JPWO2016170698A1 - Water-based surface treatment agent, film production method and surface treatment material - Google Patents
Water-based surface treatment agent, film production method and surface treatment material Download PDFInfo
- Publication number
- JPWO2016170698A1 JPWO2016170698A1 JP2016534758A JP2016534758A JPWO2016170698A1 JP WO2016170698 A1 JPWO2016170698 A1 JP WO2016170698A1 JP 2016534758 A JP2016534758 A JP 2016534758A JP 2016534758 A JP2016534758 A JP 2016534758A JP WO2016170698 A1 JPWO2016170698 A1 JP WO2016170698A1
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- JP
- Japan
- Prior art keywords
- surface treatment
- film
- castor oil
- treatment agent
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- 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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract
【課題】 エネルギー線を照射しなくても、成型加工性及び親水持続性に優れた皮膜を形成することができる水系表面処理剤、該水系表面処理剤を用いた皮膜の製造方法、及び、該皮膜の製造方法によって形成された皮膜を有する表面処理材を提供すること。【解決手段】親水皮膜形成成分(A)と、ポリオキシエチレンひまし油又はポリオキシエチレン硬化ひまし油(B)と、非イオン性界面活性剤(但しポリオキシエチレンひまし油及びポリオキシエチレン硬化ひまし油を除く)(C)とを含有する水系表面処理剤を用いることにより上記課題を解決することができる。【選択図】 なしPROBLEM TO BE SOLVED: To provide an aqueous surface treatment agent capable of forming a film excellent in molding processability and hydrophilic sustainability without irradiating energy rays, a method for producing a film using the aqueous surface treatment agent, and To provide a surface treatment material having a film formed by the method for producing a film. SOLUTION: Hydrophilic film forming component (A), polyoxyethylene castor oil or polyoxyethylene hydrogenated castor oil (B), and nonionic surfactant (except polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil) ( The above-described problems can be solved by using an aqueous surface treating agent containing C). [Selection figure] None
Description
本発明は、成型加工性及び親水持続性に優れた皮膜を形成することができる水系表面処理剤、該水系表面処理剤を用いた皮膜の製造方法、及び、該皮膜の製造方法により形成された皮膜を有する表面処理材に関する。 The present invention is formed by an aqueous surface treatment agent capable of forming a film excellent in moldability and hydrophilic sustainability, a method for producing a film using the aqueous surface treatment agent, and a method for producing the film. The present invention relates to a surface treatment material having a film.
エアコンの熱交換器に用いられるフィン材に親水性等の諸性能を付与するため、従来様々な技術が提案されている。例えば、特許文献1には、水溶性及び/又は水分散型高分子化合物(A)、エネルギー線硬化性を有する水溶性及び/又は水分散型高分子化合物又はオリゴマー(B)、エネルギー線硬化性を有する親水性モノマー(C)を含有するエネルギー線硬化型親水性表面処理剤に関する技術が提案されている。この技術によれば、エネルギー線照射により成型加工性及び親水持続性に優れた皮膜を形成することができる。 Various techniques have been proposed in the past for imparting various properties such as hydrophilicity to the fin material used in the heat exchanger of an air conditioner. For example, Patent Document 1 discloses a water-soluble and / or water-dispersible polymer compound (A), a water-soluble and / or water-dispersible polymer compound or oligomer (B) having energy beam curability, and energy beam curability. A technology relating to an energy ray-curable hydrophilic surface treating agent containing a hydrophilic monomer (C) having a hydrogen atom has been proposed. According to this technique, a film excellent in molding processability and hydrophilic sustainability can be formed by energy beam irradiation.
本発明は、エネルギー線を照射しなくても、成型加工性及び親水持続性に優れた皮膜を形成することができる水系表面処理剤、該水系表面処理剤を用いた皮膜の製造方法、及び、該皮膜の製造方法によって形成された皮膜を有する表面処理材を提供することを目的とする。 The present invention provides an aqueous surface treatment agent capable of forming a film excellent in molding processability and hydrophilic sustainability without irradiation with energy rays, a method for producing a film using the aqueous surface treatment agent, and It aims at providing the surface treatment material which has a membrane | film | coat formed by the manufacturing method of this membrane | film | coat.
本発明者らは、上記課題を解決するために鋭意研究を重ねた結果、親水皮膜形成成分と、ポリオキシエチレンひまし油又はポリオキシエチレン硬化ひまし油と、ポリオキシエチレンひまし油及びポリオキシエチレン硬化ひまし油以外の非イオン性界面活性剤を配合した水系表面処理剤が、エネルギー線を照射することなく成型加工性及び親水持続性に優れた皮膜を形成することが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 solve the above problems, the present inventors have found that a hydrophilic film-forming component, polyoxyethylene castor oil or polyoxyethylene hydrogenated castor oil, polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil The water-based surface treatment agent containing a nonionic surfactant was found to be able to form a film excellent in molding processability and hydrophilic sustainability without irradiating energy rays, and completed the present invention. .
