂ CF ₂ O—[(CF ₂ O) _f2 —(CF(CF ₃ )CF ₂ O) _i1 ]—CF ₂ CH ₂ —G,
G—CH ₂ CF ₂ CF ₂ O—(CF ₂ CF ₂ CF ₂ O) _h1 — CF ₂ CF ₂ CH ₂ —G,
G—CH ₂ CF ₂ O—(CF(CF ₃ )CF ₂ O) _i2 —CF ₂ CH ₂ —G,
G—CH ₂ CF ₂ O—(CF ₂ CF ₂ O) _g2 —CF ₂ CH ₂ —G,
F-[(CF2O) ^f1- ( _CF2CF2O ) _g1 ] _{-CF2CH2 -} OC ₍ O) _{CR1 = CH2} ,
F-[(CF2O) _f2- (CF( _CF3 ) ^CF2O ) _i1 ] _{-CF2CH2 -} OC(O) _{CR1 = CH2} ,
F—(CF ₂ CF ₂ CF ₂ O) _h1 — CF ₂ CF ₂ CH ₂ —OC(O)CR ¹ =CH ₂ ,
F—(CF(CF ₃ )CF ₂ O) _i2 —CF ₂ CH ₂ —OC(O)CR ¹ =CH ₂ ,
F—(CF(CF ₃ )CF ₂ O) _i2 —CF(CF ₃ )CH ₂ —OC(O)CR ¹ =CH ₂ ,
F—CF ₂ O—(CF ₂ CF ₂ O) _g2 —CF ₂ CH ₂ —OC(O)CR ¹ =CH ₂ .
However, f1, f2, g1, h1, i1 and i2 are as described above.

Compound 5 is available as Fomblin MT70, Fluorolink MD700, Fluorolink AD1700 (all trade names of Solvay Specialty Polymers).
Compound 5 is a poly(oxypolyfluoroalkylene) having a desired molecular weight from Fluorolink, Fomblin (all product names of Solvay Specialty Polymers), Demnum (product name of Daikin Industries, Ltd.), and Krytox (product name of DuPont). ) chain-containing compounds or derivatives of poly(oxypolyfluoroalkylene) chain-containing compounds can be selected and synthesized using these compounds as starting materials. For example, a terminally methyl-esterified poly(oxypolyfluoroalkylene) chain-containing compound is reduced in anhydrous ethanol in the presence of sodium borohydride to obtain a compound with an OH group at the terminal, and then, in dehydrated acetone, Compound 5 can be obtained by reacting with acrylic acid chloride in the presence of triethylamine.

monomer d:
Monomer d is a halogenated olefin.
By combining the b unit and the d unit, the adhesion to the article is improved, so that the water repellent friction durability of the article treated with the water and oil repellent composition is improved.

Halogenated olefins include compound 6.
R ⁴ R ⁵ C=CR ⁶ R ⁷ Formula 6.
R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom or a C 1-3 perfluoroalkyl group. However, at least one of R ⁴ , R ⁵ , R ⁶ and R ⁷ is a halogen atom. The perfluoroalkyl group having 1 to 3 carbon atoms is CF ₃ —, C ₂ F ₅ —, C ₃ F ₇ —.
Halogenated olefins are preferably chlorinated olefins and fluorinated olefins.

Tetrafluoroethylene or compound 7 is preferred as the halogenated olefin.
^R8HC = ^CR9R10 Formula ⁷ .
R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a chlorine atom, a fluorine atom, or a C 1-3 perfluoroalkyl group. At least one of R ⁸ , R ⁹ and R ¹⁰ is a chlorine atom, a fluorine atom or a C 1-3 perfluoroalkyl group.
Specific examples of halogenated olefins are preferably vinyl chloride, vinylidene chloride, tetrafluoroethylene, vinylidene fluoride, and 2,3,3,3-tetrafluoro-1-propene. Vinyl chloride, vinylidene chloride and 2,3,3,3-tetrafluoro-1-propene are more preferred.

Monomer a:
Monomer a is compound 1.
(ZL) _n X Formula 1.

^Z is an RF group having 1 to 6 carbon atoms or a group 2;
C _s F _2s+1 CH ₂ CF ₂ −(CH ₂ CF ₂ ) _t (CF ₂ CF ₂ ) _u − Formula 2.
However, s is an integer of 1-6, t is an integer of 0-3, and u is an integer of 1-3.
The number of carbon atoms in the ^RF group is preferably 4-6. The ^RF group may be linear or branched, preferably linear. The arrangement of (CH ₂ CF ₂ ) _t (CF ₂ CF ₂ ) _u may be random or blockwise.

Z includes the following groups.
F( _CF2 ) _4- ,
F( _CF2 ) _5- ,
F( _CF2 ) _6- ,
(CF ₃ ) ₂ CF(CF ₂ ) ₂ - and the like.

L is a divalent organic group having no fluorine atom or a single bond.
A divalent organic group is a divalent group containing carbon atoms. However, when the terminal atom of X bonded to the divalent organic group is an etheric oxygen atom, the terminal atom of the divalent organic group bonded to X is a carbon atom.
The divalent organic group includes an alkylene group, an alkenylene group, and a group having -O-, -NH-, -CO-, -SO ₂ - or -S- at the end of the alkylene group or between the carbon-carbon atoms. is preferred. These groups may be linear or branched, and are preferably linear.

