JP6811958B2 - Manufacturing method of iron rust reduction rust preventive treatment agent - Google Patents
Manufacturing method of iron rust reduction rust preventive treatment agent Download PDFInfo
- Publication number
- JP6811958B2 JP6811958B2 JP2016219206A JP2016219206A JP6811958B2 JP 6811958 B2 JP6811958 B2 JP 6811958B2 JP 2016219206 A JP2016219206 A JP 2016219206A JP 2016219206 A JP2016219206 A JP 2016219206A JP 6811958 B2 JP6811958 B2 JP 6811958B2
- Authority
- JP
- Japan
- Prior art keywords
- rust
- reducing
- iron
- iron rust
- treatment agent
- 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.)
- Active
Links
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title claims description 114
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims description 110
- 229910052742 iron Inorganic materials 0.000 title claims description 54
- 239000003795 chemical substances by application Substances 0.000 title claims description 40
- 230000003449 preventive effect Effects 0.000 title claims description 32
- 238000004519 manufacturing process Methods 0.000 title description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 43
- 230000001603 reducing effect Effects 0.000 claims description 34
- 229910000831 Steel Inorganic materials 0.000 claims description 30
- 239000010959 steel Substances 0.000 claims description 30
- 239000011248 coating agent Substances 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 27
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 17
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 17
- 239000011707 mineral Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 11
- 239000001263 FEMA 3042 Substances 0.000 claims description 11
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 11
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 11
- 229940033123 tannic acid Drugs 0.000 claims description 11
- 235000015523 tannic acid Nutrition 0.000 claims description 11
- 229920002258 tannic acid Polymers 0.000 claims description 11
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- -1 phosphoric acid compound Chemical class 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 description 27
- 239000000463 material Substances 0.000 description 26
- 239000003973 paint Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 9
- 230000002265 prevention Effects 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 7
- 238000010422 painting Methods 0.000 description 7
- 239000004925 Acrylic resin Substances 0.000 description 6
- 229920000178 Acrylic resin Polymers 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920001864 tannin Polymers 0.000 description 2
- 235000018553 tannin Nutrition 0.000 description 2
- 239000001648 tannin Substances 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 235000011511 Diospyros Nutrition 0.000 description 1
- 244000236655 Diospyros kaki Species 0.000 description 1
- 240000007472 Leucaena leucocephala Species 0.000 description 1
- 235000010643 Leucaena leucocephala Nutrition 0.000 description 1
- 235000008577 Pinus radiata Nutrition 0.000 description 1
- 241000218621 Pinus radiata Species 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 1
- HJJOHHHEKFECQI-UHFFFAOYSA-N aluminum;phosphite Chemical compound [Al+3].[O-]P([O-])[O-] HJJOHHHEKFECQI-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910001382 calcium hypophosphite Inorganic materials 0.000 description 1
- 229940064002 calcium hypophosphite Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- LXXDUCAGSSICDI-UHFFFAOYSA-N iron(3+);phosphite Chemical compound [Fe+3].[O-]P([O-])[O-] LXXDUCAGSSICDI-UHFFFAOYSA-N 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- SEQVSYFEKVIYCP-UHFFFAOYSA-L magnesium hypophosphite Chemical compound [Mg+2].[O-]P=O.[O-]P=O SEQVSYFEKVIYCP-UHFFFAOYSA-L 0.000 description 1
- 229910001381 magnesium hypophosphite Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- CNALVHVMBXLLIY-IUCAKERBSA-N tert-butyl n-[(3s,5s)-5-methylpiperidin-3-yl]carbamate Chemical compound C[C@@H]1CNC[C@@H](NC(=O)OC(C)(C)C)C1 CNALVHVMBXLLIY-IUCAKERBSA-N 0.000 description 1
- XWKBMOUUGHARTI-UHFFFAOYSA-N tricalcium;diphosphite Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])[O-].[O-]P([O-])[O-] XWKBMOUUGHARTI-UHFFFAOYSA-N 0.000 description 1
- VMFOHNMEJNFJAE-UHFFFAOYSA-N trimagnesium;diphosphite Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])[O-].[O-]P([O-])[O-] VMFOHNMEJNFJAE-UHFFFAOYSA-N 0.000 description 1
- AUTOISGCBLBLBA-UHFFFAOYSA-N trizinc;diphosphite Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])[O-].[O-]P([O-])[O-] AUTOISGCBLBLBA-UHFFFAOYSA-N 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Landscapes
- Chemical Treatment Of Metals (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Paints Or Removers (AREA)
Description
本発明は、鉄鋼、ステンレスなど鋼鉄製基材のへの塗装に当たっての下地前処理用防錆の前処理に関する技術分野であり、鋼鉄製基材面に発生する鉄錆を下地用塗料によって還元することにより、鉄錆を機械的に除去することなく塗装出来る下地前処理を兼ねた鉄錆還元防錆処理剤に係わるものである。 The present invention is a technical field relating to pretreatment for rust prevention for base pretreatment when coating a steel base material such as steel or stainless steel, and reduces iron rust generated on the surface of the steel base material with a base paint. As a result, it relates to an iron rust reduction rust preventive treatment agent that also serves as a base pretreatment that can be applied without mechanically removing iron rust.
