JP2018053203A - Anticorrosive coating composition, coated film formed from the composition, laminate and structure having the coated film, and additive agent for anticorrosive coating - Google Patents
Anticorrosive coating composition, coated film formed from the composition, laminate and structure having the coated film, and additive agent for anticorrosive coating Download PDFInfo
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Description
本発明は、防食塗料組成物、該組成物からなる塗膜、該塗膜を備える積層体及び構造物、並びに防食塗料用添加剤に関する。 The present invention relates to an anticorrosion coating composition, a coating film comprising the composition, a laminate and a structure provided with the coating film, and an additive for anticorrosion coating.
道路橋示方書（国土交通省発行）によれば、鋼橋の施工にあたって、ボルト接合部における接触面に無機ジンクリッチペイントを塗装する場合、接触面のすべり係数が０．４５以上になるよう、適切な処理を施さなければならない。従来、有機ジンクリッチペイントは、すべり係数がせいぜい０．３０前後であり、上記接触面への塗装には用いられていなかった。 According to the Road Bridge Specification (issued by the Ministry of Land, Infrastructure, Transport and Tourism), when applying an inorganic zinc rich paint on the contact surface at the bolt joint when constructing a steel bridge, the slip coefficient of the contact surface should be 0.45 or more. Appropriate treatment must be applied. Conventionally, organic zinc rich paint has a slip coefficient of about 0.30 at most and has not been used for coating on the contact surface.
近年、有機ジンクリッチペイントを用いた場合でも、塗膜のすべり係数を向上させる技術が提案されている。例えば、特許文献１には、塗膜中に亜鉛末を９１重量％以上含有し、塗膜のすべり係数が０．４以上であることを特徴とするエポキシ樹脂防食塗料組成物が開示されている。 In recent years, even when organic zinc rich paint is used, a technique for improving the slip coefficient of a coating film has been proposed. For example, Patent Document 1 discloses an epoxy resin anticorrosive coating composition containing 91% by weight or more of zinc powder in a coating film and having a coating coefficient of 0.4 or more. .
本発明者らの検討によれば、塗膜のすべり係数を向上させた従来の有機ジンクリッチペイントから塗膜を形成し、その上に、下塗り層、中塗り層、及び上塗り層をこの順序で塗り重ねた場合、上記上塗り層の光沢度が低下することが判明した。
なお、有機ジンクリッチペイントには、亜鉛末を含む不揮発分が沈殿しないよう、貯蔵安定性に優れることが求められる。
According to the study by the present inventors, a coating film is formed from a conventional organic zinc rich paint with an improved slip coefficient of the coating film, and an undercoat layer, an intermediate coating layer, and an overcoat layer are formed in this order on the coating film. It was found that the glossiness of the topcoat layer was lowered when the coating was repeated.
Note that the organic zinc rich paint is required to have excellent storage stability so that a non-volatile component containing zinc powder does not precipitate.
本発明は、上記の問題に鑑みてなされたものであり、（１）０．４５以上のすべり係数を有する塗膜を与える有機ジンクリッチペイントとして有用であり、（２）当該塗膜上に下塗り層、中塗り層、及び上塗り層をこの順序で塗り重ねた場合、上記上塗り層の光沢度を維持することができ、（３）貯蔵安定性に優れる防食塗料組成物、該組成物からなる塗膜、該塗膜を備える積層体及び構造物、並びに防食塗料用添加剤を提供することを目的とする。 The present invention has been made in view of the above problems, and (1) is useful as an organic zinc rich paint that gives a coating film having a slip coefficient of 0.45 or more, and (2) an undercoat on the coating film. When the layer, the intermediate coating layer, and the top coating layer are applied in this order, the glossiness of the top coating layer can be maintained, and (3) an anticorrosive coating composition having excellent storage stability and a coating comprising the composition. It aims at providing the film | membrane, the laminated body and structure provided with this coating film, and the additive for anticorrosion coatings.
本発明者らは、上記目的を達成するために鋭意検討した結果、体積換算の９０％累積平均径ｄ９０が６０μｍ以下の中空粒子を亜鉛末と併用することにより、上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。 As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that the above-mentioned problems can be solved by using hollow particles having a volume-converted 90% cumulative average diameter d 90 of 60 μm or less together with zinc powder. The present invention has been completed.
即ち、本発明の一実施形態に係る防食塗料組成物は、有機樹脂と、平均粒子径１〜３０μｍの亜鉛末と、体積換算の９０％累積平均径ｄ９０が６０μｍ以下の中空粒子と、を含有し、
前記組成物に含まれる不揮発分中、前記亜鉛末及び前記中空粒子の合計の体積濃度である顔料体積濃度（ＰＶＣ）が５８％以上であり、かつ、
前記組成物に含まれる不揮発分中、前記亜鉛末及び前記中空粒子の合計に含まれる粒子径１０μｍ以上の粒子の量が３４体積％以上である。
That is, the anticorrosion coating composition according to an embodiment of the present invention comprises an organic resin, zinc powder having an average particle diameter of 1 to 30 μm, and hollow particles having a 90% cumulative average diameter d 90 in terms of volume of 60 μm or less. Contains,
In the nonvolatile content contained in the composition, the pigment volume concentration (PVC), which is the total volume concentration of the zinc powder and the hollow particles, is 58% or more, and
In the nonvolatile content contained in the composition, the amount of particles having a particle diameter of 10 μm or more contained in the total of the zinc powder and the hollow particles is 34% by volume or more.
本発明の別の実施形態に係る防食塗料組成物は、有機樹脂と、平均粒子径１〜３０μｍの亜鉛末と、体積換算の９０％累積平均径ｄ９０が６０μｍ以下の中空粒子と、を含有し、前記組成物からなる塗膜のすべり係数が０．４５以上である。 An anticorrosive coating composition according to another embodiment of the present invention contains an organic resin, zinc powder having an average particle diameter of 1 to 30 μm, and hollow particles having a volume-converted 90% cumulative average diameter d 90 of 60 μm or less. And the slip coefficient of the coating film consisting of the said composition is 0.45 or more.
