JP2014223623A - Filter for mask - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a filter which maintains oil repellency performance even in a high temperature.SOLUTION: A filter is treated with a fluorine-containing processing agent containing a fluorine-containing polymer having (a) a repeating unit induced from fluorine-containing monomer, (b) monomer homopolymer of which has the glass transition point of 50°C or more and/or a repeating unit induced from non-fluorine monomer being (meth)acrylate monomer having a cyclic hydrocarbon group, and (c) a repeating unit induced from hydrophilic monomer.

Description

  The present invention relates to a filter, and more particularly to a filter used in a dust mask, an air filter, a pollen mask, and an antiviral mask.

Conventionally, various filters have been used in, for example, dust masks, air filters (for example, filters for clean rooms and ventilation fans (such as in kitchens), pollen masks, and antiviral masks (for example, Japanese Patent Laid-Open No. Hei 8- 299723, JP2009-6313, JP2012-75802). These filters clean the air by filtering or adsorbing dust, pollen, viruses, oil mist, dust, dirt, sand, etc. floating in the air.
JP-A-8-299723 discloses a dust mask filter manufactured by mixing wool fiber with synthetic resin film slitting yarn. However, this filter has low performance, for example, low oil repellency at high temperatures. The conventional filter has a problem that it does not have oil repellency at a sufficiently high temperature.

JP-A-8-299723 JP 2009-6313 A JP 2012-75802 A

  An object of the present invention is to provide a filter that maintains oil repellency even at high temperatures.

The present invention
(A) a repeating unit derived from a fluorine-containing monomer,
(B) Repeats derived from a non-fluorine monomer in which the monomer homopolymer is a monomer having a glass transition point of 50 ° C. or higher and / or a (meth) acrylate monomer having a cyclic hydrocarbon group Provided is a filter treated with a fluorinated treating agent comprising a fluorinated polymer having a unit and (c) a repeating unit derived from a hydrophilic monomer.
The present invention further provides the above-described fluorinated treatment agent.
In addition, the present invention provides a method for treating a filter characterized by treating a filter substrate with a fluorine-containing treatment agent.
In addition, the present invention provides a dust mask using a filter.

Aspects of the present invention are as follows.
[1]
(A) a repeating unit derived from a fluorine-containing monomer,
(B) Repetition in which the homopolymer of the monomer is derived from a non-fluorine monomer which is a monomer having a glass transition temperature of 50 ° C. or higher and / or a (meth) acrylate monomer having a cyclic hydrocarbon group A filter treated with a fluorine-containing treatment agent comprising a unit and a fluorine-containing polymer having a repeating unit derived from (c) a hydrophilic monomer.
[2]
The filter according to Item [1], which is a filter used in a dust mask, an air filter, a pollen mask, and an antiviral mask.
[3]
The fluorine-containing monomer (a) has the formula:
CH ₂ = C (-X) -C (= O) -YZ-Rf
[Wherein X is a hydrogen atom, a monovalent organic group or a halogen atom,
Y is -O- or -NH-
Z is a direct bond or a divalent organic group,
Rf is a fluoroalkyl group having 1 to 6 carbon atoms. ]
The filter according to Item [1] or [2], which is a compound represented by the formula:
[4]
The non-fluorine monomer (b) has the formula:
CH ₂ = CA-T
[In the formula, A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom);
T is a hydrogen atom, a linear or cyclic hydrocarbon group having 1 to 30 carbon atoms, or a linear or cyclic organic group having 1 to 31 carbon atoms having an ester bond. ]
The filter according to any one of Items [1] to [3], which is a compound represented by the formula:
[5]
The hydrophilic monomer (c) has the formula:
CH ₂ = CX ¹ C (= O) −O− (RO) _n −X ²
[Where:
X ¹ is a hydrogen atom or a methyl group,
X ² is a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, R is an alkylene group having 2 to 6 carbon atoms,
n is an integer of 1 to 200,
It is. ]
The filter in any one of term [1]-[4] which is a compound shown by these.
[6]
The filter according to any one of Items [1] to [5], wherein the complex viscosity of the fluoropolymer is 50000 to 1000000 Pa · s at 50 ° C.
[7]
(A) a repeating unit derived from a fluorine-containing monomer,
(B) Repeats derived from a non-fluorine monomer in which the monomer homopolymer is a monomer having a glass transition point of 50 ° C. or higher and / or a (meth) acrylate monomer having a cyclic hydrocarbon group A fluorine-containing treatment agent for filter treatment comprising a unit and (c) a fluorine-containing polymer having a repeating unit derived from a hydrophilic monomer.
[8]
Item [7] containing a liquid medium.
[9]
Item [7] or [8], wherein the liquid medium is a halogen-containing solvent.
[10]
(A) a repeating unit derived from a fluorine-containing monomer,
(B) Repeats derived from a non-fluorine monomer in which the monomer homopolymer is a monomer having a glass transition point of 50 ° C. or higher and / or a (meth) acrylate monomer having a cyclic hydrocarbon group A method for treating a filter, comprising treating a substrate of the filter with a fluorine-containing treating agent comprising a unit and (c) a fluorine-containing polymer having a repeating unit derived from a hydrophilic monomer.

  The filter of the present invention has excellent oil repellency at high temperatures (for example, 50 ° C. or higher). Even if the filter is thin, the filter of the present invention provides high performance (for example, high temperature oil repellency).

  The filter is used in, for example, a dust mask, an air filter (for example, a filter for a clean room or a ventilation fan (in a kitchen)), a pollen mask, an antiviral mask, a medical mask, and the like. The filter cleans the air by filtering or adsorbing dust, pollen, viruses, oil mist, dust, earth, sand, etc. floating in the air.

