JP2009235403A - Epoxy resin-based coating material for corrosion prevention and method for preventing deterioration of water supply construction using the coating material - Google Patents
Epoxy resin-based coating material for corrosion prevention and method for preventing deterioration of water supply construction using the coating material Download PDFInfo
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- JP2009235403A JP2009235403A JP2009051228A JP2009051228A JP2009235403A JP 2009235403 A JP2009235403 A JP 2009235403A JP 2009051228 A JP2009051228 A JP 2009051228A JP 2009051228 A JP2009051228 A JP 2009051228A JP 2009235403 A JP2009235403 A JP 2009235403A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 81
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 81
- 230000003405 preventing effect Effects 0.000 title claims abstract description 11
- 230000006866 deterioration Effects 0.000 title claims description 15
- 238000000034 method Methods 0.000 title claims description 10
- 239000011248 coating agent Substances 0.000 title abstract description 34
- 238000000576 coating method Methods 0.000 title abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 21
- 239000000463 material Substances 0.000 title abstract description 14
- 238000005536 corrosion prevention Methods 0.000 title abstract description 4
- 238000010276 construction Methods 0.000 title abstract description 3
- 229920005989 resin Polymers 0.000 claims abstract description 43
- 239000011347 resin Substances 0.000 claims abstract description 43
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 42
- 239000004593 Epoxy Substances 0.000 claims abstract description 23
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000008096 xylene Substances 0.000 claims abstract description 19
- 238000005260 corrosion Methods 0.000 claims abstract description 18
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 16
- 230000007797 corrosion Effects 0.000 claims abstract description 15
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 14
- 239000003973 paint Substances 0.000 claims description 42
- 238000003973 irrigation Methods 0.000 claims description 6
- 230000002262 irrigation Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 abstract description 15
- 239000002253 acid Substances 0.000 abstract description 10
- 239000010865 sewage Substances 0.000 abstract description 9
- 150000007524 organic acids Chemical class 0.000 abstract description 8
- 239000002351 wastewater Substances 0.000 abstract description 6
- 235000005985 organic acids Nutrition 0.000 abstract description 5
- 150000007522 mineralic acids Chemical class 0.000 abstract description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 10
- 230000008859 change Effects 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- CUFXMPWHOWYNSO-UHFFFAOYSA-N 2-[(4-methylphenoxy)methyl]oxirane Chemical compound C1=CC(C)=CC=C1OCC1OC1 CUFXMPWHOWYNSO-UHFFFAOYSA-N 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
- 238000004453 electron probe microanalysis Methods 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 6
- 239000010802 sludge Substances 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000012459 cleaning agent Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 3
- 229960004889 salicylic acid Drugs 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 2
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 2
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 2
- HSDVRWZKEDRBAG-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COC(CCCCC)OCC1CO1 HSDVRWZKEDRBAG-UHFFFAOYSA-N 0.000 description 2
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920002396 Polyurea Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000013008 thixotropic agent Substances 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229910001254 electrum Inorganic materials 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- XXOYNJXVWVNOOJ-UHFFFAOYSA-N fenuron Chemical compound CN(C)C(=O)NC1=CC=CC=C1 XXOYNJXVWVNOOJ-UHFFFAOYSA-N 0.000 description 1
- 239000010794 food waste Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000891 luminescent agent Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000008041 oiling agent Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、防食用エポキシ樹脂系塗料及び該塗料を用いた水利構造物の劣化防止方法に関する。 The present invention relates to an anticorrosion epoxy resin-based paint and a method for preventing deterioration of a water use structure using the paint.
従来、下水道関連施設等の水利構造物の劣化は、強酸成分による溶解劣化現象により生じることが分かっている。この現象は、下水中の硫酸塩から汚泥中の嫌気性硫黄還元細菌によって硫化水素が生成し、さらに、生成した硫化水素が気中に放出されて水利構造物表面の結露水に溶解された後、好気性の硫黄酸化細菌によって強酸成分である硫酸が生成することが主な原因とされている。
また、商業用・オフィスビル、ホテル等の構造物、施設で発生した汚水を一時的に貯留するための水利構造物であるビルピットの劣化現象は、公共下水道施設よりもさらに顕著である。これは、ビルピット内に流入する食物残渣、油類或いは洗浄剤を含んだ有機汚泥排水に起因しており、さらには40〜50℃の温排水が定常的に流入するため、劣化現象が加速的に進行する。
Conventionally, it has been found that deterioration of irrigation structures such as sewage-related facilities is caused by a dissolution deterioration phenomenon caused by a strong acid component. This phenomenon occurs after hydrogen sulfide is generated from the sewage sulfate by anaerobic sulfur-reducing bacteria in the sludge, and the generated hydrogen sulfide is released into the air and dissolved in the condensed water on the surface of the water use structure. The main cause is that sulfuric acid, which is a strong acid component, is produced by aerobic sulfur-oxidizing bacteria.
Moreover, the deterioration phenomenon of the building pit, which is a water use structure for temporarily storing sewage generated in a commercial / office building, a hotel or other structure or facility, is more remarkable than in a public sewerage facility. This is due to organic sludge drainage containing food residues, oils or cleaning agents that flow into the building pits. Furthermore, 40-50 ° C hot wastewater flows constantly, so the deterioration phenomenon is accelerated. Proceed to.