本発明に係る塗膜は、前記組成物からなる。 The coating film which concerns on this invention consists of the said composition.
本発明に係る積層体は、前記塗膜と、前記塗膜以外の一以上の層と、を備え、前記層は、前記塗膜上に形成されている。 The laminated body which concerns on this invention is equipped with the said coating film and one or more layers other than the said coating film, and the said layer is formed on the said coating film.
本発明に係る構造物は、鋼材と、前記鋼材の表面に形成された前記塗膜と、を備え、他の部材と当接して用いられ、前記塗膜は、少なくとも、前記構造物の内、前記他の部材と当接する部分に形成されている。 The structure according to the present invention includes a steel material and the coating film formed on the surface of the steel material, and is used in contact with another member, and the coating film is at least of the structure, It is formed in the part which contacts said other member.
本発明に係る構造物の好適例において、前記塗膜は、前記鋼材の表面の全体に形成されている。 In a preferred example of the structure according to the present invention, the coating film is formed on the entire surface of the steel material.
本発明に係る防食塗料用添加剤は、体積換算の９０％累積平均径ｄ９０が６０μｍ以下の中空粒子からなる。 Protective coatings additive of the present invention, 90% cumulative average diameter d 90 of reduced volume is composed of the following hollow particles 60 [mu] m.
本発明によれば、（１）０．４５以上のすべり係数を有する塗膜を与える有機ジンクリッチペイントとして有用であり、（２）当該塗膜上に下塗り層、中塗り層、及び上塗り層をこの順序で塗り重ねた場合、上記上塗り層の光沢度を維持することができ、（３）貯蔵安定性に優れる防食塗料組成物、該組成物からなる塗膜、該塗膜を備える積層体及び構造物、並びに防食塗料用添加剤を提供することができる。 According to the present invention, (1) it is useful as an organic zinc rich paint that gives a coating film having a slip coefficient of 0.45 or more, and (2) an undercoat layer, an intermediate coating layer, and an overcoat layer are formed on the coating film. When applied in this order, the glossiness of the topcoat layer can be maintained, and (3) an anticorrosion coating composition having excellent storage stability, a coating film comprising the composition, a laminate comprising the coating film, and Structures as well as additives for anticorrosion paints can be provided.
≪防食塗料組成物≫
本発明の一実施形態に係る防食塗料組成物は、有機樹脂と、平均粒子径１〜３０μｍの亜鉛末と、体積換算の９０％累積平均径ｄ９０が６０μｍ以下の中空粒子と、を含有し、
前記組成物に含まれる不揮発分中、前記亜鉛末及び前記中空粒子の合計の体積濃度である顔料体積濃度（ＰＶＣ）が５８％以上であり、かつ、
前記組成物に含まれる不揮発分中、前記亜鉛末及び前記中空粒子の合計に含まれる粒子径１０μｍ以上の粒子の量が３４体積％以上である。この防食塗料組成物は、上記の構成をとることで、０．４５以上のすべり係数を有する塗膜を与える有機ジンクリッチペイントとして有用であり、当該塗膜上に下塗り層、中塗り層、及び上塗り層をこの順序で塗り重ねた場合、上記上塗り層の光沢度を維持することができ、貯蔵安定性に優れる。特に、上記不揮発分中、ＰＶＣが５８％以上、好ましくは６０〜８５％、より好ましくは６８〜８０％であり、かつ、上記不揮発分中、前記亜鉛末及び前記中空粒子の合計に含まれる粒子径１０μｍ以上の粒子の量が３４体積％以上、好ましくは３５〜６０体積％である点で、上記防食塗料組成物は、０．４５以上のすべり係数を有する塗膜を効果的に与えることができる。なお、本明細書において、「すべり係数」とは、「鋼構造接合部設計指針」（第３版、社団法人日本建築学会、２０１２年）の「付７ すべり係数評価試験法」に基づいて測定されたすべり係数をいう。
≪Anti-corrosion paint composition≫
The anticorrosion coating composition according to one embodiment of the present invention contains an organic resin, zinc powder having an average particle diameter of 1 to 30 μm, and hollow particles having a 90% cumulative average diameter d 90 in terms of volume of 60 μm or less. ,
In the nonvolatile content contained in the composition, the pigment volume concentration (PVC), which is the total volume concentration of the zinc powder and the hollow particles, is 58% or more, and
In the nonvolatile content contained in the composition, the amount of particles having a particle diameter of 10 μm or more contained in the total of the zinc powder and the hollow particles is 34% by volume or more. This anticorrosion coating composition is useful as an organic zinc rich paint that gives a coating film having a slip coefficient of 0.45 or more by taking the above-described configuration. An undercoat layer, an intermediate coating layer, and When the topcoat layer is applied in this order, the glossiness of the topcoat layer can be maintained, and the storage stability is excellent. In particular, in the non-volatile content, PVC is 58% or more, preferably 60 to 85%, more preferably 68 to 80%, and particles contained in the total of the zinc powder and the hollow particles in the non-volatile content. The anticorrosion coating composition effectively gives a coating film having a slip coefficient of 0.45 or more in that the amount of particles having a diameter of 10 μm or more is 34% by volume or more, preferably 35 to 60% by volume. it can. In this specification, “slip coefficient” is measured based on “Appendix 7 Slip coefficient evaluation test method” in “Guideline for Steel Structure Joint Design” (3rd edition, Architectural Institute of Japan, 2012). Is the slip coefficient.
