JP7429560B2 - Anticorrosive paint composition - Google Patents
Anticorrosive paint composition Download PDFInfo
- Publication number
- JP7429560B2 JP7429560B2 JP2020025081A JP2020025081A JP7429560B2 JP 7429560 B2 JP7429560 B2 JP 7429560B2 JP 2020025081 A JP2020025081 A JP 2020025081A JP 2020025081 A JP2020025081 A JP 2020025081A JP 7429560 B2 JP7429560 B2 JP 7429560B2
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- mass
- composition
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- epoxy resin
- resin
- Prior art date
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- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 1
- 230000000368 destabilizing effect Effects 0.000 description 1
- 239000000539 dimer Chemical class 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- ZOPZLBINMFYCGL-UHFFFAOYSA-N dodecanoic acid;phosphoric acid Chemical class OP(O)(O)=O.CCCCCCCCCCCC(O)=O.CCCCCCCCCCCC(O)=O ZOPZLBINMFYCGL-UHFFFAOYSA-N 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion 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
- OUDSFQBUEBFSPS-UHFFFAOYSA-N ethylenediaminetriacetic acid Chemical compound OC(=O)CNCCN(CC(O)=O)CC(O)=O OUDSFQBUEBFSPS-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000012703 microemulsion polymerization Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- RAFRTSDUWORDLA-UHFFFAOYSA-N phenyl 3-chloropropanoate Chemical compound ClCCC(=O)OC1=CC=CC=C1 RAFRTSDUWORDLA-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 235000010235 potassium benzoate Nutrition 0.000 description 1
- 239000004300 potassium benzoate Substances 0.000 description 1
- 229940103091 potassium benzoate Drugs 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 150000003349 semicarbazides Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 229940083982 sodium phytate Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000007592 spray painting technique Methods 0.000 description 1
- 235000020354 squash Nutrition 0.000 description 1
- HOWFTCIROIVKLW-UHFFFAOYSA-L strontium;dinitrite Chemical compound [Sr+2].[O-]N=O.[O-]N=O HOWFTCIROIVKLW-UHFFFAOYSA-L 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 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
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/106—Anti-corrosive paints containing metal dust containing Zn
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0893—Zinc
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Description
本発明は、防食塗料組成物、塗膜、塗膜付き基材およびその製造方法に関する。 The present invention relates to an anticorrosive coating composition, a coating film, a substrate with a coating film, and a method for producing the same.
従来、例えば、橋梁、タンク、プラント、(輸送用)コンテナなどの陸上や海洋構造物等の基材には、腐食防止等を目的として、防食塗膜が設けられている。この防食塗膜を形成する塗料の一例として、亜鉛末を高含量で含有するジンクリッチ塗料が使用されている。このようなジンクリッチ塗料としては、防食性、塗装作業性等の点から、有機溶剤を溶媒とする溶剤型塗料が用いられている。 BACKGROUND ART Conventionally, base materials of land and marine structures such as bridges, tanks, plants, and (transportation) containers have been provided with anticorrosive coatings for the purpose of preventing corrosion. As an example of a paint that forms this anticorrosive coating, a zinc-rich paint containing a high content of zinc powder is used. As such a zinc-rich paint, a solvent-based paint using an organic solvent as a solvent is used from the viewpoint of corrosion resistance, painting workability, etc.
近年、環境保全や作業環境の安全性などの観点から、揮発性有機化合物(VOC:Volatile Organic Compounds)の含有量に関する規制が厳しくなっており、前記のような塗料においても、溶剤型塗料から水性塗料への切り替えが望まれている。 In recent years, regulations regarding the content of volatile organic compounds (VOC) have become stricter from the perspective of environmental conservation and work environment safety. A switch to paint is desired.
このような水性のジンクリッチ塗料として、特許文献1には、エポキシ樹脂エマルジョンを含む主剤、亜鉛末を含む顔料分(粉成分)およびアミン硬化剤からなる2液1粉型の水性ジンクリッチ塗料が記載されている。
また、特許文献2には、水性ウレタン樹脂を含有するジンクリッチ塗料が記載されている。
As such a water-based zinc-rich paint, Patent Document 1 describes a two-component, one-powder type water-based zinc-rich paint consisting of a base agent containing an epoxy resin emulsion, a pigment component (powder component) containing zinc dust, and an amine curing agent. Are listed.
Further, Patent Document 2 describes a zinc-rich paint containing an aqueous urethane resin.
前記特許文献1および2などに記載されている従来の水性ジンクリッチ塗料は、乾燥性および/または硬化性が十分ではなく、さらに、得られる塗膜の防食性の点でも改良の余地があった。
また、前記特許文献1に記載されているような、エポキシ樹脂の硬化剤として使用されてきた公知のアミン系硬化剤を使用した従来の水性ジンクリッチ塗料は、乾燥性、硬化性および/またはポットライフが十分ではなく、この点で改良の余地があった。
The conventional water-based zinc-rich paints described in Patent Documents 1 and 2 do not have sufficient drying properties and/or curing properties, and there is also room for improvement in terms of the corrosion resistance of the resulting coating film. .
In addition, conventional water-based zinc-rich paints using known amine-based curing agents, which have been used as curing agents for epoxy resins, as described in Patent Document 1, have drying, curing, and/or potability. There wasn't enough life, and there was room for improvement in this respect.
本発明は、以上のことに鑑みてなされたものであり、防食性に優れる塗膜を形成でき、乾燥性および硬化性に優れる防食塗料組成物を提供することを課題とする。 The present invention has been made in view of the above, and an object of the present invention is to provide an anticorrosive coating composition that can form a coating film with excellent anticorrosion properties and has excellent drying and curing properties.
前記課題を解決する方法について鋭意検討を重ねた結果、特定の塗料組成物によれば、前記課題を解決できることを見出し、本発明を完成するに至った。
本発明の構成例は以下の通りである。
As a result of intensive studies on methods for solving the above problems, the inventors have discovered that the above problems can be solved by using a specific coating composition, and have completed the present invention.
A configuration example of the present invention is as follows.
<1> 1分子中に1個以上のカルボキシ基を有し、不揮発分の酸価が1~20mgKOH/gである水性エポキシ樹脂(A)を含む第1剤と、
亜鉛末(B)を含む第2剤と、
を含有する防食塗料組成物であって、
前記亜鉛末(B)を、前記防食塗料組成物の不揮発分100質量%に対し、43~85質量%含有する、防食塗料組成物。
<1> A first agent containing an aqueous epoxy resin (A) having one or more carboxyl groups in one molecule and having an acid value of non-volatile content of 1 to 20 mgKOH/g;
a second agent containing zinc dust (B);
An anticorrosive paint composition comprising:
An anticorrosive coating composition containing 43 to 85% by mass of the zinc powder (B) based on 100% by mass of nonvolatile content of the anticorrosion coating composition.
<2> 前記水性エポキシ樹脂(A)が、水性アミン変性エポキシ樹脂(A1)である、<1>に記載の防食塗料組成物。
<3> 前記水性エポキシ樹脂(A)の不揮発分のアミン価が1~150mgKOH/gである、<1>または<2>に記載の防食塗料組成物。
<2> The anticorrosive coating composition according to <1>, wherein the aqueous epoxy resin (A) is an aqueous amine-modified epoxy resin (A1).
<3> The anticorrosive coating composition according to <1> or <2>, wherein the nonvolatile content of the aqueous epoxy resin (A) has an amine value of 1 to 150 mgKOH/g.
<4> 前記第2剤が、グリコールエーテル系溶剤または炭素数1~3のアルコール系溶剤を含む、<1>~<3>のいずれかに記載の防食塗料組成物。 <4> The anticorrosive coating composition according to any one of <1> to <3>, wherein the second agent contains a glycol ether solvent or an alcohol solvent having 1 to 3 carbon atoms.
<5> 前記第2剤が、前記水性エポキシ樹脂(A)以外のバインダーを含む、<1>~<4>のいずれかに記載の防食塗料組成物。 <5> The anticorrosive coating composition according to any one of <1> to <4>, wherein the second agent contains a binder other than the aqueous epoxy resin (A).
<6> 前記防食塗料組成物100質量%中の揮発性有機化合物(VOC)の含有量が10質量%以下である、<1>~<5>のいずれかに記載の防食塗料組成物。 <6> The anticorrosive coating composition according to any one of <1> to <5>, wherein the content of volatile organic compounds (VOC) in 100% by mass of the anticorrosive coating composition is 10% by mass or less.
<7> <1>~<6>のいずれかに記載の防食塗料組成物から形成された塗膜。
<8> 基材と<7>に記載の塗膜とを含有する塗膜付き基材。
<7> A coating film formed from the anticorrosive coating composition according to any one of <1> to <6>.
<8> A coated base material comprising a base material and the coating film according to <7>.
<9> 下記工程[1]および[2]を含む、塗膜付き基材の製造方法。
[1]基材に、<1>~<6>のいずれかに記載の防食塗料組成物を塗装する工程
[2]基材上に塗装された組成物を乾燥させて塗膜を形成する工程
<9> A method for producing a coated base material, including the following steps [1] and [2].
[1] A step of coating a substrate with the anticorrosive coating composition according to any one of <1> to <6>. [2] A step of drying the composition coated on the substrate to form a coating film.
本発明によれば、乾燥性および硬化性、亜鉛末の分散性、貯蔵安定性、ならびに水希釈性に優れ、ポットライフの長い水性防食塗料組成物を提供することができる。また、本発明によれば、エポキシ樹脂の硬化剤として使用されてきた公知のアミン系硬化剤を使用しなくても、乾燥性および硬化性に優れる水性防食塗料組成物を提供することができる。
さらに本発明によれば、防食性および基材への付着性に優れる塗膜を形成できる。
According to the present invention, it is possible to provide a water-based anticorrosive coating composition that has excellent drying properties and hardening properties, zinc dust dispersibility, storage stability, and water dilutability, and has a long pot life. Further, according to the present invention, it is possible to provide a water-based anticorrosive coating composition that has excellent drying properties and curability without using a known amine curing agent that has been used as a curing agent for epoxy resins.
Further, according to the present invention, a coating film having excellent corrosion resistance and adhesion to a substrate can be formed.
≪防食塗料組成物≫
本発明に係る防食塗料組成物(以下単に「本組成物」ともいう。)は、
1分子中に1個以上のカルボキシ基を有し、不揮発分の酸価が1~20mgKOH/gである水性エポキシ樹脂(A)を含む第1剤と、
亜鉛末(B)を含む第2剤と、を含有し、
前記亜鉛末(B)を、本組成物の不揮発分100質量%に対し、43~85質量%含有する組成物である。
≪Anti-corrosion paint composition≫
The anticorrosive coating composition according to the present invention (hereinafter also simply referred to as "the present composition") includes:
A first agent containing an aqueous epoxy resin (A) having one or more carboxyl groups in one molecule and having an acid value of non-volatile content of 1 to 20 mgKOH/g;
a second agent containing zinc dust (B),
This composition contains 43 to 85% by mass of the zinc dust (B) based on 100% by mass of the nonvolatile content of the present composition.
本組成物は、前記第1剤と第2剤とを含む多成分型の組成物であれば特に制限されず、用いる成分によっては、前記第1剤および第2剤以外の第3剤を含む3成分型以上の組成物としてもよいが、本組成物によれば、このような3成分型以上にしなくても、乾燥性および硬化性、亜鉛末の分散性、並びに水希釈性に優れ、ポットライフの長い2成分型の組成物とすることができる。 The present composition is not particularly limited as long as it is a multi-component composition containing the first agent and the second agent, and may include a third agent other than the first agent and the second agent depending on the components used. Although it may be a three-component or more composition, the present composition has excellent drying and curing properties, zinc powder dispersibility, and water dilutability even if it is not a three-component or more composition. It can be a two-component composition with a long pot life.
このため、本組成物は、第1剤および第2剤を含む多成分型の組成物であるが、貯蔵時の省スペース化、製造容易性および塗装作業性に優れる等の点から、前記第1剤と第2剤(のみ)とからなる2成分型の組成物であることが好ましい。
このような本組成物は、第1剤が液状であり、第2剤が粉状である、1液1粉末型の組成物であってもよく、第1剤および第2剤が液状(ペースト状を含む)である、2液型の組成物であってもよいが、塗装現場でのハンドリング性(亜鉛末の混和性)、および、第2剤の保管容易性に優れる等の点から、2液型の組成物であることが好ましい。
Therefore, the present composition is a multi-component composition containing a first part and a second part. A two-component composition consisting of a first agent and a second agent (only) is preferable.