このような水利構造物の劣化現象を防止・抑制する方法として、重防食用塗料、例えば、ビニルエステル樹脂系塗料、ポリウレア樹脂系塗料、エポキシ樹脂系塗料等を塗布する方法が用いられている。
しかしながら、ビニルエステル樹脂系塗料の場合、一般的には、スチレンモノマー含有製品が使用されるため、スチレン臭気の問題がある。近年、ノンスチレンタイプのビニルエステル樹脂系塗料が開発されているが、コスト、防食性能及び塗膜表面の乾燥性等、解決すべき課題も多い。
また、ポリウレア樹脂系塗料の場合、スプレイアップによる施工が可能であり、施工性に優れた防食用塗料である反面、下水中の硫酸塩による浮き・剥がれ現象が確認され、防食性能の問題が顕在化している。
また、エポキシ樹脂系塗料の場合、近年、防食性能が著しく改善され、一般下水道の使用においては、十分な防食性能を有する結果が報告されている。しかしながら、ビルピット内における酢酸、ギ酸等の有機酸成分を含有する有機汚泥排水に対する十分な防食性能を有しているとは言い難い。
さらに、特許文献1には、キシレン樹脂を含む鉄管用塗料組成物が開示されている。当該塗料組成物は、キシレン樹脂添加により、可撓性、耐衝撃性、屈曲性が向上したものであるが、耐薬品性(防食性)は十分とは言い難く、特に有機酸に対する耐薬品性が不十分で、有機酸を含んだ排水が流入・貯留するビルピットでの使用は困難である。
As a method for preventing / suppressing the deterioration phenomenon of such a water use structure, a method of applying a heavy anticorrosion paint such as a vinyl ester resin paint, a polyurea resin paint, an epoxy resin paint or the like is used.
However, in the case of vinyl ester resin-based paints, since a styrene monomer-containing product is generally used, there is a problem of styrene odor. In recent years, non-styrene type vinyl ester resin-based paints have been developed, but there are many problems to be solved, such as cost, anticorrosion performance, and dryness of the coating surface.
In addition, in the case of polyurea resin-based paints, it can be applied by spray-up, and while it is an anticorrosion paint with excellent workability, it has been confirmed that there are floating and peeling phenomena due to sulfate in sewage, and problems with anticorrosion performance are evident. It has become.
Further, in the case of epoxy resin-based paints, the anticorrosion performance has been remarkably improved in recent years, and the results of having sufficient anticorrosion performance in the use of general sewers have been reported. However, it cannot be said that it has sufficient anticorrosion performance for organic sludge drainage containing organic acid components such as acetic acid and formic acid in the building pit.
Further, Patent Document 1 discloses an iron pipe coating composition containing a xylene resin. The coating composition is improved in flexibility, impact resistance and flexibility by adding xylene resin, but chemical resistance (corrosion resistance) is not sufficient, especially chemical resistance against organic acids. However, it is difficult to use in a building pit where wastewater containing organic acid flows in and stores.
上記事情に鑑み、本発明が解決しようとする課題は、水利構造物に流入・貯留する下水、排水中に含まれる無機酸や、油分の分解により生成される有機酸等の酸成分及び洗浄剤等に対する優れた防食性(耐薬品性)を有する防食用エポキシ樹脂系塗料を提供することである。 In view of the above circumstances, the problems to be solved by the present invention are sewage flowing into and stored in a water conserving structure, inorganic acids contained in drainage, and acid components such as organic acids generated by the decomposition of oil and cleaning agents. It is an object of the present invention to provide an anticorrosion epoxy resin paint having excellent anticorrosion properties (chemical resistance) against the above.
本発明者らは、上記課題を解決するために鋭意研究を重ねた結果、(A)エポキシ樹脂と、(B)エポキシアダクト変性芳香族アミン系硬化剤と、(C)メシチレン樹脂及び/又はキシレン樹脂と、を含有する防食用エポキシ樹脂系塗料が、下水、排水中に含まれる無機酸、有機酸等の酸成分に対する優れた防食性(耐薬品性)を有することを見い出し本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventors have (A) an epoxy resin, (B) an epoxy adduct-modified aromatic amine-based curing agent, (C) a mesitylene resin and / or xylene. The present invention has been completed by finding that an anticorrosive epoxy resin paint containing a resin has excellent anticorrosive properties (chemical resistance) against acid components such as inorganic acids and organic acids contained in sewage and wastewater. It was.
すなわち、本発明は以下のとおりである。
[1]
(A)エポキシ樹脂と、
(B)エポキシアダクト変性芳香族アミン系硬化剤と、
(C)メシチレン樹脂及び/又はキシレン樹脂と、
を含有する防食用エポキシ樹脂系塗料。
[2]
前記(A)成分を20〜60質量%、前記(B)成分を10〜30質量%、前記(C)成分を3〜10質量%含有する、上記[1]記載の防食用エポキシ樹脂系塗料。
[3]
上記[1]又は[2]記載の防食用エポキシ樹脂系塗料を水利構造物の内表面に塗布する工程を含む、水利構造物の劣化防止方法。
That is, the present invention is as follows.
[1]
(A) an epoxy resin;
(B) an epoxy adduct-modified aromatic amine curing agent;
(C) a mesitylene resin and / or a xylene resin;
Epoxy resin paint for corrosion protection.
[2]
The anticorrosion epoxy resin paint according to the above [1], comprising 20 to 60% by mass of the component (A), 10 to 30% by mass of the component (B), and 3 to 10% by mass of the component (C). .
[3]
A method for preventing deterioration of a water use structure, comprising a step of applying the anticorrosion epoxy resin paint according to the above [1] or [2] to an inner surface of the water use structure.
