JP2020172715A - Method for producing moisture-permeable waterproof fabric - Google Patents

Abstract

To provide a method for producing a moisture-permeable waterproof fabric for producing a moisture-permeable waterproof fabric excellent in peeling strength and water-repellent and oil-repellent properties which prevents strike-through of a coating composition for forming a moisture-permeable waterproof layer when a moisture-permeable waterproof layer is formed on a fabric treated with a water-repellent and oil-repellent agent composition.SOLUTION: A method for producing a moisture-permeable waterproof fabric includes: bringing a water-repellent and oil-repellent agent composition containing a fluorine-containing polymer, a liquid medium and a surface active agent into contact with a surface of a fiber base material; forming a layer containing the fluorine-containing polymer on at least one surface of the fiber base material; bringing a liquid containing a coating resin into contact with the surface of the layer containing the fluorine-containing polymer; and forming a moisture-permeable waterproof layer containing the coating resin.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a moisture permeable waterproof fabric.

In textile products whose surface has been treated with a water- and oil-repellent composition containing a fluorine-containing polymer, the back surface is moisture-permeable and waterproof in order to provide a function of releasing water vapor by sweating from the body and a function of preventing rain from entering. Layers may be provided.
A coating method is well known as a method for producing a fabric having a moisture permeable and waterproof layer. The coating method is a method in which a coating liquid for forming a moisture-permeable waterproof layer is applied to one side of the fabric and cured to form a moisture-permeable waterproof layer having fine pores on the fabric.
The moisture-permeable waterproof layer formed on the fabric is required not to be easily peeled off from the surface of the fabric. For this purpose, it is desirable that when the coating liquid is applied to the fabric, the coating liquid soaks into the fibers to some extent to form a moisture-permeable waterproof layer.
However, when the coating liquid permeates the inside of the fiber excessively and escapes from one side of the cloth coated with the coating liquid to the other side, a moisture-permeable waterproof layer is formed on both sides of the cloth, and the surface of the cloth is white. The design and texture are impaired.
Therefore, conventionally, the surface of the fabric has been treated with a water-repellent and oil-repellent composition to suppress excessive penetration of the coating composition for forming a moisture-permeable and waterproof layer into the fabric.

Patent Document 1 describes chloride, a unit having a polyfluoroalkyl group having 1 to 6 carbon atoms, as a water-repellent oil-repellent composition capable of suppressing permeation of a coating liquid for forming a moisture-permeable waterproof layer and peeling of the moisture-permeable waterproof layer. A copolymer containing a vinylidene or vinylidene fluoride unit and an acrylate or methacrylate unit having a saturated hydrocarbon group having 12 or more carbon atoms, and a unit having a polyfluoroalkyl group having 1 to 6 carbon atoms, vinylidene chloride or fluoride. A water- and oil-repellent composition containing a copolymer containing a vinylidene unit, an acrylate or methacrylate unit having a saturated hydrocarbon group having 12 or more carbon atoms, and a vinyl chloride unit, and a liquid medium is described.
Patent Document 2 describes a unit having a polyfluoroalkyl group having 1 to 6 carbon atoms as a water-repellent oil-repellent composition capable of providing an article having excellent design by suppressing the penetration of a coating liquid for forming a moisture-permeable waterproof layer. A water- and oil-repellent composition containing a copolymer (X) containing a vinyl chloride unit and having a mass average molecular weight of 60,000 or more and an aqueous medium is described.

International Publication No. 2015/080060 International Publication No. 2012/147700

However, the moisture-permeable waterproof fabric produced by applying the coating liquid for forming the moisture-permeable waterproof layer to the fabric treated with the water-repellent and oil-repellent composition described in Patent Document 1 and Patent Document 2 is a moisture-permeable waterproof layer. Both the peeling strength and the water-repellent washing durability were not sufficient.

Therefore, in the present invention, when the moisture-permeable waterproof layer is formed on the fabric treated with the water-repellent and oil-repellent composition, the coating composition for forming the moisture-permeable and waterproof layer does not strike through, resulting in peeling strength and water-repellent and oil-repellent properties. It is an object of the present invention to provide a method for producing a moisture permeable waterproof fabric for producing an excellent moisture permeable waterproof fabric.

The problem is solved by the following configuration.
[1] A water- and oil-repellent composition containing a fluorine-containing polymer, a liquid medium and a surfactant is brought into contact with the surface of the fiber base material, and a layer containing the fluorine-containing polymer is placed on at least one surface of the fiber base material. Formed in
A method for producing a moisture-permeable waterproof fabric, wherein a liquid containing a coating resin is brought into contact with the surface of a layer containing a fluorine-containing polymer to form a moisture-permeable waterproof layer containing the coating resin.
The fluorine-containing polymer is a polymer containing a unit based on a fluorine-containing compound represented by the formula (1), a unit based on a halogenated olefin, and a unit based on a (meth) acrylic acid ester represented by the formula (2). And
The content ratio of the unit based on the (meth) acrylic acid ester in the fluorine-containing polymer is 30% by mass or less.
The Hansen solubility parameter distance between the fluorine-containing polymer represented by the formula (3) and the coating resin is 3 MPa ^0.5 or more and less than 15 MPa ^0.5 .
The ratio of the total mass of the nonionic surfactant having a Hydrophilic-Lipopicular Balance value of less than 14 to the total mass of the surfactant in the water-repellent oil-repellent composition is 30% by mass or more.
A method for manufacturing a moisture-permeable and waterproof fabric.
R ^f- Y-X formula (1)
In the formula (1), R ^f is a polyfluoroalkyl group having 1 to 6 carbon atoms, Y is a divalent organic group or a single bond containing no fluorine atom, and X is a formula (4) to ~. It is a group represented by any one of (7).
−CR ¹ = CH ₂ equation (4)
-C (O) OCR ¹ = CH ₂ equation (5)
-OC (O) CR ¹ = CH ₂ equation (6)
−OCH = CH ₂ equation (7)
However, in the formulas (4) to (7), R ¹ is a hydrogen atom, a methyl group or a halogen atom.
CH ₂ = C (CH ₃ ) -C (O) OR ² equation (2)
However, in the formula (2), R ² is an aliphatic saturated hydrocarbon group having 1 to 26 carbon atoms.
(4 × (dDa-dDb) ² + (dPa-dPb) ² + (dHa-dHb) ² ) Equation ^0.5 (3)
However, in the formula (3), dDa, dPa and dHa represent the dispersion term, the polarity term and the hydrogen bond term in the Hansen solubility parameter of the fluorine-containing polymer, respectively, and dDb, dPb and dHb are the coating resins, respectively. Represents the dispersion term, polarity term and hydrogen bond term in the Hansen solubility parameter.
[2] The production method according to [1], wherein the Hansen solubility parameter distance between the fluorine-containing polymer and the coating resin is calculated before producing the moisture-permeable waterproof fabric.
[3] The dispersion term of the Hansen solubility parameter of the fluorine-containing polymer is 15 to 20 MPa ^0.5 , the polar term is 5 to 10 MPa ^0.5 , and the hydrogen bond term is ^0.5 to ⁵ MPa ^0.5 . The production method according to [1] or [2].
[4] The dispersion term of the Hansen solubility parameter of the coating resin is 15 to 25 MPa ^0.5 , the polar term is 8 to 15 MPa ^0.5 , and the hydrogen bond term is 3 to 8 MPa ^0.5 . [1] ] To [3] according to any one of the manufacturing methods.
[5] The production method according to any one of [1] to [4], wherein the content ratio of the fluorine-containing polymer in the layer containing the fluorine-containing polymer is 50 to 100% by mass.
[6] The fluorine-containing polymer contains 60 to 85% by mass of a unit based on the fluorine-containing compound represented by the formula (1) and 5 to 25% by mass of a unit based on the halogenated olefin. The production method according to any one of [1] to [5], which comprises 20% by mass or less of a unit based on the (meth) acrylic acid ester represented by (2).
[7] The unit based on the halogenated olefin includes the unit based on vinyl chloride and the unit based on vinylidene chloride, and the unit based on the vinyl chloride and the unit based on the vinylidene chloride with respect to the total amount of the unit based on the halogenated olefin. The ratio of the unit based on vinyl chloride to the total amount of the unit based on vinyl chloride and the unit based on vinylidene chloride is 50 to 100% by mass, and the ratio of the unit based on vinyl chloride is 50 to 100% by mass. [1] The production method according to any one of [6].
[8] The production method according to any one of [1] to [7], wherein the fluorine-containing polymer has a number average molecular weight of 25,000 to 100,000.
[9] The production method according to any one of [1] to [8], wherein the fluorine-containing polymer has a mass average molecular weight of 70,000 or more.
[10] Any one of [1] to [9], wherein the water and oil repellent composition contains 7 to 9.5 parts by mass of the surfactant with respect to 100 parts by mass of the fluorine-containing polymer. The manufacturing method described in.

According to the present invention, when the moisture-permeable waterproof layer is formed on the fabric treated with the water-repellent oil-repellent composition, the coating composition for forming the moisture-permeable waterproof layer does not strike through, resulting in peeling strength and water-repellent and oil-repellent properties. It is possible to provide a method for producing a moisture permeable waterproof fabric for producing an excellent moisture permeable waterproof fabric.

The meanings of the terms used herein are as follows.
The numerical range represented by "~" means a range including the numerical values at both ends thereof.
"(Meta) acrylic" is a general term for "acrylic" and "methacrylic", and individually means acrylic and methacrylic. The same applies to "(meth) acryloyl", "(meth) acryloyloxy", "(meth) acrylic acid", "(meth) acrylate" and "(meth) acrylamide".
The number average molecular weight (hereinafter referred to as "Mn") and the mass average molecular weight (hereinafter referred to as "Mw") are polystyrene-equivalent molecular weights measured by gel permeation chromatography (GPC).
Specifically, it is measured by the following method.
The polymer (A) described later is dissolved in a mixed solvent of a fluorine-based solvent (AK-225, product name of AGC) / tetrahydrofuran (THF) / hexafluoro-2-propanol = 6/3/14 (volume ratio). To prepare a solution having a solid content concentration of 0.5% by mass.
The prepared solution is passed through a 0.2 μm filter to prepare an analytical sample.
Mn and Mw of the analysis sample are measured under the following conditions.
Measurement temperature: 37 ° C,
Injection volume: 100 μL,
Outflow rate: 1 mL / min,
Eluent: A mixed solvent of a fluorine-based solvent (AK-225, AGC product name) / THF / hexafluoro-2-propanol = 6/3/14 (volume ratio).
The HLB value is a Hydrophilic-Lipophilic Balance value indicating the degree of affinity of the surfactant with water and oil, and in the present specification, the nonionic surfactant containing no repeating unit based on propylene oxide is used. , It is a value calculated by the Griffin method. That is, it is a value calculated by (20 × total of formulas of hydrophilic part / molecular weight of surfactant). The values calculated by the Davis method for nonionic surfactants and cationic surfactants having repeating units based on propylene oxide. That is, it is a value calculated by (7 + total number of hydrophilic group groups-total number of lipophilic group groups). The HLB value takes a value of 0 to 20. The closer the HLB value is to 0, the higher the lipophilicity, and the closer it is to 20, the higher the hydrophilicity. The HLB value of a mixture of two or more surfactants is a weighted average value of each surfactant.