L includes the following groups.
_-CH2- ,
_{-CH2CH2- ,}
-(CH ₂ ) ₃ -,
_{-CH2CH2CH ( CH3} )-,
-CH=CH-CH ₂ -,
-S _{- CH2CH2-} ,
_{-SO2 - CH2CH2-} ,
_{-CH2CH2CH2 - S - CH2CH2-} ,
_{-CH2CH2CH2 - SO2 - CH2CH2- and} the like.

n is 1 or 2;
X is any one of groups 3-1 to 3-5 when n is 1, and any one of groups 4-1 to 4-4 when n is 2.

-CR= _CH2 Formula 3-1,
-C(O)OCR= _CH2 formula 3-2,
-OC(O)CR= _CH2 formula 3-3,
-OCH ₂ -φ-CR=CH ₂ formula 3-4,
-OCH=CH ₂ Formula 3-5.
However, R is a hydrogen atom, a methyl group or a halogen atom, and φ is a phenylene group. R is preferably a hydrogen atom, a methyl group or a chlorine atom.

-CH[-(CH ₂ ) _m CR=CH ₂ ]- formula 4-1,
—CH[—(CH ₂ ) _m C(O)OCR=CH ₂ ]— Formula 4-2,
—CH[—(CH ₂ ) _m OC(O)CR=CH ₂ ]— Formula 4-3,
-OC(O)CH=CHC(O)O- Formula 4-4.
However, R is a hydrogen atom, a methyl group or a halogen atom, and m is an integer of 0-4. R is preferably a hydrogen atom, a methyl group or a chlorine atom.

As the compound 1, the polymerizability with other monomers, the flexibility of the film of the copolymer, the adhesiveness of the copolymer to articles, the dispersibility or solubility in liquid media, the ease of emulsion polymerization, etc. Therefore, acrylates, methacrylates and ^acrylates substituted with a ^halogen atom at the α-position are preferred, and acrylates, methacrylates and α More preferred are acrylates whose positions are substituted with halogen atoms.

Examples of compound 1 include compound 1-1.
C _p F _2p+1 C _q H _2q OCOCR=CH ₂ Formula 1-1.
However, p is an integer of 1 to 6, q is an integer of 1 to 4, and R is a hydrogen atom, a methyl group or a halogen atom. R is preferably a hydrogen atom, a methyl group or a chlorine atom.
Preferred specific examples of compound 1-1 include the following.
_{C6F13C2H4OCOC ( CH3} ) _{= CH2 ,
C6F13C2H4OCOCH = CH2 , _
C6F13C2H4OCOCCl = CH2 , _
C4F9C2H4OCOC ( CH3} ) _{= CH2 ,
C4F9C2H4OCOCH = CH2 , _
C4F9C2H4OCOCCl = CH2 . _}

Monomer e:
Monomer e is a monomer having a crosslinkable functional group (excluding monomer c).
The e unit is optionally used to further improve the rub resistance and wash durability of articles treated with the water and oil repellent composition.

As the functional group capable of cross-linking, a functional group having at least one or more of a covalent bond, an ionic bond and a hydrogen bond, or a functional group capable of forming a cross-linked structure through the interaction of such bonds is preferred.
Examples of the functional group include isocyanate group, blocked isocyanate group, alkoxysilyl group, amino group, alkoxymethylamide group, silanol group, ammonium group, amide group, epoxy group, hydroxyl group, oxazoline group, carboxyl group and alkenyl group. , a sulfonic acid group, and the like. Preferred functional groups are epoxy groups, hydroxyl groups, blocked isocyanate groups, alkoxysilyl groups, amino groups, and carboxyl groups.

As the monomer e, (meth)acrylates, acrylamides, vinyl ethers and vinyl esters are preferred.
Examples of the monomer e include the following compounds.

2-isocyanatoethyl (meth)acrylate, 2-butanone oxime adduct of 2-isocyanatoethyl (meth)acrylate, 3,5-dimethylpyrazole adduct of 2-isocyanatoethyl (meth)acrylate, 2-isocyanato ε-caprolactam adduct of ethyl (meth)acrylate.

Methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, butoxymethyl (meth)acrylamide, diacetone acrylamide, 3-methacryloyloxypropyltrimethoxysilane, trimethoxyvinylsilane, vinyltrimethoxysilane, dimethylaminoethyl (meth)acrylate , diethylaminoethyl (meth)acrylate.

t-butyl (meth)acrylamide sulfonic acid, (meth)acrylamide, N-methyl (meth)acrylamide, N-methylol (meth)acrylamide, N-butoxymethyl (meth)acrylamide, diacetone (meth)acrylamide, glycidyl (meth) Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl methacrylate, polyoxyalkylene glycol mono (meth) acrylate, ( Polycaprolactone esters of meth)acrylic acid, 2-(meth)acryloyloxyethyl acid phosphate, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-(2-vinyloxazoline)hydroxyethyl (meth)acrylate.