鋼鉄製基材への塗装時には、表面に発生している鉄錆を除去しないと、鋼鉄の酸化進行による鉄錆層の拡大、塗膜の劣化や密着性の低下による塗膜の剥離が生じていた。このため鋼鉄製基材への塗装に当たっては、鋼鉄製基材に発生している鉄錆は、サンドペーパー、ケレン、サンドブラストなどの機械的除去によって基材の前処理が必須であった。この塗装前の基材前処理は多大な労力を要し、この下地前処理の軽減化が強く求められていた。この対策として、これまで下地用塗料にリン酸、リン酸亜鉛等のリン酸化合物に配合することが提案されていたが、鉄錆内部の浸透性、還元力が小さく、塗膜の防錆性、耐久性の性能より満足できるものではなかった。 When painting on a steel base material, if the iron rust generated on the surface is not removed, the iron rust layer will expand due to the progress of oxidation of the steel, and the coating film will peel off due to deterioration of the coating film and deterioration of adhesion. It was. For this reason, when painting a steel base material, iron rust generated on the steel base material requires pretreatment of the base material by mechanical removal of sandpaper, keren, sandblasting, and the like. This base material pretreatment before painting requires a great deal of labor, and there has been a strong demand for reduction of this base material pretreatment. As a countermeasure, it has been proposed to add phosphoric acid compounds such as phosphoric acid and zinc phosphate to the base paint, but the permeability and reducing power inside the iron rust are small, and the rust preventive property of the coating film. , It was not more satisfactory than the durability performance.
本発明は、鋼鉄製基材への塗装時の下地前処理において、従来のような機械的な鉄錆除去作業を行うことなく、鋼鉄製基材に下地塗料を直接塗布することにより塗料中の還元物質が鉄錆中に浸透し、赤色や茶褐色の鉄錆と反応して、黒錆に転換を図る鉄錆還元防錆処理剤に関するものであり、同時に優れた防錆性と耐候性を有する下地塗膜の形成を行うものである。 In the present invention, in the base pretreatment at the time of painting on a steel base material, the base paint is directly applied to the steel base material without performing the conventional mechanical iron rust removing work, so that the base paint is contained in the paint. It is related to an iron rust reduction rust preventive treatment agent in which a reducing substance permeates into iron rust and reacts with red or brown iron rust to convert it to black rust. At the same time, it has excellent rust resistance and weather resistance. It forms a base coating.
本発明の第１発明は、鋼鉄製基材への塗装に当たっての下地前処理剤において、還元性物質として、還元性リン酸系鉱酸を配合し、防錆能力を高めるタンニン酸を配合し、さらに浸透性を高めるために炭素数５以下のアルコール類を配合することを特徴とする鉄錆還元防錆処理剤であり、含有している還元性リン酸系鉱酸、タンニン酸が鉄錆層への浸透性が強く、また鉄錆との還元反応性にも優れている。 In the first invention of the present invention, a reducing phosphate-based mineral acid is blended as a reducing substance, and a tannic acid that enhances rust prevention ability is blended in a base pretreatment agent for coating a steel base material. It is an iron rust reduction rust preventive treatment agent characterized by blending alcohols having 5 or less carbon atoms in order to further enhance the permeability, and the reducing phosphate-based mineral acid and tannic acid contained in the iron rust layer. It has strong permeability to iron and has excellent reduction reactivity with iron rust.
本発明の第２発明は、鋼鉄製基材への塗装における下地前処理剤において、前記の鉄錆還元防錆処理剤の還元性リン酸系鉱酸として、次亜リン酸、亜リン酸の少なくとも１種以上を含むことを特徴とする鉄錆還元防錆処理剤である。還元性リン酸系鉱酸としては、次亜リン酸、亜リン酸が鉄錆に対する還元反応性に優れており、次亜リン酸、亜リン酸の配合が好ましい。 In the second invention of the present invention, in the base pretreatment agent for coating a steel base material, hypophosphoric acid and phosphite are used as the reducing phosphoric acid-based mineral acid of the iron rust reducing rust preventive treatment agent. It is an iron rust reducing rust preventive treatment agent characterized by containing at least one kind. As the reducing phosphoric acid-based mineral acid, hypophosphorous acid and phosphoric acid are excellent in reducing reactivity with iron rust, and the combination of hypophosphorous acid and phosphoric acid is preferable.