This composition may be a one-part, one-powder type composition in which the first part is liquid and the second part is powder, and the first part and the second part are liquid (paste). A two-component composition may be used, but from the viewpoints of ease of handling at the painting site (miscibility of zinc powder) and ease of storage of the second component, A two-component composition is preferred.
これら第1~3剤等の剤(以下これらをまとめて「第n剤」ともいう。)は、通常、それぞれ別個の容器にて保存、貯蔵、運搬等され、塗装の際(例:塗装直前)に混合して本組成物とした後用いられる。つまり、これら第n剤は、本組成物を調製するためのキットの構成要素であるともいえ、さらに換言すれば、前記本組成物は、前記第1剤と第2剤とを含む防食塗料組成物用キットであるといえる。
本発明において、第n剤は、これらの剤を調製した後、本組成物を調製するまでの間貯蔵され得る剤であり、例えば、下記実施例に記載のミルベースなどは、通常、該ミルベースを調製した後ほどなくして他の成分と混合して使用されるため、本発明における第n剤には該当しない。
These first to third agents (hereinafter collectively referred to as "nth agent") are usually stored, stored, transported, etc. in separate containers, and are used at the time of painting (e.g. immediately before painting). ) to form the present composition. In other words, these nth agents can be said to be components of a kit for preparing the present composition. In other words, the present composition is an anticorrosive paint composition containing the first agent and the second agent. It can be said that it is a kit for supplies.
In the present invention, the nth agent is an agent that can be stored after the preparation of these agents until the preparation of the present composition. Since it is mixed with other ingredients and used shortly after preparation, it does not correspond to the nth agent in the present invention.
本組成物は、前記第n剤を混合して調製されるが、この調製の後またはこの調製の際に、塗装方法等に応じて、希釈して用いられることがある。
本明細書における各説明は、前記希釈に関する内容以外は、希釈される前についての説明である。
The present composition is prepared by mixing the n-th agent, but after or during this preparation, it may be diluted and used depending on the coating method and the like.
Each explanation in this specification is an explanation before being diluted, except for the content regarding the dilution.
本組成物は、前記水性エポキシ樹脂(A)を含むため、通常、水性塗料組成物となる。水性塗料組成物とは、水または水を主成分とする媒体(水性媒体)に、樹脂(A)や亜鉛末(B)等の成分を分散および/または溶解させた組成物のことをいう。
前記水性塗料組成物における水の含有量は、組成物中の分散媒および溶媒の合計量100質量%に対し、好ましくは50質量%以上、好ましくは60~100質量%、より好ましくは65~100質量%である。
Since the present composition contains the water-based epoxy resin (A), it is usually a water-based paint composition. The aqueous coating composition refers to a composition in which components such as a resin (A) and zinc dust (B) are dispersed and/or dissolved in water or a medium containing water as a main component (aqueous medium).
The content of water in the aqueous coating composition is preferably 50% by mass or more, preferably 60 to 100% by mass, more preferably 65 to 100% by mass, based on 100% by mass of the total amount of the dispersion medium and solvent in the composition. Mass%.
コンテナなどの基材に塗料を塗装する環境は、乾燥設備が十分でない場合がある。このような環境において、従来の水性ジンクリッチ塗料を塗装する際には、乾燥性が重視され、該塗料に有機溶剤が配合されてきた。
一方で、本発明によれば、乾燥性および硬化性に優れる塗料組成物が得られるため、このように有機溶剤を配合しなくても、乾燥設備が十分でない場所において、所望の塗膜を容易に形成することができる。
従って、環境保全や作業環境の安全性等の点から、本組成物100質量%中の揮発性有機化合物(VOC)の含有量は、好ましくは10質量%以下、より好ましくは8質量%以下であり、本組成物中のVOC含有量は、好ましくは200g/L以下、より好ましくは180g/L以下である。
The environment in which paint is applied to base materials such as containers may not have sufficient drying equipment. In such an environment, when applying conventional water-based zinc-rich paints, emphasis is placed on drying properties, and organic solvents have been blended into the paints.
On the other hand, according to the present invention, a coating composition with excellent drying and curable properties can be obtained, so even without incorporating an organic solvent, a desired coating film can be easily formed in places where drying equipment is insufficient. can be formed into
Therefore, from the viewpoint of environmental protection and work environment safety, the content of volatile organic compounds (VOC) in 100% by mass of this composition is preferably 10% by mass or less, more preferably 8% by mass or less. The VOC content in the present composition is preferably 200 g/L or less, more preferably 180 g/L or less.
本組成物中のVOC含有量は、組成物比重、加熱残分率(不揮発分の質量比率)および水分率の値を用い、下記式(1)および(2)から算出することができる。なお、組成物比重、加熱残分率および水分率は、以下のような測定値でも、用いる原材料から算出した値でも構わない。
VOC含有量(質量%)=(100-加熱残分率-水分率)/100・・・(1)
VOC含有量(g/L)=組成物比重×1000×(100-加熱残分率-水分率)/100・・・(2)
The VOC content in the present composition can be calculated from the following formulas (1) and (2) using the values of composition specific gravity, heating residual fraction (mass ratio of nonvolatile components), and moisture content. Note that the composition specific gravity, heating residual fraction, and moisture content may be the following measured values or values calculated from the raw materials used.
VOC content (mass%) = (100 - heating residual fraction - moisture percentage) / 100... (1)
VOC content (g/L) = Composition specific gravity x 1000 x (100 - heating residual fraction - moisture percentage) / 100... (2)
組成物比重(g/ml):23℃の温度条件下で、本組成物(第n剤を混合した直後の組成物)を内容積100mlの比重カップに充満し、該組成物の質量を計算することで算出される値。 Composition specific gravity (g/ml): Under a temperature condition of 23 ° C., fill a specific gravity cup with an internal volume of 100 ml with this composition (the composition immediately after mixing the nth agent), and calculate the mass of the composition. The value calculated by
加熱残分率(質量%):本組成物(第n剤を混合した直後の組成物)や各成分1±0.1gを平底皿に量り採り、質量既知の針金を使って均一に広げ、加熱温度125℃で1時間(常圧下)加熱した時の、加熱残分(不揮発分)および該針金の質量を測定することで算出される質量百分率の値。 Heating residual fraction (mass%): Weigh out 1 ± 0.1 g of the present composition (composition immediately after mixing the nth agent) and each component into a flat-bottomed dish, and spread it evenly using a wire with a known mass. Mass percentage value calculated by measuring the heating residue (non-volatile content) and the mass of the wire when heated at a heating temperature of 125° C. for 1 hour (under normal pressure).
水分率(質量%):カールフィッシャー法により測定される、本組成物100質量%に含まれる水の質量百分率の値。 Moisture content (mass %): The value of the mass percentage of water contained in 100 mass % of the present composition, measured by the Karl Fischer method.
本組成物は、鉄鋼(鉄、鋼、合金鉄、炭素鋼、マイルドスチール、合金鋼等)、非鉄金属(亜鉛、アルミニウム、銅、真鍮、亜鉛メッキ、亜鉛溶射等)、ステンレス(SUS304、SUS410等)などの基材に好適に用いられ、特に鉄鋼製の基材に好適に用いられる。
また、本組成物は、船舶、海洋構造物、プラント、橋梁、タンク、コンテナ等の(大型)鉄鋼構造物に好適に用いられる。
This composition can be applied to iron and steel (iron, steel, ferroalloy, carbon steel, mild steel, alloy steel, etc.), nonferrous metals (zinc, aluminum, copper, brass, galvanized, zinc sprayed, etc.), stainless steel (SUS304, SUS410, etc.) ), and is particularly suitable for steel base materials.
Further, the present composition is suitably used for (large) steel structures such as ships, offshore structures, plants, bridges, tanks, and containers.
<第1剤>
本組成物の第1剤は、前記水性エポキシ樹脂(A)を含有すれば特に制限されないが、該樹脂(A)を含むことから、通常、水を含む液状の剤である。
第1剤中の水の含有量は、所望の水性塗料組成物を容易に得ることができる等の点から、第1剤中の分散媒および溶媒の合計量100質量%に対し、好ましくは50質量%以上、より好ましくは70~100質量%、特に好ましくは80~100質量%である。
<First agent>
The first agent of the present composition is not particularly limited as long as it contains the aqueous epoxy resin (A), but since it contains the resin (A), it is usually a liquid agent containing water.
The content of water in the first part is preferably 50% by mass based on 100% by mass of the total amount of the dispersion medium and solvent in the first part, in order to easily obtain the desired aqueous coating composition. The amount is at least 70% by mass, more preferably 70 to 100% by mass, particularly preferably 80 to 100% by mass.
第1剤には、本発明の効果を損なわない範囲において、他の成分、例えば、樹脂(A)以外のバインダー、水、顔料(例:体質顔料、着色顔料)、防錆剤、フラッシュラスト防止剤、分散剤、消泡剤、搖変剤(タレ止め・沈降防止剤)、レベリング剤、湿潤剤、増粘剤、造膜助剤、ドライヤー、繊維状物質、界面活性剤、有機溶剤、防カビ剤、防腐剤、紫外線吸収剤、光安定剤、pH調整剤等の従来公知の成分を必要に応じて適宜配合してもよい。
これらはそれぞれ、1種単独で用いてもよく、2種以上を用いてもよい。
The first agent may contain other ingredients, such as a binder other than the resin (A), water, pigments (e.g. extender pigments, coloring pigments), rust preventives, flash rust prevention agents, to the extent that the effects of the present invention are not impaired. agents, dispersants, antifoaming agents, destabilizing agents (anti-sagging/anti-settling agents), leveling agents, wetting agents, thickeners, film forming aids, dryers, fibrous substances, surfactants, organic solvents, preventive agents. Conventionally known components such as fungicides, preservatives, ultraviolet absorbers, light stabilizers, and pH adjusters may be appropriately blended as needed.
Each of these may be used alone or in combination of two or more.
[水性エポキシ樹脂(A)]
前記樹脂(A)は、1分子中に1個以上のカルボキシ基を有し、不揮発分の酸価が1~20mgKOH/gである水性エポキシ樹脂であれば、特に制限されない。
樹脂(A)としては、1種を用いてもよく、2種以上を用いてもよい。
[Aqueous epoxy resin (A)]
The resin (A) is not particularly limited as long as it is an aqueous epoxy resin having one or more carboxyl groups in one molecule and having an acid value of nonvolatile content of 1 to 20 mgKOH/g.
As the resin (A), one type may be used, or two or more types may be used.
このような樹脂(A)を用いるため、VOC含有量が前記範囲にあっても、また、2成分型の組成物であっても、乾燥性、硬化性、貯蔵安定性およびポットライフに優れる組成物が得られ、防食性、耐水性、基材に対する付着性および耐衝撃性によりバランスよく優れる塗膜を容易に形成できる。
また、このような樹脂(A)を用いることで、エポキシ樹脂の硬化剤として使用されてきた従来のアミン系硬化剤を使用しなくても塗膜を形成できる。このため、乾燥性、硬化性およびポットライフにより優れる組成物を得ることができる等の点から、本組成物は該アミン系硬化剤を用いないことが好ましい。
さらに、前記第1剤が顔料を含有する場合、カルボキシ基を有する前記樹脂(A)は、顔料に対し親和性を有する傾向にあるため、顔料の分散性の向上が期待される。このため、顔料の分散性の向上に起因した生産効率の向上が期待できる。
Because such resin (A) is used, even if the VOC content is within the above range or the composition is a two-component type, the composition has excellent drying properties, curability, storage stability, and pot life. It is possible to easily form a coating film that is excellent in corrosion resistance, water resistance, adhesion to substrates, and impact resistance in a well-balanced manner.
Moreover, by using such a resin (A), a coating film can be formed without using a conventional amine-based curing agent that has been used as a curing agent for epoxy resins. Therefore, it is preferable that the amine curing agent is not used in the present composition, from the viewpoint of obtaining a composition with excellent drying properties, curability, and pot life.
Furthermore, when the first agent contains a pigment, the resin (A) having a carboxyl group tends to have an affinity for the pigment, so that improvement in the dispersibility of the pigment is expected. Therefore, improvement in production efficiency due to improvement in pigment dispersibility can be expected.