Tri(meth)allyl isocyanurate (T(M)AIC, manufactured by Nippon Kasei Co., Ltd.), triallyl cyanurate (TAC, manufactured by Nippon Kasei Co., Ltd.), 3-(methyl ethyl ketoxime) isocyanatomethyl-3,5,5-trimethyl Cyclohexyl (2-hydroxyethyl methacrylate) cyanate (Techcoat HE-6P, manufactured by Kyokinu Kasei Co., Ltd.), polyfluorovinyl ether having a hydroxyl group (CF ₂ =CFOCF ₂ CF ₂ CF ₂ CH ₂ OH, etc.).

Examples of the monomer e include N-methylol (meth)acrylamide, N-butoxymethyl (meth)acrylamide, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-isocyanatoethyl (meth) 3,5-dimethylpyrazole adduct of acrylate, diacetone acrylamide, glycidyl methacrylate, polycaprolactone ester of hydroxyethyl (meth)acrylate, polycaprolactone ester of hydroxyethyl (meth)acrylate, and Techcoat HE-6P are preferred. As the monomer e, 3,5-dimethylpyrazole addition of N-methylol (meth)acrylamide, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and 2-isocyanatoethyl (meth)acrylate Body is more preferred.

Monomer f:
Monomer f is a monomer other than monomer a, monomer b, monomer c, monomer d and monomer e.
As the monomer f, a monomer containing no perfluoroalkyl group having 7 or more carbon atoms is preferred, and a monomer containing no fluorine atom is particularly preferred.
Examples of the monomer f include the following compounds.

methyl acrylate, ethyl acrylate, propyl acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-hexyl (meth) acrylate, vinyl acetate, vinyl propionate, butene, isoprene, butadiene, Ethylene, propylene, vinylethylene, pentene, ethyl-2-propylene, butylethylene, cyclohexylpropylethylene, decylethylene, dodecylethylene, hexene, isohexylethylene, neopentylethylene, (1,2-diethoxycarbonyl)ethylene, ( 1,2-dipropoxycarbonyl)ethylene, methoxyethylene, ethoxyethylene, butoxyethylene, 2-methoxypropylene, pentyloxyethylene, cyclopentanoyloxyethylene, cyclopentylacetoxyethylene, styrene, α-methylstyrene, p-methylstyrene, hexylstyrene, octylstyrene, nonylstyrene, chloroprene.

N,N-dimethyl (meth)acrylamide, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, butyl acrylate, propyl methacrylate, benzyl (meth) acrylate, octyl (meth) acrylate, decyl methacrylate, cyclododecyl acrylate, 3- ethoxypropyl acrylate, methoxy-butyl acrylate, 2-ethylbutyl acrylate, 1,3-dimethylbutyl acrylate, 2-methylpentyl acrylate, aziridinylethyl (meth)acrylate, 2-ethylhexyl polyoxyalkylene (meth)acrylate, poly Oxyalkylene di(meth)acrylate.

Crotonic acid alkyl ester, maleic acid alkyl ester, fumaric acid alkyl ester, citraconic acid alkyl ester, mesaconic acid alkyl ester, triallyl cyanurate, allyl acetate, N-vinylcarbazole, maleimide, N-methylmaleimide, silicone in the side chain a (meth)acrylate having a urethane bond, a (meth)acrylate having a polyoxyalkylene chain with an alkyl group having 1 to 4 carbon atoms at the terminal, an alkylene di(meth)acrylate, and the like.

The ratio of b units to units based on all monomers constituting the copolymer is 30 to 80 mass from the viewpoint of water and oil repellency and durability of articles treated with the water and oil repellent composition. %, more preferably 40 to 70% by mass, particularly preferably 45 to 65% by mass.
The ratio of c units to units based on all monomers constituting the copolymer is 10 to 40 mass from the viewpoint of water and oil repellency and durability of articles treated with the water and oil repellent composition. %, more preferably 15 to 35% by mass, even more preferably 18 to 32% by mass.
The ratio of d units to units based on all monomers constituting the copolymer is 10 to 30 mass from the viewpoint of water and oil repellency and durability of articles treated with the water and oil repellent composition. %, more preferably 12 to 28% by mass, even more preferably 13 to 25% by mass.

A unit, e unit, and f unit are arbitrary structural units.
The ratio of a units to units based on all the monomers constituting the copolymer is 1% by mass or less from the viewpoint of the water repellent friction durability of the article treated with the water and oil repellent composition. Yes, preferably 0.5% by mass or less. The lower limit is not particularly limited, and may be 0% by mass.
The ratio of e units to units based on all monomers constituting the copolymer is 10% by mass or less from the viewpoint of water and oil repellency and durability of articles treated with the water and oil repellent composition. is preferred, and 5% by mass or less is more preferred. The lower limit is not particularly limited, and may be 0% by mass.
The ratio of f units to units based on all monomers constituting the copolymer is 35% by mass or less from the viewpoint of water and oil repellency and durability of articles treated with the water and oil repellent composition. is preferred, and 20% by mass or less is more preferred. The lower limit is not particularly limited, and may be 0% by mass.

The ratio of the units based on the monomers in the present invention is calculated based on the amount of the monomers charged at the time of production of the copolymer.
The fact that the ratio of units based on the monomer is 0% by mass means that the unit does not exist or, even if it exists, it cannot be detected by ordinary analytical means.