本発明の第３発明は、鋼鉄製基材への塗装における下地前処理としての鉄錆還元防錆処理剤は、還元性鉱酸と共に、さらに還元性リン酸化合物（亜鉛・アルミ・カルシウムなどの還元性リン酸との化合物）を追加の配合させることが、塗膜の還元性・耐久性の面からも更に好ましいことを見出した。 In the third invention of the present invention, the iron rust reduction rust preventive treatment agent as a base pretreatment in coating a steel base material is a reducing phosphate compound (zinc, aluminum, calcium, etc.) together with a reducing mineral acid. It has been found that it is more preferable to additionally blend (compound with reducing phosphoric acid) from the viewpoint of reducing property and durability of the coating film.
本発明の鉄錆還元防錆処理剤は、鉄錆を除去する素地調整の前処理作業を行うことなく、鉄錆発生面に塗装が可能であり、また鋼鉄製基材の酸化被膜や錆層への浸透性が高く、錆に還元化と防錆性を発現する。これより塗装作業の大幅な軽減、ならびに塗膜の耐久性が向上することから塗装費用、塗装基材の維持管理費用が大幅に軽減される。 The iron rust reduction rust preventive treatment agent of the present invention can be applied to the surface where iron rust is generated without performing pretreatment work for adjusting the base material for removing iron rust, and the oxide film or rust layer of a steel base material can be applied. It has high permeability to rust and exhibits rust reduction and rust prevention. As a result, the painting work is greatly reduced and the durability of the coating film is improved, so that the painting cost and the maintenance cost of the coating base material are significantly reduced.
本発明において使用する還元性リン酸系鉱酸としては、亜リン酸、次亜リン酸がこのましい。これらの還元性リン酸系の鉱酸は、鉄錆と反応して、酸化鉄を還元し、また鋼鉄製基材とも反応して還元性リン酸鉄を形成して防錆性を発揮する。還元性リン酸系鉱酸の配合割合は、塗料中に０．５〜３０重量％の配合が好ましい。還元性リン酸系鉱酸の配合量が０．５重量％未満では防錆性が低下し、３０重量部を超えると塗膜強度耐水性が低下する。 Phosphorous acid and hypophosphorous acid are preferable as the reducing phosphoric acid-based mineral acid used in the present invention. These reducing phosphate-based mineral acids react with iron rust to reduce iron oxide, and also react with a steel substrate to form reducing iron phosphate to exhibit rust prevention. The blending ratio of the reducing phosphoric acid-based mineral acid is preferably 0.5 to 30% by weight in the coating material. If the blending amount of the reducing phosphoric acid-based mineral acid is less than 0.5% by weight, the rust prevention property is lowered, and if it exceeds 30 parts by weight, the coating film strength and water resistance are lowered.
上記の還元性リン酸系鉱酸と共に、さらにこれらの化合物として、亜リン酸鉄、亜リン酸カルシウム、亜リン酸マグネシウム、亜リン酸アルミニウム、次亜リン酸鉄、次亜リン酸カルシウム、次亜リン酸マグネシウム、次亜リン酸アルミニウムなどを、還元性リン酸系鉱酸と共に配合してもよい。これらの還元性リン酸系鉱酸の化合物を配合すると、鉄錆との還元反応の持続性、塗膜の防錆能力が向上することから、塗料中に０．５〜２０重量％含有させることが好ましい。特に還元性リン酸系鉱酸と亜鉛、アルミ、カルシウムとの化合物が、防食性の面より優れている。 In addition to the above-mentioned reducing phosphate-based mineral acid, as these compounds, iron phosphite, calcium phosphite, magnesium phosphite, aluminum phosphite, iron hypophosphite, calcium hypophosphite, magnesium hypophosphite , Aluminum hypophosphite and the like may be blended together with reducing phosphoric acid-based mineral acid. When these reducing phosphoric acid-based mineral acid compounds are blended, the duration of the reduction reaction with iron rust and the rust preventive ability of the coating film are improved. Therefore, the content should be 0.5 to 20% by weight in the coating material. Is preferable. In particular, the compound of reducing phosphoric acid-based mineral acid and zinc, aluminum, and calcium is superior in terms of corrosion resistance.
