JP7279480B2 - Method for manufacturing moisture-permeable waterproof fabric - Google Patents

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 treated with a moisture-permeable and waterproof coating in order to impart a function to release water vapor through perspiration from the body and a function to prevent 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 and waterproof layer is applied to one side of the fabric and cured to form a moisture-permeable and 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 fabric surface. For this reason, when the coating liquid is applied to the fabric, it is desirable that the coating liquid penetrates into the interior of the fibers to some extent to form a moisture-permeable waterproof layer.
However, if the coating liquid penetrates excessively into the interior of the fiber and escapes from one side of the coated fabric to the other side, a moisture-permeable waterproof layer is formed on both sides of the fabric, and the surface of the fabric turns white. or the design and texture are impaired.
Therefore, conventionally, the fabric surface has been treated with a water and oil repellent composition to suppress excessive permeation of the coating composition for forming the moisture-permeable waterproof layer into the fabric.

Patent Document 1 describes a water and oil repellent composition capable of suppressing the penetration of a coating liquid for forming a moisture-permeable waterproof layer and the peeling of the moisture-permeable waterproof layer, a unit having a polyfluoroalkyl group having 1 to 6 carbon atoms, a chloride 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 comprising a copolymer containing a vinylidene unit, an acrylate or methacrylate unit having a saturated hydrocarbon group of 12 or more carbon atoms, and a vinyl chloride unit, and a liquid medium is disclosed.
Patent Document 2 describes a water and oil repellent composition capable of suppressing the penetration of a coating liquid for forming a moisture-permeable waterproof layer and providing an article with excellent design properties. Units having a polyfluoroalkyl group having 1 to 6 carbon atoms and a vinyl chloride unit and a copolymer (X) having a mass average molecular weight of 60000 or more, and a water and oil repellent composition containing an aqueous medium.

WO2015/080060 WO2012/147700

However, a moisture-permeable waterproof fabric manufactured by applying a coating liquid for forming a moisture-permeable waterproof layer to a fabric treated with the water and oil repellent composition described in Patent Document 1 and Patent Document 2 has no moisture-permeable waterproof layer. Both peel strength and washing durability of water repellency were not sufficient.

Therefore, the present invention provides a coating composition for forming a moisture-permeable waterproof layer that does not show through when forming a moisture-permeable waterproof layer on a fabric treated with a water and oil repellent composition, and has improved peel strength and water and oil repellency. An object of the present invention is to provide a method for producing a moisture-permeable waterproof fabric for producing an excellent moisture-permeable waterproof fabric.

The above problems are solved by the following configuration.
[1] A water and oil repellent composition containing a fluoropolymer, a liquid medium and a surfactant is brought into contact with the surface of a fibrous base material to form a layer containing the fluoropolymer on at least one surface of the fibrous base material. to form
A method for producing a moisture-permeable waterproof fabric, comprising contacting a surface of the layer containing the fluoropolymer with a liquid containing a coating resin to form a moisture-permeable waterproof layer containing the coating resin,
The fluorine-containing polymer is a polymer containing units based on a fluorine-containing compound represented by formula (1), units based on a halogenated olefin, and units based on a (meth)acrylic acid ester represented by formula (2). and
The content ratio of units based on the (meth)acrylic acid ester in the fluoropolymer is 30% by mass or less,
The Hansen solubility parameter distance between the fluorine-containing polymer represented by 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 nonionic surfactants having a Hydrophilic-Lipophilic Balance value of less than 14 to the total mass of the surfactants in the water and oil repellent composition is 30% by mass or more.
A method for producing a moisture-permeable waterproof fabric.
^Rf -YX Formula (1)
In 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 atoms, and X is the formula (4) to It is a group represented by any one of (7).
—CR ¹ =CH ₂ Formula (4)
—C(O)OCR ¹ =CH ₂ Formula (5)
—OC(O)CR ¹ =CH ₂ Formula (6)
—OCH=CH ₂ Formula (7)
However, in 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 Formula (2)
However, in formula (2), R ² is a saturated aliphatic hydrocarbon group having 1 to 26 carbon atoms.
(4 × (dDa-dDb) ² + (dPa-dPb) ² + (dHa-dHb) ² ) ^0.5 formula (3)
However, in formula (3), dDa, dPa and dHa respectively represent the dispersion term, polar term and hydrogen bond term in the Hansen solubility parameter of the fluoropolymer, and dDb, dPb and dHb respectively represent the coating resin. Represents the dispersion, polar and hydrogen bonding terms in the Hansen Solubility Parameters.
[2] The manufacturing method according to [1], wherein the Hansen Solubility Parameter distance between the fluoropolymer and the coating resin is calculated before manufacturing 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 polarity term is 5 to 10 MPa ^0.5 , and the hydrogen bonding term is 0.5 to 5 MPa ^0.5 . The manufacturing method according to [1] or [2].
[4] The coating resin has a Hansen solubility parameter dispersion term of 15 to 25 MPa ^0.5 , a polar term of 8 to 15 MPa ^0.5 , and a hydrogen bonding term of 3 to 8 MPa ^0.5 . ] to [3].
[5] The production method according to any one of [1] to [4], wherein the content of the fluoropolymer in the layer containing the fluoropolymer is 50 to 100% by mass.
[6] The fluorine-containing polymer contains 60 to 85% by mass of the units based on the fluorine-containing compound represented by the formula (1), 5 to 25% by mass of the units based on the halogenated olefin, and the formula The production method according to any one of [1] to [5], including 20% by mass or less of the units based on the (meth)acrylic acid ester represented by (2).
[7] The unit based on the halogenated olefin includes a unit based on vinyl chloride and a 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 units based on the halogenated olefin is 80 to 100% by mass, and the ratio of vinyl chloride-based units to the total amount of the vinyl chloride-based units and the vinylidene chloride-based units is 50 to 100% by mass, [1] The manufacturing method according to any one of to [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 fluoropolymer 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 fluoropolymer. The manufacturing method described in .

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

The terms used in this specification have the following meanings.
A numerical range represented by "-" means a range including numerical values at both ends thereof.
"(Meth)acryl" is a generic term for "acryl" and "methacryl", and means acryl and methacryl individually. The same applies to "(meth)acryloyl", "(meth)acryloyloxy", "(meth)acrylic acid", "(meth)acrylate" and "(meth)acrylamide".
A number average molecular weight (hereinafter referred to as “Mn”) and a 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 was dissolved in a mixed solvent of fluorinated solvent (AK-225, product name of AGC)/tetrahydrofuran (THF)/hexafluoro-2-propanol=6/3/14 (volume ratio). to prepare a solution having a solid concentration of 0.5% by mass.
The prepared solution is passed through a 0.2 μm filter and used as an analysis sample.
Mn and Mw of an analysis sample are measured under the following conditions.
Measurement temperature: 37°C,
Injection volume: 100 μL,
Outflow rate: 1 mL/min,
Eluent: mixed solvent of fluorinated solvent (AK-225, product name of AGC)/THF/hexafluoro-2-propanol=6/3/14 (volume ratio).
The HLB value is a Hydrophilic-Lipophilic Balance value that indicates the degree of affinity of the surfactant for water and oil. , is the value calculated by the Griffin method. That is, it is a value calculated by (20×sum of formula weights of hydrophilic moieties/molecular weight of surfactant). Values for nonionic surfactants and cationic surfactants having repeating units based on propylene oxide are values calculated by the Davis method. That is, it is a value calculated by (7+sum of radicals of hydrophilic groups−sum of radicals of lipophilic groups). HLB values range from 0 to 20. The closer the HLB value to 0, the higher the lipophilicity, and the closer to 20, the higher the hydrophilicity. The HLB value for mixtures of two or more surfactants is the weighted average value of each surfactant.