The mass average molecular weight (Mw) of the copolymer is preferably 8,000 to 1,000,000, more preferably 10,000 to 800,000. If the weight average molecular weight (Mw) of the copolymer is within the above range, both water repellency and oil repellency can be exhibited.
The number average molecular weight (Mn) of the copolymer is preferably 3,000 to 800,000, more preferably 5,000 to 600,000. If the number average molecular weight (Mn) of the copolymer is within the above range, both water repellency and oil repellency can be exhibited.

Preferred embodiments of the copolymer include copolymers containing units based on the following monomers.
• Stearyl (meth)acrylate/Compound 5-1/Compound 7.
• behenyl (meth)acrylate/compound 5-1/compound 7;
• Stearyl (meth)acrylate/Compound 5-2/Compound 7.
• behenyl (meth)acrylate/compound 5-2/compound 7;
Here, "stearyl (meth) acrylate / compound 5-1 / compound 7" is a copolymer containing units based on stearyl (meth) acrylate, units based on compound 5-1, and units based on compound 7. show. The same applies to other copolymers.

(liquid medium)
Examples of liquid media include water, alcohols, glycols, glycol ethers, glycol esters, halogen compounds, hydrocarbons, ketones, esters, ethers, nitrogen compounds, sulfur compounds, inorganic solvents, and organic acids. From the standpoint of ease, one or more liquid media selected from the group consisting of water, alcohols, glycols, glycol ethers and glycol esters are preferred.
Specifically, the liquid medium described in paragraphs [0069] to [0075] of International Publication No. 2016/09823 can be used without particular limitation.
As the liquid medium, propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, tripropylene glycol and acetone are preferred from the viewpoint of film-forming properties and stability, and dipropylene glycol, dipropylene glycol monomethyl ether, tripropylene glycol and Acetone is more preferred.

The liquid medium may be used singly or in combination of two or more. When two or more liquid media are mixed and used, they are preferably mixed with water. By using a mixed liquid medium, it is easy to control the solubility and dispersibility of the copolymer, and it is easy to control the permeability, wettability, solvent drying speed, etc. of the article during processing.
When the water and oil repellent composition of the present invention contains 20% by mass of the copolymer, it preferably contains 0 to 40% by mass of the liquid medium other than water, and more preferably 1 to 20% by mass. preferable.

(Surfactant)
Surfactants include hydrocarbon surfactants and fluorosurfactants, each of which includes an anionic surfactant, a nonionic surfactant, a cationic surfactant, or an amphoteric surfactant. .
As the surfactant, a combination of a nonionic surfactant and an amphoteric surfactant is preferable from the viewpoint of compatibility with additives, and a nonionic surfactant is preferred from the viewpoint of copolymer stability. A single use or a combined use of a nonionic surfactant and a cationic surfactant is preferred.
The ratio of nonionic surfactant to cationic surfactant (nonionic surfactant/cationic surfactant) is preferably 97/3 to 40/60 (mass ratio).

Examples of nonionic surfactants include the group consisting of surfactants s ¹ to s ⁶ described in WO 2010/047258 and WO 2010/123042, and the amidoamine interface described in Japanese Patent No. 5569614. One or more selected from activators are preferred.
When the surfactant contains a cationic surfactant, the cationic surfactant is preferably surfactant s7 described in ^WO2010 /047258 and WO2010/123042.
When the surfactant contains an amphoteric surfactant, the amphoteric surfactant is preferably surfactant s8 described in ^WO2010 /047258 and WO2010/123042.
Moreover, as a surfactant, surfactant s ⁹ (polymeric surfactant) described in WO 2010/047258 and WO 2010/123042 may be used.
Preferred aspects of the surfactant are the same as those described in WO2010/047258 and WO2010/123042.

Preferred specific examples of nonionic surfactants include the following compounds.
_C18H37O [ _{CH2CH ( CH3} )O] _{2- ( CH2CH2O} ) _30H ,
_C18H35O -- _{( CH2CH2O ) 13H} ,
_C18H35O -- _{( CH2CH2O ) 26H} ,
_C18H37O -- _{( CH2CH2O ) 50H} ,
_C18H35O -- _{( CH2CH2O ) 30H} ,
_{C12H35O -- ( CH2CH2O} ) _12H ,
_C16H33O [ _{CH2CH ( CH3} )O] _{5- ( CH2CH2O} ) _20H ,
_C12H25O [ _{CH2CH ( CH3} )O] _{2- ( CH2CH2O} ) _15H ,
_{( C8H17} ) _{( C6H13} )CHO- _{( CH2CH2O} ) _15H ,
_C10H21O [ _{CH2CH ( CH3} )O] _{2- ( CH2CH2O} ) _15H ,
_{C6F13CH2CH2O- ( CH2CH2O ) 15H , _
C6F13CH2CH2O} [ _{CH2CH ( CH3} ) _O ] _{2- ( CH2CH2O ) 15H} ,
_C4F9CH2CH2O [ _{CH2CH ( CH3} ) _O ] _{2- ( CH2CH2O ) 15H} ,
HO—(CH ₂ CH ₂ O) ₁₅ —(C ₃ H ₆ O) ₃₅ —(CH ₂ CH ₂ O) ₁₅ H,
HO—(CH ₂ CH ₂ O) ₈ —(C ₃ H ₆ O) ₁₈ —(CH ₂ CH ₂ O) ₈ H,
_{HO- ( CH2CH2O} ) _{8- ( C3H6O} ) _35- ( _CH2CH2O ) _8H ,
_{HO- ( CH2CH2O} ) _9- ( _C3H6O ) _20- ( _{CH2CH2O ) 9H} ,
HO—(CH ₂ CH ₂ O) ₄₅ —(C ₃ H ₆ O) ₁₇ —(CH ₂ CH ₂ O) ₄₅ H,
_{HO- ( CH2CH2O} ) _{34- ( CH2CH2CH2CH2O} ) _{28- ( CH2CH2O} ) _{34H .}
Commercially available nonionic surfactants can be used, for example, Emulgen 430, Emulgen 420, Emulgen 350, Emulgen 120 (all product names of Kao Corporation), Pronon 204, and Pronon 104 (all product names of NOF Corporation). mentioned.

