JP2016164237A - Friction reducing agent, coating material containing the same, and friction reducing method using the same - Google Patents
Friction reducing agent, coating material containing the same, and friction reducing method using the same Download PDFInfo
- Publication number
- JP2016164237A JP2016164237A JP2015045139A JP2015045139A JP2016164237A JP 2016164237 A JP2016164237 A JP 2016164237A JP 2015045139 A JP2015045139 A JP 2015045139A JP 2015045139 A JP2015045139 A JP 2015045139A JP 2016164237 A JP2016164237 A JP 2016164237A
- Authority
- JP
- Japan
- Prior art keywords
- friction reducing
- group
- reducing agent
- water
- polymer compound
- 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
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 36
- 230000001603 reducing effect Effects 0.000 title claims abstract description 19
- 239000011248 coating agent Substances 0.000 title claims abstract description 15
- 238000000576 coating method Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 8
- 239000000463 material Substances 0.000 title claims abstract 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 37
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 19
- 150000001450 anions Chemical class 0.000 claims abstract description 11
- 150000003863 ammonium salts Chemical group 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 125000000732 arylene group Chemical group 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 239000003973 paint Substances 0.000 claims description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 239000007788 liquid Substances 0.000 abstract description 17
- 239000007864 aqueous solution Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 7
- -1 heptylene group Chemical group 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000013535 sea water Substances 0.000 description 6
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 0 CCC(CC1C)N=C1NC* Chemical compound CCC(CC1C)N=C1NC* 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920001218 Pullulan Polymers 0.000 description 1
- 239000004373 Pullulan Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001409 amidines Chemical group 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl 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])* 0.000 description 1
- 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 1
- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004957 naphthylene group Chemical group 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
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T70/00—Maritime or waterways transport
- Y02T70/10—Measures concerning design or construction of watercraft hulls
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、摩擦低減剤、摩擦低減剤を含有する塗料、および摩擦低減剤を用いた摩擦低減方法に関する。 The present invention relates to a friction reducing agent, a paint containing the friction reducing agent, and a friction reducing method using the friction reducing agent.
船舶は、航行中に海水からの摩擦抵抗を受ける。また、プラント等の配管において、配管を流れる液体は、配管の内壁からの摩擦抵抗を受ける。一方、液体に少量の高分子化合物を添加すると、液体と固体との間で生じる摩擦抵抗が著しく低下する現象として、トムズ効果が知られている。
そこで、船舶が海水から受ける摩擦抵抗を低減するために、トムズ効果を利用した塗料を船底の表面に塗装することが検討されている。トムズ効果を有する高分子化合物としては、たとえばポリエチレンオキシド等の水溶性高分子化合物が知られており、特許文献１〜３には、ポリエチレンオキシド等の水溶性高分子化合物を塗料に配合する技術が開示されている。また、特許文献４には、特定のアルカリ可溶性樹脂を用いた塗料が記載されている。
Ships receive frictional resistance from seawater during navigation. Moreover, in piping of plants and the like, the liquid flowing through the piping receives frictional resistance from the inner wall of the piping. On the other hand, when a small amount of a polymer compound is added to a liquid, the Toms effect is known as a phenomenon in which the frictional resistance generated between the liquid and the solid is remarkably reduced.
Then, in order to reduce the frictional resistance which a ship receives from seawater, it is examined to paint the surface of a ship bottom using the Toms effect. For example, water-soluble polymer compounds such as polyethylene oxide are known as polymer compounds having the Toms effect, and Patent Documents 1 to 3 disclose a technique for blending a water-soluble polymer compound such as polyethylene oxide into a paint. It is disclosed. Patent Document 4 describes a paint using a specific alkali-soluble resin.
しかしながら、本発明者らの検討により、上記特許文献に記載の高分子化合物は、摩擦低減効果が充分ではないことが判明した。
本発明の目的は、水、海水、各種水溶液等の水性の液体の摩擦抵抗を大きく低減させることのできる摩擦低減剤、摩擦低減剤を含有する塗料、および摩擦低減剤を用いた摩擦低減方法を提供することである。
However, as a result of studies by the present inventors, it has been found that the polymer compound described in the above-mentioned patent document does not have a sufficient friction reducing effect.
An object of the present invention is to provide a friction reducing agent capable of greatly reducing the frictional resistance of an aqueous liquid such as water, seawater, and various aqueous solutions, a paint containing the friction reducing agent, and a friction reducing method using the friction reducing agent. Is to provide.
本発明は、以下の態様を有する。
［１］側鎖にアンモニウム塩構造を有する水溶性高分子化合物からなる、摩擦低減剤。
［２］前記水溶性高分子化合物は、下記一般式（１）または（２）で表される繰り返し単位を有する、［１］の摩擦低減剤。
［３］［１］または［２］の摩擦低減剤を含有する塗料。
［４］船底塗料である、［３］の塗料。
［５］［１］または［２］の摩擦低減剤を用いた摩擦低減方法。
The present invention has the following aspects.
[1] A friction reducing agent comprising a water-soluble polymer compound having an ammonium salt structure in the side chain.
[2] The friction reducing agent according to [1], wherein the water-soluble polymer compound has a repeating unit represented by the following general formula (1) or (2).
[3] A paint containing the friction reducing agent according to [1] or [2].
[4] The paint according to [3], which is a ship bottom paint.
[5] A friction reducing method using the friction reducing agent according to [1] or [2].
本発明によれば、水、海水、各種水溶液等の水性の液体の摩擦抵抗を大きく低減させることのできる摩擦低減剤、摩擦低減剤を含有する塗料、および摩擦低減剤を用いた摩擦低減方法を提供できる。 According to the present invention, a friction reducing agent capable of greatly reducing the frictional resistance of an aqueous liquid such as water, seawater, various aqueous solutions, a paint containing the friction reducing agent, and a friction reducing method using the friction reducing agent. Can be provided.
以下、本発明を詳細に説明する。
本発明の摩擦低減剤は、水、海水、各種水溶液等の水性の液体と固体表面との間に生じる摩擦抵抗を低減するために使用されるものであって、側鎖にアンモニウム塩構造を有する水溶性高分子化合物からなる。該摩擦低減剤を用いることによって、液体の流れを乱流から層流に変換でき、これにより摩擦抵抗を大きく低減できる。
本発明の摩擦低減剤は、たとえば、船体の船底の表面、プラント等の配管の内壁の表面等、水性の液体と接する固体の表面を塗装するための塗料に添加される態様等で使用される。
Hereinafter, the present invention will be described in detail.
The friction reducing agent of the present invention is used for reducing frictional resistance generated between an aqueous liquid such as water, seawater, various aqueous solutions and the solid surface, and has an ammonium salt structure in a side chain. It consists of a water soluble polymer compound. By using the friction reducing agent, the liquid flow can be converted from a turbulent flow to a laminar flow, thereby greatly reducing the frictional resistance.
The friction reducing agent of the present invention is used in a mode where it is added to a paint for coating a solid surface in contact with an aqueous liquid, such as the surface of the bottom of a hull, the surface of an inner wall of a pipe of a plant, etc. .
側鎖にアンモニウム塩構造を有する水溶性高分子化合物としては、たとえば、下記一般式（１）または（２）で表される繰り返し単位を有する化合物が挙げられる。 Examples of the water-soluble polymer compound having an ammonium salt structure in the side chain include compounds having a repeating unit represented by the following general formula (1) or (2).
式（１）中のＲ１は水素原子またはメチル基であり、Ａは酸素原子またはＮＨ基（−ＮＨ−）を示す。
Ｒ２は、アルキレン基またはアリーレン基である。アルキレン基の炭素数は１〜１０が好ましく、たとえば、メチレン基、エチレン基、プロピレン基、ブチレン基、ヘキシレン基、ヘプチレン基、オクチレン基、ノニレン基、デシレン基等が挙げられ、これらは直鎖状でも分岐状でもよい。アリーレン基としては、フェニレン基、ナフチレン基、ベンジレン基等が挙げられ、これらは置換基を有していてもよい。
Ｒ３〜Ｒ５は、それぞれ独立してアルキル基またはアリール基である。アルキル基の炭素数は１〜２０が好ましく、たとえば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔ−ブチル基、ｎ−ペンチル基、シクロペンチル基、ネオペンチル基、１−メチルブチル基、２−メチルブチル基、３−メチルブチル基、１，２−ジメチルプロピル基、ｎ−ヘキシル基、シクロヘキシル基、へプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基等が挙げられる。アリール基としては、たとえば、フェニル基、ナフチル基、ベンジル基等が挙げられ、これらは置換基を有していてもよい。Ｒ３〜Ｒ５は互いに同一でも異なっていてもよい。また、Ｒ３〜Ｒ５は、Ｒ３〜Ｒ５のうちの２つで、１つの環構造を形成していてもよい。
式（１）および（２）中のＸ１ −およびＸ２ −は、それぞれ１価の陰イオンを示す。１価の陰イオンとしては、Ｆ−、Ｃｌ−、Ｂｒ−、Ｉ−等のハロゲン化物イオン、Ｃ２Ｈ５ＯＳＯ３ −、ＣＨ３ＯＳＯ３ −、ＣｌＯ−等が挙げられる。なかでも、合成の容易さの点から、Ｃｌ−が好ましい。
R 1 in the formula (1) is a hydrogen atom or a methyl group, and A represents an oxygen atom or an NH group (—NH—).
R 2 is an alkylene group or an arylene group. The alkylene group preferably has 1 to 10 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, and a decylene group. However, it may be branched. Examples of the arylene group include a phenylene group, a naphthylene group, and a benzylene group, and these may have a substituent.
R 3 to R 5 are each independently an alkyl group or an aryl group. The alkyl group preferably has 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, cyclopentyl, neopentyl. Group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,2-dimethylpropyl group, n-hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group Group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group and the like. As an aryl group, a phenyl group, a naphthyl group, a benzyl group etc. are mentioned, for example, These may have a substituent. R 3 to R 5 may be the same as or different from each other. Moreover, R < 3 > -R < 5 > may form one ring structure with two of R < 3 > -R < 5 >.
X 1 − and X 2 − in the formulas (1) and (2) each represent a monovalent anion. Examples of the monovalent anion include halide ions such as F − , Cl − , Br − and I − , C 2 H 5 OSO 3 − , CH 3 OSO 3 − and ClO − . Of these, Cl − is preferable from the viewpoint of ease of synthesis.
水溶性高分子化合物の質量平均分子量は、１，０００，０００〜２０，０００，０００が好ましく、１，５００，０００〜１０，０００，０００がより好ましく、２，０００，０００〜４，０００，０００が特に好ましい。質量平均分子量が上記範囲の下限値以上であれば、水性の液体の摩擦を低減する効果が充分に得られる。質量平均分子量が上記範囲の上限値以下であれば、水への溶解性を確保できる。
なお、本明細書において、質量平均分子量は、ゲル浸透クロマトグラフィーにより測定されるプルラン（多糖類）換算の値である。
The mass average molecular weight of the water-soluble polymer compound is preferably 1,000,000 to 20,000,000, more preferably 1,500,000 to 10,000,000, and 2,000,000 to 4,000,000. 000 is particularly preferred. If the mass average molecular weight is at least the lower limit of the above range, the effect of reducing the friction of the aqueous liquid can be sufficiently obtained. If the mass average molecular weight is not more than the upper limit of the above range, solubility in water can be ensured.
In the present specification, the mass average molecular weight is a value in terms of pullulan (polysaccharide) measured by gel permeation chromatography.
式（１）および（２）で表される水溶性高分子化合物のなかでも、水性の液体の摩擦を低減する効果に特に優れることから、下記の一般式（１ａ）および（２ａ）で表される繰り返し単位を有する水溶性高分子化合物が好ましい。 Among the water-soluble polymer compounds represented by the formulas (1) and (2), since they are particularly excellent in the effect of reducing the friction of an aqueous liquid, they are represented by the following general formulas (1a) and (2a). A water-soluble polymer compound having a repeating unit is preferred.
一般式（１ａ）で表される繰り返し単位を有する水溶性高分子化合物（以下、化合物（１ａ）ともいう。）は、Ｎ，Ｎ−ジメチルアミノエチルメタクリレートベンジル４級アンモニウムクロライド（以下、モノマー（１ａ）ともいう。）を重合することにより得られる。
重合には、モノマー（１ａ）と共重合可能な、その他のモノマー（たとえば、（メタ）アクリルアミド、（メタ）アクリルアミドのＮ置換誘導体、（メタ）アクリロニトリル、（メタ）アクリル酸等の１種以上。）を必要に応じて使用してもよい。化合物（１ａ）としては、Ｎ，Ｎ−ジメチルアミノエチルメタクリレートベンジル４級アンモニウムクロライドのホモポリマー（以下、化合物（１ａ−１）ともいう。）が挙げられる。
A water-soluble polymer compound having a repeating unit represented by the general formula (1a) (hereinafter also referred to as compound (1a)) is N, N-dimethylaminoethyl methacrylate benzyl quaternary ammonium chloride (hereinafter referred to as monomer (1a). It is also obtained by polymerizing.
For the polymerization, one or more other monomers (for example, (meth) acrylamide, N-substituted derivatives of (meth) acrylamide, (meth) acrylonitrile, (meth) acrylic acid, etc.) that can be copolymerized with the monomer (1a). ) May be used as needed. Examples of the compound (1a) include a homopolymer of N, N-dimethylaminoethyl methacrylate benzyl quaternary ammonium chloride (hereinafter also referred to as compound (1a-1)).
重合は、たとえば、特開昭５９−１３５２１２号公報、特開昭６１−２１３２２４号公報等を参照して行える。 Polymerization can be carried out with reference to, for example, JP-A-59-135212 and JP-A-61-221324.
一般式（２ａ）で表される繰り返し単位を有する水溶性高分子化合物（以下、化合物（２ａ）ともいう。）は、たとえば、Ｎ−ビニルホルムアミドとアクリロニトリルとを共重合させる工程と、得られた共重合体に対して塩酸を加えて加熱し、アンモニウム塩構造を有するアミジン環（５員環）を形成する工程とを有する方法により得られる。重合時のＮ−ビニルホルムアミドとアクリロニトリルとのモル比は、Ｎ−ビニルホルムアミド：アクリロニトリル＝２０：８０〜８０：２０が好ましく、４０：６０〜６０：４０が特に好ましい。
重合には、Ｎ−ビニルホルムアミドおよびアクリロニトリルと共重合可能な、その他のモノマー（たとえば、（メタ）アクリルアミド、（メタ）アクリルアミドのＮ置換誘導体、（メタ）アクリロニトリル、（メタ）アクリル酸等の１種以上。）を必要に応じて使用してもよい。化合物（２ａ）としては、Ｎ−ビニルホルムアミドとアクリロニトリルの２元共重合体（以下、化合物（２ａ−１）ともいう。）またはその誘導体が挙げられる。
A water-soluble polymer compound having a repeating unit represented by the general formula (2a) (hereinafter also referred to as compound (2a)) was obtained by, for example, copolymerizing N-vinylformamide and acrylonitrile. And adding a hydrochloric acid to the copolymer and heating to form an amidine ring (5-membered ring) having an ammonium salt structure. The molar ratio of N-vinylformamide and acrylonitrile during polymerization is preferably N-vinylformamide: acrylonitrile = 20: 80 to 80:20, particularly preferably 40:60 to 60:40.
For polymerization, other monomers that can be copolymerized with N-vinylformamide and acrylonitrile (for example, (meth) acrylamide, N-substituted derivatives of (meth) acrylamide, (meth) acrylonitrile, (meth) acrylic acid, etc.) The above may be used as necessary. Examples of the compound (2a) include a binary copolymer of N-vinylformamide and acrylonitrile (hereinafter also referred to as compound (2a-1)) or a derivative thereof.
重合は、たとえば特開平６−２８７２３２号公報、特開平０９−０８７３２３号公報、特開平５−１９２５１３号公報等を参照して行える。 The polymerization can be carried out with reference to, for example, JP-A-6-287232, JP-A-09-087323, JP-A-5-192513.
側鎖にアンモニウム塩構造を有する水溶性高分子化合物からなる摩擦低減剤は、たとえば、船体の船底の表面、プラント等の配管の内壁の表面等の固体表面を塗装するための塗料に添加される態様等で使用される。摩擦低減剤は、塗料で形成された塗膜から水性の液体中に徐々に溶出する。これにより、長期にわたって、摩擦低減効果を奏する。
摩擦低減剤は、塗料の固形分を１００質量％とした場合、１．０〜１０質量％の範囲で添加することが好ましい。
A friction reducing agent comprising a water-soluble polymer compound having an ammonium salt structure in the side chain is added to a paint for coating a solid surface such as the surface of the bottom of a hull or the inner wall of a pipe of a plant, for example. Used in embodiments and the like. The friction reducing agent gradually dissolves into the aqueous liquid from the coating film formed of the paint. Thereby, there exists a friction reduction effect over a long period of time.
The friction reducing agent is preferably added in the range of 1.0 to 10% by mass when the solid content of the coating is 100% by mass.
本発明の塗料は、側鎖にアンモニウム塩構造を有する水溶性高分子化合物の他、水に溶解しない有機高分子化合物を含み、必要に応じて、着色剤、充填剤、溶剤等の通常の塗料配合成分を含有できる。
有機高分子化合物としては、摩擦低減剤と相溶性を有し、かつ、塗膜形成能を有する化合物が好ましく、たとえば、アクリル樹脂、エポキシ樹脂、ウレタン樹脂等が挙げられる。このような有機高分子化合物を使用することにより、塗膜に機械的強度を付与できるとともに、塗膜からの摩擦低減剤の溶出速度を調整できる。
The paint of the present invention contains an organic polymer compound that does not dissolve in water in addition to a water-soluble polymer compound having an ammonium salt structure in the side chain, and if necessary, a normal paint such as a colorant, filler, solvent, etc. A compounding component can be contained.
As the organic polymer compound, a compound having compatibility with a friction reducing agent and having a coating film-forming ability is preferable, and examples thereof include an acrylic resin, an epoxy resin, and a urethane resin. By using such an organic polymer compound, mechanical strength can be imparted to the coating film, and the elution rate of the friction reducing agent from the coating film can be adjusted.
溶剤としては、水、アセトン等のケトン系溶剤、酢酸エチル等のエステル系溶剤、テトラヒドロフラン等のエーテル系溶剤、トルエン等の芳香族系溶剤が挙げられ、塗料の粘度調整の目的で使用される。溶剤の大部分は、塗膜を乾燥させる過程で塗膜から除去される。 Examples of the solvent include water, ketone solvents such as acetone, ester solvents such as ethyl acetate, ether solvents such as tetrahydrofuran, and aromatic solvents such as toluene, which are used for the purpose of adjusting the viscosity of the paint. Most of the solvent is removed from the coating film in the course of drying the coating film.
なお、本発明の塗料を塗装する固体の表面には、あらかじめ下地塗膜を形成しておいてもよい。下地塗膜を形成するための塗料としては、たとえばアクリル系塗料、エポキシ系塗料、ウレタン系塗料等が挙げられる。 An undercoating film may be formed in advance on the solid surface to which the paint of the present invention is applied. Examples of the paint for forming the base coating film include acrylic paints, epoxy paints, urethane paints, and the like.
以上説明したように、側鎖にアンモニウム塩構造を有する水溶性高分子化合物からなる本発明の摩擦低減剤は、摩擦低減効果に優れる。そのため、本発明の摩擦低減剤は、たとえば、船体の船底の表面、プラント等の配管の内壁の表面等、水性の液体と接する固体の表面を塗装するための塗料に添加される。本発明の摩擦低減剤は、特に、船底塗料への添加に適している。 As described above, the friction reducing agent of the present invention comprising a water-soluble polymer compound having an ammonium salt structure in the side chain is excellent in the friction reducing effect. Therefore, the friction reducing agent of the present invention is added to a paint for coating a solid surface that comes into contact with an aqueous liquid, such as the surface of the bottom of a hull or the surface of an inner wall of a pipe of a plant or the like. The friction reducing agent of the present invention is particularly suitable for addition to ship bottom paints.
以下、実施例により本発明を具体的に説明する。
［実施例１］
質量平均分子量が３，０００，０００の上記化合物（１ａ−１）を１００ｐｐｍの濃度で含む水溶液（１）を調製した。また、あらかじめ、水溶液（１）の粘度（２５℃）をＢ型粘度計で測定するとともに、容量５０ｍＬのメスフラスコに秤量した水溶液（１）の質量を測定し、水溶液（１）の密度を算出しておいた。
一方、同軸二重円筒装置の内円筒に水溶液（１）を入れ、内円筒をモータで回転させ、内円筒にかかるトルク値をトルク計で計測した。なお、内円筒の回転速度は、３００〜１０００ｒｐｍの範囲内で１００ｒｐｍ刻みで変更し、それぞれの回転速度でのトルク値を測定した。
下記の数式に基づき、測定したトルク値Ｔ［Ｎｍ］の無次元化を行い、無次元化トルクＧを算出した。そして、水の無次元化トルクＧｗとの比較により、抵抗低減率（ＤＲ値，％）を算出した。レイノルズ数は以下のように定義した。
Hereinafter, the present invention will be described specifically by way of examples.
[Example 1]
An aqueous solution (1) containing the above compound (1a-1) having a mass average molecular weight of 3,000,000 at a concentration of 100 ppm was prepared. In addition, the viscosity (25 ° C.) of the aqueous solution (1) is measured with a B-type viscometer in advance, and the mass of the aqueous solution (1) weighed in a 50 mL volumetric flask is measured to calculate the density of the aqueous solution (1). I kept it.