本発明の別の実施形態に係る防食塗料組成物は、有機樹脂と、平均粒子径１〜３０μｍの亜鉛末と、体積換算の９０％累積平均径ｄ９０が６０μｍ以下の中空粒子と、を含有し、前記組成物からなる塗膜のすべり係数が０．４５以上である。この防食塗料組成物は、上記の通り、前記組成物からなる塗膜のすべり係数が０．４５以上であり、上記の構成をとることで、当該塗膜上に下塗り層、中塗り層、及び上塗り層をこの順序で塗り重ねた場合、上記上塗り層の光沢度を維持することができ、貯蔵安定性に優れる。 An anticorrosive coating composition according to another embodiment of the present invention contains an organic resin, zinc powder having an average particle diameter of 1 to 30 μm, and hollow particles having a volume-converted 90% cumulative average diameter d 90 of 60 μm or less. And the slip coefficient of the coating film consisting of the said composition is 0.45 or more. As described above, this anticorrosive coating composition has a slip coefficient of 0.45 or more of the coating film composed of the composition, and by taking the above-described configuration, an undercoat layer, an intermediate coating layer, and When the topcoat layer is applied in this order, the glossiness of the topcoat layer can be maintained, and the storage stability is excellent.
＜有機樹脂＞
有機樹脂としては、防食塗料で用いられている公知の有機樹脂を用いることができ、例えば、アクリル系樹脂、ウレタン系樹脂、エポキシ系樹脂、ビニル系樹脂、シリコーン系樹脂等が挙げられる。有機樹脂は、単独で用いることも、２種以上を併用することもできる。
<Organic resin>
As the organic resin, known organic resins used in anticorrosion paints can be used, and examples thereof include acrylic resins, urethane resins, epoxy resins, vinyl resins, and silicone resins. The organic resin can be used alone or in combination of two or more.
アクリル系樹脂は、（メタ）アクリルモノマーを構成単位とする樹脂であればよく、例えば、構成モノマーとして、（メタ）アクリル酸のアルキルエステルであるのが好ましく、このエステルにおけるアルキル基は炭素数１〜１０が好ましく、１〜８が特に好ましい。このような構成モノマーとしては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−プロピル、（メタ）アクリル酸ｉ−プロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸ｉ−ブチル、（メタ）アクリル酸ｔ−ブチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸２−エチルヘキシル等の少なくとも１種を含有している。また、アクリル系樹脂は各種変性樹脂を用いることができる。 The acrylic resin may be a resin having a (meth) acrylic monomer as a structural unit. For example, the structural monomer is preferably an alkyl ester of (meth) acrylic acid, and the alkyl group in this ester has 1 carbon atom. To 10 is preferable, and 1 to 8 is particularly preferable. Examples of such constituent monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and n-butyl (meth) acrylate. , (Meth) acrylic acid i-butyl, (meth) acrylic acid t-butyl, (meth) acrylic acid hexyl, (meth) acrylic acid 2-ethylhexyl, and the like. Various modified resins can be used as the acrylic resin.
ウレタン系樹脂は、ポリオール及びポリイソシアネートを構成単位とする樹脂であればよい。例えば、ポリオールは、アクリルポリオール、ポリエステルポリオール、ポリエーテルポリオール、ポリカーボネートポリオール等の少なくとも１種を含有していればよく、ポリイソシアネートは脂肪族ポリイソシアネートが好ましく、例えば、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、水添トリレンジイソシアネート、水添キシリレンジイソシアネート、水添メチレンジフェニルジイソシアネート等の少なくとも１種を含有している。また、ウレタン系樹脂は各種変性樹脂を用いることができる。 The urethane-based resin may be a resin having polyol and polyisocyanate as structural units. For example, the polyol only needs to contain at least one of acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol, etc., and the polyisocyanate is preferably an aliphatic polyisocyanate, such as hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl. It contains at least one of methane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated methylene diphenyl diisocyanate and the like. Various modified resins can be used as the urethane resin.
エポキシ系樹脂は、エポキシ化合物を構成単位とする樹脂であればよく、例えば、構成モノマーとして、ビスフェノールＡやビスフェノールＦ、ビスフェノールＡＤ、ビスフェノールＺ等の少なくとも１種とグリシジルエーテル類を反応させたものが好ましい。また、エポキシ系樹脂は各種変性樹脂を用いることができる。 The epoxy resin may be a resin having an epoxy compound as a structural unit. For example, a resin obtained by reacting glycidyl ethers with at least one of bisphenol A, bisphenol F, bisphenol AD, bisphenol Z and the like as a constituent monomer. preferable. Various modified resins can be used as the epoxy resin.
より具体的に、エポキシ系樹脂としては、エピクロルヒドリン−ビスフェノールＡ型エポキシ樹脂や、エピクロルヒドリン−ビスフェノールＦ型エポキシ樹脂、テトラブロモビスフェノールＡのグリシジルエーテル等の難燃型エポキシ樹脂、ノボラック型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、ビスフェノールＡプロピレンオキシド付加物のグリシジルエーテル型エポキシ樹脂、ジアミノジフェニルメタン系エポキシ樹脂、ウレタン変性エポキシ樹脂、ヒダントイン型エポキシ樹脂、エポキシ化ポリオレフィン、エポキシ化大豆油、その他各種変性エポキシ樹脂等が代表的なものとして挙げられる。エポキシ系樹脂の硬化剤としては、例えば、エチレンジアミンや、ジエチレントリアミン等の脂肪族ポリアミン、脂肪族ポリアミンをビスフェノールＡ、アクリロニトリル等で変性した変性脂肪族ポリアミン、ジアミノジフェニルメタン等の芳香族ポリアミン、Ｎ−アミノエチルピペラジン等の脂環式ポリアミン、脂環式ポリアミンをカージュラＥ、キシリレンジアミン等で変性した変性脂環族ポリアミン、ポリアミンとダイマー酸とを反応させたポリアミド、ポリアミンをエポキシ樹脂にアダクトしたアミンアダクト、ポリアミンをダイマー酸及びエポキシ樹脂にアダクトしたポリアミドアダクト等が代表的なものとして挙げられる。エポキシ系樹脂と硬化剤との混合割合は、前者のエポキシ基１当量に対し、後者の活性水素が、例えば、０．５〜３．０当量、好ましくは０．７〜１．５当量となる割合が挙げられる。 More specifically, the epoxy resin includes epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, flame retardant type epoxy resin such as tetrabromobisphenol A glycidyl ether, novolak type epoxy resin, hydrogenated resin, etc. Bisphenol A type epoxy resin, glycidyl ether type epoxy resin of bisphenol A propylene oxide adduct, diaminodiphenylmethane type epoxy resin, urethane modified epoxy resin, hydantoin type epoxy resin, epoxidized polyolefin, epoxidized soybean oil, and other various modified epoxy resins Is a typical example. Examples of epoxy resin curing agents include ethylenediamine, aliphatic polyamines such as diethylenetriamine, modified aliphatic polyamines obtained by modifying aliphatic polyamines with bisphenol A, acrylonitrile, and the like, aromatic polyamines such as diaminodiphenylmethane, and N-aminoethyl. An alicyclic polyamine such as piperazine, a modified alicyclic polyamine obtained by modifying an alicyclic polyamine with Cardura E, xylylenediamine, a polyamide obtained by reacting a polyamine with a dimer acid, an amine adduct obtained by adducting a polyamine to an epoxy resin, A typical example is a polyamide adduct in which a polyamine is adducted to a dimer acid and an epoxy resin. The mixing ratio of the epoxy resin and the curing agent is such that the active hydrogen of the latter is, for example, 0.5 to 3.0 equivalents, preferably 0.7 to 1.5 equivalents with respect to 1 equivalent of the former epoxy group. A percentage is mentioned.