Preferred specific examples of cationic surfactants include the following compounds.
stearyltrimethylammonium chloride,
cocoalkyltrimethylammonium chloride,
stearyldimethylmonoethylammoniumethylsulfate,
stearyl monomethyl di(polyethylene glycol) ammonium chloride,
fluorohexyltrimethylammonium chloride,
di(tallow alkyl)dimethylammonium chloride,
dimethyl monococonutamine acetate,
amidoamine quaternary ammonium salts described in Japanese Patent No. 5569614;
Commercially available cationic surfactants can be used, such as Lipogard 18-63 and Lipogard C-50 (all product names of Lion Corporation).

Preferred specific examples of amphoteric surfactants include the following compounds.
dodecyl betaine,
stearyl betaine,
dodecyl carboxymethyl hydroxyethyl imidazolinium betaine,
dodecyldimethylaminoacetate betaine,
Fatty acid amidopropyl dimethylamino acetate betaine.
A commercial product can be used as the amphoteric surfactant, for example, AM3130N (manufactured by Nikko Chemicals Co., Ltd.) can be mentioned.

The total amount of the surfactant is preferably 1-10 parts by mass, more preferably 2-8 parts by mass, relative to the copolymer (100 parts by mass).

(Additive)
Additives include penetrating agents, antifoaming agents, water absorbing agents, antistatic agents, anti-wrinkle agents, texture modifiers, film-forming aids, water-soluble polymers (polyacrylamide, polyvinyl alcohol, etc.), heat curing agents (melamine resins, urethane resins, methylol-based resins, etc.), epoxy curing agents (isophthalic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, 1,6-hexamethylenebis(N,N-dimethylsemicarbazide), 1, 1,1′,1′-tetramethyl-4,4′-(methylene-di-para-phenylene) disemicarbazide, spiroglycol, etc.), thermosetting catalysts, crosslinking catalysts, synthetic resins, fiber stabilizers, etc. .

(Method for producing water and oil repellent composition)
The water and oil repellent composition of the present invention can be produced, for example, by the following method (i) or (ii).
(i) In the presence of a surfactant and a polymerization initiator, a monomer component containing monomers b to d and optionally monomers a, e, and f is polymerized and copolymerized in a liquid medium. A method of adding other liquid media, other surfactants, and additives, if necessary, after obtaining a combined solution, dispersion, or emulsion.
(ii) in the presence of a surfactant and a polymerization initiator, a monomer component containing monomers b to d and optionally monomers a, e, and f is polymerized and copolymerized in a liquid medium; A method in which a copolymer is separated after obtaining a solution, dispersion or emulsion of the coalescence, and a liquid medium, a surfactant and, if necessary, an additive are added to the copolymer.
Polymerization methods include a dispersion polymerization method, an emulsion polymerization method, a suspension polymerization method, and the like.

As a method for producing the water and oil repellent composition, in the presence of a surfactant and a polymerization initiator, a monomer containing monomers b to d and optionally monomers a, e, and f in an aqueous liquid medium. A method of obtaining a copolymer emulsion by emulsion polymerization of the polymer component is preferred.
From the viewpoint of improving the yield of the copolymer, it is preferable to pre-emulsify the mixture of the monomers, the surfactant and the aqueous liquid medium before the emulsion polymerization. For example, a mixture comprising a monomer, a surfactant and an aqueous liquid medium is mixed and dispersed using a homomixer or a high-pressure emulsifier.

Examples of polymerization initiators include thermal polymerization initiators, photopolymerization initiators, radiation polymerization initiators, radical polymerization initiators, ionic polymerization initiators, etc. Water-soluble radical polymerization initiators and oil-soluble radical polymerization initiators agents are preferred.
As the radical polymerization initiator, general-purpose initiators such as azo-based polymerization initiators, peroxide-based polymerization initiators and redox-based initiators are used depending on the polymerization temperature. As the radical polymerization initiator, an azo compound is particularly preferable, and when the polymerization is carried out in an aqueous liquid medium, a salt of an azo compound is more preferable.
The polymerization temperature is preferably 20 to 150°C.

A molecular weight modifier may be used in the polymerization of the monomers. As the molecular weight modifier, aromatic compounds, mercaptoalcohols or mercaptans are preferable, and alkylmercaptans are particularly preferable. Molecular weight modifiers include mercaptoethanol, n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, stearylmercaptan, α-methylstyrene dimer (CH ₂ =C(Ph)CH ₂ C(CH ₃ ) ₂ Ph. However, Ph is a phenyl group.) and the like.

