JPH03190975A - Antifouling coating composition and production thereof - Google Patents
Antifouling coating composition and production thereofInfo
- Publication number
- JPH03190975A JPH03190975A JP32836089A JP32836089A JPH03190975A JP H03190975 A JPH03190975 A JP H03190975A JP 32836089 A JP32836089 A JP 32836089A JP 32836089 A JP32836089 A JP 32836089A JP H03190975 A JPH03190975 A JP H03190975A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- copper
- group
- cuprous oxide
- antifouling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000003373 anti-fouling effect Effects 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000008199 coating composition Substances 0.000 title 1
- 229920000642 polymer Polymers 0.000 claims abstract description 51
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 12
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 10
- 229930195729 fatty acid Natural products 0.000 claims abstract description 10
- 239000000194 fatty acid Substances 0.000 claims abstract description 10
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims abstract description 6
- 239000003973 paint Substances 0.000 claims description 22
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 14
- 239000005749 Copper compound Substances 0.000 abstract description 9
- 150000001880 copper compounds Chemical class 0.000 abstract description 9
- 239000011248 coating agent Substances 0.000 abstract description 8
- 238000000576 coating method Methods 0.000 abstract description 8
- 241001474374 Blennius Species 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000013535 sea water Substances 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 26
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 26
- 229940112669 cuprous oxide Drugs 0.000 description 26
- 239000000178 monomer Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- -1 cuprous oxide Chemical class 0.000 description 10
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000010828 elution Methods 0.000 description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 7
- 229910001431 copper ion Inorganic materials 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 5
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000003981 vehicle Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 239000002519 antifouling agent Substances 0.000 description 4
- RTIXKCRFFJGDFG-UHFFFAOYSA-N chrysin Chemical compound C=1C(O)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=CC=C1 RTIXKCRFFJGDFG-UHFFFAOYSA-N 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 229940116318 copper carbonate Drugs 0.000 description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- NYCXYKOXLNBYID-UHFFFAOYSA-N 5,7-Dihydroxychromone Natural products O1C=CC(=O)C=2C1=CC(O)=CC=2O NYCXYKOXLNBYID-UHFFFAOYSA-N 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 241000512259 Ascophyllum nodosum Species 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229940043370 chrysin Drugs 0.000 description 2
- 235000015838 chrysin Nutrition 0.000 description 2
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 235000015170 shellfish Nutrition 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- JGLMVXWAHNTPRF-CMDGGOBGSA-N CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O Chemical compound CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O JGLMVXWAHNTPRF-CMDGGOBGSA-N 0.000 description 1
- 125000006414 CCl Chemical group ClC* 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 208000002260 Keloid Diseases 0.000 description 1
- 206010023330 Keloid scar Diseases 0.000 description 1
- 241000208202 Linaceae Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- NPPQSCRMBWNHMW-UHFFFAOYSA-N Meprobamate Chemical compound NC(=O)OCC(C)(CCC)COC(N)=O NPPQSCRMBWNHMW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 101100161696 Myxine glutinosa ache gene Proteins 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 241000270708 Testudinidae Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- YUFKRVWMKLSXBA-UHFFFAOYSA-N [Cu+3].[As]([O-])([O-])[O-] Chemical compound [Cu+3].[As]([O-])([O-])[O-] YUFKRVWMKLSXBA-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000013040 bath agent Substances 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000013101 initial test Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 210000001117 keloid Anatomy 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 1
- 229940019931 silver phosphate Drugs 0.000 description 1
- 229910000161 silver phosphate Inorganic materials 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、海中の生物、例えば貝類、海藻類の海中にお
ける付着を防止する、いわゆる防汚塗料に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a so-called antifouling paint that prevents the adhesion of marine organisms such as shellfish and seaweed in the sea.
船底あるいは海中構築物等に対する海中生物の付着を防
止することは、これらの効率的運用および保守管理上極
めて重要なことである。このための対策として、従来か
ら有機錫を含有した塗料が有効なものとして使用されて
きた。しかしながら、近年、有機錫化合物の、主として
魚類における蓄積性が問題視されるようになって、公衆
衛生の面からこれを防汚剤として利用することが困難と
なる傾向にある。一方、これらの有機錫系塗料に替わっ
て魚類における蓄積性がなく、然も以前から使用実績の
ある亜酸化銅を中心とする無機銅化合物の利用が再び注
目されるようになってきた。Preventing marine organisms from adhering to ship bottoms or underwater structures is extremely important for efficient operation and maintenance management. As a countermeasure against this problem, paints containing organic tin have been used as an effective solution. However, in recent years, the accumulation of organotin compounds mainly in fish has become a problem, and it has become difficult to use them as antifouling agents from the standpoint of public health. On the other hand, as an alternative to these organic tin-based paints, the use of inorganic copper compounds, mainly cuprous oxide, which does not accumulate in fish and has been used for a long time, is attracting attention again.
しかし、従来からよく知られているように、1へりフェ
ニル錫メタクリレ−1・のような、ポリマーが水中で極
く少量づつ表面から流出する、いわゆる゛うなぎ塗料パ
的な機能を、例えば、典型的な無機銅化音物である亜酸
化銅を特徴とする特許がもつことは困難であるとされる
。However, as is well known in the past, polymers such as 1-phenyltin methacrylate (1) have a function similar to that of ``eel paints'' in which they flow out from the surface in very small amounts in water, for example. It is said that it is difficult to obtain a patent that features cuprous oxide, which is an inorganic copper compound.