On the other hand, the aqueous solution (1) was put into the inner cylinder of the coaxial double cylinder device, the inner cylinder was rotated with a motor, and the torque value applied to the inner cylinder was measured with a torque meter. The rotational speed of the inner cylinder was changed in increments of 100 rpm within a range of 300 to 1000 rpm, and the torque value at each rotational speed was measured.
Based on the following mathematical formula, the measured torque value T [Nm] was dimensionless, and the dimensionless torque G was calculated. Then, by comparing the dimensionless torque G w of water, it was calculated drag reduction ratio (DR value,%). The Reynolds number was defined as follows.
各記号は以下の意味を示す。
Ｒｅ：レイノルズ数［−］
ｒｉ：内円筒半径［ｍ］
ｒ０：外円筒半径［ｍ］
ω：角速度［ｒａｄ／ｓ］
ν：動粘度［ｍ２／ｓ］
ρ：水溶液（１）の密度［ｋｇ／ｍ３］
Ｌ：内円筒の高さ［ｍ］
Each symbol has the following meaning.
Re: Reynolds number [-]
r i : inner cylinder radius [m]
r 0 : outer cylinder radius [m]
ω: angular velocity [rad / s]
ν: Kinematic viscosity [m 2 / s]
ρ: density of aqueous solution (1) [kg / m 3 ]
L: Height of inner cylinder [m]
［実施例２］
質量平均分子量が３，０００，０００の上記化合物（２ａ−１）を１００ｐｐｍの濃度で含む水溶液（２）を調製した。該水溶液（２）を用いた以外は実施例１と同様の方法にて、抵抗低減率ＤＲ［％］を計算した。
[Example 2]
An aqueous solution (2) containing the above compound (2a-1) having a mass average molecular weight of 3,000,000 at a concentration of 100 ppm was prepared. The resistance reduction rate DR [%] was calculated in the same manner as in Example 1 except that the aqueous solution (2) was used.
［比較例１］
質量平均分子量が３，５００，０００〜４，０００，０００の範囲内にあるポリエチレンオキシドを１００ｐｐｍの濃度で含む水溶液（３）を調製した。該水溶液（３）を用いた以外は実施例１と同様の方法にて、抵抗低減率ＤＲ［％］を計算した。
[Comparative Example 1]
An aqueous solution (3) containing polyethylene oxide having a mass average molecular weight in the range of 3,500,000 to 4,000,000 at a concentration of 100 ppm was prepared. The resistance reduction rate DR [%] was calculated in the same manner as in Example 1 except that the aqueous solution (3) was used.
［比較例２］
下記一般式（α）で表される繰り返し単位からなるポリアクリルアミド（質量平均分子量：１５，０００，０００）を１００ｐｐｍの濃度で含む水溶液（４）を調製した。該水溶液（４）を用いた以外は実施例１と同様の方法にて、抵抗低減率ＤＲ［％］を計算した。
[Comparative Example 2]
An aqueous solution (4) containing polyacrylamide (mass average molecular weight: 15,000,000) consisting of repeating units represented by the following general formula (α) at a concentration of 100 ppm was prepared. The resistance reduction rate DR [%] was calculated in the same manner as in Example 1 except that the aqueous solution (4) was used.
（結果および考察）
図１に、実施例１、実施例２、比較例１および比較例２のそれぞれについて、レイノルズ数Ｒｅ（横軸）に対してＤＲ［％］（縦軸）をプロットしたグラフを示す。
図１に示すように、実施例１および実施例２においては、レイノルズ数Ｒｅが数千以上の乱流領域において、大きなＤＲ［％］が得られた。
一方、比較例１および比較例２においては、大きなＤＲ［％］は得られなかった。
液体は、レイノルズ数Ｒｅが２３００を超えると、その流れが乱流になるとされている。レイノルズ数Ｒｅが数千以上の領域で摩擦低減効果が認められるということは、乱流を層流化できることを意味し、技術的意義が大きい。
以上の結果から、側鎖にアンモニウム塩構造を有する水溶性高分子化合物は、摩擦低減効果を奏し、摩擦低減剤として優れた性能を有することが明らかとなった。
(Results and Discussion)
FIG. 1 shows a graph in which DR [%] (vertical axis) is plotted against Reynolds number Re (horizontal axis) for each of Example 1, Example 2, Comparative Example 1 and Comparative Example 2.
As shown in FIG. 1, in Example 1 and Example 2, a large DR [%] was obtained in a turbulent flow region having a Reynolds number Re of several thousand or more.