The ratio of the monomers a to f in 100% by mass of the monomer component is preferably the same as the ratio of the units a to f described above, since almost no monomers remaining after polymerization are detected. Aspects are also the same.

In the water and oil repellent composition of the present invention, the copolymer is preferably dispersed as particles in the liquid medium. The average particle size of the copolymer is preferably 10-1000 nm, more preferably 10-300 nm, and particularly preferably 10-200 nm. If the average particle size is within this range, there is no need to use a large amount of a surfactant or the like, the water and oil repellency is good, and when dyed fabrics are treated, discoloration does not occur, and the liquid medium Dispersed particles can stably exist in it without sedimentation. The average particle size of the copolymer can be measured using a dynamic light scattering device, an electron microscope, or the like.

The solid content concentration of the water and oil repellent composition of the present invention is preferably 25 to 40% by mass based on 100% by mass of the water and oil repellent composition immediately after the production of the water and oil repellent composition.
The solid content concentration of the water and oil repellent composition of the present invention is preferably 0.2 to 5% by mass based on 100% by mass of the water and oil repellent composition when treating articles.
The solid content concentration of the water and oil repellent composition is calculated from the mass of the water and oil repellent composition before heating and the mass after drying with a convection dryer at 120° C. for 4 hours.

(Mechanism of action)
Since the water and oil repellent composition of the present invention described above contains a copolymer containing b units, c units and d units and the ratio of a units is 1% by mass or less, the water repellent composition By treating an article with the oil repellent composition, it is possible to obtain an article that is water repellent and has excellent friction durability. The article has excellent water repellency, oil repellency, and texture in addition to friction durability.
In addition, in the water and oil repellent composition of the present invention, the copolymer does not necessarily contain a unit based on a monomer having an ^RF group having 7 or more carbon atoms, or rather it is a copolymer that does not contain it. Since it is preferable to ) can be made below the detection limit as an analytical value of LC-MS/MS according to the method described in WO 2009/081822.

<Goods>
The article of the present invention is an article treated with the water and oil repellent composition of the present invention.
Articles to be treated with the water and oil repellent composition of the present invention include fibers (natural fibers, synthetic fibers, blended fibers, etc.), various textile products, nonwoven fabrics, resins, paper, leather, wood, metals, stones, concrete, Examples include gypsum and glass.
The treatment method includes, for example, a method of coating or impregnating the article with the water and oil repellent composition by a known coating method, followed by drying.

When an article is treated with the water and oil repellent composition of the present invention, the film is flexible, so that the texture of the textile product becomes soft and high-grade water and oil repellency can be imparted to the article. In addition, the adhesiveness of the surface is excellent, and water and oil repellency can be imparted even by curing at a low temperature. In addition, there is little deterioration in performance due to friction or washing, and the performance at the initial stage of processing can be stably maintained. In addition, when paper is treated, excellent sizing properties, water repellency, and oil resistance can be imparted to the paper even under low-temperature drying conditions. When treated on a resin, glass or metal surface, it is possible to form a water- and oil-repellent film that has good adhesion to articles and excellent film-forming properties.

EXAMPLES The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these.
Examples 1-7 are working examples, and examples 8-10 are comparative examples.

(oil repellency)
The test fabrics were evaluated for oil repellency according to AATCC-TM118-1966 test method. Oil repellency was represented by the grade shown in Table 1. Grades marked with + (-) indicate that each property is slightly better (worse).

(water repellency)
The test cloth was evaluated for water repellency according to the JIS L 1092 spray test. The water repellency was expressed in five grades from 1 to 5. A higher score indicates better water repellency. Grades marked with +(-) indicate that the respective property is slightly better (worse) than the standard of that grade.

(Water repellent friction durability)
Using a friction tester, the friction surface of the test cloth was rubbed 1000 times or 2000 times, air-dried overnight in a room with a temperature of 25° C. and a humidity of 55%, and then the water repellency of the friction surface of the test cloth was evaluated.

(Washing durability of water repellency)
The test cloth was washed 20 times according to the water washing method in Table 103 of JIS L 0217. After washing, the test fabric was air-dried overnight in a room at a room temperature of 25° C. and a humidity of 55%, and then the water repellency of the test fabric was evaluated.

(texture)
After the test cloth was allowed to stand in a constant temperature and humidity chamber with a room temperature of 20° C.±2° C. and a humidity of 65%±2% for a whole day and night, the flexibility was determined by sensory evaluation according to the following criteria.
○: Soft.
△: Normal.
x: Hard.

(abbreviation)
Monomer a:
_C6FMA : _C6F13C2H4OC (O)C _{( CH3} ) _{= CH2} .

Monomer b:
BeA: behenyl acrylate,
STA: stearyl acrylate.

Monomer c:
PFPE-A: F—CF ₂ O—(CF ₂ CF ₂ O) _g2 —CF ₂ CH ₂ —OC(O)CH═CH ₂ (average of g2: 7, fluorine atoms to total number of fluorine atoms and hydrogen atoms ratio: about 87%),
PFPE-B: G-CH ₂ CF ₂ O-[(CF ₂ O) _f1 -(CF ₂ CF ₂ O) _g1 ]-CF ₂ CH ₂ -G (G: monofunctional urethane methacrylate structure, Fluorolink MD700, Solvay Specialty Polymers company product name, the ratio of fluorine atoms to the total number of fluorine atoms and hydrogen atoms: about 73%),
PFPE-C: G-CH ₂ CF ₂ O-[(CF ₂ O) _f1 -(CF ₂ CF ₂ O) _g1 ]-CF ₂ CH ₂ -G (G: bifunctional urethane methacrylate structure, Fomblin MT70, Solvay Specialty Polymers company product name, ratio of fluorine atoms to the total number of fluorine atoms and hydrogen atoms: about 70%).

monomer d:
VCl: vinyl chloride.