For example, a prefilter and a main filter may be used in a dust mask, but the filter of the present invention may be a dust filter prefilter and / or main filter.
The filter is a non-woven fabric, woven fabric or knitted fabric formed from fibers. Basis weight of the filter, 2~5000g / ^{m 2,} may in particular 10 ~ 3000 g / ^{m 2.}
The fiber diameter may be 0.001 μm to 300 μm, especially 0.01 μm to 150 μm, and the fiber length may be 10 μm to 300 mm, especially 1 mm to 200 mm. The aspect ratio (length / diameter) of the fibers may be 10 to 500000, in particular 100 to 50000.

The fiber may be any material, for example, natural fibers (for example, vegetable fibers such as cotton and hemp (especially cellulosic fibers) or animal fibers such as wool (especially protein fibers)). Chemical fibers (such as viscose rayon or rheocell), inorganic fibers (such as carbon fibers or glass fibers), or synthetic fibers (such as polyester, polyamide or acrylic fibers) or fibers (For example, a mixture of natural and synthetic fibers). The fiber may be a synthetic resin. Examples of the synthetic resin are polyolefin (for example, polyethylene, polypropylene), polyester (for example, polyethylene terephthalate), polycarbonate, polyamide, polyurethane, polyvinyl alcohol, and the like.
When the cloth is a non-woven fabric, the non-woven fabric may be produced either dry or wet.

In the filter, the fiber is treated (particularly surface treatment) with a fluorine-containing treatment agent (that is, a surface treatment agent). In this specification, “treatment” means that a treatment agent is applied to an object to be treated (that is, fiber) by dipping, spraying, coating, or the like. By the treatment, the fluoropolymer which is an active ingredient of the treatment agent penetrates into the treatment object and / or adheres to the surface of the treatment object. The treatment is performed before and / or after the fibers are made into a fabric (especially a non-woven fabric).
The amount of the fluorinated treatment agent may be 0.001 to 50% by weight, for example 0.01 to 10% by weight, based on the weight of the filter.
The fluorine-containing treatment agent of the present invention imparts oil repellency at high temperatures (for example, 50 ° C. or higher, for example, 60 to 100 ° C.) to fibers.

In the present invention, the fluorinated treating agent comprises a fluorinated polymer and a liquid medium. The fluorine-containing polymer is
(A) a repeating unit derived from a fluorine-containing monomer,
(B) Repeats derived from a non-fluorine monomer in which the monomer homopolymer is a monomer having a glass transition point of 50 ° C. or higher and / or a (meth) acrylate monomer having a cyclic hydrocarbon group Units and (c) repeating units derived from hydrophilic monomers.

(A) Fluorinated monomer The fluorinated monomer has the formula:
CH ₂ = C (-X) -C (= O) -YZ-Rf
[Wherein X is a hydrogen atom, a monovalent organic group or a halogen atom,
Y is -O- or -NH-
Z is a direct bond or a divalent organic group,
Rf is a fluoroalkyl group having 1 to 6 carbon atoms. ]
It is a fluorine-containing monomer shown by. Z is, for example, a linear alkylene group having 1 to 20 carbon atoms or a branched alkylene group, for example, a group represented by the formula — (CH ₂ ) _x — (wherein x is 1 to 10), Alternatively, a group represented by the formula —SO ₂ N (R ¹ ) R ² — or a formula —CON (R ¹ ) R ² (wherein R ¹ is an alkyl group having 1 to 10 carbon atoms, and R ² is Or a linear alkylene group having 1 to 10 carbon atoms or a branched alkylene group.) Or a formula —CH ₂ CH (OR ³ ) CH ₂ — (wherein R ³ is a hydrogen atom or carbon A group represented by an acyl group of 1 to 10 (for example, formyl or acetyl), or a formula —Ar—CH ₂ — (wherein Ar is an arylene group optionally having a substituent); .) a group represented _{by, - (CH 2) m -SO} 2 - (CH 2) n - group or - (CH _{2) m} S- (CH _{2) n} - group (where, m is 1 to 10, n is 0, a) may be. Specific examples of X are H, Me (methyl group), Cl, Br, I, F, CN, and CF ₃ . X is preferably a hydrogen atom, a methyl group or a chlorine atom.

The fluorine-containing monomer (a) has the general formula:
CH ₂ = C (−X) −C (= O) −Y−Z−Rf (I)
[Wherein, X represents a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (where X ¹ and X ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.), A cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, A substituted or unsubstituted phenyl group;
Y is —O— or —NH—;
Z is a direct bond or an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms or a cyclic aliphatic group,
—CH ₂ CH ₂ N (R ¹ ) SO ₂ — group (where R ¹ is an alkyl group having 1 to 4 carbon atoms) or
-CH ₂ CH (OZ ¹ ) CH ₂ -group (where Z ¹ is a hydrogen atom or an acetyl group) or
— (CH ₂ ) _m —SO ₂ — (CH ₂ ) _n — group or — (CH ₂ ) _m —S— (CH ₂ ) _n — group (where m is 1 to 10, n is 0 to 10, is there),
Rf is a linear or branched fluoroalkyl group having 1 to 6 carbon atoms. ]
An acrylate ester or acrylamide represented by

In the fluorine-containing monomer (a), the α position (of acrylate or methacrylate) may be substituted with a halogen atom or the like. Therefore, in the formula (1), X is a linear or branched alkyl group having 2 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (provided that X ¹ and X ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.), A cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group May be a substituted or unsubstituted phenyl group.