[Method for manufacturing moisture-permeable waterproof fabric]
In the method for producing a moisture-permeable waterproof fabric of the present invention, a water and oil repellent composition is brought into contact with the surface of a fiber base material to form a layer containing a fluoropolymer on at least one surface of the fiber base material, A method for producing a moisture-permeable waterproof fabric, wherein the surface of the layer containing the fluoropolymer is brought into contact with a liquid containing a coating resin to form a moisture-permeable waterproof layer.

<Water and oil repellent composition>
The water 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 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 (hereinafter referred to as "unit (a)") based on a fluorine-containing compound (hereinafter referred to as "compound (a)"), a halogenated olefin (hereinafter referred to as "compound ( b)”. unit (c)”).

Compound (a) is a compound represented by Formula (1). The unit (a) contributes to the development of water and oil repellency by the polymer (A).
^Rf -YX (1)
The symbols in formula (1) have the following meanings.

R ^f is a C 1-6 polyfluoroalkyl group, preferably a C 1-6 perfluoroalkyl group, more preferably a C 4-6 perfluoroalkyl group, and a C 4-6 A straight-chain perfluoroalkyl group is more preferred. Examples of C4-C6 perfluoroalkyl groups are F(CF ₂ ) ₄ -, F(CF ₂ ) ₅ -, F(CF ₂ ) ₆ -, (CF ₃ ) ₂ CF(CF ₂ ) ₂ - but not limited to these. R ^f is preferably F(CF ₂ ) ₄ —, F(CF ₂ ) ₅ — and F(CF ₂ ) ₆ —, and F(CF ₂ ) _6- is more preferred.

Y is a divalent organic group containing no fluorine atom (hereinafter simply referred to as a "divalent organic group") or a single bond, and the divalent organic group is a divalent group containing a carbon atom; be. However, when the terminal atom of X bonded to the divalent organic group is an etheric oxygen atom, the terminal atom of the divalent organic group bonded to X is a carbon atom.
As the divalent organic group, one or more selected from an alkylene group, an alkenylene group, and -O-, -NH-, -CO-, -S-, -SO ₂ - and -CR ¹¹ =CR ¹² - Alkylene groups having at the terminal or between carbon-carbon atoms are preferred. However, R ¹¹ and R ¹² are each independently a hydrogen atom or a methyl group. These groups may be linear or branched, more preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 6 carbon atoms, A 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 -.
In the formula, i is an integer of 2 to 30, and L ¹ and L ² are 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 1-20.
L ² is an unbranched alkylene group, an unbranched and symmetrical arylene group or an unbranched and symmetrical aralkylene group, -(CH ₂ ) ₆ -, -C ₆ H ₄ - and -C ₆ H ₄ - Any one selected from CH ₂ —C ₆ H ₄ — is preferred. -C ₆ H ₄ - represents a 1,2-phenylene group, a 1,3-phenylene group or a 1,4-phenylene group, and a plurality of -C ₆ H ₄ - represents the same kind of phenylene group.

X is a group represented by any one of formulas (4) to (7).
-CR ¹ =CH ₂ (4)
-C(O) ^OCR1 = _CH2 (5)
-OC(O) ^CR1 = _CH2 (6)
-OCH= _CH2 (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, more preferably a hydrogen atom, a methyl group or a chlorine atom, A hydrogen atom or a methyl group is more preferred.
X is preferably the group (6), more preferably -OC(O)CH=CH ₂ or -OC(O)C(CH ₃ )=CH ₂ .

From the viewpoint of the polymerizability with the compound (b) and the compound (c), the flexibility of the layer containing the polymer (A), the adhesion of the polymer (A) to the fiber substrate, and the development of water repellency, the compound (a ) is preferably a compound represented by the formula (8).
^RF - ^L3 -OC(O) ^-CR3 = _CH2 (8)
In formula (8), R ^F is a perfluoroalkyl group having 4 to 6 carbon atoms, L ³ is a single bond or a linear alkylene group having 1 to 4 carbon atoms, and R ³ is a hydrogen atom or a methyl group. , a fluorine atom or a chlorine atom.

Two or more types of units (a) in the polymer (A) may be used.

Specific examples of compound (a) include F(CF ₂ ) ₆ -CH ₂ CH ₂ -OC(O)-C(CH ₃ )=CH ₂ , F(CF ₂ ) ₆ -CH ₂ -OC(O)- CH= _CH2 , F( _CF2 ) ₆ - _{CH2CH2 -} OC(O)-C(Cl)= _CH2 , F( _CF2 ) ₄ - _{CH2CH2 -} 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)= _CH2 , F( _CF2 ) _{6- CH2} -OC(O)-C( _CH3 )= _CH2 , F( _CF2 ) ₆ - _CH2- OC(O)-CH= _CH2 , F(CF ₂ ) ₆ --CH ₂ --OC(O)--C(Cl)=CH ₂ , but not limited thereto;

As the compound (a), F(CF ₂ ) ₆ —CH ₂ CH ₂ —OC(O)—C(CH ₃ )=CH ₂ and F(CF ₂ ) ₆ —CH ₂ are used because of their excellent water and oil repellency. _CH2 -OC(O)-C(Cl)= _CH2 , F( _CF2 ) ₄ - _{CH2CH2 -} OC(O)-C( _CH3 )= _CH2 , F( _CF2 ) _4- CH At least one selected from the group consisting of _{2CH 2} -OC(O)-CH=CH ₂ and F(CF ₂ ) ₄ -CH ₂ CH ₂ -OC(O)-C(Cl)=CH ₂ is preferred. , 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 preferred, and F(CF ₂ ) ₆ —CH ₂ CH ₂ —OC(O)—C(CH ₃ )=CH ₂ is even more preferred.

The compound (b) is not particularly limited as long as one or more of the hydrogen atoms of the olefin is substituted with a halogen atom. is preferably substituted with

Two or more types of units (b) in the polymer (A) may be used.

Specific examples of compound (b) include, 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 one 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 properties for the fiber base material.

When the unit (b) contains either or both of vinyl chloride units and vinylidene chloride units, the total content of vinyl chloride units and vinylidene chloride units in units (b) is preferably 80 to 100% by mass, and 70 ~100% by mass is more preferable, and 60 to 100% by mass is even more preferable.
At this time, the mass ratio of vinyl chloride units to the total amount of vinyl chloride units and vinylidene chloride units is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and even more preferably 70 to 100% by mass. When the mass ratio of the vinyl chloride unit to 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 Formula (2). The unit (c) contributes to development of water repellency by the polymer (A) and 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 a C 1-26 aliphatic saturated hydrocarbon group. The aliphatic saturated hydrocarbon group may be a linear or branched alkyl group, or 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, more preferably 6 to 22. When the number of carbon atoms in R ² is within this range, the layer containing the polymer (A) is more excellent in water repellency.