Monomer e:
HEMA: 2-hydroxyethyl methacrylate,
N-MAM: N-methylolacrylamide.

Surfactant s ¹ :
PEO-30: 10 wt% aqueous solution of polyoxyethylene oleyl ether (adduct of ethylene oxide about 30 mol, Emulgen E430, product name of Kao Corporation).

Surfactant ^s3 :
P204: 10% by mass aqueous solution of ethylene oxide propylene oxide polymer (40% by mass of ethylene oxide, Pronon 204, product name of NOF CORPORATION).

Surfactant ^s7 :
TMAC: A mixed solution of 63 mass % isopropyl alcohol and water of stearyltrimethylammonium chloride.

Liquid medium:
DPM: dipropylene glycol monomethyl ether,
Water: deionized water.

Molecular weight modifier:
DoSH: n-dodecyl mercaptan.

Polymerization initiator:
VA061A: 10% by mass aqueous solution of acetate of 2,2′-azobis[2-(2-imidazolin-2-yl)propane] (VA061, product name of Wako Pure Chemical Industries, Ltd.).

[Example 1]
In a glass beaker, 14.7 g of BeA, 0.25 g of HEMA, 6.2 g of PFPE-A, 6.2 g of PEO-30, 0.4 g of TMAC, 1.25 g of P204, 15.0 g of DPM , 30.7 g of water, and 0.25 g of DoSH were added, heated at 60° C. for 30 minutes, and then mixed using a homomixer (Biomixer, product name of Nippon Seiki Seisakusho Co., Ltd.) to obtain a mixed solution.

The resulting mixture was treated at 40 MPa using a high-pressure emulsifier (minilab, product name of APV Ranier) while being kept at 60° C. to obtain an emulsion. The obtained emulsion was placed in a stainless steel reactor and cooled to 40° C. or below. After adding 1.25 g of VA061A and replacing the gas phase with nitrogen, 3.7 g of VCl was added. A polymerization reaction was carried out at 60° C. for 15 hours while stirring to obtain a copolymer emulsion. Table 3 shows the proportion of units based on each monomer.

After diluting the emulsion of the copolymer with distilled water and adjusting the solid content concentration to 1% by mass, a melamine resin cross-linking agent (Beckamine M3, product name of DIC Corporation) and an acid catalyst (Accelerator ACX, product name of DIC Corporation) are added. were added so that each concentration was 0.3% by mass to obtain a water and oil repellent composition.

Dyed nylon taffeta was immersed in the water and oil repellent composition and squeezed so that the wet pick-up was 45% by mass. After drying this at 110° C. for 60 seconds, it was dried at 170° C. for 60 seconds to obtain a test cloth. The test fabric was evaluated for oil repellency, water repellency, water repellent friction durability, water repellent washing durability and feel. Table 4 shows the results.

[Examples 2 to 10]
A copolymer emulsion was obtained in the same manner as in Example 1, except that the types and/or amounts of monomers charged were changed to those shown in Table 2. Table 3 shows the proportion of units based on each monomer.
A water and oil repellent composition was obtained in the same manner as in Example 1, except that the emulsion was used.
A test cloth was obtained in the same manner as in Example 1, except that the water and oil repellent composition was used. The test fabric was evaluated for oil repellency, water repellency, water repellent friction durability, water repellent washing durability and feel. Table 4 shows the results.

The water and oil repellent composition of the present invention can be used for textile products (clothing items (sportswear, coats, blousons, work clothes, uniforms, etc.), bags, industrial materials, etc.), non-woven fabrics, leather products, wood, stone materials, concrete-based It is useful as a water and oil repellent for imparting water and oil repellency to building materials and the like. It is also useful as a filtering material coating agent, a surface protective agent, an electronics coating agent, and an antifouling coating agent used in the presence of an organic solvent liquid or its vapor. Furthermore, it is also useful for imparting water and oil repellency by mixing it with polypropylene, nylon or the like, molding it, and forming it into fibers.

Claims (11)