本発明の防食用エポキシ樹脂系塗料は、水利構造物に流入・貯留する下水、排水中に含まれる無機酸や、油分の分解により生成される有機酸等の酸成分及び洗浄剤等に対する優れた防食性を有する。
また、本発明の水利構造物の劣化防止方法により、酸成分に対する優れた防食性を水利構造物に付与することが可能であるため、水利構造物の劣化現象を顕著に防止・抑制することできる。
The epoxy resin coating for anticorrosion of the present invention is excellent for acid components and cleaning agents such as sewage that flows into and stores in irrigation structures, inorganic acids contained in wastewater, organic acids generated by decomposition of oil, and the like. Has anticorrosive properties.
In addition, the method for preventing deterioration of a water use structure according to the present invention can impart excellent corrosion resistance to acid components to the water use structure, so that the deterioration phenomenon of the water use structure can be remarkably prevented / suppressed. .
以下、本発明を実施するための形態(以下、本実施の形態)について詳細に説明する。なお、本発明は、以下の実施の形態に限定されるものではなく、その要旨の範囲内で種々変形して実施することができる。 Hereinafter, a mode for carrying out the present invention (hereinafter referred to as the present embodiment) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.
本実施の形態の防食用エポキシ樹脂系塗料は、(A)エポキシ樹脂と、(B)エポキシアダクト変性芳香族アミン系硬化剤と、(C)メシチレン樹脂及び/又はキシレン樹脂と、を含有する。 The anticorrosion epoxy resin paint of this embodiment contains (A) an epoxy resin, (B) an epoxy adduct-modified aromatic amine-based curing agent, and (C) a mesitylene resin and / or a xylene resin.
本実施の形態の防食用エポキシ樹脂系塗料は、(B)エポキシアダクト変性芳香族アミン系硬化剤によるフリーアミンの低減と、(C)メシチレン樹脂及び/又はキシレン樹脂による疎水化との相乗効果により、防食性(以下、耐薬品性とも言う。)の顕著な向上が達成されたものである。 The anticorrosion epoxy resin coating of the present embodiment has a synergistic effect of (B) reduction of free amine by an epoxy adduct-modified aromatic amine curing agent and (C) hydrophobicity by mesitylene resin and / or xylene resin. , Remarkable improvement in corrosion resistance (hereinafter also referred to as chemical resistance) has been achieved.
[(A)成分:エポキシ樹脂]
本実施の形態の防食用エポキシ樹脂系塗料に含まれる(A)エポキシ樹脂としては、各種のエポキシ樹脂が使用可能であり、例えば、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ノボラック型エポキシ樹脂、ビスフェノールAD型エポキシ樹脂等の公知のエポキシ樹脂及びそれらを変性したエポキシ樹脂等を用いることができる。中でも、架橋密度による防食性(耐薬品性)向上の観点からは、多官能エポキシ樹脂が好ましく、粘度、耐摩耗性及び機械強度のバランスの観点からは、2官能エポキシ樹脂が好ましい。
[(A) component: epoxy resin]
Various epoxy resins can be used as the (A) epoxy resin contained in the anticorrosive epoxy resin paint of the present embodiment, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin. In addition, known epoxy resins such as bisphenol AD type epoxy resins and epoxy resins obtained by modifying them can be used. Among these, a polyfunctional epoxy resin is preferable from the viewpoint of improving the corrosion resistance (chemical resistance) due to the crosslink density, and a bifunctional epoxy resin is preferable from the viewpoint of a balance of viscosity, wear resistance, and mechanical strength.
防食用エポキシ樹脂系塗料中の、(A)エポキシ樹脂の含有量としては、特に限定されないが、好ましくは20〜60質量%、より好ましくは40〜50質量%である。(A)エポキシ樹脂の含有量が、60質量%よりも多いと、防食用エポキシ樹脂系塗料の粘度の上昇に伴い、施工性が著しく低下する傾向にあり、20質量%よりも少ないと、防食性(耐薬品性)が低下し、防食用エポキシ樹脂系塗料としての性能が低下する傾向にある。 Although it does not specifically limit as content of (A) epoxy resin in the epoxy resin-type coating material for anticorrosion, Preferably it is 20-60 mass%, More preferably, it is 40-50 mass%. (A) When the content of the epoxy resin is more than 60% by mass, the workability tends to be remarkably lowered with the increase in the viscosity of the epoxy resin paint for anticorrosion. Performance (chemical resistance) is lowered, and the performance as an anticorrosion epoxy resin coating tends to be lowered.
[(B)成分:エポキシアダクト変性芳香族アミン系硬化剤] [Component (B): Epoxy adduct-modified aromatic amine curing agent]
本実施の形態の防食用エポキシ樹脂系塗料は、(B)エポキシアダクト変性芳香族アミン系硬化剤を含むことにより、塗料中のフリーアミン量が低減され、フリーアミンによる酸成分の吸着が抑制されるため、防食用エポキシ樹脂系塗料の防食性(耐薬品性)を飛躍的に向上させることが可能となる。 The epoxy resin-based paint for anticorrosion of the present embodiment includes (B) an epoxy adduct-modified aromatic amine-based curing agent, so that the amount of free amine in the paint is reduced and the adsorption of acid components by free amine is suppressed. Therefore, the corrosion resistance (chemical resistance) of the anticorrosion epoxy resin coating can be dramatically improved.