On the other hand, in Comparative Example 1 and Comparative Example 2, a large DR [%] was not obtained.
When the Reynolds number Re exceeds 2300, the liquid is said to be turbulent. The fact that the friction reducing effect is recognized in the region where the Reynolds number Re is several thousand or more means that the turbulent flow can be laminarized, and has great technical significance.
From the above results, it was clarified that the water-soluble polymer compound having an ammonium salt structure in the side chain exhibits a friction reducing effect and has excellent performance as a friction reducing agent.
［実施例３および４］
実施例１で用いた化合物（１ａ−１）を５０ｐｐｍの濃度で含む水溶液（５）（実施例３）と、１０ｐｐｍの濃度で含む水溶液（６）（実施例４）とを調製し、これらの水溶液をそれぞれ用いて、実施例１と同様の方法にて、抵抗低減率ＤＲ［％］を計算した。
[Examples 3 and 4]
An aqueous solution (5) (Example 3) containing the compound (1a-1) used in Example 1 at a concentration of 50 ppm and an aqueous solution (6) (Example 4) containing a concentration of 10 ppm were prepared. Using each of the aqueous solutions, the resistance reduction rate DR [%] was calculated in the same manner as in Example 1.
（結果および考察）
図２に、実施例１と、実施例３および実施例４のそれぞれについて、レイノルズ数Ｒｅ（横軸）に対してＤＲ［％］（縦軸）をプロットしたグラフを示す。
図２に示すように、化合物（１ａ−１）の濃度が５０ｐｐｍ（実施例３）、１０ｐｐｍ（実施例４）の場合、濃度が１００ｐｐｍの場合に比較すると小さいものの、摩擦低減効果が得られることがわかった。
(Results and Discussion)
FIG. 2 shows a graph in which DR [%] (vertical axis) is plotted against Reynolds number Re (horizontal axis) for each of Example 1, Example 3 and Example 4.
As shown in FIG. 2, when the concentration of the compound (1a-1) is 50 ppm (Example 3) and 10 ppm (Example 4), the friction reducing effect is obtained although the concentration is smaller than that when the concentration is 100 ppm. I understood.
本発明の摩擦低減剤は、水、海水、各種水溶液等の水性の液体の摩擦抵抗を大きく低減させることができる。そのため、本発明の摩擦低減剤を船体の船底の表面、プラント等の配管の内壁の表面等、水性の液体と接する固体の表面を塗装するための塗料に添加することにより、船舶の航行時や液体が配管を流れる際のエネルギーのロスを大幅に低減できる。 The friction reducing agent of the present invention can greatly reduce the frictional resistance of aqueous liquids such as water, seawater and various aqueous solutions. Therefore, by adding the friction reducing agent of the present invention to a paint for coating a solid surface in contact with an aqueous liquid, such as the surface of the bottom of a hull, the surface of an inner wall of a pipe of a plant, etc. Energy loss when the liquid flows through the pipe can be greatly reduced.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015045139A JP6682764B2 (en) | 2015-03-06 | 2015-03-06 | Friction reducing agent, ship bottom paint containing the friction reducing agent, and friction reducing method using the friction reducing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015045139A JP6682764B2 (en) | 2015-03-06 | 2015-03-06 | Friction reducing agent, ship bottom paint containing the friction reducing agent, and friction reducing method using the friction reducing agent |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2019096860A Division JP2019178329A (en) | 2019-05-23 | 2019-05-23 | Coating material containing friction reducing agent, and friction reducing method using coating material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2016164237A true JP2016164237A (en) | 2016-09-08 |
| JP6682764B2 JP6682764B2 (en) | 2020-04-15 |
Family
ID=56876123
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2015045139A Active JP6682764B2 (en) | 2015-03-06 | 2015-03-06 | Friction reducing agent, ship bottom paint containing the friction reducing agent, and friction reducing method using the friction reducing agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6682764B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116515021A (en) * | 2023-05-19 | 2023-08-01 | 广东省科学院化工研究所 | Poly (N, N-dialkylaminoethyl) methacrylate quaternary ammonium salt, and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4460758A (en) * | 1983-11-02 | 1984-07-17 | Exxon Research And Engineering Co. | Drag reduction agents for aqueous salt solutions |
| US4489180A (en) * | 1983-12-12 | 1984-12-18 | Exxon Research And Engineering Co. | Drag reduction agent utilizing water soluble interpolymer complexes |
| JP2000026530A (en) * | 1998-07-09 | 2000-01-25 | Mitsubishi Chemicals Corp | Polymer of cyclic amidine structure, production and use thereof |
| JP2010275358A (en) * | 2009-05-26 | 2010-12-09 | Showa Denko Kk | Frictional resistance reducing agent composition in piping for aqueous medium and method for reducing friction of aqueous medium |
-
2015