本発明の鉄錆還元防錆処理剤において、還元性と防錆性を高めるために使用するタンニン酸としては、柿渋、アカシヤ・マンギウム・ラジアータパインなどの樹皮抽出液などを用いることが出来るが、五倍子から抽出し精製されたものが好ましい。塗料中のタンニン酸分の配合は、１〜２０重量％が好ましい。タンニンの配合量が、１重量％未満では、錆への密着性、防錆性が低下する。２０重量％を超えると耐水性が低下する。 In the iron rust reducing rust preventive treatment agent of the present invention, as the tannic acid used to enhance the reducing property and the rust preventive property, bark extracts such as persimmon astringent, acacia, mangium, and radiata pine can be used. It is preferably extracted and purified from quintuple. The content of tannic acid in the paint is preferably 1 to 20% by weight. If the blending amount of tannin is less than 1% by weight, the adhesion to rust and the rust preventive property are lowered. If it exceeds 20% by weight, the water resistance is lowered.
本発明に於いて使用するアルコール類は、炭素数が５以下の低級アルコールが鉄錆への浸透性の面より好ましい。これに該当するアルコール類はメタノール、エタノール、ｎ−プロパノール、ｉ−プロパノール、ｎ−ブタノール、ｉ−ブタノール、ｎ−ペンタノールなどである。 As the alcohols used in the present invention, lower alcohols having 5 or less carbon atoms are preferable from the viewpoint of permeability to iron rust. The alcohols corresponding to this are methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, n-pentanol and the like.
本発明の鉄錆還元防錆処理剤が水溶性であり、また、危険物第４類（引火性液体）に該当しないようにするため、アルコール類の配合量は、５〜５０重量％の範囲で使用する。鉄錆還元反応性、防錆能力、基材の錆面への浸透性の面よりより特に２０〜５０重量％の配合が好ましい。 In order to prevent the iron rust reduction rust preventive treatment agent of the present invention from being water-soluble and not falling under the category 4 dangerous substance (flammable liquid), the blending amount of alcohols is in the range of 5 to 50% by weight. Used in. In terms of iron rust reduction reactivity, rust preventive ability, and permeability of the base material to the rust surface, a blending of 20 to 50% by weight is particularly preferable.
本発明の鉄錆還元前処理剤においては、防錆性能を相乗的に高める物質として、必要に応じて還元性を有しないリン酸、リン酸化合物を添加しても良い。リン酸化合物としては、鉄、アルミ、亜鉛、カルシウムなどがリン酸塩が防食性の面よりこの好ましい。 In the iron rust reduction pretreatment agent of the present invention, phosphoric acid or a phosphoric acid compound having no reducing property may be added as a substance for synergistically enhancing the rust preventive performance. As the phosphoric acid compound, iron, aluminum, zinc, calcium and the like are preferable, and phosphate is preferable from the viewpoint of corrosion resistance.
本発明の鉄錆還元防錆処理剤は、還元性リン酸系鉱酸、タンニン酸に更にエマルジョン樹脂バインダーを配合して、形成膜の強度や耐久性、耐水性の強化を図ってもよい。 In the iron rust reduction rust preventive treatment agent of the present invention, an emulsion resin binder may be further blended with reducing phosphoric acid-based mineral acid and tannic acid to enhance the strength, durability and water resistance of the formed film.
本発明の鉄錆還元防錆処理剤の製造方法は、各原料を混合機に投入し、混合・分散の処理を行うが、分散機は微粒メディアを使用する湿式分散機で行うことが好ましい。本発明の鉄錆還元防錆処理剤は、酸性物質の添加によりＰＨを３．０〜６．５の弱酸性の範囲に調整される。酸性物質は、リン酸、クエン酸、酒石酸などを使用することが出来る。
本発明の防錆塗前処理剤は、水系塗料なので、錆の発生状態、鋼材の表面状態に応じて適宜に純水・弱酸性水で希釈して濃度調整、粘度調整して塗布することが好ましい。In the method for producing the iron rust reduction rust preventive treatment agent of the present invention, each raw material is put into a mixer and mixed / dispersed, but the disperser is preferably a wet disperser using fine media. The iron rust reduction rust preventive treatment agent of the present invention adjusts the pH to a weakly acidic range of 3.0 to 6.5 by adding an acidic substance. As the acidic substance, phosphoric acid, citric acid, tartaric acid and the like can be used.