本実施の形態の防食用エポキシ樹脂系塗料に含まれる(B)エポキシアダクト変性芳香族アミン系硬化剤とは、ビスフェノールA型エポキシ樹脂等のエポキシ化合物と芳香族アミン系硬化剤とを反応させて得ることができる。アダクト変性に用いるエポキシ化合物としては、特に限定されず、例えば、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、2−エチルヘキシルグリシジルエーテル、アルキル(C12−13)グリシジルエーテル、ブチルグリシジルエーテル、アリルグリシジルエーテル、フェニルグリシジルエーテル、クレジルグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、ヘキサンジオールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル等を挙げることができ、また、エポキシ化合物と反応させる芳香族アミン系硬化剤としては、特に限定されず、例えば、メタフェニルレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン及びこれらの変性物が挙げられる。上記の中でも、ジアミノジフェニルメタンをビスフェノールA型エポキシ樹脂で変性した化合物が好ましい。 The (B) epoxy adduct-modified aromatic amine curing agent contained in the anticorrosion epoxy resin coating of the present embodiment is a reaction between an epoxy compound such as bisphenol A type epoxy resin and an aromatic amine curing agent. Obtainable. The epoxy compound used for adduct modification is not particularly limited. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, 2-ethylhexyl glycidyl ether, alkyl (C12-13) glycidyl ether, butyl glycidyl ether, allyl glycidyl ether. , Phenyl glycidyl ether, cresyl glycidyl ether, neopentyl glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, and the like, and as an aromatic amine curing agent to be reacted with an epoxy compound Is not particularly limited, and examples thereof include metaphenyl range amine, diaminodiphenylmethane, diaminodiphenylsulfone, and modified products thereof. Among the above, a compound obtained by modifying diaminodiphenylmethane with a bisphenol A type epoxy resin is preferable.
アダクト変性に使用するエポキシ化合物の量は、芳香族アミン系硬化剤100重量部に対して、好ましくは20〜45重量部、より好ましくは25〜40重量である。 The amount of the epoxy compound used for adduct modification is preferably 20 to 45 parts by weight, more preferably 25 to 40 parts by weight with respect to 100 parts by weight of the aromatic amine curing agent.
防食用エポキシ樹脂系塗料中の、(B)エポキシアダクト変性アミン系硬化剤の含有量としては、特に限定されないが、好ましくは10〜30質量%、より好ましくは15〜25質量%である。(B)エポキシアダクト変性アミン系硬化剤の含有量が、30質量%よりも多いと、防食用エポキシ樹脂系塗料の粘度の上昇に伴い、施工性が著しく低下する傾向にあり、10質量%よりも少ないと、防食性(耐薬品性)が低下し、防食用エポキシ樹脂系塗料としての性能が低下する傾向にある。 Although it does not specifically limit as content of (B) epoxy adduct modification | denaturation amine type hardening | curing agent in the epoxy resin-type coating material for anticorrosion, Preferably it is 10-30 mass%, More preferably, it is 15-25 mass%. (B) If the content of the epoxy adduct-modified amine-based curing agent is more than 30% by mass, the workability tends to be remarkably lowered with the increase in the viscosity of the epoxy resin coating for anticorrosion. From 10% by mass If the amount is too small, the anticorrosion property (chemical resistance) decreases, and the performance as an anticorrosion epoxy resin coating tends to decrease.
[(C)成分:メシチレン樹脂及び/又はキシレン樹脂]
本実施の形態の防食用エポキシ樹脂系塗料は、(C)メシチレン樹脂及び/又はキシレン樹脂を含むことにより、塗料を疎水化し、酸成分の浸透を防止、抑制することで防食性(耐薬品性)を更に向上させることが可能となる。
[(C) component: mesitylene resin and / or xylene resin]
The epoxy resin coating for corrosion protection according to the present embodiment includes (C) a mesitylene resin and / or a xylene resin, thereby making the coating hydrophobic and preventing or suppressing the penetration of the acid component to prevent corrosion (chemical resistance). ) Can be further improved.
ここで、メシチレン樹脂とは、メシチレンとホルムアデヒドを付加縮合反応させることにより得られる樹脂であり、キシレン樹脂とは、キシレンとホルムアルデヒドを付加縮合反応させることにより得られる樹脂である。メシチレン樹脂及び/又はキシレン樹脂の有する物性としては特に制限されないが、粘度30〜100mPa・s、平均分子量150〜500、比重1.0〜1.1のものが施工性に影響する防食用エポキシ樹脂系塗料の粘度調整の観点から好ましい。 Here, the mesitylene resin is a resin obtained by an addition condensation reaction of mesitylene and formaldehyde, and the xylene resin is a resin obtained by an addition condensation reaction of xylene and formaldehyde. The physical properties of the mesitylene resin and / or xylene resin are not particularly limited, but the epoxy resin for corrosion protection has a viscosity of 30 to 100 mPa · s, an average molecular weight of 150 to 500, and a specific gravity of 1.0 to 1.1 affects the workability. From the viewpoint of adjusting the viscosity of the paint.