- 2015-03-06 JP JP2015045139A patent/JP6682764B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4460758A (en) * | 1983-11-02 | 1984-07-17 | Exxon Research And Engineering Co. | Drag reduction agents for aqueous salt solutions |
| US4489180A (en) * | 1983-12-12 | 1984-12-18 | Exxon Research And Engineering Co. | Drag reduction agent utilizing water soluble interpolymer complexes |
| JP2000026530A (en) * | 1998-07-09 | 2000-01-25 | Mitsubishi Chemicals Corp | Polymer of cyclic amidine structure, production and use thereof |
| JP2010275358A (en) * | 2009-05-26 | 2010-12-09 | Showa Denko Kk | Frictional resistance reducing agent composition in piping for aqueous medium and method for reducing friction of aqueous medium |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116515021A (en) * | 2023-05-19 | 2023-08-01 | 广东省科学院化工研究所 | Poly (N, N-dialkylaminoethyl) methacrylate quaternary ammonium salt, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6682764B2 (en) | 2020-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhao et al. | Unexpected behavior of polydimethylsiloxane/poly (2-(dimethylamino) ethyl acrylate)(charged) amphiphilic block copolymers in aqueous solution | |
| CN108368381B (en) | Coating composition for forming coating film for reducing frictional resistance, coating film, and substrate with coating film | |
| CN102119192B (en) | Polymer with salt groups and antifouling coating composition comprising the polymer | |
| RU2014129896A (en) | COMPOSITION FOR PIGMENT PAINTING BASED ON SPECIFIC ACRYLIC POLYMER AND ON THE BASIS OF SILICONE COPOLYMER AND METHOD OF PAINTING | |
| CN107892729A (en) | The copolymer and manufacture method of (methyl) acrylic acid triisopropylsilyl ester and (methyl) acrylic acid derivative | |
| JP5320266B2 (en) | Fluoropolymer and coating agent | |
| KR960017802A (en) | Paint composition | |
| RU2002135791A (en) | Copolymers containing fluorine atoms and strong groups, and their use in composites against fouling by marine organisms | |
| JP6682764B2 (en) | Friction reducing agent, ship bottom paint containing the friction reducing agent, and friction reducing method using the friction reducing agent | |
| Max et al. | Double Hydrophilic Poly (ethylene oxide)‐block‐Poly (dehydroalanine) Block Copolymers: Comparison of Two Different Synthetic Routes | |
| JP2019178329A (en) | Coating material containing friction reducing agent, and friction reducing method using coating material | |
| Grigoreva et al. | Controlled synthesis and self-assembly of amphiphilic copolymers based on 2, 2, 3, 3, 4, 4, 5, 5-octafluoropentyl acrylate and acrylic acid | |
| EP0608132A1 (en) | Coating varnish composition and antifouling coating composition | |
| CN108137982A (en) | Sealing material use water system paint base composition | |
| JPWO2019198630A1 (en) | Antifouling paint composition | |
| CN106117418A (en) | A kind of preparation method of magnetic steering super-hydrophobic acrylate rubber thin film | |
| JPWO2022054851A5 (en) | ||
| NO812903L (en) | FOUNDATION PREVENTION PAINT. | |
| Sun et al. | Synthesis and properties of cross-linkable block copolymer end-capped with 2, 2, 3, 4, 4, 4-hexafluorobutyl methacrylate | |
| JP2003201321A (en) | Coating composition | |
| JP2016080367A (en) | Gelatinous composition for gas sensors | |
| Kim et al. | Synthesis and characterization of self-polishing copolymers containing a new zinc acrylate monomer | |
| BR102015011015A2 (en) | process for reducing friction during ethanol transport through pipelines | |
| Yi et al. | Synthesis and self-assembly behavior of organic–inorganic macrocyclic molecular brushes composed of macrocyclic oligomeric silsesquioxane and poly (N-isopropylacrylamide) | |
| CA2876611C (en) | Use of a comb polymer for preparing a suspension containing calcium carbonate and having reduced temperature sensitivity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20180222 |
|
| RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20181102 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20190222 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20190326 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20190523 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20190910 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20191009 |
|
| 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: 20200225 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20200309 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 6682764 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |