WO2014007345A1 - 透湿防水布帛 - Google Patents
透湿防水布帛 Download PDFInfo
- Publication number
- WO2014007345A1 WO2014007345A1 PCT/JP2013/068415 JP2013068415W WO2014007345A1 WO 2014007345 A1 WO2014007345 A1 WO 2014007345A1 JP 2013068415 W JP2013068415 W JP 2013068415W WO 2014007345 A1 WO2014007345 A1 WO 2014007345A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fluorine
- monomer
- group
- moisture
- polymer
- Prior art date
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
- D06M15/29—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides containing a N-methylol group or an etherified N-methylol group; containing a N-aminomethylene group; containing a N-sulfidomethylene group
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/273—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having epoxy groups
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
- D06M15/295—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides containing fluorine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2437/00—Clothing
Definitions
- the present invention relates to a moisture-permeable waterproof fabric that can be used as clothing, waterproof sheets, shoes, gloves, and the like.
- the fluoropolymer not only gives water and oil repellency and water pressure resistance to the fabric, but also prevents the synthetic resin from exuding to the opposite side of the fabric substrate when applying a synthetic resin that forms a moisture-permeable waterproof layer. It is also used as an agent.
- the fluoroalkyl group-containing polymer having 6 or less carbon atoms corresponding to environmental problems has a low anti-bleeding effect when a synthetic resin is applied, and the synthetic resin is not soaked into the opposite side of the cloth substrate. The problem is that it tends to occur. Further, when a synthetic resin film is attached, the adhesive penetrates into the fabric, so that the adhesive effect is weakened and the peel strength of the synthetic resin film is lowered.
- the present inventors have found that the above-mentioned object can be achieved when an intermediate layer containing a specific fluoropolymer is provided between the cloth substrate and the moisture-permeable waterproof layer. It came.
- the present invention A moisture-permeable waterproof fabric comprising an intermediate layer containing a fluoropolymer, and a moisture-permeable waterproof layer containing a synthetic resin,
- a moisture permeable waterproof fabric which is a fluoropolymer having dynamic viscoelasticity at 160 ° C. of 400 Pa ⁇ s or more is provided.
- A. (I) applying a fluorine-containing treatment agent comprising a fluorine-containing polymer to a fiber fabric to form an intermediate layer containing the fluorine-containing polymer; and (ii) on the intermediate layer of the fluorine-containing polymer.
- Manufacturing a moisture permeable waterproof fabric characterized by applying a synthetic resin (for example, by applying a synthetic resin or by attaching a synthetic resin film) to form a moisture permeable waterproof layer Method.
- B. A method for treating a fiber fabric, comprising applying a fluorine-containing treatment agent comprising a fluoropolymer to the fiber fabric to form an intermediate layer of the fluoropolymer.
- a fluorine-containing treatment agent for moisture-permeable and waterproof fabrics comprising a fluorine-containing polymer having dynamic viscoelasticity at 160 ° C. of 400 Pa ⁇ s or more.
- D. A method for producing a fluoropolymer in a moisture permeable waterproof fabric, The manufacturing method is (I) a step of obtaining a first polymer by polymerizing the fluorine-containing monomer (a) and optionally a non-fluorine monomer (c), and (II) a halogenated olefin in the presence of the first polymer.
- a production method comprising a step of producing a second polymer formed by the halogenated olefin monomer (b) by polymerizing the monomer (b) to obtain a fluoropolymer.
- the moisture permeable waterproof fabric of the present invention is excellent in moisture permeability, water resistance, and washing resistance. According to the present invention, when the synthetic resin forming the moisture permeable waterproof layer is applied to the cloth base material, the synthetic resin does not exude to the surface on the opposite side of the cloth base material.
- the moisture permeable waterproof fabric has a cloth base, an intermediate layer comprising a fluoropolymer on one surface of the cloth base, and a moisture permeable waterproof layer on the intermediate layer.
- the intermediate layer may be formed inside the cloth base material. You may provide the pattern layer which exposes a pattern or a decoration on a moisture-permeable waterproof layer. It is not necessary to provide a layer on the other surface of the cloth substrate.
- the cloth base is generally formed from natural fibers and / or synthetic fibers.
- the fibers of the fabric substrate may be natural fibers (such as cotton or wool), chemical fibers (such as viscose rayon or rheocell), or synthetic fibers (such as polyester, polyamide or acrylic fibers). Alternatively, it may be a mixture of fibers (eg, a mixture of natural and synthetic fibers). Examples of the form of the cloth substrate include woven fabric, knitted fabric, non-woven fabric, and raised fabric.
- the thickness of the cloth base is generally 0.05 to 10 mm, for example 0.1 to 1 mm.
- the moisture permeable waterproof layer comprises a synthetic resin.
- the moisture permeable waterproof layer is generally a microporous membrane.
- Specific examples of the synthetic resin include polyurethane resins, polyamino acid urethane resins, acrylic resins, polyester resins, polytetrafluoroethylene resins, and the like.
- the moisture permeable waterproof layer may be formed only from a synthetic resin, or may contain an additive such as an isocyanate.
- the thickness of the moisture permeable waterproof layer is generally 10 to 100 ⁇ m, for example 20 to 50 ⁇ m.
- the intermediate layer contains a fluoropolymer.
- the intermediate layer may be formed of only a fluoropolymer, or may contain additives such as melamine resin and blocked isocyanate.
- the thickness of the intermediate layer is generally 0.1 to 1 ⁇ m, for example 0.2 to 0.3 ⁇ m.
- the intermediate layer is excellent in solvent repellency and repels organic solvents such as dimethylformamide, toluene and methyl ethyl ketone.
- the fluoropolymer has a dynamic viscoelasticity at 160 ° C. of 400 Pa ⁇ s or more.
- the dynamic viscoelasticity of the fluoropolymer at 150 ° C. is preferably 500 Pa ⁇ s or more, particularly 900 Pa ⁇ s or more.
- the dynamic viscoelasticity of the fluoropolymer at 160 ° C. is preferably 400 Pa ⁇ s or more, particularly 600 Pa ⁇ s or more, for example, 800 Pa ⁇ s or more.
- the dynamic viscoelasticity of the fluoropolymer at 170 ° C. is preferably 300 Pa ⁇ s or more, particularly preferably 700 Pa ⁇ s or more.
- the dynamic viscoelasticity of the fluoropolymer at 160 ° C. may be 2500 Pa ⁇ s or less, particularly 2300 Pa ⁇ s or less, for example, 2100 Pa ⁇ s or less.
- the dynamic viscoelasticity at 170 ° C. of the fluoropolymer may be 2300 Pa ⁇ s or less, for example, 2000 Pa ⁇ s or less.
- the manufacture of moisture permeable waterproof fabric (I) applying a fluorine-containing treatment agent comprising a fluorine-containing polymer to a fiber fabric to form an intermediate layer of the fluorine-containing polymer; and (ii) on the intermediate layer of the fluorine-containing polymer, It can be performed by a method having a step of forming a moisture-permeable waterproof layer of synthetic resin.
- the moisture permeable waterproof layer can be formed, for example, by applying a synthetic resin or by attaching a synthetic resin film.
- the fluorine-containing polymer has a repeating unit derived from a fluorine-containing monomer as an essential component.
- the fluorine-containing polymer may further have a repeating unit derived from a non-fluorine monomer.
- a fluorine-containing polymer having a repeating unit derived from a fluorine-containing monomer and a non-fluorine monomer can be produced by batch charging (one-stage polymerization) or divided charging (multi-stage polymerization, particularly two-stage polymerization). Since the effect of preventing the seepage of the synthetic resin is increased, split charging is preferable.
- Split charging means delaying the charging of one or more monomers (starting polymerization) and charging the other one or more monomers (starting polymerization).
- Two-stage polymerization refers to a second single polymer containing one or more other monomers in the presence of a first polymer obtained by polymerizing a first monomer containing one or more monomers. It means carrying out polymerization of a monomer.
- Multi-stage polymerization is polymerization of two or more stages, for example, two-stage polymerization, three-stage polymerization and four-stage polymerization.
- a third polymer charged behind the second polymer is used.
- a fourth or more monomer is further used.
- two-stage polymerization which is representative of multistage polymerization, will be described.
- the fluoropolymer is A fluorine-containing polymer comprising a first polymer formed from a first monomer and a second polymer formed from a second monomer, The second monomer is polymerized in the presence of the first polymer; At least one of the first monomer and the second monomer contains the fluorine-containing monomer (a), The first monomer does not include the halogenated olefin monomer (b), The second monomer is a fluoropolymer containing the halogenated olefin monomer (b).
- Split charging (particularly two-stage polymerization) A process for producing a fluoropolymer comprising a first polymer formed from a first monomer and a second polymer formed from a second monomer,
- the manufacturing method is (I) a step of obtaining a first polymer by polymerizing the first monomer, and (II) a second polymer is obtained by polymerizing the second monomer in the presence of the first polymer.
- At least one of the first monomer and the second monomer contains a fluorine-containing monomer
- the first monomer comprises a non-fluorine non-crosslinkable monomer, does not contain a halogenated olefin monomer
- the second monomer is a process comprising a halogenated olefin monomer.
- the first monomer may or may not contain a halogenated olefin monomer.
- the first monomer preferably does not contain a halogenated olefin monomer.
- the fluoropolymer of the present invention has a repeating unit derived from the first monomer and a repeating unit derived from the second monomer.
- the first polymer and the second polymer may be copolymerized. That is, the first polymer and the second polymer may be chemically bonded. Alternatively, the first polymer and the second polymer may be physically bonded without forming a chemical bond.
- An example of a physical bond is a core / shell structure in which a first polymer forms a core and a second polymer forms a shell. In the core / shell structure, the first polymer and the second polymer may not be chemically bonded, but may be chemically bonded.
- a fluorine-containing monomer (a) and a halogenated olefin monomer (b) are used as monomers.
- the non-fluorine monomer (c) may be used as necessary, and may be a non-fluorine non-crosslinkable monomer and / or a non-fluorine crosslinkable monomer.
- the non-fluorine monomer (c) is preferably a non-fluorine non-crosslinkable monomer (c1) and / or may be a non-fluorine crosslinkable monomer (c2).
- At least one of the first monomer and the second monomer contains a fluorine-containing monomer. It is preferable that the first monomer contains a fluorine-containing monomer and the second monomer does not contain a fluorine-containing monomer.
- the first monomer preferably does not contain a halogenated olefin monomer, and the second monomer preferably contains a halogenated olefin monomer.
- the second monomer may consist only of a halogenated olefin monomer.
- the first monomer may contain a non-fluorine non-crosslinkable monomer. It is preferable that the second monomer does not contain a non-fluorine non-crosslinkable monomer.
- the second monomer does not contain a non-fluorine non-crosslinkable monomer, in the processing of the treatment agent containing the fluoropolymer, the performance of preventing roll contamination due to the polymer adhering to the roll is excellent. Yes.
- At least one of the first monomer and the second monomer may contain a non-fluorine crosslinkable monomer.
- the fluoropolymer contains a non-fluorine crosslinkable monomer
- the first monomer does not contain a non-fluorine crosslinkable monomer
- the second monomer contains a non-fluorine crosslinkable monomer.
- the first monomer may contain a non-fluorine crosslinkable monomer
- the second monomer may not contain a non-fluorine crosslinkable monomer.
- Preferred types of monomers in the first monomer and the second monomer include the following aspects.
- embodiment 2 (the first monomer is a fluorine-containing monomer and a non-fluorine non-crosslinkable monomer, and the second monomer is a halogenated olefin monomer) is particularly preferred.
- An embodiment in which each of the fluorinated monomer and the non-fluorine crosslinkable monomer is present in both the first monomer and the second monomer is also preferred. That is, an embodiment similar to Embodiments 1 to 7 except that the fluorine-containing monomer is present in both the first monomer and the second monomer, and the non-fluorine crosslinkable monomer is the first monomer and the second monomer.
- Aspects similar to Aspects 1-7 are also preferred except that they are present in both of the two monomers.
- Z is, for example, a linear alkylene group having 1 to 20 carbon atoms or a branched alkylene group, such as a group represented by the formula — (CH 2 ) x — (wherein x is 1 to 10), Alternatively, a group represented by the formula —SO 2 N (R 1 ) R 2 — or a formula —CON (R 1 ) R 2 (wherein R 1 is an alkyl group having 1 to 10 carbon atoms, and R 2 is , A straight-chain alkylene group or a branched alkylene group having 1 to 10 carbon atoms), or a formula —CH 2 CH (OR 3 ) CH 2 — (wherein R 3 is a hydrogen atom or carbon A group represented by an acyl group of 1 to 10 (for example, formyl or acetyl), or a formula —Ar—CH 2 — (wherein Ar is an arylene group optionally having a substituent) .) a group represented by, - (
- X is a linear or branched alkyl group having 2 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (provided that X 1 and X 2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.),
- a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group May be a substituted or unsubstituted phenyl group.
- the Rf group is preferably a perfluoroalkyl group.
- the Rf group has 1 to 6 carbon atoms, particularly 4 to 6 carbon atoms.
- Examples of Rf groups are -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF (CF 3 ) 2 , -CF 2 CF 2 CF 2 CF 3 , -CF 2 CF (CF 3 ).
- Z is an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms or a cyclic aliphatic group, -CH 2 CH 2 N (R 1 ) SO 2 -group (where R 1 is an alkyl group having 1 to 4 carbon atoms) or -CH 2 CH (OZ 1 ) CH 2 -group (where Z 1 is a hydrogen atom or an acetyl group) or — (CH 2 ) m —SO 2 — (CH 2 ) n — group or — (CH 2 ) m —S— (CH 2 ) n — group (where m is 1 to 10, n is 0 to 10, Preferably).
- the aliphatic group is preferably an alkylene group (particularly having 1 to 4, for example, 1 or 2 carbon atoms).
- the aromatic group or cycloaliphatic group may be substituted or unsubstituted.
- the S group or SO 2 group may be directly bonded to the Rf group.
- fluorine-containing monomer (a) include, for example, the following, but are not limited thereto.
- the halogenated olefin monomer (b) is preferably an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine, bromine or iodine atoms.
- the halogenated olefin monomer (b) is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms having 1 to 5 chlorine atoms.
- halogenated olefin monomer (b) are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide and vinylidene halides such as vinylidene chloride, vinylidene bromide and vinylidene iodide.
- Vinyl chloride is preferred because of high water resistance (particularly water resistance durability).
- the non-fluorine monomer (c) may be a non-fluorine non-crosslinkable monomer (c1) and / or a non-fluorine crosslinkable monomer (c2).
- the non-fluorine non-crosslinkable monomer (c1) is a monomer containing no fluorine atom.
- the non-fluorine non-crosslinkable monomer (c1) does not have a crosslinkable functional group.
- the non-fluorine noncrosslinkable monomer (c1) is noncrosslinkable.
- the non-fluorine non-crosslinkable monomer (c1) is preferably a non-fluorine monomer having a carbon-carbon double bond.
- the non-fluorine non-crosslinkable monomer (c1) is preferably a vinyl monomer containing no fluorine.
- the non-fluorine non-crosslinkable monomer (c1) is generally a compound having one carbon-carbon double bond.
- linear or cyclic hydrocarbon group having 1 to 30 carbon atoms examples include a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic aliphatic group having 4 to 30 carbon atoms, and 6 to 6 carbon atoms. 30 aromatic hydrocarbon groups, and aromatic aliphatic hydrocarbon groups having 7 to 30 carbon atoms.
- Straight chain or branched aliphatic hydrocarbon group having 12 to 30 carbon atoms (particularly 18 to 30), cyclic aliphatic group having 4 to 30 carbon atoms, aromatic hydrocarbon group having 6 to 30 carbon atoms, 7 to 7 carbon atoms
- a araliphatic hydrocarbon group having 30 carbon atoms is preferable, and a linear or branched aliphatic hydrocarbon group having 12 to 30 carbon atoms (particularly 18 to 30 carbon atoms) and a cyclic aliphatic group having 4 to 30 carbon atoms are particularly preferable.
- non-fluorine non-crosslinkable monomer (c1) examples include, for example, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, Methoxy polypropylene glycol (meth) acrylate and vinyl alkyl ether are included.
- the non-fluorine non-crosslinkable monomer (c1) is not limited to these examples.
- the non-fluorine non-crosslinkable monomer (c1) may be a (meth) acrylate ester having an alkyl group.
- the number of carbon atoms in the alkyl group may be 1-30, for example, 6-30 (eg 10-30).
- An acrylate represented by Since the polymer adhesion preventing property to the roll becomes high, the fluoropolymer was derived from an acrylate (CH 2 CA 1 COOA 2 ) in which A 2 is an alkyl group having 12 to 30 carbon atoms, particularly 18 to 30 carbon atoms. It is preferable to have a repeating unit.
- the non-fluorine non-crosslinkable monomer (c1) may be a (meth) acrylate monomer having a cyclic hydrocarbon group.
- the (meth) acrylate monomer (B) having a cyclic hydrocarbon group is a compound having a (preferably monovalent) cyclic hydrocarbon group and a monovalent (meth) acrylate group.
- the monovalent cyclic hydrocarbon group and the monovalent (meth) acrylate group are directly bonded.
- Examples of the cyclic hydrocarbon group include saturated or unsaturated monocyclic groups, polycyclic groups, and bridged cyclic groups.
- the cyclic hydrocarbon group is preferably saturated.
- the carbon number of the cyclic hydrocarbon group is preferably 4-20.
- Examples of the cyclic hydrocarbon group include a cyclic aliphatic group having 4 to 20 carbon atoms, particularly 5 to 12 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and an araliphatic group having 7 to 20 carbon atoms.
- the number of carbon atoms of the cyclic hydrocarbon group is particularly preferably 15 or less, for example 10 or less. It is preferred that the carbon atom in the ring of the cyclic hydrocarbon group is directly bonded to the ester group in the (meth) acrylate group.
- the cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group.
- cyclic hydrocarbon group examples include a cyclohexyl group, a t-butylcyclohexyl group, an isobornyl group, a dicyclopentanyl group, and a dicyclopentenyl group.
- the (meth) acrylate group is an acrylate group or a methacrylate group, but is preferably a methacrylate group.
- the monomer having a cyclic hydrocarbon group examples include cyclohexyl methacrylate, t-butylcyclohexyl methacrylate, benzyl methacrylate, isobornyl methacrylate, isobornyl acrylate, dicyclopentanyl methacrylate, dicyclopentanyl acrylate, And cyclopentenyl acrylate.
- the fluoropolymer of the present invention may have a repeating unit derived from the non-fluorine crosslinkable monomer (c2).
- the non-fluorine crosslinkable monomer (c2) is a monomer containing no fluorine atom.
- the non-fluorine crosslinkable monomer (c2) may be a compound having at least two reactive groups and / or carbon-carbon double bonds and not containing fluorine.
- the non-fluorine crosslinkable monomer (c2) may be a compound having at least two carbon-carbon double bonds, or a compound having at least one carbon-carbon double bond and at least one reactive group.
- the non-fluorine crosslinkable monomer (c2) may be mono (meth) acrylate, (meth) diacrylate or mono (meth) acrylamide having a reactive group.
- the non-fluorine crosslinkable monomer (c2) may be di (meth) acrylate.
- non-fluorine crosslinkable monomer (c2) examples include diacetone (meth) acrylamide, (meth) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 3- Chloro-2-hydroxypropyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, butadiene, isoprene, chloroprene, glycidyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di ( Examples include, but are not limited to, (meth) acrylate. In the present specification, “(meth) acrylate” means acrylate or methacrylate, and “(meth) acrylamide” means acrylamide or methacrylamide.