Since the rust preventive coating pretreatment agent of the present invention is a water-based paint, it can be appropriately diluted with pure water or weakly acidic water according to the state of rust generation and the surface condition of the steel material to adjust the concentration and viscosity before application. preferable.
本発明の鉄錆還元防錆処理剤の使用方法は、塗装の前処理として塗布対象の鋼鉄基材の表面に対して発生している錆層を除去することなく、鉄錆還元防錆処理剤を塗布することにより、表面の錆や酸化膜を還元し、酸化の進行を防御する防錆皮膜を形成することが出来る。つまり本発明の鉄錆還元防錆処理剤の使用により鋼鉄製基材の錆剥離の前処理（素地整備／ケレン作業）を行うことなく塗装することが出来、基材の錆層を還元し、防錆性、耐候性、密着性が優れた防錆皮膜を形成することが本発明の特徴である。 The method of using the iron rust reduction rust preventive treatment agent of the present invention is to use the iron rust reduction rust preventive treatment agent without removing the rust layer generated on the surface of the steel base material to be coated as a pretreatment for painting. By applying, it is possible to reduce the rust and oxide film on the surface and form a rust preventive film that prevents the progress of oxidation. In other words, by using the iron rust reduction rust preventive treatment agent of the present invention, it is possible to paint without pretreatment (base maintenance / cleaning work) for rust peeling of the steel base material, and the rust layer of the base material is reduced. A feature of the present invention is to form a rust-preventive film having excellent rust-preventive properties, weather resistance, and adhesion.
即ち、還元性リン酸系鉱酸が、塗布対象の鋼鉄製基材に発生している鉄の赤錆（Ｆｅ２Ｏ３）を還元反応によって黒錆（Ｆｅ３Ｏ４）に転換し、また鋼鉄製基材とも反応して防錆能力が高いリン酸鉄を形成し、同時にタンニンが還元された鉄イオンと結合して、高い防錆力と密着性を発揮するものである。That is, the reducing phosphate-based mineral acid converts iron red rust (Fe 2 O 3 ) generated on the steel base material to be coated into black rust (Fe 3 O 4 ) by the reduction reaction, and also steel. It also reacts with the base material to form iron phosphate with high rust-preventive ability, and at the same time, tannin is combined with reduced iron ions to exhibit high rust-preventive power and adhesion.
また、前記の理由より本発明の鉄錆還元反応水系防錆塗料は、錆の発生していない鋼鉄製基材や構築物に対しても、通常の酸化鉄（ベンガラ）系下地塗料に比べて優れた防錆性、防食性を発揮することが出来る。 Further, for the above reason, the iron rust reduction reaction water-based rust preventive paint of the present invention is superior to the usual iron oxide (Bengala) -based base paint even for steel substrates and structures without rust. It can also exhibit rust and corrosion resistance.
以下本発明の実施例と比較例を示す。 Examples and comparative examples of the present invention are shown below.
純水：３０重量部、エチルアルコール：３００重量部、タンニン酸：３００重量部 、次亜リン酸：１００重量部を湿式分散機に加えて混合分散して、実施例１の鉄錆還元防錆処理剤を得た。 Pure water: 30 parts by weight, ethyl alcohol: 300 parts by weight, tannic acid: 300 parts by weight, hypophosphorous acid: 100 parts by weight were added to a wet disperser and mixed and dispersed to reduce iron rust in Example 1. A treatment agent was obtained.
浮き錆のみを除いた鋼板（ケレン未処理品）に対して、実施例１の鉄錆還元防錆処理剤を塗布量：１００ｇ／ｍ２で塗布し、２５℃×１日の乾燥後、防水膜用クリア塗料としてアクリル樹脂エマルジョン（昭和高分子製ＡＰ１３５０）を１５０ｇ／ｍ２の割合で塗布し、２５℃×５日間で静置・乾燥して試験片とした。その後、耐水性は試験片を５０℃の温水中に７日間浸漬し、また、煮沸試験は沸騰水で１時間加熱し、その後、取り出した試験を２５℃×１日間乾燥させた。試験片の塗膜の外観の異常の有無を観察し、また碁盤目テープ剥離試験を実施した。The iron rust reduction rust preventive treatment agent of Example 1 was applied to a steel sheet (untreated product) from which only floating rust was removed at a coating amount of 100 g / m 2 , dried at 25 ° C. for 1 day, and then waterproofed. Acrylic resin emulsion (AP1350 manufactured by Showa Polymer Co., Ltd.) was applied as a clear paint for a film at a ratio of 150 g / m 2 , and allowed to stand and dry at 25 ° C. for 5 days to prepare a test piece. Then, the test piece was immersed in warm water at 50 ° C. for 7 days for water resistance, and the boiling test was heated with boiling water for 1 hour, and then the taken-out test was dried at 25 ° C. for 1 day. The presence or absence of abnormalities in the appearance of the coating film on the test piece was observed, and a grid tape peeling test was conducted.