亜酸1ヒ銅を防汚剤としロジンをビヒクルとする塗料は
、海水中での損耗が激しく、長期の防汚作用を有する塗
料とはならず、また、塩化コム系のビヒクルを用いた防
汚塗料も、表面に分布しブこ亜酸化銅が溶出ずれは防汚
作用は消失するといわれている。Paints that use copper monoarsenite as an antifouling agent and rosin as a vehicle are subject to severe wear and tear in seawater, and do not have long-term antifouling effects; It is said that the antifouling effect of the dirty paint disappears if cuprous oxide is distributed on the surface and the cuprous oxide is eluted.
亜酸化銅を含む塗膜が防汚作用を示すためには、8−1
]μ9/ can2/口の亜鉛fヒ銅の溶出がな(゛
)れはならないとされており、この値を長期間にわたっ
て一定値に保つことか、安定な働きをする防汚塗料とし
て必須のものとなる。8-1 In order for a coating film containing cuprous oxide to exhibit antifouling effect,
]μ9/can2/It is said that there should be no elution of zinc f arsenic, and it is necessary to maintain this value at a constant value over a long period of time, which is essential for an antifouling paint that works stably. Become something.
すなわち、亜酸化銅を必要足台h、表面の塗膜が絶えず
十分な量の亜酸化銅を供給し得るように更新される塗料
用のビヒクルを得るために、数多くの研究が行われてい
る。Numerous studies have been carried out in order to obtain vehicles for paints in which cuprous oxide is required, and the surface coating is continually renewed in such a way that it can supply a sufficient amount of cuprous oxide. .
それらの中には、水溶性ポリマーを形成するモノマー、
例えはヒニルビロリトンを共重合ポリマーの一成分に用
いる例、あるいは第3級アミノ基を有するモノマーを使
用する例なとがある。Among them are monomers that form water-soluble polymers,
For example, there are examples in which hinylvirolitone is used as one component of the copolymer, or examples in which a monomer having a tertiary amino group is used.
しかし、既存のこれらポリマーをビヒクルとする防汚塗
料は、それか使用環境により物性の変(ヒを示さない、
すなわちポリマーの溶解性に経口変化を生じているわけ
てはない。However, existing antifouling paints that use these polymers as vehicles do not exhibit any change in physical properties depending on the environment in which they are used.
In other words, there is no oral change in the solubility of the polymer.
望ましい傾向は前出した゛うなき塗料°′的な傾向、す
なわち亜酸化銅を含みなから表面のポリマーか常に亜酸
化銅の一定量づつを供給できるように更新されていくこ
とである。A desirable trend is to update the previously mentioned trend of paints so that the surface polymer, which does not contain cuprous oxide, always supplies a constant amount of cuprous oxide.
本発明者らは、亜酸化銅なとの無機銅化合物を防汚剤に
用い、長期間にわたって防汚作用を示すに十分な量の銅
イオンを放出てきるビヒクルについて検討を進めてきた
結果、少なくとも一成分としてアセ1〜アセデル基を有
するポリマーを用いることにより目的を達成できること
を見いたした。The present inventors have studied a vehicle that uses an inorganic copper compound such as cuprous oxide as an antifouling agent and releases a sufficient amount of copper ions to exhibit antifouling effects over a long period of time. It has been found that the object can be achieved by using a polymer having ace1 to acedel groups as at least one component.
特に、アセ1−アセチル基を有するポリマーと、ロジン
て代表される、分子中に1個のカルボキシル基を有する
樹脂または脂肪酸を配合するときは、長期間にわたる防
汚作用かあることをみいたし7′S。In particular, it has been found that when a polymer having an ace-1-acetyl group is blended with a resin or fatty acid having one carboxyl group in the molecule, such as rosin, there is a long-term antifouling effect7. 'S.
しかしながら、アセ1ヘアセチル基ぐ有するポリマーを
ビヒクルとする防汚塗料は、亜酸化銅なとの無機質銅化
合物と併用、混合すると、数1]間は塗装可能な状態を
維持するが、やがてケル状となることかある。特に、カ
ルボキシル基および/またはヒドロキシル基(アセトア
セチル基も含め、以下これらを反応性官能基と略称する
)をアセトアセチル基と共有する多元共重合ポリマーは
、甚だしい場合には数分でケル状となることも見出され
た。したがって、これらの防汚塗料の作業性を向上する
ためには、可使時間をできるたけ長くすることか望まし
い。However, when an antifouling paint using a polymer having acetylacetyl groups as a vehicle is used in combination with or mixed with an inorganic copper compound such as cuprous oxide, it remains paintable for a period of time, but eventually it becomes like a kelp. It may happen. In particular, multi-component copolymers that share carboxyl groups and/or hydroxyl groups (including acetoacetyl groups, hereinafter referred to as reactive functional groups) with acetoacetyl groups can, in extreme cases, turn into a keloid within a few minutes. It was also found that Therefore, in order to improve the workability of these antifouling paints, it is desirable to extend their pot life as much as possible.
本発明者らは、これら反応性官能基を有する多元ポリマ
ーと亜酸化銅で代表される銅化物を十分な使用期間をも
・って混自可能な状態とずl\く検討を重ねた結果、意
外にも、17ジンで代表されるカルボキシル基を分子中
に1個有する化合物と亜酸化銅を予め十分に混練してお
りば、この混練物を反応性官能基をもったポリマー中に
添加しても早急なゲル状態にはならないことを見出し、
本発明のもう1つの目的を達成することかてきた。The present inventors have conducted extensive studies to find a state in which these multi-component polymers having reactive functional groups and cuprates represented by cuprous oxide can be mixed together over a sufficient period of use. Surprisingly, if a compound having one carboxyl group in the molecule, such as 17-gin, and cuprous oxide are sufficiently kneaded in advance, this kneaded product can be added to a polymer having a reactive functional group. It was discovered that the gel state did not occur immediately even if
Another object of the invention has been achieved.
すなわち本発明は、その1面に」しいて、(a、)無(
幾銅化1勿および/またはt同(b)分子量3ooo以
Fて、分子中に1個のカルホキジル基を有する樹脂また
は脂肪酸、および(c)アセl−アセチル基を存するポ
リマーを併用することよりなる防汚塗料絹成糊を提供す
るものである。That is, in one aspect of the present invention, (a) nothing (
(b) A resin or fatty acid having a molecular weight of 3 ooo or more and having one carphokidyl group in the molecule, and (c) a polymer having an acetyl group. The present invention provides an antifouling paint silk paste.
さらにまた本発明は、他の面において、(a)無機銅化
物および/または銅、および(b))分子i 3000
以十゛て、分子中に1個のカルボキシル基を有する樹脂
または脂肪酸をあらかしめ混合し、次いて、
(c)アセI・アセデル基を有するポリマーを添加する
こと特徴とする、防汚塗料組成物の製造方法を提供する
ものである。Yet another aspect of the invention provides that (a) an inorganic copperide and/or copper; and (b)) a molecule i 3000
An antifouling paint composition characterized in that: (1) a resin or a fatty acid having one carboxyl group in the molecule is mixed together, and then (c) a polymer having an acetyl/acetyl group is added. It provides a method for manufacturing products.
アセI・アセチル基を有するポリマーと例えは亜酸化銅
との併用か、なぜ一定量の銅イオンを放出することかで
きるのかは必ずしも明らかてはないが、アセI・アセデ
ル基と銅化合物とのキレ−1〜結合の形成、さらにはア
セI・アセチル基のアルカリ外水溶液中ての加水分解の
促進によるし1−口Nシルツメ、の再生と、これに伴う
ポリマーの水溶性の増大とい−)た1f実か、何らかの
関1系を有していることも1(f−測される。It is not always clear whether a polymer with aceI/acetyl groups is used in combination with, for example, cuprous oxide, or why a certain amount of copper ions can be released, but the interaction between aceI/acedel groups and copper compounds is not clear. Formation of acetyl-1 bond, and further, regeneration of the acetyl group by promoting hydrolysis of the acetyl group in an alkaline aqueous solution, and an accompanying increase in the water solubility of the polymer. It is also 1(f-measured) that 1f is real or has some function 1 system.
本発明に利用されるアセl−アセチル基を有するポリマ
ーは、アセトアセチル基をイ1するモノマーの重合によ
ってか、あるいはヒドロキシル基を有するポリマーにジ
ケテンを反応させることによりき成される。The polymer having an acetyl-acetyl group used in the present invention can be prepared by polymerizing a monomer having an acetoacetyl group or by reacting a polymer having a hydroxyl group with diketene.
C1l。C1l.
ncll、・−C−
C−=0 ’0 01
11 lIC1,、−CH2−
C1120−C−CIl□−C−CI+3113
亀
(cII、、−、−C)−:、:
と−000
111N
0−CIl、CL−0−C−C112−、、、C−C1
1゜(アセトアセチル基を有するポリマー)0−CI(
、、−CL−OH
CL R
1
−・ −壬(−CH12−C)(、CH2−CII)
÷□
C=0 0 01
II ll0−C112−C
112−0−C−C1l□−c−cl13(アセトアセ
チル基を有するポリマー)ジケテンの重合体は、単独重
合体ても、あるいは共重合可能なモノマーとの共重合体
ても合成が可能である。ncll, ・-C- C-=0 '0 01
11 lIC1,, -CH2-
C1120-C-CIl□-C-CI+3113 Tortoise (cII,,-,-C)-:,: and-000 111N 0-CIl, CL-0-C-C112-,,,C-C1
1° (polymer with acetoacetyl group) 0-CI (
,, -CL-OH CL R 1 - - 壬(-CH12-C)(,CH2-CII)
÷□ C=0 0 01
II ll0-C112-C
112-0-C-C1l□-c-cl13 (polymer having an acetoacetyl group) A diketene polymer can be synthesized as a homopolymer or as a copolymer with a copolymerizable monomer. .
よく知られているように、アセ1ヘアセチル基は典型的
なケ1−−−エノール互変異性を示ずためか、0
0 0 ’0111I II
lI
C−Cl+2−C−−C−CIl=C
ケ1〜型 エノール型
アセトアセデル基を有するモノマーの単独重合ては、前
述したケ1〜−−エノールの互変異性か関係するものと
考えられるが、重合率か高まるにつれ急速にゲル状とな
るために、重合調節剤を多量に用いなければ安定したポ
リマーを得ることが難しかった。As is well known, the 0
0 0 '0111I II
lI C-Cl+2-C--C-CIl=C Ke1-type The homopolymerization of a monomer having an enol-type acetoacedel group is thought to be related to the tautomerism of enol mentioned above. However, as the polymerization rate increases, the polymer rapidly becomes gel-like, making it difficult to obtain a stable polymer unless a large amount of polymerization regulator is used.
本発明に用いられるアセl−アセチル基を有するポリマ
ーを/j;るためのモノマーには、例えは次の不飽和ア
ルコールとジケテンとの反応生成物かあげられる。Examples of monomers for forming the polymer having acel-acetyl groups used in the present invention include the following reaction products of unsaturated alcohols and diketenes.
2−ヒドロキシエチルアクリレ−1〜、2−ヒドロキシ
プロピルアクリレート、2−しドロキシエチルメタクリ
レ=1・、2−ヒドロへ一ジプロピルメタクリレー1・
、ポリエチレングリコールモノメタクリレ−I・、アリ
ルアルコール等である。2-Hydroxyethyl acrylate 1-, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate 1., 2-hydro-dipropyl methacrylate 1.
, polyethylene glycol monomethacrylate-I., allyl alcohol, and the like.
−級アルコールの方がジケテンとの反応は容易であり、
本発明のためには」−分である。-grade alcohols react more easily with diketene,
For the present invention, it is "-minutes."
ヒF tつキシル基を存するポリマーは、ヒドロキシル
基を有するモノマーの重合または他モノマーと共重合す
る他に、例えばポリ酢酸ビニルまたはその共重き体のけ
ん化物、あるいはそのアセタール、ポルマール、ブチラ
ール化ポリマーがある。Polymers containing xyl groups can be produced by polymerization of monomers having hydroxyl groups or copolymerization with other monomers, for example, saponified products of polyvinyl acetate or copolymers thereof, or acetals, polymers, and butyralized polymers thereof. There is.
ヒドロキシル基とジケテンの反応は、密閉容器中60℃
前後の温度、有機錫化合物、3級アミン等の触媒存在下
で行われる。The reaction between hydroxyl groups and diketene is carried out in a closed container at 60°C.
It is carried out at different temperatures and in the presence of a catalyst such as an organic tin compound or a tertiary amine.
ロジンはカルボキシル基1個を有する化合物の代表例で
あるか、本発明てロジンと同様に利用される成分として
は、C12以上の天然油脂の加水分解成分である脂肪酸
、あるいはテルペン類と無水マレイン酸付加物のモノエ
ステル類、石油樹脂と無水マレイン酸付加物のモノエス
テル類、ポリブタジェンオリゴマーと無水マレイン酸付
加物のモノエステル類、等のように、無水マレイン酸を
イ」加することのてきる不飽和炭化水素オリゴマーと、
無水マレイン酸を付加させ、さらにその酸無水物基を所
望のアルコール類てモノエステル化した種類の、実質的
に1分子中に1個のカルボキシル基を有する分子i 3
000以下のオリゴマーである。Rosin is a typical example of a compound having one carboxyl group, and components that can be used similarly to rosin in the present invention include fatty acids, which are hydrolyzed components of natural fats and oils of C12 or higher, or terpenes and maleic anhydride. Monoesters of adducts, monoesters of petroleum resin and maleic anhydride adducts, monoesters of polybutadiene oligomer and maleic anhydride adducts, etc. an unsaturated hydrocarbon oligomer that can
A molecule having substantially one carboxyl group in one molecule, which is obtained by adding maleic anhydride and monoesterifying the acid anhydride group with a desired alcohol.3
000 or less oligomer.
分子量を3000と規定した理由は、ポリマーとの相溶
性に限界を生ずる分子量がほぼこの付近であり、もちろ
ん構造にもよるが、これ以上の高分子量化は亜酸化銅と
の混練物をポリマーに添加する時、その安定化効果が損
なわれるからでもある。The reason for specifying the molecular weight as 3000 is that the molecular weight that causes a limit to compatibility with the polymer is approximately around this range, and of course it depends on the structure, but increasing the molecular weight higher than this will require mixing the mixture with cuprous oxide into the polymer. This is also because when it is added, its stabilizing effect is impaired.
最も望ましいカルボキシル基を1個有するオリゴマーの
分子量は200以上1500以下である。The most desirable molecular weight of the oligomer having one carboxyl group is 200 or more and 1,500 or less.
本発明はアセ1−アセデル基を有するポリマー単独でも
、また反応性官能基を含むかあるいは含まない水溶性モ
ノマー、さらには非水溶性モノマーの併用による多元共
重合ポリマーのいずれてもよい。In the present invention, a polymer having an ace1-acedel group may be used alone, or a multicomponent copolymer may be used in combination with a water-soluble monomer containing or not containing a reactive functional group, or a water-insoluble monomer.
アセI・アセチル基を有するモノマー類と共重合してポ
リマーを形成するモノマー類は、特に制限を加える必要
はないか、例えは疎水性モノマーの代表例としてはスヂ
レン、ヒニルトルエン、メタクリル酸メチルか、また親
水性モノマーの例としては、ヒニルピロリドン、アクリ
ルアミド、アクリル酸、メタクリル酸、無水マレイン酸
、マレイン酸モノエステル類、フマル酸モノエステル類
、イタコン酸、2−ヒドロキシエチルアクリレ−1へ、
2−ヒト1フキシエヂルメタクリレ−1へ、2−ヒドロ
キシプロピルアクリレ−32−ヒ1へロキシプロビルメ
タクリレ−1−、アリルアルコールかあげられる。Is there any particular restriction on the monomers that copolymerize with monomers having acetyl/acetyl groups to form a polymer? For example, representative examples of hydrophobic monomers include sutyrene, hinyltoluene, and methyl methacrylate. Examples of hydrophilic monomers include hinylpyrrolidone, acrylamide, acrylic acid, methacrylic acid, maleic anhydride, maleic acid monoesters, fumaric acid monoesters, itaconic acid, 2-hydroxyethyl acrylate-1,
Examples include 2-human 1-fuxyedyl methacrylate-1, 2-hydroxypropyl acrylate-32-hydroxypropyl methacrylate-1-1, and allyl alcohol.
アクリロニ1へシルはそのポリマーが水溶性ではないど
ころから、疎水性的に扱われる。Acryloni-1-hesyl is treated as hydrophobic since the polymer is not water soluble.
重合は既存の諸方法により行われる。本発明に利用され
る無機銅化合物は、亜酸化銅が代表的てあり本発明の目
的には十分であるか、その他には銅粉、塩基性塩化銅、
塩基性硫酸鋼、炭酸銅、塩基性炭酸銅、塩基性リン酸銀
、水酸化銅、珪酸銀をあげることかできる。その使用量
は樹脂100部に対して10〜200部であり必要によ
り増減される。Polymerization is carried out by existing methods. The inorganic copper compound used in the present invention is typically cuprous oxide, which is sufficient for the purpose of the present invention; other examples include copper powder, basic copper chloride,
Examples include basic sulfuric acid steel, copper carbonate, basic copper carbonate, basic silver phosphate, copper hydroxide, and silver silicate. The amount used is 10 to 200 parts per 100 parts of resin, and may be increased or decreased as necessary.
本発明は前記の銅化合物の他に公知の防汚剤、例えばジ
チオカルバミン酸j同、などの併用は妨げない。The present invention does not preclude the use of known antifouling agents, such as dithiocarbamic acid, in addition to the copper compound described above.
本発明の防汚塗料組成物は、
(a)無機銅化物および/または銅
(b))分子1.3000以下で、分子中に1個のカル
ホキシル基を有する樹脂J、たは脂肪酸、および(c)
アセ1ヘアセヂル基を右するポリマーを併用することよ
り得られるか、製造こ直ちに使用する場合はよいが、時
間をおいて使用しようとすると、ケル化の問題がある。The antifouling paint composition of the present invention comprises (a) an inorganic copperide and/or copper (b) a resin J having 1.3000 or less molecules and one carboxyl group in the molecule, or a fatty acid; c)
It is fine if it is obtained by using a polymer containing an acetylene group or used immediately after production, but if it is used after a period of time, there is a problem of kelization.
すなわち、反応性官能基を有するポリマーにロジンを添
加しておき、この系にさらに亜酸化銅を加えると、早期
のゲル化か起こることがある。That is, if rosin is added to a polymer with reactive functional groups and then cuprous oxide is added to the system, premature gelation may occur.
1
しかしながら、前述したようにロジンと亜酸化銅とを予
め混練して増粘状態にしておりば、この混合系を反応性
官能基を有するポリマーに添加しても、ゲル化は起こり
難い。1. However, as described above, if the rosin and cuprous oxide are kneaded in advance to a thickened state, gelation is unlikely to occur even when this mixed system is added to a polymer having a reactive functional group.
実際にはロジンは溶剤に溶解した形となっており、ポリ
マーもまた同様であるが、実用的にはこれで十分である
。In reality, rosin is in a form dissolved in a solvent, and the same is true for polymers, but this is sufficient for practical purposes.
本発明の防汚塗料組成物には、必要に応じて着色剤、フ
ィラー、浴剤を用いることかできることは勿論である。It goes without saying that the antifouling paint composition of the present invention may contain colorants, fillers, and bath agents, if necessary.
本発明の理解を助けるために以下に実施例を示す。 Examples are provided below to aid in understanding the invention.
割1蝕」−
腹重]」輩とに私]α合1
撹拌機、還流コンデンサー、温度計、ガス導入管を付し
た1pセパラブルフラスコに、2−アセトアセデルエチ
ルメタクリレ−1−3002、メタアクリル酸イソフヂ
ル57g、アクリル酸1.4g、1゜ブヂルラウリルメ
ル力ブタン3g、アソヒスイ2
ソフヂロニ1〜リル3g、酢酸エチル330 gを仕込
み、窒素気流中温度65〜70℃で12時間重合した。1. In a 1P separable flask equipped with a stirrer, reflux condenser, thermometer, and gas inlet tube, add 2-acetoacedelethyl methacrylate-1-3002. , 57 g of isofidyl methacrylate, 1.4 g of acrylic acid, 3 g of 1゜butyl lauryl mer-butane, 3 g of ASOJIS 2 soph diron, 3 g of ethyl acetate, and polymerized for 12 hours at a temperature of 65 to 70°C in a nitrogen stream. did.
この間4時間毎に、アゾビスイソフチロニトリル各1.
5dづつを2回にわたり添加した。During this period, administer 1 dose each of azobisisophthyronitrile every 4 hours.
Two portions of 5 d each were added.
重合率約95%で、淡黄色の多元共重合ポリマー(A)
が得られた。数平均分子量的68000てあった。Pale yellow multi-component copolymer (A) with a polymerization rate of about 95%
was gotten. The number average molecular weight was 68,000.
ロジンと亜 との の 造
WW級のウッドロジン(分子量的340〜350)30
0sをトルエン3003に溶解、これに亜酸化銅220
0gを密閉ミキサー中て混合し、ペースト状の混練物(
B)とした。WW grade wood rosin (molecular weight 340-350) made from rosin and flax
Dissolve 0s in toluene 3003, add cuprous oxide 220 to this
0g in a closed mixer to form a paste-like kneaded product (
B).
この混練物(B)は密閉容器に保存する限り安定で、流
動状態を保っていた。This kneaded product (B) was stable and maintained a fluid state as long as it was stored in a closed container.
ポリマー(A、)100部(重量、以下間し)に、混練
物(B)135部、トルエン15部を混合し、混合塗料
(b)を得な。この混合塗料は1週間以上にわたり安定
で塗装可能てあった。Mix 135 parts of the kneaded material (B) and 15 parts of toluene to 100 parts (by weight) of the polymer (A) to obtain a mixed paint (b). This mixed paint was stable and paintable for over a week.
しかし一方、ポリマー(ハ)1.00部にロジンのトル
エン溶液(50%)を60部、亜酸化銅150部混音し
た系は、混自後約10分てゲル化した。On the other hand, on the other hand, a system in which 1.00 parts of polymer (c), 60 parts of a toluene solution of rosin (50%) and 150 parts of cuprous oxide were mixed turned into a gel about 10 minutes after mixing.
ポリマー(A、)と混練物(Bl)の混合塗料を、裏面
をエポキシ樹脂で防食塗装したホンプライI−鋼板上に
、乾燥塗膜厚約70〜100μになるように混合塗料(
r)を塗装、乾燥した。A mixed paint of polymer (A,) and kneaded product (Bl) was applied onto a Honply I-steel plate whose back side was anti-corrosion coated with epoxy resin, so that the dry coating thickness was approximately 70 to 100μ.
r) was painted and dried.
鉛筆硬度2H〜3 T−1、コハン目密着テスト]、
OO/ 100の塗膜か得られた。Pencil hardness 2H to 3T-1, diagonal adhesion test],
A coating of OO/100 was obtained.
銅イオン溶出試験
上記の塗装された試料について、レケム(Re c h
u m )のクリシン溶液を用いる方法に準して、銅
イオン溶出のリーチンクテス1へを行った。Copper ion elution test The above painted sample was tested by Rechem (Rech).
Leaching test 1 for elution of copper ions was carried out according to the method using chrysin solution (um).
すなわち、
クリシン 1.785g食塩
27.960y0.1%苛性ソータ 28.
8 cc蒸留水 1.000 cc
でpHを10.5に調整した液を用いる。That is, chrysin 1.785g salt
27.960y0.1% caustic sorter 28.
8 cc distilled water 1.000 cc
Use a solution whose pH has been adjusted to 10.5.
促進倍率は普通20−30倍と言われているか、ここて
は20倍として計算した。The acceleration magnification is usually said to be 20-30 times, but here we calculated it as 20 times.
試験開始当初の3日間(60日相当)の銅イオンの溶出
量は平均1−03 μg7 cm2/日〜84μy/c
m2/日と多少はらついていたか、360日相当て43
μg7 cm27日、以後760口相当て37μy/
cm’/日とほぼ一定となった。The elution amount of copper ions during the first 3 days (equivalent to 60 days) of the start of the test was 1-03 μg7 cm2/day to 84 μy/c on average.
It was somewhat inconsistent with m2/day, or 43, equivalent to 360 days.
μg7 cm27th, after that 760 mouths equivalent 37μy/
It became almost constant at cm'/day.
撹拌機、還流コンデンサー、カス導入管、温度計をイ」
シた1aセパラフルフラスコに、2−アセ1ヘアセチル
エチルアクリレート200 g、2−ビニルピリジン6
2y、スチレン42g、MI Mエチル2969、l−
フチルラウリルメルカブタン3g、アソヒスイソフチロ
ニl−リル3gを仕込み、70〜75℃、窒素気流中°
ζ12時間重合を行った。Install the stirrer, reflux condenser, waste inlet tube, and thermometer.
In a separate flask, add 200 g of 2-acetylacetyl ethyl acrylate and 60 g of 2-vinylpyridine.
2y, 42g of styrene, MIM ethyl 2969, l-
Add 3 g of phthyl lauryl mercabutane and 3 g of asohis isophthylonyl-l-lyl, and heat at 70 to 75°C in a nitrogen stream.
Polymerization was carried out for ζ12 hours.
途中4時間毎に2回にわたり、アソヒスイソフヂロニト
リル]、、5yづつを追加し、た。During the course of the reaction, 5 y of Asohisophiduronitrile was added twice every 4 hours.
重合率96%で、数平均分子量69000のポリマーが
得られた。A polymer with a polymerization rate of 96% and a number average molecular weight of 69,000 was obtained.
この共重合ポリマーに、塩化ベンジル76gを加え、ヘ
ンシルピリジニウムクロライド型の第45
級アンモニウj\塩化した。淡黄褐色、粘度約60ボイ
スの共重合ポリマー(B)が得られた。To this copolymer, 76 g of benzyl chloride was added to convert hensylpyridinium chloride type 45th-class ammonium chloride. A copolymer (B) having a light yellowish brown color and a viscosity of about 60 voices was obtained.
亜酸化銅と1〜−ル油脂肪酸との混練物(n)の製造
I・−ル油脂肪酸として゛′バーI〜−ルFA−1°“
播磨化成(株)を(分子量的300)150部、1〜ル
工ン150gに溶解し、これに亜酸化銅10009をミ
キザー撹拌してベースト状の混練物(IT)を製造した
。Preparation of kneaded product (n) of cuprous oxide and 1--2 oil fatty acid.
150 parts of Harima Kasei Co., Ltd. (molecular weight: 300) were dissolved in 150 g of 1 to 1 kg, and cuprous oxide 10009 was stirred with a mixer to produce a base-like kneaded product (IT).
この混練!l勿(b)は室温密閉容器内で1週間以上安
定であった。This kneading! 1 (b) was stable for more than a week in a sealed container at room temperature.
ポリマー(B)を100g、混練後1週間放置した混練
物(II)を130g、混練した系は1週間以−4二放
置してもゲル化はみちれず塗装可能であった。100 g of polymer (B) was mixed with 130 g of kneaded product (II) which was left to stand for one week after kneading.The kneaded system could be coated without gelation even if it was left to stand for one week or more.
しかし、ポリマー(B)100yに亜酸化銅80 gを
混合した系は、3B後には増粘して塗装困難となった。However, the system in which 80 g of cuprous oxide was mixed with 100 y of polymer (B) became thicker after 3B and became difficult to coat.
別に、ポリマー(B)に1〜−ル油脂肪酸15gを加え
、さらに亜酸化銅80g添加後混練した系も殆と同一の
状態であった。Separately, a system obtained by adding 15 g of 1-1-1-1-1-1-1-1-1-1-2-1-1-1-1-1-1-1-1-1-1-2-1-2-1-2-1-2-1-2-1-3 fatty acids and then kneading the mixture was the result of almost the same condition as the system in which 80 g of cuprous oxide was added and then kneaded.
ポリマー(B)100g、混練物(IT)1.30y、
1・6
ルエン20yを加え、均一溶液とし、ポンチライ1〜鋼
板上に最終膜厚的70μになるように2回に渡り塗装、
乾燥した。Polymer (B) 100g, kneaded product (IT) 1.30y,
1.6 Add 20y of luene to make a homogeneous solution, and apply it twice to a final film thickness of 70μ on Punchirai 1~ steel plate.
Dry.
裏面は錆の発生を防ぐために、昭和高分子(株)製゛′
スプレィタムC−200’″を約2+nm厚に塗装、実
施例1と同様に促進テス1へを行った。The back side is made by Showa Kobunshi Co., Ltd. to prevent rust.
Spraytum C-200''' was applied to a thickness of about 2+ nm, and accelerated test 1 was performed in the same manner as in Example 1.
試験開始時の溶出量 ]1/1μg/cm2/日、6
00日経過分の溶出量 3 ]μg/ C1l+2/日
、と十分な防汚量が認められた。Elution amount at the start of the test] 1/1μg/cm2/day, 6
The elution amount after 00 days was 3 μg/C1l+2/day, which was a sufficient antifouling amount.
及引」ユ
丑重人ポリマー(cc!′)A
撹拌機、還流コンデンサー、滴下ロー1−、ガス導入管
付温度計を(=t した1βセパラフルフラスコに、ス
チレン4]1.2−ヒ1〜ロキシエチルメタクリレート
208g、1−フヂルラウリルメルカブタン15g、ア
ゾヒスイソフチロニ1〜リル2.5g、酢酸エチル25
0gを加え、窒素気流中70〜75℃て16時間重合し
た。``Yuushi Shigeto Polymer (cc!') A Styrene 4] 1.2-H 208 g of 1-oxyethyl methacrylate, 15 g of 1-phydyllauryl mercabutane, 2.5 g of azohisisophthyloni, 25 g of ethyl acetate
0 g was added, and polymerization was carried out at 70 to 75° C. for 16 hours in a nitrogen stream.
この間2回にわたり4時間毎にアソヒスイソフヂロニ1
ヘリル15gつつを追加した。During this period, take 1 dose of Asohisofujironi every 4 hours twice.
Added 15g of Heril.
重合率約96%、数平均分子量的70000てあっノこ
。The polymerization rate is approximately 96%, and the number average molecular weight is 70,000.
温度を60℃に下(す、ジブチル銭シラウレー1〜1g
加え、ジケテン9CNtを約1時間問、−わたり滴下し
/ご。滴下終了後、60℃にて6時間保持しな。Lower the temperature to 60℃.
In addition, diketene 9CNt was added dropwise for about 1 hour. After finishing dropping, keep at 60°C for 6 hours.
赤外分析の結果、ヒドロキシル基の約70%はアセトア
セデル化されたものと推定された。As a result of infrared analysis, it was estimated that about 70% of the hydroxyl groups were acetoacetylated.
得られたポリマーは、2−アセl−アセチルエチルメタ
クリレ−I・約50モル%、スチレン20モル%、2−
ヒドロキシエチルメタクリレ−1・約30モル%の多元
共重合ポリマーに相当するものと7)られな。The obtained polymer contained approximately 50 mol% of 2-acetyl-acetyl ethyl methacrylate-I, 20 mol% of styrene, and 2-acetyl ethyl methacrylate-I.
Hydroxyethyl methacrylate-1 corresponds to about 30 mol % of a multicomponent copolymer 7).
淡黄褐色、シラツブ状の共重きポリマー(c)が得られ
た。A pale yellowish brown, sill-like copolymer (c) was obtained.
混練物(lI)の製造
α−テルピネン〜無水マレイン酸付加物のモノメチルエ
ステル(50%メヂメチヂエチI〜ン溶液)を100部
、亜酸化銅50部、塩基性炭酸銅50部、銅粉50部の
混合物を混練してペースト状の混練物(III)を製造
した。Production of kneaded product (lI) 100 parts of monomethyl ester of α-terpinene-maleic anhydride adduct (50% solution of methane), 50 parts of cuprous oxide, 50 parts of basic copper carbonate, and 50 parts of copper powder. The mixture was kneaded to produce a paste-like kneaded product (III).
この混練物(IT[)は密閉状態てkl: 1週間以」
二安定でケル化の傾向はみられなかった。This kneaded material (IT) is kept in a sealed state for at least 1 week.
It was bistable and showed no tendency toward Kelization.
ポリマー(c)100部に混練物(Tll)100部、
メチルエチルケI・720部を混合し、実施例2と同様
に約70 t、を厚になるように塗装、乾燥した。100 parts of kneaded material (Tll) to 100 parts of polymer (c),
720 parts of Methyl Ethyl Ke I was mixed, and in the same manner as in Example 2, approximately 70 tons was coated to a thickness and dried.
ポリマー(c)と混練物(b)の混き系はやや増粘した
がゲル化には至らず、1ケ月以・」二その状態を保持し
ていて安定てあった。The mixed system of polymer (c) and kneaded product (b) slightly thickened, but did not gel, and remained stable for more than one month.
別にポリマー(c)100部に亜酸化銅50部、塩基性
炭酸鋼50部、銅粉50部を混合した系は一夜放置後ケ
ル状態となった。Separately, a system in which 100 parts of polymer (c), 50 parts of cuprous oxide, 50 parts of basic carbonated steel, and 50 parts of copper powder were mixed turned into a kelp state after being left overnight.
塗膜の銅イオン溶出テスI・では、試験当初113μ7
/ cm2/日かイ足進テスl−て480日相当て27
μy/ctn2/日てあった。In the coating film copper ion elution test I, the initial test value was 113 μ7.
/ cm2/day, equivalent to 480 days, is 27
It was μy/ctn2/day.
火韮」1遇。1st prize for “Fire Niro”.
30cmX 30cmX O,5c+nのスレー)・板
に、昭和高分子(株)スプレイタl\C−500を約2
+nm厚になるように塗装、硬化後、実施例コ、2.3
て製造した各ポリマーと混練物の混合系をそれぞれ約7
0へ一100μmになるように塗装し、乾燥後9
4月から10月にわたって干潮水深1mの海中に放置し
、テスl〜を行った。比較例として未塗装のスレー1〜
板を用いた。30cm x 30cm
After coating and curing to a thickness of +nm, Example 2.3
The mixture system of each polymer and kneaded product manufactured by
After drying, it was left in the sea at a depth of 1 m at low tide from April to October, and tests were carried out. As a comparative example, unpainted Slay 1~
A board was used.
テスト終了時の状態は未塗装のスレート板には、い貝、
ふしつぼ、海藻か無数に付着し、表面か完全にこれら海
中生物て覆われていたが、本発明によるポリマーと、カ
ルボキシル基を含むオリゴマーと無機銅化合物との混練
物、との混合系を塗装した板は、どれもf値かに海藻様
の14着物があったが、貝類の了り着は認められなかっ
た。At the end of the test, the unpainted slate board had shells,
The surface of the pot was completely covered with seaweed and seaweed, but it was coated with a mixture of the polymer of the present invention, a mixture of an oligomer containing a carboxyl group, and an inorganic copper compound. All of the boards tested had 14 seaweed-like f values, but no shellfish was observed.
本発明の防汚塗料組成物は前述のように構成したので、
ゲル化時間が長く基材への塗装性にすぐれており、海水
中に浸漬された場合特定官能基の濃度コンl−ロールに
より銅イオンの溶出速度を規定できるため長期間防汚性
に優れた塗膜性能を示すことかできる。Since the antifouling paint composition of the present invention is configured as described above,
It has a long gelation time and has excellent paintability on substrates, and when immersed in seawater, the elution rate of copper ions can be controlled by controlling the concentration of specific functional groups, so it has excellent stain resistance for a long time. It is possible to show the coating film performance.
2、2,
Claims (1)
シル基を有する樹脂または脂肪酸、 および (c)アセトアセチル基を有するポリマー、を併用する
ことよりなる防汚塗料組成物。 2、(a)無機銅化物および/または銅、および(b)
分子量3000以下で、分子中に1個のカルボキシル基
を有する樹脂または脂肪酸をあらかじめ混合し、次いで
、 (c)アセトアセチル基を有するポリマーを添加するこ
と特徴とする、防汚塗料組成物の製造方法。[Scope of Claims] 1. (a) an inorganic copperide and/or copper, (b) a resin or fatty acid having a molecular weight of 3000 or less and having one carboxyl group in the molecule, and (c) a polymer having an acetoacetyl group. An antifouling paint composition comprising the combination of . 2. (a) inorganic copperbide and/or copper, and (b)
A method for producing an antifouling paint composition, characterized in that a resin or fatty acid having a molecular weight of 3000 or less and having one carboxyl group in the molecule is mixed in advance, and then (c) a polymer having an acetoacetyl group is added. .
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1328360A JPH0757847B2 (en) | 1989-12-20 | 1989-12-20 | Method for producing antifouling coating composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1328360A JPH0757847B2 (en) | 1989-12-20 | 1989-12-20 | Method for producing antifouling coating composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH03190975A true JPH03190975A (en) | 1991-08-20 |
JPH0757847B2 JPH0757847B2 (en) | 1995-06-21 |
Family
ID=18209378
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1328360A Expired - Lifetime JPH0757847B2 (en) | 1989-12-20 | 1989-12-20 | Method for producing antifouling coating composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0757847B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010280864A (en) * | 2009-06-08 | 2010-12-16 | Nitto Kasei Co Ltd | Antifouling coating composition, antifouling coating film formed by using the composition, coated product having the coating film on the surface, and method for antifouling treatment by forming the coating film |
WO2017170593A1 (en) * | 2016-03-28 | 2017-10-05 | 東洋製罐グループホールディングス株式会社 | Dispersion liquid, method for producing same, and copper compound particles |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03126771A (en) * | 1989-10-12 | 1991-05-29 | Showa Highpolymer Co Ltd | Antifouling coating composition |
-
1989
- 1989-12-20 JP JP1328360A patent/JPH0757847B2/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03126771A (en) * | 1989-10-12 | 1991-05-29 | Showa Highpolymer Co Ltd | Antifouling coating composition |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010280864A (en) * | 2009-06-08 | 2010-12-16 | Nitto Kasei Co Ltd | Antifouling coating composition, antifouling coating film formed by using the composition, coated product having the coating film on the surface, and method for antifouling treatment by forming the coating film |
WO2010143553A1 (en) * | 2009-06-08 | 2010-12-16 | 日東化成株式会社 | Antifouling coating composition, antifouling coating film formed from the composition, coated object having the coating film on surface, and method of antifouling treatment by forming the coating film |
WO2017170593A1 (en) * | 2016-03-28 | 2017-10-05 | 東洋製罐グループホールディングス株式会社 | Dispersion liquid, method for producing same, and copper compound particles |
US11324222B2 (en) | 2016-03-28 | 2022-05-10 | Toyo Seikan Group Holdings, Ltd. | Dispersion liquid, method for producing the same, and copper compound particles |
Also Published As
Publication number | Publication date |
---|---|
JPH0757847B2 (en) | 1995-06-21 |
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