ビニル系樹脂は、炭素−炭素不飽和結合を有する化合物（（メタ）アクリルモノマー等の（メタ）アクリル系化合物を除く。）を構成単位とする樹脂であればよく、例えば、構成モノマーとして、塩化ビニル、酢酸ビニル、スチレン、アクリロニトリル等の少なくとも１種を含有している。また、ビニル系樹脂は各種変性樹脂を用いることができる。 The vinyl resin only needs to be a resin having a structural unit of a compound having a carbon-carbon unsaturated bond (excluding (meth) acrylic compounds such as (meth) acrylic monomers). It contains at least one of vinyl, vinyl acetate, styrene, acrylonitrile and the like. Various modified resins can be used as the vinyl resin.
シリコーン系樹脂は、アルキルシリケートの部分加水分解縮合物あるいはその変性物が挙げられる。 Examples of the silicone resin include a partially hydrolyzed condensate of alkyl silicate or a modified product thereof.
このような部分加水分解縮合物として、例えば、一般式Ｒ１ ｎＳｉ（ＯＲ２）４−ｎ〔式中、Ｒ１は炭素数１〜８の有機基であり、Ｒ２は炭素数１〜５のアルキル基であり、ｎは０又は１である。〕で示されるアルキルシリケートの加水分解縮合物が好適に挙げられる。上記式において、Ｒ１としての有機基としては、例えば、アルキル基、シクロアルキル基、アリール基、ビニル基等が挙げられる。ここで、アルキル基としては、直鎖でも分岐したものでもよい。アルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｉ−ブチル基、ｓ−ブチル基、ｔ−ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基等のアルキル基が挙げられる。好ましいアルキル基は炭素数が１〜４個のものである。シクロアルキル基としては、例えば、シクロヘキシル基、シクロヘプチル基、シクロオクチル基等が好適に挙げられる。アリール基としては、例えば、フェニル基、ナフチル基等が挙げられる。上記各官能基は任意に置換基を有してもよい。このような置換基としては、例えば、ハロゲン原子（例えば、塩素原子、臭素原子、フッ素原子等）、（メタ）アクリロイル基、アミノ基、メルカプト基、グリシドキシ基、エポキシ基、脂環式基等が挙げられる。Ｒ２としてのアルキル基としては直鎖でも分岐したものでもよい。このようなアルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｉ−ブチル基、ｓ−ブチル基、ｔ−ブチル基、ペンチル基等が挙げられ、好ましいアルキル基は炭素数が１〜２個のものである。 As such a partial hydrolysis-condensation product, for example, general formula R 1 n Si (OR 2 ) 4-n [wherein R 1 is an organic group having 1 to 8 carbon atoms, and R 2 has 1 to 1 carbon atoms. 5 is an alkyl group, and n is 0 or 1. Preferred examples thereof include hydrolysis condensates of alkyl silicates represented by the following formula: In the above formula, examples of the organic group as R 1 include an alkyl group, a cycloalkyl group, an aryl group, and a vinyl group. Here, the alkyl group may be linear or branched. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, heptyl. And alkyl groups such as an octyl group. Preferred alkyl groups are those having 1 to 4 carbon atoms. Preferred examples of the cycloalkyl group include a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like. Examples of the aryl group include a phenyl group and a naphthyl group. Each of the above functional groups may optionally have a substituent. Examples of such substituents include halogen atoms (eg, chlorine atoms, bromine atoms, fluorine atoms, etc.), (meth) acryloyl groups, amino groups, mercapto groups, glycidoxy groups, epoxy groups, alicyclic groups, and the like. Can be mentioned. The alkyl group as R 2 may be linear or branched. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, and a pentyl group. Preferred alkyl groups are those having 1 to 2 carbon atoms.
このようなアルキルシリケートの具体例としては、テトラメチルシリケート、テトラエチルシリケート、テトラ−ｎ−プロピルシリケート、テトラ−ｉ−プロピルシリケート、テトラ−ｎ−ブチルシリケート等のｎが０の場合のアルキルシリケート；メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、ｎ−プロピルトリメトキシシラン、ｎ−プロピルトリエトキシシラン、ｉ−プロピルトリメトキシシラン、ｉ−プロピルトリエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−メタクリルオキシプロピルトリメトキシシラン、γ−メタクリルオキシプロピルトリエトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルトリエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、γ−アミノプロピルトリメトキシシラン、３，４−エポキシシクロヘキシルエチルトリメトキシシラン、３，４−エポキシシクロヘキシルエチルトリエトキシシラン等の、ｎが１の場合のアルキルシリケート等が挙げられる。これらは単独又は２種以上組み合わせて用いてもよい。またシリコーン系樹脂は各種変性樹脂を用いることができる。 Specific examples of such alkyl silicates include alkyl silicates in the case where n is 0, such as tetramethyl silicate, tetraethyl silicate, tetra-n-propyl silicate, tetra-i-propyl silicate, tetra-n-butyl silicate; Trimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, γ-glycine Sidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropyltrimeth Xysilane, γ-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-aminopropyltrimethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltriethoxysilane, etc. And alkyl silicate when n is 1. You may use these individually or in combination of 2 or more types. Various modified resins can be used as the silicone resin.
＜平均粒子径１〜３０μｍの亜鉛末＞
本発明で用いる亜鉛末は、平均粒子径が、通常、１〜３０μｍであり、好ましくは２〜２０μｍであり、より好ましくは３〜１５μｍである。上記平均粒子径が上記範囲内であると、得られる組成物は、０．４５以上のすべり係数を有する塗膜を与えやすく、当該塗膜上に下塗り層、中塗り層、及び上塗り層をこの順序で塗り重ねた場合、上記上塗り層の光沢度を維持しやすく、貯蔵安定性が向上しやすい。亜鉛末は、単独で用いても、２種以上を併用してもよい。
なお、本明細書において、平均粒子径とは、レーザー回折法により測定される体積換算の値をいう。
<Zinc powder with an average particle size of 1 to 30 μm>
The zinc powder used in the present invention has an average particle size of usually 1 to 30 μm, preferably 2 to 20 μm, more preferably 3 to 15 μm. When the average particle diameter is within the above range, the resulting composition tends to give a coating film having a slip coefficient of 0.45 or more, and an undercoat layer, an intermediate coating layer, and an overcoat layer are formed on the coating film. When applied in order, it is easy to maintain the glossiness of the topcoat layer and to improve storage stability. Zinc powder may be used alone or in combination of two or more.
In addition, in this specification, an average particle diameter means the value of volume conversion measured by a laser diffraction method.
＜体積換算の９０％累積平均径ｄ９０が６０μｍ以下の中空粒子＞
本発明で用いる中空粒子は、体積換算の９０％累積平均径ｄ９０が、通常、６０μｍ以下であり、好ましくは１０〜５８μｍであり、より好ましくは２０〜５５μｍである。上記ｄ９０が上記範囲内であると、得られる組成物は、当該組成物からなる塗膜上に下塗り層、中塗り層、及び上塗り層をこの順序で塗り重ねた場合、上記上塗り層の光沢度を維持しやすい。
なお、本明細書において、体積換算の９０％累積平均径ｄ９０とは、レーザー回折法により測定される値をいう。
<Hollow particles whose 90% cumulative average diameter d 90 in terms of volume is 60 μm or less>
The hollow particles used in the present invention, 90% cumulative average diameter d 90 of reduced volume is usually at 60μm or less, preferably 10～58Myuemu, more preferably 20～55Myuemu. When the d 90 is within the above range, the resulting composition, the undercoat layer on the coating film formed of the composition, an intermediate layer, and when recoated overcoat layer in this order, the gloss of the topcoat layer Easy to maintain the degree.
In the present specification, the 90% cumulative average diameter d 90 in terms of volume refers to a value measured by a laser diffraction method.
本発明で用いる中空粒子の平均粒子径は、特に限定されず、ｄ９０が６０μｍ以下の場合には、５０μｍ以下でよい。 The average particle diameter of the hollow particles used in the present invention is not particularly limited, and may be 50 μm or less when d 90 is 60 μm or less.
中空粒子としては、特に限定されず、例えば、ガラス等の無機材料からなる中空粒子；熱硬化性ポリイミド等の有機材料からなる中空粒子が挙げられ、具体的には、中空ガラス粒子等が挙げられる。中空粒子は、単独で用いても、２種以上を併用してもよい。 The hollow particles are not particularly limited, and examples thereof include hollow particles made of an inorganic material such as glass; hollow particles made of an organic material such as thermosetting polyimide, and specifically, hollow glass particles and the like. . The hollow particles may be used alone or in combination of two or more.
＜その他の成分＞
本発明に係る防食塗料組成物は、必要に応じ、沈降防止剤等の添加剤；上述の各成分を溶解又は分散する溶剤を含有してもよい。沈降防止剤の代表例としては、有機ベントナイト、酸化ポリエチレン系沈降防止剤、脂肪酸アマイド系沈降防止剤、シリカ等が挙げられる。溶剤としては、トルエン、キシレン等の芳香族炭化水素類、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類、酢酸エチル、酢酸ブチル、プロピレングリコールモノメチルエーテルアセテート等のエステル類、イソプロピルアルコール、ブチルアルコール等のアルコール類、水等が代表的なものとして挙げられる。
<Other ingredients>
The anticorrosion coating composition according to the present invention may contain an additive such as an anti-settling agent and a solvent that dissolves or disperses the above-described components as necessary. Representative examples of the anti-settling agent include organic bentonite, polyethylene oxide anti-settling agent, fatty acid amide anti-settling agent, silica and the like. Solvents include aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate, isopropyl alcohol and butyl alcohol. Representative examples include alcohols and water.
＜配合割合＞
本発明に係る防食塗料組成物に含まれる不揮発分中、有機樹脂の配合割合は、例えば、３〜２０質量％、好ましくは５〜１９質量％とすることができ、前記亜鉛末の配合割合は、例えば、５２〜９０質量％、好ましくは５３〜８７質量％とすることができ、前記中空粒子の配合割合は、例えば、０．１〜２１質量％、好ましくは０．２〜１８質量％とすることができる。これらの配合割合が上述の範囲内であると、０．４５以上のすべり係数を有する塗膜がより得られやすく、上述の上塗り層の光沢度をより維持しやすく、前記組成物の貯蔵安定性がより向上しやすい。なお、本明細書において、防食塗料組成物に含まれる不揮発分とは、防食塗料組成物を１１０℃オーブンで３時間乾燥させた後に残留する成分をいう。
<Combination ratio>
In the nonvolatile content contained in the anticorrosive coating composition according to the present invention, the blending ratio of the organic resin can be, for example, 3 to 20% by mass, preferably 5 to 19% by mass, and the blending ratio of the zinc powder is For example, it can be 52 to 90% by mass, preferably 53 to 87% by mass, and the mixing ratio of the hollow particles is, for example, 0.1 to 21% by mass, preferably 0.2 to 18% by mass. can do. When these blending ratios are within the above-mentioned range, a coating film having a slip coefficient of 0.45 or more is more easily obtained, the glossiness of the above-mentioned topcoat layer is more easily maintained, and the storage stability of the composition Is easier to improve. In the present specification, the nonvolatile content contained in the anticorrosion coating composition refers to a component remaining after the anticorrosion coating composition is dried in an oven at 110 ° C. for 3 hours.
本発明に係る防食塗料組成物中の溶剤の配合割合は、塗装作業性等を考慮し、任意の量とすることができ、後述する膜厚が得られやすい点で、例えば、３〜２０質量％、好ましくは５〜２０質量％とすることができる。 The blending ratio of the solvent in the anticorrosive coating composition according to the present invention can be set to an arbitrary amount in consideration of coating workability and the like. %, Preferably 5 to 20% by mass.
≪塗膜、積層体、及び構造物≫
本発明に係る塗膜は、本発明に係る組成物からなり、通常、すべり係数が０．４５以上である。上記塗膜は、本発明に係る組成物を基材に塗布することにより製造することができる。基材としては、特に限定されず、鋼材、特に、一般的な鋼構造物基材として用いられる鋼材全般を対象とすることができる。鋼材としては、例えば、一般構造用圧延鋼材や、溶接構造用圧延鋼材、建築構造用圧延鋼材、高耐候性圧延鋼材、鉄塔用高張力鋼鋼材等が挙げられる。塗布手段としては、特に限定されず、例えば、スプレー塗装、ハケ塗装等の従来から公知の各種塗布手段が採用可能である。得られる塗膜の乾燥膜厚は、好ましくは５０〜１８０μｍ、より好ましくは６０〜１５０μｍである。上記乾燥膜厚が上記範囲内であると、すべり係数が低下しにくく、長期防食性も維持されやすい。
≪Coating film, laminate, and structure≫
The coating film which concerns on this invention consists of a composition which concerns on this invention, and a slip coefficient is 0.45 or more normally. The said coating film can be manufactured by apply | coating the composition which concerns on this invention to a base material. It does not specifically limit as a base material, The whole steel materials used as a steel material, especially a general steel structure base material can be made into object. Examples of the steel material include a general structural rolled steel, a welded structural rolled steel, a building structural rolled steel, a high weather resistance rolled steel, and a high-tensile steel for steel tower. The application means is not particularly limited, and various conventionally known application means such as spray coating and brush coating can be employed. The dry film thickness of the obtained coating film is preferably 50 to 180 μm, more preferably 60 to 150 μm. When the dry film thickness is within the above range, the slip coefficient is unlikely to decrease and long-term corrosion resistance is easily maintained.
本発明に係る積層体は、本発明に係る塗膜と、前記塗膜以外の一以上の層と、を備え、前記層は、前記塗膜上に形成されている。前記積層体としては、例えば、前記塗膜、下塗り層、中塗り層、及び上塗り層をこの順序で備える積層体が挙げられる。この積層体において、上塗り層は、光沢度が良好に維持されている。 The laminate according to the present invention includes the coating film according to the present invention and one or more layers other than the coating film, and the layer is formed on the coating film. Examples of the laminate include a laminate including the coating film, the undercoat layer, the intermediate coat layer, and the overcoat layer in this order. In this laminate, the topcoat layer maintains a good glossiness.
本発明に係る構造物は、鋼材と、前記鋼材の表面に形成された前記塗膜と、を備え、他の部材と当接して用いられる構造物であって、前記塗膜は、少なくとも、前記構造物の内、前記他の部材と当接する部分に形成されている。また、前記構造物において、前記塗膜は、前記鋼材の表面の全体に形成されていることが好ましい。前記構造物としては、例えば、ボルト接合部を有する構造物が挙げられ、前記他の部材と当接する部分としては、ボルト接合部における接触面が挙げられる。前記塗膜は、すべり係数が０．４５以上であるので、前記接触面に好適に用いることができる。また、前記塗膜は、前記接触面以外の部分に用いても、良好な防食性を示し、上塗り層の光沢度を維持することができるので、前記鋼材の表面の全体に形成することができる。したがって、前記構造物において、前記他の部材と当接する部分とそれ以外の部分とで、防食塗料組成物の塗り分けをする必要がないため、大幅な省力化及び工期短縮が可能である。 The structure according to the present invention comprises a steel material and the coating film formed on the surface of the steel material, and is a structure used in contact with another member, wherein the coating film is at least the Of the structure, it is formed in a portion that contacts the other member. Moreover, the said structure WHEREIN: It is preferable that the said coating film is formed in the whole surface of the said steel materials. Examples of the structure include a structure having a bolt joint portion, and examples of the portion that comes into contact with the other member include a contact surface in the bolt joint portion. Since the coating film has a slip coefficient of 0.45 or more, it can be suitably used for the contact surface. Moreover, since the said coating film shows favorable corrosion resistance and can maintain the glossiness of an overcoat layer even if it uses it in parts other than the said contact surface, it can form in the whole surface of the said steel materials. . Accordingly, in the structure, it is not necessary to separately coat the anticorrosion coating composition at the portion that contacts the other member and the other portion, so that it is possible to save labor and shorten the construction period.
≪防食塗料用添加剤≫
本発明に係る防食塗料用添加剤は、体積換算の９０％累積平均径ｄ９０が６０μｍ以下の中空粒子からなる。上記中空粒子については、上述の通りである。上記防食塗料用添加剤において、上記中空粒子は、単独で用いることも、２種以上を併用することもできる。
≪Anti-corrosive paint additive≫
Protective coatings additive of the present invention, 90% cumulative average diameter d 90 of reduced volume is composed of the following hollow particles 60 [mu] m. The hollow particles are as described above. In the anticorrosive paint additive, the hollow particles can be used alone or in combination of two or more.
本発明に係る防食塗料用添加剤を防食塗料、特に、有機樹脂と、平均粒子径１〜３０μｍの亜鉛末とを含む防食塗料に添加することで、当該防食塗料の塗膜のすべり係数が０．４５以上となりやすく、また、当該塗膜上に下塗り層、中塗り層、及び上塗り層をこの順序で塗り重ねた場合、上記上塗り層の光沢度を維持しやすく、更に、当該防食塗料の貯蔵安定性が優れたものとなりやすい。 By adding the additive for an anticorrosive paint according to the present invention to an anticorrosive paint, particularly an anticorrosive paint containing an organic resin and zinc powder having an average particle diameter of 1 to 30 μm, the slip coefficient of the coating film of the anticorrosive paint is 0. When the undercoat layer, the intermediate coat layer, and the overcoat layer are repeatedly applied in this order on the coating film, the glossiness of the overcoat layer is easily maintained, and the anticorrosive paint is stored. It tends to be excellent in stability.
以下に、実施例を挙げて本発明を更に詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
［粗面皮膜形成剤の調製］
表１に示す配合処方に従い、主剤成分と硬化剤成分とを混合して、防食塗料組成物を調製した。なお、上記配合処方における数値の単位は質量％である。
[Preparation of rough surface film-forming agent]
According to the formulation shown in Table 1, the main ingredient component and the curing agent component were mixed to prepare an anticorrosion coating composition. In addition, the unit of the numerical value in the said compounding prescription is the mass%.
注１）ダウ・ケミカル日本（株）社製商品名「Ｄ．Ｅ．Ｒ． ＴＭ６７１−Ｘ７０」、不揮発分７０質量％、エポキシ当量（不揮発分換算値）４４５〜５００。
注２）平均粒子径４．０μｍ（粒子径１０μｍ以上の粒子の量：１５体積％）
注３）平均粒子径７．０μｍ（粒子径１０μｍ以上の粒子の量：３０体積％）
注４）平均粒子径１０．０μｍ（粒子径１０μｍ以上の粒子の量：８０体積％）
注５）平均粒子径４２μｍ（粒子径１０μｍ以上の粒子の量：１００体積％）
注６）中空ガラス粒子（ｄ９０＝２２μm、粒子径１０μｍ以上の粒子の量：５０体積％）
注７）中空ガラス粒子（ｄ９０＝３０μｍ、粒子径１０μｍ以上の粒子の量：９０体積％）、もしくは、中空ガラス粒子（ｄ９０＝３７μｍ、粒子径１０μｍ以上の粒子の量：９０体積％）
注８）中空ガラス粒子（ｄ９０＝４８μｍ、粒子径１０μｍ以上の粒子の量：１００体積％）、もしくは、中空ガラス粒子（ｄ９０＝５３μｍ、粒子径１０μｍ以上の粒子の量：１００体積％）
注９）中空ガラス粒子（ｄ９０＝９８μｍ、粒子径１０μｍ以上の粒子の量：１００体積％）
注１０）有機ベントナイト
注１１）エアープロダクツ社製商品名「サンマイドＥ−１００１Ｓ」、不揮発分５０質量％、ポリアミンのアミン価１００
注１２）表１に示す主剤成分及び硬化剤成分を塗装直前に混合し、塗料を調製した。該塗料を乾燥膜厚が７５μｍなるように、エアスプレーにてグリッドブラスト処理を行ったＳＭ４９０板の両面に塗布し、１ヶ月間乾燥させて、塗装試験体を得た。作製した塗装試験体をトルシア形高力ＴＣボルト（Ｍ２２）にて締め付け、引張試験機を用いて、すべり係数を測定し、下記基準にて評価した。
○：すべり係数が０．４５以上
×：すべり係数が０．４５未満
注１３）上記塗料を乾燥膜厚が７５μｍとなるようにエアスプレーにてグリッドブラスト板（１５０ｍｍ×７０ｍｍ×３．２ｍｍ）に塗布し、１日間乾燥させて塗膜を得た後、同塗膜表面に、
下塗塗料：大日本塗料社製商品名「エポニックス＃３０下塗」
中塗塗料：大日本塗料社製商品名「Ｖフロン＃１００Ｈ中塗」
上塗塗料：大日本塗料社製商品名「Ｖフロン＃１００Ｈ上塗」
を、乾燥膜厚がそれぞれ１２０μｍ、２５μｍ、３０μｍとなるように、塗装間隔を１日間として、エアスプレー塗装し、７日間自然乾燥させた後、光沢計を用いて２０°光沢度を測定し、下記基準にて評価した。
○：２０°光沢度が６０以上
×：２０°光沢度が６０未満
注１４）ＪＩＳ Ｋ ５５５３に準じ、上記塗料を乾燥膜厚が７５μｍとなるようにエアスプレーにてグリッドブラスト板（１５０ｍｍ×７０ｍｍ×３．２ｍｍ）に塗布し、７日間乾燥させた後に素地に達する切削線を施し、耐塩水噴霧試験に１５００時間供し、下記基準にて評価した。
○：一般部の塗膜に異常がなく、切削部からの錆膨れ幅が２ｍｍ未満
×：一般部の塗膜に錆もしくは膨れが発生、又は、切削部からの錆膨れ幅が２ｍｍ以上
注１５）表１の主剤成分及び硬化剤成分を５０℃にて４週間静置後、室温に戻し、下記基準にて評価した。
○：沈殿が生じない、又は、沈殿が生じるが、手攪拌で均一に混合できる。
×：沈殿が生じ、手攪拌では均一に混合ができない。
Note 1) Trade name “DER TM 671-X70” manufactured by Dow Chemical Japan Co., Ltd., nonvolatile content 70 mass%, epoxy equivalent (nonvolatile content conversion value) 445 to 500.
Note 2) Average particle size: 4.0 μm (Amount of particles having a particle size of 10 μm or more: 15% by volume)
Note 3) Average particle size: 7.0 μm (amount of particles having a particle size of 10 μm or more: 30% by volume)
Note 4) Average particle size 10.0 μm (amount of particles having a particle size of 10 μm or more: 80% by volume)
Note 5) Average particle size 42 μm (amount of particles having a particle size of 10 μm or more: 100% by volume)
Note 6) Hollow glass particles (d 90 = 22 μm, amount of particles having a particle diameter of 10 μm or more: 50% by volume)
Note 7) Hollow glass particles (d 90 = 30 μm, amount of particles having a particle size of 10 μm or more: 90% by volume) or hollow glass particles (d 90 = 37 μm, amount of particles having a particle size of 10 μm or more: 90% by volume)
Note 8) Hollow glass particles (d 90 = 48 μm, amount of particles having a particle size of 10 μm or more: 100% by volume) or hollow glass particles (d 90 = 53 μm, amount of particles having a particle size of 10 μm or more: 100% by volume)
Note 9) Hollow glass particles (d 90 = 98 μm, amount of particles having a particle diameter of 10 μm or more: 100% by volume)
Note 10) Organic bentonite Note 11) Product name “Sunmide E-1001S” manufactured by Air Products, nonvolatile content 50% by mass, polyamine amine value 100
Note 12) A main component and a curing agent component shown in Table 1 were mixed immediately before coating to prepare a paint. The paint was applied to both surfaces of an SM490 plate that had been subjected to grid blasting by air spray so that the dry film thickness was 75 μm, and dried for one month to obtain a coating specimen. The produced coating test body was clamped with a Torcia type high strength TC bolt (M22), the slip coefficient was measured using a tensile tester, and evaluated according to the following criteria.
○: Slip coefficient is 0.45 or more ×: Slip coefficient is less than 0.45 Note 13) The paint is applied to a grid blast plate (150 mm × 70 mm × 3.2 mm) by air spray so that the dry film thickness becomes 75 μm. After coating and drying for 1 day to obtain a coating film,
Undercoat: Brand name “Eponix # 30 Undercoat” manufactured by Dainippon Paint Co., Ltd.
Intermediate coating: Brand name “V Freon # 100H intermediate coating” manufactured by Dainippon Paint Co., Ltd.
Topcoat: Brand name “V Freon # 100H Topcoat” manufactured by Dainippon Paint Co., Ltd.
The coating interval was set to 1 day so that the dry film thickness would be 120 μm, 25 μm, and 30 μm, respectively, and after air drying for 7 days, the glossiness was measured at 20 ° using a gloss meter, Evaluation was performed according to the following criteria.
○: 20 ° glossiness of 60 or more ×: 20 ° glossiness of less than 60 Note 14) In accordance with JIS K 5553, the paint is grid-blasted (150 mm × 70 mm) by air spray so that the dry film thickness is 75 μm. × 3.2 mm), a cutting line reaching the substrate after drying for 7 days was applied, subjected to a salt spray resistance test for 1500 hours, and evaluated according to the following criteria.
○: No abnormality in the coating film of the general part, and the rust swelling width from the cutting part is less than 2 mm ×: Rust or swelling occurs in the coating film of the general part, or the rust swelling width from the cutting part is 2 mm or more Note 15 The main component and the curing agent component in Table 1 were allowed to stand at 50 ° C. for 4 weeks, then returned to room temperature, and evaluated according to the following criteria.
○: Precipitation does not occur or precipitation occurs, but can be uniformly mixed by hand stirring.
X: Precipitation occurs, and uniform mixing cannot be achieved by manual stirring.
表１から明らかな通り、実施例１〜９では、良好な防食性を得つつ、塗膜のすべり係数が０．４５以上であり、上塗り層の光沢度を維持することができ、組成物の貯蔵安定性に優れていた。一方、比較例１〜５では、良好な防食性を得つつも、塗膜のすべり係数が０．４５未満であるか、上塗り層の光沢度を維持することができなかったか、組成物の貯蔵安定性に劣っていた。 As is apparent from Table 1, in Examples 1 to 9, while obtaining good anticorrosion properties, the slip coefficient of the coating film was 0.45 or more, and the glossiness of the overcoat layer could be maintained, and the composition Excellent storage stability. On the other hand, in Comparative Examples 1 to 5, while obtaining good anticorrosion properties, the slip coefficient of the coating film was less than 0.45, or the glossiness of the topcoat layer could not be maintained, or the composition was stored. It was inferior in stability.
Claims (7)
前記組成物に含まれる不揮発分中、前記亜鉛末及び前記中空粒子の合計の体積濃度である顔料体積濃度（ＰＶＣ）が５８％以上であり、かつ、
前記組成物に含まれる不揮発分中、前記亜鉛末及び前記中空粒子の合計に含まれる粒子径１０μｍ以上の粒子の量が３４体積％以上である組成物。 An anticorrosive coating composition comprising an organic resin, zinc powder having an average particle diameter of 1 to 30 μm, and hollow particles having a volume-converted 90% cumulative average diameter d 90 of 60 μm or less,
In the nonvolatile content contained in the composition, the pigment volume concentration (PVC), which is the total volume concentration of the zinc powder and the hollow particles, is 58% or more, and
The composition whose quantity of the particle | grains of 10 micrometers or more of particle diameter contained in the sum total of the said zinc dust and the said hollow particle is 34 volume% or more in the non volatile matter contained in the said composition.
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