本発明において、「水性樹脂」とは、水または水を主な溶媒もしくは分散媒とする樹脂、または、水と混合可能(水で希釈可能)な樹脂であり、より具体的には、水分散型樹脂、水溶性樹脂および自己乳化性樹脂等が挙げられる。このような水性樹脂は、従来公知の方法、例えば、溶液重合法、懸濁重合法、乳化重合法、シード重合法、ミニエマルジョン重合法、マイクロエマルジョン重合法、無乳化剤(ソープフリー)乳化重合法等で合成することができる。また、これらの他に、樹脂を既知の方法、例えば、転相乳化、D相乳化、強制乳化、ゲル乳化、反転乳化、高圧乳化等で乳化させる方法でも、水性樹脂を得ることができる。 In the present invention, "aqueous resin" refers to water, a resin that uses water as a main solvent or dispersion medium, or a resin that is mixable with water (dilutable with water), and more specifically, a water-based resin that is water-based. Examples include mold resins, water-soluble resins, and self-emulsifying resins. Such aqueous resins can be produced by conventionally known methods, such as solution polymerization, suspension polymerization, emulsion polymerization, seed polymerization, miniemulsion polymerization, microemulsion polymerization, and emulsifier-free (soap-free) emulsion polymerization. It can be synthesized with etc. In addition to these methods, the aqueous resin can also be obtained by emulsifying the resin by known methods such as phase inversion emulsification, D-phase emulsification, forced emulsification, gel emulsification, inversion emulsification, and high-pressure emulsification.
なお、エポキシ基を有さない樹脂も、エポキシ基を有する化合物を原料とする樹脂であれば、「エポキシ」を含む通称が使用されているため、本発明における「エポキシ樹脂」も同様に、エポキシ基を有さない樹脂を含む。 Note that even for resins that do not have epoxy groups, if the resin is made from a compound that has epoxy groups, a common name that includes "epoxy" is used, so the "epoxy resin" in the present invention also includes epoxy. Contains resins without groups.
前記樹脂(A)の不揮発分のエポキシ当量は、乾燥性および/または硬化性により優れる組成物を容易に得ることができる等の点から、好ましくは1500以上、より好ましくは2000以上であり、樹脂(A)は、エポキシ基を有さないことが特に好ましい。
前記エポキシ当量は、JIS K 7236:2001に準拠して測定できる。
The epoxy equivalent of the non-volatile content of the resin (A) is preferably 1500 or more, more preferably 2000 or more, from the viewpoint of easily obtaining a composition with better drying properties and/or curability. It is particularly preferable that (A) does not have an epoxy group.
The epoxy equivalent can be measured according to JIS K 7236:2001.
前記樹脂(A)の不揮発分の酸価は、20mgKOH/g以下、好ましくは15mgKOH/g以下、より好ましくは10mgKOH/g以下、さらに好ましくは9mgKOH/g以下、特に好ましくは8mgKOH/g以下、さらに好ましくは7mgKOH/g以下であり、1mgKOH/g以上、好ましくは1.5mgKOH/g以上、特に好ましくは2mgKOH/g以上である。
酸価が前記範囲にある樹脂(A)を用いることで、乾燥性および/または硬化性により優れる組成物を容易に得ることができ、また、防食性に優れる塗膜を容易に形成できる。
前記酸価は、JIS K 0070:1992に準拠して測定できる。
The acid value of the nonvolatile content of the resin (A) is 20 mgKOH/g or less, preferably 15 mgKOH/g or less, more preferably 10 mgKOH/g or less, even more preferably 9 mgKOH/g or less, particularly preferably 8 mgKOH/g or less, and It is preferably 7 mgKOH/g or less, 1 mgKOH/g or more, preferably 1.5 mgKOH/g or more, particularly preferably 2 mgKOH/g or more.
By using the resin (A) having an acid value within the above range, a composition with better drying properties and/or curability can be easily obtained, and a coating film with excellent anticorrosion properties can be easily formed.
The acid value can be measured in accordance with JIS K 0070:1992.
前記樹脂(A)の不揮発分のアミン価は、好ましくは150mgKOH/g以下、より好ましくは100mgKOH/g以下、特に好ましくは75mgKOH/g以下であり、好ましくは1mgKOH/g以上、より好ましくは25mgKOH/g以上、特に好ましくは50mgKOH/g以上である。
アミン価が前記範囲にある樹脂(A)を用いることで、乾燥性および/または硬化性により優れる組成物を容易に得ることができ、また、防食性に優れる塗膜を容易に形成できる。
前記アミン価は、JIS K 7273:1995に準拠して測定できる。
The amine value of the non-volatile content of the resin (A) is preferably 150 mgKOH/g or less, more preferably 100 mgKOH/g or less, particularly preferably 75 mgKOH/g or less, preferably 1 mgKOH/g or more, more preferably 25 mgKOH/g. g or more, particularly preferably 50 mgKOH/g or more.
By using the resin (A) having an amine value within the above range, a composition with better drying properties and/or curability can be easily obtained, and a coating film with excellent anticorrosion properties can be easily formed.
The amine value can be measured according to JIS K 7273:1995.
前述のようなエポキシ当量(エポキシ基を有さない)、酸価および/またはアミン価を満たす樹脂(A)としては、エポキシ樹脂(a1)と、エポキシ基と反応性を有する従来公知の化合物(a2)との反応生成物(但し、該反応生成物は、分子中に1個以上のカルボキシ基を有する)が挙げられる。 The resin (A) that satisfies the epoxy equivalent (not having an epoxy group), acid value and/or amine value as described above may include an epoxy resin (a1) and a conventionally known compound having reactivity with an epoxy group ( a2) (provided that the reaction product has one or more carboxy groups in the molecule).
前記エポキシ基と反応性を有する化合物(a2)としては、エポキシ基との反応容易性等の点からアミン類が好ましい。
前記化合物(a2)は、単独でまたは2種以上を使用することができる。
As the compound (a2) having reactivity with the epoxy group, amines are preferable from the viewpoint of ease of reaction with the epoxy group.
The compound (a2) can be used alone or in combination of two or more.
前記アミン類としては特に制限されず、脂肪族アミン類、脂環式アミン類、芳香族アミン類、芳香脂肪族アミン類、複素環アミン類等のモノアミン、ポリアミンが挙げられる。アミン類は、1種単独で用いてもよく、2種以上を用いてもよい。 The amines are not particularly limited, and include monoamines and polyamines such as aliphatic amines, alicyclic amines, aromatic amines, araliphatic amines, and heterocyclic amines. The amines may be used alone or in combination of two or more.
前記アミン類としては特に制限されず、例えば、ブチルアミン、オクチルアミン、オレイルアミン、2-エチルヘキシルアミン等の一級アルキルアミン類、モノエタノールアミン、2-エトキシエタノールアミン、2-ヒドロキシプロパノールアミン等の一級アルカノールアミン類、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン等の脂肪族ポリアミン類、1,3-ジアミノシクロヘキサン、イソホロンジアミン等の脂環式ポリアミン類、ジアミノジフェニルメタン等の芳香族ポリアミン類、o-キシレンジアミン、m-キシレンジアミン、p-キシレンジアミン等の芳香脂肪族アミン類、ポリアミン類とアルデヒド化合物と1価または多価フェノール類との重縮合物からなるマンニッヒ塩基、ポリアミン類とポリカルボン酸やダイマー酸と反応により得られるポリアミドポリアミン類、ポリオキシエチレンアミン、ポリオキシプロピレンアミン等のポリオキシアルキレンアミン類が挙げられる。水性媒体への分散性およびその貯蔵安定性に優れる点から、一級アルキルアミン類、一級アルカノールアミン類、ポリオキシアルキレンアミン類が好ましく、一級アルカノールアミン類、ポリオキシアルキレンポリアミン類がより好ましい。 The amines are not particularly limited, and include, for example, primary alkylamines such as butylamine, octylamine, oleylamine, and 2-ethylhexylamine, and primary alkanolamines such as monoethanolamine, 2-ethoxyethanolamine, and 2-hydroxypropanolamine. aliphatic polyamines such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine, alicyclic polyamines such as 1,3-diaminocyclohexane and isophoronediamine, aromatic polyamines such as diaminodiphenylmethane, o-xylene diamine, Mannich bases consisting of aromatic aliphatic amines such as m-xylene diamine and p-xylene diamine, polycondensates of polyamines, aldehyde compounds, and monohydric or polyhydric phenols; polyamines and polycarboxylic acids and dimer acids; Examples include polyamide polyamines obtained by the reaction, polyoxyalkylene amines such as polyoxyethylene amine, and polyoxypropylene amine. From the standpoint of excellent dispersibility in aqueous media and storage stability, primary alkylamines, primary alkanolamines, and polyoxyalkylene amines are preferred, and primary alkanolamines and polyoxyalkylene polyamines are more preferred.
前記ポリオキシアルキレンアミン類としては、例えば、下記構造式(a2-1)で表される化合物が挙げられる。 Examples of the polyoxyalkylene amines include compounds represented by the following structural formula (a2-1).
前記ポリオキシアルキレンアミン類の分子量は、貯蔵安定性および防食性に優れる組成物を容易に得ることができる等の点から、重量平均分子量(Mw)が、好ましくは300~5,000、より好ましくは400~1,500である。 The molecular weight of the polyoxyalkylene amines is preferably a weight average molecular weight (Mw) of 300 to 5,000, more preferably 300 to 5,000, from the viewpoint of easily obtaining a composition with excellent storage stability and anticorrosion properties. is 400 to 1,500.
前記ポリオキシアルキレンアミン類としては、市販品を用いてもよく、該市販品としては、例えば、「ジェファーミン M-600」(重量平均分子量:600)、「ジェファーミン M-1000」(重量平均分子量:1,000)、「ジェファーミン M-2005」(重量平均分子量:2,000)、「ジェファーミン M-2070」(重量平均分子量:2,000)(以上、いずれもハンツマン社製)が挙げられる。これらの中でも、「ジェファーミン M-600」、「ジェファーミン M-1000」が好ましい。 Commercial products may be used as the polyoxyalkylene amines, and examples of the commercial products include "Jeffamine M-600" (weight average molecular weight: 600), "Jeffamine M-1000" (weight average molecular weight: 600), "Jeffamine M-1000" (weight average molecular weight: 600), Molecular weight: 1,000), "Jeffamine M-2005" (weight average molecular weight: 2,000), "Jeffamine M-2070" (weight average molecular weight: 2,000) (all manufactured by Huntsman) Can be mentioned. Among these, "Jeffamine M-600" and "Jeffamine M-1000" are preferred.
前記アミン類を用いて得られる樹脂(A)は、水性アミン変性エポキシ樹脂(A1)であるといえる。樹脂(A1)を用いることで、乾燥性および硬化性により優れる組成物を容易に得ることができ、また、防食性および基材に対する付着性により優れる塗膜を容易に形成できる。
なお、本発明における変性エポキシ樹脂は、該樹脂を構成する全てのモノマー成分100質量%に対し、エポキシ樹脂を構成するモノマー成分が50質量%を超える樹脂をいう。
The resin (A) obtained using the above amines can be said to be an aqueous amine-modified epoxy resin (A1). By using the resin (A1), a composition with better drying properties and curability can be easily obtained, and a coating film with better corrosion resistance and adhesion to substrates can be easily formed.
Note that the modified epoxy resin in the present invention refers to a resin in which the monomer components constituting the epoxy resin exceed 50% by mass based on 100% by mass of all the monomer components constituting the resin.
前記エポキシ樹脂(a1)としては、得られる塗膜の強靭性および基材に対する付着性等の点から、ビスフェノール型エポキシ樹脂が好ましく、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、ビスフェノールAD型エポキシ樹脂が好ましく、ビスフェノールA型エポキシ樹脂がより好ましい。
前記エポキシ樹脂(a1)は、単独でまたは2種以上を使用することができる。
The epoxy resin (a1) is preferably a bisphenol type epoxy resin from the viewpoint of the toughness of the resulting coating film and its adhesion to the substrate, and bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, etc. Resins are preferred, and bisphenol A epoxy resins are more preferred.
The epoxy resin (a1) can be used alone or in combination of two or more.