A copolymer containing a unit based on the following monomer b, a unit based on the following monomer c, and a unit based on the following monomer d, and a liquid medium,
A water and oil repellent composition, wherein the ratio of units based on the following monomer a to units based on all monomers constituting the copolymer is 1% by mass or less.
Monomer b: (meth)acrylate having no polyfluoroalkyl group and having an alkyl group having 12 or more carbon atoms.
Monomer c: A monomer having a poly(oxypolyfluoroalkylene) chain in which the ratio of the number of fluorine atoms to the total number of fluorine atoms and hydrogen atoms is 70% or more.
Monomer d: halogenated olefin.
Monomer a: A compound represented by Formula 1 below.
(ZL) _n X Formula 1.
However, Z is a perfluoroalkyl group having 1 to 6 carbon atoms or a group represented by the following formula 2, L is a divalent organic group or a single bond having no fluorine atom, n is 1 or 2, and X is any of the groups represented by the following formulas 3-1 to 3-5 when n is 1, and when n is 2, the following formulas 4-1 to Any of the groups represented by formula 4-4.
C _s F _2s+1 CH ₂ CF ₂ −(CH ₂ CF ₂ ) _t (CF ₂ CF ₂ ) _u − Formula 2.
However, s is an integer of 1-6, t is an integer of 0-3, and u is an integer of 1-3.
-CR= _CH2 Formula 3-1,
-C(O)OCR= _CH2 formula 3-2,
-OC(O)CR= _CH2 formula 3-3,
-OCH ₂ -φ-CR=CH ₂ formula 3-4,
-OCH=CH ₂ Formula 3-5.
However, R is a hydrogen atom, a methyl group or a halogen atom, and φ is a phenylene group.
-CH[-(CH ₂ ) _m CR=CH ₂ ]- formula 4-1,
—CH[—(CH ₂ ) _m C(O)OCR=CH ₂ ]— Formula 4-2,
—CH[—(CH ₂ ) _m OC(O)CR=CH ₂ ]— Formula 4-3,
-OC(O)CH=CHC(O)O- Formula 4-4.
However, R is a hydrogen atom, a methyl group or a halogen atom, and m is an integer of 0-4. The ratio of units based on the monomer b to units based on all the monomers constituting the copolymer is 30 to 80% by mass,
The ratio of units based on the monomer c to units based on all the monomers constituting the copolymer is 10 to 40% by mass,
2. The water and oil repellent composition according to claim 1, wherein the proportion of structural units based on said monomer d with respect to units based on all monomers constituting said copolymer is 10 to 30% by mass. 3. The water/oil repellent composition according to claim 1, wherein the monomer b is a (meth)acrylate having an alkyl group having 14 to 30 carbon atoms. The water/oil repellent composition according to any one of claims 1 to 3, wherein the monomer b is a (meth)acrylate having an alkyl group having 16 to 24 carbon atoms. The water repellent according to any one of claims 1 to 4, wherein the ratio of units based on the following monomer e to units based on all monomers constituting the copolymer is 10% by mass or less. Oil repellent composition.
Monomer e: a monomer having a crosslinkable functional group. The water repellent according to any one of claims 1 to 5, further comprising a surfactant, wherein the liquid medium is an aqueous liquid medium, and the copolymer is emulsified in the aqueous liquid medium. Oil composition. In the presence of a surfactant and a polymerization initiator, a monomer component containing the following monomer b, the following monomer c, and the following monomer d is polymerized in a liquid medium to form a copolymer. , a method for producing a water and oil repellent composition,
A method for producing a water and oil repellent composition, wherein the ratio of the following monomer a to the entire monomer component is 1% by mass or less.
Monomer b: (meth)acrylate having no polyfluoroalkyl group and having an alkyl group having 12 or more carbon atoms.
Monomer c: A monomer having a poly(oxypolyfluoroalkylene) chain in which the ratio of the number of fluorine atoms to the total number of fluorine atoms and hydrogen atoms is 70% or more.
Monomer d: halogenated olefin.
Monomer a: A compound represented by Formula 1 below.
(ZL) _n X Formula 1.
However, Z is a perfluoroalkyl group having 1 to 6 carbon atoms or a group represented by the following formula 2, L is a divalent organic group or a single bond having no fluorine atom, n is 1 or 2, and X is any of the groups represented by the following formulas 3-1 to 3-5 when n is 1, and when n is 2, the following formulas 4-1 to Any of the groups represented by formula 4-4.
C _s F _2s+1 CH ₂ CF ₂ −(CH ₂ CF ₂ ) _t (CF ₂ CF ₂ ) _u − Formula 2.
However, s is an integer of 1-6, t is an integer of 0-3, and u is an integer of 1-3.
-CR= _CH2 Formula 3-1,
-C(O)OCR= _CH2 formula 3-2,
-OC(O)CR= _CH2 formula 3-3,
-OCH ₂ -φ-CR=CH ₂ formula 3-4,
-OCH=CH ₂ Formula 3-5.
However, R is a hydrogen atom, a methyl group or a halogen atom, and φ is a phenylene group.
-CH[-(CH ₂ ) _m CR=CH ₂ ]- formula 4-1,
—CH[—(CH ₂ ) _m C(O)OCR=CH ₂ ]— Formula 4-2,
—CH[—(CH ₂ ) _m OC(O)CR=CH ₂ ]— Formula 4-3,
-OC(O)CH=CHC(O)O- Formula 4-4.
However, R is a hydrogen atom, a methyl group or a halogen atom, and m is an integer of 0-4. The ratio of the monomer b to the total monomer component is 30 to 80% by mass,
The ratio of the monomer c to the total monomer component is 10 to 40% by mass,
8. The method for producing a water/oil repellent composition according to claim 7, wherein the ratio of said monomer d to said total monomer component is 10 to 30% by mass. The method for producing a water/oil repellent composition according to claim 7 or 8, wherein the ratio of the following monomer e to the entire monomer component is 10% by mass or less.
Monomer e: a monomer having a crosslinkable functional group. An article treated with the water and oil repellent composition according to any one of claims 1 to 6. 11. The article of claim 10, which is a textile product.