[Manufacturing method of breathable waterproof fabric]
In the method for producing a moisture-permeable and waterproof fabric of the present invention, the water-repellent and oil-repellent composition is brought into contact with the surface of the fiber base material to form a layer containing a fluorine-containing polymer on at least one surface of the fiber base material. This is a method for producing a moisture-permeable waterproof fabric, in which a liquid containing a coating resin is brought into contact with the surface of the layer containing the fluorine-containing polymer to form a moisture-permeable waterproof layer.

<Water and oil repellent composition>
The water-repellent and oil-repellent composition is a liquid composition used for forming a layer containing a fluorine-containing polymer (hereinafter referred to as "polymer (A)") in the method for producing a moisture-permeable and waterproof fabric of the present invention. It is a thing.
The water and oil repellent composition contains a polymer (A), a liquid medium and a surfactant.

(Polymer (A))
The polymer (A) is a unit based on a fluorine-containing compound (hereinafter referred to as "compound (a)") (hereinafter referred to as "unit (a)"), a halogenated olefin (hereinafter referred to as "compound (a)"). B) ”) based units (hereinafter referred to as“ unit (b) ”) and (meth) acrylic acid ester (hereinafter referred to as“ compound (c) ”) units (hereinafter referred to as“ compound (c) ”). Unit (c) ”is included.

The compound (a) is a compound represented by the formula (1). The unit (a) contributes to the development of water and oil repellency by the polymer (A).
R ^f- Y-X (1)
The meanings of the symbols in the formula (1) are as follows.

R ^f is a polyfluoroalkyl group having 1 to 6 carbon atoms, preferably a perfluoroalkyl group having 1 to 6 carbon atoms, more preferably a perfluoroalkyl group having 4 to 6 carbon atoms, and having 4 to 6 carbon atoms. A linear perfluoroalkyl group is more preferred. Examples of perfluoroalkyl groups having 4 to 6 carbon _{atoms, F (CF 2) 4 -} , F (CF 2) 5 -, F (CF 2) 6 -, (CF 3) 2 CF (CF 2) 2 - However, it is not limited to these. As R ^f , F (CF ₂ ) ₄ −, F (CF ₂ ) ₅ − and F (CF ₂ ) ₆ − are preferable, and F (CF ₂ ) ₆ − is preferable because the polymer (A) has more excellent water and oil repellency. ₂ ) ₆ − is more preferable.

Y is a divalent organic group containing no fluorine atom (hereinafter, simply referred to as "divalent organic group") or a single bond, and the divalent organic group is a divalent group containing a carbon atom. is there. However, when the terminal atom of X bonded to the divalent organic group is an ethereal oxygen atom, the terminal atom of the divalent organic group bonded to X is a carbon atom.
Examples of the divalent organic group, an alkylene group, an alkenylene group, and -O -, - NH -, - CO -, - S -, - SO 2 - and ^-CR 11 = ^{CR 12} - 1 or more selected from An alkylene group having a terminal or between carbon-carbon atoms is preferable. However, R ¹¹ and R ¹² are independently hydrogen atoms or methyl groups, respectively. These groups may be linear or branched, with a linear alkylene group being more preferred, a linear alkylene group having 1 to 6 carbon atoms being more preferred, and 2 to 6 carbon atoms. The linear alkylene group of 4 is more preferred.
Specific examples of the divalent organic group include −CH ₂ −, − (CH ₂ ) ₂ −, − (CH ₂ ) ₃ −, −CH ₂ CH ₂ CH (CH ₃ ) −, −CH = CH −CH. _2- , -SO _2- CH ₂ CH _2- , -CH ₂ CH ₂ CH _2- S-CH ₂ CH _2- , -CH ₂ CH ₂ CH _2- SO _2- CH ₂ CH _2- , -L ^1- , And -L ^1- OC (O) NH-L ² -NHC (O) O- (CH ₂ ) _i- , but not limited to these.
In the formula, i is an integer of 2 to 30, and L ¹ and L ² will be described later.
L ¹ is any ^one selected from −SO ₂ N (R ¹³ ) − (CH ₂ ) _j −, −CONH − (CH ₂ ) _j −, and − (CH ₂ ) _k −. However, R ¹³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, j is an integer of 2-8, and k is an integer of 1 to 20.
L ² is a non-branched alkylene group, a non-branched and symmetric arylene group or a non-branched and symmetric aralkylene group, − (CH ₂ ) ₆ −, −C ₆ H ₄ − and −C ₆ H ₄ −. CH ₂ -C ₆ H ₄ - one selected from but preferred. -C ₆ H ₄ - is a 1,2-phenylene group, a 1,3-phenylene group or 1,4-phenylene group, a plurality of _-C 6 _{H 4} - represents a phenylene group of the same type.

X is a group represented by any one of the formulas (4) to (7).
−CR ¹ = CH ₂ (4)
-C (O) OCR ¹ = CH ₂ (5)
-OC (O) CR ¹ = CH ₂ (6)
−OCH = CH ₂ (7)
In formulas (4) to (7), R ¹ is a hydrogen atom, a methyl group or a halogen atom, preferably a hydrogen atom, a methyl group, a chlorine atom or a fluorine atom, and more preferably a hydrogen atom, a methyl group or a chlorine atom. A hydrogen atom or a methyl group is more preferable.
As X, the group (6) is preferable, and -OC (O) CH = CH ₂ or -OC (O) C (CH ₃ ) = CH ₂ is more preferable.

From the viewpoints of polymerizability with compound (b) and compound (c), flexibility of the layer containing the polymer (A), adhesion of the polymer (A) to the fiber substrate, and development of water repellency, the compound (a) ), The compound represented by the formula (8) is preferable.
^{R F -L 3 -OC (O)} -CR 3 = CH 2 (8)
Wherein (8), R ^F is a perfluoroalkyl group having 4 to 6 carbon atoms, L ³ represents a single bond or an alkylene group with a straight chain having 1 to 4 carbon atoms, R ³ is a hydrogen atom, a methyl group , Fluorine atom or chlorine atom.

The unit (a) in the polymer (A) may be two or more.

Specific examples of compound (a) are F (CF ₂ ) _6- CH ₂ CH _2- OC (O) -C (CH ₃ ) = CH ₂ , F (CF ₂ ) _6- CH _2- OC (O)-. CH = CH ₂ , F (CF ₂ ) _6- CH ₂ CH _2- OC (O) -C (Cl) = CH ₂ , F (CF ₂ ) _4- CH ₂ CH _2- OC (O) -C (CH) ₃ ) = CH ₂ , F (CF ₂ ) _4- CH ₂ CH _2- OC (O) -CH = CH ₂ , F (CF ₂ ) _4- CH ₂ CH _2- OC (O) -C (Cl) = _{CH 2, F (CF 2)} 6 -CH 2 -OC (O) -C (CH 3) = CH 2, F (CF 2) 6 -CH 2 -OC (O) -CH = CH 2, F (CF ₂ ) _6- CH _2- OC (O) -C (Cl) = CH ₂ , but is not limited thereto.

Since compound (a) has excellent water and oil repellency, F (CF ₂ ) _6- CH ₂ CH _2- OC (O) -C (CH ₃ ) = CH ₂ , F (CF ₂ ) _6- CH ₂ CH _2- OC (O) -C (Cl) = CH ₂ , F (CF ₂ ) _4- CH ₂ CH _2- OC (O) -C (CH ₃ ) = CH ₂ , F (CF ₂ ) _4- CH ₂ One or more selected from the group consisting of CH _2- OC (O) -CH = CH ₂ and F (CF ₂ ) _4- CH ₂ CH _2- OC (O) -C (Cl) = CH ₂ is preferable. , F (CF ₂ ) _6- CH ₂ CH _2- OC (O) -C (CH ₃ ) = CH ₂ and F (CF ₂ ) _6- CH ₂ CH _2- OC (O) -C (Cl) = CH One or more selected from the group consisting of ₂ is more preferable, and F (CF ₂ ) _6- CH ₂ CH _2- OC (O) -C (CH ₃ ) = CH ₂ is further preferable.

The compound (b) is not particularly limited as long as one or more hydrogen atoms of the olefin are replaced with halogen atoms, but the halogen atoms of the olefin having 2 to 10 carbon atoms can be changed from 1 to a maximum of 10. The one replaced with is preferable.

The unit (b) in the polymer (A) may be two or more.

Specific examples of the compound (b) are, but are not limited to, vinyl chloride, vinylidene chloride, vinyl fluoride, tetrafluoroethylene, vinylidene fluoride, vinyl bromide, vinylidene bromide, vinyl iodide, and vinylidene iodide. ..
As the compound (b), either or both of vinyl chloride and vinylidene chloride are preferable, and vinyl chloride is more preferable, because the polymer (A) has excellent affinity and film-forming property with respect to the fiber base material.

When the unit (b) contains either one or both of the vinyl chloride unit and the vinylidene chloride unit, the total content of the vinyl chloride unit and the vinylidene chloride unit in the unit (b) is preferably 80 to 100% by mass, preferably 70. ~ 100% by mass is more preferable, and 60 to 100% by mass is further preferable.
At this time, the ratio of the mass of the vinyl chloride unit to the total amount of the vinyl chloride unit and the vinylidene chloride unit is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, still more preferably 70 to 100% by mass. When the mass ratio of the vinyl chloride unit and the vinylidene chloride unit is within this range, the adhesion between the layer containing the polymer (A) and the moisture-permeable waterproof layer is more excellent.

Compound (c) is a compound represented by the formula (2). The unit (c) contributes to the development of water repellency by the polymer (A) and the development of flexibility of the layer containing the polymer (A).
CH ₂ = C (CH ₃ ) -C (O) OR ² (2)
In formula (2), R ² is an aliphatic saturated hydrocarbon group having 1 to 26 carbon atoms. The aliphatic saturated hydrocarbon group may be a linear or branched alkyl group, or may be a monocyclic or polycyclic cycloalkyl group.
The number of carbon atoms in R ² is not particularly limited as long as it is 1 to 26, preferably 4 to 22, 6 to 22 is more preferable. When the number of carbon atoms of R ² is within this range, the water repellency of the layer containing the polymer (A) is more excellent.