In the above formula (1), the Rf group is preferably a perfluoroalkyl group. The Rf group has 1 to 6 carbon atoms, particularly 4 to 6 carbon atoms. Examples of Rf _{groups, -CF 3, -CF 2 CF 3} , -CF 2 CF 2 CF 3, -CF (CF 3) 2, -CF 2 CF 2 CF 2 CF 3, -CF 2 CF (CF 3) ₂ , -C (CF ₃ ) ₃ ,-(CF ₂ ) ₄ CF ₃ ,-(CF ₂ ) ₂ CF (CF ₃ ) ₂ , -CF ₂ C (CF ₃ ) ₃ , -CF (CF ₃ ) CF ₂ CF ₂ CF ₃ , — (CF ₂ ) ₅ CF ₃ , — (CF ₂ ) ₃ CF (CF ₃ ) _{2 and the} like.

Z is an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms or a cyclic aliphatic group,
—CH ₂ CH ₂ N (R ¹ ) SO ₂ — group (where R ¹ is an alkyl group having 1 to 4 carbon atoms) or
-CH ₂ CH (OZ ¹ ) CH ₂ -group (where Z ¹ is a hydrogen atom or an acetyl group) or
— (CH ₂ ) _m —SO ₂ — (CH ₂ ) _n — group or — (CH ₂ ) _m —S— (CH ₂ ) _n — group (where m is 1 to 10, n is 0 to 10, Preferably). The aliphatic group is preferably an alkylene group (particularly having 1 to 4, for example, 1 or 2 carbon atoms). The aromatic group or cycloaliphatic group may be substituted or unsubstituted. The S group or SO ₂ group may be directly bonded to the Rf group.

Specific examples of the fluorine-containing monomer (a) include, for example, the following, but are not limited thereto.
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ −Rf
CH ₂ = C (−H) −C (= O) −O−C ₆ H ₄ −Rf
CH ₂ = C (−Cl) −C (= O) −O− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CH ₃ ) −C (= O) −O− (CH ₂ ) ₂ −Rf
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ N (−CH ₃ ) SO ₂ −Rf
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ N (−C ₂ H ₅ ) SO ₂ −Rf
CH ₂ = C (-H) -C (= O) -O-CH ₂ CH (-OH) CH ₂ -Rf

CH ₂ = C (-H) -C (= O) -O-CH ₂ CH (-OCOCH ₃ ) CH ₂ -Rf
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (-H) -C (= O) -NH- (CH ₂ ) ₂ -Rf
CH ₂ = C (−CH ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−CH ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CH ₃ ) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ = C (−CH ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (-CH ₃ ) -C (= O) -NH- (CH ₂ ) ₂ -Rf

CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ −Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (-F) -C (= O) -NH- (CH ₂ ) ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -S-Rf
CH ₂ = C (−Cl) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -SO ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CH ₂ ) ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -NH- (CH ₂ ) ₂ -Rf

CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ −Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (-CF ₃ ) -C (= O) -NH- (CH ₂ ) ₂ -Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ −Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (-CF ₂ H) -C (= O) -NH- (CH ₂ ) ₂ -Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ −Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (-CN) -C (= O) -NH- (CH ₂ ) ₂ -Rf

CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ −Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (-CF ₂ CF ₃ ) -C (= O) -NH- (CH ₂ ) ₂ -Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₃ −S−Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₃ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (-F) -C (= O) -NH- (CH ₂ ) ₃ -Rf

CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₃ -S-Rf
CH ₂ = C (−Cl) −C (= O) −O− (CH ₂ ) ₃ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₃ -SO ₂ -Rf
CH ₂ = C (−Cl) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −S−Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₃ −S−Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₃ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ − (CH ₂ ) ₂ −Rf

CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₃ −S−Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₃ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −S−Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
[In the above formula, Rf is a fluoroalkyl group having 1 to 6 carbon atoms. ]

(B) Non-fluorine monomer The non-fluorine monomer (b) is a monomer whose monomer homopolymer has a glass transition point of 50 ° C. or higher (in this specification, “high glass transition point monomer”). And at least one monomer selected from the group consisting of (meth) acrylate monomers having a cyclic hydrocarbon group.
The non-fluorine monomer (b) may be a (meth) acrylate ester.
A specific monomer (for example, cyclohexyl methacrylate) corresponds to both a monomer having a glass transition point of 50 ° C. or higher and a (meth) acrylate monomer having a cyclic hydrocarbon group.

The non-fluorine monomer (b) has the formula:
CH ₂ = CA-T
[In the formula, A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom);
T is a hydrogen atom, a linear or cyclic hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20), or a linear or cyclic carbon number having an ester bond of 1 to 31 (for example, 1 to 20). Is an organic group. ]
It may be a compound shown by these.

  Examples of the linear or cyclic hydrocarbon group having 1 to 30 carbon atoms include linear or branched aliphatic hydrocarbon groups having 1 to 30 carbon atoms, cyclic aliphatic groups having 4 to 30 carbon atoms, and 6 to 6 carbon atoms. 30 aromatic hydrocarbon groups, and C 7-30 araliphatic hydrocarbon groups.

  Examples of the linear or cyclic organic group having 1 to 31 carbon atoms having an ester bond are -C (= O) -OQ and -OC (= O) -Q (where Q is 1-30 carbon atoms). A straight or branched aliphatic hydrocarbon group, a cyclic aliphatic group having 4 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an araliphatic hydrocarbon group having 7 to 30 carbon atoms). . Straight chain or branched aliphatic hydrocarbon group having 12 to 30 carbon atoms (particularly 18 to 30), cyclic aliphatic group having 4 to 30 carbon atoms, aromatic hydrocarbon group having 6 to 30 carbon atoms, and 7 to 7 carbon atoms 30 araliphatic hydrocarbon groups are preferable, linear or branched aliphatic hydrocarbon groups having 12 to 30 carbon atoms (particularly 18 to 30), and cyclic aliphatic groups having 4 to 30 carbon atoms are particularly preferable.