防食用エポキシ樹脂系塗料中の、(C)メシチレン樹脂及び/又はキシレン樹脂の含有量としては、特に限定されないが、好ましくは3〜10質量%、より好ましくは5〜7質量%である。(C)メシチレン樹脂及び/又はキシレン樹脂の含有量が、10質量%よりも多いと、塗膜の機械的強度(物性)が低下する傾向にあり、3質量%よりも少ないと、防食用エポキシ樹脂系塗料の疎水化が不十分で、防食性能が低下する傾向にある。 Although it does not specifically limit as content of (C) mesitylene resin and / or xylene resin in the epoxy resin coating material for anticorrosion, Preferably it is 3-10 mass%, More preferably, it is 5-7 mass%. (C) If the content of the mesitylene resin and / or xylene resin is more than 10% by mass, the mechanical strength (physical properties) of the coating film tends to decrease, and if it is less than 3% by mass, the anticorrosion epoxy The resin-based paint is not sufficiently hydrophobized and the anticorrosion performance tends to decrease.
本実施の形態の防食用エポキシ樹脂系塗料は、通常、上記(A)エポキシ樹脂を含む主剤と、(B)エポキシアダクト変性アミン系硬化剤を含む硬化剤とを混合することにより得ることができ、(C)メシチレン樹脂及び/又はキシレン樹脂は、主剤中に含まれていても、硬化剤中に含まれていてもよい。 The epoxy resin-based paint for anticorrosion of the present embodiment can be usually obtained by mixing (A) a main agent containing an epoxy resin and (B) a curing agent containing an epoxy adduct-modified amine curing agent. (C) The mesitylene resin and / or the xylene resin may be contained in the main agent or in the curing agent.
さらに、本実施の形態の防食用エポキシ樹脂系塗料中には、防食性(耐薬品性)を損なわない範囲内で、粘度調整のための希釈剤、着色用の顔料、揺変剤、カップリング剤、界面活性剤、充填材、消泡剤等の、その他の添加剤を含有してもよい。希釈剤としては、例えば、2−エチルヘキシルグリシジルエーテル、アルキル(C12−13)グリシジルエーテル、ブチルグリシジルエーテル、アリルグリシジルエーテル、フェニルグリシジルエーテル、クレジルグリシジルエーテル等の単官能型反応性希釈剤、ネオペンチルグリコールジグリシジルエーテル、ヘキサンジオールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル等の多官能型反応性希釈剤、ベンジルアルコール、フタル酸ジブチル等の非反応性希釈剤等;着色用の顔料としては、カーボンブラック、酸化チタン等;揺変剤としては、球状シリカ等;カップリング剤としてはシラン系カップリング剤等;界面活性剤としては、ノニオン、カチオン系界面活性剤等;充填材としては、炭酸カルシウム、ガラスフレーク、天然又は合成シリカ、硫酸バリウム等;消泡剤としてはポリブタジエン系消泡剤等の公知の添加剤が挙げられ、それら添加剤は単独で用いても、併用してもよい。さらには、上記その他の添加剤は、主剤中に含まれていても、硬化剤中に含まれていてもよい。 Furthermore, the anticorrosive epoxy resin paint of the present embodiment includes a diluent for adjusting the viscosity, a pigment for coloring, a thixotropic agent, and a coupling within a range that does not impair the anticorrosion property (chemical resistance). You may contain other additives, such as an agent, surfactant, a filler, an antifoamer. Diluents include, for example, monofunctional reactive diluents such as 2-ethylhexyl glycidyl ether, alkyl (C12-13) glycidyl ether, butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, and neopentyl. Polyfunctional reactive diluents such as glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, non-reactive diluents such as benzyl alcohol and dibutyl phthalate, etc .; Black, titanium oxide, etc .; as thixotropic agent, spherical silica, etc .; as coupling agent, silane coupling agent, etc .; as surfactant, nonion, cationic surfactant, etc .; as filler, calcium carbonate , Las flakes, natural or synthetic silica, barium sulfate and the like; As the antifoaming agent include known additives such as polybutadiene-based defoaming agent, be used those additives alone or in combination. Furthermore, the above-mentioned other additives may be contained in the main agent or in the curing agent.
本実施の形態においては、硬化剤の低温時の流動性を確保するため、硬化剤中にベンジルアルコール及び/又はフタル酸ジブチルを、10〜40質量%添加することが好ましい。 In this Embodiment, in order to ensure the fluidity | liquidity at the time of the low temperature of a hardening | curing agent, it is preferable to add 10-40 mass% of benzyl alcohol and / or dibutyl phthalate in a hardening | curing agent.
[水利構造物の劣化防止方法]
本実施の形態の水利構造物の劣化防止方法は、防食用エポキシ樹脂系塗料を水利構造物
の内表面に塗布する工程を含む。
[How to prevent deterioration of water use structures]
The method for preventing deterioration of a water utilization structure according to the present embodiment includes a step of applying an anticorrosion epoxy resin coating to the inner surface of the water utilization structure.
水利構造物としては、例えば、汚泥濃縮槽、汚泥消化槽、汚泥貯留槽等から構成される公共下水道、ビルピット等が挙げられる。また、水利構造物の内表面材は、一般的にはコンクリートであるが、コンクリート以外の対象となる材料としては、モルタル、鋼材、FRP、各種プラスチック材料等が挙げられ、特に、コンクリート、モルタル等が好ましい。 Examples of the irrigation structures include public sewers, bill pits, and the like that are composed of a sludge concentration tank, a sludge digestion tank, a sludge storage tank, and the like. In addition, the inner surface material of the irrigation structure is generally concrete, but examples of materials other than concrete include mortar, steel, FRP, various plastic materials, etc., in particular, concrete, mortar, etc. Is preferred.