すなわち、本発明は、
(1)親水皮膜形成成分(A)と、ポリオキシエチレンひまし油又はポリオキシエチレン硬化ひまし油(B)と、非イオン性界面活性剤(但しポリオキシエチレンひまし油及びポリオキシエチレン硬化ひまし油を除く)(C)とを含有する水系表面処理剤;
(2)前記親水皮膜形成成分(A)が、少なくとも1種の水溶性有機高分子を含む上記(1)に記載の水系表面処理剤;
(3)前記親水皮膜形成成分(A)が、架橋剤をさらに含む上記(2)に記載の水系表面処理剤;
(4)アルミニウム材若しくはアルミニウム合金材又はそれらのめっき材の表面に皮膜を製造する方法であって、上記(1)〜(3)のいずれかに記載の水系表面処理剤を前記表面に接触させる工程と、前記水系表面処理剤を接触させた前記表面を乾燥させる工程を含む皮膜の製造方法;
(5)上記(4)に記載の皮膜の製造方法により形成された皮膜を有する表面処理材;
などである。That is, the present invention
(1) Hydrophilic film forming component (A), polyoxyethylene castor oil or polyoxyethylene hydrogenated castor oil (B), and nonionic surfactant (except polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil) (C Water-based surface treatment agent containing
(2) The aqueous surface treating agent according to the above (1), wherein the hydrophilic film forming component (A) contains at least one water-soluble organic polymer;
(3) The aqueous surface treating agent according to (2), wherein the hydrophilic film-forming component (A) further contains a crosslinking agent;
(4) A method for producing a film on the surface of an aluminum material or an aluminum alloy material or a plating material thereof, and bringing the aqueous surface treating agent according to any one of (1) to (3) into contact with the surface A method for producing a film, comprising a step and a step of drying the surface in contact with the aqueous surface treatment agent;
(5) A surface treatment material having a film formed by the method for producing a film according to (4) above;
Etc.
本発明によれば、エネルギー線を照射しなくても、成型加工性及び親水持続性に優れた皮膜を形成することができる水系表面処理剤、該水系表面処理剤を用いた皮膜の製造方法、及び、該皮膜の製造方法によって形成された皮膜を有する表面処理材を提供することができる。 According to the present invention, an aqueous surface treatment agent capable of forming a film excellent in moldability and hydrophilic sustainability without irradiation with energy rays, a method for producing a film using the aqueous surface treatment agent, And the surface treatment material which has a membrane | film | coat formed by the manufacturing method of this membrane | film | coat can be provided.
[水系表面処理剤]
本発明に係る水系表面処理剤は、親水皮膜形成成分(A)と、ポリオキシエチレンひまし油又はポリオキシエチレン硬化ひまし油(B)と、ポリオキシエチレンひまし油及びポリオキシエチレン硬化ひまし油以外の非イオン性界面活性剤(C)とを含有する。本発明に係る水系表面処理剤は、これらの成分を含むことにより、液安定性に優れ、長期間(少なくとも3ヶ月)の貯蔵が可能となる。また、調製直後の水系表面処理剤を用いても、一定期間(例えば3ヶ月)貯蔵した水系表面処理剤を用いても同様に、成型加工性及び親水持続性に優れた皮膜を金属基材上に形成することができる。それゆえ、本発明に係る水系表面処理剤は、水系の金属表面処理剤として有用である。[Aqueous surface treatment agent]
The aqueous surface treatment agent according to the present invention comprises a hydrophilic film-forming component (A), polyoxyethylene castor oil or polyoxyethylene hydrogenated castor oil (B), nonionic interface other than polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil. And an active agent (C). By including these components, the aqueous surface treating agent according to the present invention is excellent in liquid stability and can be stored for a long period (at least 3 months). In addition, even if an aqueous surface treatment agent immediately after preparation is used or an aqueous surface treatment agent stored for a certain period (for example, 3 months) is used, a film excellent in molding processability and hydrophilic sustainability is similarly formed on a metal substrate. Can be formed. Therefore, the aqueous surface treatment agent according to the present invention is useful as an aqueous metal surface treatment agent.
水系表面処理剤は、例えば、溶媒(液体媒体)を攪拌しながら上記成分(A)〜(C)を一つずつあるいは同時に添加することにより調製することができる。 The aqueous surface treatment agent can be prepared, for example, by adding the above components (A) to (C) one by one or simultaneously while stirring the solvent (liquid medium).
水系表面処理剤に用いられる溶媒(液体媒体)としては、水を主成分(例えば、全溶媒の質量を基準として水が70質量%以上)とするが、塗布後の焼き付け速度の調整や、塗装状態の改善のために、メタノール、エタノール等の水溶性アルコール、アセトン等の水溶性ケトン、メチルセロソルブ、エチルセロソルブ等のセロソルブ等の水溶性溶剤を本発明の趣旨、及び、皮膜性能を損なわない範囲で任意の割合で併用してもよい。 As a solvent (liquid medium) used for the water-based surface treatment agent, water is a main component (for example, water is 70% by mass or more based on the mass of the total solvent). In order to improve the state, water-soluble alcohols such as methanol and ethanol, water-soluble ketones such as acetone, and water-soluble solvents such as cellosolve such as methyl cellosolve and ethyl cellosolve are within the scope of the present invention and do not impair the film performance And may be used in any proportion.
親水皮膜形成成分(A)としては、親水皮膜を形成できるものであれば特に制限されるものではなく、例えば、公知の水溶性有機高分子又は親水皮膜形成組成物を挙げることができる。 The hydrophilic film forming component (A) is not particularly limited as long as it can form a hydrophilic film, and examples thereof include known water-soluble organic polymers or hydrophilic film forming compositions.