The unit (c) in the polymer (A) may be two or more.

As the compound (c), ^{R 2} is an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms (meth) one or more and, ^{R 2} is an aliphatic saturated hydrocarbon group having 12 to 26 carbon atoms of acrylic acid ester It may be used in combination with one or more kinds of (meth) acrylic acid esters. The compound (c) may contain a (meth) acrylic acid ester in which R ² is an aliphatic saturated hydrocarbon group having 12 to 26 carbon atoms in that water repellency tends to be good and peel strength tends to be high. preferable.

Specific examples of the compound (c) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and cyclohexyl (meth). Acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isobornyl (meth) acrylate, dodecyl (meth) acrylate (also known as lauryl (also known as lauryl). Meta) acrylate), tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (also known as cetyl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate ( Alias: Stearyl (meth) acrylate), Nonadecil (meth) acrylate, Icosyl (meth) acrylate, Henkoisyl (meth) acrylate (also known as behenyl (meth) acrylate), Docosyl (meth) acrylate, Tricosyl (meth) acrylate, Tetracocil ( Meta) acrylate, pentacocil (meth) acrylate, and hexacocil (meth) acrylate, but are not limited thereto.
Examples of the compound (c) include hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, isobornyl (meth) acrylate, and lauryl (meth) acrylate. , Cetyl (meth) acrylate, stearyl (meth) acrylate and behenyl (meth) acrylate are preferable, and lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate and behenyl (meth) acrylate tend to have good water repellency. Meta) acrylate is more preferred.

In addition to the unit (a), the unit (b) and the unit (c), the polymer (A) is a unit based on another compound (hereinafter, referred to as “compound (d)”) (hereinafter, ““ compound (d) ”). Unit (d) ”) may be included.

The unit (d) in the polymer (A) may be two or more.

Compound (d) does not contain a fluorine atom and has a polymerizable functional group copolymerizable with compound (a), compound (b) and compound (c). Specific examples of such a polymerizable functional group are ethylenically unsaturated groups such as vinyl group and allyl group, but are not limited thereto.

The compound (d) is not particularly limited as long as it is a monomer copolymerizable with the compound (a), the compound (b) and the compound (c), and conventionally known monomers can be used. For example, among the monomers (a5) described in International Publication No. 2015/080060, compounds other than the above compounds (a), compound (b) and compound (c), International Publication No. 2012/147700 Among the monomer (c) and the monomer (e) described in the above, compounds other than the above-mentioned compound (a), compound (b) and compound (c) can be used.

Examples of the compound (d) include glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, and dimethylaminoethyl (meth). Polycaprolactone ester of acrylate, diethylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate (FA of trade name "Plaxel", product name of FM series Daicel Chemical Industry Co., Ltd.), 2-Isocyanatoethyl (meth) acrylate, 3- 3 of isocyanatopropyl (meth) acrylate, 2-butanone oxime adduct of 2-isocyanatoethyl (meth) acrylate, pyrazole adduct of 2-isocyanatoethyl (meth) acrylate, 2-isocyanatoethyl (meth) acrylate , 5-Dimethylpyrazole adduct, 3-Methylpyrazole adduct of 2-isocyanatoethyl (meth) acrylate, N-methylolacrylamide and neopentyl glycol diacrylate are preferable, and water repellency durability tends to be good. More preferred are N-methylolacrylamide, 2-hydroxyethyl (meth) acrylate, 3,5-dimethylpyrazole adduct of 2-isocyanatoethyl (meth) acrylate and neopentyl glycol diacrylate.

The content ratio of the unit (a) in the polymer (A) is preferably 60 to 85% by mass, and more preferably 65 to 80% by mass from the viewpoint that the water and oil repellency tends to be good.
The content ratio of the unit (b) in the polymer (A) is preferably 5 to 25% by mass, and more preferably 15 to 25% by mass from the viewpoint that the water and oil repellency tends to be good.
The content ratio of the unit (c) in the polymer (A) is 30% by mass or less, preferably 30% by mass or less from the viewpoint of adhesion between the layer containing the polymer (A) and the moisture-permeable waterproof layer. It is more preferably 25% by mass or less, and further preferably 20% by mass or less. The content ratio of the unit (c) in the polymer (A) is preferably 3% by mass or more, more preferably 5% by mass or more, from the viewpoint of water repellency and flexibility. From the viewpoint of the adhesion between the layer containing the polymer (A) and the moisture-permeable waterproof layer and the overall balance of water repellency and flexibility of the moisture-permeable waterproof fabric, the content ratio of the unit (c) in the polymer (A) is It is preferably 3 to 25% by mass, more preferably 5 to 20% by mass.

The content ratio of the unit (a), the unit (b) and the unit (c) in the polymer (A) (unit (a) / unit (b) / unit (c)) is 60 to 85% by mass / 5 to 25. Mass% / 0 to 20% by mass is preferable, and 65 to 80% by mass / 15 to 25% by mass / 3 to 15% by mass is obtained in that the adhesion between the layer containing the polymer (A) and the moisture-permeable waterproof layer is more excellent. % Is more preferable.

When the polymer (A) contains the unit (d), the content ratio of the unit (d) to the polymer (A) is not particularly limited, but is preferably 0.1 to 10% by mass, and 0.2 to 7%. The mass% is more preferable, and 0.3 to 5% by mass is further preferable.

The Mn of the polymer (A) is preferably 25,000 to 100,000, more preferably 30,000 to 100,000, and even more preferably 35,000 to 100,000.
The Mw of the polymer (A) is preferably 70,000 or more, more preferably 70,000 to 350,000, even more preferably 100,000 to 350,000, and even more preferably 150,000 to 350,000.
The polymer (A) preferably satisfies at least one of the above-mentioned Mn range and Mw range, and more preferably both.
When at least one of Mn and Mw of the polymer (A) is within the above range, the water- and oil-repellent properties of the layer containing the polymer (A) are more excellent, and the film-forming property of the water- and oil-repellent agent composition is improved. It becomes better, and when the moisture permeable waterproof layer is formed, the liquid containing the coating resin (C) is less likely to permeate the fiber base material excessively.

The method for producing the polymer (A) is not particularly limited, but for example, the monomer component containing the above-mentioned compound is polymerized in a liquid medium in the presence of a polymerization initiator to obtain the polymer (A). It can be produced by a method for obtaining a containing solution, dispersion or emulsion.
The polymerization method of the monomer component is not particularly limited, and a solution polymerization method, a dispersion polymerization method, an emulsion polymerization method or a suspension polymerization method is preferable, and an emulsion polymerization method is more preferable. In addition, each of the above-mentioned polymerization methods may be a batch polymerization or a multi-stage polymerization.

In the emulsion polymerization of the polymer (A), a monomer component containing the above-mentioned compound is emulsion-polymerized in an aqueous medium in the presence of a surfactant and a polymerization initiator to obtain an emulsion of the polymer (A). The method is preferred.
From the viewpoint of improving the yield of the polymer (A), it is preferable to emulsify a mixture consisting of a monomer component, a surfactant and an aqueous medium in advance before emulsion polymerization. For example, a mixture consisting of a monomer component, a surfactant and an aqueous medium is mixed and dispersed by an ultrasonic stirrer, a homomixer or a high-pressure emulsifier.

Examples of the polymerization initiator include thermal polymerization initiators, photopolymerization initiators, radiation polymerization initiators, radical polymerization initiators, ionic polymerization initiators and the like, and water-soluble or oil-soluble radical polymerization initiators are preferable.
As the radical polymerization initiator, a general-purpose initiator such as an azo-based polymerization initiator, a peroxide-based polymerization initiator, or a redox-based polymerization initiator is used depending on the polymerization temperature. As the radical polymerization initiator, an azo compound is particularly preferable, and when polymerization is carried out in an aqueous medium, a salt of the azo compound is more preferable. The polymerization temperature is preferably 20 to 150 ° C.
The amount of the polymerization initiator added is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the total of the monomer components.

A molecular weight modifier may be used for the polymerization of the monomer component. As the molecular weight modifier, aromatic compounds, mercaptoalcohols or mercaptans are preferable, and alkyl mercaptans are particularly preferable.
The amount of the molecular weight adjusting agent added may be appropriately adjusted so that Mn and Mw of the polymer (A) are within the above-mentioned ranges.

Examples of the liquid medium include water, alcohols, monoalkyl ethers of polyhydric alcohols, halogen compounds, hydrocarbons, ketones, esters, ethers other than monoalkyl ethers of polyhydric alcohols, nitrogen compounds, sulfur compounds, inorganic solvents, and the like. Organic acids can be mentioned.
As the liquid medium, an aqueous medium is preferable from the viewpoint of solubility and ease of handling.

The aqueous medium may be a water-soluble organic solvent or a mixture of a water-soluble organic solvent and water.
Examples of the water-soluble organic solvent include alcohols and monoalkyl ethers of polyhydric alcohols. Two or more kinds of water-soluble organic solvents may be used in combination.
Specific examples of the alcohol are, but are not limited to, tert-butyl alcohol, propylene glycol, dipropylene glycol, and tripropylene glycol.
Specific examples of the monoalkyl ether of the polyhydric alcohol are 3-methoxymethylbutanol and dipropylene glycol monomethyl ether, but are not limited thereto.
As the water-soluble organic solvent, one or more selected from the group consisting of dipropylene glycol, tripropylene glycol and dipropylene glycol monomethyl ether is preferable.
When the aqueous medium is a mixture of a water-soluble organic solvent and water, the content of the water-soluble organic solvent with respect to 100 parts by mass of water is preferably 1 to 80 parts by mass, more preferably 10 to 60 parts by mass.

The surfactant is one or more selected from the group consisting of hydrocarbon-based surfactants and fluorine-based surfactants. Hydrocarbon-based surfactants and fluorine-based surfactants can all be classified into anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants.
The surfactant used in producing the polymer (A) is usually brought into the water-repellent oil-repellent composition and becomes one of the components of the water-repellent oil-repellent composition.
From the viewpoint of compatibility with additives that may be contained in the water / oil repellent composition, the surfactant is preferably used in combination with a nonionic surfactant and an amphoteric surfactant. Further, from the viewpoint of adhesion between the layer containing the polymer (A) and the moisture-permeable waterproof layer, the surfactant may be used alone as a nonionic surfactant or in combination with a nonionic surfactant and a cationic surfactant. preferable. The mass ratio of the nonionic surfactant to the cationic surfactant when the nonionic surfactant and the cationic surfactant are used in combination as the surfactant is not particularly limited, but the total mass of the nonionic surfactant / the cationic surfactant. The total mass of the agent = 97/3 to 40/60 is preferable, 95/5 to 50/50 is more preferable, and 93/7 to 60/40 is even more preferable.