前記反応生成物が、分子中に1個以上のカルボキシ基を有する樹脂となるには、エポキシ樹脂(a1)として、カルボキシ基を有する化合物を用いてもよく、前記化合物(a2)として、カルボキシ基を有する化合物を用いてもよく、これらを反応させる際にカルボキシ基を生じさせてもよく、また、これらを反応させた後、最終的に得られる樹脂がカルボキシ基を有するように変性などを行ってもよいが、前記反応の際に、前記エポキシ樹脂(a1)および化合物(a2)以外の、不飽和カルボン酸(a3)を用いることが好ましい。 In order for the reaction product to be a resin having one or more carboxyl groups in the molecule, a compound having a carboxyl group may be used as the epoxy resin (a1), and a compound having a carboxyl group as the compound (a2) may be used. A compound may be used, and a carboxyl group may be generated when these are reacted, or after reacting these, modification etc. may be performed so that the resin finally obtained has a carboxyl group. However, it is preferable to use an unsaturated carboxylic acid (a3) other than the epoxy resin (a1) and compound (a2) in the reaction.
前記不飽和カルボン酸(a3)としては、例えば、(メタ)アクリル酸が挙げられる。これらは、単独でまたは2種以上を使用することができる。 Examples of the unsaturated carboxylic acid (a3) include (meth)acrylic acid. These can be used alone or in combination of two or more.
前記エポキシ樹脂(a1)、化合物(a2)および不飽和カルボン酸(a3)を反応させる順番は特に制限されないが、前述のような酸価およびアミン価を満たす樹脂を容易に得ることができる等の点から、エポキシ樹脂(a1)と化合物(a2)とを反応(以下「反応1」ともいう。)させ、次いで、反応1で得られた化合物と、不飽和カルボン酸(a3)とを反応(以下「反応2」ともいう。)させることが好ましい。
これらの反応1および2は、従来公知の方法で行うことができる。
The order in which the epoxy resin (a1), the compound (a2), and the unsaturated carboxylic acid (a3) are reacted is not particularly limited, but it is possible to easily obtain a resin that satisfies the acid value and amine value as described above. From this point, the epoxy resin (a1) and the compound (a2) are reacted (hereinafter also referred to as "reaction 1"), and then the compound obtained in reaction 1 and the unsaturated carboxylic acid (a3) are reacted ( (hereinafter also referred to as "reaction 2") is preferred.
These reactions 1 and 2 can be performed by conventionally known methods.
前記反応1における、エポキシ樹脂(a1)と化合物(a2)との混合比は、得られる樹脂(A)にエポキシ基が残存すると、本組成物の貯蔵安定性が低下する場合があるため、得られる樹脂(A)にエポキシ基ができるだけ残存しないような比であることが好ましく、例えば、エポキシ基1モルに対し、アミノ基が、好ましくは1.1~1.5モル程度となる量、より好ましくは1.1~1.3モル程度となる量である。 The mixing ratio of the epoxy resin (a1) and the compound (a2) in the reaction 1 is determined depending on the mixing ratio of the epoxy resin (a1) and the compound (a2), since if the epoxy group remains in the resulting resin (A), the storage stability of the composition may decrease. The ratio is preferably such that no epoxy groups remain as much as possible in the resin (A), for example, the amount of amino groups is preferably about 1.1 to 1.5 mol per 1 mol of epoxy groups. The amount is preferably about 1.1 to 1.3 moles.
前記反応2における、前記反応1で得られた化合物と、前記不飽和カルボン酸(a3)との混合比は、得られる樹脂(A)に前記アミノ基が残存すると、得られる塗膜の防食性が低下する場合があるため、アミノ基1モルに対し、カルボキシ基が1.1~1.5モル程度となる量が好ましく、1.1~1.3モル程度となるように混合することがより好ましい。 In the reaction 2, the mixing ratio of the compound obtained in the reaction 1 and the unsaturated carboxylic acid (a3) is such that when the amino group remains in the resulting resin (A), the corrosion resistance of the resulting coating film increases. may decrease, so the amount of carboxy group is preferably about 1.1 to 1.5 mol per 1 mol of amino group, and it is preferable to mix so that the amount is about 1.1 to 1.3 mol. More preferred.
前記樹脂(A)としては、市販品を用いてもよく、例えば、ビスフェノールA構造および1分子中に1個以上のカルボキシ基を有する水性アミン変性エポキシ樹脂である、EPICLON C-250EP(DIC(株)製、エポキシ基不含、酸価:5.7mgKOH/g、アミン価:60mgKOH/g)が挙げられる。 As the resin (A), a commercially available product may be used, such as EPICLON C-250EP (manufactured by DIC Corporation), which is an aqueous amine-modified epoxy resin having a bisphenol A structure and one or more carboxyl groups in one molecule. ), epoxy group-free, acid value: 5.7 mgKOH/g, amine value: 60 mgKOH/g).
本組成物の不揮発分100質量%に対する樹脂(A)の不揮発分の含有量は、乾燥性および硬化性に優れる組成物を容易に得ることができ、防食性および基材に対する付着性によりバランスよく優れる塗膜を容易に形成できる等の点から、好ましくは5~30質量%、より好ましくは6~20質量%である。 The nonvolatile content of the resin (A) relative to 100% by mass of the nonvolatile content of the present composition is such that it is possible to easily obtain a composition with excellent drying properties and curability, and to maintain a good balance between corrosion resistance and adhesion to substrates. The content is preferably 5 to 30% by mass, more preferably 6 to 20% by mass, from the standpoint of being able to easily form an excellent coating film.
前記樹脂(A)100質量%中の不揮発分(樹脂)の含有量は、調製容易性、保存安定性等により優れる組成物を得ることができる等の点から、好ましくは30~75質量%、より好ましくは35~60質量%である。
前記樹脂(A)の残分には、水が含まれていればよく、必要により、界面活性剤等の従来公知の成分が含まれていてもよい。
The content of non-volatile matter (resin) in 100% by mass of the resin (A) is preferably 30 to 75% by mass, from the viewpoint of obtaining a composition with better preparation ease, storage stability, etc. More preferably, it is 35 to 60% by mass.
The remainder of the resin (A) only needs to contain water, and may contain conventionally known components such as a surfactant, if necessary.
[水]
前記樹脂(A)には水が含まれている場合があるが、本組成物の調製をより容易にし、塗装作業性に優れる組成物を得られる等の点から、第1剤にはさらに水を配合することが好ましい。
前記水としては特に制限されず、水道水等を用いてもよいが、イオン交換水等を用いることが好ましい。
第1剤中の水の含有量(樹脂(A)等に含まれ得る水を含む)は、特に制限されないが、好ましくは20~70質量%である。
[water]
Although the resin (A) may contain water, water may be added to the first part in order to facilitate the preparation of the present composition and obtain a composition with excellent coating workability. It is preferable to blend.
The water is not particularly limited, and tap water or the like may be used, but it is preferable to use ion exchange water or the like.
The content of water in the first agent (including water that may be contained in the resin (A), etc.) is not particularly limited, but is preferably 20 to 70% by mass.
[搖変剤(タレ止め・沈降防止剤)]
本組成物は、塗装時の厚塗り性、タレ止め性の向上、亜鉛末(B)や顔料等の水や有機溶剤に対する不溶分の沈降防止のため、搖変剤を含有することが好ましい。特に、本組成物は、乾燥性に優れるため、厚膜(例:80μm以上)の塗膜を形成する場合、クラックが生じやすいが、搖変剤を用いることで、クラックの発生を抑制することができる。
搖変剤としては、1種を用いてもよく、2種以上を用いてもよい。
[Stirring agent (anti-sagging/anti-settling agent)]
The present composition preferably contains a stimulant in order to improve thick coating properties and anti-sagging properties during coating, and to prevent sedimentation of insoluble substances such as zinc dust (B) and pigments in water and organic solvents. In particular, since this composition has excellent drying properties, cracks are likely to occur when forming a thick film (e.g. 80 μm or more), but by using a modifier, the occurrence of cracks can be suppressed. I can do it.
As the modifier, one type may be used, or two or more types may be used.
搖変剤としては、例えば、Al、Ca、Znのステアレート塩、レシチン塩、アルキルスルホン酸塩などの有機粘土系塩類、酸化ポリエチレン系ワックス、エチレン・酢酸ビニル系ワックス、ポリアマイド系ワックス、水添ヒマシ油系ワックス、合成微粉シリカが挙げられる。これらの中でも、耐クラック性に優れる塗膜を容易に形成できる等の点から、酸化ポリエチレン系ワックス、エチレン・酢酸ビニル系ワックス、ポリアマイド系ワックスなどの有機系搖変剤が好ましい。 Examples of the modifier include organic clay salts such as stearate salts of Al, Ca, and Zn, lecithin salts, and alkyl sulfonates, oxidized polyethylene waxes, ethylene/vinyl acetate waxes, polyamide waxes, and hydrogenated waxes. Examples include castor oil wax and synthetic fine powder silica. Among these, organic swaying agents such as oxidized polyethylene waxes, ethylene/vinyl acetate waxes, and polyamide waxes are preferred because they can easily form a coating film with excellent crack resistance.
本組成物の不揮発分100質量%に対する搖変剤の不揮発分の含有量は、耐クラック性に優れる塗膜を容易に形成できる等の点から、好ましくは0.01~3.5質量%、より好ましくは0.05~3質量%である。 The nonvolatile content of the stimulant based on 100% by mass of the nonvolatile content of the present composition is preferably 0.01 to 3.5% by mass, from the viewpoint of easily forming a coating film with excellent crack resistance. More preferably, it is 0.05 to 3% by mass.
[分散剤]
本組成物は、該組成物における亜鉛末(B)や顔料等の分散性を向上し、外観が良好な硬化膜を容易に形成でき、耐クラック性に優れる塗膜を容易に形成できる等の点から、分散剤を含有することが好ましい。
分散剤としては、1種を用いてもよく、2種以上を用いてもよい。
[Dispersant]
This composition improves the dispersibility of zinc powder (B), pigments, etc. in the composition, and can easily form a cured film with a good appearance, and can easily form a coating film with excellent crack resistance. From this point of view, it is preferable to contain a dispersant.
As the dispersant, one type may be used, or two or more types may be used.
分散剤としては、特に限定されないが、例えば、カルボキシ基、リン酸基、アミノ基、これらの塩の基、アンモニウム塩基等の顔料吸着基を有し、脂肪酸、ポリアミノ、ポリエーテル、ポリエステル、ポリウレタン、ポリアクリレート等の相溶性鎖を有する共重合体等の各種分散剤が挙げられる。 Dispersants include, but are not particularly limited to, pigment adsorption groups such as carboxy groups, phosphoric acid groups, amino groups, salt groups thereof, and ammonium bases, and include fatty acids, polyaminos, polyethers, polyesters, polyurethanes, Examples include various dispersants such as copolymers having compatible chains such as polyacrylate.
本組成物の不揮発分100質量%に対する分散剤の不揮発分の含有量は、耐クラック性に優れる塗膜を容易に形成できる等の点から、好ましくは0.1~3質量%、より好ましくは0.1~2.5質量%である。 The nonvolatile content of the dispersant based on 100% by mass of the nonvolatile content of the present composition is preferably 0.1 to 3% by mass, more preferably It is 0.1 to 2.5% by mass.
[フラッシュラスト防止剤]
水性塗料を活性な鋼材表面などに塗装する場合、塗装直後から乾燥過程において、該鋼材表面から鉄イオンが溶出することなどに起因する、発錆およびその錆などが塗膜表面に浮き出てくるフラッシュラストが起こる場合がある。特に、高温多湿条件下においてフラッシュラストの発生が顕著な場合がある。
このようなフラッシュラストを抑制する目的で、本組成物にはフラッシュラスト防止剤を用いることが好ましい。
フラッシュラスト防止剤としては、1種を用いてもよく、2種以上を用いてもよい。
[Flash last prevention agent]
When a water-based paint is applied to an active steel surface, a flash occurs in which rust occurs and the rust appears on the surface of the paint film due to iron ions being eluted from the surface of the steel material immediately after painting and during the drying process. The last thing may happen. In particular, the occurrence of flash last may be noticeable under high temperature and high humidity conditions.
In order to suppress such flash last, it is preferable to use a flash last inhibitor in the present composition.
As the flash last inhibitor, one type may be used, or two or more types may be used.