防錆性についてはこの試験片を５％の食塩水、３５℃中で７２時間噴霧し、錆の発生の有無を観察した。さらに耐候性はサンシャインウエザオメーター試験で１，０００時間後の塗膜状況を観察した。その結果を表１に示す。 For rust prevention, this test piece was sprayed in 5% saline solution at 35 ° C. for 72 hours, and the presence or absence of rust was observed. Furthermore, the weather resistance was observed in the sunshine weather meter test after 1,000 hours. The results are shown in Table 1.
純水：３００重量部、エチルアルコール：３００重量部、タンニン酸：３００重量部、亜リン酸：１００重量部を湿式分散機に加えて混合分散して、実施例２の鉄錆還元防錆処理剤を得た。この実施例２の鉄錆還元防錆処理剤を浮き錆のみを除いた鋼板（ケレン未処理品）に対して、実施例１の鉄錆還元防錆処理剤を塗布量：１００ｇ／ｍ２の割合で塗布し、２５℃×１日の乾燥をした。その後、防水膜用クリア塗料としてアクリル樹脂エマルジョン（昭和高分子製ＡＰ１３５０）を１５０ｇ／ｍ２の割合で塗布し、２５℃×５日間で静置・乾燥して試験片とした。実施例１と同様に塗膜を評価し、測定結果を表１に示す。Pure water: 300 parts by weight, ethyl alcohol: 300 parts by weight, tannic acid: 300 parts by weight, phosphorous acid: 100 parts by weight were added to a wet disperser and mixed and dispersed to reduce iron rust in Example 2. I got the agent. The iron rust reduction rust preventive treatment agent of Example 2 was applied to the steel sheet (untreated product) from which only floating rust was removed, and the iron rust reduction rust prevention treatment agent of Example 1 was applied in an amount of 100 g / m 2 . It was applied at a ratio and dried at 25 ° C. for 1 day. Then, an acrylic resin emulsion (AP1350 manufactured by Showa Polymer Co., Ltd.) was applied as a clear paint for a waterproof film at a ratio of 150 g / m 2 , and allowed to stand and dry at 25 ° C. for 5 days to prepare a test piece. The coating film was evaluated in the same manner as in Example 1, and the measurement results are shown in Table 1.
純水：３００重量部、エチルアルコール：３００重量部、タンニン酸：３００重量部、亜リン酸：５０重量部、亜リン酸亜鉛：５０重量部を湿式分散機に加えて混合分散して、実施例３の鉄錆還元防錆処理剤を得た。この実施例３の鉄錆還元防錆処理剤を浮き錆のみを除いた鋼板（ケレン未処理品）に対して、実施例１の鉄錆還元防錆処理剤を塗布量：１００ｇ／ｍ２の割合で塗布し、２５℃×１日の乾燥をした。その後、防水膜用クリア塗料としてアクリル樹脂エマルジョン（昭和高分子製ＡＰ１３５０）を１５０ｇ／ｍ２の割合で塗布し、２５℃×５日間で静置・乾燥して試験片とした。実施例１と同様に塗膜を評価し、測定結果を表１に示す。Pure water: 300 parts by weight, ethyl alcohol: 300 parts by weight, tannic acid: 300 parts by weight, phosphorous acid: 50 parts by weight, zinc phosphite: 50 parts by weight were added to a wet disperser and mixed and dispersed. The iron rust reduction rust preventive treatment agent of Example 3 was obtained. The iron rust reduction rust preventive treatment agent of Example 3 was applied to the steel sheet (untreated product) from which only floating rust was removed, and the iron rust reduction rust prevention treatment agent of Example 1 was applied in an amount of 100 g / m 2 . It was applied at a ratio and dried at 25 ° C. for 1 day. Then, an acrylic resin emulsion (AP1350 manufactured by Showa Polymer Co., Ltd.) was applied as a clear paint for a waterproof film at a ratio of 150 g / m 2 , and allowed to stand and dry at 25 ° C. for 5 days to prepare a test piece. The coating film was evaluated in the same manner as in Example 1, and the measurement results are shown in Table 1.