- non-fluorine non-crosslinkable monomer (c1) and / or the non-fluorine crosslinkable monomer (c2) By copolymerizing the non-fluorine non-crosslinkable monomer (c1) and / or the non-fluorine crosslinkable monomer (c2), water and oil repellency and antifouling properties, and cleaning resistance and washing resistance of these performances Various properties such as solubility, solubility in solvents, hardness, and feel can be improved as necessary.
- the amount of halogenated orenfin (b) is 2 to 500 parts by weight, for example 5 to 200 parts by weight, in particular 10 to 150 parts by weight, especially 20 to 50 parts by weight;
- the amount of non-fluorine monomer (c) may be 1200 parts by weight or less, for example 0.1 to 400 parts by weight, in particular 0.5 to 250 parts by weight, in particular 1 to 50 parts by weight.
- the amount of the non-fluorine non-crosslinkable monomer (c1) is 1000 parts by weight or less, for example, 0.1 to 300 parts by weight, particularly 1 to 200 parts by weight
- the amount of the non-fluorine crosslinkable monomer (c2) may be 50 parts by weight or less, for example, 30 parts by weight or less, particularly 0.1 to 20 parts by weight.
- the same kind of monomer for example, halogenated olefin monomer and fluorine-containing monomer
- the same kind in the first monomer is 3 to 97:97 to 3, for example 5 to It may be 90: 95-10, in particular 10-70: 90-30.
- the fluoropolymer in the present invention can be produced by any ordinary polymerization method, and the conditions for the polymerization reaction can be arbitrarily selected.
- Examples of such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization.
- solution polymerization a method in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen substitution, is heated and stirred in the range of 30 to 120 ° C. for 1 to 10 hours.
- the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. Can be mentioned.
- the polymerization initiator is used in the range of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.
- the organic solvent is inert to the monomer and dissolves them.
- an ester for example, an ester having 2 to 30 carbon atoms, specifically, ethyl acetate or butyl acetate
- a ketone for example, carbon It may be a ketone having a number of 2 to 30, specifically methyl ethyl ketone or diisobutyl ketone, or an alcohol (for example, an alcohol having 1 to 30 carbon atoms, specifically, isopropyl alcohol).
- organic solvent examples include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, Examples include diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, and the like.
- the organic solvent is used in the range of 10 to 2000 parts by weight, for example, 50 to 1000 parts by weight with respect to 100 parts by weight of the total
- Emulsion polymerization employs a method in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen substitution, is stirred and copolymerized in the range of 50 to 80 ° C. for 1 to 10 hours. .
- Polymerization initiators include benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, azo Water-soluble materials such as bisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide Oil-soluble ones such as t-butyl peroxypivalate and diisopropyl peroxydicarbonate are used.
- the polymerization initiator is used in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.
- the monomer is finely divided into water using an emulsifier that can impart strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer. It is desirable to polymerize using a soluble polymerization initiator.
- an emulsifier various anionic, cationic or nonionic emulsifiers can be used, and the emulsifier is used in the range of 0.5 to 20 parts by weight with respect to 100 parts by weight of the monomer. Preference is given to using anionic and / or nonionic and / or cationic emulsifiers.
- a compatibilizing agent such as a water-soluble organic solvent or a low molecular weight monomer that is sufficiently compatible with these monomers.
- a compatibilizing agent By adding a compatibilizing agent, it is possible to improve emulsifying properties and copolymerization properties.
- the water-soluble organic solvent include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol and the like, and 1 to 50 parts by weight with respect to 100 parts by weight of water. For example, it may be used in the range of 10 to 40 parts by weight.
- low molecular weight monomer examples include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc., and 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of monomers. For example, it may be used in the range of 10 to 40 parts by weight.
- a chain transfer agent may be used.
- the molecular weight of the copolymer can be varied.
- chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol and thioglycerol (especially alkyl mercaptans (for example, having 1 to 30 carbon atoms)), inorganic salts such as sodium hypophosphite and sodium bisulfite. Etc.
- the chain transfer agent may be used in an amount of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight with respect to 100 parts by weight of the total amount of monomers.
- Copolymerization of the fluorine-containing polymer can be produced by batch charging (one-stage polymerization) or divided charging (multi-stage polymerization, particularly two-stage polymerization).
- Split charging is preferable, but when a crosslinkable monomer is used, batch charging may be used.
- a polymerization reaction is carried out with a liquid containing a first monomer to produce a first polymer, and then a polymer reaction is carried out with a liquid containing the first polymer and the second monomer.
- the second polymer is produced to obtain a fluoropolymer composed of the first polymer and the second polymer.
- the polymerization of the second polymer may be started during the polymerization of the first polymer, or the polymerization of the second polymer may be started after the completion of the polymerization of the first polymer.
- the polymerization reaction of the first polymer (that is, the polymerization reaction of the first monomer) is 10% or more (that is, 10 to 100%), for example, 40% or more (that is, 40 to 100%), particularly 70% or more ( That is, after the completion of 70 to 100%), the polymerization of the second polymer may be started.
- the polymerization reaction completion rate% (that is, the polymerization reaction progress rate%) means the mol% of the reacted monomer (polymerized monomer).
- the polymerized monomer when the polymerization reaction is completed by 10%, the polymerized monomer is 10 mol% and the unreacted (unpolymerized) monomer is 90 mol%.
- the first monomer is a combination of at least two monomers, the mole% of the first monomer is based on the total mole of at least two monomers in the first monomer.
- the term “during polymerization of the first polymer” means that the polymerization reaction of the first polymer (that is, the polymerization reaction of the first monomer) is not completely completed. For example, polymerization of the first polymer is completed at 10% to less than 40%, 40% to less than 70%, or 70% to less than 100% (especially 80% to 99%, especially 85% to 98%) After that, the polymerization of the second polymer may be started.
- the term “after completion of polymerization of the first polymer” means that the polymerization reaction of the first polymer (that is, the polymerization reaction of the first monomer) is completed about 100%.
- the second polymer When the polymerization of the second polymer is initiated during the polymerization of the first polymer, the second polymer has a repeating unit derived from the first monomer and the second monomer. When the polymerization of the second polymer is started after completion of the polymerization of the first polymer, the second polymer has a repeating unit derived from only the second monomer.
- the first polymer is chemically bonded or not chemically bonded to the second polymer.
- substantially no unreacted non-fluorine non-crosslinkable monomer in the polymerization system at the time of starting the polymerization of the second monomer. “Substantially not present” means that the amount of the unreacted non-fluorine non-crosslinkable monomer at the time of starting the polymerization of the second monomer is It means 10 mol% or less, preferably 8 mol% or less, more preferably 5 mol% or less, especially 3 mol% or less, especially 1 mol% or less. Due to the substantial absence of unreacted non-fluorine non-crosslinkable monomer, it has excellent performance to prevent roll contamination due to the polymer adhering to the roll in the processing of the treatment agent containing the fluoropolymer. Yes.
- the fluoropolymer of the present invention is preferably produced by emulsion polymerization.
- the second polymer may surround the first polymer, and the fluoropolymer is separated from the first polymer by the shell of the second polymer. It may have a core / shell structure in which a monopolymer core is surrounded.
- the fluoropolymer can be applied to the base fabric by any of the known methods for forming a polymer film on the base fabric. Generally, after a liquid containing a fluoropolymer and a liquid medium is applied onto a cloth substrate, the liquid medium is removed by drying or the like, whereby a fluoropolymer film can be formed on the polymer. In the liquid containing the fluoropolymer and the liquid medium, the concentration of the fluoropolymer may be, for example, 0.01 to 20% by weight, particularly 0.05 to 10% by weight.
- the substrate cloth may be immersed in the solution, or the liquid may be attached to or sprayed on the substrate cloth.
- the base fabric to which the liquid is applied is dried, for example, to exhibit liquid repellency, and preferably heated at, for example, 100 ° C. to 200 ° C.
- the textile products to be treated are typically fabrics, which include woven, knitted and non-woven fabrics, fabrics and carpets in clothing form, but fibers or yarns or intermediate fiber products (eg sliver or It may be a roving yarn).
- the textile product material may be natural fibers (such as cotton or wool), chemical fibers (such as viscose rayon or rheocell), or synthetic fibers (such as polyester, polyamide or acrylic fibers), or May be a mixture of fibers, such as a mixture of natural and synthetic fibers.
- the production polymer of the present invention is particularly effective in making cellulosic fibers (such as cotton or rayon) oleophobic and oleophobic.
- the method of the present invention also generally makes the textile product hydrophobic and water repellent.
- the fibrous base material may be leather.
- aqueous solutions or aqueous emulsifications at various stages of leather processing, for example during the wet processing of leather or during the finishing of leather You may apply it to leather from things.
- the fibrous substrate may be paper.
- the production polymer may be applied to preformed paper or may be applied at various stages of papermaking, for example during the drying period of the paper.
- the surface treatment agent (fluorine treatment agent) of the present invention is preferably in the form of a solution, an emulsion or an aerosol.
- the surface treatment agent comprises a fluorine-containing polymer (active component of the surface treatment agent) and a medium (particularly a liquid medium such as an organic solvent and / or water).
- the concentration of the fluoropolymer may be, for example, 0.01 to 50% by weight.
- the surface treatment agent (fluorine treatment agent) of the present invention preferably comprises a fluoropolymer and an aqueous medium.
- the “aqueous medium” refers to a medium composed only of water and an organic solvent in addition to water (the amount of the organic solvent is 80 parts by weight or less, for example, 0.1 to 50 parts by weight, in particular 5 to 30 parts by weight).
- the fluoropolymer is preferably produced by a dispersion of the fluoropolymer by emulsion polymerization.
- the surface treating agent is preferably an aqueous dispersion in which the fluoropolymer particles are dispersed in an aqueous medium.
- the average particle size of the fluoropolymer is preferably 0.01 to 200 micrometers, such as 0.1 to 5 micrometers, particularly 0.05 to 0.2 micrometers.
- the average particle diameter can be measured with a dynamic light scattering device, an electron microscope or the like.
- the surface treatment agent of the present invention can be applied to an object to be treated by a conventionally known method.
- the surface treatment agent is dispersed in an organic solvent or water, diluted, and attached to the surface of the object to be treated by a known method such as dip coating, spray coating, foam coating, etc., and then dried. It is done. Further, if necessary, it may be applied together with an appropriate crosslinking agent and cured.
- an insect repellent, a softening agent, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixing agent, an anti-wrinkle agent, and the like can be added to the surface treatment agent of the present invention.
- the concentration of the fluoropolymer in the treatment liquid brought into contact with the substrate may be 0.01 to 20% by weight, particularly 0.05 to 10% by weight (particularly in the case of dip coating).
- the monomer composition in the polymer was subjected to elemental analysis (F atom, Cl atom and C atom), IR spectroscopy, 1H NMR spectroscopy and 19F NMR spectroscopy to determine the monomer composition (wt%) in the polymer.
- a sample polymer for measurement was obtained by separating 10 g of an aqueous dispersion of a dynamic viscoelasticity measurement polymer in 20 g of methanol and separating the acrylic polymer and the emulsifier by centrifuging at 10,000 rpm for 60 minutes.
- the complex viscosity ( ⁇ *) of this polymer was measured with a dynamic viscoelasticity measuring device RHEOSOL-G3000 (manufactured by UBM).
- Sample polymer 1g, frequency 0.5Hz, measurement temperature 40 ° C to 180 ° C was heated at 5 ° C / min, and dynamic viscoelasticity was measured.
- a treatment liquid was prepared by diluting an aqueous dispersion of a solvent-repellent polymer with water so that the solid concentration was 1% by weight.
- a nylon cloth was immersed in the treatment liquid, squeezed with a mangle at 4 kg / cm 2 and 4 m / min, and heat treated at 170 ° C. for 1 minute, and then the solvent repellency of the treated cloth was evaluated.
- the solvent repellency was measured by adding time for each time the solvent was absorbed by the cloth up to 120 seconds by adding one drop of DMF, MEK, toluene, and ethyl acetate onto the test cloth. A higher value indicates better solvent repellency.
- a treatment liquid was prepared by diluting an aqueous dispersion of the back-through polymer of the coating resin with water so that the solid concentration was 1% by weight.
- a nylon cloth is dipped in a treatment solution, squeezed with a mangle at 4 kg / cm 2 and 4 m / min, heat treated at 170 ° C. for 1 minute, and then a polyurethane resin having a concentration of 30% using MEK / toluene / DMF as a solvent (Daiichi Seisen) Chemically Resamin ME-3612LP) was uniformly applied to one side of a nylon cloth, dried at 100 ° C. for 1 minute, and then heat-treated at 150 ° C. for 1 minute. The non-coated surface was observed visually, and the penetration of the resin was evaluated as follows. ⁇ : There is no show-through ⁇ : There is a slight show-through ⁇ : There is a lot of show-through
- the aqueous dispersion of the peel strength polymer of the synthetic film was diluted with water so that the solid content concentration was 1% by weight to prepare a treatment solution.
- a nylon cloth is dipped in a treatment solution, squeezed with a mangle at 4 kg / cm 2 and 4 m / min, heat treated at 170 ° C. for 1 minute, and then a urethane resin-based adhesive having a concentration of 50% using MEK and ethyl acetate as a solvent ( Crisbon 4010FT manufactured by DIC Corporation) was applied to one side of a nylon cloth in a dot shape, and a polyurethane synthetic film was pressure-bonded, followed by heat treatment at 120 ° C. for 2 minutes.
- C6SFMA stearyl acrylate
- Example 2 A polymer dispersion was obtained in the same manner as in Example 1 except that 0.025 g of lauryl mercaptan was added after emulsification. At the time of filling vinyl chloride (when one-stage polymerization was completed), the polymerization reaction was 99% for C6SFMA and 96% for StA.
- Example 3 A polymer dispersion was obtained in the same manner as in Example 1 except that 0.12 g of lauryl mercaptan was added after emulsification. At the time of filling vinyl chloride (when one-stage polymerization was completed), the polymerization reaction was 99% for C6SFMA and 95% for StA.
- Example 4 A polymer dispersion was obtained in the same manner as in Example 1 except that 0.19 g of lauryl mercaptan was added after emulsification. At the time of filling vinyl chloride (when one-stage polymerization was completed), the polymerization reaction was 99% for C6SFMA and 96% for StA.
- C6SFA C 6 F 13 CH 2 CH 2 OCOCH ⁇ CH 2
- Example 6 A polymer dispersion was obtained in the same manner as in Example 2 except that 25 g of cyclohexyl methacrylate (CHMA) was used instead of 25 g of stearyl acrylate (StA). At the time of filling vinyl chloride (when one-stage polymerization was completed), the polymerization reaction was 99% for C6SFMA and 98% for CHMA.
- CHMA cyclohexyl methacrylate
- StA stearyl acrylate
- Example 7 A polymer dispersion was obtained in the same manner as in Example 2 except that 25 g of isobornyl acrylate (IBMA) was used instead of 25 g of stearyl acrylate (StA). At the time of filling vinyl chloride (at the end of the one-stage polymerization), the polymerization reaction was 99% for C6SFMA and 99% for IBMA.
- IBMA isobornyl acrylate
- StA stearyl acrylate
- Example 8 A polymer dispersion was obtained in the same manner as in Example 2, except that 0.25 g of neopentyl glycol diacrylate (NP-A) was added to Example 2. At the time of filling vinyl chloride (at the end of the first stage polymerization), the polymerization reaction was 99% for C6SFMA and 96% for StA.
- NP-A neopentyl glycol diacrylate
- Example 9 A polymer dispersion was obtained in the same manner as in Example 2, except that 2.25 g of diacetone acrylamide (DAAM) was added to Example 2. At the time of filling vinyl chloride (at the end of the first stage polymerization), the polymerization reaction was 99% for C6SFMA and 96% for StA.
- DAAM diacetone acrylamide
- Example 10 A polymer dispersion was obtained in the same manner as in Example 2, except that 2.25 g of glycidyl methacrylate (GLA) was added to Example 2. At the time of filling vinyl chloride (at the end of the first stage polymerization), the polymerization reaction was 99% for C6SFMA and 96% for StA.
- GLA glycidyl methacrylate
- Example 11 A polymer dispersion was obtained in the same manner as in Example 2, except that 2.25 g of isopropylacrylamide (NIPAM) was added to Example 2. At the time of filling vinyl chloride (at the end of the first stage polymerization), the polymerization reaction was 99% for C6SFMA and 96% for StA.
- NIPAM isopropylacrylamide
- Comparative Example 1 A polymer dispersion was obtained in the same manner as in Example 1 except that 0.25 g of lauryl mercaptan was added after emulsification. At the time of filling vinyl chloride (when one-stage polymerization was completed), the polymerization reaction was 99% C6SFMA completed and 95% StA was completed.
- Comparative Example 2 A polymer dispersion was obtained in the same manner as in Example 1 except that 0.38 g of lauryl mercaptan was added after emulsification. At the time of filling vinyl chloride (when one-stage polymerization was completed), the polymerization reaction was 99% for C6SFMA and 96% for StA.
- Comparative Example 3 A polymer dispersion was obtained in the same manner as in Example 2, except that 0.38 g of neopentyl glycol diacrylate was added to Example 2. At the time of filling vinyl chloride (at the end of the first stage polymerization), the polymerization reaction was 99% for C6SFMA and 96% for StA.
- Comparative Example 4 A polymer dispersion was obtained in the same manner as in Example 12 except that neopentyl glycol diacrylate was not added.
- Comparative Example 5 A polymer dispersion was obtained in the same manner as in Comparative Example 4 except that the amount of lauryl mercaptan added after emulsification was changed to 1.25 g.
- Table A shows the characteristics of each example.
- the moisture permeable waterproof fabric of the present invention is excellent in moisture permeability, water resistance and washing resistance.
- the moisture-permeable waterproof fabric of the present invention can be used for clothing such as sports clothing and winter clothing, waterproof sheets such as tents, sleeping bags and antifouling waterproof sheets, shoes and gloves.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Laminated Bodies (AREA)
Abstract
Description
含フッ素重合体は布帛に対して撥水撥油性及び耐水圧性を付与するだけでなく、透湿防水層を形成する合成樹脂を塗布する際、布基材反対側への合成樹脂の染み出し防止剤としても利用されている。
しかしながら、環境問題に対応したフルオロアルキル基炭素数が6以下のフルオロアルキル基含有重合体では、合成樹脂を塗布した場合の染み出し防止効果が低く、布基材反対側への合成樹脂の染み込みが起こり易いことが問題となっている。
また、合成樹脂のフィルムを貼り付ける場合は、接着剤が布帛に浸透してしまうため、接着効果が弱くなり、合成樹脂フィルムの剥離強度が低下することが問題となっている。
本発明の別の目的は、透湿防水層を形成する合成樹脂を布基材に塗布する際に、布基材の反対側の表面への合成樹脂の染み出しがない透湿防水布帛を提供することにある。
含フッ素重合体を含む中間層、および合成樹脂を含む透湿防水層を有してなる透湿防水布帛であって、
含フッ素重合体が、
(a)式:
CH2=C(-X)-C(=O)-Y-Z-Rf
[式中、Xは、水素原子またはメチル基であり、
Y は、-O- または -NH-であり、
Zは、直接結合または二価の有機基であり、
Rfは、炭素数1~6のフルオロアルキル基である。]
で示される含フッ素単量体、
(b)ハロゲン化オレフィン単量体、および
(c)必要により使用する、フッ素原子を有さず、少なくとも1つの炭素-炭素二重結合を有する非フッ素単量体
から誘導された繰り返し単位を有してなり、400Pa・s以上の160℃における動的粘弾性を有する含フッ素重合体である透湿防水布帛を提供する。
A.(i)含フッ素重合体を含んでなる含フッ素処理剤を繊維布帛に適用して、含フッ素重合体を含む中間層を形成する工程、および
(ii)含フッ素重合体の中間層の上に、合成樹脂を適用することによって(例えば、合成樹脂を塗布することによって、あるいは合成樹脂のフィルムを貼り付けることによって)、透湿防水層を形成する工程
を特徴とする、透湿防水布帛の製造方法。
B. 含フッ素重合体を含んでなる含フッ素処理剤を繊維布帛に適用して、含フッ素重合体の中間層を形成することを特徴とする繊維布帛の処理方法。
C.(a)式:
CH2=C(-X)-C(=O)-Y-Z-Rf
[式中、Xは、水素原子またはメチル基であり、
Y は、-O- または -NH-であり、
Zは、直接結合または二価の有機基であり、
Rfは、炭素数1~6のフルオロアルキル基である。]
で示される含フッ素単量体、
(b)ハロゲン化オレフィン単量体、および
(c)必要により使用する、フッ素原子を有さず、少なくとも1つの炭素-炭素二重結合を有する非フッ素単量体
から誘導された繰り返し単位を有してなり、400Pa・s以上の160℃における動的粘弾性を有する含フッ素重合体を含んでなる透湿防水布帛用の含フッ素処理剤。
D.透湿防水布帛における含フッ素重合体の製法であって、
製法は、
(I)含フッ素単量体(a)および必要により非フッ素単量体(c)を重合して第1重合体を得る工程、および
(II)第1重合体の存在下で、ハロゲン化オレフィン単量体(b)を重合することによって、ハロゲン化オレフィン単量体(b)によって形成される第2重合体を製造し、含フッ素重合体を得る工程
を有してなる製法。
本発明によれば、透湿防水層を形成する合成樹脂を布基材に塗布する際に、布基材の反対側の表面への合成樹脂の染み出しがない。
含フッ素重合体の150℃における動的粘弾性が500Pa・s以上、特に900Pa・s以上であることが好ましい。含フッ素重合体の160℃における動的粘弾性は、400Pa・s以上、特に600Pa・s以上、例えば800Pa・s以上であることが好ましい。含フッ素重合体の170℃における動的粘弾性が300Pa・s以上、特に700Pa・s以上であることが好ましい。
含フッ素重合体の150℃における動的粘弾性は、2500Pa・s以下、例えば2200Pa・s以下であってよい。含フッ素重合体の160℃における動的粘弾性は、2500Pa・s以下、特に2300Pa・s以下、例えば2100Pa・s以下であってよい。含フッ素重合体の170℃における動的粘弾性は、2300Pa・s以下、例えば2000Pa・s以下であってよい。
動的粘弾性が低すぎる(例えば、160℃における動的粘弾性が400Pa・s未満である)場合には、裏抜けが生じ、透湿防水層の剥離が生じやすい。動的粘弾性が一定値よりも低い場合には、透湿防水層が充分に中間層に密着している。
(i)含フッ素重合体を含んでなる含フッ素処理剤を繊維布帛に適用して、含フッ素重合体の中間層を形成する工程、および
(ii)含フッ素重合体の中間層の上に、合成樹脂の透湿防水層を形成する工程
を有する方法によって行える。透湿防水層の形成は、例えば、合成樹脂を塗布することによって、あるいは合成樹脂のフィルムを貼り付けることによって、行える。
含フッ素単量体および非フッ素単量体から誘導された繰り返し単位を有する含フッ素重合体は、一括仕込み(一段重合)または分割仕込み(多段重合、特に二段重合)によって製造できる。合成樹脂の染み出し防止の効果が高くなるので、分割仕込みが好ましい。分割仕込み(多段重合、特に二段重合)とは、1種以上の単量体の仕込み(重合開始)に遅らせて、他の1種以上単量体の仕込み(重合開始)を行うことを意味する。二段重合とは、1種以上の単量体を含む第1単量体を重合して得られた第1重合体の存在下で、他の1種以上の単量体を含む第2単量体の重合を行うことを意味する。
以下、多段重合の代表である二段重合について説明する。
第1単量体から形成されている第1重合体と、第2単量体から形成されている第2重合体を含んでなる含フッ素重合体であって、
第1重合体の存在下で、第2単量体が重合されており、
第1単量体および第2単量体の少なくとも一方は、含フッ素単量体(a)を含み、
第1単量体は、ハロゲン化オレフィン単量体(b)を含まず、
第2単量体は、ハロゲン化オレフィン単量体(b)を含む含フッ素重合体である。
第1単量体から形成されている第1重合体と、第2単量体から形成されている第2重合体を含んでなる含フッ素重合体の製法であって、
製法は、
(I)第1単量体を重合して第1重合体を得る工程、および
(II)第1重合体の存在下で、第2単量体を重合することによって、第2重合体を得る工程
を有してなり、
第1単量体および第2単量体の少なくとも一方は、含フッ素単量体を含み、
第1単量体は、非フッ素非架橋性単量体を含んで成り、ハロゲン化オレフィン単量体を含まず、
第2単量体は、ハロゲン化オレフィン単量体を含んで成る製法である。
本発明において、第1単量体はハロゲン化オレフィン単量体を含んでも含まなくてもどちらでもよい。第1単量体はハロゲン化オレフィン単量体を含まないことが好ましい。
第1単量体がハロゲン化オレフィン単量体を含まず、第2単量体はハロゲン化オレフィン単量体を含むことが好ましい。第2単量体はハロゲン化オレフィン単量体のみからなってもよい。
第1単量体が非フッ素非架橋性単量体を含んでいてよい。第2単量体が非フッ素非架橋性単量体を含まないことが好ましい。第2単量体が非フッ素非架橋性単量体を含まないことによって、含フッ素重合体を含む処理剤の加工処理において、ロールへポリマーが付着することによるロール汚れを防止する性能が優れている。
第1単量体および第2単量体の少なくとも一方が非フッ素架橋性単量体を含んでいてもよい。含フッ素重合体が非フッ素架橋性単量体を含む場合には、第1単量体が非フッ素架橋性単量体を含まず、第2単量体が非フッ素架橋性単量体を含んでもよいし、あるいは第1単量体が非フッ素架橋性単量体を含み、第2単量体が非フッ素架橋性単量体を含まなくてよい。
含フッ素単量体および非フッ素架橋性単量体のそれぞれが第1単量体と第2単量体の両方に存在する態様も好ましい。すなわち、含フッ素単量体が第1単量体と第2単量体の両方に存在する以外は態様1~7と同様の態様、非フッ素架橋性単量体が第1単量体と第2単量体の両方に存在する以外は態様1~7と同様の態様も好ましい。
含フッ素単量体は式:
CH2=C(-X)-C(=O)-Y-Z-Rf
[式中、Xは、水素原子またはメチル基であり、
Y は、-O- または -NH-であり、
Zは、直接結合または二価の有機基であり、
Rfは、炭素数1~6のフルオロアルキル基である。]
で示される含フッ素単量体である。Zは、例えば、炭素数1~20の直鎖アルキレン基または分枝状アルキレン基、例えば、式-(CH2)x-(式中、xは1~10である。)で示される基、あるいは、式-SO2N(R1)R2-または式-CON(R1)R2で示される基(式中、R1は、炭素数1~10のアルキル基であり、R2は、炭素数1~10の直鎖アルキレン基または分枝状アルキレン基である。)、あるいは、式-CH2CH(OR3)CH2-(式中、R3は、水素原子、または、炭素数1~10のアシル基(例えば、ホルミルまたはアセチルなど)を表す。)で示される基、あるいは、式-Ar-CH2-(式中、Arは、置換基を必要により有するアリーレン基である。)で示される基、-(CH2)m-SO2-(CH2)n-基 または -(CH2)m-S-(CH2)n-基(但し、mは1~10、nは0~10、である)であってよい。
CH2=C(-X)-C(=O)-Y-Z-Rf (I)
[式中、Xは、水素原子またはメチル基であり;
Yは、-O-または-NH-であり;
Zは、炭素数1~10の脂肪族基、炭素数6~18の芳香族基または環状脂肪族基、
-CH2CH2N(R1)SO2-基(但し、R1は炭素数1~4のアルキル基である。)または
-CH2CH(OZ1) CH2-基(但し、Z1は水素原子またはアセチル基である。)または
-(CH2)m-SO2-(CH2)n-基または -(CH2)m-S-(CH2)n-基(但し、mは1~10、nは0~10、である)、
Rfは、炭素数1~6の直鎖状または分岐状のフルオロアルキル基である。]
で示されるアクリレートエステルまたはアクリルアミドであることが好ましい。
-CH2CH2N(R1)SO2-基(但し、R1は炭素数1~4のアルキル基である。)または
-CH2CH(OZ1) CH2-基(但し、Z1は水素原子またはアセチル基である。)または
-(CH2)m-SO2-(CH2)n-基 または -(CH2)m-S-(CH2)n-基(但し、mは1~10、nは0~10、である)であることが好ましい。脂肪族基は、アルキレン基(特に炭素数は1~4、例えば1または2である。)であることが好ましい。芳香族基または環状脂肪族基は、置換または非置換であってよい。S 基または SO2基はRf基に直接に結合していてよい。
CH2=C(-H)-C(=O)-O-(CH2)2-Rf
CH2=C(-H)-C(=O)-O-C6H4-Rf
CH2=C(-H)-C(=O)-O-(CH2)2N(-CH3) SO2-Rf
CH2=C(-H)-C(=O)-O-(CH2)2N(-C2H5) SO2-Rf
CH2=C(-H)-C(=O)-O-CH2CH(-OH) CH2-Rf
CH2=C(-H)-C(=O)-O-(CH2)2-S-Rf
CH2=C(-H)-C(=O)-O-(CH2)2-S-(CH2)2-Rf
CH2=C(-H)-C(=O)-O-(CH2)3-SO2-Rf
CH2=C(-H)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf
CH2=C(-H)-C(=O)-NH-(CH2)2-Rf
CH2=C(-CH3)-C(=O)-O-(CH2)2-S-Rf
CH2=C(-CH3)-C(=O)-O-(CH2)2-S-(CH2)2-Rf
CH2=C(-CH3)-C(=O)-O-(CH2)3-SO2-Rf
CH2=C(-CH3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf
CH2=C(-CH3)-C(=O)-NH-(CH2)2-Rf
[上記式中、Rfは、炭素数1~6のフルオロアルキル基である。]
ハロゲン化オレフィン単量体(b)は、1~10の塩素原子、臭素原子またはヨウ素原子で置換されている炭素数2~20のオレフィンであることが好ましい。ハロゲン化オレフィン単量体(b)は、炭素数2~20の塩素化オレフィン、特に1~5の塩素原子を有する炭素数2~5のオレフィンであることが好ましい。ハロゲン化オレフィン単量体(b)の好ましい具体例は、ハロゲン化ビニル、例えば塩化ビニル、臭化ビニル、ヨウ化ビニル、ハロゲン化ビニリデン、例えば塩化ビニリデン、臭化ビニリデン、ヨウ化ビニリデンである。耐水性(特に耐水性の耐久性)が高くなるので、塩化ビニルが好ましい。
非フッ素非架橋性単量体(c1)は、フッ素原子を含まない単量体である。非フッ素非架橋性単量体(c1)は、架橋性官能基を有さない。非フッ素非架橋性単量体(c1)は、架橋性単量体(c2)とは異なり、非架橋性である。非フッ素非架橋性単量体(c1)は、好ましくは、炭素-炭素二重結合を有する非フッ素単量体である。非フッ素非架橋性単量体(c1)は、好ましくは、フッ素を含まないビニル単量体である。非フッ素非架橋性単量体(c1)は一般には、1つの炭素-炭素二重結合を有する化合物である。
CH2=CA-T
[式中、Aは、水素原子、メチル基、または、フッ素原子以外のハロゲン原子(例えば、塩素原子、臭素原子およびヨウ素原子)であり、
Tは、水素原子、炭素数1~30(例えば、1~20)の鎖状または環状の炭化水素基、またはエステル結合を有する鎖状または環状の炭素数1~31(例えば、1~20)の有機基である。]
で示される化合物であってよい。
CH2=CA1COOA2
[式中、A1は、水素原子、メチル基、または、フッ素原子以外のハロゲン原子(例えば、塩素原子、臭素原子およびヨウ素原子)であり、
A2は、CnH2n+1(n=1~30)によって表されるアルキル基である。]
で示されるアクリレートであってよい。
ロールへのポリマー付着防止性が高くなるので、含フッ素重合体が、A2が炭素数12~30、特に18~30のアルキル基であるアクリレート(CH2=CA1COOA2)から誘導された繰り返し単位を有することが好ましい。
本発明の含フッ素重合体は、非フッ素架橋性単量体(c2)から誘導された繰り返し単位を有していてよい。非フッ素架橋性単量体(c2)は、フッ素原子を含まない単量体である。非フッ素架橋性単量体(c2)は、少なくとも2つの反応性基および/または炭素-炭素二重結合を有し、フッ素を含有しない化合物であってよい。非フッ素架橋性単量体(c2)は、少なくとも2つの炭素-炭素二重結合を有する化合物、あるいは少なくとも1つの炭素-炭素二重結合および少なくとも1つの反応性基を有する化合物であってよい。反応性基の例は、ヒドロキシル基、エポキシ基、クロロメチル基、ブロックイソシアネート基、アミノ基、カルボキシル基などである。非フッ素架橋性単量体(c2)は、反応性基を有するモノ(メタ)アクリレート、(メタ)ジアクリレートまたはモノ(メタ)アクリルアミドであってよい。あるいは、非フッ素架橋性単量体(c2)は、ジ(メタ)アクリレートであってよい。
本明細書において、「(メタ)アクリレート」とは、アクリレートまたはメタクリレートを意味し、「(メタ)アクリルアミド」とは、アクリルアミドまたはメタクリルアミドを意味する。
ハロゲン化オレンフィン(b)の量が2~500重量部、例えば5~200重量部、特に10~150重量部、特別に20~50重量部であり、
非フッ素単量体(c)の量が1200重量部以下、例えば0.1~400重量部、特に0.5~250重量部、特別に1~50重量部であってよい。
含フッ素重合体において、含フッ素単量体(a)100重量部に対して、
非フッ素非架橋性単量体(c1)の量が1000重量部以下、例えば0.1~300重量部、特に1~200重量部であり、
非フッ素架橋性単量体(c2)の量が50重量部以下、例えば30重量部以下、特に0.1~20重量部であってよい。
同様の種類の単量体(例えば、ハロゲン化オレフィン単量体および含フッ素単量体)が第1単量体と第2単量体の両方に含まれる場合に、第1単量体における同種単量体(特に、ハロゲン化オレフィン単量体)と第2単量体における同種単量体(特に、ハロゲン化オレフィン単量体)の重量比は、3~97:97~3、例えば5~90:95~10、特に10~70:90~30であってよい。
水溶性有機溶剤としては、アセトン、メチルエチルケトン、酢酸エチル、プロピレングリコール、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコール、トリプロピレングリコール、エタノールなどが挙げられ、水100重量部に対して、1~50重量部、例えば10~40重量部の範囲で用いてよい。また、低分子量の単量体としては、メチルメタクリレート、グリシジルメタクリレート、2,2,2-トリフルオロエチルメタクリレートなどが挙げられ、単量体の総量100重量部に対して、1~50重量部、例えば10~40重量部の範囲で用いてよい。
二段重合において、一般に、第1単量体を含む液で重合反応を行って第1重合体を製造し、次いで、第1重合体および第2単量体を含む液で重合体反応を行って第2重合体を製造し、第1重合体と第2重合体から構成される含フッ素重合体を得る。第1重合体の重合中に第2重合体の重合を開始させてもよいし、あるいは第1重合体の重合完了後に第2重合体の重合を開始させてもよい。第1重合体の重合反応(すなわち、第1単量体の重合反応)が10%以上(すなわち、10~100%)、例えば40%以上(すなわち、40~100%)、特に70%以上(すなわち、70~100%)終了した後に、第2重合体の重合を開始させてよい。重合反応終了割合%(すなわち、重合反応進行割合%)は、反応済みの単量体(重合した単量体)のモル%を意味する。例えば、重合反応が10%終了している場合に、重合済み単量体が10モル%であり、未反応(未重合)単量体が90モル%である。第1単量体が少なくとも2種の単量体の組合せである場合には、第1単量体のモル%は、第1単量体における少なくとも2種の単量体の合計モルに基づく。
第1重合体の重合完了後とは、第1重合体の重合反応(すなわち、第1単量体の重合反応)が約100%終了していることを意味する。
本発明の含フッ素重合体において、第1重合体は、第2重合体に化学結合しているかまたは化学結合していない。
あるいは、繊維状基材は紙であってもよい。製造重合体を、予め形成した紙に適用してよく、または、製紙の様々な段階で、例えば、紙の乾燥期間中に適用してもよい。
以下において、部または%は、特記しない限り、重量部または重量%を表す。
特性は、次のようにして測定した。
ポリマーについて、元素分析(F原子、Cl原子およびC原子)、IR分光法、1H NMR分光法および19F NMR分光法を行って、ポリマーにおけるモノマー組成(重量%)を求めた。
重合体の水性分散液10gをメタノール20gに分散したものを60分間10000rpmで遠心分離器にかけてアクリルポリマーと乳化剤を分離し、測定用サンプルポリマーを得た。このポリマーの複素粘性率(η*)を動的粘弾性測定装置RHEOSOL-G3000((株)UBM製)で測定した。サンプルポリマー 1g、周波数0.5Hz、測定温度40℃から180℃まで5℃/分で昇温し動的粘弾性を測定した。
重合体の水性分散液を固形分濃度が1重量%になるよう水で希釈して処理液を調整した。ナイロン布を処理液に浸漬し、マングルで4kg/cm2、4m/分で絞って、170℃で1分間熱処理した後に、処理布の撥溶剤性を評価した。
撥溶剤性はDMF,MEK,トルエン,酢酸エチルをそれぞれ試験布上に一滴たらし、溶剤が布に吸収される時間を最大120秒まで測定し、撥溶剤性として時間で示した。数値が高い方が良好な撥溶剤性を示すこととなる。
重合体の水性分散液を固形分濃度が1重量%になるよう水で希釈して処理液を調整した。ナイロン布を処理液に浸漬し、マングルで4kg/cm2、4m/分で絞って、170℃で1分間熱処理した後、MEK/トルエン/DMFを溶媒とする濃度30%のポリウレタン樹脂(大日精化工業製 レザミンME-3612LP)をナイロン布の片面に均一に塗布し、100℃で1分間乾燥後、150℃で1分間熱処理した。非塗布面を目視にて観察し、樹脂の裏抜けを下記にて評価した。
◎: 全く裏抜けがない
○: ごく僅かに裏抜けがある
×: 多量に裏抜けがある
重合体の水性分散液を固形分濃度が1重量%になるよう水で希釈して処理液を調整した。ナイロン布を処理液に浸漬し、マングルで4kg/cm2、4m/分で絞って、170℃で1分間熱処理した後、MEKと酢酸エチルを溶媒とする濃度50%のウレタン樹脂系接着剤(DIC株式会社製 クリスボン4010FT)をナイロン布の片面にドット状に塗布し、ポリウレタンの合成フィルムを圧着後、120℃で2分間熱処理した。得られたナイロン布をAATCC 88B(1)(III)で20回繰り返し洗濯を行なった後、合成フィルムの剥離状態を目視にて観察し、その状態を下記にて評価した。
◎: 全く剥離がない
○: ごく僅かに剥離がある
×: はっきりと剥離がわかる
二段重合:
1LオートクレーブにC6F13CH2CH2OCOC(CH3)=CH2(「C6SFMA」と略す。)179g、ステアリルアクリレート(StA) 25g、トリプロピレングリコール 75.8g、純水 446g、ポリオキシエチレンラウリルエーテル 12.7g、ポリオキシエチレンオレイルエーテル 2.47g、ポリオキシエチレンイソトリデシルエーテル5.05g、ジアルキル(牛脂)ジメチルアンモニウムクロライド 2.66gを入れ、60℃で加温後、高圧ホモジナイザーで乳化分散させた。乳化分散後、2,2-アゾビス(2-アミジノプロパン)2塩酸塩 1.92gを添加し60℃で1時間反応させた(重合反応C6SFMA99%終了、StA 97%終了)。次いで、塩化ビニル 60gを圧入充填し、さらに2時間反応させ、重合体の水性分散液を得た。その固形分濃度が30重量%となるように純水で濃度調整した水性分散液の特性を測定した。結果を表Aに示す。
乳化後にラウリルメルカプタン 0.025gを加えた以外は実施例1と同様の方法にて重合体の分散液を得た。
塩化ビニル充填時点(一段重合終了時点)において重合反応は、C6SFMAは99%終了、StAは96%終了していた。
乳化後にラウリルメルカプタン 0.12gを加えた以外は実施例1と同様の方法にて重合体の分散液を得た。
塩化ビニル充填時点(一段重合終了時点)において重合反応は、C6SFMAは99%終了、StAは95%終了していた。
乳化後にラウリルメルカプタン 0.19gを加えた以外は実施例1と同様の方法にて重合体の分散液を得た。
塩化ビニル充填時点(一段重合終了時点)において重合反応は、C6SFMAは99%終了、StAは96%終了していた。
C6F13CH2CH2OCOC(CH3)=CH2 179gの替わりにC6F13CH2CH2OCOCH=CH2 (C6SFA)179gを使用した以外は実施例2同様の方法にて重合体の分散液を得た。
塩化ビニル充填時点(一段重合終了時点)において重合反応は、C6SFAは99%終了、StAは95%終了していた。
ステアリルアクリレート(StA) 25gの替わりにシクロヘキシルメタクリレート(CHMA)25gを使用した以外は実施例2同様の方法にて重合体の分散液を得た。
塩化ビニル充填時点(一段重合終了時点)において重合反応は、C6SFMAは99%終了、CHMAは98%終了していた。
ステアリルアクリレート(StA) 25gの替わりにイソボロニルアクリレート(IBMA)25gを使用した以外は実施例2同様の方法にて重合体の分散液を得た。
塩化ビニル充填時点(一段重合終了時点)において重合反応は、C6SFMAは99%終了、IBMAは99%終了していた。
実施例2にネオペンチルグリコールジアクリレート(NP-A) 0.25gを加えた以外は、実施例2と同様の方法にて重合体の分散液を得た。
塩化ビニル充填時点(一段重合終了時点)において重合反応は、C6SFMAは99%終了、StAは96%終了していた。
実施例2にジアセトンアクリルアミド(DAAM) 2.25gを加えた以外は、実施例2と同様の方法にて重合体の分散液を得た。
塩化ビニル充填時点(一段重合終了時点)において重合反応は、C6SFMAは99%終了、StAは96%終了していた。
実施例2にグリシジルメタクリレート(GLA) 2.25gを加えた以外は、実施例2と同様の方法にて重合体の分散液を得た。
塩化ビニル充填時点(一段重合終了時点)において重合反応は、C6SFMAは99%終了、StAは96%終了していた。
実施例2にイソプロピルアクリルアミド(NIPAM) 2.25gを加えた以外は、実施例2と同様の方法にて重合体の分散液を得た。
塩化ビニル充填時点(一段重合終了時点)において重合反応は、C6SFMAは99%終了、StAは96%終了していた。
一段重合:
1LオートクレーブにC6F13CH2CH2OCOC(CH3)=CH2 179g、ステアリルアクリレート 25g、ネオペンチルグリコールジアクリレート 0.25g、トリプロピレングリコール 75.8g、純水 446g、ポリオキシエチレンラウリルエーテル 12.7g、ポリオキシエチレンオレイルエーテル 2.47g、ポリオキシエチレンイソトリデシルエーテル5.05g、ジアルキル(牛脂)ジメチルアンモニウムクロライド 2.66gを入れ、60℃で加温後、高圧ホモジナイザーで乳化分散させた。乳化後、ラウリルメルカプラン 0.025gを加え、塩化ビニル 60gを圧入充填した。さらに2,2-アゾビス(2-アミジノプロパン)2塩酸塩1.92gを添加し、60℃で3時間反応させ、重合体の水性分散液を得た。その固形分濃度が30重量%となるように純水で濃度調整した水性分散液の特性を測定した。結果を表Aに示す。
乳化後にラウリルメルカプタン 0.25gを加えた以外は実施例1と同様の方法にて重合体の分散液を得た。
塩化ビニル充填時点(一段重合終了時点)において重合反応は、C6SFMA99%終了、StAは95%終了していた。
乳化後にラウリルメルカプタン 0.38gを加えた以外は実施例1と同様の方法にて重合体の分散液を得た。
塩化ビニル充填時点(一段重合終了時点)において重合反応は、C6SFMAは99%終了、StAは96%終了していた。
実施例2にネオペンチルグリコールジアクリレート 0.38gを加えた以外は、実施例2と同様の方法にて重合体の分散液を得た。
塩化ビニル充填時点(一段重合終了時点)において重合反応は、C6SFMAは99%終了、StAは96%終了していた。
ネオペンチルグルコールジアクリレートを加えなかった以外は実施例12と同様の方法にて重合体の分散液を得た。
乳化後に加えたラウリルメルカプタン量を1.25gに替えた以外は比較例4と同様の方法にて重合体の分散液を得た。
本発明の透湿防水布帛は、衣料、例えば、スポーツ衣料や防寒衣料、防水シート、例えば、テント、寝袋および防汚防水シート、靴ならびに手袋などに使用できる。
Claims (19)
- 含フッ素重合体を含む中間層、および合成樹脂を含む透湿防水層を有してなる透湿防水布帛であって、
含フッ素重合体が、
(a)式:
CH2=C(-X)-C(=O)-Y-Z-Rf
[式中、Xは、水素原子またはメチル基であり、
Y は、-O- または -NH-であり、
Zは、直接結合または二価の有機基であり、
Rfは、炭素数1~6のフルオロアルキル基である。]
で示される含フッ素単量体、
(b)ハロゲン化オレフィン単量体、および
(c)必要により使用する、フッ素原子を有さず、少なくとも1つの炭素-炭素二重結合を有する非フッ素単量体
から誘導された繰り返し単位を有してなり、400Pa・s以上の160℃における動的粘弾性を有する含フッ素重合体である透湿防水布帛。 - 含フッ素単量体(a)は、
CH2=C(-X)-C(=O)-Y-Z-Rf (I)
[式中、Xは、水素原子またはメチル基であり;
Yは、-O-または-NH-であり;
Zは、炭素数1~10の脂肪族基、炭素数6~18の芳香族基または環状脂肪族基、
-CH2CH2N(R1)SO2-基(但し、R1は炭素数1~4のアルキル基である。)または
-CH2CH(OZ1) CH2-基(但し、Z1は水素原子またはアセチル基である。)または
-(CH2)m-SO2-(CH2)n-基 または -(CH2)m-S-(CH2)n-基(但し、mは1~10、nは0~10、である)、
Rfは、炭素数1~6の直鎖状または分岐状のフルオロアルキル基である。]
で示されるものである請求項1に記載の透湿防水布帛。 - ハロゲン化オレフィン単量体(b)は、塩素原子、臭素原子またはヨウ素原子で置換されている炭素数2~20のオレフィンである請求項1または2に記載の透湿防水布帛。
- ハロゲン化オレフィン単量体(b)は、塩化ビニル、臭化ビニル、ヨウ化ビニル、塩化ビニリデン、臭化ビニリデンおよびヨウ化ビニリデンからなる群から選択された少なくとも1種である請求項1~3のいずれかに記載の透湿防水布帛。
- 非フッ素単量体(c)は非架橋性単量体または架橋性単量体である請求項1~4のいずれかに記載の透湿防水布帛。
- 非フッ素単量体(c)は、式:
CH2=CA-T
[式中、Aは、水素原子、メチル基、または、フッ素原子以外のハロゲン原子(例えば、塩素原子、臭素原子およびヨウ素原子)であり、
Tは、水素原子、炭素数1~30の鎖状または環状の炭化水素基、またはエステル結合を有する鎖状または環状の炭素数1~31の有機基である。]
で示される請求項1~5のいずれかに記載の透湿防水布帛。 - 架橋性単量体である非フッ素単量体(c)は、反応性基を有するモノ(メタ)アクリレート、(メタ)ジアクリレートまたはモノ(メタ)アクリルアミドである請求項1~6のいずれかに記載の透湿防水布帛。
- 合成樹脂が、ポリウレタン樹脂、アクリル樹脂およびポリエステル樹脂からなる群から選択された少なくとも1種である請求項1~7のいずれかに記載の透湿防水布帛。
- 透湿防水層が、合成樹脂を塗布することによって、あるいは合成樹脂のフィルムを貼り付けることによって形成されている請求項1~8のいずれかに記載の透湿防水布帛。
- 合成樹脂のフィルムは、接着剤によって含フッ素重合体の中間層に付着している請求項9に記載の透湿防水布帛。
- 含フッ素重合体の150℃、170℃における動的粘弾性がそれぞれ500Pa・s以上、300Pa・s以上である請求項1~10のいずれかに記載の透湿防水布帛。
- (i)含フッ素重合体を含んでなる含フッ素処理剤を繊維布帛に適用して、含フッ素重合体を含む中間層を形成する工程、および
(ii)含フッ素重合体の中間層の上に合成樹脂を適用することによって、透湿防水層を形成する工程
を特徴とする、請求項1に記載の透湿防水布帛の製造方法。 - 合成樹脂の適用が、合成樹脂を塗布することによって、あるいは合成樹脂のフィルムを貼り付けることによって行われる請求項12に記載の製造方法。
- 合成樹脂が、ポリウレタン樹脂、アクリル樹脂およびポリエステル樹脂からなる群から選択された少なくとも1種である請求項12または13に記載の製造方法。
- 合成樹脂のフィルムを、接着剤によって含フッ素重合体の中間層に付着させる請求項13または14に記載の製造方法。
- 含フッ素重合体を含んでなる含フッ素処理剤を繊維布帛に適用して、含フッ素重合体の中間層を形成することを特徴とする繊維布帛の処理方法。
- (a)式:
CH2=C(-X)-C(=O)-Y-Z-Rf
[式中、Xは、水素原子またはメチル基であり、
Y は、-O- または -NH-であり、
Zは、直接結合または二価の有機基であり、
Rfは、炭素数1~6のフルオロアルキル基である。]
で示される含フッ素単量体、
(b)ハロゲン化オレフィン単量体、および
(c)必要により使用する、フッ素原子を有さず、少なくとも1つの炭素-炭素二重結合を有する非フッ素単量体
から誘導された繰り返し単位を有してなり、400Pa・s以上の160℃における動的粘弾性を有する含フッ素重合体を含んでなる透湿防水布帛用の含フッ素処理剤。 - 請求項1に記載の透湿防水布帛における含フッ素重合体の製法であって、
製法は、
(I)含フッ素単量体(a)および必要により非フッ素単量体(c)を重合して第1重合体を得る工程、および
(II)第1重合体の存在下で、ハロゲン化オレフィン単量体(b)を重合することによって、ハロゲン化オレフィン単量体(b)によって形成される第2重合体を製造し、含フッ素重合体を得る工程
を有してなる製法。 - 第2単量体の重合を開始させる時点において、重合系の中に未反応の非フッ素非架橋性単量体が実質的に存在しない請求項18に記載の製法。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201380035883.3A CN104411880B (zh) | 2012-07-06 | 2013-07-04 | 透湿防水布帛 |
JP2014523793A JP5922774B2 (ja) | 2012-07-06 | 2013-07-04 | 透湿防水布帛 |
KR1020147036912A KR101665226B1 (ko) | 2012-07-06 | 2013-07-04 | 투습 방수 포백 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012-152745 | 2012-07-06 | ||
JP2012152745 | 2012-07-06 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014007345A1 true WO2014007345A1 (ja) | 2014-01-09 |
Family
ID=49882096
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/068415 WO2014007345A1 (ja) | 2012-07-06 | 2013-07-04 | 透湿防水布帛 |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP5922774B2 (ja) |
KR (1) | KR101665226B1 (ja) |
CN (1) | CN104411880B (ja) |
TW (1) | TWI605939B (ja) |
WO (1) | WO2014007345A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015194049A1 (ja) * | 2014-06-20 | 2015-12-23 | 日華化学株式会社 | 撥水撥油剤組成物及び撥水撥油性繊維製品の製造方法 |
JP2019196463A (ja) * | 2018-05-11 | 2019-11-14 | ダイキン工業株式会社 | 撥水撥油剤および繊維製品 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10842902B2 (en) | 2017-09-01 | 2020-11-24 | Ppg Industries Ohio, Inc. | Treated membrane for fragrance delivery |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009242675A (ja) * | 2008-03-31 | 2009-10-22 | Komatsu Seiren Co Ltd | 透湿性防水布帛用接着剤 |
JP2010100766A (ja) * | 2008-10-24 | 2010-05-06 | Asahi Glass Co Ltd | 撥水撥油剤組成物およびその製造方法 |
WO2010123042A1 (ja) * | 2009-04-23 | 2010-10-28 | 旭硝子株式会社 | 撥水撥油剤組成物、その製造方法および物品の処理方法 |
WO2010126117A1 (ja) * | 2009-05-01 | 2010-11-04 | セーレン株式会社 | 透湿防水性布帛およびその製造方法 |
JP2010255132A (ja) * | 2009-04-23 | 2010-11-11 | Unitika Trading Co Ltd | 透湿防水性布帛及びその製造方法 |
WO2011078135A1 (ja) * | 2009-12-25 | 2011-06-30 | 旭硝子株式会社 | 撥水撥油剤組成物、その製造方法および物品の処理方法 |
WO2012147700A1 (ja) * | 2011-04-25 | 2012-11-01 | 旭硝子株式会社 | 撥水撥油剤組成物、その製造方法および物品 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6047955A (ja) | 1983-08-25 | 1985-03-15 | Tokyo Yogyo Co Ltd | 高温水素センサ−素子の製造方法 |
JP2719841B2 (ja) | 1990-05-11 | 1998-02-25 | 日本農薬株式会社 | チオ尿素誘導体及びその製造方法 |
CN1131279C (zh) * | 1996-11-18 | 2003-12-17 | 大金工业株式会社 | 耐久性斥水剂及其涂覆制品和应用 |
KR100889714B1 (ko) * | 2001-04-13 | 2009-03-23 | 아사히 가라스 가부시키가이샤 | 발수발유제 조성물 |
EP1329548A1 (en) * | 2002-01-21 | 2003-07-23 | 3M Innovative Properties Company | Method of treatment of a textile or non-woven substrate to render same water and oil repellent |
GB2416781A (en) * | 2004-08-04 | 2006-02-08 | Lightex Ltd | Breathable fabric |
CN101952386A (zh) * | 2008-02-22 | 2011-01-19 | 大金工业株式会社 | 水性聚合物分散组合物和拨水拨油剂 |
CN101970512B (zh) * | 2008-03-12 | 2013-11-20 | 旭硝子株式会社 | 共聚物及其制造方法 |
-
2013
- 2013-07-04 KR KR1020147036912A patent/KR101665226B1/ko active IP Right Grant
- 2013-07-04 JP JP2014523793A patent/JP5922774B2/ja active Active
- 2013-07-04 WO PCT/JP2013/068415 patent/WO2014007345A1/ja active Application Filing
- 2013-07-04 CN CN201380035883.3A patent/CN104411880B/zh active Active
- 2013-07-05 TW TW102124135A patent/TWI605939B/zh active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009242675A (ja) * | 2008-03-31 | 2009-10-22 | Komatsu Seiren Co Ltd | 透湿性防水布帛用接着剤 |
JP2010100766A (ja) * | 2008-10-24 | 2010-05-06 | Asahi Glass Co Ltd | 撥水撥油剤組成物およびその製造方法 |
WO2010123042A1 (ja) * | 2009-04-23 | 2010-10-28 | 旭硝子株式会社 | 撥水撥油剤組成物、その製造方法および物品の処理方法 |
JP2010255132A (ja) * | 2009-04-23 | 2010-11-11 | Unitika Trading Co Ltd | 透湿防水性布帛及びその製造方法 |
WO2010126117A1 (ja) * | 2009-05-01 | 2010-11-04 | セーレン株式会社 | 透湿防水性布帛およびその製造方法 |
WO2011078135A1 (ja) * | 2009-12-25 | 2011-06-30 | 旭硝子株式会社 | 撥水撥油剤組成物、その製造方法および物品の処理方法 |
WO2012147700A1 (ja) * | 2011-04-25 | 2012-11-01 | 旭硝子株式会社 | 撥水撥油剤組成物、その製造方法および物品 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015194049A1 (ja) * | 2014-06-20 | 2015-12-23 | 日華化学株式会社 | 撥水撥油剤組成物及び撥水撥油性繊維製品の製造方法 |
JP2019196463A (ja) * | 2018-05-11 | 2019-11-14 | ダイキン工業株式会社 | 撥水撥油剤および繊維製品 |
JP7157307B2 (ja) | 2018-05-11 | 2022-10-20 | ダイキン工業株式会社 | 撥水撥油剤および繊維製品 |
Also Published As
Publication number | Publication date |
---|---|
KR20150015535A (ko) | 2015-02-10 |
KR101665226B1 (ko) | 2016-10-11 |
JP5922774B2 (ja) | 2016-05-24 |
JPWO2014007345A1 (ja) | 2016-06-02 |
CN104411880A (zh) | 2015-03-11 |
TW201410456A (zh) | 2014-03-16 |
TWI605939B (zh) | 2017-11-21 |
CN104411880B (zh) | 2018-05-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5445632B2 (ja) | 撥水撥油剤組成物 | |
JP5855749B2 (ja) | 含フッ素重合体の製造方法 | |
JP5949853B2 (ja) | 透湿防水布帛およびその製法 | |
JP2014129532A (ja) | 撥水撥油剤組成物 | |
JP5862745B2 (ja) | 含フッ素重合体および処理剤 | |
JP2018095879A (ja) | 撥水剤 | |
CN112105706B (zh) | 拨水拨油剂和纤维制品 | |
WO2013058333A1 (ja) | 表面処理剤組成物およびその用途 | |
WO2017159754A1 (ja) | 表面処理剤 | |
WO2013058334A1 (ja) | 含フッ素組成物 | |
JP5922774B2 (ja) | 透湿防水布帛 | |
JP6191736B2 (ja) | 含フッ素組成物および含フッ素重合体 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13813451 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2014523793 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20147036912 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 13813451 Country of ref document: EP Kind code of ref document: A1 |