CN105793487B - The manufacture method of dryingagent composition, water-repellancy fibre and water-repellancy fibre - Google Patents
The manufacture method of dryingagent composition, water-repellancy fibre and water-repellancy fibre Download PDFInfo
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- CN105793487B CN105793487B CN201580002779.3A CN201580002779A CN105793487B CN 105793487 B CN105793487 B CN 105793487B CN 201580002779 A CN201580002779 A CN 201580002779A CN 105793487 B CN105793487 B CN 105793487B
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- CQXMAMUUWHYSIY-UHFFFAOYSA-N Lignoceric acid Natural products CCCCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 CQXMAMUUWHYSIY-UHFFFAOYSA-N 0.000 description 1
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- JFONEZZUCJNYEG-UHFFFAOYSA-N N=NC=NN.N=NC=NN.CC(C(=O)O)=C Chemical compound N=NC=NN.N=NC=NN.CC(C(=O)O)=C JFONEZZUCJNYEG-UHFFFAOYSA-N 0.000 description 1
- AKQOBHZKBDHWQI-BZEFIUHZSA-N O[C@H]1C[C@@H](CCC1)N1C(C2(C3=C1N=C(N=C3)NC1=CC=C(C=C1)S(=O)(=O)NC([2H])([2H])[2H])CC2)=O Chemical compound O[C@H]1C[C@@H](CCC1)N1C(C2(C3=C1N=C(N=C3)NC1=CC=C(C=C1)S(=O)(=O)NC([2H])([2H])[2H])CC2)=O AKQOBHZKBDHWQI-BZEFIUHZSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021319 Palmitoleic acid Nutrition 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- 240000000528 Ricinus communis Species 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- SSOONFBDIYMPEU-UHFFFAOYSA-N [3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COCC(CO)(CO)COC(=O)C=C SSOONFBDIYMPEU-UHFFFAOYSA-N 0.000 description 1
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- JAZBEHYOTPTENJ-JLNKQSITSA-N all-cis-5,8,11,14,17-icosapentaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O JAZBEHYOTPTENJ-JLNKQSITSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229940114079 arachidonic acid Drugs 0.000 description 1
- 235000021342 arachidonic acid Nutrition 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000020226 cashew nut Nutrition 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229940127108 compound 5g Drugs 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- MAWOHFOSAIXURX-UHFFFAOYSA-N cyclopentylcyclopentane Chemical group C1CCCC1C1CCCC1 MAWOHFOSAIXURX-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 235000020673 eicosapentaenoic acid Nutrition 0.000 description 1
- 229960005135 eicosapentaenoic acid Drugs 0.000 description 1
- JAZBEHYOTPTENJ-UHFFFAOYSA-N eicosapentaenoic acid Natural products CCC=CCC=CCC=CCC=CCC=CCCCC(O)=O JAZBEHYOTPTENJ-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 1
- KPXFIETUTLCJAC-UHFFFAOYSA-N isocyanic acid;naphthalene Chemical class N=C=O.C1=CC=CC2=CC=CC=C21 KPXFIETUTLCJAC-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 235000021290 n-3 DPA Nutrition 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- HNHVTXYLRVGMHD-UHFFFAOYSA-N n-butyl isocyanate Chemical compound CCCCN=C=O HNHVTXYLRVGMHD-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 229940099427 potassium bisulfite Drugs 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- QZZGJDVWLFXDLK-UHFFFAOYSA-N tetracosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(O)=O QZZGJDVWLFXDLK-UHFFFAOYSA-N 0.000 description 1
- 229940095068 tetradecene Drugs 0.000 description 1
- 125000005040 tridecenyl group Chemical group C(=CCCCCCCCCCCC)* 0.000 description 1
- 229940113165 trimethylolpropane Drugs 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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- 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
- D06M15/27—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of alkylpolyalkylene glycol esters of unsaturated carboxylic acids
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- 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
- D06M15/347—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated ethers, acetals, hemiacetals, ketones or aldehydes
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- 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The present invention is dryingagent composition, it includes non-fluorine based polymer, the non-fluorine based polymer contains the Component units from (methyl) acrylate monomer (A), the Component units with coming from reactive emulsifier (B), (methyl) acrylate monomer (A) have also can have substituent carbon number be more than 12 1 valency alkyl, the reactive emulsifier (B) be selected from HLB for 7~18, it is at least one kind of in compound (B1)~(B3) comprising repeatability unsaturated group.
Description
【Technical field】
The present invention is the manufacture method on dryingagent composition, water-repellancy fibre and water-repellancy fibre.
【Background technology】
It is in the past known to have containing fluorine-based fluorine system dryingagent, it is known that by the way that the fluorine system dryingagent is carried out in fibre etc.
Processing, the fibre of water-repellancy is assigned to its surface.Fluorine system dryingagent so is generally by making the list with fluoroalkyl
Body polymerize or copolymerization and manufacture.
Though excellent water-repellancy is played with the fibre that fluorine system dryingagent is handled, in order to show water-repellancy, due to must
The regiospecific of fluoroalkyl must be adjusted, fluorine system dryingagent is attached to after fibre, it is necessary to which heat is implemented with the temperature more than 130 DEG C
Processing.However, in the necessary high-energy of heat treatment of high temperature, therefore be problematic in terms of the energetic trend of international province.
Further, the monomer with fluoroalkyl is due to being high price, therefore not in the satiable monomer in economic face, and then with fluorine
The monomer of alkyl is due to hard-decomposed therefore problematic even in environment face.
In addition, in the field of the drying processing of fibre, stabilisation and cost cutting for quality, even if expecting low
Concentration or low heat treatment temperature, also can by excellent water-repellancy assign fibre dryingagent.
Therefore, just studied for not fluorine-containing non-fluorine system dryingagent in recent years.For example, in non-patent literature 1, it is open
The hydrocarbon compound, fatty acid metal salts or ureine of such as paraffin or wax is set to carry out the dryingagent of emulsion dispersion.
Further, in patent document 1, motion will assign water-repellancy work not a halfpenny the worse with the conventional fluorine system dryingagent compared with
For the purpose of, the dryingagent of the specific non-fluorine based polymer of emulsion dispersion.
[prior art literature]
[non-patent literature]
[non-patent literature 1] " new trend of super drying processing, the full appearance of processing agent and moisture-permeability waterproof material ", (strain) Osaka
Chemical Marketing Center distribution, 1996, p.7~9
[patent document]
[patent document 1] JP 2006-328624 publications
【The content of the invention】
The invention problem to be solved
However, in the non-fluorine system dryingagent that non-patent literature 1 is recorded, it is difficult to obtain having with conventional fluorine system dryingagent
The fibre of same water-repellancy when being handled.Further, the fibre through processing is hardened, for sense of touch
It can say not enough.
The situation for the non-fluorine system dryingagent that patent document 1 is recorded, in order to ensure storage stability, non-fluorine based polymer coordinates
During the surfactant of the abundant amount through emulsion dispersion, there is the water-repellancy of the fibre obtained by reduction, realize storage
The satisfactory to both parties actually difficulty of stability and water-repellancy.
The present invention is to complete in view of the foregoing, it is therefore intended that there is provided while superior storage stability, even if in
Situation about not being heat-treated, also can assign fibre etc. by sufficient water-repellancy, can obtain sense of touch and water-repellancy is excellent
The dryingagent composition of water-repellancy fibre and the manufacture using its water-repellancy fibre and water-repellancy fibre
Method.
[means for solving the problems]
The present invention is to provide dryingagent composition, and it includes non-fluorine based polymer, and the non-fluorine based polymer, which contains, to be come from down
State the Component units of (methyl) acrylate monomer (A) of formula (A-1) expression, the composition with coming from reactive emulsifier (B)
Unit, the reactive emulsifier (B) is at least one kind of in (B1)~(B3), and (B1) HLB is 7~18 following formulas (I-1)
The compound of expression, following formulas that (B2) HLB is 7~18 (I I-1) represent compound and (B3) HLB be 7~18,
The compound of the epoxyalkane of addition carbon number 2~4 in the grease with hydroxyl and polymerism unsaturated group.
[changing 1]
[in formula (A-1), R1Represent hydrogen or methyl, R2Represent can also there is 1 valency alkyl of the carbon number more than 12 of substituent].
[changing 2]
[in formula (I-1), R3Hydrogen or methyl are represented, X represents the alkylidene of the straight or branched of carbon number 1~6, Y1Expression is included
The divalent group of the alkylene oxide group of carbon number 2~4].
[changing 3]
[in formula (II-1), R4Represent 1 valency unsaturated alkyl of the carbon number 13~17 with polymerism unsaturated group, Y2Table
Show the divalent group of the alkylene oxide group comprising carbon number 2~4].
Above-mentioned non-fluorine based polymer, which further can contain to come from, is selected from what is be made up of following (C1), (C2), (C3) and (C4)
The Component units of the 2nd at least one kind of (methyl) acrylate monomer (C) in group.
(C1) (methyl) acrylate monomer that following formulas (C-1) represent
[changing 4]
[in formula (C-1), R5Represent hydrogen or methyl, R6Represent to have and select free hydroxyl, amino, carboxyl, epoxy radicals, isocyanic acid
1 valency chain alkyl of the carbon number 1~11 of at least one kind of functional group in the group that ester group and (methyl) acryloxy are constituted.In formula,
It is less than 2 in the number of (methyl) acryloxy of intramolecular].
(C2) (methyl) acrylate monomer that following formulas (C-2) represent
[changing 5]
[in formula (C-2), R7Represent hydrogen or methyl, R8Represent can also there is 1 valency cyclic hydrocarbon of the carbon number 1~11 of substituent
Base].
(C3) methacrylate monomers that following formulas (C-3) represent
[changing 6]
[in formula (C-3), R9Represent 1 valency chain alkyl of unsubstituted carbon number 1~4].
(C4) (methyl) acrylate monomer that following formulas (C-4) represent
[changing 7]
[in formula (C-4), R10Hydrogen or methyl are represented, p represents more than 2 integer, and S represents the organic group of (p+1) valency, T tables
Show the 1 valency organic group with polymerism unsaturated group].
The present invention also provides dryingagent composition, and it includes non-fluorine based polymer, and the non-fluorine based polymer is to make emulsion
Or dispersion carries out emulsion polymerization or dispersin polymerization is formed, the emulsion or dispersion are represented comprising above-mentioned formula (A-1)
(methyl) acrylate monomer (A) and reactive emulsifier (B), the reactive emulsifier (B) are selected from (B1)~(B3) extremely
It is few a kind, the above-mentioned formula (II- that the compound for above-mentioned formula (I-1) expression that (B1) HLB is 7~18, (B2) HLB are 7~18
1) represent compound and (B3) HLB for 7~18, the addition carbon in the grease with hydroxyl and polymerism unsaturated group
The compound of the epoxyalkane of number 2~4.
Above-mentioned emulsion or above-mentioned dispersion can further include to be selected from and be made up of above-mentioned (C1), (C2), (C3) and (C4)
Group in the 2nd at least one kind of (methyl) acrylate monomer (C).
According to the dryingagent composition of the present invention, while superior storage stability, even if in the feelings not being heat-treated
Condition, also can assign fibre etc. by sufficient water-repellancy, can realize sense of touch and the excellent water-repellancy fiber system of water-repellancy
Product.
The present invention also provides water-repellancy fibre, and it is formed by the fibre of attachment non-fluorine based polymer, and this is non-
Fluorine system polymer contain from above-mentioned formula (A-1) represent (methyl) acrylate monomer (A) Component units, with it is reflexive
The Component units of answering property emulsifying agent (B), the reactive emulsifier (B) is at least one kind of in (B1)~(B3), and (B1) HLB is 7
Compound that~18 above-mentioned formula (I-1) is represented, (B2) HLB for 7~18 above-mentioned formula (I I-1) represent compound,
And (B3) HLB for 7~18, in the grease with hydroxyl and polymerism unsaturated group addition carbon number 2~4 epoxyalkane
Compound.