A high glass transition point monomer (ie, a high Tg monomer) is a monomer whose monomer homopolymer has a glass transition temperature of 50 ° C. or higher, preferably 55 ° C. or higher, particularly 60 ° C. or higher. is there. The glass transition temperature of the homopolymer of the high glass transition point monomer may be 230 ° C. or lower, for example, 200 ° C. or lower.
The glass transition point (glass transition temperature) of the homopolymer was obtained by using a differential scanning calorimeter (Metler, DSC822e) to obtain a DSC curve by heating 10 mg of the sample at 10 ° C./min. It can be determined as the temperature indicating the intersection of the baseline extension before and after the next transition and the tangent at the inflection point of the DSC curve.

Preferred examples of high Tg monomers include
Cyclohexyl acrylate, isobornyl acrylate, bornyl acrylate, adamantyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, tricyclodecanyl acrylate, phenyl acrylate, naphthyl acrylate, benzyl acrylate, 2-t-butylphenyl acrylate, naphthyl Acrylate esters such as acrylates;
Methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, bornyl methacrylate, adamantyl methacrylate, dicyclopentanyl methacrylate, dicyclopentenyl methacrylate, tricyclodecanyl methacrylate, phenyl methacrylate, naphthyl Methacrylate esters such as methacrylate, benzyl methacrylate, (2-dimethylamino) ethyl methacrylate, aziridinyl methacrylate, aziridylinyl ethyl methacrylate, dicyclopentenyl methacrylate;
Although chloroacrylate ester, such as methyl chloroacrylate, can be illustrated, it is not limited to these.

The non-fluorine monomer (b) may be a (meth) acrylate ester which is an ester of a hydrocarbon group (particularly an alkyl group) and (meth) acrylic acid. The number of carbon atoms of the hydrocarbon group (particularly an alkyl group) may be 1 to 30, for example, 6 to 30 (for example, 10 to 30).
For example, the non-fluorine monomer (b) has the general formula:
CH ₂ = CA ¹ COOA ²
[Wherein, A ¹ is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom),
A ² is an alkyl group having 1 to 30 carbon atoms and / or a cyclic hydrocarbon group having 4 to 30 carbon atoms. ]
An acrylate represented by Alkyl groups (straight or branched) may be represented by C _n H _{2n + 1} (n = 1-30) and cyclic hydrocarbon groups may be C _m H _2m-1 or C _m H _2m-3 (m = 4˜ 30, for example m = 5-25).

  The non-fluorine monomer (b) may be a (meth) acrylate monomer having a cyclic hydrocarbon group. The (meth) acrylate monomer having a cyclic hydrocarbon group is a compound having a (preferably monovalent) cyclic hydrocarbon group and a monovalent (meth) acrylate group. The monovalent cyclic hydrocarbon group and the monovalent (meth) acrylate group are directly bonded. Examples of the cyclic hydrocarbon group include saturated or unsaturated monocyclic groups, polycyclic groups, and bridged cyclic groups. The cyclic hydrocarbon group is preferably saturated. The cyclic hydrocarbon group preferably has 4 to 20 carbon atoms. Examples of the cyclic hydrocarbon group include a cyclic aliphatic group having 4 to 20 carbon atoms, particularly 5 to 12 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and an araliphatic group having 7 to 20 carbon atoms. The number of carbon atoms of the cyclic hydrocarbon group is particularly preferably 15 or less, for example 10 or less. It is preferred that the carbon atom in the ring of the cyclic hydrocarbon group is directly bonded to the ester group in the (meth) acrylate group. The cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group. Specific examples of the cyclic hydrocarbon group are a cyclohexyl group, a t-butylcyclohexyl group, an isobornyl group, a dicyclopentanyl group, and a dicyclopentenyl group. The (meth) acrylate group is an acrylate group or a methacrylate group, but is preferably a methacrylate group. Specific examples of the monomer having a cyclic hydrocarbon group include cyclohexyl methacrylate, t-butylcyclohexyl methacrylate, benzyl methacrylate, isobornyl methacrylate, isobornyl acrylate, dicyclopentanyl methacrylate, dicyclopentanyl acrylate, And cyclopentenyl acrylate.

  By using non-fluorine monomer (b) (especially high Tg monomer), the polymer can maintain its hardness even at high temperatures (50 ° C or higher, especially 60 ° C or higher) and maintain oil repellency. it can.

(C) Hydrophilic monomer The hydrophilic monomer (namely, water-soluble monomer) (c) is a monomer having a hydrophilic group (for example, a hydroxyl group or an oxyalkylene group). The hydrophilic monomer (c) preferably has a hydrophilic group that is an oxyalkylene group (an alkylene group having 2 to 6 carbon atoms). It is preferable that the hydrophilic monomer (c) does not contain a fluorine atom.
The hydrophilic monomer (c) may be a monomer having a hydrophilic group which is an oxyalkylene group (an alkylene group having 2 to 6 carbon atoms) and a carbon-carbon double bond. The hydrophilic monomer (c) may be a (meth) acrylate having an oxyalkylene group.
The hydrophilic group which is an oxyalkylene group is nonionic. The number of oxyalkylene groups in the hydrophilic monomer (c) may be 1 to 200, for example 2 to 50.
The hydrophilic monomer (c) may be alkylene glycol mono (meth) acrylate [monoalkylene glycol mono (meth) acrylate or polyalkylene glycol mono (meth) acrylate] or polyalkylene glycol di (meth) acrylate.
The molecular weight of the hydrophilic monomer (c) may be 100 to 3000.

The alkylene glycol mono (meth) acrylate has the formula:
CH ₂ = CX ¹ C (= O) −O− (RO) _n −X ²
[Where:
X ¹ is a hydrogen atom or a methyl group,
X ² is a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, R is an alkylene group having 2 to 6 carbon atoms,
n is an integer of 1 to 200,
It is. ]
It is preferable that it is a compound shown by these. n may in particular be 1-100, for example 2-30.

