JP6589560B2 - Water and oil repellent with excellent storage stability - Google Patents

Description

  The present invention relates to a water / oil repellent composition having improved storage stability by adding a fungicide and fungicide. More specifically, the present invention includes an antibacterial and antifungal agent, which has a long-term antibacterial and antifungal effect even when water contaminated with fungi and bacteria is used. The present invention relates to a water / oil repellent composition containing an aqueous dispersion of a fluoropolymer. The present invention also relates to a water- and oil-repellent composition that sterilizes fungi and bacteria mixed during use of the composition and exhibits a long-term antibacterial and antifungal effect.

  Aqueous dispersions of fluoropolymers are widely used as water and oil repellents. There are a wide variety of substrates that can be treated with water and oil repellent treatments, including textiles, carpets, leather, non-woven fabrics, paper, and stone. Cationic, anionic or nonionic dispersions are properly used depending on the purpose and application of the aqueous dispersion. For example, a cationic or nonionic dispersion is generally used in textile applications, and an anionic dispersion is often used in carpet applications because of its combined use with a stain blocking agent. In paper applications, anionic, nonionic or cationic dispersions are generally used depending on the treatment method and application. As described above, aqueous dispersions of fluoropolymers have already been used in large quantities in the industry, and their application range has been expanded to new applications.

  Long-term storage stability is required for an aqueous dispersion of a fluoropolymer. Needless to say resistance to temperature change and vibration, resistance to fungi and bacteria is also required. If the resistance to fungi and bacteria is insufficient, these fungi may grow during storage to produce floating substances, which may become unusable or may have a strange odor transferred to the object to be treated. Contaminants of these fungi are used when deionized water, pumps, reaction vessels and piping used in the production of aqueous dispersions of fluoropolymers, and on-site treatment of water and oil repellents. Examples include contamination from ruby lacquer, pumps and piping, and contamination from the air when opened. Since water and oil repellents are used in various usage environments, it is difficult to completely prevent fungal contamination. Therefore, even when fungi are mixed, there is a need for practically stable (resistance) that has no problem.

  An anionic or nonionic water / oil repellent composition produced using an anionic emulsifier or a nonionic emulsifier does not have a fungicidal and antifungal effect. Therefore, antibacterial and antifungal agents may be used for such water and oil repellent compositions depending on the environment in which they are used. On the other hand, the cationic water and oil repellent composition produced using a cationic emulsifier has a fungicidal and antifungal effect, so no antifungal and antifungal agent is used, but the content of the cationic emulsifier is low. In some cases, fungal growth may occur.

  Japanese Patent No. 3981818 discloses a water-based water repellent composition for wood containing a cohydrolyzed condensate containing an organosilicon compound, a pyrethroid insecticide, and water. The water repellent used in this water-based water repellent composition is a cohydrolyzed condensate containing an organosilicon compound.

Japanese Patent No. 3981818

  As a result of intensive studies in view of the above-described problems, the present inventors have added a specific antibacterial and antifungal agent to the aqueous dispersion of the fluoropolymer, regardless of the environment during production or use, The present inventors have found that a water / oil repellent composition exhibiting sufficient antibacterial and antifungal effects can be provided, and have completed the present invention.

That is, the present invention provides, for example,
[1] A water- and oil-repellent composition containing an aqueous dispersion of a fluoropolymer and a fungicide and fungicide, wherein the cationic strength of the aqueous dispersion of the fluoropolymer is per 100 g of the solid content of the aqueous dispersion. A water and oil repellent composition that is 0 to 2.5 mmol;
[2] The water / oil repellent composition according to [1], which contains a nonionic surfactant;
[3] The water / oil repellent composition according to [2], comprising an anionic surfactant;
[4] It contains at least one selected from a cationic surfactant and an amphoteric surfactant, and the cation strength of the fluoropolymer aqueous dispersion is 0.1 to 2.5 mmol per 100 g of the solid content of the aqueous dispersion. 1] or [2] water- and oil-repellent composition;
[5] The water / oil repellent composition according to any one of [1] to [4], comprising 1 × 10 ⁵ to 1 × 10 ⁷ cfu / ml fungus;
[6] The water / oil repellent composition according to any one of [1] to [4], which contains 1 × 10 ⁷ to 1 × 10 ⁹ cfu / ml bacteria;
[7] The water and oil repellent composition according to any one of [1] to [6], wherein the antibacterial and antifungal agent is one or more antibacterial and antifungal agents that suppress both fungal and bacterial growth;
[8] The water and oil repellent composition according to [7], wherein the antibacterial and antifungal agent is an isothiazoline type;
[9] The water / oil repellent composition according to any one of [1] to [8], which contains an antibacterial and antifungal agent having an active ingredient concentration of 1.5 to 450 ppm;
[10] A process for producing a treated article, comprising applying the water / oil repellent composition according to any one of [1] to [9] to the article.

  The storage stability of the water / oil repellent composition of the present invention is improved by a high antibacterial and antifungal effect. Therefore, even in an environment where sewage containing various bacteria is used, the water / oil repellent composition can be used after long-term storage. Moreover, even if various germs are mixed during the use of the water / oil repellent composition, it can be sterilized to prevent proliferation.

The water / oil repellent composition of the present invention contains (1) a fluorine-containing polymer, (2) a fungicide and a fungicide, and (3) water.
A water- and oil-repellent composition is obtained by mixing an aqueous dispersion of a fluoropolymer and a fungicide and fungicide.

(1) Fluoropolymer The fluoropolymer used in the present invention generally has the formula:
CH ₂ = C (-X) -C (= O) -YZ-Rf
[Wherein X is a hydrogen atom, a monovalent organic group or a halogen atom,
Y is -O- or -NH-
Z is a direct bond or a divalent organic group,
Rf is a perfluoroalkyl group having 1 to 20 carbon atoms. ]
And a repeating unit derived from the fluorine-containing monomer (a).

  Y is preferably -O-.

Z is, for example, a direct bond, a linear alkylene group having 1 to 20 carbon atoms or a branched alkylene group [for example, the formula — (CH ₂ ) _x — (wherein x is 1 to 10). 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) R ² is a linear alkylene group having 1 to 10 carbon atoms or a branched alkylene group.) Or a formula —CH ₂ CH (OR ³ ) CH ₂ — (wherein R ³ is a hydrogen atom Or a group represented by an acyl group having 1 to 10 carbon atoms (for example, formyl or acetyl), or a formula —Ar—CH ₂ — (wherein Ar optionally has a substituent) An arylene group), a — (CH ₂ ) _m —SO ₂ — (CH ₂ ) _n — group or a — (CH ₂ ) _m —S— (CH ₂ ) _n — group (provided that m 1-10, n is 0-10).
In the fluoropolymer of the present invention, Z is preferably a direct bond, an alkylene group having 1 to 20 carbon atoms, or —SO ₂ N (R ¹ ) R ² —.

Rf is preferably a perfluoroalkyl group, but may be a fluoroalkyl group having a hydrogen atom. Specific examples of Rf _{are, -CF 3, -C 2 F 5} , -C 3 F 7, -C 4 F 9, -C 5 F 11, -C 6 F 13, -C 8 F 17, -C 10 F ₂₁ , -C ₁₂ F ₂₅ .

  The fluorine-containing polymer may be a homopolymer or a copolymer of the fluorine-containing monomer (a). The fluorine-containing polymer may have a repeating unit derived from the non-fluorine monomer (b) in addition to the repeating unit derived from the fluorine-containing monomer. These fluoropolymers can be used alone or in combination of two or more.

The non-fluorine monomer (b) may be a non-fluorine non-crosslinkable monomer (b1) or a non-fluorine crosslinkable monomer (b2).
Specific examples of the non-fluorine non-crosslinkable monomer (b1) are represented by the formula:
CH ₂ = CA-T
[In the formula, A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom),
T is a hydrogen atom, a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom), a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms, or a chain or ring having an ester bond An organic group having 1 to 30 carbon atoms. ]
It may be a compound shown by these.

  Examples of the linear or cyclic hydrocarbon group having 1 to 30 carbon atoms include a linear or branched saturated or unsaturated (eg, ethylenically unsaturated) aliphatic hydrocarbon group having 1 to 30 carbon atoms, carbon number 4 to 30 saturated or unsaturated (for example, ethylenically unsaturated) cycloaliphatic groups, C6 to C30 aromatic hydrocarbon groups, and C7 to C30 araliphatic hydrocarbon groups.

Examples of the linear or cyclic organic group having 1 to 30 carbon atoms having an ester bond are -C (= O) -OQ and -OC (= O) -Q (where Q is 1 to 20 carbon atoms). Linear or branched saturated or unsaturated (eg, ethylenically unsaturated) aliphatic hydrocarbon group, saturated or unsaturated (eg, ethylenically unsaturated) cyclic aliphatic group having 4 to 20 carbon atoms, carbon An aromatic hydrocarbon group having 6 to 20 carbon atoms and an araliphatic hydrocarbon group having 7 to 20 carbon atoms).
In addition, the non-fluorine non-crosslinkable monomer may be a (meth) acrylate ester monomer (b1-1), a halogenated olefin monomer (b1-2), or the like.
Specific examples of the (meth) acrylate ester monomer (b1-1) are
CH ₂ = CA ²¹ -C (= O) -OA ²²
[Wherein, A ²¹ represents a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom, and A ²² represents a hydrocarbon group having 1 to 30 carbon atoms. ]
It may be a compound shown by these.
A ²¹ is preferably a hydrogen atom, a methyl group, or a chlorine atom.
A ²² (hydrocarbon group) may be an acyclic aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic hydrocarbon-containing group having 4 to 30 carbon atoms, or the like.
Specific examples of the (meth) acrylate ester monomer having an acyclic aliphatic hydrocarbon group include lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate. .
Specific examples of the (meth) acrylate ester monomer having a cyclic hydrocarbon-containing group are cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopenta Nyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, tricyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) Acrylate, 2-ethyl-2-adamantyl (meth) acrylate, and the like.
The halogenated olefin monomer (b1-2) does not have a fluorine atom.
The halogenated olefin monomer may be an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine, bromine or iodine atoms. The halogenated olefin monomer 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. Preferred specific examples of the halogenated olefin monomer are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides such as vinylidene chloride, vinylidene bromide, vinylidene iodide. Vinyl chloride and vinylidene chloride are preferred because of high water and oil repellency (especially durability of water and oil repellency).

  Further, the non-fluorine crosslinkable monomer (b2) is a monomer containing no fluorine atom. The non-fluorine crosslinkable monomer may be a compound having at least two reactive groups and / or olefinic carbon-carbon double bonds (preferably (meth) acrylate groups) and not containing fluorine. The non-fluorine crosslinkable monomer is a compound having at least two olefinic carbon-carbon double bonds (preferably a (meth) acrylate group), or at least one olefinic carbon-carbon double bond and at least one It may be a compound having a reactive group. Examples of reactive groups are hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amino groups, carboxyl groups and the like.

  The non-fluorine crosslinkable monomer may be mono (meth) acrylate, di (meth) acrylate or mono (meth) acrylamide having a reactive group. Alternatively, the non-fluorine crosslinkable monomer may be di (meth) acrylate.

One example of a non-fluorine crosslinkable monomer is a vinyl monomer having a hydroxyl group.
Examples of non-fluorine crosslinkable monomers include diacetone (meth) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and 2,3-dihydroxypropyl (meth) acrylate. , 3-chloro-2-hydroxypropyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth) acrylate, 1,4-butanediol Examples include, but are not limited to, di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like. Not a thing.

In addition, the non-fluorine crosslinkable monomer may be an isocyanato acrylate monomer.
Specific examples of the isocyanato acrylate monomer include 2-isocyanatoethyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, 4-isocyanatobutyl (meth) acrylate, and 2-isocyanatoethyl (meth) acrylate. 2-butanone oxime adduct, 2-isocyanatoethyl (meth) acrylate pyrazole adduct, 2-isocyanatoethyl (meth) acrylate 3,5-dimethylpyrazole adduct, 2-isocyanatoethyl (meth) acrylate 3-methylpyrazole adduct, ε-caprolactam adduct of 2-isocyanatoethyl (meth) acrylate, 2-butanone oxime adduct of 3-isocyanatopropyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate Pyrazole adduct of 3-isocyanatopropi 3,5-dimethylpyrazole adduct of ru (meth) acrylate, 3-methylpyrazole adduct of 3-isocyanatopropyl (meth) acrylate, ε-caprolactam adduct of 3-isocyanatopropyl (meth) acrylate, 4- 2-butanone oxime adduct of isocyanatobutyl (meth) acrylate, pyrazole adduct of 4-isocyanatobutyl (meth) acrylate, 3,5-dimethylpyrazole adduct of 4-isocyanatobutyl (meth) acrylate, 4- Examples include 3-methylpyrazole adduct of isocyanatobutyl (meth) acrylate and ε-caprolactam adduct of 4-isocyanatobutyl (meth) acrylate.

  Examples of other monomer (c) include, for example, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol ( Meth) acrylates, vinyl alkyl ethers and the like are included. Other monomers are not limited to these examples.

  In the present specification, “(meth) acrylate” means acrylate or methacrylate, and “(meth) acrylamide” means acrylamide or methacrylamide.

  Each of the monomers (a) to (c) may be a single monomer or a mixture of two or more.

The amount of monomer (a) may be 10% by weight or more, for example 40% by weight or more, based on the polymer. The amount of monomer (a) may be 95% by weight or less, for example 80% by weight or less, alternatively 75% by weight or less, alternatively 70% by weight or less based on the polymer.
In the polymer, with respect to 100 parts by weight of the monomer (a),
The amount of the repeating unit (b1) is 0 to 200 parts by weight, preferably 1 to 40 parts by weight,
The amount of the repeating unit (b2) is 0 to 100 parts by weight, preferably 1 to 30 parts by weight,
The amount of the repeating unit (c) may be 0 to 100 parts by weight, preferably 1 to 30 parts by weight.
More specifically, in the polymer, with respect to 100 parts by weight of the monomer (a),

The amount of the repeating unit (b1-1) is 0 to 150 parts by weight, preferably 1 to 30 parts by weight,
The amount of the repeating unit (b1-2) is 0 to 50 parts by weight, preferably 1 to 10 parts by weight,
The amount of the repeating unit (b2) is 0 to 100 parts by weight, preferably 1 to 30 parts by weight,
The amount of the repeating unit (c) may be 0 to 100 parts by weight, preferably 1 to 30 parts by weight.

The amount of the fluorinated polymer (solid content) is about 0.01 to 60% by weight, preferably about 0.1 to 40% by weight, particularly preferably about 5 to 35% by weight, based on the whole water / oil repellent composition. It may be an amount.
The fluoropolymer is used in the water / oil repellent composition of the present invention as an aqueous dispersion.

(2) Antibacterial and antifungal agent The antibacterial and antifungal agent is at least one antibacterial and antifungal agent that suppresses the growth of microorganisms such as fungi, preferably both fungi and bacteria. The antibacterial and antifungal agent is not particularly limited, and the following commonly used antibacterial and antifungal agents listed in Journal of Japanese Society for Antifungal and Antibiotics 1998 VOL.26 are used. be able to.

Amines such as Bis (3-aminopropyl) dodecylamine (trialkyltriamine),
Ethyl alcohol (ethyl alcohol, ethanol), Iso-propyl alcohol (isopropanol), Propyl alcohol (propyl alcohol, propanol), Tris (hydroxymethyl) nitromethane (trisnitro), 1,1,1-Trichloro-2-methyl-2-propanol Alcohols such as (chlorobutanol), 2-Bromo-2-nitropropane-1,3-diol (pronobol, pronosol, pronocot),
Aldehydes such as 1,5-Pentanediol (glutaraldehyde), Formaldehyde, α-Bromocinnamic aldehyde (α-bromcinamaldehyde),
2-n-Octyl-4-isothiazolin-3-one (Skane M-8), 5-Chloro-2-methyl-4-isothiazolin-3-one / 2-Methyl-4-isothiazolin-3-one (Caisson CG NS-500W), 1,2-Benzisothiazolone-3 (BIT), N-n-Butyl-1,2-benzisothiazolone-3 (n-butyl BIT),
Isothiocyanate series such as Allyl isothiocyanate (aryl isothiocyanate)
Imidazoles such as 2- (4-Thiazolyl) -benzimidazole (thiabendazole, TBZ), Methyl-2-benzimidazole carbamate (methyl 2-benzimidazolylcarbamate, preventol BCM),
Esters such as Glycerol laurate (lauricidin, glyceryl monolaurate, monoglyceride)
Oxazolidines such as 4,4-Dimethyl-1,3-oxazolidine (Biopan CS-1135, Oxazine A),
Carbanilides such as 3,4,4'-Trichlorocarbanilide (triclocarban, trichlorocarbanilide), 4,4'-Dichloro-3- (3-Fluoromethyl) -carbanilide (halocarban, cloflucarban),
Carbamate systems such as 3-Iodo-2-propynylbutyl carbamate (Glytical),
Benzoic acid (benzoic acid, benzenecarboxylic acid), Flexa-2,4-dienoic acid (sorbic acid, 2-propanylacrylic acid), Octanoic acid (caprylic acid), Propionic acid (propionic acid), Undecylenic acid (10- Undecylenic acid, 10-undecenoic acid), Potassium hexa-2,4-dienoic acid (potassium sorbate, 2-propenyl acrylate), Potassium propionate (potassium propionate), Calcium propionate (calcium propionate), Sodium benzoate ( Carboxylic acid series such as sodium benzoate), sodium propionate, sodium (2-), bis (2-carboxybenzene carboperoxato) dihydrogene (monomagnesium phthalate), zinc undecylenate (zinc undecylenate),
Quinoline systems such as 8-Hydroxyquinoline (8-hydroxyquinoline), Bis (quinolin-8-olate) copper (quinoline copper, oxine copper, 8-quinolinol copper),
Sulfides such as Bis (dimethylthiocarbamoyl) disulfide (TMTD, Thiuram)
Diphenyl ethers such as 2,4,4'-Trichloro-2'-hydroxydiphenyl (Triclosan, Irgasan DP300),
N, N-Dimethyl-N '-(fluorodichloromethylthio) -N "-phenylsulfamide (cyclofluoride, Priventol A4-S), N-Dichlorofluoromethylthio-N', N'-dimethyl-N-p-torylsulfamide (Trifluamide, Sulfamides such as Priventol A5)
Protamine (shirako protein, shirako degradation product, nuclear protein) Hen egg lysozyme (egg white lysozyme) and other protein systems,
Thiazoles such as 2- (4-Thiocyanomethylthio) benzothiazol (benchazole),
Thiocarbamate systems such as Sodium N-methyldithiocarbamate (sodium N-methyldithiocarbamate)
Hexahydro-1,3,5-tris (hydroxyethyl) -S-triadine (Biopan GK, Triazine),
CAVINON (100,200) (Cabinon (100,200)), α- [2- (4-Chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol ( Debuconazole) and other triazines,
Tropolone series such as 4-Isopropyl-2-hydroxy-cyclohepta-2,4,6-triene-1-one (hinokitiol, β-tsuyaprisin),
Nitriles such as 2,4,5,6-Tetrachloroisophthalonitrile (Tetrachloroisophthalonitrile), 1,2-Dibromo-2,4-dicyanobutane (Tectamar 38),
1,1 ′-(Hexamethylene bis [5- (4-chlorophenyl) biguanide] digluconate (chlorhexidine glucuronate), Bis (p-chlorophenyldiguanide) hexane dihydrochloride (chlorhexidine hydrochloride),
Hydantoin systems such as 1-Bromo-3-chloro-5,5'-dimethyl hydantoin (dantobrom), 1,3-Bis- (hydroxymethyl) -5,5'-dimethyl hydantoin (glidanto, dantguard),
Sodium pyridine thiol-1-oxide (sodium pyrithione), Zinc bis (2-pyridylthio-1-oxide) (zinc pyrithione, zinc omazine, ZPT), 2,3,5,6-Tetrachloro-4- (methylsulphonyl) pyridine (Dencil) , Pyridine series such as Copper bis (2-pyridylthio-1-oxide) (copper pyrithione, copper oma margin, CuPT),
2-Isopropyl-5-methylphenol (Thymol, 2-Isopropyl-5-methylphenol), 3-Methyl-4-iso-propylphenol (Isopropylmethylphenol, Piozol), o-Phenylphenol (OPP), Phenol ( Phenol, Carcoic acid), Butyl-p-hydroxybenzoate (Butylparaben), Ethyl-p-hydroxybenzoate (Ethylparaben), Methyl-p-hydroxybenzoate (Methylparaben), Propyl-p-hydroxybenzoate (Propylparaben), m-Methylphenol (Metacresol) ), O-Methylphenol (orthocresol), p-Methylphenol (paracresol), o-Phenylsodiumphenoxide (orthophenylphenol sodium), 2-Benzyl-4-chlorophenol (chlorophene), p-Chlorophenol (parachlorphenol), 4 -Chloro-3,5-dimethylphenol, 2-Methyl-3-chlorophen phenolic such as ol (parachlorometacresol),
Phthalimides such as N- (Fluorodichloromethylthio) -phthalimide (Fluorophorpet, Briventol A3),
peptide systems such as ε-Poly-L-lysine (polylysine, ε-polylysine),
Morpholine series such as 4- (2-Nitrobutyl) morpholine / 4,4 '-(2-nitrotrimethylene) dimorpholine (Biopan P-1487),
Diiodomethyl-p-trylsulfone, Polyvinylpyrolidone iodide (polyvinylpyrrolidone iodine, povidone iodine, isodine), p-Chlorophenyl-3-iodopropagyl formal (parachlorophenyl-3-iodopropagyl formal), 3- Iodine such as Bromo-2,3-diiodo-2-propenylethylcarbonate
Chlorine systems such as Sodium hypochlorite, Sodium dichlorinated isocyanurate, Sodium chlorisocyanurate, Trichlorinated isocyanuric acid,
Peroxides such as Hydrogen peroxide, Chlorine dioxide (Stabilized chlorine dioxide, Biotalk), Peracetic acid (Peracetic acid),
Copper naphthenate, Silver / Zirconium phosphate (Novaron AG300), Silver chloride / Titanium oxide, Silver-Zinc / Calcium phosphate (Silver / Zinc Calcium Phosphate, Silver Ace), Silver- Metal salt systems such as Zinc / Zeolite (silver zinc aluminosilicate, silver zinc zeolite), Zinc oxide, Silver / Zirconium phosphate (Novaron AGZ330), N-Stearoyl-L-glutamic acid AgCu salt (holon killer),
1-L- (1,3,5 / 2,4) -1,5-Diamino-4-O- (2,5-dideoxy-α-D-glucopyranosyl) -2,3-cyclohexandiol (ST-7) Antibiotics such as
Oxides such as Ethylene oxide (EO, ethylene oxide), Propylene oxide (PO, propylene oxide),
4,4 '-(Tetramethylenedicarbonyldiamino) bis (1-decylpyridinium bromide) (Dimer 135), Decyldimethylbenzylammonium chloride, Didecyldimethylammonium chloride (Didecyldimethylammonium chloride, Bardac 2250/80), Diisobutylphenoxyethoxydimethylbenzylammonium chloride (Benzotonium chloride) , Hyamine 1622), Hexadecyl trimethyl ammonium bromide (cetyl ammonium bromide, cetrimide, CTAB, Secbron), N, N'-Hexamethylenebis (4-carbamoyl-1-decylpyridinium bromide) (Dimer 38), N-Alkyl-N, N -Dimethyl-N-benzylammonium chloride (benzalkonium chloride, Hyamine 3500J), N-Decyl-N-isononyl-N, N'-dimethylammonium chloride (Bardac 170P), 5- (Trimethoxysilyl) propyldimethyloctadecylammonium (DC-5700), Hexadecyl pyridinium chloride, cetyl pyridinium chloride Which quaternary ammonium salt system,
carbohydrates such as β-1,4-Poly-D-glucosamine (chitosan),
Examples include ureas such as N ′-(3,4-Dichlorophenyl) -N, N-dimethylurea (duuron, DCMU, briventol A6). In particular a mixture of 2-n-octyl-4-isothiazolin-3-one (skane M6), 5-chloro-2-methyl-4-isothiazolin-3-one / 2-methyl-4-isothiazolin-3-one, 1 1,2-benzisothiazolin-3-one (BIT), Nn-butyl-1,2-benzisothiazolin-3-one (BBIT), and the like are preferred isothiazoline antibacterial and antifungal agents.

In particular, a mixture of 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one / 2-methyl-4-isothiazolin-3-one, 1,2- An isothiazoline antibacterial and antifungal agent such as benzisothiazolin-3-one (BIT) and Nn-butyl-1,2-benzisothiazolin-3-one (BBIT) is preferable. These antibacterial and antifungal agents can be used alone or in combination of two or more.
The amount of the antibacterial and antifungal agent may be about 1.5 to 450 ppm, preferably about 7.5 to 300 ppm, particularly preferably about 75 to 150 ppm, as the active ingredient concentration, with respect to the entire water / oil repellent composition. The amount of the antibacterial and antifungal agent may be about 4.5 to 1350 ppm, preferably about 22.5 to 900 ppm, particularly preferably about 225 to 450 ppm, based on the fluoropolymer.

(3) water used for water and oil repellent composition of the water present invention may be water that is normally used in the art. In particular, in the present invention, the use of the antibacterial and antifungal agent suppresses the growth of microorganisms such as fungi, particularly when water containing bacteria or fungi is mixed, and the water-based water and oil repellent agent. The long-term storage stability of the composition is maintained. In general, when the dilution water contains microorganisms, the water / oil repellent composition before storage contains microorganisms.

In the preparation of the water / oil repellent composition of the present invention, the water has the storage stability of the water / oil repellent composition even when microorganisms such as fungi, preferably fungi and / or bacteria are present. Therefore, particularly advantageous effects can be exhibited when preparing using water or equipment contaminated by these microorganisms. In water it is preferred that there are no fungi, preferably both fungi and bacteria, but one or both of fungi and bacteria may be present. The amount of fungus can be, for example, 1 × 10 ⁵ to 1 × 10 ⁷ cfu / ml, in particular 1 × 10 ⁶ to 1 × 10 ⁷ cfu / ml. The amount of bacteria can be, for example, 1 × 10 ⁷ to 1 × 10 ⁹ cfu / ml, in particular 1 × 10 ⁸ to 1 × 10 ⁹ cfu / ml.
The water / oil repellent composition can suppress the growth of microorganisms over a long period of time without being stored particularly at a low temperature.

  In general, the water / oil repellent composition may contain a surfactant as another component. The surfactant may be used to disperse the monomer (and polymer) in producing the fluoropolymer, and / or may be added to the produced polymer.

(4) Surfactant In the water / oil repellent composition of the present invention, the surfactant may contain a nonionic surfactant. Further, the surfactant may include one or more surfactants selected from a cationic surfactant, an anionic surfactant and an amphoteric surfactant. It is preferable to use a combination of a nonionic surfactant and a cationic surfactant.

(A) Nonionic surfactant Examples of the nonionic surfactant include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides.
Examples of the ether are compounds having an oxyalkylene group (preferably a polyoxyethylene group).
Examples of esters are alcohol and fatty acid esters. Examples of the alcohol are 1 to 6 valent (particularly 2 to 5 valent) alcohols having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, in particular 5 to 30 carbon atoms.
An example of the ester ether is a compound obtained by adding an alkylene oxide (particularly, ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of the alcohol are 1 to 6 valent (particularly 2 to 5 valent) alcohols having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, in particular 5 to 30 carbon atoms.
Examples of alkanolamides are formed from fatty acids and alkanolamines. The alkanolamide may be a monoalkanolamide or dialkanolamino. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, in particular 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms having 1 to 3 amino groups and 1 to 5 hydroxyl groups.
The polyhydric alcohol may be a divalent to pentavalent alcohol having 3 to 30 carbon atoms.
The amine oxide may be an oxide (for example, 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).

The nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms of the alkylene group in the oxyalkylene group is preferably 2 to 10. In general, the number of oxyalkylene groups in the nonionic surfactant molecule is preferably 2 to 100.
The nonionic surfactant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides, and is preferably a nonionic surfactant having an oxyalkylene group.
Nonionic surfactants are alkylene oxide adducts of linear and / or branched aliphatic (saturated and / or unsaturated) groups, linear and / or branched fatty acids (saturated and / or unsaturated). Polyalkylene glycol ester, polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), alkylene oxide adduct of acetylene glycol, and the like. Among these, the structures of the alkylene oxide addition moiety and the polyalkylene glycol moiety are polyoxyethylene (POE) or polyoxypropylene (POP) or POE / POP copolymer (random copolymer or block copolymer) Is preferred).
The nonionic surfactant preferably has a structure that does not contain an aromatic group because of environmental problems (biodegradability, environmental hormones, etc.).

Nonionic surfactants have the formula:
R ¹ O- (CH ₂ CH ₂ O) _p- (R ² O) _q -R ³
[Wherein, R ¹ represents an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or an acyl group,
Each of R ² is independently the same or different and is an alkylene group having 3 or more carbon atoms (for example, 3 to 10);
R ³ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms,
p is a number greater than or equal to 2,
q is 0 or a number of 1 or more. ]
It may be a compound shown by these.
R ¹ preferably has 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms. Preferable specific examples of R ¹ include a lauryl group, a tridecyl group, and an oleyl group.
Examples of R ² are a propylene group and a butylene group.
In the nonionic surfactant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, — (R ² O) _q — may form a polyoxyalkylene chain.
The nonionic surfactant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly, a polyoxyalkylene chain) in the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain, among which an oxypropylene chain is preferable.
Preferred nonionic surfactants have the formula:
R ¹ O- (CH ₂ CH ₂ O) _p -H
[Wherein, R ¹ and p are as defined above. ]
Is a surfactant.

Specific examples of nonionic surfactants are:
C ₁₀ H ₂₁ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -H
C ₁₂ H ₂₅ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -H
C ₁₆ H ₃₁ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -H
C ₁₆ H ₃₃ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -H
C ₁₈ H ₃₅ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -H
C ₁₈ H ₃₇ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -H
C ₁₂ H ₂₅ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -C ₁₂ H ₂₅
C ₁₆ H ₃₁ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -C ₁₆ H ₃₁
C ₁₆ H ₃₃ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -C ₁₂ H ₂₅
iso-C ₁₃ H ₂₇ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -H
C ₁₀ H ₂₁ COO- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -H
C ₁₆ H ₃₃ COO- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -C ₁₂ H ₂₅
[Wherein, p and q are as defined above. ]
Etc.

Specific examples of nonionic surfactants include ethylene oxide and hexylphenol, isooctylphenol, hexadecanol, oleic acid, alkane (C ₁₂ -C ₁₆ ) thiol, sorbitan monofatty acid (C ₇ -C ₁₉ ) or alkyl Condensation products with (C ₁₂ -C ₁₈ ) amine and the like are included.
The nonionic surfactants can be used alone or in combination of two or more.
The nonionic surfactant is preferably a combination of two or more. In a combination of two or more, at least one nonionic surfactant is R ¹ O— (CH ₂ CH) in which the R ¹ group (and / or R ³ group) is a branched alkyl group (eg, an isotridecyl group). It may be a compound represented by ₂ O) _p- (R ² O) _q -R ³ [particularly R ¹ O- (CH ₂ CH ₂ O) _p -H]. The amount of the nonionic surfactant in which R ¹ group is a branched alkyl group is 5 to 100 parts by weight, for example, 8 to 50 parts by weight, particularly 10 to 40 parts by weight, based on 100 parts by weight of the nonionic surfactant. It may be part by weight. In a combination of two or more, the remaining nonionic surfactant is a group in which the R ¹ group (and / or R ³ group) is a (saturated and / or unsaturated) linear alkyl group (eg, lauryl group (n- R ¹ O— (CH ₂ CH ₂ O) _p — (R ² O) _q —R ³ [particularly R ¹ O— (CH ₂ CH ₂ O) _p —H], which is a lauryl group)) It may be.

  Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester , Polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkylolamide, alkyl alkanolamide, acetylene glycol, oxyethylene adduct of acetylene glycol, Examples thereof include polyethylene glycol polypropylene glycol block copolymers.

(B) Cationic surfactant The cationic surfactant is preferably a compound having no amide group.

  The cationic surfactant may be an amine salt, a quaternary ammonium salt, or an oxyethylene addition type ammonium salt. Specific examples of the cationic surfactant include, but are not limited to, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt type surfactants such as imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, Quaternary ammonium salt type surfactants such as alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like can be mentioned.

Preferred examples of the cationic surfactant are:
^{R 21 -N + (-R 22)} (- R 23) (- R 24) X -
[Wherein R ²¹ , R ²² , R ²³ and R ²⁴ are hydrocarbon groups having 1 to 30 carbon atoms,
X is an anionic group. ]
It is a compound of this.
Specific examples of R ²¹ , R ²² , R ²³ and R ²⁴ are alkyl groups (for example, methyl group, butyl group, stearyl group, palmityl group). Specific examples of X are halogen (for example, chlorine) and acid (for example, hydrochloric acid, acetic acid).
The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (alkyl having 4 to 30 carbon atoms).

The cationic surfactant is preferably an ammonium salt. The cationic surfactant has the formula:
R ¹ _p -N ⁺ R ² _q X ⁻
[Wherein R ¹ is a linear and / or branched aliphatic (saturated and / or unsaturated) group of C ₁₂ or more (for example, C _{12 to} C ₅₀ ),
R ² is H or a C ₁ -C ₄ alkyl group, benzyl group, polyoxyethylene group (number of oxyethylene groups, for example, 1 (particularly 2, particularly 3) to 50)
(CH ₃ and C ₂ H ₅ are particularly preferred),
X is a halogen atom (e.g.,), fatty bases C ₁ -C _4,
p is 1 or 2, q is 2 or 3, and p + q = 4. ]
It may be an ammonium salt represented by The carbon number of R ¹ may be 12-50, such as 12-30.

  Specific examples of the cationic surfactant include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl) trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyl Di (hydropolyoxyethylene) ammonium chloride, benzyldodecyl di (hydropolyoxyethylene) ammonium chloride, N- [2- (diethylamino) ethyl] oleamide hydrochloride, dialkyl (reduced tallow) dimethylammonium chloride .

(C) Anionic surfactant Specific examples of the anionic surfactant include sodium lauryl sulfate, triethanolamine lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene nonylphenyl ether sulfate, and polyoxyethylene lauryl. Triethanolamine ether sulfate, sodium cocoyl sarcosine, sodium N-cocoyl methyl taurine, sodium polyoxyethylene palm alkyl ether sulfate, sodium diether hexyl sulfosuccinate, sodium α-olefin sulfonate, sodium lauryl phosphate, polyoxyethylene lauryl ether Examples include sodium phosphate and perfluoroalkylcarboxylate (trade name Unidyne DS-101, 102 (manufactured by Daikin Industries)). Can.

(D) Amphoteric surfactants Specific examples of amphoteric surfactants include alanines, imidazolinium betaines, amide betaines, and betaine acetate. Specific examples include lauryl betaine, stearyl betaine, and lauryl carboxy. Examples include methylhydroxyethyl imidazolinium betaine, lauryl dimethylaminoacetic acid betaine, and fatty acid amidopropyldimethylaminoacetic acid betaine.

Each of the nonionic surfactant, the cationic surfactant, the anionic surfactant, and the amphoteric surfactant may be one or a combination of two or more.
The amount of the surfactant may be 0.05 to 10 parts by weight, for example, 0.1 to 8 parts by weight with respect to 100 parts by weight of the polymer. The total amount of the surfactant may be 0.1 to 20 parts by weight, for example, 0.2 to 10 parts by weight with respect to 100 parts by weight of the polymer.

  The aqueous dispersion of the fluoropolymer of the present invention has a cation strength of about 0 to about 2.5 millimoles, preferably about 0 to about 2.3 millimoles, more preferably about 0 to about 2.0 millimoles per 100 g of the solid content of the aqueous dispersion. Have. The cation strength when using a cationic surfactant is about 0.1 to about 2.5 mmol, more preferably about 0.5 to about 2.3 mmol, more preferably about 0.6 to about 2.0 mmol, per 100 g of solid content of the aqueous dispersion. Here, “cationic strength” means an amino group (eg, primary amino group, secondary amino group) contained in a substance other than the antibacterial and antifungal agent present in 100 g of the solid content of the water / oil repellent composition. Group, tertiary amino group and quaternary amino group). Amino groups are generally included in fluoropolymers and surfactants.

  The water / oil repellent composition of the present invention includes an insecticide, a colorant, an ultraviolet absorber, an ultraviolet scattering agent, and a flameproofing agent in addition to the above-mentioned aqueous dispersion of a fluoropolymer and an antifungal agent. In addition, optional components such as a flame retardant, a fragrance, and a viscosity modifier can be included depending on the use environment, the object to be treated, and the like.

  The water / oil repellent composition of the present invention can be applied to an object (article) to be treated by a conventionally known method. Usually, the water / oil repellent composition is dispersed and diluted in water, and is attached to the surface of an object (article) by a known method such as dip coating, spray coating, foam coating, etc., and dried. The method is taken. If necessary, curing may be carried out by applying together with a suitable crosslinking agent (for example, blocked isocyanate). Furthermore, a softener, a flame retardant, an antistatic agent, a paint fixing agent, an anti-wrinkle agent and the like can be added to the water / oil repellent composition of the present invention.

  Examples of the object to be treated with the water / oil repellent composition of the present invention include textile products, stones, filters (for example, electrostatic filters), dust masks, fuel cell components (for example, gas diffusion electrodes and gas diffusion supports). Body), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, plasters and the like. Various examples can be given as textile products. For example, natural animal and vegetable fibers such as cotton, hemp, wool, silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, semi-synthetic fibers such as rayon and acetate, glass fibers, carbon fibers , Inorganic fibers such as asbestos fibers, or mixed fibers thereof.

The fiber product may be in the form of a fiber, a cloth or the like.
The treatment agent composition of the present invention can also be used as an internal release agent or an external release agent.

  The water / oil repellent composition of the present invention can be applied to a fibrous substrate (eg, a fiber product, etc.) by any of the known methods for treating a fiber product with a liquid. When the textile product is a fabric, the fabric may be immersed in the solution, or the solution may be attached or sprayed onto the fabric. The treated textile is dried and preferably heated at, for example, 100 ° C. to 200 ° C. in order to develop oil repellency.

  Alternatively, the copolymer may be applied to the textile by a cleaning method, for example, it may be applied to the textile by a laundry application or a dry cleaning method.

  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.

Alternatively, the fibrous base material may be leather. In order to make the production polymer hydrophobic and oleophobic, 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.
Alternatively, 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.

  “Treatment” means that a treatment agent is applied to an object to be treated by dipping, spraying, coating, or the like. By the treatment, the copolymer which is an active ingredient of the treatment agent penetrates into the treatment object and / or adheres to the surface of the treatment object.

Synthesis Example 1 Cation strength (0.6 mmol / 100 g)
In a 500 ml autoclave, 57 g of C _n F _{2n + 1} CH ₂ CH ₂ OCOCH═CH ₂ (mixture of n = 8,10 compound in a mass ratio of about 8: 2), 7.8 g of stearyl acrylate, 2 g of N-methylol acrylamide, tripropylene Add 25 g of glycol, 148 g of deionized water, 2.41 g of polyoxyethylene tridecyl ether, 5.64 g of polyoxyethylene lauryl ether, 2.7 g of polyoxyethylene oleyl ether and 0.72 g of dialkyl (reduced beef tallow) dimethylammonium chloride. The mixture was emulsified and dispersed with ultrasonic waves at 30 ° C. for 30 minutes. After emulsification, 0.4 g of n-dodecyl mercaptan was added and then 21 g of vinyl chloride was press-filled.
Add a solution of 0.56 g of azobisamidide propane dihydrochloride in 15 g of deionized water, react at 60 ° C for 5 hours, remove unreacted vinyl chloride, and then the solid content concentration becomes 30 mass% As described above, deionized water was added to prepare an aqueous dispersion (D1) containing a fluoropolymer.

Synthesis Example 2 Cation strength (1.8 mmol / 100 g)
In a 500 ml autoclave, 57 g of C _n F _{2n + 1} CH ₂ CH ₂ OCOCH═CH ₂ (mixture of n = 8,10 compound in a mass ratio of about 8: 2), 7.8 g of stearyl acrylate, 2 g of N-methylol acrylamide, tripropylene Add 25 g of glycol, 148 g of deionized water, 2.41 g of polyoxyethylene tridecyl ether, 5.64 g of polyoxyethylene lauryl ether, 1.26 g of polyoxyethylene oleyl ether, 2.16 g of dialkyl (reduced beef tallow) dimethylammonium chloride and add 40 under stirring. The mixture was emulsified and dispersed with ultrasonic waves at 30 ° C. for 30 minutes. After emulsification, 0.4 g of n-dodecyl mercaptan was added and then 21 g of vinyl chloride was press-filled.
Add a solution of 0.56 g of azobisamidide propane dihydrochloride in 15 g of deionized water, react at 60 ° C for 5 hours, remove unreacted vinyl chloride, and then the solid content concentration becomes 30 mass% Thus, deionized water was added to prepare an aqueous dispersion (D2) containing a fluoropolymer.

Synthesis example 3 nonionic type
In a 500 ml autoclave, 57 g of C _n F _{2n + 1} CH ₂ CH ₂ OCOCH═CH ₂ (mixture of n = 8,10 compound in a mass ratio of about 8: 2), 7.8 g of stearyl acrylate, 2 g of N-methylol acrylamide, tripropylene Add 25 g of glycol, 148 g of deionized water, 2.41 g of polyoxyethylene tridecyl ether, 6.36 g of polyoxyethylene lauryl ether, and 2.7 g of polyoxyethylene oleyl ether, and emulsify and disperse ultrasonically at 40 ° C. for 30 minutes. I let you. After emulsification, 0.4 g of n-dodecyl mercaptan was added and then 21 g of vinyl chloride was press-filled.
Add a solution of 0.56 g of azobisamidide propane dihydrochloride in 15 g of deionized water, react at 60 ° C for 5 hours, remove unreacted vinyl chloride, and then the solid content concentration becomes 30 mass% Thus, deionized water was added to prepare an aqueous dispersion (D3) containing a fluoropolymer.

Synthesis Example 4 Nonionic Type In a 100 ml four-necked flask equipped with a reflux condenser, a nitrogen inlet, a thermometer and a stirrer, C ₆ F ₁₃ CH ₂ CH ₂ OCOCH = CH ₂ 16.6 g, 2-hydroxyethyl methacrylate 5 g, polyethylene glycol diacrylate _{CH 2 = CHC (= O)} O- (CH 2 CH 2 O) n-C (= O) CH = CH 2 ( average of n is 7) 8.4 g, 2-mercaptoethanol 0.45 g, further 45 g of methyl ethyl ketone was charged, and nitrogen bubbling was performed for 30 minutes.
After raising the internal temperature to 50-65 ° C. under a nitrogen stream, 0.4 g of t-butyl peroxypivalate was added and reacted at 60-65 ° C. for 6 hours.
Methyl ethyl ketone was distilled off from the resulting solution under reduced pressure at about 70 ° C., and deionized water was further added to prepare an aqueous dispersion (D4) having a solid content concentration of about 20%.

Synthesis Example 5 Anion Type A 500 ml reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet and a heating device was prepared, and 100 parts of solvent methyl ethyl ketone was added. Subsequently, under stirring, C ₆ F ₁₃ CH ₂ CH ₂ OCOCH = CH ₂ 70 g, hydroxyethyl acrylate 18 g, CH ₂ = CHC (═O) O— (CH ₂ CH ₂ O) n—H (the average value of n is 7) 7 g, 5 g of methacrylic acid, and 0.5 g of 4,4′-azobis (4-cyanopentanoic acid) were added, and the mixture was stirred and reacted in a nitrogen atmosphere at 70 ° C. for 12 hours. The solid content concentration of the obtained copolymer-containing solution (S1) was 50 mass%.
After adding 23% ammonia water and deionized water to 50 g of S1 solution and emulsifying and dispersing, heating with an evaporator and distilling off methyl ethyl ketone under reduced pressure, an aqueous dispersion with a solid content concentration of 20 mass% ( D5) was prepared.

Synthesis Example 6 Cation strength (3.0 mmol / 100 g)
In a 500 ml autoclave, 57 g of C _n F _{2n + 1} CH ₂ CH ₂ OCOCH═CH ₂ (mixture of n = 8,10 compound in a mass ratio of about 8: 2), 7.8 g of stearyl acrylate, 2 g of N-methylol acrylamide, tripropylene Add 25 g of glycol, 148 g of deionized water, 2.41 g of polyoxyethylene tridecyl ether, 5.64 g of polyoxyethylene lauryl ether, 1.26 g of polyoxyethylene oleyl ether, 3.6 g of dialkyl (reduced beef tallow) dimethylammonium chloride and add 40 under stirring. The mixture was emulsified and dispersed with ultrasonic waves at 30 ° C. for 30 minutes. After emulsification, 0.4 g of n-dodecyl mercaptan was added and then 21 g of vinyl chloride was press-filled.
Add a solution of 0.56 g of azobisamidide propane dihydrochloride in 15 g of deionized water, react at 60 ° C for 5 hours, remove unreacted vinyl chloride, and then the solid content concentration becomes 30 mass% As described above, deionized water was added to prepare an aqueous dispersion (D6) containing a fluoropolymer.

Example 1 (cationic strength (0.6 mmol / 100 g) + antibacterial and antifungal agent)
To the dispersion of D1 prepared in Synthesis Example 1, benzisothiazolin-3-one 75 ppm, and further 5-chloro-2-methyl-2H-isothiazol-3-one and 2-methyl-2H-isothiazol-3-one The contamination test was carried out by adding 75 ppm of the mixture (weight ratio 3: 1).

Example 2 (cationic strength (1.8 mmol / 100 g) + antibacterial and antifungal agent)
In the dispersion of D2 prepared in Synthesis Example 2, benzisothiazolin-3-one 75 ppm, and further 5-chloro-2-methyl-2H-isothiazol-3-one and 2-methyl-2H-isothiazol-3-one The contamination test was carried out by adding 75 ppm of the mixture (weight ratio 3: 1).

Example 3 (Nonionic + antifungal agent)
To the dispersion of D3 prepared in Synthesis Example 3, benzisothiazolin-3-one 75 ppm, and further 5-chloro-2-methyl-2H-isothiazol-3-one and 2-methyl-2H-isothiazol-3-one The contamination test was carried out by adding 75 ppm of the mixture (weight ratio 3: 1).

Example 4 (nonionic + antibacterial and antifungal agent)
In the dispersion of D4 prepared in Synthesis Example 4, benzisothiazolin-3-one 75 ppm, and further 5-chloro-2-methyl-2H-isothiazol-3-one and 2-methyl-2H-isothiazol-3-one The contamination test was carried out by adding 75 ppm of the mixture (weight ratio 3: 1).

Example 5 (anionic + antifungal agent)
To the dispersion of D5 prepared in Synthesis Example 5, benzisothiazolin-3-one 75 ppm, and further 5-chloro-2-methyl-2H-isothiazol-3-one and 2-methyl-2H-isothiazol-3-one The contamination test was carried out by adding 75 ppm of the mixture (weight ratio 3: 1).

Comparative Example 1 (cation strength (0.6 mmol / 100 g))
Using the D1 dispersion prepared in Synthesis Example 1 as it was, a contamination degree test was performed.

Comparative Example 2 (cation strength (1.8 mmol / 100 g))
Using the D2 dispersion prepared in Synthesis Example 2 as it was, a contamination degree test was performed.

Comparative Example 3 (nonionic property)
Using the dispersion liquid of D3 prepared in Synthesis Example 3 as it was, a contamination degree test was performed.

Comparative Example 4 (nonionic property)
Using the dispersion liquid of D4 prepared in Synthesis Example 4 as it was, a contamination degree test was performed.

Comparative Example 5 (anionic)
Using the D5 dispersion prepared in Synthesis Example 5 as it was, a contamination degree test was performed.

Reference Example 1 (cationic strength (3.0 mmol / 100 g))
Using the D6 dispersion prepared in Synthesis Example 6 as it was, a contamination degree test was performed.

Pollution degree test The pollution degree test was carried out under the following conditions based on the antifungal efficacy evaluation test method of the antifungal agent of the Antibacterial Product Technical Council.

Contamination degree (antibacterial and antifungal effect) test method 1. Prepare fungi (Aspergillus flavus), bacteria (mixed with Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, etc.).
2. Prepare the stock solution of the following concentration.
Fungi: 10 ⁵ to 10 ⁶ cfu / ml, bacteria: 10 ⁷ to 10 ⁸ cfu / ml
3. Add 50 μl of the above bacterial stock solution to 5 ml of the sample and mix well.
4). The specimen is stored at a predetermined temperature (fungus = 30 ° C., bacteria = 35 ° C.) to promote the growth of the fungus.
5. Check the number of bacteria after 2 weeks to determine the degree of contamination.

汚染度が0または1の検体を効果ありとした。 Judgment criteria

Samples with a contamination degree of 0 or 1 were considered effective.

Test results

As shown in Tables 2 and 3, it was found that the addition of the antibacterial and antifungal agent suppresses the growth of microorganisms in the water / oil repellent composition (see Examples 3 and 4 and Comparative Examples 3 and 4). In addition to the addition of the antibacterial and antifungal agent, it has been found that when the cation strength of the aqueous dispersion of the fluoropolymer is increased, the growth of microorganisms is further suppressed (Examples 1 and 2). In addition, it was found that a cation strength of about 3.0 mmol / 100 g is necessary to suppress the growth of microorganisms only by the cation strength of the aqueous dispersion without adding a fungicide and fungicide.
It was also found that the cation strength of the antibacterial and antifungal agent and the aqueous dispersion does not reduce the water / oil repellency of the water / oil repellent composition and does not impair its performance.

  Even if the water / oil repellent composition of the present invention uses water or a device contaminated with fungi or bacteria during production or application, the growth of these microorganisms is suppressed and high storage stability is exhibited. Therefore, it can be manufactured in various environments, such as textile products, stone, filters, glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, And can be used for plaster etc.

Claims (9)

A water / oil repellent composition comprising an aqueous dispersion of a fluoropolymer , an antibacterial and antifungal agent, and at least one selected from a cationic surfactant and an amphoteric surfactant , The cation strength of the aqueous dispersion of the polymer is 0. 0 per 100 g of the solid content of the aqueous dispersion . A water / oil repellent composition having a concentration of 1 to 2.5 mmol. The water / oil repellent composition according to claim 1, comprising a nonionic surfactant. The water / oil repellent composition according to claim 2 comprising an anionic surfactant. ^{1 × 10 5 ~1 × 10 7} cfu / water and oil repellent composition according to any one of claims 1 to 3 including a fungus ml. The water / oil repellent composition according to any one of claims 1 to 3 , comprising 1 x 10 ⁷ to 1 x 10 ⁹ cfu / ml of bacteria. The water / oil repellent composition according to any one of claims 1 to 5 , wherein the antibacterial and antifungal agent is one or more antibacterial and antifungal agents that suppress the growth of both fungi and bacteria. The water / oil repellent composition according to claim 6 , wherein the antibacterial and antifungal agent is an isothiazoline type. The water / oil repellent composition according to any one of claims 1 to 7 , which comprises an antibacterial and antifungal agent having an active ingredient concentration of 1.5 to 450 ppm. Comprising applying a water and oil repellent composition according to the article in any of claims 1-8, the treated article production method.