Two or more types of units (c) in the polymer (A) may be used.

As the compound (c), one or more (meth)acrylic acid esters in which R ² is a C 1-10 saturated aliphatic hydrocarbon group, and R ² is a C 12-26 C 12-26 aliphatic saturated hydrocarbon group. It may be used in combination with one or more of (meth)acrylic acid esters. As the compound (c), a (meth)acrylic acid ester in which R ² is an aliphatic saturated hydrocarbon group having 12 to 26 carbon atoms is preferably included in that the water repellency is likely to be good and the peel strength is likely 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. 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 ( meth) 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), nonadecyl (meth) acrylate, icosyl (meth) acrylate, henkoisyl (meth) acrylate (alias: behenyl (meth) acrylate), docosyl (meth) acrylate, tricosyl (meth) acrylate, tetracosyl ( meth)acrylate, pentacosyl (meth)acrylate, hexacosyl (meth)acrylate, but not limited to these.
Compound (c) includes 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 preferred, and lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate and behenyl ( More preferred are meth)acrylates.

In addition to the unit (a), the unit (b) and the unit (c), the polymer (A) further includes units based on other compounds (hereinafter referred to as "compound (d)") (hereinafter referred to as " unit (d)”) may be included.

Two or more types of units (d) in the polymer (A) may be used.

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 polymerizable functional groups are, but are not limited to, ethylenically unsaturated groups such as vinyl groups and allyl groups.

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 WO 2015/080060, compounds other than the above compound (a), compound (b) and compound (c), WO 2012/147700 Among the monomers (c) and (e) described in 1. above, compounds other than the above compounds (a), (b) and (c) can be used.

As the compound (d), glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, dimethylaminoethyl (meth) Acrylate, diethylaminoethyl (meth)acrylate, polycaprolactone ester of hydroxyethyl (meth)acrylate (FA, FM series under the trade name "PLAXEL", product name of Daicel Chemical Industries, Ltd.), 2-isocyanatoethyl (meth)acrylate, 3- Isocyanatopropyl (meth)acrylate, 2-butanone oxime adduct of 2-isocyanatoethyl (meth)acrylate, pyrazole adduct of 2-isocyanatoethyl (meth)acrylate, 3 of 2-isocyanatoethyl (meth)acrylate ,5-dimethylpyrazole adduct, 3-methylpyrazole adduct of 2-isocyanatoethyl (meth)acrylate, N-methylolacrylamide and neopentylglycol diacrylate are preferred, since 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 of the unit (a) in the polymer (A) is preferably 60 to 85% by mass, and more preferably 65 to 80% by mass because the water and oil repellency tends to be good.
The content of the unit (b) in the polymer (A) is preferably from 5 to 25% by mass, and more preferably from 15 to 25% by mass because the water and oil repellency tends to be good.
The content of the unit (c) in the polymer (A) is 30% by mass or less, and preferably 30% by mass or less from the viewpoint of adhesion between the layer containing the polymer (A) and the moisture-permeable waterproof layer, 25% by mass or less is more preferable, and 20% by mass or less is even more preferable. The content 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 overall balance between the adhesion between the layer containing the polymer (A) and the moisture-permeable waterproof layer and the water repellency and flexibility of the moisture-permeable waterproof fabric, the content of the unit (c) in the polymer (A) is , preferably 3 to 25% by mass, more preferably 5 to 20% by mass.

The content ratio of units (a), units (b) and units (c) in the polymer (A) (units (a)/units (b)/units (c)) is 60 to 85% by mass/5 to 25 % by mass/0 to 20% by mass is preferable, and in terms of better adhesion between the layer containing the polymer (A) and the moisture-permeable waterproof layer, it is 65 to 80% by mass/15 to 25% by mass/3 to 15% by mass. % is more preferred.

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. % by mass is more preferred, and 0.3 to 5% by mass is even more preferred.

Mn of the polymer (A) is preferably 25,000 to 100,000, more preferably 30,000 to 100,000, even more preferably 35,000 to 100,000.
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, even more preferably 150,000 to 350,000.
The polymer (A) preferably satisfies at least one of the ranges of Mn and Mw described above, and more preferably satisfies both.
When at least one of Mn and Mw of the polymer (A) is within the above range, the layer containing the polymer (A) has more excellent water and oil repellency, and the water and oil repellent composition has good film-forming properties. When the moisture-permeable waterproof layer is formed, the liquid containing the coating resin (C) is less likely to excessively permeate the fiber base material.

The method for producing the polymer (A) is not particularly limited, but for example, in the presence of a polymerization initiator, in a liquid medium, the monomer component containing the compound described above is polymerized to produce the polymer (A). It can be prepared by a method of obtaining a solution, dispersion or emulsion containing the
The method for polymerizing the monomer component is not particularly limited, and solution polymerization, dispersion polymerization, emulsion polymerization or suspension polymerization is preferred, and emulsion polymerization is more preferred. Moreover, each of the polymerization methods may be batch polymerization or multi-stage polymerization.

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

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

A molecular weight modifier may be used in the polymerization of the monomer component. As the molecular weight modifier, aromatic compounds, mercaptoalcohols or mercaptans are preferable, and alkylmercaptans are particularly preferable.
The amount of the molecular weight modifier to be added may be appropriately adjusted so that the Mn and Mw of the polymer (A) are within the ranges described above.

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, Organic acids are 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 water-soluble organic solvents include monoalkyl ethers of alcohols and polyhydric alcohols. Two or more water-soluble organic solvents may be used in combination.
Specific examples of said alcohols are, but are not limited to, tert-butyl alcohol, propylene glycol, dipropylene glycol, tripropylene glycol.
Specific examples of the monoalkyl ethers of polyhydric alcohols include, but are not limited to, 3-methoxymethylbutanol and dipropylene glycol monomethyl ether.
The water-soluble organic solvent is preferably one or more selected from the group consisting of dipropylene glycol, tripropylene glycol and dipropylene glycol monomethyl ether.
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 surfactants and fluorosurfactants. Both hydrocarbon surfactants and fluorosurfactants can be classified into anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants.
The surfactant used in producing the polymer (A) is usually incorporated into the water and oil repellent composition and becomes one of the components of the water and oil repellent composition.
From the viewpoint of compatibility with additives that may be contained in the water/oil repellent composition, the surfactant is preferably a combination of a nonionic surfactant and an amphoteric surfactant. In addition, from the viewpoint of adhesion between the layer containing the polymer (A) and the moisture-permeable waterproof layer, the surfactant may be a nonionic surfactant alone or a combination of a nonionic surfactant and a cationic surfactant. preferable. When a nonionic surfactant and a cationic surfactant are used in combination as the surfactant, the mass ratio of the nonionic surfactant and the cationic surfactant is not particularly limited, but the total mass of the nonionic surfactant/cationic surfactant The total mass of the agent is preferably 97/3 to 40/60, more preferably 95/5 to 50/50, even more preferably 93/7 to 60/40.

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

The nonionic surfactant is preferably one or more selected from the group consisting of surfactants s1 to s6 described in WO 2010/080060 or WO 2010/123042.
When the surfactant contains a cationic surfactant, the cationic surfactant is preferably surfactant s7 described in the above literature.
When the surfactant contains an amphoteric surfactant, the amphoteric surfactant is preferably surfactant s8 described in the above literature.
Further, as the surfactant, surfactant s9 (polymeric surfactant) described in the above document may be used.
Preferred embodiments of the surfactant are the same as the preferred embodiments described in the above literature.

The nonionic surfactant is preferably one or more selected from the group consisting of surfactants represented by the following formulas.
_{C10H21O- ( CH2CH2O ) p-} ( _C3H6O ) _q - _H
C12H25O- ( _{CH2CH2O ) p-} ( _{C3H6O ) q} - _{H
C16H31O- ( CH2CH2O ) p-} ( _C3H6O ) _q - _H
C16H33O- ( _{CH2CH2O ) p- ( C3H6O} ) _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
_C12H25O- ( _{CH2CH2O ) p- ( C3H6O ) q - C12H25}
C ₁₆ H ₃₁ O—(CH ₂ CH ₂ O) _p —(C ₃ H ₆ O) _q —C ₁₆ H _{31
C16H33O -- ( CH2CH2O} ) _p -- _{( C3H6O} ) _{q -- C12H25
iso - Ci3H27O-} ( _CH2CH2O ) _{p- ( C3H6O} ) _q -H
_{C10H21C (} O _{) O-(CH2CH2O)p-(C3H6O ) q - H
C16H33C} (O _{) O- ( CH2CH2O} ) _p- ( _C3H6O ) _{q - C12H25}
In the above formula, p is an integer of 3 or more, and q is an integer of 2 or more. For example, p is preferably from 5 to 200, and q is preferably from 5 to 200, for example.

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

The amphoteric surfactant is preferably one or more selected from the group consisting of dodecylbetaine, stearylbetaine, dodecylcarboxymethylhydroxyethylimidazolinium betaine, dodecyldimethylaminoacetic acid betaine, and fatty acid amidopropyldimethylaminoacetic acid betaine.

Since almost 100% of each compound is polymerized, the molar ratio of each compound in the monomer component when producing the polymer (A) is the same as the molar ratio of units based on each compound in the polymer (A). and preferred embodiments are also the same.

The solid content concentration in the emulsion is preferably 20 to 40% by mass immediately after the polymer (A) is produced. The solid content refers to the components contained in the emulsion excluding the liquid medium, and usually contains a surfactant in addition to the polymer (A). After the production of the polymer (A), the polymerization initiator usually does not remain. The content 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 by dividing the mass of the solid content by the mass of the emulsion before heat drying, with the mass of the solid content after drying the emulsion for 4 hours in a convection dryer at 120 ° C. Calculate by multiplying (unit: % by mass).

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

The water and oil repellent composition may contain additives in addition to the polymer (A), liquid medium and surfactant.
Examples of the additives include penetrants, antifoaming agents, water absorbing agents, antistatic agents, antistatic polymers, anti-wrinkle agents, texture modifiers, film-forming aids, water-soluble polymers, thermosetting agents, and epoxy curing agents. agents, thermosetting catalysts, cross-linking catalysts, synthetic resins, fiber stabilizers, pH adjusters and inorganic fine particles. As these additives, conventionally known ones can be used without particular limitation.

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

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

The content of the surfactant in the water and oil repellent composition is not particularly limited, but the total amount of the surfactant is preferably 1 to 12 parts by mass with respect to the total 100 parts by mass of the polymer (A), and 3 to 12 parts by mass. 11 parts by mass is more preferable, 5 to 10 parts by mass is more preferable, and 7 to 9.5 parts by mass is even more preferable. When the content of the surfactant is within this range, the moisture-permeable waterproof layer has a higher peel strength, and the moisture-permeable waterproof layer is more difficult to peel off from the fiber base material having the layer containing the polymer (A).

The solid content concentration of the water/oil repellent composition is not particularly limited, but is preferably 0.2 to 5% by mass when treating a fiber base material. When the solid content concentration of the water and oil repellent composition is within this range, the water and oil repellency can be satisfactorily exhibited, and the penetration of the liquid containing the coating resin (C) can be satisfactorily prevented.
The solid content concentration of the water and 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 the moisture-permeable waterproof layer in the method for producing the moisture-permeable waterproof fabric of the present invention.
The moisture-permeable waterproof layer formed from the liquid containing the coating resin (C) contains the coating resin (C).

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

The coating resin (C) is obtained by reacting a polyisocyanate component and a polyol component, since 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.

Aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and the like are used as the polyisocyanate component.
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, 4,4′- Diphenylmethane diisocyanate, but not limited to.
A specific example of the aliphatic diisocyanate is hexamethylene diisocyanate, but is not limited thereto.
Specific examples of the alicyclic diisocyanate include, but are not limited to, 1,4-cyclohexane diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), and isophorone diisocyanate.
As for the isocyanate component, the diisocyanate is used as a main component, and a tri- or higher functional polyisocyanate may be used as 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, polyether polyol, polyester polyol, and the like are used.
Specific examples of the polyether polyol are polyethylene glycol, polypropylene glycol, and polytetraethylene glycol, but are not limited to these.
The polyester polyol is a condensation polymer of a diol and a dibasic acid, a ring-opening polymer of a lactone, a condensation polymer of a hydroxy acid, or the like. Specific examples of the diol are ethylene glycol and propylene glycol, but are not limited to these. Specific examples of the dibasic acid include, but are not limited to, adipic acid and sebacic acid. A specific example of the lactone is ε-caprolactone, but is not limited thereto. Specific examples of the hydroxy acid include, but are not limited to, lactic acid and hydroxybutyric acid.
A hydroxyl group-terminated urethane prepolymer having two or more hydroxyl groups in one molecule can also be used as the polyol component.

As the 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.
Commercially available one-liquid type polyurethane resins include, for example, Lezamin CU-4700 (product name of Dainichiseika Kogyo Co., Ltd.) and Crisbon 8006HV (product name of DIC Corporation).

The content 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 0.2 to 0.2% by mass. 15% by mass is more preferred, and 0.4 to 13% by mass is even more preferred.

The liquid containing the coating resin (C) may further contain a solvent.
The solvent is not particularly limited, but examples include toluene, methyl ethyl ketone, N,N-dimethylformamide (hereinafter referred to as "DMF"), N,N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, hexamethylenephosphone. Amides can be mentioned. As the solvent, a polar organic solvent is preferable.
The content 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.
Although the auxiliary agent is not particularly limited, examples thereof include fluorine-based water repellent agents and cross-linking agents.
The content 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% by mass. % by mass is more preferred.

<Relationship between polymer (A) and coating resin (C)>
The Hansen solubility parameter distance between the polymer (A) represented by 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 formula (3), dDa, dPa and dHa respectively represent the dispersion term, polar term and hydrogen bond term in the Hansen solubility parameters of the polymer (A), and dDb, dPb and dHb respectively represent the coating resin (C ) represents the dispersion, polar and hydrogen bonding terms in the Hansen solubility parameters.

The Hansen Solubility Parameter (hereinafter referred to as "HSP") is an index indicating the compatibility between substances, and means that the closer the coordinates of two substances in a three-dimensional space, the higher the compatibility. The definition and calculation method of HSP are described in the following references.
Charles M. Hansen, "Hansen Solubility Parameters: A Users Handbook," CRC Press, 2007.
The HSP of a solvent whose literature value is not known 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 values are used for the solvents registered in the database, and the estimated values are used for the solvents not registered.
The HSP of a particular substance is usually determined by a solubility test that confirms the solubility of that substance in the solvent in which the HSP is established. Specifically, a substance whose HSP is to be determined is subjected to a solubility test using various solvents whose HSP is determined, and the HSP coordinates of all the solvents used are shown in a three-dimensional space, and the substance is dissolved. Find a sphere (solubility sphere) in which all the coordinates of the dissolved solvent are contained inside the sphere and the coordinates of the insoluble solvent are outside the sphere, and the central coordinates of the solubility sphere are taken as the HSP of the substance. In the solubility test of the present invention, the substance was mixed with a solvent and allowed to stand at 30±3° C. for about 15 hours.

The HSP is represented by a three-dimensional vector (dispersion term, polar term, and hydrogen bond term) having components of a dispersion term, a polar term, and a hydrogen bond term. When the HSP of the first substance is represented by (dD ₁ , dP ₁ , dH ₁ ) and the HSP of the second substance by (dD ₂ , dP ₂ , dH ₂ ), the relationship between the first substance and the second substance is 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 the 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 of the polymer (A) and the coating resin (C) is high, and when the moisture-permeable waterproof layer is formed, it becomes difficult for the moisture-permeable waterproof layer to separate from the fiber base material having the layer containing the polymer (A). Moreover, excessive permeation of the liquid containing the coating resin (C) into the layer containing the polymer (A) is suppressed, and strike-through of the liquid containing the coating resin (C) is eliminated.
The HSP distance is preferably 3 to 14 MPa ^0.5 , more preferably 3 to 12.5 MPa ^0.5 . If the HSP distance between the polymer (A) and the coating resin (C) is within this range, the coating resin will not excessively permeate into the details of the fiber structure of the fiber base material, but will permeate moderately. Therefore, the moisture-permeable waterproof layer containing the coating resin exhibits an appropriate anchoring effect on the fiber base material, and is less likely 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 polar term of 5 to 10 MPa ^0.5 , and a hydrogen bond term of 0 in terms of better compatibility with the coating resin. It is preferably ^0.5 to 5 MPa, the dispersion term is ^0.5 to 16 to 20 MPa, the polar term is ^0.5 to 6 to 10 MPa, and the hydrogen bonding term is 0.6 to ⁵ MPa. It is more preferable to have

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 bonding term of 3 in that it is easily dissolved by the solvent used during coating. ~8 MPa ^0.5 is preferable, the dispersion term is 16 to 24 MPa ^0.5 , the polar term is 9 to 14 MPa ^0.5 , and the hydrogen bonding term is 4 to 8 MPa ^0.5 . preferable.

<Fibrous base material>
The form of the fiber base material on which the layer containing the polymer (A) and the moisture-permeable waterproof layer are formed in the method for producing the moisture-permeable waterproof fabric of the present invention is not particularly limited, but for example, woven fabric, knitted fabric, non-woven fabric, or raised fabric. It is a fabric like The fibers of the fiber base material are not particularly limited, but for example, natural fibers such as cotton, wool, silk or cellulose, synthetic fibers such as polyester, polyamide, acrylic or aramid, chemical fibers such as rayon, viscose rayon or lyocell. , blended fibers of natural and synthetic fibers, and blended fibers of natural and chemical fibers. Examples of fibers when the fiber substrate 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, even more preferably 0.10 to 5 mm, from the viewpoint that the tear strength of the moisture-permeable waterproof fabric to be produced is superior. In addition, the thickness of the fiber base material is preferably 0.01 to 1 mm, more preferably 0.01 to 0.7 mm, and more preferably 0.01 to 0.5 mm, in order to easily reduce the weight of the moisture-permeable waterproof fabric to be produced. More preferred.

<Formation of layer containing polymer (A)>
In the method for producing the moisture-permeable waterproof fabric of the present invention, the water and oil repellent composition described above 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 only on one surface of the fiber base material, or may be formed on both surfaces.
Depending 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 contacted with the water and oil repellent composition is The water and oil repellent composition may reach the opposite surface to form a layer containing the polymer (A) on both sides of the fiber base material.
In order 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 It is preferable that the water and oil repellent composition is repeatedly brought into contact with the water and oil repellent composition to reach the surface opposite to the surface to which the water and oil repellent composition is applied.

The method for bringing the water/oil repellent composition into contact with the surface of the fiber substrate is not particularly limited, and conventionally known methods can be used. For example, a method of immersing a fiber substrate in a bath containing a water and oil repellent composition, a method of spray coating a diluted water and oil repellent composition on at least one surface of a fiber substrate, and a known foaming agent and water repellent. A method of mixing with an oil repellent composition and foam-coating it on at least one surface of a fiber base material may be mentioned. After the water and oil repellent composition is adhered to the surface of the fiber base material by these known methods, the water and oil repellent composition is dried by a method such as heat drying, and the polymer (A) is included. 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.

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

After the water and oil repellent composition is brought into contact with a 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. may These treatments may be performed on either the surface on which the layer containing the polymer (A) of the fiber base 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 the moisture-permeable waterproof fabric of the present invention, the surface of the layer containing the polymer (A) is brought into contact with the liquid containing the coating resin (C), and the moisture-permeable waterproof layer containing the coating resin (C) is to form
When the layer containing the polymer (A) is formed on one surface of the fiber base material, the surface of the layer containing the polymer (A) formed on the one surface contains the coating resin (C). Bring liquid into contact.
When the layers containing the polymer (A) are formed on both sides of the fiber base, one of the layers containing the polymer (A) formed on both sides of the fiber base is coated with a coating resin (C ).

The method for contacting the surface of the layer containing the polymer (A) with the liquid containing the coating resin (C) is not particularly limited, and conventionally known methods 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 brush, a knife coater, a knife over roll coater, a blade coater, a reverse roll coater, a spin coater, or A method of uniformly applying a liquid containing the coating resin (C) to the surface of the layer containing the polymer (A) using a kiss roll can be used. After applying the liquid containing the coating resin (C) to the surface of the layer containing the polymer (A) by these known methods, the coating resin (C) is allowed to stand for a predetermined time, and then dried by heating or immersed in water. Forms a moisture-permeable waterproof layer.
When a highly volatile and low water-soluble solvent such as toluene or methyl ethyl ketone is used as the solvent for the liquid containing the coating resin (C), a method of drying by heating is preferred. 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 micropores are formed in the film. It becomes a porous moisture-permeable waterproof layer, and it becomes possible to express the moisture-permeable waterproof function.
When a polar organic solvent such as DMF, N,N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone or hexamethylenephosphonamide is used as the solvent for the liquid containing the coating resin (C), a method of immersing in water. is preferred. 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) moves to the aqueous phase. A large number of minute holes are formed, forming a porous moisture-permeable and waterproof layer, and the moisture-permeable and waterproof function can be exhibited.
The size of the pores in the moisture permeable and waterproof layer is not particularly limited, but is preferably 0.1 to 10 μm, more preferably 0.1 to 5 μm, more preferably 0.1 to 3 μm, in order to improve the moisture permeable and waterproof function. More preferred. The size of pores in the moisture-permeable waterproof layer can be measured with a scanning electron microscope.
The lower limit of 0.1 μm means that the size of the pores that can be confirmed with a scanning electron microscope is 0.1 μm or more, and it is considered that smaller pores are present.

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

[Moisture-permeable waterproof fabric]
The moisture-permeable waterproof fabric manufactured by the moisture-permeable waterproof fabric manufacturing method 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. have layers.
When the fiber base material has the 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 layers containing the polymer (A) on both surfaces, the fiber base material has a moisture-permeable waterproof layer on one surface of the layers containing the polymer (A). .
The moisture-permeable and waterproof layer is a film containing the coating resin (C), and preferably has a porous structure having a large number of fine pores in order to easily achieve both waterproofness and moisture permeability. The moisture-permeable waterproof layer has, for example, a Gurley air permeability of 10 to 2000 sec/100 cc and a moisture permeability of 5000 to 100000 g/(m ² d) according to JIS Z-0208:1976 A-1 method. mentioned.
The moisture-permeable waterproof layer is difficult to peel from the fiber base material having the layer containing the polymer (A), and has excellent peel strength.
In the combination of the polymer (A) and the coating resin (C) in the method for producing the 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). can not 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 only on one surface. Thereby, 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 having 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 waterproof layer is 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 skiwear, rainwear, coats, blousons, windbreakers, down jackets, sportswear, work clothes, uniforms, rucksacks, backpacks, bags, tents, bilts, and the like.

<Effect>
In the method for producing a moisture-permeable 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. , 15 MPa less than ^0.5 , the coating composition for forming a moisture-permeable waterproof layer does not strike through when forming a moisture-permeable waterproof layer on the fabric treated with the water and oil repellent composition, and excellent peeling is achieved. A moisture-permeable waterproof layer having strength can be formed.
Since the polymer (A) and the coating resin (C) whose HSP distance is within the above predetermined range are moderately compatible, the coating resin (C) has a layer containing the polymer (A). The fiber base material having a layer containing the polymer (A) and the coating resin (C) penetrate moderately into the interior, and the moisture-permeable waterproof layer formed by the coating resin (C) is formed by the anchoring effect of the coating resin (C). It is thought that it became difficult to peel from the fiber base material having the layer containing.

Although the present invention will be described in more detail below with reference to examples, the present invention is not limited to these examples, and various modifications are possible without changing the gist of the present invention.

[Measurement method and test method]
<Method for Measuring Average Molecular Weight of Fluoropolymer>
(Separation of fluoropolymer)
6 g of the emulsion containing the fluorine-containing polymer was added dropwise to a total of 60 g of a mixed liquid of 6 g of hexane and 54 g of 2-butanol, and stirred to precipitate a solid. The resulting solid was separated after centrifugation at 3000 rpm for 5 minutes. To the separated solid, 30 g of denatured isopropyl alcohol (hereinafter referred to as "IPA") and 30 g of deionized water were added and well stirred. After centrifugation at 3000 rpm for 5 minutes, the resulting solid was separated from the supernatant and vacuum dried at 35° C. overnight to obtain a fluoropolymer.

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

・Measurement conditions Apparatus: High-speed GPC apparatus (HLC-8320GPC, product name of Tosoh Corporation)
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) were connected in series. Connected.
Measurement temperature: 37°C
Injection volume: 100 μL
Flow rate: 1 mL/min Standard sample: polystyrene (prepared polystyrene kit, Agilent EasiCal PS-2, Agilent Technologies product name)
Eluent: mixed solvent of fluorinated solvent (AK-225, product name of AGC)/THF/hexafluoro-2-propanol = 6/3/1 (volume ratio)

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

<Method for evaluating water repellency (after washing 20 times)>
The test cloth was washed 20 times according to the water washing method in Table 103 of JIS L 0217:1995. After washing, it was air-dried overnight in a room with a room temperature of 25°C and a humidity of 60%. Thereafter, the water repellency of the test fabric after 20 washes was evaluated in the same manner as for the water repellency (initial stage).

<Method for evaluating oil repellency (initial)>
The test fabrics were evaluated for oil repellency according to AATCC TM118-1966. Oil repellency was represented by the grade shown in Table 1. A grade with a + indicates slightly better oil repellency than the standard level for that grade. A grade with a minus sign indicates slightly worse oil repellency than the standard level for that grade.

<Method for evaluating peel strength>
A heat-sealing tape (width 2.5 cm, length 15 cm) was attached to 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 (peel strength, unit: N/2.5 cm) applied when the heat-sealable tape is peeled off was measured. The measurement was performed three times, and the arithmetic mean value of the peel strength (hereinafter referred to as "mean value of peel strength") was obtained. A higher average value of peel strength indicates that the moisture-permeable waterproof layer is less likely to be peeled off. An average value of peel strength of 6 N/2.5 cm or more was evaluated as excellent peel strength.

<Method for evaluating strike-through resistance>
The surface of the test fabric with a moisture-permeable waterproof layer on which the liquid containing the coating resin was not applied was visually observed to determine whether or not the coating resin oozed out.
The case where there was exudation was evaluated as "×", and the case where there was no exudation was evaluated as "○".

<Method for Evaluating DMF Resistance>
A droplet of DMF (12 μL) was left still on the test cloth before forming the moisture-permeable waterproof layer, and the time (unit: seconds) until the droplet completely soaked into the test cloth was measured. The measurement of time was completed 600 seconds after the DMF droplet was allowed to stand. The time when the droplet had not completely soaked into the test cloth after 600 seconds from the start of the measurement was defined as ">600".
The liquid containing the coating resin used for forming the moisture-permeable and waterproof layer contains DMF as a solvent. Therefore, the permeability of the DMF droplet is an index of the permeability of the liquid containing the coating resin. It can be evaluated that the longer the time required for the DMF droplets to completely permeate, the better the permeation suppression performance of the liquid containing the coating resin.

<How to calculate Hansen solubility parameter (HSP) and Hansen solubility parameter distance (HSP distance)>
(HSP of fluoropolymer)
6 g of the emulsion containing the fluoropolymer was added dropwise to a total of 60 g of a mixed liquid of 6 g of hexane and 54 g of 2-butanol, and stirred to precipitate a solid. The resulting solid was separated after centrifugation at 3000 rpm for 5 minutes. 30 g of IPA-denatured alcohol and 30 g of ion-exchanged water were added to the separated solid and thoroughly stirred. After centrifugation at 3000 rpm for 5 minutes, the resulting solid was separated from the supernatant and vacuum dried at 35° C. overnight to obtain a fluoropolymer.
23 kinds of solvents with different solubility (DMF, acrylonitrile, methanol, N-methylpyrrolidone, dimethylpolysiloxane, 1,4-dioxane, dimethylsulfoxide, dodecane, dimethylacetamide, 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 , 1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, cyclopentyl methyl ether, 2-methoxy-2-propanol, IPA, 1-hexene), respectively. mixed with After standing for 15 hours in an environment of 30 ° C, the dissolved state was confirmed, and the state from the state where the fluoropolymer was liquefied and separated into two layers with the solvent to the state where it was completely mixed and became a single layer was "dissolved". ” he decided. Based on the information on solubility in each solvent thus obtained, Hansen Solubility Parameters in Practice (HSPiP) ver. 5 to calculate the Hansen solubility parameters. The dispersion term, polar 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 (Rezamin CU-4700, product name of Dainichiseika Kogyo Co., Ltd.: polyethylene adipate/MDI prepolymer), 0.5 g of cross-linking agent (Coronate HL, product name of Tosoh Corporation), and 25 g of DMF. By mixing, a liquid containing the coating resin was prepared.
6 g of the liquid containing the coating resin was dropped into 60 g of ion-exchanged water and stirred to precipitate a solid. After centrifugation at 3000 rpm for 5 minutes, the resulting solid was isolated and vacuum dried overnight at 35° C. to obtain a sample for Hansen solubility parameter measurement of the coating resin.
The Hansen solubility parameter of the coating resin was calculated in the same manner as for the fluoropolymer. The dispersion term, polar term, and hydrogen bond term of the Hansen solubility parameters of the coating resin were set to dDb, dPb, and dHb, respectively.

(HSP distance between fluoropolymer and coating resin)
The HSP distance (unit: MPa ^0.5 ) between the fluoropolymer 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.

[Production of fluoropolymer]
<Production Example 1>
Fluorinated compound (monomer (a)), halogenated olefin (monomer (b)), (meth)acrylate (monomer (c)), polymerizability used for producing fluoropolymer 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 weight of FMA, 19 parts by weight of StA, 10 parts by weight of 10% by weight aqueous solution of NMAM (1 part by weight as NMAM), 30 parts by weight of 10% by weight aqueous solution of PES-50 (3 parts by weight as PES-50), 1 part by weight of AGE-10, 2.4 parts by weight of a 63% by weight solution of STMAC (1.5 parts by weight as STMAC), 1 part by weight of P204, 0.5 parts by weight of StSH, 30 parts by weight of DPG, and 160 parts by weight of water and heated at 60° C. for 30 minutes, and then mixed using a homomixer (product name of Nippon Seiki Seisakusho Co., Ltd.) to obtain a mixed solution.
While the resulting mixture was kept at 60° C., it was treated at 40 MPa using a high-pressure emulsifier (minilab, product name of APV Ranier) to obtain an emulsion. The resulting emulsion was placed in a stainless steel reactor and cooled to below 30°C.
After adding 0.15 parts by mass of VA061A to the cooled emulsion and replacing the gas phase with nitrogen, 15 parts by mass of VCM and 5 parts by mass of VDC were introduced, and the polymerization reaction was allowed to proceed at 60°C for 15 hours while stirring. to obtain an emulsion containing a fluoropolymer. The fluoropolymer and emulsion produced in Production Example 1 are sometimes referred to as fluoropolymer 1 and emulsion 1, respectively.
The mass ratio of each monomer unit in the obtained fluoropolymer coincides with the charging ratio of each monomer used in the production of the fluoropolymer.

The content ratio (unit: mass %) of the unit (c) in the fluoropolymer 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 fluoropolymer measured by the method described above are shown in the corresponding columns of Table 2.

<Production Examples 2 to 19>
The fluoropolymers of Production Examples 2 to 19 were produced in the same manner as in Production Example 1 except that the amount of each raw material charged was as shown in Tables 2 to 4.

The content ratio (unit: mass %) of the unit (c) in the fluoropolymer 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 fluoropolymer measured by the method described in "Method for measuring average molecular weight of fluoropolymer" are shown in the corresponding columns of Tables 2-4.

Abbreviations in Tables 2 to 4 have the following meanings.
・Monomer (a)
FMA: F( _CF2 ) _{6 - CH2CH2} -OC(O)-C( _CH3 )= _CH2
・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-isocyanatoethyl methacrylate 3,5-dimethylpyrazole adduct

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

・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 weight aqueous solution of acetate V-50: 2,2'-azobis (2-methylpropionamidine) 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 tetragyme: tetraethylene glycol dimethyl ether Water: deionized water

[Examples 1 to 19]
<Formation of Layer Containing Fluoropolymer>
Ion-exchanged water was added to the emulsions containing the fluoropolymers obtained in Production Examples 1 to 19 to adjust the solid content concentration to 30% by mass.
This emulsion with a solid content concentration of 30% by mass is diluted with tap water to a solid content concentration of 1.2% by mass and an isocyanate cross-linking agent (Meikanate FM-1, product name of Meisei Chemical Industry Co., Ltd.) concentration of 1% by mass. A water and oil repellent composition was prepared by mixing so that
A base fabric (nylon high-density taffeta) was immersed in the prepared water and oil repellent composition by a padding method, and then squeezed so that the wet pickup was 45 to 50% by mass. This was dried by heating at 170°C for 60 seconds, left to stand overnight in a room of 23°C and 50% humidity to form a layer containing the fluoropolymer on both sides of the base fabric, thereby removing the fluoropolymer. A test fabric with a layer containing
DMF resistance was evaluated by the evaluation method described above using the layered test cloth containing the produced fluoropolymer. 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 (Rezamin CU-4700, product name of Dainichiseika Kogyo Co., Ltd., polyethylene adipate/MDI prepolymer), 0.5 g of cross-linking agent (Coronate HL, product name of Tosoh Corporation), and coloring agent (Seika Seven 1.0 g of ALT#8000 (manufactured by 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 was 0.1 m/sec and the temperature of the liquid containing the coating resin was 35°C so that the thickness after drying was 40 μm. A liquid containing a coating resin was applied onto one of the layers containing the fluoropolymer of the base fabric on which the layers containing the fluoropolymer were formed on both sides. After applying the liquid containing the coating resin, the test cloth with the layer containing the fluoropolymer was allowed to stand for 1 minute, then immersed in water at 20°C for 2 minutes, and then in water at 40°C for 2 minutes. C. for 60 seconds to produce a test fabric with a moisture-permeable and waterproof layer.
Using the manufactured test cloth with a moisture-permeable waterproof layer, peel strength, strike-through resistance, water repellency (initial), water repellency (after 20 washings), and oil repellency (initial) were evaluated by the evaluation methods described above. . The evaluation results are shown in the corresponding columns of Tables 5 and 6.

<HSP, HSP distance>
By the method of calculating HSP and HSP distance described above, the HSP of the fluoropolymer and the Hansen solubility HSP distance (unit: MPa ^0.5 ) between the fluoropolymer and the coating resin are obtained, and are filled 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 the emulsion used to produce the water and oil repellent composition. "Manufacturing example" indicates which of manufacturing examples 1 to 19 the emulsion was manufactured. "Solid content concentration" indicates the solid content concentration of the emulsion in mass percentage. A solid content is a component except a liquid medium from an emulsion.
・Surfactant content: The content of the surfactant contained in the water and oil repellent composition is parts by weight when the total weight of the fluoropolymer contained in the water and oil repellent composition is 100 parts by weight. Represented by
Proportion of nonionic surfactant: the ratio of the total mass of nonionic surfactants having an HLB value of less than 14 with respect to the total mass of surfactants contained in the water and oil repellent composition in mass percentage [unit: mass%] show.

[Examples 20-31]
<Formation of Layer Containing Fluoropolymer>
A surfactant and ion-exchanged water were added to the emulsions containing the fluoropolymers obtained in Production Examples 6 and 15 to 18 to adjust the solid content concentration to 30% by mass.
Using this emulsion with a solid content concentration of 30% by mass, a water and oil repellent composition was prepared in the same manner as in Examples 1 to 19 to produce a test cloth with a layer containing a fluoropolymer.
DMF resistance was evaluated by the evaluation method described above using the layered test cloth containing the produced fluoropolymer. 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 waterproof layer was produced in the same manner as in Examples 1 to 19, and the peel strength, strike-through resistance, water repellency (initial), water repellency (after 20 washings) and Oil repellency (initial) was evaluated. The evaluation results are shown in the corresponding columns of Tables 7 and 8.

Abbreviations in Tables 7 and 8 that are not listed in Tables 2 to 4 have the following meanings.
・Surfactant AGE-4: acetylene glycol ethylene oxide adduct (ethylene oxide about 4 mol adduct) (Surfinol 440, product name of Nissin Chemical Industry Co., Ltd.)
The meanings of the terms in Tables 7 and 8 that are not described in Tables 5 and 6 are as follows.
Emulsion solid content concentration: Shows which production example the emulsion used in the production of the water and oil repellent 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 and oil repellent composition.

[Description of results]
Examples 1-9 and 20-26 correspond to examples of the invention. Examples 10-19 and 27-31 correspond to comparative examples of the invention.
In Examples 1 to 9 and Examples 20 to 26, 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 surfactant in the water and oil repellent composition In this example, the ratio of the total mass of nonionic surfactants having an HLB value of less than 14 to the total mass of the agents 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 has excellent peel strength. In addition, the grade of water repellency and oil repellency was 3 or higher, indicating excellent water 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 surfactant in the water and oil repellent composition This is an example that does not satisfy at least one condition that the ratio of the total mass of nonionic surfactants having an HLB value of less than 14 to the total mass of the agents is 30% by mass or more. One or more of the peel strength, water repellency, and oil repellency of the moisture-permeable waterproof layer was inferior.
Examples 13 and 14 are examples in which the content of the unit (c) in the fluoropolymer exceeded 30% by mass, and the peel strength of the moisture-permeable waterproof layer was inferior.
Examples 20 to 26 are examples in which water and oil repellents were prepared by mixing the fluoropolymer emulsion of Production Example 6 with a surfactant.
Examples 20-26 are examples with a higher surfactant content than Example 6. As in Example 6, the water and oil repellency was good, and the peel strength of the moisture-permeable and waterproof layer was the same or higher.
In Examples 27 to 29, the amount of surfactants having an HLB value of less than 14 was less than 30% by mass with respect to the total amount of surfactants.
Examples 30 and 31 are examples in which water and oil repellent compositions were prepared by mixing two kinds of fluoropolymers. 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 amount of surfactant having an HLB value of less than 14 was less than 30% by mass with respect to the total amount of surfactant, and thus the water repellency was poor.

The moisture-permeable waterproof fabric manufactured by the moisture-permeable waterproof fabric manufacturing method of the present invention has excellent water and oil repellency, the moisture-permeable waterproof layer does not easily peel off, and the surface design is not impaired. Suitable for rainwear, coats, blousons, windbreakers, down jackets, sportswear, work clothes, uniforms, rucksacks, backpacks, bags, tents, bilts, etc.

Claims (10)

A water and oil repellent composition containing a fluoropolymer, a liquid medium and a surfactant is brought into contact with the surface of a fibrous base material to form a layer containing the fluoropolymer on at least one surface of the fibrous base material. ,
A method for producing a moisture-permeable waterproof fabric, comprising contacting a surface of the layer containing the fluoropolymer with a liquid containing a coating resin to form a moisture-permeable waterproof layer containing the coating resin,
The fluoropolymer contains units based on a fluorine-containing compound represented by formula (1) and units based on a halogenated olefin , and units based on a (meth)acrylic acid ester represented by formula (2). A polymer that may comprise
The content ratio of units based on the (meth)acrylic acid ester in the fluoropolymer is 30% by mass or less,
The Hansen solubility parameter distance between the fluorine-containing polymer represented by formula (3) and the coating resin is 3 MPa ^0.5 or more and less than 15 MPa ^0.5 ,
The water and oil repellent composition contains 1 to 12 parts by mass of the surfactant with respect to 100 parts by mass of the fluoropolymer,
The ratio of the total mass of nonionic surfactants having a Hydrophilic-Lipophilic Balance value of less than 14 to the total mass of the surfactants in the water and oil repellent composition is 30% by mass or more.
A method for producing a moisture-permeable waterproof fabric.
^Rf -YX Formula (1)
In 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 atoms, and X is the formula (4) to It is a group represented by any one of (7).
-CR ¹ =CH ₂ Formula (4)
—C(O)OCR ¹ =CH ₂ Formula (5)
—OC(O)CR ¹ =CH ₂ Formula (6)
—OCH=CH ₂ Formula (7)
However, in 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 Formula (2)
However, in formula (2), R ² is a saturated aliphatic hydrocarbon group having 1 to 26 carbon atoms.
(4 × (dDa-dDb) ² + (dPa-dPb) ² + (dHa-dHb) ² ) ^0.5 formula (3)
However, in formula (3), dDa, dPa and dHa respectively represent the dispersion term, polar term and hydrogen bond term in the Hansen solubility parameter of the fluoropolymer, and dDb, dPb and dHb respectively represent the coating resin. Represents the dispersion, polar and hydrogen bonding terms in the Hansen Solubility Parameters. The manufacturing method according to claim 1, wherein the Hansen solubility parameter distance between the fluoropolymer and the coating resin is calculated before manufacturing the moisture-permeable waterproof fabric. 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 bonding term is 0.5 to 5 MPa ^0.5 . 3. The manufacturing method according to Item 1 or 2. Claims 1 to 3, wherein the Hansen solubility parameter of the coating resin has a dispersion term of 15 to 25 MPa ^0.5 , a polar term of 8 to 15 MPa ^0.5 , and a hydrogen bonding term of 3 to 8 MPa ^0.5 . The manufacturing method according to any one of. The production method according to any one of claims 1 to 4, wherein the content of the fluoropolymer in the layer containing the fluoropolymer is 50 to 100% by mass. The fluorine-containing polymer comprises 60 to 85% by mass of the units based on the fluorine-containing compound represented by the formula (1), 5 to 25% by mass of the units based on the halogenated olefin, and the formula (2). The production method according to any one of claims 1 to 5, comprising 20% by mass or less of units based on (meth) acrylic acid ester represented by. The units based on the halogenated olefin include units based on vinyl chloride and units based on vinylidene chloride, and the total amount of the units based on the vinyl chloride and the units based on the vinylidene chloride with respect to the total amount of the units based on the halogenated olefin is 80 to 100% by mass, and the ratio of units based on vinyl chloride is 50 to 100% by mass with respect to the total amount of units based on vinyl chloride and units based on vinylidene chloride. The manufacturing method according to any one of the items. 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 fluoropolymer 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 and oil repellent composition contains 7 to 9.5 parts by mass of the surfactant with respect to 100 parts by mass of the fluoropolymer. .