R in the formula is particularly preferably an ethylene group. R in the formula may be a combination of two or more alkylene groups. In that case, at least one of R is preferably an ethylene group. Examples of the combination of R include an ethylene group / propylene group combination and an ethylene group / butylene group combination.
The hydrophilic monomer (c) may be a mixture of two or more. It is preferred that the case is at least a hydrophilic monomer (c) in one formula ^{_{(CH 2 = CX 1 C (}} = O) -O- (RO) n -X 2) R in is an ethylene group .

Specific examples of the hydrophilic monomer (c) include, for example, the following, but are not limited thereto.
CH ₂ = CX ¹ COO- (CH ₂ CH ₂ O) _n -H
CH ₂ = CX ^1- (CH ₂ CH ₂ O) _n -CH ₃
CH ₂ = CX ¹ COO- (CH ₂ CH (CH ₃ ) O) _n -H
CH ₂ = CX ¹ COO- (CH ₂ CH (CH ₃ ) O) _n -CH ₃
CH ₂ = CX ¹ COO- (CH ₂ CH ₂ O) _5- (CH ₂ CH (CH ₃ ) O) ₂ -H
CH ₂ = CX ¹ COO- (CH ₂ CH ₂ O) _5- (CH ₂ CH (CH ₃ ) O) ₃ -CH _{3
^{CH 2 = CX 1 COO- (CH}} 2 CH 2 O) 8 - (CH 2 CH (CH 3) O) 6 -CH 2 CH (C 2 H 5) C 4 H 9
CH ₂ = CX ¹ COO- (CH ₂ CH ₂ O) ₂₃ -OOC (CH ₃ ) C = CH _{2
^{CH 2 = CX 1 COO- (CH}} 2 CH 2 O) 20 - (CH 2 CH (CH 3) O) 5 -CH 2 -CH = CH 2
[Wherein X ¹ represents a hydrogen atom or a methyl group,
n is an integer of 1 to 200. ]

In the fluorine-containing polymer, with respect to 100 parts by weight of the fluorine-containing monomer (a),
The amount of the non-fluorine monomer (b) is 2 to 500 parts by weight, such as 5 to 200 parts by weight, particularly 10 to 150 parts by weight,
The amount of hydrophilic monomer (c) may be 1 to 500 parts by weight, for example 2 to 200 parts by weight, in particular 5 to 150 parts by weight.

The weight average molecular weight of the copolymer of the present invention may be 1,000 to 1,000,000, preferably 5,000 to 500,000. The weight average molecular weight is a value obtained by gel permeation chromatography in terms of polystyrene.
The weight average molecular weight is preferably low, for example 1000-50000, in particular 2000-20000. By having a low weight average molecular weight, the fluoropolymer is easily dissolved in a solvent, and stable high temperature oil repellency can be obtained.

  The complex viscosity η * (Pa · s) of the fluoropolymer is preferably 50,000 to 1,000,000 Pa · s at 50 ° C, or 5,000 to 100,000 Pa · s at 70 ° C. The complex viscosity is obtained under the conditions of a sample amount of 1.0 g and a frequency of 0.5 Hz using a dynamic viscoelasticity measuring device Rheosol-G3000 (manufactured by UBM Co., Ltd.).

In the present invention, the monomers (a) to (c) are particularly preferably as follows:
(A) C6FMA (methacrylate monomer having C6 fluoroalkyl group)
(B) CHMA (cyclohexyl methacrylate monomer)
(C) HEMA (2-hydroxyethyl methacrylate monomer)

The fluoropolymer in the present invention can be produced by any ordinary polymerization method, and the polymerization reaction conditions can be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization. Solution polymerization is preferred.
The method for obtaining the organic solvent solution of the fluoropolymer is not limited. For example, after producing a fluoropolymer by emulsion polymerization in water, water is removed and an organic solvent is added to obtain an organic solvent solution of the fluoropolymer.

  In solution polymerization, a method in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen substitution, is heated and stirred in the range of 30 to 120 ° C. for 1 to 10 hours. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, and the like. Can be mentioned. The polymerization initiator is used in the range of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.

  The organic solvent is inactive to the monomer and dissolves them. For example, an ester (for example, an ester having 2 to 30 carbon atoms, specifically, ethyl acetate or butyl acetate), a ketone (for example, carbon It may be a ketone having 2 to 30 (specifically, methyl ethyl ketone, diisobutyl ketone) or an alcohol (for example, an alcohol having 1 to 30 carbon atoms, specifically, isopropyl alcohol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, Examples include diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, and trichlorotrifluoroethane. The organic solvent is used in the range of 10 to 2000 parts by weight, for example, 50 to 1000 parts by weight with respect to 100 parts by weight of the total amount of monomers.

  The dilution solvent is preferably a halogen-containing solvent, particularly a chlorine-containing solvent such as trichloroethylene. By using a halogen-containing solvent, the performance of the filter is improved.

  In emulsion polymerization, a method is employed in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen substitution, is stirred and copolymerized in the range of 50 to 80 ° C. for 1 to 10 hours. . Polymerization initiators include benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, azo Water-soluble materials such as bisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide Oil-soluble ones such as t-butyl peroxypivalate and diisopropyl peroxydicarbonate are used. The polymerization initiator is used in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.

  In order to obtain an aqueous copolymer dispersion having excellent storage stability, the monomer is finely divided into water using an emulsifier that can impart strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer. It is desirable to polymerize using a soluble polymerization initiator. As the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and the emulsifier is used in the range of 0.5 to 20 parts by weight with respect to 100 parts by weight of the monomer. Preference is given to using anionic and / or nonionic and / or cationic emulsifiers. When the monomers are not completely compatible with each other, it is preferable to add a compatibilizing agent such as a water-soluble organic solvent or a low molecular weight monomer that is sufficiently compatible with these monomers. By adding a compatibilizing agent, it is possible to improve emulsifying properties and copolymerization properties.

  Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol and the like, and 1 to 50 parts by weight with respect to 100 parts by weight of water. For example, you may use in the range of 10-40 weight part. Examples of the low molecular weight monomer include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc., and 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of monomers, For example, you may use in the range of 10-40 weight part.

  In the polymerization, a chain transfer agent may be used. Depending on the amount of chain transfer agent used, the molecular weight of the fluoropolymer can be varied. Examples of chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (particularly alkyl mercaptans (for example, having 1 to 30 carbon atoms)), inorganic salts such as sodium hypophosphite and sodium bisulfite. Etc. You may use the usage-amount of a chain transfer agent in 0.01-10 weight part with respect to 100 weight part of total amounts of a monomer, for example, 0.1-5 weight part.

  The fluoropolymer can be applied to the fibrous substrate by any of the methods known for treating textiles with liquids. The concentration of the fluoropolymer in the solution applied to the fiber may be, for example, 0.05 wt% to 50 wt%, or 0.5 wt% to 10 wt%. The fiber fabric may be dipped into the solution, or the solution may be deposited or sprayed onto the fiber fabric. The treated fabric is dried and preferably heated at, for example, 100 ° C. to 200 ° C. in order to develop oil repellency.

The fluorinated treating agent in the present invention is preferably in the form of a solution, an emulsion or an aerosol. The fluorinated treating agent comprises a fluorinated polymer (active component of the fluorinated treating agent) and a medium (particularly, a liquid medium such as an organic solvent and / or water). In the fluorinated treatment agent, the concentration of the fluorinated polymer may be, for example, 0.01 to 80% by weight.
In the fluorine-containing treatment agent, the concentration of the fluorine-containing polymer may be 0.01 to 95% by weight, for example, 0.1 to 50% by weight.

  The fluorinated treating agent in the present invention is preferably a solution or dispersion containing a fluorinated polymer and an organic solvent. The organic solvent is an ester (for example, an ester having 2 to 30 carbon atoms, specifically ethyl acetate or butyl acetate), a ketone (for example, a ketone having 2 to 30 carbon atoms, specifically methyl ethyl ketone or diisobutyl ketone). , Alcohol (for example, alcohol having 1 to 30 carbon atoms, specifically, isopropyl alcohol), more preferably isopropyl alcohol. Alternatively, the organic solvent may be a petroleum-based organic solvent and / or a hydrocarbon-based organic solvent, more preferably a petroleum-based hydrocarbon and / or an aliphatic hydrocarbon. Other preferred examples of organic solvents include halogen-containing hydrocarbons, especially hydrocarbons that are at least partially substituted with chlorine atoms (preferably having a carbon number of 1-10, especially 2-5), such as 1,1,2, 2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, and trichlorotrifluoroethane.

Next, an Example, a comparative example, and a test example are given and this invention is demonstrated concretely. However, these explanations do not limit the present invention.
In the following, parts or% represents parts by weight or% by weight unless otherwise specified.
The test procedure is as follows.

[Collection efficiency]
Air containing dioctyl phthalate (particle diameter: 0.15 to 0.25 μm, concentration: about 25 mg / m ³ ) is passed through the filter attached to the particle collection efficiency measuring instrument at a flow rate of 85 L / min. In the process until dioctyl phthalate supplied to 200 mg reached 200 mg, the concentration of dioctyl phthalate before and after passing through the filter was continuously measured by a dioctyl phthalate concentration measuring device using a scattered light method. The collection efficiency is calculated by (DOP concentration after sample aeration) / (DOP concentration before sample aeration) × 100%. When the collection efficiency is 95% or more, “◯”, and when it is less than 95%, “× The evaluation results were recorded.

[Intake resistance value]
The pressure difference between the inside and outside was measured when air was passed through the filter attached to the ventilation resistance tester at a flow rate of 40 L / min. When the pressure difference was 80 Pa or less, the evaluation result was recorded as “◯”, and when it was larger than 80 Pa, the evaluation result was recorded as “x”.

[High temperature oil repellency test]
One drop each of n-hexadecane and oleic acid heated to 50 ° C. is dropped on the evaluation fabric (cloth), and after 15 seconds, the droplet is wiped off and the state of penetration is observed. The evaluation result was recorded as “◯” when there was no soaking, “Δ” when there was a slight soaking mark, and “X” when soaking was seen.

Synthesis example 1
A reactor having a volume of 300 ml equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet and a heating device was prepared, and 45 parts of the solvent isopropyl alcohol (IPA) was added. Subsequently, under stirring, F (CF ₂ ) ₆ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ (referred to as “C6FMA”) 60 parts, cyclohexyl methacrylate (CHMA) 25 parts and 2-hydroxyethyl methacrylate ( HEMA) 5 parts of chain transfer agent lauryl mercaptan (L-SH) is added to 15 parts monomer (monomer total 100 parts), 1 part perpivalic acid-t-butyl initiator is added in this order, This mixture was mixed and stirred for 12 hours under a nitrogen atmosphere at 60 ° C. to carry out copolymerization. Next, this reaction mixture was cooled to room temperature to obtain a fluorinated copolymer solution (S1). The solid content concentration of this solution was 70% by weight. The monomer composition of the fluorinated copolymer almost coincided with the charged monomer composition. The weight average molecular weight of the fluorinated copolymer was 9000.

Synthesis example 2
Monomer consisting of 65 parts of F (CF ₂ ) ₆ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ (C6FMA), 20 parts of isobornyl methacrylate (IBMA), 15 parts of 2-hydroxyethyl methacrylate (HEMA) In the same manner as in Synthesis Example 1, except that 5 parts of chain transfer agent lauryl mercaptan (L-SH) and 1 part of perpivalic acid-t-butyl initiator are added in this order to 100 parts in total. Polymerization and post-treatment were performed to obtain a fluorinated copolymer solution (S2). The monomer composition of the fluorinated copolymer almost coincided with the charged monomer composition.

Synthesis example 3
F (CF ₂ ) ₆ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ (C6FMA) 60 parts, cyclohexyl methacrylate (CHMA) 30 parts, 2-hydroxyethyl methacrylate (HEMA) 10 parts (monomer total 100) In the same manner as in Synthesis Example 1, except that 5 parts of chain transfer agent lauryl mercaptan (L-SH) is added and 1 part of perpivalic acid-t-butyl initiator is added in this order. Post-treatment was performed to obtain a fluorinated copolymer solution (S3). The monomer composition of the fluorinated copolymer almost coincided with the charged monomer composition.

Synthesis example 4
A reactor having a volume of 300 ml equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet and a heating device was prepared, and 45 parts of the solvent isopropyl alcohol (IPA) was added. Subsequently, under stirring, a monomer comprising 60 parts of F (CF ₂ ) ₆ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ (referred to as “C6FMA”) and 40 parts of stearyl acrylate (StA) (monomer total 100 parts) ), 5 parts of chain transfer agent lauryl mercaptan (L-SH) is added, 1 part of perpivalic acid-t-butyl initiator is added in this order, and the mixture is added under a nitrogen atmosphere at 60 ° C. for 12 hours. The mixture was stirred and copolymerized. The solid content concentration of the obtained copolymer-containing solution (R1) was 70% by weight. The monomer composition of the fluorinated copolymer almost coincided with the charged monomer composition. The weight average molecular weight of the fluorinated copolymer was 6000.

Synthesis example 5
F (CF ₂ ) ₈ CH ₂ CH ₂ OCOCH═CH ₂ (C8FA) 70 parts, stearyl acrylate (StA) 33 parts, polyethylene glycol dimethacrylate CH ₂ ═C (CH ₃ ) COO— (CH ₂ CH ₂ O) _n -COC (CH ₃ ) = CH ₂ (NK ester 23G, manufactured by Shin-Nakamura Chemical Co., Ltd., polyoxyethylene group average polymerization degree n≈23) Copolymerization and post-treatment were performed in the same manner as in Synthesis Example 4 except that 1 part of pivalic acid-t-butyl was added in this order to obtain a fluorinated copolymer solution (R2). The monomer composition of the fluorinated copolymer almost coincided with the charged monomer composition.

Synthesis Example 6
F (CF ₂ ) ₆ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ (C6FMA) 60 parts, stearyl acrylate (StA) 30 parts, 2-hydroxyethyl methacrylate (HEMA) 10 parts (monomers total 100) In the same manner as in Synthesis Example 4, except that 5 parts of chain transfer agent lauryl mercaptan (L-SH) is added and 1 part of perpivalic acid-t-butyl initiator is added in this order. Post-treatment was performed to obtain a fluorinated copolymer solution (R3). The monomer composition of the fluorinated copolymer almost coincided with the charged monomer composition.

Preparation Example 1
Trichloroethylene 293.57 g was added to 6.43 g of the fluorine-containing copolymer solution (S1) obtained in Synthesis Example 1 and diluted to obtain a solvent dispersion liquid (SD1) having a solid content concentration of 1.5 wt%. .

Preparation Examples 2 and 3
The fluorine-containing copolymer solutions (S2 and S3) obtained in Synthesis Examples 2 and 3 were diluted with trichlorethylene in the same manner as in Preparation Example 1 to obtain a solvent dispersion (SD2 and S2) having a solid content concentration of 1.5 wt%. SD3) was obtained respectively.

Comparative Preparation Example 1
The fluorine-containing copolymer solution (R1) obtained in Synthesis Example 4 was diluted with trichlorethylene in the same manner as in Preparation Example 1 to obtain a solvent dispersion (RD1) having a solid content concentration of 1.5 wt%.

Comparative Preparation Examples 2 and 3
The fluorine-containing copolymer solutions (R2 and R3) obtained in Synthesis Examples 5 and 6 were diluted with trichlorethylene in the same manner as in Preparation Example 1 to obtain a solvent dispersion (RD2 and RD3) was obtained.

Example 1
A non-woven filter material of 500 g / m ² formed of wool fibers is immersed in the fluorinated copolymer solvent dispersion (SD1) of Preparation Example 10 for 10 seconds, then taken out and dried at room temperature for 12 hours to obtain a treated filter. It was.
Table 1 shows the performance evaluation results of the obtained treatment filter.

  The polyester cloth was immersed in the fluorine-containing copolymer solvent dispersion (SD1) of Preparation Example 10 for 10 seconds, then taken out and dried at room temperature for 12 hours to obtain a treated cloth. Table 1 shows the performance evaluation results of the obtained treated cloth.

Examples 2-3
Instead of SD1 of the fluorinated copolymer solvent dispersion in Example 1, the solvent dispersions SD2 to SD3 of the fluorinated copolymer obtained in Preparation Examples 2 to 3 were used, respectively. The experiment was conducted. Table 1 shows the performance evaluation results of the treatment filter and treatment cloth obtained.

Comparative Examples 1-3
Instead of SD1 of the fluorinated copolymer solvent dispersion in Example 1, it was the same as in Example 1 except that each of the fluorinated copolymer solvent dispersions RD1 to RD3 obtained in Comparative Preparation Examples 1 to 3 was used. The experiment was conducted. Table 1 shows the performance evaluation results of the treatment filter and treatment cloth obtained.

  The filter of the present invention is used in dust masks, air filters, pollen masks, and antiviral masks.