水溶性有機高分子としては、20℃100gの水に1g以上溶解するものであれば特に制限されるものではなく、例えば、(メタ)アクリル酸系の重合体又は共重合体、ポリビニルアルコール又は変性ポリビニルアルコール、セルロース誘導体の重合体又は共重合体等を挙げることができる。これらは単独で用いてもよいし、2以上を組み合わせて用いてもよい。また、水溶性有機高分子が非自己硬化型のものである場合には、架橋剤を組み合わせて用いることが好ましい。なお、水溶性有機高分子が自己硬化型であっても、架橋剤を組み合わせて用いてもよい。また、水溶性有機高分子は重量平均分子量が1000以上のものであることが好適である。尚、当該重量平均分子量はGPCにより測定された値とする。 The water-soluble organic polymer is not particularly limited as long as 1 g or more can be dissolved in 100 g of water at 20 ° C., for example, a (meth) acrylic acid polymer or copolymer, polyvinyl alcohol, or modified Examples include polyvinyl alcohol, a polymer or copolymer of a cellulose derivative, and the like. These may be used alone or in combination of two or more. When the water-soluble organic polymer is a non-self-curing type, it is preferable to use a combination of crosslinking agents. In addition, even if a water-soluble organic polymer is a self-hardening type, you may use it combining a crosslinking agent. The water-soluble organic polymer preferably has a weight average molecular weight of 1000 or more. The weight average molecular weight is a value measured by GPC.
上記親水皮膜形成組成物としては、例えば、上述の2以上の水溶性有機高分子の混合物、上述の1以上の水溶性有機高分子と架橋剤との混合物等を挙げることができるがこれらに限定されるものではなく、親水性を向上させるために、例えば、アルカリ珪酸塩等の珪酸化合物、コロイダルシリカ、コロイダルシリカに有機官能基(例えば、グリシジル基、ビニル基、アミノ基など)を有するオルガノアルコキシシランを修飾させた無機化合物などが上記混合物に配合されていてもよい。 Examples of the hydrophilic film-forming composition include, but are not limited to, a mixture of two or more water-soluble organic polymers described above, a mixture of one or more water-soluble organic polymers and a crosslinking agent described above, and the like. In order to improve hydrophilicity, for example, organoalkoxysilicates such as silicate compounds such as alkali silicates, colloidal silica, and colloidal silica having an organic functional group (for example, glycidyl group, vinyl group, amino group, etc.) An inorganic compound modified with silane may be blended in the mixture.
(メタ)アクリル酸系重合体としては、例えば、アクリル酸、メタクリル酸、エタクリル酸、クロトン酸、イタコン酸、マレイン酸、フマル酸、2−アクリルアミド−2−メチルプロパンスルホン酸、2−アクリルアミドエチルスルホン酸、ビニルスルホン酸、スルホエチルアクリレート、スルホエチルメタクリレート、アリルスルホン酸、メタリルスルホン酸、スチレンスルホン酸、2−ヒドロキシエチルアクリレート、2−ヒドロキシプロピルアクリレート、2−ヒドロキシエチルメタクリレート、2−ヒドロキシプロピルメタクリレート、2−メトキシエチルアクリレート、アクリルアミド等の単量体又はその塩の重合体を用いることができる。また、(メタ)アクリル酸系共重合体としては、例えば、上記単量体又はその塩を適宜組み合わせた共重合体を挙げる事ができる。 Examples of (meth) acrylic acid polymers include acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-acrylamido-2-methylpropanesulfonic acid, and 2-acrylamidoethylsulfone. Acid, vinyl sulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate , Monomers such as 2-methoxyethyl acrylate and acrylamide, or a polymer of a salt thereof can be used. Moreover, as a (meth) acrylic-acid type copolymer, the copolymer which combined the said monomer or its salt suitably can be mentioned, for example.
ポリビニルアルコールとしては、例えば、けん化度70モル%以上、好適には90モル%〜100モル%のポリビニルアルコールを挙げることができる。尚、このけん化度は、JIS K6726に従って測定した値である。 Examples of polyvinyl alcohol include polyvinyl alcohol having a saponification degree of 70 mol% or more, preferably 90 mol% to 100 mol%. The degree of saponification is a value measured according to JIS K6726.
変性ポリビニルアルコールとしては、例えばカルボキシル基、スルホン基、ホスホノ基等を有するアニオン変性PVA、アミノ基等を有するカチオン変性PVA、アセトアセチル基を有するアセトアセチル基変性PVA等を挙げることができる。 Examples of the modified polyvinyl alcohol include an anion-modified PVA having a carboxyl group, a sulfone group, a phosphono group, a cation-modified PVA having an amino group, and an acetoacetyl group-modified PVA having an acetoacetyl group.
セルロース誘導体としては、例えば、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルメチルセルロース等を挙げることができる。 Examples of the cellulose derivative include carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, and the like.
水溶性有機高分子としては、上述したものの他、ポリビニルピロリドン、ポリアクリルアミド、ポリアミド、ポリエチレングリコール、キトサン誘導体の重合体又は共重合体等を挙げることができる。 Examples of the water-soluble organic polymer include, in addition to those described above, a polymer or copolymer of polyvinylpyrrolidone, polyacrylamide, polyamide, polyethylene glycol, chitosan derivative, and the like.