本実施の形態の劣化防止方法においては、防食用エポキシ樹脂系塗料を水利構造物の内表面に塗布し、塗膜を形成させる。この際、内表面に直接塗布して塗膜を形成してもよく、対象物(下地)との接着性を向上させるため、プライマー層を形成した後、防食用エポキシ樹脂系塗料を塗布してもよい。用いるプライマーは、下地と防食用エポキシ樹脂系塗料との接着性及び作業性等を考慮して選択される。ピンホールによる対象物の劣化を防止する観点からは、紫外線ランプ等を照射することによりピンホールを容易に発見できる発光剤含有のプライマーが好適に使用できる。 In the deterioration preventing method of the present embodiment, an anticorrosion epoxy resin coating is applied to the inner surface of the water conserving structure to form a coating film. At this time, it may be applied directly to the inner surface to form a coating film. In order to improve the adhesion to the object (underlying), after forming a primer layer, an anti-corrosion epoxy resin coating is applied. Also good. The primer to be used is selected in consideration of the adhesiveness and workability between the base and the anticorrosive epoxy resin paint. From the viewpoint of preventing deterioration of an object due to a pinhole, a luminescent agent-containing primer that can easily find a pinhole by irradiating an ultraviolet lamp or the like can be preferably used.
プライマーとしては、例えば、エポキシ樹脂系(水系)、エポキシ樹脂系(無溶剤系)、ウレタン樹脂系等の公知のプライマーが使用可能であり、中でも、安全衛生の観点からエポキシ樹脂系(無溶剤系)のプライマーが好ましい。また、プライマーの塗布量は、塗布面の状況により変化するが、0.1〜0.5kg/m2であるのが、接着性、コストの観点から好ましい。 As the primer, for example, known primers such as epoxy resin (water), epoxy resin (solvent-free), urethane resin and the like can be used, and among them, epoxy resin (solvent-free) from the viewpoint of health and safety. ) Is preferred. Moreover, although the application quantity of a primer changes with the conditions of an application surface, it is preferable from a viewpoint of adhesiveness and cost that it is 0.1-0.5 kg / m < 2 >.
防食用エポキシ樹脂系塗料の塗布量は、要求される耐久年数や、下水、排水の酸濃度条件等により変化するが、好ましくは0.5〜2.0kg/m2であり、より好ましくは0.8〜1.7kg/m2である。 The coating amount of the epoxy resin coating for anticorrosion varies depending on the required durability, the acid concentration conditions of sewage and wastewater, etc., but is preferably 0.5 to 2.0 kg / m 2 , more preferably 0. .8 to 1.7 kg / m 2 .
また、防食用エポキシ樹脂系塗料を、施工条件により他の防食用塗料、副資材と併用してもよい。具体的には、対象構造物背面からの水圧に対する抵抗力を向上させる場合には、ガラス繊維及びガラス繊維に含浸可能な粘性を有する他の防食用塗料を塗布した後、前記防食用エポキシ樹脂塗料を塗布する、或いは、対象構造物の変位による損傷、剥がれを防止するために、可撓性を有する他の防食用塗料を塗布した後、前記防食用エポキシ樹脂塗料を塗布する場合等がある。 Moreover, you may use together the epoxy resin-type coating material for anti-corrosion with another anti-corrosion coating material and auxiliary material by construction conditions. Specifically, in the case of improving the resistance to water pressure from the back of the target structure, the anticorrosion epoxy resin paint is applied after applying glass fiber and another anticorrosion paint having viscosity capable of impregnating the glass fiber. Or, in order to prevent damage or peeling due to displacement of the target structure, the anticorrosion epoxy resin paint may be applied after applying another flexible anticorrosion paint.
以下に、本実施の形態の防食用エポキシ樹脂系塗料に関し、実施例に基づいて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the anticorrosion epoxy resin paint of the present embodiment will be specifically described based on examples, but the present invention is not limited to these examples.
[評価方法]
防食用エポキシ樹脂系塗料の防食性(耐薬品性)の評価は、下記の重量変化率及びEPMA分析により行った。
[Evaluation methods]
The corrosion resistance (chemical resistance) of the anticorrosion epoxy resin paint was evaluated by the following weight change rate and EPMA analysis.
(試験用サンプルの作製方法)
φ50mm×厚さ約5mm、重量約10gの各種防食用エポキシ樹脂系塗料の硬化物を、20℃で7日養生したものを重量変化率用試験サンプルとした。重量変化率を測定した試験サンプルを切り出し、EPMA分析用試験サンプルを採取した。なお、EPMA分析には、(株)島津製作所製EPMA−1400を用い、加速電圧15KVでスキャン分析を行った。
(Method for preparing test samples)
Cured products of various anticorrosion epoxy resin paints having a diameter of 50 mm × thickness of about 5 mm and a weight of about 10 g were cured at 20 ° C. for 7 days to prepare test samples for weight change rate. A test sample whose weight change rate was measured was cut out, and a test sample for EPMA analysis was collected. For EPMA analysis, EPMA-1400 manufactured by Shimadzu Corporation was used, and scan analysis was performed at an acceleration voltage of 15 KV.
(評価条件:浸漬溶液及び温度条件)
防食性試験に用いた浸漬溶液は、10%硫酸水溶液、5%ギ酸水溶液及び5%プロピオン酸水溶液であり、水溶液の温度は、20℃及び40℃とした。
(Evaluation conditions: immersion solution and temperature conditions)
The immersion solutions used in the anticorrosion test were 10% sulfuric acid aqueous solution, 5% formic acid aqueous solution and 5% propionic acid aqueous solution, and the temperature of the aqueous solution was 20 ° C. and 40 ° C.
(評価方法1:重量変化率)
試験サンプルを各浸漬溶液に浸漬し、7日後、30日後及び120日後に水溶液からサンプルを採取した後、流水で水洗してウエスで水を拭き取り、直ちにサンプルの重量を測定して初期重量に対する重量変化率を測定した。各条件共にサンプル数を3とし、重量変化率はその平均値とした。
(Evaluation Method 1: Weight Change Rate)
After immersing the test sample in each immersion solution, collecting the sample from the aqueous solution after 7, 30 and 120 days, rinsing with running water, wiping off the water with a waste cloth, and immediately measuring the weight of the sample to determine the weight relative to the initial weight. The rate of change was measured. The number of samples was 3 for each condition, and the weight change rate was the average value.
(評価方法2:EPMA分析)
40℃、10%硫酸水溶液に180日間浸漬した試験サンプルのEPMA(Elect
ron Probe Micro Analyzer)分析により、硫酸の浸透度を測定した。
(Evaluation method 2: EPMA analysis)
EPMA (Electrum) of test sample immersed in 10% sulfuric acid aqueous solution at 40 ° C. for 180 days
The permeability of sulfuric acid was measured by ron Probe Micro Analyzer analysis.
(実施例1)
(1)ビスフェノールA型エポキシ樹脂(旭化成ケミカルズ(株)製 AER250、以下同様)70重量部、メシチレン樹脂(フドー(株)製 NIKANOL Y−51、 以下同様)10重量部、クレジルグリシジルエーテル15重量部、球状シリカ(日本アエロジル(株)製 アエロジル200、以下同様)4重量部、酸化チタン1重量部を混合したものを主剤とした。
(2)ビスフェノールA型エポキシ樹脂20重量部、ジアミノジフェニルメタン60重量
部、フタル酸ジブチル25重量部、フェニルグリシジルエーテル5重量部、サリチル酸5重量部を混合したものを硬化剤とした。
(3)上記組成からなる主剤100重量部と硬化剤50重量部を混合し、防食用エポキシ
樹脂系塗料を製造した。
Example 1
(1) 70 parts by weight of bisphenol A type epoxy resin (AER250 manufactured by Asahi Kasei Chemicals Co., Ltd., the same shall apply hereinafter), 10 parts by weight of mesitylene resin (NIKANOL Y-51 manufactured by Fudou Co., Ltd.), 15 wt% of cresyl glycidyl ether The main component was a mixture of 4 parts by weight of spherical silica (Aerosil 200 manufactured by Nippon Aerosil Co., Ltd., the same applies hereinafter) and 1 part by weight of titanium oxide.
(2) A mixture of 20 parts by weight of bisphenol A type epoxy resin, 60 parts by weight of diaminodiphenylmethane, 25 parts by weight of dibutyl phthalate, 5 parts by weight of phenylglycidyl ether, and 5 parts by weight of salicylic acid was used as a curing agent.
(3) 100 parts by weight of the main agent having the above composition and 50 parts by weight of the curing agent were mixed to produce an anticorrosion epoxy resin coating.
(実施例2)
(1)ビスフェノールA型エポキシ樹脂70重量部、キシレン樹脂(フドー(株)製 NIKANOL−LLL、以下同様)10重量部、クレジルグリシジルエーテル15重量部、球状シリカ4重量部、酸化チタン1重量部を混合したものを主剤とした。
(2)ビスフェノールA型エポキシ樹脂20重量部、ジアミノジフェニルメタン60重量部、フタル酸ジブチル25重量部、フェニルグリシジルエーテル5重量部、サリチル酸5重量部を混合したものを硬化剤とした。
(3)上記組成からなる主剤100重量部と硬化剤50重量部を混合し、防食用エポキシ樹脂系塗料を製造した。
(Example 2)
(1) 70 parts by weight of bisphenol A type epoxy resin, 10 parts by weight of xylene resin (NICANOL-LLL manufactured by Fudo Co., Ltd.), 15 parts by weight of cresyl glycidyl ether, 4 parts by weight of spherical silica, 1 part by weight of titanium oxide The mixture was used as the main agent.
(2) A mixture of 20 parts by weight of a bisphenol A type epoxy resin, 60 parts by weight of diaminodiphenylmethane, 25 parts by weight of dibutyl phthalate, 5 parts by weight of phenylglycidyl ether, and 5 parts by weight of salicylic acid was used as a curing agent.
(3) 100 parts by weight of the main agent having the above composition and 50 parts by weight of the curing agent were mixed to produce an anticorrosion epoxy resin coating.
(比較例1)
(1)ビスフェノールA型エポキシ樹脂70重量部、フェノール変性炭化水素低重合体( 東邦化学工業(株)製 TRE200)10重量部、クレジルグリシジルエーテル15重量部、球状シリカ4重量部、酸化チタン1重量部を混合したものを主剤とした。
(2)ビスフェノールA型エポキシ樹脂20重量部、ジアミノジフェニルメタン60重量
部、フタル酸ジブチル25重量部、フェニルグリシジルエーテル5重量部、サリチル酸5重量部を混合したものを硬化剤とした。
(3)上記組成からなる主剤100重量部と硬化剤50重量部を混合し、防食用エポキシ樹脂系塗料を製造した。
(Comparative Example 1)
(1) 70 parts by weight of bisphenol A type epoxy resin, 10 parts by weight of phenol-modified hydrocarbon low polymer (TRE200 manufactured by Toho Chemical Industry Co., Ltd.), 15 parts by weight of cresyl glycidyl ether, 4 parts by weight of spherical silica, titanium oxide 1 A mixture of parts by weight was used as the main agent.
(2) A mixture of 20 parts by weight of bisphenol A type epoxy resin, 60 parts by weight of diaminodiphenylmethane, 25 parts by weight of dibutyl phthalate, 5 parts by weight of phenylglycidyl ether, and 5 parts by weight of salicylic acid was used as a curing agent.
(3) 100 parts by weight of the main agent having the above composition and 50 parts by weight of the curing agent were mixed to produce an anticorrosion epoxy resin coating.
(比較例2)
(1)ビスフェノールA型エポキシ樹脂70重量部、メシチレン樹脂10重量部、クレジルグリシジルエーテル15重量部、球状シリカ4重量部、酸化チタン1重量部を混合したものを主剤とした。
(2)上記組成からなる主剤100重量部と、マンニッヒ変性メタキシレンジアミン硬化剤(ビィ・ティ・アール・ジャパン(株)製 DS−4)50重量部を混合し、防食用エポキシ樹脂系塗料を製造した。
(Comparative Example 2)
(1) A mixture of 70 parts by weight of bisphenol A type epoxy resin, 10 parts by weight of mesitylene resin, 15 parts by weight of cresyl glycidyl ether, 4 parts by weight of spherical silica, and 1 part by weight of titanium oxide was used as a main agent.
(2) Mixing 100 parts by weight of the main component having the above composition with 50 parts by weight of Mannich-modified metaxylenediamine curing agent (DS-4, manufactured by BRT Japan KK), an epoxy resin coating for anticorrosion Manufactured.
(比較例3)
(1)ビスフェノールA型エポキシ樹脂75重量部、クレジルグリシジルエーテル20重量部、球状シリカ4重量部、酸化チタン1重量部を混合したものを主剤とした。
(2)上記組成からなる主剤100重量部と、変性脂肪族アミン系硬化剤(株式会社ADEKA製 アデカハードナーEH220)50重量部を混合し、防食用エポキシ樹脂系塗料を製造した。
(Comparative Example 3)
(1) A mixture of 75 parts by weight of a bisphenol A type epoxy resin, 20 parts by weight of cresyl glycidyl ether, 4 parts by weight of spherical silica, and 1 part by weight of titanium oxide was used as a main agent.
(2) 100 parts by weight of the main agent having the above composition and 50 parts by weight of a modified aliphatic amine-based curing agent (ADEKA HARDNER EH220 manufactured by ADEKA Co., Ltd.) were mixed to produce an epoxy resin coating for anticorrosion.
重量変化率の測定結果及びEPMA分析の結果を表1〜表4に示す。 The measurement results of the rate of weight change and the results of EPMA analysis are shown in Tables 1 to 4.
表1〜表4の結果から明らかなように、本実施の形態の防食用エポキシ樹脂系塗料(実施例1及び2)は、各浸漬溶液に浸漬した後の重量変化率が小さく、EPMA分析における硫黄侵入深さも小さかった。上記結果から、本実施の形態の防食用エポキシ樹脂系塗料は、防食性(耐薬品性)に極めて優れていることが分かった。
これに対して比較例1の塗料は、(C)メチシレン樹脂及び/又はキシレン樹脂を含有しておらず、比較例2の塗料は、(B)エポキシアダクト変性芳香族アミン系硬化剤を含有していないため、試験サンプルの重量変化率が大きく防食性に劣っていた。特に、比較例3の塗料は、(C)メチシレン樹脂及び/又はキシレン樹脂と、(B)エポキシアダクト変性芳香族アミン系硬化剤を共に含有しておらず、防食性が顕著に劣っていた。
As is clear from the results of Tables 1 to 4, the anticorrosion epoxy resin paints of the present embodiment (Examples 1 and 2) have a small weight change rate after being immersed in each immersion solution, and in EPMA analysis. The sulfur penetration depth was also small. From the above results, it was found that the anticorrosion epoxy resin coating of the present embodiment is extremely excellent in anticorrosion (chemical resistance).
On the other hand, the paint of Comparative Example 1 does not contain (C) a methicylene resin and / or a xylene resin, and the paint of Comparative Example 2 contains (B) an epoxy adduct-modified aromatic amine curing agent. Therefore, the weight change rate of the test sample was large and the corrosion resistance was poor. In particular, the coating material of Comparative Example 3 did not contain both (C) a methicylene resin and / or xylene resin and (B) an epoxy adduct-modified aromatic amine-based curing agent, and the corrosion resistance was significantly inferior.
本発明の防食用エポキシ樹脂形塗料は、極めて優れた防食性を有しており、下水道関連
施設の防食用塗料としての適用は勿論のこと、耐有機酸性が要求されるビルピットの防食
用塗料としての産業上利用可能性を有する。
The epoxy resin-type paint for corrosion prevention of the present invention has extremely excellent anticorrosion properties, and can be used as an anticorrosion paint for sewer related facilities as well as an anticorrosion paint for building pits that require organic acid resistance. Has industrial applicability.
Claims (3)
(B)エポキシアダクト変性芳香族アミン系硬化剤と、
(C)メシチレン樹脂及び/又はキシレン樹脂と、
を含有する防食用エポキシ樹脂系塗料。 (A) an epoxy resin;
(B) an epoxy adduct-modified aromatic amine curing agent;
(C) a mesitylene resin and / or a xylene resin;
Epoxy resin paint for corrosion protection.
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