Claims (11)

(A) Formula:
CH ₂ = C (-X) -C (= O) -YZ-Rf
[Wherein X is a hydrogen atom, a monovalent organic group or a halogen atom,
Y is -O- or -NH-
Z is a direct bond or a divalent organic group,
Rf is a fluoroalkyl group having 1 to 6 carbon atoms. ]
A repeating unit derived from a fluorine-containing monomer, which is a compound represented by
(B) Formula:
CH ₂ = CA ¹ COOA ²
[Wherein, A ¹ is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom),
A ² is a cyclic hydrocarbon group having 4 to 30 carbon atoms. ]
A repeating unit derived from a non-fluorine monomer which is an acrylate represented by formula (c):
CH ₂ = CX ¹ C (= O) −O− (RO) _n −X ²
[Where:
X ¹ is a hydrogen atom or a methyl group,
X ² is a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, R is an alkylene group having 2 to 6 carbon atoms,
n is an integer of 1 to 200,
It is. ]
A filter having a repeating unit derived from a hydrophilic monomer that is a compound represented by the formula (II) and treated with a fluorinated treating agent comprising a fluorinated polymer having a weight average molecular weight of 1,000 to 20,000. The filter according to claim 1, which is a filter used in a dust mask, an air filter, a pollen mask, or an antiviral mask. The cyclic hydrocarbon group is a cyclohexyl group, t-butylcyclohexyl group, isobornyl group, dicyclopentanyl group, dicyclopentenyl group, bornyl group, adamantyl group, tricyclodecanyl group, phenyl group, or naphthyl group. Item 3. The filter according to Item 1 or 2. The filter according to any one of claims 1 to 3, wherein the fluoropolymer has a complex viscosity of 500000 to 1000000 Pa · s at 50 ° C. The filter according to any one of claims 1 to 4, wherein the fluorinated treatment agent is a solution or dispersion containing a liquid medium that is an organic solvent. The filter according to any one of claims 1 to 5, wherein the fluoropolymer has a weight average molecular weight of 2000 to 20000. (A) Formula:
CH ₂ = C (-X) -C (= O) -YZ-Rf
[Wherein X is a hydrogen atom, a monovalent organic group or a halogen atom,
Y is -O- or -NH-
Z is a direct bond or a divalent organic group,
Rf is a fluoroalkyl group having 1 to 6 carbon atoms. ]
A repeating unit derived from a fluorine-containing monomer, which is a compound represented by
(B) Formula:
CH ₂ = CA ¹ COOA ²
[Wherein, A ¹ is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom),
A ² is a cyclic hydrocarbon group having 4 to 30 carbon atoms. ]
A repeating unit derived from a non-fluorine monomer which is an acrylate represented by formula (c):
CH ₂ = CX ¹ C (= O) −O− (RO) _n −X ²
[Where:
X ¹ is a hydrogen atom or a methyl group,
X ² is a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, R is an alkylene group having 2 to 6 carbon atoms,
n is an integer of 1 to 200,
It is. ]
The fluorine-containing processing agent for filter processing containing the fluorine-containing polymer which has a repeating unit induced | guided | derived from the hydrophilic monomer which is a compound shown by and has a weight average molecular weight 1000-20000. The fluorine-containing treatment agent according to claim 7, which is a solution or dispersion containing a liquid medium that is an organic solvent. The fluorinated treating agent according to claim 7 or 8, wherein the liquid medium is a halogen-containing solvent. (A) Formula:
CH ₂ = C (-X) -C (= O) -YZ-Rf
[Wherein X is a hydrogen atom, a monovalent organic group or a halogen atom,
Y is -O- or -NH-
Z is a direct bond or a divalent organic group,
Rf is a fluoroalkyl group having 1 to 6 carbon atoms. ]
A repeating unit derived from a fluorine-containing monomer, which is a compound represented by
(B) Formula:
CH ₂ = CA ¹ COOA ²
[Wherein, A ¹ is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom),
A ² is a cyclic hydrocarbon group having 4 to 30 carbon atoms. ]
A repeating unit derived from a non-fluorine monomer which is an acrylate represented by formula (c):
CH ₂ = CX ¹ C (= O) −O− (RO) _n −X ²
[Where:
X ¹ is a hydrogen atom or a methyl group,
X ² is a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, R is an alkylene group having 2 to 6 carbon atoms,
n is an integer of 1 to 200,
It is. ]
Treating the filter substrate with a fluorinated treating agent comprising a fluorinated polymer having a repeating unit derived from a hydrophilic monomer that is a compound represented by formula (II) and having a weight average molecular weight of 1,000 to 20,000. Characteristic filter processing method. (A) Formula:
CH ₂ = C (-X) -C (= O) -YZ-Rf
[Wherein X is a hydrogen atom, a monovalent organic group or a halogen atom,
Y is -O- or -NH-
Z is a direct bond or a divalent organic group,
Rf is a fluoroalkyl group having 1 to 6 carbon atoms. ]
A repeating unit derived from a fluorine-containing monomer, which is a compound represented by
(B) Formula:
CH ₂ = CA ¹ COOA ²
[Wherein, A ¹ is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom),
A ² is a cyclic hydrocarbon group having 4 to 30 carbon atoms. ]
A repeating unit derived from a non-fluorine monomer which is an acrylate represented by formula (c):
CH ₂ = CX ¹ C (= O) −O− (RO) _n −X ²
[Where:
X ¹ is a hydrogen atom or a methyl group,
X ² is a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, R is an alkylene group having 2 to 6 carbon atoms,
n is an integer of 1 to 200,
It is. ]
A fluorine-containing treatment agent for filter treatment comprising a fluorine-containing polymer consisting of only a repeating unit derived from a hydrophilic monomer which is a compound represented by formula (II) and having a weight average molecular weight of 1,000 to 20,000.