架橋剤としては、前記水溶性有機高分子とは異なる成分であり、親水性皮膜を形成させるために用いられているものであれば特に制限されるものでなく、例えば、多価カルボン酸又はその塩、グリオキサール、イソシアネート、ブロックイソシアネート、カルボジイミド等を挙げることができる。尚、架橋剤の分子量は1000未満であることが好適である。 The cross-linking agent is a component different from the water-soluble organic polymer and is not particularly limited as long as it is used for forming a hydrophilic film. A salt, glyoxal, isocyanate, block isocyanate, carbodiimide, etc. can be mentioned. The molecular weight of the crosslinking agent is preferably less than 1000.
多価カルボン酸としては、例えば、イソフタル酸、アジピン酸、ピロメリット酸、マレイン酸、イタコン酸、フマル酸、1,2,4−トリメリット酸、1,2,3,4−ブタンテトラカルボン酸、3,3’,4,4’−ジフェニルスルホンテトラカルボン酸、シクロヘキサン−1,2,4−トリカルボン酸、2−ホスホノブタン−1,2,4−トリカルボン酸等の2以上のカルボキシル基を有する化合物を挙げることができる。これらは単独で用いてもよいし、併用してもよい。多価カルボン酸の塩としては、例えば、ナトリウム、カリウム、リチウム、アンモニウム等の塩を挙げることができる。 Examples of the polyvalent carboxylic acid include isophthalic acid, adipic acid, pyromellitic acid, maleic acid, itaconic acid, fumaric acid, 1,2,4-trimellitic acid, 1,2,3,4-butanetetracarboxylic acid. , 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, cyclohexane-1,2,4-tricarboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid and other compounds having two or more carboxyl groups Can be mentioned. These may be used alone or in combination. Examples of the polyvalent carboxylic acid salt include salts of sodium, potassium, lithium, ammonium and the like.
架橋剤(a1)の配合量としては、架橋剤(a1)と水溶性有機高分子(a2)の固形分質量比(a1/a2)が0.01〜0.7の範囲となる量であることが好ましい。固形分質量比(a1/a2)をこの範囲内に調整することにより、形成される皮膜の親水持続性及び成型加工性をより向上させることができる。 As a compounding quantity of a crosslinking agent (a1), it is the quantity from which the solid content mass ratio (a1 / a2) of a crosslinking agent (a1) and a water-soluble organic polymer (a2) becomes the range of 0.01-0.7. It is preferable. By adjusting the solid content mass ratio (a1 / a2) within this range, the hydrophilic durability and molding processability of the formed film can be further improved.
ポリオキシエチレンひまし油又はポリオキシエチレン硬化ひまし油(B)としては、ひまし油にエチレンオキサイドを重合付加したもの、又はひまし油に水素を付加した硬化ひまし油にさらにエチレンオキサイドを重合付加したもの等であれば特に制限されるものではないが、HLB(グリフィン法に依る。)が2.5〜13のものを用いることが好ましい。HLBが上記数値範囲内であるポリオキシエチレンひまし油又はポリオキシエチレン硬化ひまし油を水系表面処理剤に配合することにより、親水皮膜形成成分(A)によって形成される皮膜の親水性を維持しつつ、成型加工性をより向上させることができる。なお、本明細書において「ひまし油」とは、トウゴマの種子から抽出された不乾性油であって、リシノール酸のトリグリセリドを主成分とするものである。 The polyoxyethylene castor oil or the polyoxyethylene hydrogenated castor oil (B) is not particularly limited as long as it is obtained by polymerizing and adding ethylene oxide to castor oil, or by polymerizing and adding ethylene oxide to hydrogenated castor oil. Although not used, it is preferable to use one having an HLB (depending on the Griffin method) of 2.5 to 13. By blending polyoxyethylene castor oil or polyoxyethylene hydrogenated castor oil whose HLB is within the above numerical range with an aqueous surface treatment agent, molding is performed while maintaining the hydrophilicity of the film formed by the hydrophilic film forming component (A). Workability can be further improved. In the present specification, “castor oil” is a non-drying oil extracted from castor bean seeds, and is mainly composed of triglyceride of ricinoleic acid.
ポリオキシエチレンひまし油又はポリオキシエチレン硬化ひまし油(B)の配合量は、水系表面処理剤における固形分の合計質量に対して、固形分換算質量の割合で1質量%〜15質量%であることが好ましい。配合量をこの範囲内に調整することにより、親水皮膜形成成分(A)によって形成される皮膜の親水性を維持しつつ、成型加工性をより向上させた皮膜を得ることができる。 The blending amount of the polyoxyethylene castor oil or the polyoxyethylene hydrogenated castor oil (B) is 1% by mass to 15% by mass in terms of the mass in terms of solid content with respect to the total mass of the solid content in the aqueous surface treatment agent. preferable. By adjusting the blending amount within this range, it is possible to obtain a film with improved moldability while maintaining the hydrophilicity of the film formed by the hydrophilic film forming component (A).
非イオン性界面活性剤(C)は、ポリオキシエチレンひまし油及びポリオキシエチレン硬化ひまし油以外であれば特に制限されるものではないが、ポリアルキレンオキシド鎖[具体的には、ポリオキシエチレン鎖{(CH2CH2O)m}、ポリオキシプロピレン{(CH2CH(CH3)O)n}とポリオキシエチレン{(CH2CH2O)i}との連結鎖等]と、アルキル基(CnH2n+1)とのエーテル結合で構成されるポリオキシアルキレンアルキルエーテル類、特にポリオキシエチレンアルキルエーテル類から選ばれることが好ましい。ポリオキシアルキレンアルキルエーテル類としては、例えば、ポリオキシアルキレン分岐デシルエーテル、ポリオキシアルキレントリデシルエーテル、ポリオキシアルキレンラウリルエーテル等が挙げられ、ポリオキシエチレンアルキルエーテル類としては、例えば、ポリオキシエチレンイソデシルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンオレイルセチルエーテル、ポリオキシエチレントリデシルエーテル等が挙げられる。これらは単独で用いてもよいし、2種類以上混合して使用しても良い。The nonionic surfactant (C) is not particularly limited as long as it is other than polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil, but polyalkylene oxide chain [specifically, polyoxyethylene chain {( CH 2 CH 2 O) m }, polyoxypropylene {(CH 2 CH (CH 3 ) O) n } and polyoxyethylene {(CH 2 CH 2 O) i }, etc.], and an alkyl group ( It is preferably selected from polyoxyalkylene alkyl ethers composed of an ether bond with C n H 2n + 1 ), particularly polyoxyethylene alkyl ethers. Examples of polyoxyalkylene alkyl ethers include polyoxyalkylene branched decyl ether, polyoxyalkylene tridecyl ether, polyoxyalkylene lauryl ether, and the like. Examples of polyoxyethylene alkyl ethers include polyoxyethylene isopropyl ether. Examples include decyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl cetyl ether, and polyoxyethylene tridecyl ether. These may be used alone or in combination of two or more.
水系表面処理剤に配合させる、ポリオキシエチレンひまし油又はポリオキシエチレン硬化ひまし油(B)と非イオン性界面活性剤(C)の固形分合計質量は、水系表面処理剤における固形分の合計質量に対して、25質量%を超えない範囲で調整し、かつこれらの合計HLBが13以上となるように配合することが好ましい。上述のように、成分(B)と成分(C)との固形分合計質量、これらの成分の合計HLBを所定の数値範囲内に調整することにより、水系表面処理剤の貯蔵安定性をより向上させたり、親水皮膜形成成分(A)によって形成される皮膜の親水性を維持させることができる。 The total solid mass of the polyoxyethylene castor oil or polyoxyethylene hydrogenated castor oil (B) and the nonionic surfactant (C) to be added to the aqueous surface treatment agent is based on the total mass of the solid content in the aqueous surface treatment agent. Thus, it is preferable to adjust the amount so as not to exceed 25% by mass and to blend such that the total HLB is 13 or more. As described above, the storage stability of the water-based surface treatment agent is further improved by adjusting the total solid mass of the component (B) and the component (C) and the total HLB of these components within a predetermined numerical range. Or the hydrophilicity of the film formed by the hydrophilic film forming component (A) can be maintained.
ここで、成分(B)と成分(C)の合計HLBは、各々のHLBの加重平均として算出される。例えば、成分(B)のHLBが12.5、成分(B)及び成分(C)の固形分合計質量に対する成分(B)の固形分換算質量の割合が42質量%、成分(C)のHLBが16.8、並びに、成分(B)及び(C)の固形分合計質量に対する成分(C)の固形分換算質量の割合が58質量%である場合の合計HLBは、以下の通りである。
(12.5×0.42)+(16.8×0.58)=15.0Here, the total HLB of the component (B) and the component (C) is calculated as a weighted average of each HLB. For example, the HLB of the component (B) is 12.5, the ratio of the solid content converted mass of the component (B) to the total solid mass of the component (B) and the component (C) is 42 mass%, the HLB of the component (C) 16.8, and the total HLB when the ratio of the solid content converted mass of the component (C) to the total solid mass of the components (B) and (C) is 58% by mass is as follows.
(12.5 × 0.42) + (16.8 × 0.58) = 15.0
なお、上述においては、溶媒以外に、親水皮膜形成成分(A)と、ポリオキシエチレンひまし油又はポリオキシエチレン硬化ひまし油(B)と、非イオン性界面活性剤(但しポリオキシエチレンひまし油及びポリオキシエチレン硬化ひまし油を除く)(C)のみを配合させた水系表面処理剤について説明したが、該水系表面処理剤によって形成される皮膜に各種性能を付与するために、酸化防止剤、消泡剤、レベリング剤、防錆剤、抗菌剤、抗かび剤、抗菌抗かび剤、着色剤等を本発明の趣旨、及び皮膜性能を損なわない限り、任意の割合でさらに配合してもよい。 In the above, in addition to the solvent, the hydrophilic film forming component (A), polyoxyethylene castor oil or polyoxyethylene hydrogenated castor oil (B), and nonionic surfactant (however, polyoxyethylene castor oil and polyoxyethylene are used). (Excluding hardened castor oil) The water-based surface treatment agent containing only (C) has been described. To impart various performances to the film formed by the water-based surface treatment agent, antioxidants, antifoaming agents, and leveling agents are used. An agent, a rust inhibitor, an antibacterial agent, an antifungal agent, an antibacterial antifungal agent, a colorant, and the like may be further blended at an arbitrary ratio as long as the gist of the present invention and the film performance are not impaired.
[皮膜の製造方法及び表面処理材]
本発明に係る表面処理材は、上記水系表面処理剤を用いて、熱交換器用フィン材等の金属基材の表面上に皮膜を製造することにより得る事ができる。[Film Production Method and Surface Treatment Material]
The surface treatment material according to the present invention can be obtained by producing a film on the surface of a metal substrate such as a heat exchanger fin material using the aqueous surface treatment agent.
皮膜の製造方法としては、上記水系表面処理剤を金属基材の表面に接触させる工程と、該水系表面処理剤を接触させた金属基材表面を乾燥させる工程を含むものであれば特に制限されるものではなく、上記水系表面処理剤を金属基材の表面に接触させる前に、脱脂処理を行なう工程、耐食皮膜を形成する工程等が含まれていてもよい。 The method for producing the film is particularly limited as long as it includes a step of bringing the aqueous surface treatment agent into contact with the surface of the metal substrate and a step of drying the metal substrate surface in contact with the aqueous surface treatment agent. However, before the aqueous surface treatment agent is brought into contact with the surface of the metal substrate, a step of performing a degreasing treatment, a step of forming a corrosion-resistant film, and the like may be included.
上記水系表面処理剤を接触させる方法としては、例えば、ロールコーター処理、スプレー処理、エアレススプレー処理、ローラー塗装、ハケ塗り、バーコーター処理、シャワー絞り、浸漬処理等の方法を挙げることができる。 Examples of the method for bringing the aqueous surface treatment agent into contact include methods such as roll coater treatment, spray treatment, airless spray treatment, roller coating, brush coating, bar coater treatment, shower squeezing, and immersion treatment.
上記金属基材表面の乾燥は、例えば、熱風による対流式、電熱管による輻射式のオーブン等によって行なうことができる。乾燥温度としては、金属基材の最高到達温度が150℃〜250℃であることが好ましい。 The metal substrate surface can be dried by, for example, a convection type using hot air or a radiation type oven using an electric heating tube. As a drying temperature, it is preferable that the highest temperature reached by the metal substrate is 150 ° C to 250 ° C.
上述のようにして製造された皮膜の付着量は、金属基材表面における皮膜の均一性、並びに作業性及び生産性の観点から、0.05g/m2〜20g/m2の範囲内とすることが好ましく、0.2g/m2〜10g/m2の範囲内とすることがより好ましい。The adhesion amount of the film produced as described above is in the range of 0.05 g / m 2 to 20 g / m 2 from the viewpoint of the uniformity of the film on the surface of the metal substrate, and workability and productivity. it is preferable, more preferably in the range of 0.2g / m 2 ~10g / m 2 .
金属基材としては、例えば、アルミニウム材若しくはアルミニウム合金材又はそれらのめっき材を挙げることができる。アルミニウム材としては、例えば、JIS H4000に規定される1000系の純アルミニウム材を、アルミニウム合金材としては、例えば、3000系又は8000系のアルミニウム合金材等をそれぞれ挙げることができるが、これらに限定されるものではない。アルミニウム材又はアルミニウム合金材のめっき材の種類としては、例えば、JIS G3314に規定される溶融アルミニウムめっき鋼板、JIS G3321に規定される溶融55%アルミニウム−亜鉛合金めっき鋼板等を挙げることができるが、これらに限定されるものではない。 As a metal base material, an aluminum material, an aluminum alloy material, or those plating materials can be mentioned, for example. Examples of the aluminum material include a 1000 series pure aluminum material defined in JIS H4000, and examples of the aluminum alloy material include a 3000 series or 8000 series aluminum alloy material, but are not limited thereto. Is not to be done. Examples of the type of plating material of aluminum material or aluminum alloy material include, for example, a hot-dip aluminum-plated steel sheet specified in JIS G3314, a molten 55% aluminum-zinc alloy-plated steel sheet specified in JIS G3321, It is not limited to these.
上記金属基材表面の脱脂処理としては、ハジキが無く、上記水系表面処理剤、及び、耐食皮膜を形成するための表面処理剤を塗布することができる程度に金属基材表面の油分を除去できればいかなる方法を適用してもよく、例えば、アルカリ系、酸系の脱脂剤等による公知の脱脂処理方法を適用することができる。 As the degreasing treatment on the surface of the metal substrate, there is no repellency, so long as the oil on the surface of the metal substrate can be removed to such an extent that the aqueous surface treatment agent and the surface treatment agent for forming a corrosion-resistant film can be applied. Any method may be applied. For example, a known degreasing treatment method using an alkaline or acid degreasing agent may be applied.
上記耐食皮膜を形成する方法としては、例えば、塗布型クロメート処理、りん酸クロメート処理、ジルコニウム系化成処理、チタニウム系化成処理等の化成処理方法、又はアクリル樹脂、ウレタン樹脂、エポキシ樹脂等を含む表面処理剤を塗布する方法等の公知の方法を用いることができるが、これらの方法に制限されるものではない。 Examples of the method of forming the corrosion-resistant film include a chemical conversion treatment method such as a coating type chromate treatment, a phosphoric acid chromate treatment, a zirconium chemical conversion treatment, a titanium chemical conversion treatment, or a surface containing an acrylic resin, a urethane resin, an epoxy resin, or the like. A known method such as a method of applying a treatment agent can be used, but it is not limited to these methods.
以上のように、本発明に係る水系表面処理剤を用いて金属基材表面上に皮膜を形成することにより、親水持続性と成型加工性を兼ね備えた表面処理材を得る事ができる。また、本発明に係る皮膜の製造方法により、親水皮膜の上層に潤滑皮膜を形成することなく、親水持続性と成型加工性に優れた表面処理材を製造することができるので、熱交換器用プレコートフィン材の製造を効率よく行なう事が可能となる。 As described above, by forming a film on the surface of a metal substrate using the aqueous surface treatment agent according to the present invention, a surface treatment material having both hydrophilic sustainability and molding processability can be obtained. In addition, the method for producing a film according to the present invention can produce a surface treatment material excellent in hydrophilic sustainability and molding processability without forming a lubricating film on the upper layer of the hydrophilic film. The fin material can be manufactured efficiently.
以下に本発明を、実施例及び比較例を用いて、具体的に説明する。これらの実施例は本発明の説明のために記載するものであり、本発明を何ら限定するものではない。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. These examples are described for the purpose of illustrating the present invention and are not intended to limit the present invention in any way.
[試験板の作製]
(1)供試材
JIS A1050、板厚0.26mmのアルミニウム材に、アルカリ脱脂剤(ファインクリーナーFC−4477の2%水溶液:日本パーカライジング株式会社製)を、60℃で15秒間スプレーすることにより脱脂を行った。その後、水洗して水切りし、表面を乾燥させたものを供試材として使用した。[Preparation of test plate]
(1) Test material By spraying an alkali degreasing agent (2% aqueous solution of Fine Cleaner FC-4477: manufactured by Nihon Parkerizing Co., Ltd.) for 15 seconds at 60 ° C. on an aluminum material of JIS A1050 and plate thickness 0.26 mm. Degreasing was performed. Then, it washed with water, drained, and what dried the surface was used as a test material.
(2)水系表面処理剤の調製
後述の実施例1〜19及び比較例1〜3の試験板を作製するために用いた各水系表面処理剤の組成を表1に示す。表1中の各成分の配合量は、水系表面処理剤の固形分合計質量に対する質量割合(%)を示す。また、表1中の種類の欄に示す各記号は、表2に示す物質をそれぞれ意味する。なお、水系表面処理剤における固形分は全て10質量%とした。また、水系表面処理剤は、溶媒である水を攪拌しながら、各成分を順次添加することにより調製した。(2) Preparation of aqueous surface treatment agent Table 1 shows the composition of each aqueous surface treatment agent used for preparing test plates of Examples 1 to 19 and Comparative Examples 1 to 3 described later. The compounding amount of each component in Table 1 indicates a mass ratio (%) to the total solid mass of the aqueous surface treatment agent. In addition, each symbol shown in the type column in Table 1 means the substance shown in Table 2. In addition, all the solid content in an aqueous surface treating agent was 10 mass%. The aqueous surface treatment agent was prepared by sequentially adding each component while stirring water as a solvent.
(3)皮膜の形成
供試材の表面に、アクリル系樹脂及び炭酸ジルコニウムアンモニウムを含むアクリル系耐食塗料をバーコーター#5で塗布し、熱風循環式乾燥炉で乾燥して耐食皮膜を形成した。続いて、耐食皮膜の上に各水系表面処理剤をバーコーター#5で塗布し、熱風循環式乾燥炉で乾燥して親水性皮膜を形成させ、実施例1〜19及び比較例1〜3の試験板を作製した。これらの試験板を用いて以下の性能評価を行った。(3) Formation of film An acrylic corrosion-resistant paint containing acrylic resin and ammonium zirconium carbonate was applied to the surface of the test material with a bar coater # 5 and dried in a hot air circulation drying furnace to form a corrosion-resistant film. Subsequently, each aqueous surface treatment agent was applied on the corrosion-resistant film with a bar coater # 5, and dried in a hot air circulation type drying furnace to form a hydrophilic film. Examples 1 to 19 and Comparative Examples 1 to 3 A test plate was prepared. The following performance evaluation was performed using these test plates.
[性能評価]
(1)親水性
実施例1〜19及び比較例1〜3の試験板の表面に10μLの純水を滴下し、水滴の接触角を協和界面科学株式会社製自動接触角計「DM−501」を用いて測定した後、以下の評価基準に基づいて親水性を評価した。この評価は、親水性皮膜形成直後の各試験板(初期親水性)、及び「0.5L/minの流水に8時間浸漬した後、80℃で16時間乾燥する処理」を1サイクルとして5サイクル繰り返して行った各試験板(サイクル後親水性)に対し実施した。
<評価基準>
◎・・・接触角10°未満
○・・・10°以上30°未満
△・・・30°以上40°未満
×・・・40°以上[Performance evaluation]
(1) Hydrophilicity 10 μL of pure water is dropped on the surfaces of the test plates of Examples 1 to 19 and Comparative Examples 1 to 3, and the contact angle of the water drops is an automatic contact angle meter “DM-501” manufactured by Kyowa Interface Science Co., Ltd. Then, the hydrophilicity was evaluated based on the following evaluation criteria. In this evaluation, each test plate immediately after the formation of the hydrophilic film (initial hydrophilicity) and “treatment of dipping in 0.5 L / min of flowing water for 8 hours and then drying at 80 ° C. for 16 hours” are defined as 5 cycles. The test was repeated for each test plate (hydrophilic after cycle).
<Evaluation criteria>
◎ ・ ・ ・ Contact angle less than 10 ° ○ ・ ・ ・ 10 ° or more and less than 30 ° △ ・ ・ ・ 30 ° or more and less than 40 ° × ... 40 ° or more
(2)成型加工性
成型加工性を評価するために下記の評価を実施した。(2) Molding processability The following evaluation was carried out in order to evaluate molding processability.
[評価1]
各試験板表面の動摩擦係数を、新東科学株式会社製表面性測定器「HEYDON TYPE:14FW」を用いて測定し、以下の評価基準に基づいて潤滑性を評価した。
<試験条件>
荷重:200g、鋼球:3mmφ、ストローク:10mm、摺動速度:10mm/sec、摺動回数:30往復
<評価基準>
◎・・・摩擦係数0.2未満
○・・・0.2以上0.3未満
△・・・0.3以上0.5未満
×・・・0.5以上[Evaluation 1]
The dynamic friction coefficient of each test plate surface was measured using a surface property measuring instrument “HEYDON TYPE: 14FW” manufactured by Shinto Kagaku Co., Ltd., and the lubricity was evaluated based on the following evaluation criteria.
<Test conditions>
Load: 200 g, steel ball: 3 mmφ, stroke: 10 mm, sliding speed: 10 mm / sec, number of sliding times: 30 reciprocations <Evaluation criteria>
◎ ・ ・ ・ Friction coefficient less than 0.2 ○ ・ ・ ・ 0.2 or more and less than 0.3 Δ ・ ・ ・ 0.3 or more and less than 0.5 × ・ ・ ・ 0.5 or more
[評価2]
試験板の取り扱い(加工を含む)において問題となる表面のベタツキを以下の評価基準に基づいて評価した。具体的には、水平に置いた各試験板表面に軽く指を押し当て、そのまま指を水平方向に動かしたときの感触にて判定した。
<評価基準>
○・・・粘着感を感じる事無く、なめらかに指を動かせる。
△・・・指触直後にやや粘着感を感じるが、ほとんど抵抗無く指を動かせる。
×・・・指に粘着感があり、指が移動し難い。[Evaluation 2]
Surface stickiness, which is a problem in handling the test plate (including processing), was evaluated based on the following evaluation criteria. Specifically, a finger was lightly pressed against the surface of each test plate placed horizontally, and the determination was made based on the feeling when the finger was moved in the horizontal direction.
<Evaluation criteria>
○ ・ ・ ・ You can move your finger smoothly without feeling sticky.
Δ: Feels a little sticky immediately after touching the finger, but moves the finger almost without resistance.
X: The finger is sticky and the finger is difficult to move.
(3)貯蔵安定性
実施例1〜19及び比較例1〜3の試験板を作製するために用いた各水系表面処理剤を、ポリ容器に封入し、25℃で3ヶ月静置した後の状態を観察し、以下の評価基準に基づいて貯蔵安定性を評価した。
<評価基準>
○・・・凝集又は沈殿が認められない。
×・・・凝集又は沈殿が認められた。(3) Storage stability Each water type surface treating agent used in order to produce the test plates of Examples 1 to 19 and Comparative Examples 1 to 3 was sealed in a plastic container and allowed to stand at 25 ° C. for 3 months. The state was observed and storage stability was evaluated based on the following evaluation criteria.
<Evaluation criteria>
○: No aggregation or precipitation is observed.
X: Aggregation or precipitation was observed.
表3に示すように、本発明の実施例(実施例1〜19)は比較例(比較例1〜3)に対して貯蔵安定性に優れ、一定期間保管しても調製直後と同程度の、成型加工性及び親水持続性に優れた皮膜を形成することができる。 As shown in Table 3, the examples of the present invention (Examples 1 to 19) are superior to the comparative examples (Comparative Examples 1 to 3) in terms of storage stability, and even if stored for a certain period of time, they are almost the same as immediately after preparation. A film excellent in molding processability and hydrophilic sustainability can be formed.
Claims (5)
請求項1〜3のいずれか一項に記載の水系表面処理剤を前記表面に接触させる工程と、前記水系表面処理剤を接触させた前記表面を乾燥させる工程を含む皮膜の製造方法。A method for producing a film on the surface of an aluminum material or an aluminum alloy material or a plating material thereof,
The manufacturing method of the membrane | film | coat including the process of making the surface contacted with the aqueous surface treating agent as described in any one of Claims 1-3, and the process of making the said surface contacted with the aqueous surface treating agent.
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JPH07109436A (en) * | 1993-10-14 | 1995-04-25 | Dainippon Toryo Co Ltd | Coating composition and coated aluminum material |
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JP4942251B2 (en) * | 2001-03-27 | 2012-05-30 | 日本ペイント株式会社 | Hydrophilization treatment agent, hydrophilization treatment method, and hydrophilized aluminum material or aluminum alloy material |
JP2002285140A (en) * | 2001-03-27 | 2002-10-03 | Nippon Paint Co Ltd | Hydrophilizing agent, method for hydrophilizing and aluminum or aluminum alloy material subjected to hydrophilizing |
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