鉄錆還元防錆処理剤で前処理することなく、対象の鋼板（ケレン未処理品）に対して、防水膜用クリア塗料としてアクリル樹脂エマルジョン（昭和高分子製ＡＰ１３５０）：１５０ｇ／ｍ２の割合で塗布し、２５℃×５日間で静置・乾燥して試験片とした。実施例１と同様に塗膜を評価し、測定結果を表１に示す。Acrylic resin emulsion (AP1350 made by Showa Polymer Co., Ltd.): 150 g / m 2 as a clear paint for waterproof film to the target steel sheet (untreated product) without pretreatment with iron rust reduction rust preventive agent. Was applied, and allowed to stand and dry at 25 ° C. for 5 days to prepare a test piece. The coating film was evaluated in the same manner as in Example 1, and the measurement results are shown in Table 1.
純水：７００重量部、タンニン酸：３００重量部を湿式分散機に加えて混合分散して、比較例２の前処理剤を得た。この実施例２の前処理剤を浮き錆のみを除いた鋼板（ケレン未処理品）に対して、比較例２の前処理剤を塗布量：１００ｇ／ｍ２の割合で塗布し、２５℃×１日の乾燥をした。その後、防水膜用クリア塗料としてアクリル樹脂エマルジョン（昭和高分子製ＡＰ１３５０）を１５０ｇ／ｍ２の割合で塗布し、２５℃×５日間で静置・乾燥して試験片とした。実施例１と同様に塗膜を評価し、測定結果を表１に示す。Pure water: 700 parts by weight and tannic acid: 300 parts by weight were added to a wet disperser and mixed and dispersed to obtain a pretreatment agent of Comparative Example 2. The pretreatment agent of Comparative Example 2 was applied to a steel sheet (untreated product with rust) from which only floating rust was removed, and the pretreatment agent of Comparative Example 2 was applied at a coating amount of 100 g / m 2 to 25 ° C. × It was dried for one day. Then, an acrylic resin emulsion (AP1350 manufactured by Showa Polymer Co., Ltd.) was applied as a clear paint for a waterproof film at a ratio of 150 g / m 2 , and allowed to stand and dry at 25 ° C. for 5 days to prepare a test piece. The coating film was evaluated in the same manner as in Example 1, and the measurement results are shown in Table 1.
純水：６００重量部、タンニン酸：３００重量部、還元性リン酸の代わりに通常のリン酸１００重量部を湿式分散機に加えて混合分散して、比較例３の前処理剤を得た。浮き錆のみを除いた鋼板（ケレン未処理品）に対して、この比較例３の前処理剤を鋼板基材の表面に塗布量：１００ｇ／ｍ２の割合で塗布し、２５℃×１日の乾燥をした。その後、防水膜用クリア塗料としてアクリル樹脂エマルジョン（昭和高分子製ＡＰ１３５０）を１５０ｇ／ｍ２の割合で塗布し、２５℃×５日間で静置・乾燥して試験片とした。実施例１と同様に塗膜を評価し、測定結果を表１に示す。Pure water: 600 parts by weight, tannic acid: 300 parts by weight, and 100 parts by weight of ordinary phosphoric acid instead of reducing phosphoric acid were added to a wet disperser and mixed and dispersed to obtain a pretreatment agent of Comparative Example 3. .. The pretreatment agent of Comparative Example 3 was applied to the surface of the steel sheet base material at a ratio of 100 g / m 2 to the steel sheet (untreated product) from which only floating rust was removed, and 25 ° C. × 1 day. Was dried. Then, an acrylic resin emulsion (AP1350 manufactured by Showa Polymer Co., Ltd.) was applied as a clear paint for a waterproof film at a ratio of 150 g / m 2 , and allowed to stand and dry at 25 ° C. for 5 days to prepare a test piece. The coating film was evaluated in the same manner as in Example 1, and the measurement results are shown in Table 1.
Claims (3)
前記アルコールが、メタノール、エタノール、イソプロパノール、および、ノルマルプロパノールの内、少なくとも１種であることを特徴とする鉄錆還元防錆処理剤。 In the iron rust pretreatment agent for coating steel substrates, reducing phosphoric acid-based mineral acid and tannic acid, which are reducing substances of iron rust, and 5% to 50% by weight of alcohol are blended.
An iron rust reduction rust preventive treatment agent, wherein the alcohol is at least one of methanol, ethanol, isopropanol, and normal propanol.
前記還元性リン酸化合物が、アルミニウム、亜鉛、および、カルシウムの内の１種以上であることを特徴とする請求項１又は２に記載の鉄錆還元防錆処理剤。 A reducing phosphoric acid compound is further blended in the base pretreatment agent for coating a steel substrate.