When the HLB value of the surfactant is close to 20, the hydrophilicity of the surfactant is high, and the water repellency of the layer containing the polymer (A) formed on the fiber substrate by the water-repellent oil-repellent composition tends to decrease. ..
It preferably contains a surfactant having an HLB value of less than 14. The HLB value of the surfactant is preferably 3 or more, and more preferably 6 or more, because the water-repellent washing durability is more excellent.
From the viewpoint of water repellency, the content ratio of the nonionic surfactant having an HLB value of less than 14 with respect to the surfactant is 30% by mass or more, preferably 30 to 90% by mass, based on the total mass of the surfactant. 30 to 80% by mass is more preferable, and 30 to 60% by mass is further preferable. When the content ratio of the nonionic surfactant having an HLB value of less than 14 is within this range, the water-repellent washing durability of the layer containing the polymer (A) is more excellent.

As the nonionic surfactant, one or more selected from the group consisting of the surfactants s1 to s6 described in International Publication No. 2010/080060 or International Publication No. 2010/123042 is preferable.
When the surfactant contains a cationic surfactant, the surfactant s7 described in the above document is preferable as the cationic surfactant.
When the surfactant contains an amphoteric surfactant, the surfactant s8 described in the above document is preferable as the amphoteric surfactant.
Further, as the surfactant, the surfactant s9 (polymer surfactant) described in the above document may be used.
The preferred embodiment of the surfactant is the same as the preferred embodiment described in the above literature.

As the nonionic surfactant, one or more selected from the group consisting of surfactants represented by the following formulas is preferable.
C ₁₀ H ₂₁ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q- H
C ₁₂ H ₂₅ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q- H
C ₁₆ H ₃₁ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q- H
C ₁₆ H ₃₃ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q- H
C ₁₈ H ₃₅ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q- H
C ₁₈ H ₃₇ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q- H
C ₁₂ H ₂₅ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q- C ₁₂ H ₂₅
C ₁₆ H ₃₁ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q- C ₁₆ H ₃₁
C ₁₆ H ₃₃ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q- C ₁₂ H ₂₅
iso-C ₁₃ H ₂₇ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q- H
C ₁₀ H ₂₁ C (O) O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q- H
C ₁₆ H ₃₃ C (O) O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q- C ₁₂ H ₂₅
In the above formula, p is an integer of 3 or more, and q is an integer of 2 or more. p is preferably, for example, 5 to 200, and q is preferably, for example, 5 to 200.

Examples of the cationic surfactant include monostearyltrimethylammonium chloride, monostearyldimethylmonoethylammonium ethyl sulfate, mono (stearyl) monomethyldi (polyethylene glycol) ammonium chloride, monofluorohexyltrimethylammonium chloride, and di (beef alkyl) dimethylammonium. One or more selected from the group consisting of chloride and dimethylmonococonutamine acetate is preferable.

As the amphoteric surfactant, one or more selected from the group consisting of dodecyl betaine, stearyl betaine, dodecylcarboxymethyl hydroxyethyl imidazolinium betaine, dodecyldimethylaminoacetic acid betaine and fatty acid amide propyldimethylaminoacetic acid betaine is preferable.

The molar ratio of each compound in the monomer component when producing the polymer (A) is the same as the molar ratio of the unit based on each compound in the polymer (A) because each compound polymerizes almost 100%. The same applies to the preferred embodiment.

The solid content concentration in the emulsion is preferably 20 to 40% by mass immediately after the production of the polymer (A). The solid content refers to a component obtained by removing the liquid medium from the component contained in the emulsion, and usually contains a surfactant in addition to the polymer (A). After the production of the polymer (A), usually no polymerization initiator remains. The content ratio of the polymer (A) in the emulsion is preferably 18 to 40% by mass immediately after the production of the polymer (A).
The solid content concentration of the emulsion is 100, which is obtained by dividing the solid content mass by the mass of the emulsion before heating and drying, where the mass after heating and drying the emulsion in a convection dryer at 120 ° C. for 4 hours is taken as the solid content mass. Calculate by multiplying (unit: mass%).

The emulsion of the polymer (A) obtained by emulsion polymerization contains a liquid medium and a surfactant as described above.
In the method for producing a moisture-permeable and waterproof fabric of the present invention, the water- and oil-repellent composition used to form the layer containing the polymer (A) may be the emulsion itself of the polymer (A). If necessary, one or more of the above-mentioned liquid media may be added to dilute, or one or more of the above-mentioned surfactants may be added to improve the permeability and stability.

The water- and oil-repellent composition may contain additives in addition to the polymer (A), the liquid medium and the surfactant.
Examples of the additive include a penetrant, a defoaming agent, a water absorbing agent, an antistatic agent, an antistatic polymer, a wrinkle-proofing agent, a texture adjusting agent, a film-forming aid, a water-soluble polymer, a thermosetting agent, and an epoxy curing agent. Examples thereof include agents, thermosetting catalysts, cross-linking catalysts, synthetic resins, fiber stabilizers, PH adjusters, and inorganic fine particles. As these additives, conventionally known additives can be used without particular limitation.

The water-repellent and oil-repellent composition may further contain a polymer containing no fluorine atom other than the polymer (A) (hereinafter referred to as "polymer (B)").
The polymer (B) is preferably one that improves at least one of the water repellency and the oil repellency of the water and oil repellent composition. Such a polymer (B) can be selected from, for example, a water repellent agent, an oil repellent agent, a water repellent oil repellent agent, and an antifouling agent.
Examples of the water-repellent and oil-repellent agent include paraffin compounds, aliphatic amide compounds, alkylethylene urea compounds and silicone compounds.

The content ratio of the polymer (A) in the solid content of the water / oil repellent composition is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and even more preferably 70 to 100% by mass. The solid content of the water / oil repellent composition is a component of the layer containing the polymer (A) formed by bringing the water / oil repellent composition into contact with the fiber base material. The content ratio of the polymer (A) in the layer containing the polymer (A) is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, still more preferably 70 to 100% by mass. When the content ratio of the polymer (A) in the solid content of the water / oil repellent composition and the content ratio of the polymer (A) in the layer containing the polymer (A) are within this range, the fiber base material is superior. Water and oil repellency can be imparted.

The content of the surfactant in the water-repellent oil-repellent composition is not particularly limited, but is preferably 1 to 12 parts by mass in total of the surfactant with respect to 100 parts by mass in total of the polymer (A). 11 parts by mass is more preferable, 5 to 10 parts by mass is further preferable, and 7 to 9.5 parts by mass is even more preferable. When the content of the surfactant is within this range, the peel strength of the moisture-permeable waterproof layer is higher, and the moisture-permeable waterproof layer is more difficult to peel from the fiber base material having the layer containing the polymer (A).

The solid content concentration of the water-repellent oil-repellent composition is not particularly limited, but is preferably 0.2 to 5% by mass when the fiber base material is treated. When the solid content concentration of the water / oil repellent composition is within this range, the water / oil repellent performance can be satisfactorily exhibited, and the permeation of the liquid containing the coating resin (C) can be satisfactorily prevented.
The solid content concentration of the water / oil repellent composition is the same as the method for calculating the solid content concentration of the emulsion described above.

<Liquid containing coating resin (C)>
The liquid containing the coating resin (C) is a liquid composition used for forming a moisture-permeable waterproof layer in the method for producing a moisture-permeable waterproof fabric of the present invention.
The moisture-permeable waterproof layer formed by the liquid containing the coating resin (C) contains the coating resin (C).

The coating resin (C) is not particularly limited, but is, for example, a polyurethane resin obtained by reacting a polyisocyanate component with a polyol component, a polycarbonate copolymer-based polyurethane resin, a polyurethane resin obtained by copolymerizing silicone, fluorine, amino acids, or the like. , Acrylic resin, polyester resin, polyether copolymer type, synthetic rubber, vinyl resin such as polyvinyl chloride, and polytetrafluoroethylene resin.
The coating resin (C) is not limited to one type, and may be two or more types.

The coating resin (C) can be obtained by reacting a polyisocyanate component with a polyol component because it is easy to process a moisture-permeable waterproof fabric having a layer containing the polymer (A) and a moisture-permeable waterproof layer. Conventionally known polyurethane resins are preferred.

As the polyisocyanate component, aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate and the like are used.
Specific examples of the aromatic diisocyanate include m-xylylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and 4,4'-. Diphenylmethane diisocyanate, but not limited to these.
Specific examples of the aliphatic diisocyanate are hexamethylene diisocyanate, but the present invention is not limited thereto.
Specific examples of the alicyclic diisocyanate are 1,4-cyclohexanediisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), and isophorone diisocyanate, but are not limited thereto.
As the isocyanate component, the diisocyanate may be used as a main component, and a trifunctional or higher functional polyisocyanate may be used if necessary.
As the isocyanate component, an isocyanate group-terminated urethane prepolymer having two or more isocyanate groups in one molecule can also be used.

As the polyol component, a polyether polyol, a polyester polyol, or the like is used.
Specific examples of the polyether polyol are polyethylene glycol, polypropylene glycol, and polytetraethylene glycol, but are not limited thereto.
The polyester polyol is a condensed polymer of a diol and a dibasic acid, a ring-opening polymer of a lactone, a condensed polymer of a hydroxy acid, and the like. Specific examples of the diol are ethylene glycol and propylene glycol, but the diol is not limited thereto. Specific examples of the dibasic acid are, but are not limited to, adipic acid and sebatic acid. Specific examples of the lactone are, but are not limited to, ε-caprolactone. Specific examples of the hydroxy acid are, but are not limited to, lactic acid and hydroxybutyric acid.
As the polyol component, a hydroxyl group-terminated urethane prepolymer having two or more hydroxyl groups in one molecule can also be used.

As a component to be the coating resin (C) in the moisture permeable waterproof layer contained in the liquid containing the coating resin (C), a commercially available one-component polyurethane resin or two-component polyurethane resin may be used.
Examples of commercially available one-component polyurethane resins include Resamine CU-4700 (product name of Dainichiseika Kogyo Co., Ltd.) and Chrisbon 8006HV (product name of DIC Corporation).

The content ratio of the component to be the coating resin (C) in the moisture-permeable waterproof layer contained in the liquid containing the coating resin (C) is not particularly limited, but is preferably 0.1 to 15% by mass, and is 0.2 to 15% by mass. 15% by mass is more preferable, and 0.4 to 13% by mass is further preferable.

The liquid containing the coating resin (C) may further contain a solvent.
The solvent is not particularly limited, but is, for example, toluene, methylethylketone, N, N-dimethylformamide (hereinafter referred to as “DMF”), N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, hexamethylenephosphone. Amid is mentioned. As the solvent, a polar organic solvent is preferable.
The content ratio of the solvent in the liquid containing the coating resin (C) is not particularly limited, but is preferably 40 to 99.9% by mass, more preferably 50 to 99.9% by mass, and 60 to 80% by mass. More preferred.

The liquid containing the coating resin (C) may further contain an auxiliary agent.
The auxiliary agent is not particularly limited, and examples thereof include a fluorine-based water repellent and a cross-linking agent.
The content ratio of the auxiliary agent in the liquid containing the coating resin (C) is not particularly limited, but is preferably 0.1 to 10% by mass, more preferably 0.2 to 8% by mass, and 0.5 to 5%. Mass% is more preferred.

<Relationship between polymer (A) and coating resin (C)>
The Hansen solubility parameter distance between the polymer (A) represented by the formula (3) and the coating resin (C) is 3 MPa ^0.5 or more and less than 15 MPa ^0.5 .
(4 × (dDa-dDb) ² + (dPa-dPb) ² + (dHa-dHb) ² ) ^0.5 (3)
In the formula (3), dDa, dPa and dHa represent the dispersion term, the polarity term and the hydrogen bond term in the Hansen solubility parameter of the polymer (A), respectively, and dDb, dPb and dHb are the coating resin (C), respectively. ) Represents the dispersion term, polarity term and hydrogen bond term in the Hansen solubility parameter.

The Hansen solubility parameter (hereinafter referred to as "HSP") is an index showing the compatibility between substances, and the closer the coordinates of the two substances in the three-dimensional space are, the higher the compatibility is. The definition and calculation method of HSP are described in the following documents.
Charles M. Hansen, "Hansen Solubility Parameters: A Users Handbook", CRC Press, 2007.
Further, the HSP of a solvent whose literature value is unknown can be easily estimated from its chemical structure by using computer software (Hansen Solubility Parameters in Practice (HSPiP)).
In the present invention, HSPiP version 5 is used, and the value is used for the solvent registered in the database, and the estimated value is used for the solvent not registered.
The HSP of a particular substance is usually determined by a solubility test confirming the solubility of that substance in a solvent for which the HSP has been determined. Specifically, for a substance for which HSP is to be obtained, a solubility test is conducted using various solvents for which HSP has been determined, the coordinates of HSP of all the solvents used are shown in a three-dimensional space, and the substance is dissolved. A sphere (solubility sphere) is searched so that all the coordinates of the solvent are contained inside the sphere and the coordinates of the insoluble solvent are outside the sphere, and the center coordinates of the solubility sphere are set as the HSP of the substance. In the solubility test of the present invention, the solubility was determined by confirming the state after mixing the substance with a solvent and allowing it to stand at 30 ± 3 ° C. for about 15 hours.

HSP is represented by a three-dimensional vector (dispersion term, polarity term, hydrogen bond term) having a dispersion term, a polarity term and a hydrogen bond term as components. When the HSP of the first substance is represented by (dD ₁ , dP ₁ , dH ₁ ) and the HSP of the second substance is represented by (dD ₂ , dP ₂ , dH ₂ ), the first substance and the second substance The HSP distance is {4 × (dD _{1 −} dD ₂ ) ² + (dP _{1 −} dP ₂ ) ² + (dH _{1 −} dH ₂ ) ² } ^0.5 . Each component of the vector representing HSP has a dimension of L ^-1 MT ^-2 (L: length, M: mass, T: time), and the unit is usually MPa ^0.5 .

In the present invention, when the HSP distance between the polymer (A) and the coating resin (C) is 3 MPa ^0.5 or more and less than 15 MPa ^0.5 , the compatibility between the polymer (A) and the coating resin (C) When the moisture permeable waterproof layer is formed, the moisture permeable waterproof layer is less likely to be peeled off from the fiber base material having the layer containing the polymer (A). In addition, excessive penetration of the liquid containing the coating resin (C) into the layer containing the polymer (A) is suppressed, and the liquid containing the coating resin (C) does not strike through.
The HSP distance is preferably 3~14MPa ^0.5, 3~12.5MPa ^0.5 is more preferable. When the HSP distance between the polymer (A) and the coating resin (C) is within this range, the coating resin does not excessively permeate into the details of the fiber structure of the fiber base material, but permeates appropriately. Therefore, the moisture-permeable and waterproof layer containing the coating resin exhibits an appropriate anchoring effect on the fiber base material, and is difficult to peel off from the fiber base material.

The HSP of the polymer (A) has a dispersion term of 15 to 20 MPa ^0.5 , a polarity term of 5 to 10 MPa ^0.5 , and a hydrogen bond term of 0 in that it has better compatibility with the coating resin. It is preferably 5 to ⁵ MPa ^0.5 , the dispersion term is 16 to 20 MPa ^0.5 , the polar term is 6 to 10 MPa ^0.5 , and the hydrogen bond term is 0.6 to ⁵ MPa ^0.5 . More preferably.

The HSP of the coating resin (C) has a dispersion term of 15 to 25 MPa ^0.5 , a polar term of 8 to 15 MPa ^0.5 , and a hydrogen bond term of 3 in that it is easily dissolved by the solvent used at the time of coating. is preferably ~8MPa ^0.5, dispersion term is 16~24MPa ^0.5, polarity term is 9~14MPa ^0.5, more can hydrogen bond is 4-8 MPa ^0.5 preferable.

<Fiber base material>
In the method for producing a moisture-permeable waterproof fabric of the present invention, the form of the fiber base material on which the layer containing the polymer (A) and the moisture-permeable waterproof layer are formed is not particularly limited, but for example, a woven fabric, a knitted fabric, a non-woven fabric or a brushed cloth. It is a cloth like. The fibers of the fiber base material are not particularly limited, but are, for example, natural fibers such as cotton, wool, silk or cellulose, synthetic fibers such as polyester, polyamide, acrylic or aramid, and chemical fibers such as rayon, biscous rayon or lyocell. , A blended fiber of natural fiber and synthetic fiber, and a blended fiber of natural fiber and chemical fiber. Examples of the fiber when the fiber base material is a non-woven fabric include polyethylene, polypropylene, polyolefin, glass and rayon.
The thickness of the fiber base material is not particularly limited, but is usually 0.01 to 5 mm. The thickness of the fiber base material is preferably 0.02 to 5 mm, more preferably 0.05 to 5 mm, still more preferably 0.10 to 5 mm, from the viewpoint of more excellent tear strength of the moisture-permeable waterproof fabric to be produced. Further, the thickness of the fiber base material is preferably 0.01 to 1 mm, more preferably 0.01 to 0.7 mm, and preferably 0.01 to 0.5 mm from the viewpoint of easily reducing the weight of the moisture-permeable waterproof fabric to be manufactured. More preferred.

<Formation of a layer containing the polymer (A)>
In the method for producing a moisture-permeable and waterproof fabric of the present invention, the above-mentioned water-repellent and oil-repellent composition is brought into contact with the surface of the fiber base material, and the layer containing the polymer (A) is formed on at least one surface of the fiber base material. To form.
The layer containing the polymer (A) may be formed on only one surface of the fiber base material, or may be formed on both surfaces.
Although it depends on the thickness of the fiber base material, even when the water and oil repellent composition is brought into contact with only one surface of the fiber base material, the surface on the side with which the water and oil repellent composition is brought into contact is The water- and oil-repellent composition may reach the surface on the opposite side to form a layer containing the polymer (A) on both sides of the fiber base material.
To form a layer containing the polymer (A) on both surfaces of the fiber substrate, the water and oil repellent composition is brought into contact with both surfaces of the fiber substrate, or one surface of the fiber substrate is formed. It is preferable that the water and oil repellent composition is repeatedly brought into contact with the water and oil repellent composition so that the water and oil repellent composition reaches the surface opposite to the surface on which the water and oil repellent composition is applied.

The method of bringing the water-repellent oil-repellent composition into contact with the surface of the fiber base material is not particularly limited, and a conventionally known method can be used. For example, a method of immersing the fiber base material in a bath containing the water repellent oil repellent composition, a method of spraying a diluted water repellent oil repellent composition onto at least one surface of the fiber base material, a known foaming agent and water repellent. Examples thereof include a method of mixing with an oil repellent composition and applying foam to at least one surface of the fiber base material. After adhering the water-repellent oil-repellent composition to the surface of the fiber base material by these known methods, the water-repellent oil-repellent composition is dried by a method such as heat drying to contain the polymer (A). Form a layer. Since the formed layer containing the polymer (A) is a film containing the polymer (A), it exhibits excellent water and oil repellency.

The thickness of the layer containing the polymer (A) is not particularly limited, but is usually 0.1 nm to 1 μm. The thickness of the layer containing the polymer (A) is preferably 0.2 to 600 nm, more preferably 10 to 300 nm, still more preferably 20 to 60 nm, from the viewpoint of more excellent water repellency of the moisture-permeable waterproof fabric to be produced.

After the water-repellent and oil-repellent composition is brought into contact with the fiber base material to form a layer containing the polymer (A), further processing such as antistatic processing, softening processing, antibacterial processing, deodorizing processing or waterproof processing is performed. You may. These processes may be performed on either the surface on which the layer containing the polymer (A) of the fiber base material is formed or the surface on which the layer containing the polymer (A) is not formed.

<Formation of moisture permeable waterproof layer>
In the method for producing a moisture-permeable waterproof fabric of the present invention, a liquid containing the coating resin (C) is brought into contact with the surface of the layer containing the polymer (A) to bring the moisture-permeable waterproof layer containing the coating resin (C) into contact with the surface. To form.
When the layer containing the polymer (A) is formed on one surface of the fiber base material, the coating resin (C) is contained on the surface of the layer containing the polymer (A) formed on the one surface. Bring the liquid into contact.
When the layer containing the polymer (A) is formed on both sides of the fiber base material, the coating resin (C) is formed on one surface of the layer containing the polymer (A) formed on both sides of the fiber base material. ) Is brought into contact with the liquid.

The method of bringing the liquid containing the coating resin (C) into contact with the surface of the layer containing the polymer (A) is not particularly limited, and a conventionally known method can be used. For example, a method of applying a liquid containing the coating resin (C) to the surface of the layer containing the polymer (A) using a spatula or a brush, a knife coater, a knife overroll coater, a blade coater, a reverse roll coater, a spin coater, or the like. A method of uniformly applying the liquid containing the coating resin (C) to the surface of the layer containing the polymer (A) using a kiss roll can be mentioned. By these known methods, a liquid containing the coating resin (C) is applied to the surface of the layer containing the polymer (A), and then the solution is allowed to stand for a predetermined time and then dried by heating or immersed in water. Form a moisture permeable and waterproof layer.
When a solvent having high volatility and low water solubility such as toluene or methyl ethyl ketone is used as the solvent of the liquid containing the coating resin (C), a method of heating and drying is preferable. The coating resin (C) in the liquid containing the coating resin (C) volatilizes the solvent in the liquid containing the coating resin (C) by heating and drying to form a film, and a large number of minute pores are formed in the film. It becomes a porous moisture-permeable and waterproof layer, and can exhibit the moisture-permeable and waterproof function.
When a polar organic solvent such as DMF, N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone or hexamethylenephosphonamide is used as the solvent of the liquid containing the coating resin (C), a method of immersing it in water. Is preferable. By immersing in water, the coating resin in the liquid containing the coating resin (C) forms a film, and the polar organic solvent in the liquid containing the coating resin (C) is transferred to the aqueous phase. A large number of minute holes are formed to form a porous moisture-permeable and waterproof layer, which enables the moisture-permeable and waterproof function to be exhibited.
The size of the holes in the moisture-permeable waterproof layer is not particularly limited, but 0.1 to 10 μm is preferable, 0.1 to 5 μm is more preferable, and 0.1 to 3 μm is preferable because the moisture-permeable waterproof function becomes better. More preferred. The size of the holes in the moisture permeable and waterproof layer can be measured by a scanning electron microscope.
The lower limit of 0.1 μm means that the size of the holes that can be confirmed with a scanning electron microscope is 0.1 μm or more, and it is considered that smaller holes are present.

The thickness of the moisture-permeable waterproof layer is not particularly limited, but is usually 5 to 100 μm. The thickness of the moisture-permeable waterproof layer is preferably 10 to 100 μm from the viewpoint of being more excellent in waterproofness, and more preferably 10 to 80 μm from the viewpoint of being more excellent in moisture permeability.

[Moisture-permeable waterproof fabric]
The moisture-permeable waterproof fabric produced by the method for producing the moisture-permeable waterproof fabric of the present invention (hereinafter referred to as "the moisture-permeable waterproof fabric of the present invention") contains the polymer (A) on at least one surface of the fiber base material. Has a layer.
When the fiber base material has a layer containing the polymer (A) on only one surface, the fiber base material has a moisture-permeable waterproof layer on the surface of the layer containing the polymer (A).
When the fiber base material has a layer containing the polymer (A) on both surfaces, the fiber base material has a moisture-permeable waterproof layer on one surface of the layer containing the polymer (A). ..
The moisture-permeable waterproof layer is a film containing the coating resin (C), and is preferably a porous structure having a large number of minute pores in that both waterproofness and moisture permeability can be easily achieved. As the moisture permeable and waterproof layer, for example, a gale air permeability of 10 to 2000 sec / 100 cc and a moisture permeability of 5000 to 100,000 g / (m ² · d) in the JIS Z-0208: 1976 A-1 method are used. Can be mentioned.
The moisture-permeable waterproof layer is difficult to peel off from the fiber base material having the layer containing the polymer (A), and has excellent peeling strength.
In the combination of the polymer (A) and the coating resin (C) in the method for producing a moisture-permeable waterproof fabric of the present invention, the liquid containing the coating resin (C) for forming the moisture-permeable waterproof layer is the polymer (A). It cannot pass through the layer containing the coating resin (C), and the strike-through of the liquid containing the coating resin (C) is suppressed. Therefore, in the moisture-permeable waterproof fabric of the present invention, the moisture-permeable waterproof layer is formed on only one surface. As a result, whitening of the surface of the moisture-permeable waterproof fabric can be suppressed.

The moisture-permeable waterproof fabric of the present invention is preferably used with the side with the moisture-permeable waterproof layer as the back surface and the side without the moisture-permeable waterproof layer as the front surface. When the side without the moisture permeable and waterproof layer is used as the surface, whitening of the surface is suppressed and the design and texture are not impaired.

The moisture-permeable waterproof fabric of the present invention is particularly suitable for textile products that require waterproofness and moisture permeability. Examples of such textile products include ski wear, rainwear, coats, blousons, windbreakers, down jackets, sportswear, work clothes, uniforms, backpacks, backpacks, bags, tents, zelts and the like.

<Effect>
In the method for producing a moisture-permeable and waterproof fabric of the present invention, the HSP distance between the polymer (A) in the water- and oil-repellent composition and the coating resin (C) in the liquid containing the coating resin (C) is 3 MPa ^0.5 or more. By setting the value to less than 15 MPa ^0.5 , the coating composition for forming the moisture-permeable waterproof layer does not strike through when the moisture-permeable waterproof layer is formed on the fabric treated with the water-repellent oil-repellent composition, and excellent peeling is achieved. A strong moisture-permeable waterproof layer can be formed.
Since the polymer (A) and the coating resin (C) having an HSP distance within the above-mentioned predetermined range are appropriately compatible with each other, the coating resin (C) is a fiber base material having a layer containing the polymer (A). Due to the anchor effect of the coating resin (C) and the fiber base material having the layer containing the polymer (A), the moisture-permeable and waterproof layer formed by the coating resin (C) forms the polymer (A). It is considered that it became difficult to peel off from the fiber base material having the containing layer.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples, and various modifications can be made without changing the gist of the present invention.

[Measurement method and test method]
<Measuring method of average molecular weight of fluorine-containing polymer>
(Separation of fluorine-containing polymer)
6 g of the emulsion containing the fluorine-containing polymer was added dropwise to a total of 60 g of a mixed solution of 6 g of hexane and 54 g of 2-butanol, and the mixture was stirred to precipitate a solid. After centrifugation at 3000 rpm for 5 minutes, the resulting solid was separated. To the separated solid, 30 g of isopropyl alcohol (hereinafter referred to as "IPA") modified alcohol and 30 g of ion-exchanged water were added and stirred well. After centrifugation at 3000 rpm for 5 minutes, the obtained solid was separated from the supernatant and vacuum dried at 35 ° C. overnight to obtain a fluorine-containing polymer.

(Measurement of number average molecular weight and mass average molecular weight)
The obtained fluorine-containing polymer is used as a fluorine-based solvent (AK-225, AGC product name) / THF /
Hexafluoro-2-propanol = 6/3/1 (volume ratio) was dissolved in a mixed solvent to prepare a solution having a solid content concentration of 0.1% by mass.
The prepared solution was passed through a 0.2 μm filter to prepare an analytical sample.
The number average molecular weight (Mn) and mass average molecular weight (Mw) of the fluorine-containing polymer contained in the analysis sample were measured by gel permeation chromatography (GPC) under the following measurement conditions.

-Measurement condition device: High-speed GPC device (HLC-8320GPC, Tosoh product name)
Column: An organic GPC column (PLgel 5 μm MIXED-C, 300 mm × 7.5 mm, Polymer Laboratories product name) and an organic GPC column (PLgel 3 μm 100 Å, 300 mm × 7.5 mm, Polymer Laboratories product name) are connected in series. Connected.
Measurement temperature: 37 ° C
Injection volume: 100 μL
Outflow rate: 1 mL / min Standard sample: Polystyrene (adjusted polystyrene kit, Agilent EasiCal PS-2, Agilent Technologies product name)
Eluent: Fluorine-based solvent (AK-225, AGC product name) / THF / hexafluoro-2-propanol = 6/3/1 (volume ratio) mixed solvent

<Evaluation method of water repellency (initial)>
The water repellency of the test cloth was evaluated according to the spray test method of JIS L 1092: 1998.
Water repellency was expressed in 5 grades from 1 to 5. The higher the grade, the better the water repellency. Those having a grade of 3 or higher were evaluated as exhibiting water repellency. A grade with a + indicates that the water repellency is slightly better than the standard level for that grade. A grade marked with-indicates that the water repellency is slightly worse than the standard level for that grade.

<Evaluation method of water repellency (after washing 20 times)>
For the test cloth, the washing of the test cloth was repeated 20 times according to the washing method of Appendix 103 of JIS L 0217: 1995. After washing, it was air-dried overnight in a room at room temperature of 25 ° C. and humidity of 60%. Then, the water repellency of the test cloth after washing 20 times was evaluated in the same manner as in the water repellency (initial stage).

<Evaluation method of oil repellency (initial)>
The oil repellency of the test cloth was evaluated according to AATCC TM118-1966. The oil repellency is represented by the grade shown in Table 1. An addition of + to the grade indicates that the oil repellency is slightly better than the standard level of the grade. An addition of-to the grade indicates that the oil repellency is slightly worse than the standard level of the grade.

<Evaluation method of peel strength>
A heat-sealing tape (width 2.5 cm, length 15 cm) was attached on the moisture-permeable waterproof layer of the test cloth by a heat press. Using a Tensilon universal tester (AGS-X, product name of Shimadzu Corporation), the force (peeling strength, unit: N / 2.5 cm) applied when the heat-sealing tape was peeled off was measured. The measurement was performed three times, and the arithmetic mean value of the peel strength (hereinafter referred to as "the average value of the peel strength") was obtained. The larger the average value of the peel strength, the more difficult it is for the moisture-permeable waterproof layer to peel off. An average peel strength of 6 N / 2.5 cm or more was evaluated as having excellent peel strength.

<Evaluation method of strike-through resistance>
The surface of the test cloth with the moisture permeable and waterproof layer on the side not coated with the liquid containing the coating resin was visually observed to determine whether or not the coating resin had exuded.
The case of exudation was evaluated as "x", and the case of no exudation was evaluated as "○".

<Evaluation method of DMF resistance>
A droplet (12 μL) of DMF was allowed to stand on the test cloth before forming the moisture-permeable waterproof layer, and the time (unit: seconds) until the droplet completely permeated the test cloth was measured. The time measurement was completed 600 seconds after the DMF droplets were allowed to stand. The time when the droplets were not completely soaked into the test cloth at the time when 600 seconds had passed from the start of the measurement was set to ">600".
The liquid containing the coating resin used to form the moisture-permeable waterproof layer contains DMF as a solvent. Therefore, the permeability of the DMF droplets is a measure of the permeability of the liquid containing the coating resin. It can be evaluated that the longer it takes for the DMF droplets to completely permeate, the better the permeation suppressing performance of the liquid containing the coating resin.

<Calculation method of Hansen solubility parameter (HSP) and Hansen solubility parameter distance (HSP distance)>
(HSP of fluorine-containing polymer)
6 g of the emulsion containing the fluorine-containing polymer was added dropwise to a total of 60 g of a mixed solution of 6 g of hexane and 54 g of 2-butanol, and the mixture was stirred to precipitate a solid. After centrifugation at 3000 rpm for 5 minutes, the resulting solid was separated. To the separated solid, 30 g of IPA-modified alcohol and 30 g of ion-exchanged water were added and stirred well. After centrifugation at 3000 rpm for 5 minutes, the obtained solid was separated from the supernatant and vacuum dried at 35 ° C. overnight to obtain a fluorine-containing polymer.
Twenty-three solvents with different solubilities (DMF, acrylonitrile, methanol, N-methylpyrrolidone, dimethylpolysiloxane, 1,4-dioxane, dimethylsulfoxide, dodecane, dimethylacetamide, etc., so that the fluorine-containing polymer is 10% by mass. Ethylene glycol dimethyl ether, methyl tert-butyl ether, toluene, tetrahydrofuran, hexafluoroisopropanol, cyclopentanone, butyl acetate, hexane, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, 1 , 1,1,2,2,3,3,4,5,5,6,6-tridecafluorohexane, cyclopentylmethyl ether, 2-methoxy-2-propanol, IPA, 1-hexene) Mixed with. After allowing to stand for 15 hours in an environment of 30 ° C., the dissolved state was confirmed, and the state in which the fluorine-containing polymer was liquefied and separated from the solvent in two layers to the state in which the polymer was completely mixed to form a single layer was "dissolved". I decided. Based on the information on the solubility in each solvent thus obtained, Hansen Solubility Parameters in Practice (HSPiP) ver. The Hansen solubility parameter was calculated according to 5. The dispersion term, polarity term, and hydrogen bond term of the Hansen solubility parameter of the fluorine-containing polymer were set to dDa, dPa, and dHa, respectively.

(HSP of coating resin)
50 g of urethane prepolymer (Resamine CU-4700, Dainichiseika Kogyo product name: polyethylene adipate / MDI prepolymer), 0.5 g of cross-linking agent (Coronate HL, Tosoh product name), and 25 g of DMF. Mixing was performed to prepare a liquid containing a coating resin.
6 g of the liquid containing the coating resin was added dropwise to 60 g of ion-exchanged water, and the mixture was stirred to precipitate a solid. After centrifugation at 3000 rpm for 5 minutes, the obtained solid was separated and vacuum dried at 35 ° C. overnight to obtain a sample for measuring the Hansen solubility parameter of the coating resin.
The Hansen solubility parameter of the coating resin was calculated in the same manner as that of the fluorine-containing polymer. The dispersion term, polarity term, and hydrogen bond term of the Hansen solubility parameter of the coating resin were set to dDb, dPb, and dHb, respectively.

(HSP distance between fluorine-containing polymer and coating resin)
The HSP distance (unit: MPa ^0.5 ) between the fluorine-containing polymer and the coating resin was calculated by the following formula.
{4 × (dDa-dDb) ² + (dPa-dPb) ² + (dHa-dHb) ² } ^0.5
dDa, dPa, dHa, dDb, dPb and dHb are the same as above, respectively.

[Manufacturing of fluorine-containing polymer]
<Manufacturing example 1>
Fluorine-containing compound (monomer (a)), halogenated olefin (monomer (b)), (meth) acrylate (monomer (c)), polymerizable used for producing a fluorine-containing polymer. The types and amounts (unit: parts by mass) of the compound (monomer (d)), surfactant, molecular weight modifier, initiator, and liquid medium are shown in the corresponding columns of Table 1.
In a glass container, 60 parts by mass of FMA, 19 parts by mass of StA, 10 parts by mass of a 10% by mass aqueous solution of NMAM (1 part by mass as NMAM), 30 parts by mass of a 10% by mass aqueous solution of PES-50 (3 parts by mass as PES-50), 1 part by mass of AGE-10, 2.4 parts by mass of 63% by mass solution of STMAC (1.5 parts by mass as STMAC), 1 part by mass of P204, 0.5 parts by mass of StSH, 30 parts by mass of DPG, and 160 parts by mass of water. Was added and 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.
While maintaining the obtained mixed solution at 60 ° C., it was treated at 40 MPa using a high-pressure emulsifier (Minilab, product name of APV Lanier) to obtain an emulsion. The obtained emulsion was placed in a stainless steel reactor and cooled to 30 ° C. or lower.
0.15 parts by mass of VA061A was added to the cooled emulsion to replace the gas phase with nitrogen, then 15 parts by mass of VCM and 5 parts by mass of VDC were introduced, and the polymerization reaction was carried out at 60 ° C. for 15 hours with stirring. This was carried out to obtain an emulsion containing a fluorine-containing polymer. The fluorinated polymer and emulsion produced in Production Example 1 may be referred to as fluorinated polymer 1 and emulsion 1, respectively.
The mass ratio of each monomer unit in the obtained fluorine-containing polymer is consistent with the charging ratio of each monomer used in the production of the fluorine-containing polymer.

The content ratio (unit: mass%) of the unit (c) in the fluorine-containing polymer and the solid content concentration (unit: mass%) of the emulsion are shown in the corresponding columns of Table 2.
The Mn and Mw of the fluorine-containing polymer measured by the above method are shown in the corresponding columns of Table 2.

<Manufacturing Examples 2 to 19>
The fluorine-containing polymers of Production Examples 2 to 19 were produced in the same manner as in Production Example 1 with the amounts of each raw material charged as shown in Tables 2 to 4.

The content ratio (unit: mass%) of the unit (c) in the fluorine-containing polymer and the solid content concentration (unit: mass%) of the emulsion are shown in the corresponding columns of Tables 2 to 4.
The Mn and Mw of the fluorinated polymer measured by the method described in the above-mentioned "Method for measuring the average molecular weight of the fluorinated polymer" are shown in the columns of Tables 2 to 4.

The meanings of the abbreviations in Tables 2 to 4 are as follows.
・ Monomer (a)
FMA: F (CF ₂ ) _6- CH ₂ CH _2- OC (O) -C (CH ₃ ) = CH ₂
・ Monomer (b)
VCM: Vinyl chloride VDC: Vinylidene chloride monomer (c)
StA: Stearyl Acrylate BeA: Behenyl Acrylate BeMA: Behenyl Methacrylate Monomer (d)
NMAM: N-methylolacrylamide HEMA: 2-hydroxyethyl methacrylate NP-A: Neopentyl glycol diacrylate D-BI: 2,5-dimethylpyrazole adduct of 2-isocyanatoethyl methacrylate

-Surfactant PES-50: Polyoxyethylene stearyl ether (additive of about 50 mol of ethylene oxide) (HLB value = 17.8, Emargen E350, Kao Corporation product name)
PEO-13: Polyoxyethylene oleyl ether (about 12.8 mol adduct of ethylene oxide) (HLB value = 13.6, Emargen E420, Kao product name)
PEO-30: Polyoxyethylene oleyl ether (addition of about 30 mol of ethylene oxide) (HLB value = 16.6, Emargen E430, Kao product name)
AGE-10: Acetylene glycol ethylene oxide adduct (about 10 mol of ethylene oxide adduct) (HLB value = 13, surfinol 465, product name of Nissin Chemical Industry Co., Ltd.)
AGE-30: Acetylene glycol ethylene oxide adduct (about 30 mol of ethylene oxide adduct) (HLB value = 17, Surfinol 485, Nissin Chemical Industry Co., Ltd. product name)
STMAC: Alkyl chloride (carbon number: 16-18) trimethylammonium chloride 63% by mass water and isopropyl alcohol solution (HLB value = 6.4, lipocard 18-63, Lion product name)
CTMAC: Alkyl chloride (carbon number: 8-18) 50% by mass water of trimethylammonium chloride and isopropyl alcohol solution (HLB value = 8.3, Lipocard C-50 Lion product name)
P204: Ethylene oxide propylene oxide polymer (containing 40% by mass of ethylene oxide) (HLB value = 13.7, propafenone 204, NOF product name)

-Molecular weight modifier StSH: Stearyl mercaptan DoSH: Dodecyl mercaptan-polymerization initiator VA061A: 2,2'-azobis [2- (2-imidazolin-2-yl) propane] (VA-061, product name of Wako Pure Chemical Industries, Ltd.) 10% by mass aqueous solution of acetate V-50: 2,2'-azobis (2-methylpropion amidine), dihydrochloride (V-50, product name of Wako Pure Chemical Industries, Ltd.)
V-601: Dimethyl-2,2'-azobis (2-methylpropionate) (V-601, product name of Wako Pure Chemical Industries, Ltd.)
-Liquid medium DPG: Dipropylene glycol DPGMME: Dipropylene glycol Monomethyl ether terragyme: Tetraethylene glycol dimethyl ether Water: Ion-exchanged water

[Examples 1 to 19]
<Formation of a layer containing a fluorine-containing polymer>
Ion-exchanged water was added to the emulsion containing the fluorine-containing polymer obtained in Production Examples 1 to 19 to adjust the solid content concentration to 30% by mass.
This emulsion having a solid content concentration of 30% by mass is diluted with tap water to have a solid content concentration of 1.2% by mass and an isocyanate-based cross-linking agent (Meicanate FM-1, product name of Meisei Chemical Industry Co., Ltd.) of 1% by mass. A water- and oil-repellent repellent composition was prepared by mixing so as to be.
After immersing the base cloth (nylon high-density taffeta) in the prepared water- and oil-repellent composition by the padding method, the wet pickup was squeezed to 45 to 50% by mass. This is heated and dried at 170 ° C. for 60 seconds and allowed to stand overnight in a room at 23 ° C. and 50% humidity to form a layer containing a fluorine-containing polymer on both sides of the base cloth to form a fluorine-containing polymer. A layered test cloth containing was produced.
The DMF resistance was evaluated by the above-mentioned evaluation method using the produced layered test cloth containing the fluorine-containing polymer. The evaluation results are shown in the corresponding columns of Tables 5 and 6.

<Formation of moisture permeable waterproof layer>
50 g of urethane prepolymer (Resamine CU-4700, Dainichiseika Kogyo product name, polyethylene adipate / MDI prepolymer), 0.5 g of cross-linking agent (Coronate HL, Tosoh company product name), and colorant (Seika Seven) 1.0 g of ALT # 8000 (product name of Dainichiseika Kogyo Co., Ltd.) and 25 g of DMF were mixed to prepare a liquid containing a coating resin for forming a moisture permeable waterproof layer.

Using an applicator (RK Print Coat Instruments Ltd.), the coating speed is 0.1 m / sec and the temperature of the liquid containing the coating resin is 35 ° C. so that the thickness after drying is 40 μm. A liquid containing a coating resin was applied onto one of the layers containing the fluorine-containing polymer of the base cloth on which the layers containing the fluorine-containing polymer were formed on both sides. After applying the liquid containing the coating resin, the layered test cloth containing the fluorine-containing polymer was allowed to stand for 1 minute, then immersed in water at 20 ° C. for 2 minutes, and then immersed in water at 40 ° C. for 2 minutes. A test cloth with a moisture permeable and waterproof layer was produced by drying at ° C. for 60 seconds.
Using the manufactured test cloth with a moisture-permeable waterproof layer, the peel strength, strike-through resistance, water repellency (initial), water repellency (after 20 times of washing) and oil repellency (initial) were evaluated by the above-mentioned evaluation method. .. The evaluation results are shown in the corresponding columns of Tables 5 and 6.

<HSP, HSP distance>
The HSP of the fluorine-containing polymer and the Hansen solubility HSP distance (unit: MPa ^0.5 ) between the fluorine-containing polymer and the coating resin were obtained by the above-mentioned method for calculating the HSP and HSP distance, and are shown in the corresponding columns of Tables 5 and 6. Indicated.

The meanings of the terms described in Tables 5 and 6 are as follows.
-Emulsion: Indicates an emulsion used to produce a water / oil repellent composition. "Production example" indicates which of Production Examples 1 to 19 the emulsion was produced. "Solid content concentration" indicates the solid content concentration of the emulsion as a mass percentage. The solid content is a component obtained by removing the liquid medium from the emulsion.
-Surfactant content: When the total mass of the fluorine-containing polymer contained in the water-repellent oil-repellent composition is 100 parts by mass, the content of the surfactant contained in the water-repellent oil-repellent composition is mass parts. It is represented by.
-Ratio of nonionic surfactant: The ratio of the total mass of the nonionic surfactant having an HLB value of less than 14 to the total mass of the surfactant contained in the water-repellent oil-repellent composition is calculated by mass percentage [unit: mass%]. Represent.

[Examples 20 to 31]
<Formation of a layer containing a fluorine-containing polymer>
A surfactant and ion-exchanged water were added to the emulsion containing the fluorine-containing polymer obtained in Production Examples 6 and 15-18 to adjust the solid content concentration to 30% by mass.
Using this emulsion having a solid content concentration of 30% by mass, a water-repellent oil-repellent composition was prepared in the same manner as in Examples 1 to 19 to produce a layered test cloth containing a fluorine-containing polymer.
The DMF resistance was evaluated by the above-mentioned evaluation method using the produced layered test cloth containing the fluorine-containing polymer. The evaluation results are shown in the corresponding columns of Tables 7 and 8.

<Formation of moisture permeable waterproof layer>
A test cloth with a moisture permeable and waterproof layer was produced in the same manner as in Examples 1 to 19, and peel strength, strike-through resistance, water repellency (initial), water repellency (after 20 times of washing) and water repellency (after 20 times of washing) were produced by the evaluation method described above. The oil repellency (initial) was evaluated. The evaluation results are shown in the corresponding columns of Tables 7 and 8.

Of the abbreviations in Tables 7 and 8, those not listed in Tables 2 to 4 have the following meanings.
-Surfactant AGE-4: Acetylene glycol ethylene oxide adduct (about 4 mol of ethylene oxide adduct) (Surfinol 440, product name of Nissin Chemical Industry Co., Ltd.)
Among the terms in Tables 7 and 8, the meanings of those not described in Tables 5 and 6 are as follows.
-Emulsion solid content concentration: Indicates which production example the emulsion used for producing the water-repellent and oil-repellent agent composition was produced, and the solid content concentration.
-Surfactant solid content concentration: Represents the solid content concentration of the additional surfactant used in the production of the water-repellent oil-repellent agent composition.

[Explanation of results]
Examples 1-9 and 20-26 correspond to the examples of the present invention. Examples 10 to 19 and Examples 27 to 31 correspond to comparative examples of the present invention.
In Examples 1 to 9 and Examples 20 to 26, the HSP distance between the fluorine-containing polymer and the coating resin is within the range of 3 MPa ^0.5 or more and less than 15 MPa ^0.5 , and the surface activity in the water-repellent oil-repellent composition. This is an example in which the ratio of the total mass of the nonionic surfactant having an HLB value of less than 14 to the total mass of the agent is 30% by mass or more. The peel strength of the moisture-permeable waterproof layer was 6 N / 2.5 cm or more, indicating that the moisture-permeable waterproof layer had excellent peel strength. Moreover, the grade of water repellency and oil repellency was 3 or more, and it was shown that it had excellent water repellency and oil repellency.
In Examples 10 to 19 and Examples 27 to 31, the HSP distance between the fluoropolymer and the coating resin is in the range of 3 MPa ^0.5 or more and less than 15 MPa ^0.5 , and the surface activity in the water-repellent oil-repellent composition. This is an example in which the ratio of the total mass of the nonionic surfactant having an HLB value of less than 14 to the total mass of the agent is not at least one of 30% by mass or more. One or more of the peel strength, water repellency and oil repellency of the moisture permeable and waterproof layer was inferior.
Examples 13 and 14 are examples in which the content ratio of the unit (c) in the fluorine-containing polymer exceeds 30% by mass, and the peel strength of the moisture-permeable waterproof layer is inferior.
Examples 20 to 26 are examples of preparing a water- and oil-repellent agent in which a surfactant is mixed with the fluorine-containing polymer emulsion of Production Example 6.
Examples 20 to 26 are examples in which the surfactant content is higher than that of Example 6. Similar to Example 6, the water and oil repellency was good, and the peel strength of the moisture permeable and waterproof layer was equal to or higher than that of Example 6.
In Examples 27 to 29, the amount of the surfactant having an HLB value of less than 14 was less than 30% by mass with respect to the total amount of the surfactant, so that the water repellency was inferior to that of Example 6.
Examples 30 and 31 are examples of preparing a water-repellent oil-repellent composition in which two kinds of fluorine-containing polymers are mixed. In Example 30, the HSP distance was 15 or more, and the peel strength of the moisture-permeable waterproof layer was inferior. In Examples 30 and 31, the water repellency was inferior because the amount of the surfactant having an HLB value of less than 14 was less than 30% by mass with respect to the total amount of the surfactant.

The moisture-permeable waterproof fabric produced by the method for producing the moisture-permeable waterproof fabric of the present invention has excellent water and oil repellency, the moisture-permeable waterproof layer is not easily peeled off, and the design of the surface is not impaired. Suitable for rainwear, coats, bruzon, windbreakers, down jackets, sportswear, work clothes, uniforms, backpacks, backpacks, bags, tents, zelts, etc.

Claims (10)

A water- and oil-repellent composition containing a fluorine-containing polymer, a liquid medium and a surfactant is brought into contact with the surface of the fiber base material to form a layer containing the fluorine-containing polymer on at least one surface of the fiber base material. ,
A method for producing a moisture-permeable waterproof fabric, wherein a liquid containing a coating resin is brought into contact with the surface of a layer containing a fluorine-containing polymer to form a moisture-permeable waterproof layer containing the coating resin.
The fluorine-containing polymer is a polymer containing a unit based on a fluorine-containing compound represented by the formula (1), a unit based on a halogenated olefin, and a unit based on a (meth) acrylic acid ester represented by the formula (2). And
The content ratio of the unit based on the (meth) acrylic acid ester in the fluorine-containing polymer is 30% by mass or less.
The Hansen solubility parameter distance between the fluorine-containing polymer represented by the formula (3) and the coating resin is 3 MPa ^0.5 or more and less than 15 MPa ^0.5 .
The ratio of the total mass of the nonionic surfactant having a Hydrophilic-Lipopicular Balance value of less than 14 to the total mass of the surfactant in the water-repellent oil-repellent composition is 30% by mass or more.
A method for manufacturing a moisture-permeable and waterproof fabric.
R ^f- Y-X formula (1)
In the formula (1), R ^f is a polyfluoroalkyl group having 1 to 6 carbon atoms, Y is a divalent organic group or a single bond containing no fluorine atom, and X is a formula (4) to ~. It is a group represented by any one of (7).
−CR ¹ = CH ₂ equation (4)
-C (O) OCR ¹ = CH ₂ equation (5)
-OC (O) CR ¹ = CH ₂ equation (6)
−OCH = CH ₂ equation (7)
However, in the formulas (4) to (7), R ¹ is a hydrogen atom, a methyl group or a halogen atom.
CH ₂ = C (CH ₃ ) -C (O) OR ² equation (2)
However, in the formula (2), R ² is an aliphatic saturated hydrocarbon group having 1 to 26 carbon atoms.
(4 × (dDa-dDb) ² + (dPa-dPb) ² + (dHa-dHb) ² ) Equation ^0.5 (3)
However, in the formula (3), dDa, dPa and dHa represent the dispersion term, the polarity term and the hydrogen bond term in the Hansen solubility parameter of the fluorine-containing polymer, respectively, and dDb, dPb and dHb are the coating resins, respectively. Represents the dispersion term, polarity term and hydrogen bond term in the Hansen solubility parameter. The manufacturing method according to claim 1, wherein the Hansen solubility parameter distance between the fluorine-containing polymer and the coating resin is calculated before manufacturing the moisture-permeable waterproof fabric. Claimed that the dispersion term of the Hansen solubility parameter of the fluorine-containing polymer is 15 to 20 MPa ^0.5 , the polar term is 5 to 10 MPa ^0.5 , and the hydrogen bond term is ^0.5 to ⁵ MPa ^0.5. Item 2. The manufacturing method according to Item 1 or 2. Claims 1 to 3 that the dispersion term of the Hansen solubility parameter of the coating resin is 15 to 25 MPa ^0.5 , the polar term is 8 to 15 MPa ^0.5 , and the hydrogen bond term is 3 to 8 MPa ^0.5. The production method according to any one of the above. The production method according to any one of claims 1 to 4, wherein the content ratio of the fluorine-containing polymer in the layer containing the fluorine-containing polymer is 50 to 100% by mass. The fluorine-containing polymer contains 60 to 85% by mass of a unit based on the fluorine-containing compound represented by the formula (1), 5 to 25% by mass of a unit based on the halogenated olefin, and the above formula (2). The production method according to any one of claims 1 to 5, which comprises 20% by mass or less of a unit based on the (meth) acrylic acid ester represented by. The unit based on the halogenated olefin includes a unit based on vinyl chloride and a unit based on vinylidene chloride, and the sum of the unit based on vinyl chloride and the unit based on vinylidene chloride with respect to the total amount of the unit based on the halogenated olefin. The ratio of the unit based on vinyl chloride is 50 to 100% by mass, and the ratio of the unit based on vinyl chloride to the total amount of the unit based on vinyl chloride and the unit based on vinylidene chloride is 50 to 100% by mass. The manufacturing method according to any one item. The production method according to any one of claims 1 to 7, wherein the fluorine-containing polymer has a number average molecular weight of 25,000 to 100,000. The production method according to any one of claims 1 to 8, wherein the fluorine-containing polymer has a mass average molecular weight of 70,000 or more. The production method according to any one of claims 1 to 9, wherein the water-repellent and oil-repellent composition contains 7 to 9.5 parts by mass of the surfactant with respect to 100 parts by mass of the fluorine-containing polymer. ..