フラッシュラスト防止剤としては、例えば、亜硝酸ナトリウム、亜硝酸カリウム、亜硝酸カルシウム、亜硝酸ストロンチウム、亜硝酸バリウム、亜硝酸アンモニウムなどの亜硝酸塩;安息香酸ナトリウム、安息香酸カリウム、安息香酸カルシウム、安息香酸アンモニウムなどの安息香酸塩;フィチン酸ナトリウム、フィチン酸カリウムなどのフィチン酸塩;セバシン酸、ドデカン酸などの脂肪酸塩;アルキルリン酸、ポリリン酸などのリン酸誘導体;タンニン酸塩;N-(2-ヒドロキシエチル)エチレンジアミン三酢酸(HEDTA)、エチレンジアミン四酢酸(EDTA)、ジエチレントリアミン五酢酸(DTPA)、プロピレンジアミン四酢酸(PDTA)、イミノ二酢酸、ニトリロ三酢酸(NTA)、ジエチレントリアミンペンタメチレンホスホン酸(DTPMP)、これらのアルカリ金属塩などのアミン系キレート剤;4-メチル-γ-オキソ-ベンゼンブタン酸とN-エチルモルホリンの付加反応物;モノアルキルアミンやポリアミン、第四級アンモニウムイオンなどをトリポリリン酸二水素アルミニウムなどの層状リン酸塩にインターカレートしてなる層間化合物;ヒドラジド化合物、セミカルバジド化合物、ヒドラゾン化合物などのヒドラジン誘導体が挙げられる。 Examples of flash last inhibitors include nitrites such as sodium nitrite, potassium nitrite, calcium nitrite, strontium nitrite, barium nitrite, and ammonium nitrite; sodium benzoate, potassium benzoate, calcium benzoate, and ammonium benzoate. benzoates such as; phytates such as sodium phytate and potassium phytate; fatty acid salts such as sebacic acid and dodecanoic acid; phosphoric acid derivatives such as alkyl phosphoric acid and polyphosphoric acid; tannates; Hydroxyethyl) ethylenediaminetriacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), propylenediaminetetraacetic acid (PDTA), iminodiacetic acid, nitrilotriacetic acid (NTA), diethylenetriaminepentamethylenephosphonic acid (DTPMP) ), amine-based chelating agents such as these alkali metal salts; addition reaction products of 4-methyl-γ-oxo-benzenebutanoic acid and N-ethylmorpholine; monoalkylamines, polyamines, quaternary ammonium ions, etc. Examples include intercalation compounds formed by intercalating layered phosphates such as aluminum dihydrogen; hydrazine derivatives such as hydrazide compounds, semicarbazide compounds, and hydrazone compounds.
これらの中でも、耐フラッシュラスト性に優れ、安価である等の点から、亜硝酸塩(例:ナトリウム、カリウム、カルシウム等の金属塩、アンモニウム塩)、安息香酸塩(例:ナトリウム、カリウム、カルシウム等の金属塩、アンモニウム塩)が好ましく、使用量が少なくても、高い耐フラッシュラスト性を示す組成物を容易に得ることができる等の点から、亜硝酸塩がより好ましく、亜硝酸ナトリウムが特に好ましい。 Among these, nitrites (e.g., metal salts such as sodium, potassium, calcium, ammonium salts), benzoates (e.g., sodium, potassium, calcium, etc.) have excellent flash rust resistance and are inexpensive. metal salts, ammonium salts) are preferred, nitrites are more preferred, and sodium nitrite is particularly preferred because a composition exhibiting high flash last resistance can be easily obtained even if the amount used is small. .
本組成物の不揮発分100質量%に対するフラッシュラスト防止剤の含有量は、耐フラッシュラスト性に優れる組成物を容易に形成できる等の点から、好ましくは0.01~2質量%、より好ましくは0.05~1.0質量%である。 The content of the flash rust inhibitor based on 100 mass % of the nonvolatile content of the present composition is preferably 0.01 to 2 mass %, more preferably It is 0.05 to 1.0% by mass.
[有機溶剤]
第1剤が水を含有する場合、冬季における凍結を抑制するため、また、塗装作業性により優れる組成物を得るため、任意の量で水と混和可能な有機溶剤を用いてもよい。
有機溶剤としては、1種を用いてもよく、2種以上を用いてもよい。
このような有機溶剤としては、イソプロピルアルコール、エチレングリコール等の炭素数1~3のアルコール系溶剤、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル等のグリコールエーテル系溶剤等が挙げられる。
[Organic solvent]
When the first agent contains water, an arbitrary amount of a water-miscible organic solvent may be used in order to suppress freezing in winter and to obtain a composition with better coating workability.
As the organic solvent, one type may be used, or two or more types may be used.
Examples of such organic solvents include alcohol solvents having 1 to 3 carbon atoms such as isopropyl alcohol and ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and propylene glycol monomethyl. Examples include glycol ether solvents such as ether and propylene glycol monoethyl ether.
<第2剤>
本組成物の第2剤は、亜鉛末(B)を含有すれば特に制限されず、実質的に該亜鉛末(B)のみからなってもよいし、本発明の効果を損なわない範囲において、該亜鉛末(B)以外の成分を含んでいてもよい。
該他の成分はそれぞれ、1種単独で用いてもよく、2種以上を用いてもよい。
<Second agent>
The second agent of the present composition is not particularly limited as long as it contains zinc dust (B), and may consist essentially only of the zinc dust (B), as long as it does not impair the effects of the present invention. It may contain components other than the zinc powder (B).
These other components may be used alone or in combination of two or more.
[亜鉛末(B)]
亜鉛末(B)としては、金属亜鉛の粉末、または、亜鉛を主体(亜鉛の含有量が全体の90質量%以上)とする合金(例:亜鉛とアルミニウム、マグネシウムおよび錫から選択される少なくとも1種との合金、好ましくは亜鉛-アルミニウム合金、亜鉛-錫合金)の粉末が挙げられる。
亜鉛末(B)としては、1種を用いてもよく、2種以上を用いてもよい。
[Zinc dust (B)]
The zinc powder (B) is a metallic zinc powder or an alloy mainly composed of zinc (zinc content is 90% by mass or more of the total) (e.g., at least one selected from zinc and aluminum, magnesium, and tin). Examples include powders of alloys with seeds, preferably zinc-aluminum alloys, zinc-tin alloys).
As zinc dust (B), one type may be used, or two or more types may be used.
亜鉛末(B)の形状は特に制限されないが、より防食性に優れる塗膜を容易に得ることができる等の点から、メディアン径(D50)が、好ましくは2~15μm、より好ましくは2~7μmである粒子状亜鉛末が望ましい。
該D50は、レーザー散乱回折式粒度分布測定装置、例えば「SALD 2200」((株)島津製作所製)を用いて測定することができる。
The shape of the zinc powder (B) is not particularly limited, but the median diameter (D50) is preferably 2 to 15 μm, more preferably 2 to 15 μm, since a coating film with better corrosion resistance can be easily obtained. Particulate zinc dust having a diameter of 7 μm is preferred.
The D50 can be measured using a laser scattering diffraction particle size distribution analyzer, for example, "SALD 2200" (manufactured by Shimadzu Corporation).
本組成物の不揮発分100質量%に対する亜鉛末(B)の含有量は、43~85質量%であり、より防食性に優れる塗膜を容易に得ることができる等の点から、好ましくは45~85質量%、より好ましくは50~85質量%、特に好ましくは65~82質量%である。
亜鉛末(B)の前記含有量が43質量%未満であると、亜鉛の犠牲陽極作用が不十分となり防食性の低下を引き起こしやすくなり、85質量%を超えると、乾燥塗膜中の顔料分が過多となり、耐透水性の低下を引き起こしやすくなる。
The content of zinc dust (B) based on 100% by mass of the nonvolatile content of the present composition is 43 to 85% by mass, and is preferably 45% by mass from the viewpoint of easily obtaining a coating film with better corrosion resistance. ~85% by weight, more preferably 50-85% by weight, particularly preferably 65-82% by weight.
If the content of zinc powder (B) is less than 43% by mass, the sacrificial anode effect of zinc will be insufficient and the corrosion resistance will tend to deteriorate, and if it exceeds 85% by mass, the pigment content in the dried coating film will be reduced. becomes excessive, which tends to cause a decrease in water permeability.
前記亜鉛末(B)以外の成分としては、前記第1剤の欄に記載した他の成分と同様の成分が挙げられる。
前述の通り、第2剤は、液状(ペースト状)であることが好ましく、この場合、該第2剤は、亜鉛末(B)の分散性に優れ、前記第1剤との混和性に優れ、亜鉛末(B)が均一に分散した本組成物を容易に得ることができる等の点から、有機溶剤を含むことが好ましい。
このような有機溶剤の具体例としては、第1剤の欄で挙げた有機溶剤と同様の有機溶剤が好ましい。
なお、亜鉛末(B)と水とが反応することにより、亜鉛末(B)の酸化による防食性の低下、水素の発生による火災の危険性が高まる等の点から、第2剤は、水を含まないことが好ましい。
Components other than the zinc dust (B) include the same components as the other components listed in the column of the first agent.
As mentioned above, the second agent is preferably liquid (paste-like), and in this case, the second agent has excellent dispersibility of the zinc dust (B) and excellent miscibility with the first agent. It is preferable that an organic solvent is included because it is possible to easily obtain the present composition in which the zinc dust (B) is uniformly dispersed.
As a specific example of such an organic solvent, the same organic solvents as those mentioned in the section of the first agent are preferable.
In addition, since the reaction between zinc dust (B) and water will reduce corrosion resistance due to oxidation of zinc dust (B) and increase the risk of fire due to the generation of hydrogen, the second agent should not be used with water. Preferably, it does not contain.
第2剤中の有機溶剤の含有量は、本組成物中のVOC量が前記範囲となる量であることが好ましいが、亜鉛末(B)の分散性に優れる等の点から、第2剤100質量%に対し、好ましくは1~10質量%、より好ましくは3~8質量%である。 The content of the organic solvent in the second agent is preferably such that the amount of VOC in the composition falls within the above range. It is preferably 1 to 10% by weight, more preferably 3 to 8% by weight based on 100% by weight.
また、第2剤は、前記と同様の理由、および、第2剤の輸送性や貯蔵安定性等の点から、搖変剤を含有することが好ましく、該搖変剤としては、第1剤の欄で挙げた搖変剤と同様の搖変剤等が挙げられる。 Further, the second agent preferably contains a swaying agent for the same reason as above and from the viewpoint of transportability and storage stability of the second agent, and as the swaying agent, the first agent Examples include the same stimulants as the stimulants listed in the section above.
[樹脂(A)以外のバインダー]
第2剤は、樹脂(A)以外のバインダーを含有することが好ましく、樹脂(A)と反応性を有する化合物がより好ましい。このような化合物としては、例えば、エポキシ樹脂、イソシアネート系硬化剤、カルボジイミド系硬化剤、エポキシ基含有シランカップリング剤が挙げられ、より防食性に優れる塗膜を容易に得ることができる等の点から、エポキシ樹脂が特に好ましい。
[Binder other than resin (A)]
The second agent preferably contains a binder other than the resin (A), and more preferably a compound that is reactive with the resin (A). Examples of such compounds include epoxy resins, isocyanate-based curing agents, carbodiimide-based curing agents, and epoxy group-containing silane coupling agents. Epoxy resins are particularly preferred.
前記エポキシ樹脂は、1分子中に2個以上のエポキシ基を有していることが好ましく、該樹脂の分子量、エポキシ当量等の樹脂物性値は特に制限されないが、本組成物のVOC含有量の増加を抑制できる等の点から、常温(23℃)において液状であることが好ましい。
なお、前記エポキシ樹脂を用いる場合、亜鉛末(B)との混合性等の点から、前記有機溶剤と併用することが好ましい。
該エポキシ樹脂は、1種を用いてもよく、2種以上を用いてもよい。
The epoxy resin preferably has two or more epoxy groups in one molecule, and the resin physical properties such as molecular weight and epoxy equivalent are not particularly limited, but the VOC content of the composition is It is preferable to be liquid at room temperature (23° C.) from the viewpoint of suppressing the increase.
In addition, when using the said epoxy resin, it is preferable to use it together with the said organic solvent from points of miscibility with zinc dust (B), etc.
These epoxy resins may be used alone or in combination of two or more.
前記エポキシ樹脂としては、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(例えば、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂)、脂環式エポキシ樹脂、脂肪酸変性エポキシ樹脂が挙げられる。これらの中でも、より防食性に優れる塗膜を容易に得ることができる点、粘度が低く、第2剤の製造作業性に優れる点などから、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂が好ましい。 Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin (e.g., phenol novolac type epoxy resin, cresol novolac type epoxy resin), alicyclic epoxy resin, and fatty acid-modified epoxy resin. can be mentioned. Among these, bisphenol A type epoxy resin and bisphenol F type epoxy resin are preferable because a coating film with better corrosion resistance can be easily obtained, their viscosity is low, and the second agent has excellent workability. .
前記エポキシ樹脂としては、市販品を用いてもよく、該市販品としては、例えば、カルボキシ基を有さないエポキシ樹脂である、jER828(三菱ケミカル(株)製、ビスフェノールA型エポキシ樹脂、酸価:<1mgKOH/g)、jER807(三菱ケミカル(株)製、ビスフェノールF型エポキシ樹脂、酸価:<1mgKOH/g)が挙げられる。 As the epoxy resin, a commercially available product may be used, and examples of the commercially available product include jER828 (manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, acid value : <1 mgKOH/g) and jER807 (manufactured by Mitsubishi Chemical Corporation, bisphenol F type epoxy resin, acid value: <1 mgKOH/g).
このようなエポキシ樹脂を含有する場合、該樹脂の含有量は、より防食性に優れる塗膜を容易に得ることができる等の点から、本組成物の不揮発分100質量%に対して、好ましくは0.1~10質量%、より好ましくは0.5~5質量%である。 When such an epoxy resin is contained, the content of the resin is preferably set to 100% by mass of the non-volatile content of the present composition, from the viewpoint of easily obtaining a coating film with better corrosion resistance. is 0.1 to 10% by weight, more preferably 0.5 to 5% by weight.
<防食塗料組成物の調製方法>
前記第1剤および第2剤は、これらの剤に配合する各成分を混合(混練)することで、調製することができ、この混合(混練)の際には、各成分を一度に添加・混合してもよく、複数回に分けて添加・混合してもよい。
本組成物は、これら第1剤、第2剤および必要に応じて用いられる他の剤(例:第3剤)を混合(混練)することで、調製することができる。
前記混合(混練)の際には、従来公知の混合機、分散機、攪拌機等の装置を使用でき、該装置としては、例えば、ディスパー、混合・分散ミル、モルタルミキサー、ロール、ペイントシェーカー、ホモジナイザーが挙げられる。なお、前記混合(混練)の際には、季節、環境等に応じて加温、冷却等しながら行ってもよい。
また、前記各剤を混合して本組成物を調製する際には、得られる組成物中の亜鉛末(B)の含有量が前記範囲となるように調整して混合すればよい。
<Method for preparing anticorrosion paint composition>
The first agent and the second agent can be prepared by mixing (kneading) the respective components to be added to these agents, and during this mixing (kneading), each component is added/mixed at once. They may be mixed, or may be added and mixed in multiple batches.
The present composition can be prepared by mixing (kneading) these first agent, second agent, and other agents (eg, third agent) used as necessary.
During the mixing (kneading), conventionally known devices such as mixers, dispersers, stirrers, etc. can be used, such as dispers, mixing/dispersing mills, mortar mixers, rolls, paint shakers, homogenizers, etc. can be mentioned. The mixing (kneading) may be performed while heating, cooling, etc. depending on the season, environment, etc.
Moreover, when preparing the present composition by mixing each of the above-mentioned agents, the content of zinc dust (B) in the resulting composition may be adjusted and mixed so that it falls within the above-mentioned range.
≪塗膜、塗膜付き基材≫
本発明に係る塗膜(以下「本塗膜」ともいう。)は、前記本組成物を用いて形成され、本発明に係る塗膜付き基材(以下「本塗膜付き基材」ともいう。)は、本塗膜と基材とを有する積層体である。
≪Coating film, base material with coating film≫
The coating film according to the present invention (hereinafter also referred to as "main coating film") is formed using the above-mentioned composition, and the coating film according to the present invention (hereinafter also referred to as "substrate with main coating film") is formed using the above-mentioned composition. ) is a laminate having a main coating film and a base material.
前記基材の材質としては特に制限されず、例えば、鉄鋼(鉄、鋼、合金鉄、炭素鋼、マイルドスチール、合金鋼等)、非鉄金属(亜鉛、アルミニウム、銅、真鍮、亜鉛メッキ、亜鉛溶射等)、ステンレス(SUS304、SUS410等)が挙げられる。
また、前記基材として、例えば、マイルドスチール(SS400等)を用いる場合、必要により、グリットブラスト等で基材表面を研磨するなど、素地調整(例:算術平均粗さ(Ra)が30~75μm程度になるよう調整)しておくことが望ましい。
前記基材としては、さらに、基材に付着した錆、汚れ、塗料(旧塗膜)等を落とす洗浄処理やブラスト処理等の前処理を行った基材であってもよい。
The material of the base material is not particularly limited, and includes, for example, steel (iron, steel, ferroalloy, carbon steel, mild steel, alloy steel, etc.), non-ferrous metals (zinc, aluminum, copper, brass, galvanized, zinc sprayed, etc.). etc.), stainless steel (SUS304, SUS410, etc.).
In addition, when using mild steel (SS400, etc.) as the base material, if necessary, the surface of the base material may be polished by grit blasting or the like to adjust the base material (for example, the arithmetic mean roughness (Ra) is 30 to 75 μm). It is desirable to adjust it to a certain degree.
The base material may be a base material that has been subjected to pretreatment such as cleaning or blasting treatment to remove rust, dirt, paint (old paint film), etc. that have adhered to the base material.
前記基材としては特に制限されず、防食性が求められる基材に対し、制限なく使用することができるが、本組成物を用いる効果がより発揮される等の点から、好ましくは、船舶、海洋構造物、プラント、橋梁、タンク、コンテナなどの(鉄鋼)構造物等が挙げられる。 The base material is not particularly limited and can be used without any restriction for base materials that require anti-corrosion properties, but ships, ships, Examples include (steel) structures such as offshore structures, plants, bridges, tanks, and containers.
本塗膜の乾燥膜厚は特に限定されないが、十分な防食性を有する塗膜が得られる等の点から、通常は10~100μm、好ましくは15~80μm、より好ましくは20~60μmである。 The dry thickness of the coating film is not particularly limited, but from the viewpoint of obtaining a coating film with sufficient anticorrosion properties, it is usually 10 to 100 μm, preferably 15 to 80 μm, and more preferably 20 to 60 μm.
本塗膜付き基材は、本塗膜と基材とを含む積層体であって、本塗膜上に、さらに防食性の向上を目的とした中塗り塗膜や、耐候性や美観等に優れる上塗り塗膜を形成してもよい。前記中塗り塗膜としては、アクリル樹脂系、エポキシ樹脂系、ウレタン樹脂系等の各種中塗り塗料組成物より形成される塗膜等が挙げられる。また、前記上塗り塗膜としては、アクリル樹脂系、アクリルシリコン樹脂系、ウレタン樹脂系、シリコーン樹脂系、フッ素樹脂系等の各種上塗り塗料組成物より形成される塗膜等が挙げられる。 The base material with the main coating film is a laminate containing the main coating film and the base material, and on top of the main coating film, an intermediate coating film is added for the purpose of improving corrosion resistance, weather resistance, aesthetics, etc. It may also form an excellent top coat. Examples of the intermediate coating film include coating films formed from various intermediate coating compositions such as acrylic resin, epoxy resin, and urethane resin. Examples of the top coat film include those formed from various top coat compositions such as acrylic resin, acrylic silicone resin, urethane resin, silicone resin, and fluorine resin.
≪塗膜付き基材の製造方法≫
本発明に係る塗膜付き基材の製造方法(以下「本方法」ともいう。)は、下記工程[1]および[2]を含む。
工程[1]:本組成物を基材に塗装する工程
工程[2]:基材上に塗装された本組成物を乾燥させて塗膜を形成する工程
≪Method for manufacturing base material with coating film≫
The method for producing a coated substrate according to the present invention (hereinafter also referred to as "the present method") includes the following steps [1] and [2].
Step [1]: Step of coating the present composition on a substrate Step [2]: Step of drying the present composition coated on the substrate to form a coating film.
<工程[1]>
前記工程[1]における塗装方法としては、特に制限されず、例えば、エアレススプレー塗装、エアースプレー塗装等のスプレー塗装、はけ塗り、ローラー塗りなどの従来公知の方法が挙げられる。これらの中でも、前記構造物などの大面積の基材を容易に塗装できる等の点から、スプレー塗装が好ましい。
このような塗装の際には、得られる塗膜の乾燥膜厚が前記範囲となるように塗装することが好ましい。
<Step [1]>
The coating method in step [1] is not particularly limited, and examples thereof include conventionally known methods such as spray coating such as airless spray coating and air spray coating, brush coating, and roller coating. Among these, spray coating is preferred because it can easily coat large-area base materials such as the above-mentioned structures.
In such coating, it is preferable to apply the coating so that the dry film thickness of the resulting coating film falls within the above range.
前記スプレー塗装の条件は、形成したい乾燥膜厚に応じて適宜調整すればよいが、例えば、エアレススプレー塗装の場合、1次(空気)圧:0.3~0.6MPa程度、2次(塗料)圧:10~15MPa程度、ガン移動速度50~120cm/秒程度が好ましい。 The spray coating conditions may be adjusted as appropriate depending on the desired dry film thickness. For example, in the case of airless spray coating, the primary (air) pressure: about 0.3 to 0.6 MPa, the secondary (paint ) Pressure: preferably about 10 to 15 MPa and gun movement speed of about 50 to 120 cm/sec.
なお、本組成物を塗装する際に、所望に応じて、適正な塗料組成物の粘度に調整してもよい。このような粘度調整に用いる希釈剤としては、水を用いることが好ましい。
この場合、各塗装方法に適した塗料粘度となるように希釈剤を用いることが好ましく、例えば、エアレススプレー塗装する場合、本組成物100質量部に対する希釈剤の使用量は、好ましくは1~30質量部、より好ましくは1~20質量部である。
In addition, when coating the present composition, the viscosity of the coating composition may be adjusted to an appropriate value as desired. It is preferable to use water as the diluent used for such viscosity adjustment.
In this case, it is preferable to use a diluent to obtain a paint viscosity suitable for each coating method. For example, in the case of airless spray painting, the amount of diluent used per 100 parts by mass of the present composition is preferably 1 to 30 parts by mass. Parts by weight, more preferably 1 to 20 parts by weight.
前記スプレー塗装に適した本組成物(必要により希釈された組成物)の粘度は、測定器としてB型粘度計(リオン(株)製、型式VT-06)を用いた、23℃の測定条件下での粘度が、好ましくは3,000~15,000mPa・s、より好ましくは5,000~12,000mPa・sである。 The viscosity of this composition (composition diluted if necessary) suitable for the above-mentioned spray coating was determined using a B-type viscometer (manufactured by Rion Co., Ltd., model VT-06) at 23°C. The viscosity below is preferably 3,000 to 15,000 mPa·s, more preferably 5,000 to 12,000 mPa·s.
<工程[2]>
前記工程[2]における乾燥条件としては、特に制限されず、塗膜の形成方法、基材の種類、用途、塗装環境等に応じて適宜設定すればよいが、乾燥温度は、常温乾燥の場合、通常5~35℃、より好ましくは10~30℃であり、熱風乾燥機等で強制乾燥する場合、通常30~90℃、より好ましくは40~80℃である。本組成物によれば、このような常温乾燥でも組成物を硬化させることができる。
乾燥時間は、塗膜の乾燥方法によって異なり、常温乾燥の場合、従来の塗料と同様に1日~7日程度であってもよいが、本組成物によれば、好ましくは3時間~12時間、より好ましくは5時間~10時間で乾燥させることができる。また、強制乾燥する場合、従来の塗料と同様に5分~60分程度であってもよいが、本組成物によれば、好ましくは5分~30分、より好ましくは10分~20分で乾燥させることができる。
<Step [2]>
The drying conditions in step [2] are not particularly limited and may be set appropriately depending on the coating film formation method, type of substrate, application, coating environment, etc., but the drying temperature is when drying at room temperature. The temperature is usually 5 to 35°C, more preferably 10 to 30°C, and when forced drying with a hot air dryer etc., the temperature is usually 30 to 90°C, more preferably 40 to 80°C. According to the present composition, the composition can be cured even by drying at room temperature.
The drying time varies depending on the drying method of the coating film, and in the case of drying at room temperature, it may be about 1 to 7 days like conventional paints, but according to the present composition, it is preferably 3 hours to 12 hours. The drying time can be more preferably 5 hours to 10 hours. In addition, when forced drying, it may take about 5 to 60 minutes like conventional paints, but according to the present composition, it is preferably 5 to 30 minutes, more preferably 10 to 20 minutes. Can be dried.
本発明について実施例を挙げ、更に詳細に説明するが、本発明はこれらによって限定されるものではない。 The present invention will be described in more detail by way of examples, but the present invention is not limited thereto.
[実施例1]
容器に、イオン交換水を18.1質量部、分散剤1を2質量部、消泡剤を0.5質量部、フラッシュラスト防止剤を0.3質量部、体質顔料を8質量部、および、揺変剤1を1.5質量部添加し、ハイスピードディスパーで粒ゲージ40μm以下まで分散し、ミルベースを作製した。得られたミルベースに、水分散型エポキシ樹脂Aを63質量部、造膜助剤を2.5質量部、レベリング剤を0.1質量部、増粘剤を4質量部添加した後、ハイスピードディスパーで混合し、実施例1の第1剤を調製した。
次に、前述のようにして得られた第1剤40質量部と、第2剤である亜鉛末60質量部とを、均一になるまでハイスピードディスパーで混合し、実施例1の塗料組成物を調製した。
[Example 1]
In a container, 18.1 parts by mass of ion exchange water, 2 parts by mass of dispersant 1, 0.5 parts by mass of antifoaming agent, 0.3 parts by mass of flash last inhibitor, 8 parts by mass of extender, and , 1.5 parts by mass of thixotropic agent 1 was added and dispersed with a high-speed disperser to a grain size of 40 μm or less to prepare a mill base. After adding 63 parts by mass of water-dispersed epoxy resin A, 2.5 parts by mass of a film-forming agent, 0.1 parts by mass of a leveling agent, and 4 parts by mass of a thickener to the obtained mill base, high speed The first agent of Example 1 was prepared by mixing with a disper.
Next, 40 parts by mass of the first part obtained as described above and 60 parts by mass of zinc powder, which is the second part, were mixed with a high-speed disperser until uniform. was prepared.
[実施例2]
実施例1と同様にして、第1剤を調製した。
次に、容器に、有機溶剤を7質量部、分散剤2を2質量部、揺変剤2を3質量部、湿潤剤を1質量部、および、亜鉛末を87質量部添加し、ハイスピードディスパーで混合し、実施例2の第2剤を調製した。
その後、第1剤30質量部と、第2剤70質量部とを、均一になるまでハイスピードディスパーで混合し、実施例2の塗料組成物を調製した。
[Example 2]
A first agent was prepared in the same manner as in Example 1.
Next, 7 parts by mass of an organic solvent, 2 parts by mass of dispersant 2, 3 parts by mass of thixotropic agent 2, 1 part by mass of wetting agent, and 87 parts by mass of zinc powder were added to the container, and high speed The second agent of Example 2 was prepared by mixing with a disper.
Thereafter, 30 parts by mass of the first part and 70 parts by mass of the second part were mixed using a high-speed disperser until they became uniform, thereby preparing the coating composition of Example 2.
[実施例3]
実施例1と同様にして、第1剤を調製した。
次に、容器に、有機溶剤を5質量部、分散剤2を2質量部、揺変剤2を3質量部、湿潤剤を1質量部、樹脂(A)以外のバインダー2質量部、および、亜鉛末を87質量部添加し、ハイスピードディスパーで混合し、実施例3の第2剤を調製した。
その後、第1剤30質量部と、第2剤70質量部とを、均一になるまでハイスピードディスパーで混合し、実施例3の塗料組成物を調製した。
[Example 3]
A first agent was prepared in the same manner as in Example 1.
Next, in a container, 5 parts by mass of an organic solvent, 2 parts by mass of dispersant 2, 3 parts by mass of thixotropic agent 2, 1 part by mass of a wetting agent, 2 parts by mass of a binder other than the resin (A), and 87 parts by mass of zinc powder was added and mixed using a high-speed disperser to prepare the second agent of Example 3.
Thereafter, 30 parts by mass of the first part and 70 parts by mass of the second part were mixed using a high-speed disperser until they became uniform, thereby preparing the coating composition of Example 3.
[実施例4~7および比較例5~7]
表2に記載の各原材料を、該表に記載の量で用いた以外は実施例2と同様にして、塗料組成物を調製した。
[Examples 4 to 7 and Comparative Examples 5 to 7]
A coating composition was prepared in the same manner as in Example 2, except that each of the raw materials listed in Table 2 was used in the amounts listed in the table.
[比較例1]
表1に記載の各原材料を、該表に記載の量で用いた以外は実施例1と同様にして、第1剤を調製した。
次に、容器に、水溶性アミンを45質量部、消泡剤を0.2質量部、および、イオン交換水を54.8質量部添加した後、ハイスピードディスパーで混合し、比較例1の硬化剤を調製した。
その後、第1剤30質量部と、硬化剤5質量部と、第2剤である亜鉛末65質量部とを、均一になるまでハイスピードディスパーで混合し、比較例1の塗料組成物を調製した。
[Comparative example 1]
A first agent was prepared in the same manner as in Example 1, except that each of the raw materials listed in Table 1 was used in the amounts listed in the table.
Next, 45 parts by mass of a water-soluble amine, 0.2 parts by mass of an antifoaming agent, and 54.8 parts by mass of ion-exchanged water were added to the container, and then mixed with a high-speed disper. A curing agent was prepared.
Thereafter, 30 parts by mass of the first part, 5 parts by mass of the curing agent, and 65 parts by mass of zinc dust as the second part were mixed with a high-speed disper until uniform, to prepare the coating composition of Comparative Example 1. did.
[比較例2~4]
表1に記載の各原材料を、該表に記載の量で用いた以外は実施例1と同様にして、各塗料組成物を調製した。
[Comparative Examples 2 to 4]
Each coating composition was prepared in the same manner as in Example 1 except that each raw material listed in Table 1 was used in the amount listed in the table.
表1および2中の各剤(第1剤、第2剤または硬化剤)の欄の数値は、「質量部」を表す。
表1および2中の原材料の詳細を表3に示す。
The numerical value in the column for each agent (first agent, second agent, or curing agent) in Tables 1 and 2 represents "parts by mass."
Details of the raw materials in Tables 1 and 2 are shown in Table 3.
<1.亜鉛末混和性試験>
(1)手撹拌による亜鉛末混和性試験
容器に、各実施例および比較例で用いた第2剤160質量部を入れ、そこに、水と各試験例の第1剤で使用した樹脂との合計が40質量部となるように添加し(但し、硬化剤を用いない場合は、各試験例で用いた樹脂の不揮発分が15質量部となる量を使用[例えば、実施例1の場合は、水分散型エポキシ樹脂A(不揮発分42%)35.7質量部と水4.3質量部とを使用]。なお、比較例1の場合は、水分散エポキシ樹脂B(不揮発分52%)24.6質量部と水溶性アミン(不揮発分75%)3.0質量部との混合物に水12.4質量部を加えて使用)、スパチュラを用いて5分間撹拌(手撹拌)した。続いて、JIS K 5600-2-5;1999に準拠し、粒ゲージ(0~100μm)を用いて亜鉛末の分散度を測定した。
<1. Zinc dust miscibility test>
(1) Zinc powder miscibility test by manual stirring 160 parts by mass of the second agent used in each example and comparative example was placed in a container, and water and the resin used in the first agent of each test example were mixed into a container. Add so that the total is 40 parts by mass (however, if no curing agent is used, use an amount that makes the nonvolatile content of the resin used in each test example 15 parts by mass [for example, in the case of Example 1 , using 35.7 parts by mass of water-dispersed epoxy resin A (42% non-volatile content) and 4.3 parts by mass of water].In the case of Comparative Example 1, water-dispersed epoxy resin B (52% non-volatile content) was used. A mixture of 24.6 parts by mass and 3.0 parts by mass of a water-soluble amine (75% non-volatile content) with 12.4 parts by mass of water was stirred for 5 minutes using a spatula (hand stirring). Subsequently, the degree of dispersion of the zinc powder was measured using a particle gauge (0 to 100 μm) in accordance with JIS K 5600-2-5; 1999.
(2)ディスパー撹拌による亜鉛末混和性試験
前記(1)において、手攪拌の代わりに、ハイスピードディスパー(回転数1000rpm)で5分間撹拌(ディスパー撹拌)した以外は同様にして亜鉛末の分散度を測定した。
(2) Zinc powder miscibility test using disper stirring In the same manner as in (1) above, except that instead of manual stirring, stirring was performed for 5 minutes using a high-speed disper (rotation speed: 1000 rpm) (disper stirring). was measured.
前記(1)および(2)の試験において測定した亜鉛末の分散度を基に、亜鉛末混和性を下記基準により評価した。
・評価基準
○:前記(1)の試験における分散度が30μm未満
△:前記(1)の試験における分散度が30μm以上であり、かつ、前記(2)の試験における分散度が30μm未満
×:前記(2)の試験における分散度が30μm以上
Based on the dispersion degree of zinc powder measured in the tests (1) and (2) above, the miscibility of zinc powder was evaluated according to the following criteria.
・Evaluation criteria ○: Dispersity in the test (1) above is less than 30 μm △: Dispersity in the test (1) above is 30 μm or more, and dispersity in the test (2) above is less than 30 μm ×: The degree of dispersion in the test (2) above is 30 μm or more
<2.乾燥性試験>
23℃下で、ガラス板上に、実施例および比較例の各塗料組成物を、すき間0.075mmのアプリケータを用いて塗装し、経時での乾燥状態を測定した。乾燥性は、JIS K 5600-1-1:1999に基づき、塗膜面の乾燥状態が、半硬化乾燥状態に達するまでの時間により評価した。なお、「半硬化乾燥」状態とは、塗膜面の中央付近を指先で静かに軽くこすり、塗膜にすり跡が付かない状態のことをいう。
・評価基準
○:30分以下で半硬化乾燥状態に達した
×:30分経過しても半硬化乾燥状態に達しなかった
<2. Drying test>
Each of the coating compositions of Examples and Comparative Examples was applied onto a glass plate at 23° C. using an applicator with a gap of 0.075 mm, and the drying state over time was measured. The drying property was evaluated based on JIS K 5600-1-1:1999 based on the time required for the dry state of the coated film surface to reach a semi-cured dry state. The "semi-cured and dry" state refers to a state where no scratches are left on the paint film by gently and lightly rubbing the center of the paint film surface with your fingertips.
・Evaluation criteria ○: A semi-cured and dry state was reached in 30 minutes or less. ×: A semi-cured and dry state was not reached even after 30 minutes had passed.
<3.硬化性試験>
23℃下で、ガラス板(200mm×180mm×厚み3mm)上に、実施例および比較例の各塗料組成物を、すき間75μmのアプリケータを用いて塗装し、10分間静置した後、50℃で10分間強制乾燥し、次いで、室温で1日静置することで、硬化性試験用試験体を作成した。該試験体の塗膜について、JIS K 5600-5-4:1999に基づいて、ひっかき硬度(鉛筆法)を測定した。塗膜表面にきず跡が生じなかった最も硬い鉛筆硬度を塗膜硬度とし、下記評価基準に従って評価した。
・評価基準
○:鉛筆硬度が2B以上(例:2B、B、HB・・・)
×:鉛筆硬度が2B未満(例:3B、4B、5B・・・)
<3. Curing test>
The coating compositions of Examples and Comparative Examples were applied onto a glass plate (200 mm x 180 mm x 3 mm thickness) at 23°C using an applicator with a gap of 75 μm, and after standing for 10 minutes, the coating composition was heated at 50°C. A test specimen for hardening test was prepared by force drying for 10 minutes at room temperature, and then allowing it to stand at room temperature for one day. The scratch hardness (pencil method) of the coating film of the test specimen was measured based on JIS K 5600-5-4:1999. The hardest pencil hardness without any scratches on the surface of the coating film was defined as the coating hardness, and evaluation was made according to the following evaluation criteria.
・Evaluation criteria ○: Pencil hardness is 2B or more (Example: 2B, B, HB...)
×: Pencil hardness is less than 2B (e.g. 3B, 4B, 5B...)
<4.ポットライフ試験>
実施例および比較例の各塗料組成物を調製した直後の組成物(以下「塗料組成物(直後)」ともいう。)と、実施例および比較例の各塗料組成物を容器に1000g量り採り、35℃の恒温槽中で5時間保持した後の塗料組成物(以下「塗料組成物(5時間後)」ともいう。)とを用い、塗料状態と塗膜硬度を観察または測定した。
塗料状態は、塗料組成物(5時間後)の状態(沈殿や凝集の有無)を目視により観察した。
また、塗膜硬度は、前記塗料組成物(直後)または塗料組成物(5時間後)を用い、前記硬化性試験と同様の方法で測定した鉛筆硬度の差を基に、下記評価基準に従って評価した。
・評価基準
○:塗料組成物(5時間後)に沈殿および凝集がなく、かつ、塗料組成物(直後)から得られた塗膜の塗膜硬度と、塗料組成物(5時間後)から得られた塗膜の塗膜硬度とに差がない
×:塗料組成物(5時間後)に沈殿および凝集が発生、または、塗料組成物(直後)から得られた塗膜の塗膜硬度と、塗料組成物(5時間後)から得られた塗膜の塗膜硬度とに差が生じた
<4. Pot life test>
Weigh out 1000 g of the composition immediately after preparing each coating composition of Examples and Comparative Examples (hereinafter also referred to as "coating composition (immediately)") and each coating composition of Examples and Comparative Examples into a container, The paint condition and coating hardness were observed or measured using the paint composition after being kept in a constant temperature bath at 35° C. for 5 hours (hereinafter also referred to as "paint composition (after 5 hours)").
The state of the paint composition (after 5 hours) was visually observed (presence of precipitation or agglomeration).
In addition, coating film hardness was evaluated according to the following evaluation criteria based on the difference in pencil hardness measured using the coating composition (immediately) or the coating composition (after 5 hours) in the same manner as the curing test. did.
・Evaluation criteria ○: There is no precipitation or agglomeration in the coating composition (after 5 hours), and the hardness of the coating film obtained from the coating composition (immediately) and the coating film obtained from the coating composition (after 5 hours) are There is no difference between the hardness of the paint film obtained from the paint composition (immediately after 5 hours), or the hardness of the paint film obtained from the paint composition (immediately after 5 hours). There was a difference in the hardness of the paint film obtained from the paint composition (after 5 hours).
<5.水希釈性試験>
実施例および比較例の各塗料組成物100質量部に対して、水を15質量部添加、混合した後、23℃下で、水平な台の上に置いたガラス板(200mm×150mm×厚み2mm)に、得られた混合物を、ASTM D 4400に記載のサグテスター(elcometer社製、型式:4270、隙間100~600μm)を用いて塗布した後、直ちに該ガラス板をサグテスターの軌道線が水平になるように垂直に立て、タレ止め性を測定した。サグテスターの各隙間によって形成された塗料層と塗料層との間の間隙(3mm)に流れ出た組成物が、該間隙距離の1/2に達しない場合(サグテスターによって形成された塗料層から垂れた長さが1.5mmに達しない場合)をタレが発生していないとし、また、前記間隙距離の1/2に達した場合をタレが発生していると判断した。
なお、タレ止め性は、前記流れ出た組成物が、前記間隙距離の1/2に達しない場合の最大の膜厚(ガラス板に塗装したウェット塗膜の膜厚(サグテスターの隙間))を指し、15%希釈時のタレ止め性と、塗料組成物混合時(無希釈時)のタレ止め性との差を基に、水希釈性を評価した。
・評価基準
○:無希釈時と15%希釈時のタレ止め性の差が250μm以内
×:無希釈時と15%希釈時のタレ止め性の差が250μmを越える
<5. Water dilubility test>
After adding and mixing 15 parts by mass of water to 100 parts by mass of each coating composition of Examples and Comparative Examples, a glass plate (200 mm x 150 mm x 2 mm thick) placed on a horizontal stand at 23 ° C. ), using a sag tester (manufactured by Elcometer, model: 4270, gap 100-600 μm) as described in ASTM D 4400, and immediately place the glass plate so that the trajectory line of the sag tester becomes horizontal. The anti-sagging property was measured by standing it vertically. If the composition flowing out into the gap (3 mm) between the paint layers formed by each gap of the sag tester does not reach 1/2 of the gap distance (the composition drips from the paint layer formed by the sag tester) When the length did not reach 1.5 mm), it was determined that no sag occurred, and when the gap distance reached 1/2 of the gap distance, it was determined that sagging occurred.
In addition, anti-sagging property refers to the maximum film thickness (thickness of a wet coating film applied to a glass plate (sag tester gap)) when the flowing out composition does not reach 1/2 of the gap distance. The water dilutability was evaluated based on the difference between the anti-sagging property when diluted by 15% and the anti-sagging property when the coating composition was mixed (without dilution).
・Evaluation criteria ○: Difference in anti-sagging properties between undiluted and 15% dilution is within 250 μm ×: Difference in anti-sagging properties between undiluted and 15% diluted exceeds 250 μm
<6.防食性試験>
前記水希釈性試験と同様に測定したタレ止め性が50μmとなるように、イオン交換水を用いて、実施例および比較例の各塗料組成物を調整した。
このように調整後の各塗料組成物を、ブラスト処理鋼板(SS400、寸法:150mm×70mm×1.6mm(厚))上に、平均乾燥膜厚が30μmとなるようにエアースプレーで塗布し、常温下で10分間乾燥した後、50℃で10分間熱風乾燥することで塗膜を形成した。その後、23℃、相対湿度50%の環境下で7日間乾燥することで、試験体(塗膜付き基材)を作成した。
<6. Corrosion resistance test>
Each of the coating compositions of Examples and Comparative Examples was adjusted using ion-exchanged water so that the anti-sagging property measured in the same manner as the water dilubility test was 50 μm.
Each paint composition thus adjusted was applied by air spray onto a blast-treated steel plate (SS400, dimensions: 150 mm x 70 mm x 1.6 mm (thickness)) so that the average dry film thickness was 30 μm, After drying at room temperature for 10 minutes, a coating film was formed by drying with hot air at 50° C. for 10 minutes. Thereafter, a test specimen (base material with a coating film) was created by drying it for 7 days in an environment of 23° C. and 50% relative humidity.
JIS K 5600-7-1:1999に基づいて、塩水濃度5wt%、温度35℃、相対湿度98%の塩水噴霧条件の塩水噴霧試験機中に、前記各試験体を24時間保持することで塩水噴霧試験を行った。この塩水噴霧試験後の各試験体を下記評価基準に従って評価した。
・評価基準
○:試験体の塗膜面の全面積に対して、錆の発生面積が0.03%以下であり、かつ、塗膜に膨れが発生していない。
×:試験体の塗膜面の全面積に対して、錆の発生面積が0.03%を超えた、または、塗膜に膨れが発生した。
Based on JIS K 5600-7-1:1999, each test specimen was kept in a salt spray tester for 24 hours under the conditions of salt water concentration 5wt%, temperature 35°C, and relative humidity 98%. A spray test was conducted. Each test piece after this salt spray test was evaluated according to the following evaluation criteria.
-Evaluation Criteria ○: The area where rust occurs is 0.03% or less of the total area of the coating surface of the test piece, and no blistering occurs in the coating film.
×: The area where rust occurred exceeded 0.03% of the total area of the coating surface of the test piece, or blistering occurred in the coating film.
Claims (8)
1分子中に1個以上のカルボキシ基を有し、不揮発分の酸価が1~20mgKOH/gである水性エポキシ樹脂(A)を含む第1剤と、
亜鉛末(B)を含む第2剤と、
を含有し、
前記亜鉛末(B)を、前記防食塗料組成物の不揮発分100質量%に対し、43~85質量%含有し、
前記水性エポキシ樹脂(A)の不揮発分のアミン価が1~150mgKOH/gである、
防食塗料組成物。 An anticorrosive paint composition, comprising:
A first agent containing an aqueous epoxy resin (A) having one or more carboxyl groups in one molecule and having an acid value of non-volatile content of 1 to 20 mgKOH/g;
a second agent containing zinc dust (B);
Contains
The zinc powder (B) is contained in an amount of 43 to 85% by mass based on 100% by mass of the non-volatile content of the anticorrosive coating composition,
The amine value of the nonvolatile content of the aqueous epoxy resin (A) is 1 to 150 mgKOH/g.
Anticorrosive paint composition.
[1]基材に、請求項1~5のいずれか1項に記載の防食塗料組成物を塗装する工程
[2]基材上に塗装された組成物を乾燥させて塗膜を形成する工程 A method for producing a coated substrate, including the following steps [1] and [2].
[1] A step of coating a substrate with the anticorrosive coating composition according to any one of claims 1 to 5. [2] A step of drying the composition coated on the substrate to form a coating film.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000053745A (en) | 1998-08-10 | 2000-02-22 | Mitsui Chemicals Inc | Water soluble epoxy resin composition and manufacture of the same |
JP2007146100A (en) | 2005-10-24 | 2007-06-14 | Kansai Paint Co Ltd | Aqueous dispersion and aqueous coating material containing the same |
JP2008050454A (en) | 2006-08-24 | 2008-03-06 | Kansai Paint Co Ltd | Water-based coating composition |
JP2013199546A (en) | 2012-03-23 | 2013-10-03 | Dainippon Toryo Co Ltd | Water-soluble anticorrosive paint composition and corrosion protection method |
CN104693417A (en) | 2013-12-05 | 2015-06-10 | 青岛惠城石化科技有限公司 | Preparation of amino acid salt modified epoxy resin and waterborne epoxy anticorrosive paint |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1099044A (en) * | 1977-03-08 | 1981-04-07 | William J. Birkmeyer | Water-based coating compositions based on epoxy resin- amino acid adducts and their use as coatings for beverage containers |
US4299747A (en) * | 1977-03-08 | 1981-11-10 | Ppg Industries, Inc. | Reaction products of a polyglycidyl ether of a polyphenol and an amino acid and aqueous solubilized products therefrom |
JPS606380B2 (en) * | 1980-12-03 | 1985-02-18 | 大日本インキ化学工業株式会社 | Resin composition for water-based anticorrosion paint |
JPS62169870A (en) * | 1985-08-09 | 1987-07-27 | Kansai Paint Co Ltd | Water-based corrosion-resistant paint composition |
US5569687A (en) * | 1995-03-16 | 1996-10-29 | Rohm And Haas Company | Waterborne zinc-rich primer compositions |
DE19650157A1 (en) * | 1996-12-04 | 1998-06-10 | Basf Coatings Ag | Process for coating substrates, preferably of metal |
CN1215137C (en) * | 2002-07-30 | 2005-08-17 | 关西涂料株式会社 | Paint composition and coating method |
JP4457819B2 (en) * | 2004-09-15 | 2010-04-28 | Jfeスチール株式会社 | High corrosion resistance surface-treated steel sheet and method for producing the same |
JP5610785B2 (en) * | 2009-04-06 | 2014-10-22 | 関西ペイント株式会社 | Cationic electrodeposition coating composition |
JP5637722B2 (en) * | 2009-04-24 | 2014-12-10 | 関西ペイント株式会社 | Cationic electrodeposition coating composition |
CN102993900A (en) * | 2012-10-16 | 2013-03-27 | 益阳祥瑞科技有限公司 | Epoxy resin coating for seawater |
CN103694851A (en) * | 2013-12-10 | 2014-04-02 | 山东蓝星清洗防腐公司 | Anti-corrosion coating |
EP3385072B1 (en) * | 2015-11-30 | 2023-09-06 | Chugoku Marine Paints, Ltd. | Antifouling composite coating film, antifouling substrate, and method for manufacturing antifouling substrate |
-
2020
- 2020-02-18 JP JP2020025081A patent/JP7429560B2/en active Active
- 2020-02-24 CN CN202010111044.7A patent/CN111621211B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000053745A (en) | 1998-08-10 | 2000-02-22 | Mitsui Chemicals Inc | Water soluble epoxy resin composition and manufacture of the same |
JP2007146100A (en) | 2005-10-24 | 2007-06-14 | Kansai Paint Co Ltd | Aqueous dispersion and aqueous coating material containing the same |
JP2008050454A (en) | 2006-08-24 | 2008-03-06 | Kansai Paint Co Ltd | Water-based coating composition |
JP2013199546A (en) | 2012-03-23 | 2013-10-03 | Dainippon Toryo Co Ltd | Water-soluble anticorrosive paint composition and corrosion protection method |
CN104693417A (en) | 2013-12-05 | 2015-06-10 | 青岛惠城石化科技有限公司 | Preparation of amino acid salt modified epoxy resin and waterborne epoxy anticorrosive paint |
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