Above-mentioned non-fluorine based polymer can further include in the group being made up of above-mentioned (C1), (C2), (C3) and (C4)
At least one kind of Component units for coming from the 2nd (methyl) acrylate monomer (C).
The present invention also provides water-repellancy fibre, and it is formed by the fibre of attachment non-fluorine based polymer, and this is non-
Fluorine system polymer is to form emulsion or dispersion progress emulsion polymerization or dispersin polymerization, and the emulsion or dispersion are comprising upper
(methyl) acrylate monomer (A) and reactive emulsifier (B) of formula (A-1) expression are stated, the reactive emulsifier (B) is selected from
(B1) it is at least one kind of in~(B3), compound that above-mentioned formula (I-1) that (B1) HLB is 7~18 is represented, (B2) HLB be 7~
Compound that 18 above-mentioned formula (I I-1) is represented and (B3) HLB for 7~18, with hydroxyl and polymerism unsaturated group
The compound of the epoxyalkane of addition carbon number 2~4 in the grease of group.
Above-mentioned emulsion or above-mentioned dispersion can further include to be selected from and be made up of above-mentioned (C1), (C2), (C3) and (C4)
Group in the 2nd at least one kind of (methyl) acrylate monomer (C).
Even if the water-repellancy fibre of the present invention is during room foreign minister in use, sense of touch and drying can be maintained fully
Property.
The present invention also provides the manufacture method of water-repellancy fibre, and it possesses fibre with comprising the invention described above
The process that the treatment fluid for the dryingagent composition being related to is handled.
According to the present invention water-repellancy fibre manufacture method, while by using superior storage stability, i.e.,
Make in situation about not being heat-treated, the dryingagent of the invention that sufficient water-repellancy can also be assigned to fibre etc. is combined
Thing, can stablize manufacture sense of touch and the excellent water-repellancy fibre of water-repellancy.Further, water-repellancy fibre of the invention
Manufacture method is due to the unnecessary heat treatment in high temperature, while can realizing that province is energetic, due to using non-fluorine system dryingagent,
The load to environment can be lowered.
The effect of invention
In accordance with the invention it is possible to while superior storage stability is provided, even if in situation about not being heat-treated, also may be used
Fibre etc. is assigned by sufficient water-repellancy, the dryingagent of sense of touch and the excellent water-repellancy fibre of water-repellancy can be obtained
Composition.
Even if the dryingagent composition of the present invention is not comprising the dryingagent composition with fluoroalkyl or the compound of fluorine,
Excellent water-repellancy is displayed that, can be utilized, can be eliminated to fluorine supply source or ring as the dryingagent of substitution fluorine system dryingagent
The mystery of the influence in border etc..In addition, dryingagent composition is attached to after fibre etc., though it is preferred that generally carry out hot place
Reason, but the present invention dryingagent composition due to the monomer with fluoroalkyl is not used, even if therefore to be gentle in less than 130 DEG C
The situation that condition is heat-treated, can also make it play high water repellency, also have, with what is be heat-treated more than 130 DEG C of high temperature
In situation, situation that can be by heat treatment time compared with fluorine system dryingagent more shortens.Therefore, because suppressing to be processed by thermally-induced
Thing it is rotten, therefore sense of touch is limbered up, and also excellent in terms of heat treatment can lower the costs such as the heat.
And then, according to the present invention, as the emulsifying dispersant of emulsification or dispersin polymerization used in non-fluorine based polymer, pass through
General surfactant is replaced using specific reactive emulsifier, the surface work that dryingagent composition is included can be lowered
The amount of property agent.As a result, the reduction of the water-repellancy of the fibre of gained etc. can be suppressed, it can realize than conventional non-fluorine system
The higher water-repellancy of dryingagent.Further, dryingagent composition of the invention, due to the emulsification of non-fluorine based polymer in itself point can be made
Property lifting is dissipated, even if making an addition to the situation of processing bath, stable emulsified state also can be easily maintained, the fiber for making correspondence various
It is processed into possibility.
【Embodiment】
The dryingagent composition of present embodiment, it includes non-fluorine based polymer, and the non-fluorine based polymer, which contains, to be come from down
State the Component units of (methyl) acrylate monomer (A) (hereinafter also referred to " (A) composition ") of formula (A-1) expression, with coming from
The Component units of reactive emulsifier (B) (hereinafter also referred to " (B) composition "), the reactive emulsifier (B) be selected from (B1)~
(B3) at least one kind of in, compound that following formulas (I-1) that (B1) HLB is 7~18 are represented, (B2) HLB are under 7~18
State formula (II-1) expression compound and (B3) HLB for 7~18, in the oil with hydroxyl and polymerism unsaturated group
The compound of the epoxyalkane of addition carbon number 2~4 in fat.
[changing 8]
[in formula (A-1), R1Represent hydrogen or methyl, R2Represent can also there is 1 valency alkyl of the carbon number more than 12 of substituent.]
[changing 9]
[in formula (I-1), R3Hydrogen or methyl are represented, X represents the alkylidene of the straight or branched of carbon number 1~6, Y1Expression is included
The divalent group of the alkylene oxide group of carbon number 2~4].
[changing 10]
[in formula (II-1), R4Represent 1 valency unsaturated alkyl of the carbon number 13~17 with polymerism unsaturated group, Y2Table
Show the divalent group of the alkylene oxide group comprising carbon number 2~4].
Here, so-called " (methyl) acrylate " refers to " acrylate " or its corresponding " methacrylate ", even if
In " (methyl) acrylic acid ", " (methyl) acrylamide " etc. also to be synonymous.
Further, so-called " reactive emulsifier ", refers to the emulsifying dispersant with free-radical reactive, that is, refers to intramolecular tool
There is the surfactant of the polymerism unsaturated group of more than 1, be that the monomer that can make itself and such as (methyl) acrylate is carried out
The reactive emulsifier of copolymerization.
Further, so-called " HLB ", refers to inferior ethoxyl being considered as hydrophilic group, is all considered as lipophilic group beyond it, by Griffin
Method and the HLB value calculated.
(methyl) acrylate monomer (A) that the above-mentioned formula (A-1) used in present embodiment is represented, with can have
The carbon number of substituent is more than 12 1 valency alkyl.This alkyl can be straight-chain, or branched can be saturated hydrocarbyl, also may be used
For unsaturated alkyl, and then can also have ester ring type or aromatic ring-type.Among these, the preferably alkyl of straight-chain, more
The preferably alkyl of straight-chain.In this case, the more excellent person of water-repellancy can be turned into.1 valency alkyl of carbon number more than 12 has substitution
During base, as its substituent, hydroxyl, amino, carboxyl, epoxy radicals, NCO, blocked isocyanate base and (first can be enumerated
Base) more than a kind among acryloxy etc..In present embodiment, in above-mentioned formula (A-1), R2Preferably unsubstituted hydrocarbon
Base.
The carbon number of above-mentioned alkyl is preferably 12~24.When carbon number is less than 12, non-fluorine based polymer is set to be attached to fibre
Deng when, it is impossible to play sufficient water-repellancy.On the other hand, when carbon number is more than 24, compared with situation of the carbon number for above range, make
When non-fluorine based polymer is attached to fibre etc., the sense of touch for having the tendency of fibre becomes thick and stiff.
The carbon number of above-mentioned alkyl, more preferably 12~21.When carbon number is this scope, water-repellancy becomes especially excellent with sense of touch.
It is particularly preferably the alkyl for the straight-chain that carbon number is 12~18 as alkyl.
As above-mentioned (A) composition, for example, it can enumerate (methyl) octadecyl acrylate, (methyl) Process Conditions of Cetane Acrylate, (first
Base) lauryl acrylate, (methyl) dodecyl acrylate, (methyl) myristyl ester, the five-ester of (methyl) acrylic acid ten,
The ester of (methyl) acrylic acid 17, the ester of (methyl) acrylic acid 19, the ester of (methyl) acrylic acid 20, (methyl) acrylic acid 21
Ester, (methyl) Behenyl acrylate, (methyl) acrylic acid silk amine acyl ester, (methyl) acrylic acid beeswax ester.
Above-mentioned (A) composition can have hydroxyl, amino, carboxyl, epoxy radicals and the isocyanic acid being selected from by that can be reacted with crosslinking agent
At least one kind of functional group in the group that ester group is constituted.In this case, the durable drying of the fibre of gained can be lifted further
Property.NCO can form the blocked isocyanate base protected with end-capping reagent.Further, can when above-mentioned (A) composition has amino
The sense of touch of fibre obtained by further being lifted.
Above-mentioned (A) composition is preferably (methyl) acrylic acid that 1 intramolecular has the simple function of 1 polymerism unsaturated group
Ester monomer.
Above-mentioned (A) composition can a kind exclusive use, also can be combined two or more use.
The HLB of above-mentioned (B1)~(B3) used in present embodiment compound is 7~18, from dialling for present embodiment
The emulsion polymerization for the non-fluorine based polymer (the hereinafter referred to as non-fluorine based polymer of present embodiment) that aqua composition is included divides
From the point of view of in terms of emulsion stability (later single to be referred to as emulsion stability) in composition when dissipating polymerization and after polymerization, it is preferably
9~15.And then in terms of the storage stability of dryingagent composition, it is more preferably and different with having in above-mentioned scope
HLB reactive emulsifier of more than two kinds (B).
In the reactive emulsifier (B1) that the above-mentioned formula (I-1) that present embodiment is used is represented, R3For hydrogen or methyl,
In terms of the copolymerizable of (A) composition, more preferably methyl.X is the alkylidene of the straight or branched of carbon number 1~6, from this implementation
From the point of view of in terms of the emulsion stability of the non-fluorine based polymer of mode, the more preferably straight-chain alkyl-sub of carbon number 2~3.Y1For bag
The divalent group of alkylene oxide group containing carbon number 2~4.For in Y1Alkylene oxide group species, combination and adduct number, can in as
As the mode in the range of above-mentioned HLB is suitably selected.Further, when alkylene oxide group is two or more, these can have block addition
Structure or random addition structure.
The compound represented as above-mentioned formula (I-1), the compound that preferably following formulas (I-2) represent.
[changing 11]
[in formula (I-2), R3Hydrogen or methyl are represented, X represents the alkylidene of the straight or branched of carbon number 1~6, A1O represents carbon
The alkylene oxide group of number 2~4, m can turn into the mode in the range of above-mentioned HLB such as and suitably select, specifically, and preferably 1~80
Integer, m be more than 2 when, m A1O can be identical or different].
In the compound that above-mentioned formula (I-2) represents, R3For hydrogen or methyl, with the copolymerizable of (A) composition in terms of from the point of view of,
More preferably methyl.X is the alkylidene of the straight or branched of carbon number 1~6, from the emulsification of the non-fluorine based polymer of present embodiment
From the point of view of in terms of stability, the more preferably straight-chain alkyl-sub of carbon number 2~3.A1O is the alkylene oxide group of carbon number 2~4.For A1O
Species and combination and m number, the mode in the range of above-mentioned HLB such as that can turn into suitably select.From present embodiment
Non-fluorine based polymer emulsion stability in terms of from the point of view of, m is preferably 1~80 integer, more preferably 1~60 integer.m
For more than 2 when, m A1O can be identical or different.Further, A1When O is two or more, these can have block addition structure or nothing
Advise addition structure.
The reactive emulsifier (B1) that above-mentioned formula (I-2) represents can be obtained with known method, not limited especially
It is fixed.Further, than commercially available product be easier obtain, can for example enumerate Kao Corp " LATEMUL PD-420 ",
" LATEMUL PD-430 ", " LATEMUL PD-450 " etc..
In the reactive emulsifier (B2) that the above-mentioned formula (I I-1) that present embodiment is used is represented, R4For with poly-
1 valency unsaturated alkyl of the carbon number 13~17 of conjunction property unsaturated group, can enumerate tridecylene base (Tridecenyl), 13
Carbon dialkylene (Tridedienyl), tetradecene base, 14 carbon dialkylenes, 15 carbene bases, 15 carbon dialkylenes, 15 carbon
Trialkenyl, heptadecene base, 17 carbon dialkylenes, 17 carbon trialkenyls etc..From the breast of the non-fluorine based polymer of present embodiment
From the point of view of changing in terms of stability, more preferably R4For 1 valency unsaturated alkyl of carbon number 14~16.
Y2It is the divalent group of the alkylene oxide group comprising carbon number 2~4.For in Y2Alkylene oxide group species, combination and add
Into number, the mode in the range of above-mentioned HLB such as that can turn into suitably is selected.Further, when alkylene oxide group is two or more, these can
With block addition structure or random addition structure.Come in terms of the emulsion stability of the non-fluorine based polymer of present embodiment
See, alkylene oxide group is more preferably inferior ethoxyl.
The compound represented as above-mentioned formula (II-1), the compound that preferably following formulas (II-2) represent.
[changing 12]
[in formula (II-2), R4Represent 1 valency unsaturated alkyl of the carbon number 13~17 with polymerism unsaturated group, A2O
The alkylene oxide group of carbon number 2~4 is represented, n can turn into the mode in the range of above-mentioned HLB such as and suitably select, specifically, preferably
For 1~50 integer, when n is more than 2, n A2O can be identical or different].
The R of the compound represented in above-mentioned formula (II-2)4, can enumerate and the R in above-mentioned formula (II-1)4Same
Group.
A2O is the alkylene oxide group of carbon number 2~4.In terms of the emulsion stability of the non-fluorine based polymer of present embodiment
From the point of view of, for A2O species and combination and n number, the mode in the range of above-mentioned HLB such as that can turn into suitably are selected.From
From the point of view of in terms of the emulsion stability of the non-fluorine based polymer of present embodiment, A2O is more preferably inferior ethoxyl, and n is preferably 1~
50 integer, more preferably 5~20 integer, more preferably 8~14 integer.When n is more than 2, n A2O can be phase
It is same or different.Further, A2When O is two or more, these can have block addition structure or random addition structure.
The reactive emulsifier (B2) that the above-mentioned formula (II-2) used in present embodiment is represented, can be by using conventional public affairs
The method known, addition alkylene oxide to be synthesized, and is not particularly limited in the corresponding phenol with unsaturated alkyl.For example make
With the alkali catalyst of caustic soda, caustic potash etc., under elevated pressure, 120~170 DEG C, it can be synthesized by the alkylene oxide of addition specified quantitative.
In phenol with above-mentioned corresponding unsaturated alkyl, in addition to sterling or mixture manufactured by industrialness,
Include the phenol existed as sterling or mixture from extracting and refinings such as plants.Extracted such as can enumerate the shell from cashew nut
Take, collectively referred to as anacardol, 3- [8 (Z), 11 (Z), 14- 15 carbon trialkenyl] phenol, 3- [8 (Z), 11 (Z)-ten five carbon dialkylene]
Phenol, 3- [8 (Z)-ten five carbene base] phenol, 3- [11 (Z)-ten five carbene base] phenol etc..
The reactive emulsifier (B3) used in present embodiment is HLB for 7~18, with hydroxyl and polymerism
The compound of the epoxyalkane of addition carbon number 2~4 in the grease of unsaturated group.As with hydroxyl and polymerism unsaturated group
The grease of group, can enumerate can include hydroxyl unrighted acid (palmitoleic acid, oleic acid, linoleic acid, alpha-linolenic acid, 20 carbon four
Olefin(e) acid (Arachidonic acid), eicosapentaenoic acid, clupanodonic acid etc.) aliphatic acid monoglyceride or glycerine
Diester, include at least one kind of hydroxyl unrighted acid (ricinoleic acid, ricinelaidic acid (Ricinoelaidic acid), 2- hydroxyls
Tetracosanoic acid etc.) aliphatic acid triglycerides.Come in terms of the emulsion stability of the non-fluorine based polymer of present embodiment
See, the alkylene oxide addition product of the triglycerides of the aliphatic acid more preferably comprising at least one kind of hydroxyl unrighted acid, castor-oil plant
The alkylene oxide addition product of the carbon number 2~4 of oil (triglycerides of the aliphatic acid comprising ricinoleic acid), more preferably castor oil
Ethylene oxide adduct.And then, the mode that the addition molal quantity of epoxyalkane can be suitably in the range of as such as above-mentioned HLB is come
Selection, in terms of the emulsion stability of the non-fluorine based polymer of present embodiment, more preferably 20~50 moles, enters one
Step is preferably 25~45 moles.Further, when alkylene oxide is two or more, these can have block addition structure or random addition knot
Structure.
The reactive emulsifier (B3) used in present embodiment, can be by using known method, addition alkylene oxide
In the grease with hydroxyl and polymerism unsaturated group, to be synthesized, and it is not particularly limited.For example using including ricinoleic acid
Aliphatic acid triglycerides, i.e., in alkali catalyst of the castor oil using caustic soda, caustic potash etc., under elevated pressure, 120~170 DEG C,
It can be synthesized by the alkylene oxide of addition specified quantitative.
In the Component units from (A) composition and the composition from (B) composition of the non-fluorine based polymer of present embodiment
The content ratio of unit, from the emulsion stability of the water-repellancy of the fibre of gained and the non-fluorine based polymer of present embodiment
Aspect from the point of view of, the quality of (A) composition of cooperation and mass ratio (A)/(B) of (B) composition are preferably 85/15~99/1, more
Preferably 90/10~97/3.(A) when/(B) is less than 85/15, the water-repellancy of the fibre of gained has change not enough sufficiently to incline
To.(A) when/(B) is more than 99/1, the emulsion stability of the non-fluorine based polymer of present embodiment has change to be not enough sufficiently inclined to.
Further, total quality of the quality of (A) composition of cooperation and the quality of (B) composition, will constitute non-fluorine based polymer
Monomer component total amount as benchmark, preferably 80~100 mass %, more preferably 85~99 mass %, more preferably
90~98 mass %.
The weight average molecular weight of the non-fluorine based polymer of present embodiment, preferably more than 100,000.Weight average molecular weight is less than 10
Wan Shi, the water-repellancy of the fibre of gained has change to be not enough sufficiently inclined to.And then, the weight average molecular weight of non-fluorine based polymer is more
Preferably more than 500,000.In this case, the fibre of gained can more make it play sufficient water-repellancy.Non-fluorine based polymer
The upper limit of weight average molecular weight, preferably 5,000,000 or so.
In present embodiment, melt viscosity of the non-fluorine based polymer at 105 DEG C, preferably below 1000Pas.105
DEG C melt viscosity more than 1000Pas when, the sense of touch of the fibre of gained has the tendency of to become thick and stiff.Further, non-fluorine system is gathered
When the melt viscosity of compound is too high, when emulsification or scattered non-fluorine based polymer are as dryingagent composition, non-fluorine based polymer has
When separate out or Shen drops sometimes, the storage stability of dryingagent composition has the tendency of reduction.In addition, in 105 DEG C of melt viscosity,
More preferably below 500Pas.In this case, fibre of gained etc. is while play sufficient water-repellancy, while as tactile
The more excellent person of sense.
So-called " melt viscosity at 105 DEG C ", refers to use overhead system flow tester (such as Shimadzu Seisakusho Ltd. CFT-
500) 1g non-fluorine based polymers, are put into the cylinder with mould (length 10mm, diameter 1mm), are kept for 6 minutes at 105 DEG C, are led to
Cross plunger and apply 100kgf/cm2Viscosity of loading when being measured.
When the weight average molecular weight of the non-fluorine based polymer of present embodiment is equal, non-fluorine system (methyl) acrylate monomer
Mixing ratio is higher, make its adhere to fibre water-repellancy just have the tendency of it is higher.Further, it is copolymerizable non-by making
Fluorine system monomer carries out copolymerization, can make the performance boost of the durable water-repellancy or sense of touch of the fibre of attachment etc..
The non-fluorine based polymer that the dryingagent composition of present embodiment is included, from the resistance to of the fibre that can lift gained
From the point of view of in terms of long water-repellancy, except (A) composition and (B) composition, preferably comprise selected from by following (C1), (C2), (C3) and
(C4) at least one kind of the 2nd (methyl) acrylate monomer (C) (hereinafter also referred to " C compositions ") in the group constituted is used as monomer
Composition.
(C1) (methyl) acrylate monomer that following formulas (C-1) represent
[changing 13]
[in formula (C-1), R5Represent hydrogen or methyl, R6Represent to have and select free hydroxyl, amino, carboxyl, epoxy radicals, isocyanic acid
1 valency chain alkyl of the carbon number 1~11 of at least one kind of functional group in the group that ester group and (methyl) acryloxy are constituted.Formula
In, it is less than 2 in the number of (methyl) acryloxy of intramolecular].
(C2) (methyl) acrylate monomer that following formulas (C-2) represent
[changing 14]
[in formula (C-2), R7Represent hydrogen or methyl, R8Represent can also there is 1 valency cyclic hydrocarbon of the carbon number 1~11 of substituent
Base].
(C3) methacrylate monomers that following formulas (C-3) represent
[changing 15]
[in formula (C-3), R9Represent 1 valency chain alkyl of unsubstituted carbon number 1~4].
(C4) (methyl) acrylate monomer that following formulas (C-4) represent
[changing 16]
[in formula (C-4), R10Hydrogen or methyl are represented, p represents more than 2 integer, and S represents the organic group of (p+1) valency, T tables
Show the 1 valency organic group with polymerism unsaturated group].
In the Component units from (A) composition and the composition from (B) composition of the non-fluorine based polymer of present embodiment
The content ratio of unit and the Component units from (C) composition, the conjunction of the quality of (A) composition of cooperation and the quality of (B) composition
Mass ratio (A)+(B)/(C), preferably 70/30~99.9/0.1, more preferably 75/25~99/1 of meter and (C) composition.
The monomer of above-mentioned (C1) is to contain to have in ester moiety to select free hydroxyl, amino, carboxyl, epoxy radicals, isocyanates
(the first of 1 valency chain alkyl of the carbon number 1~11 of at least one kind of functional group in the group that base and (methyl) acryloxy are constituted
Base) acrylate monomer.From the point of view of in terms of being reacted with crosslinking agent, 1 valency chain alkyl of above-mentioned carbon number 1~11 is preferably
With at least one kind of functional group in the group for selecting free hydroxyl, amino, carboxyl, epoxy radicals and NCO to constitute.It will contain
The non-fluorine based polymer of the monomer of (C1) of the base that can be reacted with the crosslinking agent with these, fibre is arised from crosslinking agent one
During processing, the sense of touch of the fibre of gained can be directly maintained, and lifts durable water-repellancy.NCO can be with end-capping reagent
The blocked isocyanate base of protection.
Above-mentioned chain alkyl can be straight-chain, or branched, can be saturated hydrocarbyl, or unsaturated alkyl.Also
Have, chain alkyl can further have substituent in addition to above-mentioned functional group.Wherein, so that the fibre of gained can be lifted
From the point of view of in terms of durable water-repellancy, preferably straight-chain and/or saturated hydrocarbyl.
As the monomer of specific (C1), (methyl) acrylic acid 2- hydroxyl ethyl esters, (methyl) acrylic acid dimethylamino can be enumerated
Double (acryloyloxymethyl) ethyl isocyanates of base ethyl ester, (methyl) glycidyl acrylate, 1,1- etc..These monomers can
1 kind of exclusive use, can be combined two or more and uses.Wherein, come with the aspect of the durable water-repellancy for the fibre that can lift gained
See, be preferably (methyl) acrylic acid 2- hydroxyl ethyl esters, (methyl) glycidyl acrylate, double (acryloyloxymethyl) second of 1,1-
Based isocyanate.And then from make gained fibre sense of touch lifting in terms of from the point of view of, be preferably (methyl) acrylic acid diformazan
Base amino ethyl ester.
The composition of the monomer of above-mentioned (C1), from the viewpoint of the water-repellancy and sense of touch of the fibre of gained, phase
For constitute non-fluorine based polymer monomer component total amount, preferably 0.1~30 mass %, more preferably 1~25 mass %,
More preferably 5~20 mass %.
The monomer of above-mentioned (C2) is (methyl) the acrylate list for the 1 valency cyclic hydrocarbon group for having carbon number 1~11 in ester moiety
Body, as cyclic hydrocarbon group, can enumerate isobornyl, cyclohexyl, bicyclopentyl etc..These cyclic hydrocarbon groups can have alkyl etc.
Substituent.In formula, substituent is the situation of alkyl, the carbon number of substituent and cyclic hydrocarbon group it is total be selected to less than 11 hydrocarbon
Base.Further, though these cyclic hydrocarbon groups directly can be bonded with ester bond, from the viewpoint of durable water-repellancy is lifted preferably.Ring-type
Alkyl can be alternatively aromatic series for ester ring type, and the situation of ester ring type can be alternatively unsaturated alkyl for saturated hydrocarbyl.As specific
Monomer, (methyl) isobornyl acrylate, (methyl) cyclohexyl acrylate, the ring pentyl ester of (methyl) acrylic acid two etc. can be enumerated.
These monomers can a kind exclusive use, can be combined two or more use.Wherein, with the durable drying for the fibre that can lift gained
Property in terms of from the point of view of, be preferably (methyl) isobornyl acrylate, cyclohexyl methacrylate, more preferably methacrylic acid is different
Norbornene ester.
The composition of the monomer of above-mentioned (C2), from the viewpoint of the water-repellancy and sense of touch of the fibre of gained, phase
For constitute non-fluorine based polymer monomer component total amount, preferably 0.1~30 mass %, more preferably 1~25 mass %,
More preferably 5~20 mass %.
The monomer of above-mentioned (C3) is the 1 valency chain alkyl in the unsubstituted carbon number 1~4 of the ester bond Direct Bonding of ester moiety
Methacrylate monomers.As the chain alkyl of carbon number 1~4, preferably the straight-chain alkyl of carbon number 1~2 and, carbon number 3~4
Branched hydrocarbyl.As the chain alkyl of carbon number 1~4, for example, it can enumerate methyl, ethyl, n-propyl, isopropyl, normal-butyl, uncle
Butyl etc..As specific compound, can enumerate methyl methacrylate, EMA, n propyl methacrylate,
Isopropyl methacrylate, n-BMA, Isobutyl methacrylate, Tert-butyl Methacrylate.These monomers
Can a kind exclusive use, can be combined two or more use.Wherein, with can be lifted gained fibre durable water-repellancy aspect
From the point of view of, preferably methyl methacrylate, isopropyl methacrylate, Tert-butyl Methacrylate, more preferably metering system
Sour methyl esters.
The composition of the monomer of above-mentioned (C3) is from the viewpoint of the water-repellancy and sense of touch of the fibre of gained, relatively
In the total amount for the monomer component for constituting non-fluorine based polymer, preferably 0.1~30 mass %, more preferably 1~25 mass % enter
One step is preferably 5~20 mass %.
The monomer of above-mentioned (C4) is (methyl) acrylate for the polymerism unsaturated group for having more than 3 in 1 intramolecular
Monomer.In present embodiment, be preferably above-mentioned formula (C-4) T for (methyl) acryloxy, in 1 intramolecular have 3
Polyfunctional (methyl) acrylate monomer of (methyl) acryloxy above.In formula (C-4), p T can be identical or not
Together.As specific compound, for example, it can enumerate tetramethylol methane tetraacrylate, tetramethylol methane tetramethyl acrylic acid
Ester, trimethylolpropane trimethacrylate, trimethylol-propane trimethacrylate, pentaerythritol triacrylate, season penta
Tetrol trimethyl acrylic ester, dipentaerythritol acrylate, dipentaerythritol hexamethacrylate etc..These monomers can
1 kind of exclusive use, also can be combined two or more and uses.Wherein, with can be lifted gained fibre durable water-repellancy aspect
From the point of view of, more preferably tetramethylol methane tetraacrylate.
The composition of the monomer of above-mentioned (C4) is from the viewpoint of the water-repellancy and sense of touch of the fibre of gained, relatively
In the total amount for the monomer component for constituting non-fluorine based polymer, preferably 0.1~5 mass %.
The non-fluorine based polymer that the dryingagent composition of present embodiment is included, except (A) composition, (B) composition and (C) into
/ it is outer, can in the scope of effect of the present invention is not undermined, can containing can be with the simple function of these copolymerization monomer (D).
As the monomer of above-mentioned (D), for example, it can enumerate (methyl) third with the alkyl beyond (A) composition and (C) composition
Olefin(e) acid ester, (methyl) acrylic acid, fumarate, maleate, fumaric acid, maleic acid, (methyl) acrylamide, N- methylols
Acrylamide, vinyl ethers, vinyl ester, vinyl chloride, vinylidene chloride, ethene, styrene etc. do not include the ethene of fluorine
Base system monomer etc..In addition, (methyl) acrylate with alkyl beyond (A) composition and (C) composition, can have ethene in alkyl
The substituent of base, hydroxyl, amino, epoxy radicals and NCO, blocked isocyanate base etc., can have can be with quaternary ammonium group etc.
Substituent beyond the base of crosslinking agent reaction, can have ehter bond, ester bond, amido link or amino-formate bond etc..As (A) into
Point and (C) composition beyond (methyl) acrylate, can for example enumerate methyl acrylate, (methyl) 2-EHA,
(methyl) benzyl acrylate, ethylene glycol two (methyl) acrylate etc..
The composition of the monomer of above-mentioned (D) is from the viewpoint of the water-repellancy and sense of touch of the fibre of gained, relatively
In the total amount for the monomer component for constituting non-fluorine based polymer, preferably below 10 mass %.
The non-fluorine based polymer that the dryingagent composition of present embodiment is included, though with selected from by that can be reacted with crosslinking agent
Hydroxyl, at least one kind of functional group in the group that constitutes of amino, carboxyl, epoxy radicals and NCO, but due to making gained
The durable water-repellancy lifting event of fibre is preferably.NCO can form the blocked isocyanate base protected with end-capping reagent.
Further, though non-fluorine based polymer has amino, due to also making the sense of touch lifting event of fibre of gained preferred.
Additive etc. can also be added according to necessity in the dryingagent composition of present embodiment.As additive, it can enumerate
Other dryingagents, crosslinking agent, Antibiotic-odor Resistant Agent, fire retardant, antistatic additive, softening agent, anti-creasing agent etc..
Secondly, the manufacture method for the dryingagent composition of the non-fluorine based polymer comprising present embodiment is said
It is bright.
Dryingagent composition comprising non-fluorine based polymer can be manufactured by radical polymerization.Further, this freedom
It is preferably with emulsion polymerization method or scattered poly- in terms of the performance of the dryingagent of gained and environment among base polymerization
It is legal to be polymerize.
For example, in medium, at least one kind of reactive emulsifier among the compound selected from above-mentioned (B1)~(B3)
(B) in the presence of, (methyl) acrylate monomer (A) that can be represented by emulsion polymerization or the above-mentioned formula of dispersin polymerization (A-1),
And obtain non-fluorine based polymer.More specifically, for example (A) composition, (B) composition are added in medium and according to necessary breast
Change adjuvant or disperse additive, this mixed liquor is emulsified or scattered, and obtain emulsion or dispersion.In the emulsification of gained
Thing or dispersion, by adding polymerization initiator, start polymerisation, can be polymerize monomer and reactive emulsifier.Separately
Outside, as making above-mentioned mixed liquor emulsify or scattered means, homogeneous mixer, high-pressure emulsification machine or ultrasonic wave etc. can be enumerated.
As above-mentioned emulsion adjuncts or disperse additive etc. (hereinafter also referred to " emulsion adjuncts etc. "), it can be used and be selected from
Nonionic surfactant, cationic surfactant, anion surfactant beyond above-mentioned reactive emulsifier (B),
And more than a kind in amphoteric surfactant.Relative to whole mass parts of monomer 100, the content of emulsion adjuncts etc. is preferably
0.5~30 mass parts, more preferably 1~20 mass parts, more preferably 1~10 mass parts.Above-mentioned emulsion adjuncts etc.
When content is less than 0.5 mass parts, the content of emulsion adjuncts etc. is compared with the situation in above range, the stably dispersing of mixed liquor
Property have the tendency of reduction, when the content of emulsion adjuncts etc. is more than 30 mass parts, the content of emulsion adjuncts etc. with above-mentioned model
Situation about enclosing is compared, and the water-repellancy of the non-fluorine based polymer of gained has the tendency of reduction.
, also can mixing water and organic solvent according to necessity as emulsion polymerization or the medium of dispersin polymerization, preferably water.Make
For organic solvent now, if the organic solvent that can be mixed with water, though and it is not particularly restricted, can for example enumerate methanol or second
Ethers of ketone, the Anaesthetie Ether of esters, acetone or the methyl ethyl ketone of alcohols, the ethyl acetate of alcohol etc. etc. etc. etc. etc., the third two
The glycols of alcohol, DPG, tripropylene glycol etc..In addition, the ratio of water and organic solvent and being not particularly limited.
As above-mentioned polymerization initiator, it can suitably use and gather known to azo system, peroxide system or redox system etc.
Close initiator.Relative to whole mass parts of monomer 100, the content of polymerization initiator is preferably the mass of polymerization initiator 0.01~2
Part.When the content of polymerization initiator is above range, it can effectively manufacture the non-fluorine system that weight average molecular weight is more than 100,000 and polymerize
Thing.
Further, in polymerisation, using molecular weight adjustment as purpose, lauryl mercaptan, tert-butyl group alcohol etc. can be used
Chain-transferring agent.Relative to whole mass parts of monomer 100, the content of chain-transferring agent is preferably below 0.3 mass parts, more preferably
Below 0.1 mass parts.When the content of chain-transferring agent is more than 0.1 mass parts, cause molecular weight to reduce, become difficult to effectively make
Make the tendency for the non-fluorine based polymer that weight average molecular weight is more than 100,000.
In addition, in order to which polymerization inhibitor can be used in molecular weight adjustment.By the addition of polymerization inhibitor, can easily it obtain
To the non-fluorine based polymer with desired weight average molecular weight.
The temperature of polymerisation is preferably 20 DEG C~150 DEG C.When temperature is less than 20 DEG C, temperature and the situation in above range
Compare, polymerization has change to be not enough sufficiently inclined to, when temperature is more than 150 DEG C, the control for having reaction heat becomes difficult situation.
In polymerisation, the weight average molecular weight of the non-fluorine based polymer of gained can be by above-mentioned polymerization initiator, chain tra nsfer
Agent, the increase and decrease of the content of polymerization inhibitor are adjusted, in 105 DEG C of melt viscosity, can by polyfunctional monomer content and, it is poly-
The increase and decrease for closing the content of initiator is adjusted.In addition, make 105 DEG C melt viscosity reduction situation, reduce have 2 with
The content of the monomer of upper polymerizable functional group increases the content of polymerization initiator.
By emulsion polymerization or dispersin polymerization gained polymer emulsified liquid or dispersion liquid non-fluorine based polymer content,
From the viewpoint of the storage stability and operability of composition, relative to the total amount of emulsion or dispersion liquid, preferably into 10~
50 mass %, more preferably as 20~40 mass %.
The water-repellancy fibre of present embodiment is the fibre by non-fluorine based polymer of the above-mentioned present embodiment of attachment
Fiber products.
Manufacture method for the water-repellancy fibre of present embodiment is illustrated.
The water-repellancy fibre of present embodiment, by the way that fibre is included into the place of above-mentioned dryingagent composition
Reason liquid is handled, and can obtain making non-fluorine based polymer be attached to fibre.As the material of the fibre, not especially
Limitation, can enumerate the natural fiber of silk floss, fiber crops, thin,tough silk, wool etc.；The semisynthetic fibre of artificial silk, acetic acid esters etc.；It is nylon, polyester, poly-
The synthetic fibers of carbamate, polypropylene etc. and these composite fibre, blend fibre etc..The form of fibre can be fibre
Any form of dimension, silk, cloth, non-woven fabrics, paper etc..
As the method for being handled fibre with above-mentioned treatment fluid, such as can enumerate dipping, spraying, coating
Processing method.Further, when dryingagent composition contains water, it is attached to after fibre makes it to go to remove water
Dry.
To adhesion amount from dryingagent composition to fibre, though the degree of water-repellancy that can be as requested, appropriate adjustment,
But relative to fibre 100g, the adhesion amount of the preferably non-fluorine based polymer that dryingagent composition is included is adjusted to 0.01~
10g, is more preferably adjusted to 0.05~5g.When the adhesion amount of non-fluorine based polymer is less than 0.01g, the attachment of non-fluorine based polymer
Amount is compared with the situation in above range, and fibre has the tendency of that sufficient water-repellancy can not be played, during more than 10g, non-fluorine
The adhesion amount of based polymer is compared with the situation in above range, and the sense of touch of fibre has the tendency of to become thick and stiff.
Further, the non-fluorine based polymer of present embodiment is attached to after fibre, preferably carried out at appropriate heat
Reason.Though temperature conditionss are simultaneously not particularly restricted, when using the dryingagent composition of present embodiment, pass through 100~130 DEG C of temperature
And condition, fibre can be made to show fully good water-repellancy.Though temperature conditionss can (be preferably to 200 for more than 130 DEG C
DEG C) high-temperature process, but in this case, also more can shorten processing time compared with the conventional situation using fluorine system dryingagent.According to
This, according to the water-repellancy fibre of present embodiment, suppresses rotten, fiber during drying processing of the fibre by heat
The sense of touch of product limbers up, and gentle heat treatment condition, namely abundant can assign fibre under low temperature curing conditions
Water-repellancy.
Particularly to make the situation of durable water-repellancy lifting, by the processing that dryingagent composition is included comprising being preferably
Liquid handles the above-mentioned operation of fibre, with that will have more than 1 melamine methylol, NCO or block isocyanic acid
The crosslinking agent that the compound of ester group is represented, the method for making it be attached to fibre and heat this process, drying processing fiber
Product.And then when more lifting the situation of durable water-repellancy, preferably dryingagent composition comprising copolymerization have can with it is above-mentioned
Crosslinking agent reaction functional group monomer non-fluorine based polymer.
As the compound with more than 1 NCO, butyl isocyanate, phenyl isocyanate, first can be enumerated
The monoisocyanates of phenyl isocyanate, naphthalene isocyanates etc.；Xylyl diisocyanate, diphenylmethane diisocyanate
Ester, tetramethyl xylylene diisocyanate, the diisocyanate of hydrogenation methyl diphenylene diisocyanate etc. and these is different
Three amount bodies of cyanurate ring, trimethylolpropane adduct.Further, as the change with more than 1 blocked isocyanate base
Compound, can enumerate the compound that the compound with above-mentioned NCO is protected to NCO with end-capping reagent.It is used as this
When the end-capping reagent that uses, the organic of secondary alcohol or tertiary alcohols, activity methene compound, phenols, oximes, lactams etc. can be enumerated
It is the bisulfites of end-capping reagent or sodium hydrogensulfite, potassium bisulfite etc..Above-mentioned crosslinking agent can a kind exclusive use, also may be used
Combination plural number is planted.
Crosslinking agent, such as by the way that crosslinking agent is dissolved in into organic solvent or dipping treated object (fibre) in emulsification
The treatment fluid of water is scattered in, the method for drying the treatment fluid for being attached to treated object can adhere to treated object.And pass through
Heating is attached to the crosslinking agent of treated object, can carry out the reaction of crosslinking agent and treated object and non-fluorine based polymer.In order that
The reaction of crosslinking agent is fully carried out, and can more effectively lift cleaning durability, and heating now carries out 1~5 with 110~180 DEG C
Minute.The process of attachment and the heating of crosslinking agent, can be with being handled with the treatment fluid comprising above-mentioned dryingagent composition
Process simultaneously carry out.Simultaneously carry out when, for example make the treatment fluid containing dryingagent composition and crosslinking agent be attached to by
Processed material, goes after water removal, and then heats the crosslinking agent for being attached to treated object.Consider simplification or the heat of drying manufacturing procedure
It is preferably to be carried out simultaneously with the treatment process of dryingagent composition when the reduction of amount, economy.
When further, excessively using crosslinking agent, there is the worry of infringement sense of touch.Above-mentioned crosslinking agent is relative to treated object (fiber
Product), it is preferable to use 0.1~50 mass % amount, is particularly preferably 0.1~10 mass % of use amount.
The water-repellancy fibre of present embodiment obtained by so, even if during room foreign minister in use, also can be abundant
Water-repellancy is played, is also had, above-mentioned water-repellancy fibre can turn into the system friendly to environment because the compound of fluorine system is not used
Product.
More than, though being illustrated for the suitable embodiment of the present invention, the present invention is not defined to above-mentioned implementation
Mode.
For example, in the case of the non-fluorine based polymer that the dryingagent composition of the manufacture present invention is included, in above-mentioned embodiment party
Formula, though polymerisation can be carried out by radical polymerization, also can by irradiate as ultraviolet, electron beam, γ lines ionization
The photopolymerization of radioactive ray etc., carries out polymerisation.
Further, in the present invention, though by dryingagent compositions-treated into fibre as water-repellancy fibre, to make
With the product of dryingagent compositions-treated, to be not limited to the article of fibre purposes, or metal, glass, resin etc..
Further, can be because in this case, making dryingagent composition be attached to the method for above-mentioned article or the adhesion amount of dryingagent
Answer species of treated object etc., arbitrary decision.
[embodiment]
Hereinafter, though the present invention is further illustrated by embodiment, the present invention is not limited by these embodiment.
<The adjustment of polymer dispersion liquid>
By the mixed liquor with the composition (in table, numerical value represents (g)) shown in table 1~5, carried out by order as shown below
Polymerization, and obtain polymer dispersion liquid.
(embodiment 1)
Octadecyl acrylate 60g, LATEMUL PD-420 (Kao Corp's system, polyoxyalkylene are added in 500mL flasks
Base alkene ether, HLB=12.6) 2g, LATEMUL PD-430 (Kao Corp's system, polyoxyalkylenes alkene ether, HLB=
14.4) 2g, octadecyldimethylamine hydrochloride 3g, tripropylene glycol 20g and water 162.75g, and mixed at 45 DEG C
And as mixed liquor.Make whole monomer emulsion dispersions in this mixed liquor irradiation ultrasonic wave.Secondly, by azo two (isobutyl amidine) two
Hydrochloride 0.25g makes an addition to mixed liquor, in making its radical polymerization 6 hours under nitrogen atmosphere at 60 DEG C, and obtains polymer concentration
26 mass % non-fluorine based polymer dispersion liquid.
(embodiment 2)
Octadecyl acrylate 55g, LATEMUL PD-420 (Kao Corp's system, polyoxyalkylene are added in 500mL flasks
Base alkene ether, HLB=12.6) 2g, LATEMUL PD-430 (Kao Corp's system, polyoxyalkylenes alkene ether, HLB=
14.4) 2g, acrylic acid 2- hydroxyl ethyl esters 5g, octadecyldimethylamine hydrochloride 3g, lauryl mercaptan 0.15g, tripropylene glycol
20g and water 162.6g, and mixed together at 45 DEG C as mixed liquor.Make whole monomers in this mixed liquor irradiation ultrasonic wave
Emulsion dispersion.Secondly, (isobutyl amidine) dihydrochloride of azo two 0.25g is made an addition into mixed liquor, in making under nitrogen atmosphere at 60 DEG C
Its radical polymerization 6 hours, and obtain the mass % of polymer concentration 26 non-fluorine based polymer dispersion liquid.
(embodiment 3)
Octadecyl methacrylate 55g, LATEMUL PD-420 (Kao Corp's system, polyoxy are added in 500mL flasks
Change alkenyl alkene ether, HLB=12.6) 2g, LATEMUL PD-430 (Kao Corp's system, polyoxyalkylenes alkene ether, HLB
=14.4) 2g, acrylic acid 2- hydroxyl ethyl esters 5g, octadecyldimethylamine hydrochloride 3g, lauryl mercaptan 0.05g, 3 the third two
Alcohol 20g and water 162.7g, and mixed together at 45 DEG C as mixed liquor.Make whole lists in this mixed liquor irradiation ultrasonic wave
Body emulsion dispersion.Secondly, (isobutyl amidine) dihydrochloride of azo two 0.25g is made an addition into mixed liquor, under nitrogen atmosphere at 60 DEG C
Make its radical polymerization 6 hours, and obtain the mass % of polymer concentration 26 non-fluorine based polymer dispersion liquid.
(embodiment 4)
Octadecyl acrylate 55g, LATEMUL PD-420 (Kao Corp's system, polyoxyalkylene are added in 500mL flasks
Base alkene ether, HLB=12.6) 2g, LATEMUL PD-430 (Kao Corp's system, polyoxyalkylenes alkene ether, HLB=
14.4) 2g, acrylic acid 2- hydroxyl ethyl esters 5g, octadecyldimethylamine hydrochloride 3g, tripropylene glycol 20g and water 162.75g, and
45 DEG C are mixed together as mixed liquor.Make whole monomer emulsion dispersions in this mixed liquor irradiation ultrasonic wave.Secondly, will be even
(isobutyl amidine) dihydrochloride of nitrogen two 0.25g makes an addition to mixed liquor, in making its radical polymerization 6 hours under nitrogen atmosphere at 60 DEG C,
And obtain the mass % of polymer concentration 26 non-fluorine based polymer dispersion liquid.
(embodiment 5)
Process Conditions of Cetane Acrylate 55g, LATEMUL PD-420 (Kao Corp's system, polyoxyalkylene are added in 500mL flasks
Base alkene ether, HLB=12.6) 2g, LATEMUL PD-430 (Kao Corp's system, polyoxyalkylenes alkene ether, HLB=
14.4) 2g, acrylic acid 2- hydroxyl ethyl esters 5g, octadecyldimethylamine hydrochloride 3g, tripropylene glycol 20g and water 162.75g, and
45 DEG C are mixed together as mixed liquor.Make whole monomer emulsion dispersions in this mixed liquor irradiation ultrasonic wave.Secondly, will be even
(isobutyl amidine) dihydrochloride of nitrogen two 0.25g makes an addition to mixed liquor, in making its radical polymerization 6 hours under nitrogen atmosphere at 60 DEG C,
And obtain the mass % of polymer concentration 26 non-fluorine based polymer dispersion liquid.
(embodiment 6)
Lauryl acrylate 55g, LATEMUL PD-420 (Kao Corp's system, polyoxyalkylene are added in 500mL flasks
Base alkene ether, HLB=12.6) 2g, LATEMUL PD-430 (Kao Corp's system, polyoxyalkylenes alkene ether, HLB=
14.4) 2g, acrylic acid 2- hydroxyl ethyl esters 5g, octadecyldimethylamine hydrochloride 3g, tripropylene glycol 20g and water 162.75g, and
45 DEG C are mixed together as mixed liquor.Make whole monomer emulsion dispersions in this mixed liquor irradiation ultrasonic wave.Secondly, will be even
(isobutyl amidine) dihydrochloride of nitrogen two 0.25g makes an addition to mixed liquor, in making its radical polymerization 6 hours under nitrogen atmosphere at 60 DEG C,
And obtain the mass % of polymer concentration 26 non-fluorine based polymer dispersion liquid.
(embodiment 7)
12.5 moles of addition product (HLB=of ethylene oxide of octadecyl acrylate 55g, anacardol are added in 500mL flasks
12.9th, in table, represent " anacardol 12.5EO ") 2g, anacardol 8.3 moles of addition products of ethylene oxide (in HLB=11.0, table,
Represent " anacardol 8.3EO ") 2g, acrylic acid 2- hydroxyl ethyl esters 5g, octadecyldimethylamine hydrochloride 3g, tripropylene glycol 20g and
Water 162.75g, and mixed together at 45 DEG C as mixed liquor.Whole monomers are emulsified in this mixed liquor irradiation ultrasonic wave
It is scattered.Secondly, (isobutyl amidine) dihydrochloride of azo two 0.25g is made an addition into mixed liquor, in make under nitrogen atmosphere at 60 DEG C its from
It is polymerize 6 hours by base, and obtains the mass % of polymer concentration 26 non-fluorine based polymer dispersion liquid.
(embodiment 8)
42 moles of addition product (HLB=of ethylene oxide of octadecyl acrylate 55g, castor oil are added in 500mL flasks
13.3rd, in table, represent " castor oil 42EO ") 2g, castor oil 30 moles of addition products of ethylene oxide (in HLB=11.7, table, table
Show " castor oil 30EO ") 2g, acrylic acid 2- hydroxyl ethyl esters 5g, octadecyldimethylamine hydrochloride 3g, tripropylene glycol 20g and water
162.75g, and mixed together at 45 DEG C as mixed liquor.Make whole monomer emulsifications point in this mixed liquor irradiation ultrasonic wave
Dissipate.Secondly, (isobutyl amidine) dihydrochloride of azo two 0.25g is made an addition into mixed liquor, in making its freedom at 60 DEG C under nitrogen atmosphere
Base polymerize 6 hours, and obtains the mass % of polymer concentration 26 non-fluorine based polymer dispersion liquid.
(embodiment 9)
Octadecyl acrylate 57g, LATEMUL PD-420 (Kao Corp's system, polyoxyalkylene are added in 500mL flasks
Base alkene ether, HLB=12.6) 2g, LATEMUL PD-430 (Kao Corp's system, polyoxyalkylenes alkene ether, HLB=
14.4) 2g, tetramethylol methane tetraacrylate 3g, octadecyldimethylamine hydrochloride 3g, tripropylene glycol 20g and water
162.75g, and mixed together at 45 DEG C as mixed liquor.Make whole monomer emulsifications point in this mixed liquor irradiation ultrasonic wave
Dissipate.Secondly, (isobutyl amidine) dihydrochloride of azo two 0.25g is made an addition into mixed liquor, in making its freedom at 60 DEG C under nitrogen atmosphere
Base polymerize 6 hours, and obtains the mass % of polymer concentration 26 non-fluorine based polymer dispersion liquid.
(embodiment 10)
Octadecyl acrylate 55g, LATEMUL PD-420 (Kao Corp's system, polyoxyalkylene are added in 500mL flasks
Base alkene ether, HLB=12.6) 2g, LATEMUL PD-430 (Kao Corp's system, polyoxyalkylenes alkene ether, HLB=
14.4) 2g, dimethylaminoethyl methacrylate 5g, octadecyldimethylamine hydrochloride 3g, tripropylene glycol 20g and water
162.75g, and mixed together at 45 DEG C as mixed liquor.Make whole monomer emulsifications point in this mixed liquor irradiation ultrasonic wave
Dissipate.Secondly, (isobutyl amidine) dihydrochloride of azo two 0.25g is made an addition into mixed liquor, in making its freedom at 60 DEG C under nitrogen atmosphere
Base polymerize 6 hours, and obtains the mass % of polymer concentration 26 non-fluorine based polymer dispersion liquid.
(embodiment 11)
Octadecyl acrylate 55g, LATEMUL PD-420 (Kao Corp's system, polyoxyalkylene are added in 500mL flasks
Base alkene ether, HLB=12.6) 2g, LATEMUL PD-430 (Kao Corp's system, polyoxyalkylenes alkene ether, HLB=
14.4) 2g, GMA 5g, octadecyldimethylamine hydrochloride 3g, tripropylene glycol 20g and water
162.75g, and mixed together at 45 DEG C as mixed liquor.Make whole monomer emulsifications point in this mixed liquor irradiation ultrasonic wave
Dissipate.Secondly, (isobutyl amidine) dihydrochloride of azo two 0.25g is made an addition into mixed liquor, in making its freedom at 60 DEG C under nitrogen atmosphere
Base polymerize 6 hours, and obtains the mass % of polymer concentration 26 non-fluorine based polymer dispersion liquid.
(embodiment 12)
Octadecyl acrylate 55g, LATEMUL PD-420 (Kao Corp's system, polyoxyalkylene are added in 500mL flasks
Base alkene ether, HLB=12.6) 2g, LATEMUL PD-430 (Kao Corp's system, polyoxyalkylenes alkene ether, HLB=
14.4) the methyl ethyl ketone oxime end-blocking compound 5g, octadecyl two of double (acryloyloxymethyl) ethyl isocyanates of 2g, 1,1-
Methylamine hydrochloride 3g, tripropylene glycol 20g and water 162.75g, and mixed together at 45 DEG C as mixed liquor.It is mixed in this
Closing liquid irradiation ultrasonic wave makes whole monomer emulsion dispersions.Secondly, (isobutyl amidine) dihydrochloride of azo two 0.25g is made an addition to mixed
Liquid is closed, in making its radical polymerization 6 hours under nitrogen atmosphere at 60 DEG C, and the mass % of polymer concentration 26 non-fluorine system polymerization is obtained
Thing dispersion liquid.
(embodiment 13)
Octadecyl acrylate 51g, LATEMUL PD-420 (Kao Corp's system, polyoxyalkylene are added in 500mL flasks
Base alkene ether, HLB=12.6) 4g, LATEMUL PD-430 (Kao Corp's system, polyoxyalkylenes alkene ether, HLB=
14.4) 4g, acrylic acid 2- hydroxyl ethyl esters 5g, octadecyldimethylamine hydrochloride 3g, tripropylene glycol 20g and water 162.75g, and
45 DEG C are mixed together as mixed liquor.Make whole monomer emulsion dispersions in this mixed liquor irradiation ultrasonic wave.Secondly, will
(isobutyl amidine) dihydrochloride of azo two 0.25g makes an addition to mixed liquor, in making its radical polymerization 6 small at 60 DEG C under nitrogen atmosphere
When, and obtain the mass % of polymer concentration 26 non-fluorine based polymer dispersion liquid.
(embodiment 14)
Octadecyl acrylate 56g, LATEMUL PD-420 (Kao Corp's system, polyoxyalkylene are added in 500mL flasks
Base alkene ether, HLB=12.6) 0.5g, LATEMUL PD-430 (Kao Corp's system, polyoxyalkylenes alkene ether, HLB=
14.4) 0.5g, polyoxyethylene (10 moles) lauryl ether 2g, acrylic acid 2- hydroxyl ethyl esters 5g, octadecyldimethylamine hydrochloride
3g, tripropylene glycol 20g and water 162.75g, and mixed together at 45 DEG C as mixed liquor.Ultrasound is irradiated in this mixed liquor
Ripple makes whole monomer emulsion dispersions.Secondly, (isobutyl amidine) dihydrochloride of azo two 0.25g is made an addition into mixed liquor, in nitrogen atmosphere
Make its radical polymerization 6 hours under enclosing at 60 DEG C, and obtain the mass % of polymer concentration 26 non-fluorine based polymer dispersion liquid.
(embodiment 15)
Octadecyl acrylate 45g, LATEMUL PD-420 (Kao Corp's system, polyoxyalkylene are added in 500mL flasks
Base alkene ether, HLB=12.6) 2g, LATEMUL PD-430 (Kao Corp's system, polyoxyalkylenes alkene ether, HLB=
14.4) 2g, acrylic acid 2- hydroxyl ethyl esters 5g, isobornyl acrylate 10g, octadecyldimethylamine hydrochloride 3g, tripropylene glycol
20g and water 162.75g, and mixed together at 45 DEG C as mixed liquor.Make whole lists in this mixed liquor irradiation ultrasonic wave
Body emulsion dispersion.Secondly, (isobutyl amidine) dihydrochloride of azo two 0.25g is made an addition into mixed liquor, under nitrogen atmosphere at 60 DEG C
Make its radical polymerization 6 hours, and obtain the mass % of polymer concentration 26 non-fluorine based polymer dispersion liquid.
(embodiment 16)
Octadecyl acrylate 45g, LATEMUL PD-420 (Kao Corp's system, polyoxyalkylene are added in 500mL flasks
Base alkene ether, HLB=12.6) 2g, LATEMUL PD-430 (Kao Corp's system, polyoxyalkylenes alkene ether, HLB=
14.4) 2g, acrylic acid 2- hydroxyl ethyl esters 5g, isobornyl methacrylate 10g, octadecyldimethylamine hydrochloride 3g, 3 third
Glycol 20g and water 162.75g, and mixed together at 45 DEG C as mixed liquor.Make entirely in this mixed liquor irradiation ultrasonic wave
Portion's monomer emulsion dispersion.Secondly, (isobutyl amidine) dihydrochloride of azo two 0.25g is made an addition into mixed liquor, under nitrogen atmosphere
60 DEG C make its radical polymerization 6 hours, and obtain the mass % of polymer concentration 26 non-fluorine based polymer dispersion liquid.
(embodiment 17)
Octadecyl acrylate 45g, LATEMUL PD-420 (Kao Corp's system, polyoxyalkylene are added in 500mL flasks
Base alkene ether, HLB=12.6) 2g, LATEMUL PD-430 (Kao Corp's system, polyoxyalkylenes alkene ether, HLB=
14.4) 2g, acrylic acid 2- hydroxyl ethyl esters 5g, cyclohexyl methacrylate 10g, octadecyldimethylamine hydrochloride 3g, 3 the third two
Alcohol 20g and water 162.75g, and mixed together at 45 DEG C as mixed liquor.Make whole in this mixed liquor irradiation ultrasonic wave
Monomer emulsion dispersion.Secondly, (isobutyl amidine) dihydrochloride of azo two 0.25g is made an addition into mixed liquor, under nitrogen atmosphere 60
DEG C make its radical polymerization 6 hours, and obtain the mass % of polymer concentration 26 non-fluorine based polymer dispersion liquid.
(embodiment 18)
Octadecyl acrylate 45g, LATEMUL PD-420 (Kao Corp's system, polyoxyalkylene are added in 500mL flasks
Base alkene ether, HLB=12.6) 2g, LATEMUL PD-430 (Kao Corp's system, polyoxyalkylenes alkene ether, HLB=
14.4) 2g, acrylic acid 2- hydroxyl ethyl esters 5g, methyl methacrylate 10g, octadecyldimethylamine hydrochloride 3g, tripropylene glycol
20g and water 162.75g, and mixed together at 45 DEG C as mixed liquor.Make whole lists in this mixed liquor irradiation ultrasonic wave
Body emulsion dispersion.Secondly, (isobutyl amidine) dihydrochloride of azo two 0.25g is made an addition into mixed liquor, under nitrogen atmosphere at 60 DEG C
Make its radical polymerization 6 hours, and obtain the mass % of polymer concentration 26 non-fluorine based polymer dispersion liquid.
(comparative example 1)
Following logical formula (III)s are added in 500mL flasks：
[changing 17]
CnF2n+1CH2CH2OCOCH=CH2 (III)
Shown, n average value turns into 8 mixture (in addition, being mixed with the change that n is 6,8,10,12,14 in the mixture
Compound) 60g, octadecyldimethylamine hydrochloride 3g, polyoxyethylene (10 moles) lauryl ether 7g, tripropylene glycol 20g and water
158.5g, and mixed together at 45 DEG C as mixed liquor.Said mixture is emulsified in this mixed liquor irradiation ultrasonic wave
It is scattered.Secondly, (isobutyl amidine) dihydrochloride of azo two 1.5g is made an addition into mixed liquor, in making its freedom at 60 DEG C under nitrogen atmosphere
Base polymerize 6 hours, and obtains the mass % of polymer concentration 24 fluorine system polymer dispersion liquid.
(comparative example 2)
Octadecyl acrylate 55g, polyoxyethylene (10 moles) lauryl ether 4g, acrylic acid 2- hydroxyls are added in 500mL flasks
Ethyl ester 5g, octadecyldimethylamine hydrochloride 3g, tripropylene glycol 20g and water 162.75g, and mixed at 45 DEG C and
As mixed liquor.Make whole monomer emulsion dispersions in this mixed liquor irradiation ultrasonic wave.Secondly, by azo two (isobutyl amidine) disalt
Hydrochlorate 0.25g makes an addition to mixed liquor, in making its radical polymerization 6 hours under nitrogen atmosphere at 60 DEG C, and obtains polymer concentration 24
Quality % non-fluorine based polymer dispersion liquid.
(comparative example 3)
Octadecyl acrylate 55g, polyoxyethylene (10 moles) lauryl ether 4g, acrylic acid 2- hydroxyls are added in 500mL flasks
Ethyl ester 5g, octadecyldimethylamine hydrochloride 7g, tripropylene glycol 20g and water 158.75g, and mixed at 45 DEG C and
As mixed liquor.Make whole monomer emulsion dispersions in this mixed liquor irradiation ultrasonic wave.Secondly, by azo two (isobutyl amidine) disalt
Hydrochlorate 0.25g makes an addition to mixed liquor, in making its radical polymerization 6 hours under nitrogen atmosphere at 60 DEG C, and obtains polymer concentration 24
Quality % non-fluorine based polymer dispersion liquid.
(comparative example 4)
500mL flasks add octadecyl acrylate 55g, NOIGEN XL-100 (Di-ichi Kogyo Seiyaku Co., Ltd.'s system,
Polyoxyalkylenes branched chain decyl ether, HLB=14.7) 2g, NOIGEN XL-60 (Di-ichi Kogyo Seiyaku Co., Ltd.'s system, polyoxygenated
Alkenyl branched chain decyl ether, HLB=12.5) 2g, acrylic acid 2- hydroxyl ethyl esters 5g, octadecyldimethylamine hydrochloride 3g, 3 the third two
Alcohol 20g and water 162.75g, and mixed together at 45 DEG C as mixed liquor.Make whole in this mixed liquor irradiation ultrasonic wave
Monomer emulsion dispersion.Secondly, (isobutyl amidine) dihydrochloride of azo two 0.25g is made an addition into mixed liquor, under nitrogen atmosphere 60
DEG C make its radical polymerization 6 hours, and obtain the mass % of polymer concentration 24 non-fluorine based polymer dispersion liquid.
In addition, each polymer in the polymer dispersion liquid of embodiment 1~18 and the gained of comparative example 1~4, is identified through
Gas chromatography (GC-15APTF, (strain) Shimadzu Seisakusho Ltd. system), has polymerize more than the 98% of whole monomers.
It is directed to the polymer dispersion liquid of above-mentioned gained and is evaluated with the polymer obtained by method as shown below.
(evaluation of physical property of non-fluorine based polymer)
Polymer dispersion liquid 50g as obtained by embodiment 1~18 and comparative example 1~4 adds acetone 500mL, makes to gather
Compound is separated with emulsifying agent with leaching polymer, it is dried under reduced pressure at 25 DEG C 24 hours in this polymer.By the polymerization of gained
Thing is for example following to be evaluated.Show the result in table 6~9.
(1) assay method of melt viscosity
The embodiment 1~18 of above-mentioned gained and the polymer of comparative example 2~4 are directed to, overhead system flow tester is used
1g polymer is put into CFT-500 ((strain) Shimadzu Seisakusho Ltd. system), the cylinder with mould (length 10mm, diameter 1mm), in 105
DEG C keep 6 minutes, 100kgf/cm is applied by plunger2Loading, determine in 105 DEG C of melt viscosity.
(2) assay method of weight average molecular weight
The embodiment 1~18 of above-mentioned gained and the polymer of comparative example 2~4 are directed to, (Tosoh (strain) makes by GPC devices
GPC " HLC-8020 "), under conditions of 40 DEG C of column temperature, flow 1.0ml/ minutes, determined in eluat using tetrahydrofuran,
Determine the weight average molecular weight converted with polystyrene standard.In addition, post is the trade name for installing 3 Tosoh (strain) systems of connection
TSK-GEL G5000HHR、G4000HHR、G3000HHR。
(the storage stability evaluation of dryingagent composition)
By the stability in the polymer dispersion liquid of embodiment 1~18 or the gained of comparative example 1~4 when preserving 2 weeks for 45 DEG C,
With following benchmark evaluation.Show the result in table 6~9.
A：Without cosmetic variation
B：Confirmation only has grease near liquid level, has polymer precipitate in container wall
C：Confirm the fallout of polymer, separation, gelation
(the water-repellancy evaluation of fibre)
According to JIS L 1092 (1998) spray, enter to be about to shower water temperature and be set to 27 DEG C to be tested., will in this experiment
The cloth of polyester 100% or nylon 100% dyed be distributed in by the polymer dispersion liquid of embodiment 1~18 or comparative example 1~4 with
Water is diluted in treatment fluid of the content of polymer as 3 mass % and carried out after impregnation process (the mass % of pickup rate 60), in
130 DEG C of dryings 2 minutes, and then be heat-treated with the condition as shown in table 6~9, the water-repellancy of the cloth obtained by evaluation.Result is
Evaluated by visual observation with following grades.In addition, the only micro- good situation of sense of touch, grade is designated as "+", by sense of touch only it is micro- not
Good situation, grade is designated as "-".Show the result in table 6~9.
Water-repellancy：State
5：In surface attachment without moistening
4：Micro- moistening is only shown in surface attachment
3：Moistened in surface display portion
2：Moistening is shown in surface
1：Moistening is integrally shown in surface
0：Two sides shows what is moistened completely in table
(the sense of touch evaluation of fibre)
Sense of touch is using the polymer being distributed in the polyester dyed 100% by embodiment 1~18 or comparative example 1~4
Dispersion liquid, which is turned into the content of water diluted polymer in 3 mass % treatment fluid, carries out impregnation process (the mass % of pickup rate 60)
Afterwards, dry 2 minutes, and then evaluated with 170 DEG C of 30 seconds persons of heat treatment in 130 DEG C.Result is as shown below by operating
5 stages evaluated.Show the result in table 6~9.
1：Firmly~5：It is soft
(the durable water-repellancy evaluation of fibre)
According to JIS L 1092 (1998) spray, entering to be about to shower water temperature turns into 27 DEG C of experiment.In this experiment, it will carry out
The cloth of polyester 100% of dyeing, the content of polymer turns into 3 mass %, UNIKA RESIN 380-K (the chemical works of crosslinking agent, joint
Industry Co. Ltd. system, trimethylol melamine resin) content turn into 0.3 mass % and UNIKA CATALYST 3-P (tables
The chemical Industrial Co., Ltd's system of face activating agent, joint, amino alcohol hydrochloride salt) content turn into 0.2 mass % mode, in will be real
Apply the polymer dispersion liquid and above-mentioned each medicament of example 1~18 or comparative example 1~4 and impregnation process is carried out with water-reducible treatment fluid
After (the mass % of pickup rate 60), dry 2 minutes, and then in 170 DEG C of cloth (L-0) being heat-treated obtained by 60 seconds and carry out in 130 DEG C
The water-repellancy of cloth after the cleaning that 10 times (L-10) passes through JIS L 0217 (1995) 103 methods, with above-mentioned water-repellancy evaluation side
Method is equally evaluated.Further, the situation of the cloth of nylon 100%, except by heat treatment temperature from addition to 170 DEG C are changed to 160 DEG C,
It is same with the situation of the cloth of polyester 100% to be evaluated.Show the result in table 6~9.
[table 1]
[table 2]
[table 3]
[table 4]
[table 5]
[table 8]
[table 9]
The fibre of the dryingagent composition of Processing Example 1~18, even if nonheat-treated situation is confirmed, with using
The situation of conventional fluorine system dryingagent (comparative example 1) plays water-repellancy, the durable water-repellancy more than equal, and sense of touch is also good.
Further, the storage stability for confirming composition is also good.
When comparing embodiment 2 and embodiment 4, even if confirming to approach the composition of non-fluorine based polymer, the weight of polymer
When average molecular weight is different, the big side of weight average molecular weight, water-repellancy are excellent.
The dryingagent composition of comparative example 2 using the general surfactant of not reactive emulsifier, confirms and made
In amount of surfactant with the same amount of embodiment 4 of reactive emulsifier, the storage stability reduction of composition.
The dryingagent composition of comparative example 3 is compared with comparative example 2, for the purpose of the storage stability for lifting composition, is increased
Plus emulsion adjuncts (general surfactant) amount when, have treatment compositions fibre water-repellancy reduction incline
To.
The dryingagent composition substitution reaction emulsifying agent of comparative example 4, and with the preferred scope with the present invention
HLB general surfactant, carries out emulsion polymerization, confirms the water-repellancy reduction of the fibre of processing.
By the above, according to the present invention, while confirmation can provide superior storage stability, even if in not being heat-treated
Situation, also can assign fibre etc. by sufficient water-repellancy, sense of touch and the excellent water-repellancy fiber of water-repellancy can be obtained
The dryingagent composition of product.
[industrial applicability]
The dryingagent composition of the present invention is especially effective in fibre purposes.By the dryingagent composition of the present invention
During used in fibre purposes, after by fibre with dryingagent compositions-treated, it is heat-treated even if in low temperature
Fully excellent water-repellancy can be showed, in thermo-responsive specialty fibers or natural fiber, can also make its performance abundant
Water-repellancy.And then by and with crosslinking agent or make reactive monomer copolymerization, durable water-repellancy or sense of touch can be lifted.Further,
The dryingagent composition of the present invention contains fluorine-based due to not including, therefore is low cost, few as the harmful effect to human body or environment
Dryingagent composition be useful.Further, compared with conventional dryingagent, the usage amount of surfactant can be lowered, can
The various fiber process of correspondence.
Claims (9)
1. dryingagent composition, it includes non-fluorine based polymer, and the non-fluorine based polymer contains to be represented from following formulas (A-1)
(methyl) acrylate monomer (A) Component units, with the Component units from reactive emulsifier (B), the reactivity is newborn
Agent (B) is selected from least one of following (B1)~(B3), the chemical combination that following formulas (I-1) that (B1) HLB is 7~18 are represented
The compound and (B3) HLB that thing, following formulas (II-1) that (B2) HLB is 7~18 are represented be 7~18, with hydroxyl and
The compound of the epoxyalkane of addition carbon number 2~4 in the grease of polymerism unsaturated group；
The weight average molecular weight of the non-fluorine based polymer is more than 100,000,
The non-fluorine based polymer is below 1000Pas in 105 DEG C of melt viscosity,
[changing 1]
[in formula (A-1), R1Represent hydrogen or methyl, R2Represent can also there is 1 valency alkyl of the carbon number 12~24 of substituent]；
[changing 2]
[in formula (I-1), R3Hydrogen or methyl are represented, X represents the alkylidene of the straight or branched of carbon number 1~6, Y1Represent to include carbon number
The divalent group of 2~4 alkylene oxide group]；
[changing 3]
[in formula (II-1), R4Represent 1 valency unsaturated alkyl of the carbon number 13~17 with polymerism unsaturated group, Y2Represent bag
The divalent group of alkylene oxide group containing carbon number 2~4].
2. dryingagent composition as claimed in claim 1, wherein, foregoing non-fluorine based polymer, which further contains to come from, to be selected from by following
(C1), the Component units of the 2nd at least one kind of (methyl) acrylate monomer (C) in the group that (C2), (C3) and (C4) is constituted；
(C1) (methyl) acrylate monomer that following formulas (C-1) represent
[changing 4]
[in formula (C-1), R5Represent hydrogen or methyl, R6Represent to have and select free hydroxyl, amino, carboxyl, epoxy radicals, NCO
And 1 valency chain alkyl of the carbon number 1~11 of at least one kind of functional group in the group that constitutes of (methyl) acryloxy, in formula,
The number of (methyl) acryloxy of intramolecular is less than 2]；
(C2) (methyl) acrylate monomer that following formulas (C-2) represent
[changing 5]
[in formula (C-2), R7Represent hydrogen or methyl, R8Represent can also there is 1 valency cyclic hydrocarbon group of the carbon number 1~11 of substituent]；
(C3) methacrylate monomers that following formulas (C-3) represent
[changing 6]
[in formula (C-3), R9Represent 1 valency chain alkyl of unsubstituted carbon number 1~4]；
(C4) (methyl) acrylate monomer that following formulas (C-4) represent
[changing 7]
[in formula (C-4), R10Hydrogen or methyl are represented, p represents more than 2 integer, and S represents the organic group of (p+1) valency, and T represents tool
There is 1 valency organic group of polymerism unsaturated group].
3. dryingagent composition, it includes non-fluorine based polymer, and the non-fluorine based polymer is emulsion or dispersion is carried out breast
Change polymerization or dispersin polymerization is formed, the emulsion or dispersion include (methyl) acrylate list that following formulas (A-1) are represented
Body (A) and reactive emulsifier (B), the reactive emulsifier (B) are selected from least one of following (B1)~(B3), (B1)
The change that the compound for following formulas (I-1) expression that HLB is 7~18, following formulas (II-1) that (B2) HLB is 7~18 are represented
Compound and (B3) HLB for 7~18, in the grease with hydroxyl and polymerism unsaturated group addition carbon number 2~4 ring
The compound of oxygen alkane；
The weight average molecular weight of the non-fluorine based polymer is more than 100,000,
The non-fluorine based polymer is below 1000Pas in 105 DEG C of melt viscosity,
[changing 8]
[in formula (A-1), R1Represent hydrogen or methyl, R2Represent can also there is 1 valency alkyl of the carbon number 12~24 of substituent]；
[changing 9]
[in formula (I-1), R3Hydrogen or methyl are represented, X represents the alkylidene of the straight or branched of carbon number 1~6, Y1Represent to include carbon number
The divalent group of 2~4 alkylene oxide group]；
[changing 10]
[in formula (II-1), R4Represent 1 valency unsaturated alkyl of the carbon number 13~17 with polymerism unsaturated group, Y2Represent bag
The divalent group of alkylene oxide group containing carbon number 2~4].
4. dryingagent composition as claimed in claim 3, foregoing emulsion or foregoing dispersion are further included and are selected from by following
(C1), the 2nd at least one kind of (methyl) acrylate monomer (C) in the group that (C2), (C3) and (C4) is constituted；
(C1) (methyl) acrylate monomer that following formulas (C-1) represent
[changing 11]
[in formula (C-1), R5Represent hydrogen or methyl, R6Represent to have and select free hydroxyl, amino, carboxyl, epoxy radicals, NCO
And 1 valency chain alkyl of the carbon number 1~11 of at least one kind of functional group in the group of (methyl) acryloxy composition；In formula,
The number of (methyl) acryloxy of intramolecular is less than 2]；
(C2) (methyl) acrylate monomer that following formulas (C-2) represent
[changing 12]
[in formula (C-2), R7Represent hydrogen or methyl, R8Represent can also there is 1 valency cyclic hydrocarbon group of the carbon number 1~11 of substituent]；
(C3) methacrylate monomers that following formulas (C-3) represent
[change] 3]
[in formula (C-3), R9Represent 1 valency chain alkyl of unsubstituted carbon number 1~4]；
(C4) (methyl) acrylate monomer that following formulas (C-4) represent
[changing 14]
[in formula (C-4), R10Hydrogen or methyl are represented, p represents more than 2 integer, and S represents the organic group of (p+1) valency, and T represents tool
There is 1 valency organic group of polymerism unsaturated group].
5. water-repellancy fibre, it is the water-repellancy fibre that non-fluorine based polymer is attached with fibre, and this is non-
Fluorine system polymer contain from following formulas (A-1) represent (methyl) acrylate monomer (A) Component units, with it is reflexive
The Component units of answering property emulsifying agent (B), the reactive emulsifier (B) is selected from least one of following (B1)~(B3), (B1)
The change that the compound for following formulas (I-1) expression that HLB is 7~18, following formulas (II-1) that (B2) HLB is 7~18 are represented
Compound and (B3) HLB for 7~18, in the grease with hydroxyl and polymerism unsaturated group addition carbon number 2~4 ring
The compound of oxygen alkane；
The weight average molecular weight of the non-fluorine based polymer is more than 100,000,
The non-fluorine based polymer is below 1000Pas in 105 DEG C of melt viscosity,
[changing 15]
[in formula (A-1), R1Represent hydrogen or methyl, R2Represent can also there is 1 valency alkyl of the carbon number 12~24 of substituent]；
[changing 16]
[in formula (I-1), R3Hydrogen or methyl are represented, X represents the alkylidene of the straight or branched of carbon number 1~6, Y1Represent to include carbon number
The divalent group of 2~4 alkylene oxide group]；
[changing 17]
[in formula (II-1), R4Represent 1 valency unsaturated alkyl of the carbon number 13~17 with polymerism unsaturated group, Y2Represent bag
The divalent group of alkylene oxide group containing carbon number 2~4].
6. water-repellancy fibre as claimed in claim 5, is selected under wherein foregoing non-fluorine based polymer further contains to come from
State the composition list of the 2nd at least one kind of (methyl) acrylate monomer (C) in the group of (C1), (C2), (C3) and (C4) composition
Member；
(C1) (methyl) acrylate monomer that following formulas (C-1) represent
[changing 18]
[in formula (C-1), R5Represent hydrogen or methyl, R6Represent to have and select free hydroxyl, amino, carboxyl, epoxy radicals, NCO
And 1 valency chain alkyl of the carbon number 1~11 of at least one kind of functional group in the group of (methyl) acryloxy composition；In formula,
The number of (methyl) acryloxy of intramolecular is less than 2]；
(C2) (methyl) acrylate monomer that following formulas (C-2) represent
[changing 19]
[in formula (C-2), R7Represent hydrogen or methyl, R8Represent can also there is 1 valency cyclic hydrocarbon group of the carbon number 1~11 of substituent]；
(C3) methacrylate monomers that following formulas (C-3) represent
[changing 20]
[in formula (C-3), R9Represent 1 valency chain alkyl of unsubstituted carbon number 1~4]；
(C4) (methyl) acrylate monomer that following formulas (C-4) represent
[changing 21]
[in formula (C-4), R10Hydrogen or methyl are represented, p represents more than 2 integer, and S represents the organic group of (p+1) valency, and T represents tool
There is 1 valency organic group of polymerism unsaturated group].
7. water-repellancy fibre, it is formed by the fibre of attachment non-fluorine based polymer, and the non-fluorine based polymer is to make
Emulsion or dispersion carry out emulsion polymerization or dispersin polymerization is formed, and the emulsion or dispersion include following formulas (A-1) table
(methyl) acrylate monomer (A) shown and reactive emulsifier (B), the reactive emulsifier (B) are selected from (B1)~(B3)
At least one, compound that following formulas (I-1) that (B1) HLB is 7~18 are represented, following formulas that (B2) HLB is 7~18
(II-1) represent compound and (B3) HLB for 7~18, in the grease with hydroxyl and polymerism unsaturated group plus
Into the compound of the epoxyalkane of carbon number 2~4；
The weight average molecular weight of the non-fluorine based polymer is more than 100,000,
The non-fluorine based polymer is below 1000Pas in 105 DEG C of melt viscosity,
[changing 22]
[in formula (A-1), R1Represent hydrogen or methyl, R2Represent can also there is 1 valency alkyl of the carbon number 12~24 of substituent]；
[changing 23]
[in formula (I-1), R3Hydrogen or methyl are represented, X represents the alkylidene of the straight or branched of carbon number 1~6, Y1Represent to include carbon number
The divalent group of 2~4 alkylene oxide group]；
[changing 24]
[in formula (II-1), R4Represent 1 valency unsaturated alkyl of the carbon number 13~17 with polymerism unsaturated group, Y2Represent bag
The divalent group of alkylene oxide group containing carbon number 2~4].
8. water-repellancy fibre as claimed in claim 7, wherein, foregoing emulsion or foregoing dispersion further include be selected from by
The 2nd at least one kind of (methyl) acrylate monomer (C) in the group that following (C1), (C2), (C3) and (C4) are constituted；
(C1) (methyl) acrylate monomer that following formulas (C-1) represent
[changing 25]
[in formula (C-1), R5Represent hydrogen or methyl, R6Represent to have and select free hydroxyl, amino, carboxyl, epoxy radicals, NCO
And 1 valency chain alkyl of the carbon number 1~11 of at least one kind of functional group in the group of (methyl) acryloxy composition；In formula,
The number of (methyl) acryloxy of intramolecular is less than 2]；
(C2) (methyl) acrylate monomer that following formulas (C-2) represent
[changing 26]
[in formula (C-2), R7Represent hydrogen or methyl, R8Represent can also there is 1 valency cyclic hydrocarbon group of the carbon number 1~11 of substituent]；
(C3) methacrylate monomers that following formulas (C-3) represent
[changing 27]
[in formula (C-3), R9Represent 1 valency chain alkyl of unsubstituted carbon number 1~4]；
(C4) (methyl) acrylate monomer that following formulas (C-4) represent
[changing 28]
[in formula (C-4), R10Hydrogen or methyl are represented, p represents more than 2 integer, and S represents the organic group of (p+1) valency, and T represents tool
There is 1 valency organic group of polymerism unsaturated group].
9. the manufacture method of water-repellancy fibre, it possesses fibre with comprising such as any one of Claims 1 to 4
The process that the treatment fluid of dryingagent composition is handled.
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| JP6695017B2 (en) | 2015-07-23 | 2020-05-20 | 日華化学株式会社 | Non-fluorine-based polymer, water repellent composition, water repellent fiber product, and method for producing water repellent fiber product |
| JP6741442B2 (en) * | 2016-02-29 | 2020-08-19 | 日華化学株式会社 | Water repellent aid, non-fluorine-based water repellent composition, and method for producing water repellent fiber product |
| JP6829553B2 (en) * | 2016-05-27 | 2021-02-10 | 日華化学株式会社 | Manufacturing method of water-repellent textile products |
| JP6688171B2 (en) * | 2016-06-17 | 2020-04-28 | 日華化学株式会社 | Water repellent composition, water repellent fiber product and method for producing water repellent fiber product |
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- 2015-01-22 CN CN201580002779.3A patent/CN105793487B/en active Active
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| Publication number | Publication date |
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| WO2015111668A1 (en) | 2015-07-30 |
| JPWO2015111668A1 (en) | 2017-03-23 |
| JP6209226B2 (en) | 2017-10-04 |
| TWI656161B (en) | 2019-04-11 |
| KR102153279B1 (en) | 2020-09-09 |
| TW201546147A (en) | 2015-12-16 |
| CN105793487A (en) | 2016-07-20 |
| KR20160110947A (en) | 2016-09-23 |
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