The reducing phosphate compound, aluminum, zinc, and iron rust reducing anticorrosive treatment agent according to claim 1 or 2, characterized in that at least one of calcium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016219206A JP6811958B2 (en) | 2016-10-19 | 2016-10-19 | Manufacturing method of iron rust reduction rust preventive treatment agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016219206A JP6811958B2 (en) | 2016-10-19 | 2016-10-19 | Manufacturing method of iron rust reduction rust preventive treatment agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2018066055A JP2018066055A (en) | 2018-04-26 |
| JP6811958B2 true JP6811958B2 (en) | 2021-01-13 |
Family
ID=62085731
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2016219206A Active JP6811958B2 (en) | 2016-10-19 | 2016-10-19 | Manufacturing method of iron rust reduction rust preventive treatment agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6811958B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7179298B2 (en) * | 2019-11-11 | 2022-11-29 | 株式会社サンエイジ | Antirust treatment of internal steel material of concrete structure and manufacturing method of treatment agent for preventing deterioration of concrete, and method of rust prevention treatment of steel material and deterioration prevention treatment of concrete |
| JP2023060793A (en) * | 2021-10-18 | 2023-04-28 | 株式会社サンエイジ | Method for producing iron rust-reducing rustproofing agent |
| CN114540805A (en) * | 2022-01-21 | 2022-05-27 | 山东鑫泰水处理技术股份有限公司 | One-step treatment method for rust dissolving, rust preventing and blackening of steel |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5231933A (en) * | 1975-09-08 | 1977-03-10 | Sanai Sekiyu Kk | Agents for forming rusttproofing coating on metal by rust inversion |
| JPS539239A (en) * | 1976-07-14 | 1978-01-27 | Kansai Paint Co Ltd | Preetreating agents for rusttproof coating |
| JP2000136325A (en) * | 1998-11-02 | 2000-05-16 | Shiga Yoko | Rust-inhibiting coating material and rust-inhibiting surfacer |
| JP2011168757A (en) * | 2010-02-18 | 2011-09-01 | Saneiji:Kk | Method for producing iron rust-reducing water-based rustproofing coating |
-
2016
- 2016-10-19 JP JP2016219206A patent/JP6811958B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2018066055A (en) | 2018-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6811958B2 (en) | Manufacturing method of iron rust reduction rust preventive treatment agent | |
| CN103897564B (en) | A kind of glass paint | |
| KR101986487B1 (en) | Coating and coated steel | |
| NZ610568A (en) | Coating compositions with anticorrosion properties | |
| JP2017137499A (en) | Coating composition having corrosion resistance | |
| CN106867321B (en) | A kind of low VOC total solids part cavity flooding Wax composition | |
| CN104341924A (en) | Water-based antirust and rust removing asphalt ship bottom coating and preparation method for same | |
| GB2048961A (en) | Protective compositions for steel surfaces | |
| JP2011168757A (en) | Method for producing iron rust-reducing water-based rustproofing coating | |
| DE3116736A1 (en) | DURABLE LATEXROST CONVERTER PRIMER | |
| JP6587775B2 (en) | Paint and coated steel | |
| KR102415929B1 (en) | Eco-friendly epoxy water-soluble paint composition for steel bridge protection coating and coating method for using the same | |
| JP4455712B2 (en) | Coated steel with atmospheric corrosion resistance | |
| JP4937960B2 (en) | Weatherproof steel | |
| RU2441044C1 (en) | Protective nano-inhibited lacquer | |
| CN102372983A (en) | Epoxy phenolic resin antirust paint | |
| KR20130044400A (en) | Surface treatment method for rust of steel | |
| KR20130048554A (en) | Coating composition for zinc plating materails | |
| DE102013215441A1 (en) | Metal pretreatment compositions comprising silanes and organophosphonic acids | |
| WO2023067821A1 (en) | Method for producing iron rust-reducing rustproofing agent | |
| RU2430130C2 (en) | Priming composition for protecting metal surfaces from corrosion | |
| KR20210046962A (en) | A Study on the Formation of Anti-corrosion Agent for Zinc Plated Steel Plates | |
| CN102851658A (en) | Steel/cast iron metal protective agent and preparation method thereof | |
| JPS5817833B2 (en) | Surface treatment method for weathering steel | |
| KR101044370B1 (en) | A resin composition for antirusting of steel pipe and an antirusting method of steel pipe using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170119 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20190314 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20190314 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20190411 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20200217 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20200303 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20200501 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200619 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20200728 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200917 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20201110 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20201208 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6811958 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |