JP6198913B1 - Coating composition suitable for carbon dioxide coating - Google Patents

Coating composition suitable for carbon dioxide coating Download PDF

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JP6198913B1
JP6198913B1 JP2016173955A JP2016173955A JP6198913B1 JP 6198913 B1 JP6198913 B1 JP 6198913B1 JP 2016173955 A JP2016173955 A JP 2016173955A JP 2016173955 A JP2016173955 A JP 2016173955A JP 6198913 B1 JP6198913 B1 JP 6198913B1
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coating
carbon dioxide
organic solvent
coating composition
mass
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JP2018039893A (en
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安明 西澤
安明 西澤
慎司 藤岡
慎司 藤岡
慶太 横井
慶太 横井
玄児 今井
玄児 今井
貴樹 那須
貴樹 那須
康宏 小松
康宏 小松
慎吾 田中
慎吾 田中
亮太 森
亮太 森
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Kansai Paint Co Ltd
Showa Denko Gas Products Co Ltd
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Kansai Paint Co Ltd
Showa Denko Gas Products Co Ltd
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Priority to CN201710796451.4A priority patent/CN108299929A/en
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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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • C09D125/14—Copolymers of styrene with unsaturated esters
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Abstract

【課題】二酸化炭素を希釈剤とする塗装において、良好な塗装作業性を有し、かつ仕上り外観にも優れた塗膜を得ることができる塗料組成物を提供すること。【解決手段】二酸化炭素塗装に使用するための塗料組成物であって、該塗料は、塗膜形成成分と有機溶媒とを含有し、該有機溶媒は、蒸発速度が酢酸ブチルを1としたとき０．０２以上、溶解性パラメーターが８．０（ｃａｌ／ｃｍ３）０．５〜１０．５（ｃａｌ／ｃｍ３）０．５、比重が０．９５以下である有機溶媒（Ａ）を含有する、圧力２〜３２ＭＰａ、塗料質量１に対する二酸化炭素質量比率が０．１以上である二酸化炭素の混合比率の範囲内で二酸化炭素と混合して、塗料温度を−３０〜５０℃として二酸化炭素塗装に用いるための塗料組成物。【選択図】なし[Problem] To provide a coating composition capable of obtaining a coating film having good coating workability and excellent finished appearance in coating using carbon dioxide as a diluent. A paint composition for use in carbon dioxide coating, wherein the paint contains a film-forming component and an organic solvent, and the organic solvent has an evaporation rate of 1 butyl acetate. An organic solvent (A) having a solubility parameter of 0.02 or more, 8.0 (cal / cm3) 0.5 to 10.5 (cal / cm3) 0.5, and a specific gravity of 0.95 or less, Mixing with carbon dioxide within the range of the mixing ratio of carbon dioxide having a pressure of 2 to 32 MPa and a carbon dioxide mass ratio of 0.1 or more with respect to the coating mass 1, the coating temperature is set to −30 to 50 ° C. and used for carbon dioxide coating. Paint composition for. [Selection figure] None

Description

本発明は、二酸化炭素塗装に適した塗料組成物等に関する。   The present invention relates to a coating composition suitable for carbon dioxide coating.

塗料を被塗物に塗装する方法として、塗料に二酸化炭素を混合して塗料組成物を調製し、得られた塗料組成物を被塗物に噴霧して塗装する方法が知られている。この方法では、二酸化炭素が有機溶媒とともに希釈剤として作用し、塗料組成物が塗装可能なレベルの粘度まで低下されることとなる。これにより、塗装に係るＶＯＣを削減することが可能となる。   As a method for applying a paint to an object to be coated, a method of preparing a paint composition by mixing carbon dioxide with the paint and spraying the obtained paint composition on the object to be coated is known. In this method, carbon dioxide acts as a diluent together with the organic solvent, and the viscosity is lowered to a level at which the coating composition can be applied. Thereby, it becomes possible to reduce VOC which concerns on coating.

このような二酸化炭素を使用した塗装技術は、例えば、特許文献１及び２に記載されている。   Such a coating technique using carbon dioxide is described in Patent Documents 1 and 2, for example.

特許文献１には、主として塗装装置に関する内容について、二酸化炭素塗装方法及びその装置が開示されている。   Patent Document 1 discloses a carbon dioxide coating method and an apparatus thereof mainly for the contents relating to the coating apparatus.

特許文献２には、薄膜においても、極めて良好な平滑性を有する塗膜を形成することが可能な高圧二酸化炭素塗装方法及びその塗装物が開示されている。   Patent Document 2 discloses a high-pressure carbon dioxide coating method capable of forming a coating film having extremely good smoothness even in a thin film, and a coated product thereof.

特開２０１０−２３４３４８号公報JP 2010-234348 A 特開２０１２−８６１７５号公報JP 2012-86175 A

しかしながら、特許文献１及び２の技術では、二酸化炭素塗装に適した塗料組成物の側面からの検討が不十分であり、特に、建設機械又は産業用機械等の大型で、通常、常温で乾燥硬化させる被塗物の塗装に対しては、塗装作業性（ワキやタレ等の不具合の対策）及び仕上り外観の点で不十分であった。   However, the techniques of Patent Documents 1 and 2 are insufficiently studied from the aspect of a coating composition suitable for carbon dioxide coating, particularly large-sized construction machines or industrial machines, and usually dry-cured at room temperature. For the coating of the object to be coated, it was insufficient in terms of painting workability (measures for defects such as armpits and sagging) and finished appearance.

本発明は、二酸化炭素を希釈剤として用いる塗装において、良好な塗装作業性を有し、かつ仕上り外観にも優れた塗膜を得ることができる塗料組成物を提供することを目的とする。   An object of the present invention is to provide a coating composition capable of obtaining a coating film having good coating workability and excellent finished appearance in coating using carbon dioxide as a diluent.

本発明者等は、鋭意検討した結果、塗料組成物に特定の有機溶媒を使用し、適正範囲の高圧条件において、特定の割合で二酸化炭素と混合して適性範囲の塗料粘度となる塗料組成物によれば、上記課題の解決が達成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 diligent study, the present inventors have used a specific organic solvent in the coating composition, and mixed with carbon dioxide at a specific ratio under a high pressure condition in a proper range to obtain a paint viscosity in a suitable range. According to the present invention, it has been found that the above-mentioned problems can be solved, and the present invention has been completed.

即ち、本発明は、以下の態様を包含する。   That is, this invention includes the following aspects.

項１、二酸化炭素塗装に使用するための塗料組成物であって、該塗料は、塗膜形成成分と有機溶媒とを含有し、該有機溶媒は、
蒸発速度が酢酸ブチルを1としたとき０．０２以上、
溶解性パラメーターが８．０（ｃａｌ／ｃｍ３）０．５〜１０．５（ｃａｌ／ｃｍ３）０．５、
比重が０．９５以下である有機溶媒（Ａ）を含有する、
圧力２〜３２ＭＰａ、塗料質量１に対する二酸化炭素質量比率が０．１以上である二酸化炭素の混合比率の範囲内で二酸化炭素と混合して、塗料温度を−３０〜５０℃として二酸化炭素塗装に用いるための塗料組成物。 Item 1, a coating composition for use in carbon dioxide coating, wherein the coating contains a film-forming component and an organic solvent,
Evaporation rate is 0.02 or more when butyl acetate is 1.
Solubility parameter is 8.0 (cal / cm 3 ) 0.5 to 10.5 (cal / cm 3 ) 0.5 ,
Containing an organic solvent (A) having a specific gravity of 0.95 or less,
Mixing with carbon dioxide within the range of the mixing ratio of carbon dioxide having a pressure of 2 to 32 MPa and a carbon dioxide mass ratio of 0.1 or more with respect to the coating mass 1, the coating temperature is set to −30 to 50 ° C. and used for carbon dioxide coating. Paint composition for.

項２、塗膜形成成分として、アルキド樹脂、アクリル樹脂、脂肪酸変性アクリル樹脂、ウレタン樹脂、エポキシ樹脂、ポリエステル樹脂、アクリルシリコン樹脂、フッ素樹脂、メラミン樹脂から選ばれる少なくとも１種を含有する項１に記載の塗料組成物。   Item 2, containing at least one selected from alkyd resins, acrylic resins, fatty acid-modified acrylic resins, urethane resins, epoxy resins, polyester resins, acrylic silicon resins, fluororesins, and melamine resins as a coating film forming component The coating composition as described.

項３、塗料質量の総量に対して、有機溶媒（Ａ）を５〜９０質量％含有する、項１又は２に記載の塗料組成物。   Item 3. The coating composition according to item 1 or 2, which contains 5 to 90% by mass of the organic solvent (A) based on the total amount of the coating material mass.

項４、有機溶媒の総量に対して、有機溶媒（Ａ）を８０質量％以上含有する、項１〜３のいずれか１項に記載の塗料組成物。   Item 4. The coating composition according to any one of Items 1 to 3, comprising 80% by mass or more of the organic solvent (A) based on the total amount of the organic solvent.

項５、有機溶媒（Ａ）の溶解性パラメーターが８．３（ｃａｌ／ｃｍ３）０．５〜１０．２（ｃａｌ／ｃｍ３）０．５である、項１〜４のいずれか１項に記載の塗料組成物。 Item 5, The solubility parameter of the organic solvent (A) is 8.3 (cal / cm 3 ) 0.5 to 10.2 (cal / cm 3 ) 0.5 , Any one of Items 1 to 4 The coating composition as described in 2.

項６、有機溶媒（Ａ）の比重が０．９２以下である、項１〜５のいずれか１項に記載の塗料組成物。   Item 6. The coating composition according to any one of Items 1 to 5, wherein the specific gravity of the organic solvent (A) is 0.92 or less.

項７、塗料質量１に対する二酸化炭素質量比率が０．２〜０．５、かつ、塗料温度を−１５℃として測定する塗料粘度が、１００ｍＰａ・s以下である、項１〜６のいずれか１項に記載の塗料組成物。   Item 7. Any one of Items 1 to 6, wherein the mass ratio of carbon dioxide to the mass of paint 1 is 0.2 to 0.5, and the viscosity of the paint measured at a paint temperature of −15 ° C. is 100 mPa · s or less. The coating composition according to Item.

項８、被塗物に、二酸化炭素塗装装置により、塗料温度を−３０〜５０℃として、
圧力２〜３２ＭＰａ、塗料質量１に対する二酸化炭素質量比率が０．１以上である二酸化炭素の混合比率の範囲内で項１〜７のいずれか１項に記載の塗料組成物と二酸化炭素とを混合した塗料組成物を噴霧して塗装することを特徴とする塗装方法。 Item 8, to the object to be coated, with a carbon dioxide coating device, the paint temperature is set to -30 to 50 ° C,
The coating composition according to any one of Items 1 to 7 and carbon dioxide are mixed within a range of a mixing ratio of carbon dioxide having a pressure of 2 to 32 MPa and a mass ratio of carbon dioxide to coating mass 1 of 0.1 or more. The coating method characterized by spraying and painting the prepared coating composition.

本発明によれば、二酸化炭素を希釈剤として用いる塗装において、良好な塗装作業性を有し、かつ仕上り外観にも優れた塗膜を得ることができる塗料組成物を提供することができる。   ADVANTAGE OF THE INVENTION According to this invention, the coating composition which can obtain the coating film which has favorable coating workability | operativity and was excellent also in the finishing external appearance in the coating using a carbon dioxide as a diluent.

二酸化炭素塗装装置の一例を示す。An example of a carbon dioxide coating apparatus is shown.

本発明は、二酸化炭素塗装に使用するための塗料組成物であって、該塗料は、塗膜形成成分と有機溶媒とを含有し、該有機溶媒は、
蒸発速度が酢酸ブチルを1としたとき０．０２以上、
溶解性パラメーターが８．０（ｃａｌ／ｃｍ３）０．５〜１０．５（ｃａｌ／ｃｍ３）０．５、
比重が０．９５以下である有機溶媒（Ａ）を含有する、
圧力２〜３２ＭＰａ、塗料質量１に対する二酸化炭素質量比率が０．１以上である二酸化炭素の混合比率の範囲内で二酸化炭素と混合して、塗料温度を−３０〜５０℃として二酸化炭素塗装に用いるための塗料組成物
に関する。以下、詳細に述べる。 The present invention is a coating composition for use in carbon dioxide coating, the coating contains a film-forming component and an organic solvent, the organic solvent,
Evaporation rate is 0.02 or more when butyl acetate is 1.
Solubility parameter is 8.0 (cal / cm 3 ) 0.5 to 10.5 (cal / cm 3 ) 0.5 ,
Containing an organic solvent (A) having a specific gravity of 0.95 or less,
Mixing with carbon dioxide within the range of the mixing ratio of carbon dioxide having a pressure of 2 to 32 MPa and a carbon dioxide mass ratio of 0.1 or more with respect to the coating mass 1, the coating temperature is set to −30 to 50 ° C. and used for carbon dioxide coating. The present invention relates to a coating composition. Details will be described below.

＜塗膜形成成分＞
塗膜形成成分としては、通常塗料用途に用いられる樹脂であれば特に制限はなく、具体的には例えば、アルキド樹脂、アクリル樹脂、ウレタン樹脂、エポキシ樹脂、ポリエステル樹脂、アクリルシリコン樹脂、フッ素樹脂、メラミン樹脂等を挙げることができる。 <Coating film forming component>
The coating film forming component is not particularly limited as long as it is a resin that is usually used for paint applications. Specifically, for example, alkyd resin, acrylic resin, urethane resin, epoxy resin, polyester resin, acrylic silicon resin, fluororesin, A melamine resin etc. can be mentioned.

塗膜形成成分は、脂肪酸を構成成分とする脂肪酸変性樹脂であってもよい。脂肪酸変性樹脂としては、脂肪酸変性のアルキド樹脂、脂肪酸変性アクリル樹脂等を挙げることができる。   The coating film forming component may be a fatty acid-modified resin having a fatty acid as a constituent component. Examples of fatty acid-modified resins include fatty acid-modified alkyd resins and fatty acid-modified acrylic resins.

上記樹脂は、単独で又は２種類以上を混合して使用することもできる。塗膜形成成分は、１液硬化型であっても、２液硬化型等の多液硬化型のいずれであってもよく、ＵＶ等の活性エネルギー線硬化型であってもよい。   The above resins can be used alone or in admixture of two or more. The coating film forming component may be a one-component curable type, a multi-component curable type such as a two-component curable type, or an active energy ray curable type such as UV.

建設機械又は産業用機械用塗としては、上記塗膜形成成分である樹脂のうち、アルキド樹脂、アクリル樹脂、脂肪酸変性アクリル樹脂、ウレタン樹脂、エポキシ樹脂、ポリエステル樹脂を好適に使用することができる。   Of the resins that are the coating film forming components, alkyd resins, acrylic resins, fatty acid-modified acrylic resins, urethane resins, epoxy resins, and polyester resins can be suitably used as the coating for construction machinery or industrial machinery.

＜有機溶媒（Ａ）＞
本発明の塗料組成物は、有機溶媒の一部として、蒸発速度、溶解性パラメーター及び比重の３つの条件をすべて満たす有機溶媒（Ａ）を含有することを特徴とする。 <Organic solvent (A)>
The coating composition of the present invention is characterized in that it contains an organic solvent (A) that satisfies all three conditions of evaporation rate, solubility parameter and specific gravity as a part of the organic solvent.

蒸発速度
本発明の塗料組成物が含有する有機溶媒（Ａ）の蒸発速度とは、酢酸ブチルを１とした時の相対蒸発速度によって測定される値である。蒸発速度は、ＡＳＴＭ Ｄ３５３９−１１に基づいて測定される。 Evaporation rate The evaporation rate of the organic solvent (A) contained in the coating composition of the present invention is a value measured by a relative evaporation rate when butyl acetate is 1. The evaporation rate is measured based on ASTM D3539-11.

本発明の塗料組成物が含有する有機溶媒（Ａ）の蒸発速度は、乾燥性の観点から、０．０２以上であり、好ましくは、０．０５〜１．０、さらに好ましくは０．０８〜０．８の範囲内である。   The evaporation rate of the organic solvent (A) contained in the coating composition of the present invention is 0.02 or more from the viewpoint of drying properties, preferably 0.05 to 1.0, more preferably 0.08 to. Within the range of 0.8.

なお、乾燥性は、塗料組成物を塗装し、指で触れてタック感がない状態になるまでの時間を測定することで評価することができる。   The drying property can be evaluated by measuring the time until the paint composition is applied and touched with a finger until there is no tackiness.

溶解性パラメーター
本発明の塗料組成物の有機溶媒の溶解性パラメーター（δ）とは、Ｈｉｌｄｅｂｒａｎｄの溶解性パラメーターである。溶解性パラメーターは、溶解度パラメーター、ＳＰ値とするともいう。溶解性パラメーターは、物質間の親和性の尺度を表す熱力学的なパラメーターであり、類似した溶解性パラメーターを有する物質同士は溶解しやすい傾向にあることが知られている。溶解性パラメーターは、有機溶媒のモル容積Ｖ（ｃｍ３／ｍｏｌ）及び蒸発エネルギーＥ（ｃａｌ／ｍｏｌ）を用いて、δ＝（Ｅ／Ｖ）０．５によって定義される値である。 Solubility Parameter The solubility parameter (δ) of the organic solvent of the coating composition of the present invention is a solubility parameter of Hildebrand. The solubility parameter is also referred to as a solubility parameter or SP value. The solubility parameter is a thermodynamic parameter that represents a measure of the affinity between substances, and it is known that substances having similar solubility parameters tend to be easily dissolved. The solubility parameter is a value defined by δ = (E / V) 0.5 , using the molar volume V (cm 3 / mol) of organic solvent and the evaporation energy E (cal / mol).

本発明の塗料組成物が含有する有機溶媒（Ａ）の溶解性パラメーターは、樹脂、添加剤及び炭酸ガスの溶解性の観点から、８．０（ｃａｌ／ｃｍ３）０．５〜１０．５（ｃａｌ／ｃｍ３）０．５であり、好ましくは８．３（ｃａｌ／ｃｍ３）０．５〜１０．３（ｃａｌ／ｃｍ３）０．５の範囲内である。 The solubility parameter of the organic solvent (A) contained in the coating composition of the present invention is 8.0 (cal / cm 3 ) 0.5 to 10.5 from the viewpoint of solubility of the resin, additive, and carbon dioxide gas. (Cal / cm 3 ) 0.5 , preferably 8.3 (cal / cm 3 ) 0.5 to 10.3 (cal / cm 3 ) 0.5 .

比重
本発明の塗料組成物の有機溶媒の比重とは、有機溶媒の温度が２０℃の時の標準物質である水に対する密度の比で表される比重である。 Specific gravity The specific gravity of the organic solvent in the coating composition of the present invention is a specific gravity represented by a ratio of density to water as a standard substance when the temperature of the organic solvent is 20 ° C.

本発明の塗料組成物の有機溶媒の一部として使用される有機溶媒の比重は、塗料粘度の観点から、０．９５以下であり、好ましくは０．９２以下である。   The specific gravity of the organic solvent used as a part of the organic solvent of the coating composition of the present invention is 0.95 or less, preferably 0.92 or less, from the viewpoint of coating viscosity.

上記蒸発速度、溶解性パラメーター及び比重の３つの条件をすべて満たす有機溶媒としては、
シクロヘキサン、トルエン、キシレン、イソペンタノール、ヘキシルアルコール、オクタノール、２エチルヘキサノール、ジアセトンアルコール、メチルエチルケトン、メチルプロピルケトン、メチルイソブチルケトン、メチルイソアミルケトン、ジイソブチルケトン、メチルｎ−アミルケトン、エチルアミルケトン、イソホロン、シクロヘキサノン、エチレングリコールモノブチルエーテル、エチレングリコールモノｔ−ブチルエーテル、１−メトキシプロピル-2-アセテート、3-エトキシプロピオン酸エチル、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プロピルエーテル、プロピレングリコールモノブチルエーテル、酢酸ブチル、酢酸イソブチル、酢酸プロピル、酢酸イソプロピル、酢酸アミル、酢酸イソアミル、酪酸エチルを挙げることができる。このような有機溶媒は、単独で又は２種以上を組み合わせて使用することができる。 As an organic solvent satisfying all three conditions of the evaporation rate, solubility parameter and specific gravity,
Cyclohexane, toluene, xylene, isopentanol, hexyl alcohol, octanol, 2-ethylhexanol, diacetone alcohol, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, diisobutyl ketone, methyl n-amyl ketone, ethyl amyl ketone, isophorone , Cyclohexanone, ethylene glycol monobutyl ether, ethylene glycol mono t-butyl ether, 1-methoxypropyl-2-acetate, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, butyl acetate, Isobutyl acetate, propyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate , Mention may be made of ethyl butyrate. Such an organic solvent can be used individually or in combination of 2 or more types.

上記有機溶媒のうち、乾燥性、溶解性の観点から特に、キシレン（０．８６，０．７６，８．８）、メチルイソアミルケトン（０．８１、０．４６、８．６）、ジイソブチルケトン（０．８１、０．２、８．２）、メチルｎ−アミルケトン（０．８１、０．３４、８．６）、エチレングリコールモノブチルエーテル（０．９、０．０８、１０．２）、エチレングリコールモノｔ−ブチルエーテル（０．９、０．１９、９．３５）、酢酸アミル（０．８８、０．３８、８．５）、酢酸イソアミル（０．８７、０．６８、８．３）が好ましい。   Among the above organic solvents, xylene (0.86, 0.76, 8.8), methyl isoamyl ketone (0.81, 0.46, 8.6), diisobutyl ketone are particularly preferable from the viewpoints of drying and solubility. (0.81, 0.2, 8.2), methyl n-amyl ketone (0.81, 0.34, 8.6), ethylene glycol monobutyl ether (0.9, 0.08, 10.2), Ethylene glycol mono-t-butyl ether (0.9, 0.19, 9.35), amyl acetate (0.88, 0.38, 8.5), isoamyl acetate (0.87, 0.68, 8.3) ) Is preferred.

かっこ内記載は、（比重、蒸発速度、溶解性パラメーター）の順である。   The description in parentheses is in the order of (specific gravity, evaporation rate, solubility parameter).

上記３条件を満たす有機溶媒（Ａ）の量は、乾燥性、塗料粘度の観点から、塗料質量の総量に対して、５〜９０質量％、好ましくは１５〜６０質量％の範囲内である。   The amount of the organic solvent (A) that satisfies the above three conditions is in the range of 5 to 90% by mass, preferably 15 to 60% by mass, based on the total amount of the coating material mass, from the viewpoints of drying property and coating material viscosity.

上記３条件を満たす有機溶媒（Ａ）は、有機溶媒の少なくとも一部であり、有機溶媒のすべてが有機溶媒（Ａ）であってもよい。有機溶媒（Ａ）は、有機溶媒の総量に対して、好ましくは８０質量％以上、より好ましくは９５質量％以上である。   The organic solvent (A) satisfying the above three conditions is at least a part of the organic solvent, and all of the organic solvent may be the organic solvent (A). The organic solvent (A) is preferably 80% by mass or more, more preferably 95% by mass or more, based on the total amount of the organic solvent.

本発明の塗料組成物には、通常塗料に用いられる添加剤等の上記以外の成分を必要に応じて含有することができる。   The coating composition of the present invention can contain components other than the above, such as additives usually used in coatings, as necessary.

そのような上記以外の成分（任意成分）としては、例えば、上記３条件をすべて満たす有機溶剤以外の有機溶剤、顔料、顔料分散剤、紫外線吸収剤、光安定剤、レベリング剤、密着性付与剤、レオロジーコントロール剤、消泡剤、防腐剤、重合開始剤等を挙げることができる。   Examples of such components other than the above (optional components) include, for example, organic solvents other than organic solvents that satisfy all of the above three conditions, pigments, pigment dispersants, ultraviolet absorbers, light stabilizers, leveling agents, and adhesion promoters. , Rheology control agents, antifoaming agents, preservatives, polymerization initiators and the like.

２液硬化型等の多液硬化型である場合には、塗膜形成成分として多液成分のうちの少なくとも１成分中に、通常、硬化剤が含有される。２液硬化型等の多液硬化型である場合の硬化剤としては特に限定されないが、イソシアネート等、多液硬化型塗料の硬化剤として一般に使用される硬化剤を使用することができる。   In the case of a multi-component curable type such as a two-component curable type, a curing agent is usually contained in at least one of the multi-component components as a coating film forming component. The curing agent in the case of a multi-component curable type such as a two-component curable type is not particularly limited, but a curing agent generally used as a curing agent for a multi-component curable coating such as isocyanate can be used.

＜二酸化炭素＞
二酸化炭素は、本発明の塗料組成物に対して加圧状態で有機溶媒とともに希釈剤として作用する。本発明の塗料組成物に対して、二酸化炭素は液体又は超臨界流体として存在することができる。 <CO2>
Carbon dioxide acts as a diluent together with the organic solvent under pressure on the coating composition of the present invention. For the coating composition of the present invention, carbon dioxide can be present as a liquid or a supercritical fluid.

一般に二酸化炭素の溶解性パラメーター値は、液体状態のほうが超臨界状態よりも高いので樹脂等の塗膜形成成分に対する溶解力の観点から、本発明の塗料組成物に対する二酸化炭素は液体状態であることが好ましい。   In general, the solubility parameter value of carbon dioxide is higher in the liquid state than in the supercritical state, so that the carbon dioxide in the coating composition of the present invention is in the liquid state from the viewpoint of the dissolving power with respect to coating film forming components such as resins. Is preferred.

本発明の塗料組成物に対する二酸化炭素の混合比率は、塗料粘度の観点から、圧力２〜３２ＭＰａ、好ましくは５〜２０ＭＰａ、さらに好ましくは８〜１５ＭＰａの加圧状態において、本発明の塗料組成物の塗料質量１に対して、二酸化炭素質量比率が０．１以上、好ましくは０．２〜１．０の範囲内である。   From the viewpoint of paint viscosity, the mixing ratio of carbon dioxide to the paint composition of the present invention is such that the pressure of the paint composition of the present invention is 2 to 32 MPa, preferably 5 to 20 MPa, and more preferably 8 to 15 MPa. The carbon dioxide mass ratio is 0.1 or more, preferably 0.2 to 1.0 with respect to the coating mass 1.

本明細書において、「塗料質量」とは、塗料を構成するすべての成分の合計質量をいう。すなわち、塗膜形成成分及び有機溶媒、並びに必要に応じて含有される上記任意成分の合計質量をいう。   In the present specification, “paint mass” refers to the total mass of all components constituting the paint. That is, it refers to the total mass of the coating film forming component, the organic solvent, and the optional components contained as necessary.

本発明の塗料組成物は、圧力２〜３２ＭＰａ、塗料質量１に対する二酸化炭素質量比率が０．２〜０．５である二酸化炭素の混合比率の範囲内とする条件下で二酸化塗装における、−１５℃で測定する塗料粘度が、１００ｍＰａ・ｓ以下であり、好ましくは１０〜８０ｍＰａ・ｓの範囲内である。このような特性に基づき、優れた塗装作業性及び仕上がり外観が得られる。   The coating composition of the present invention has a pressure of 2 to 32 MPa, and the carbon dioxide mass ratio with respect to the coating mass 1 is within the range of the mixing ratio of carbon dioxide that is 0.2 to 0.5. The paint viscosity measured at ° C. is 100 mPa · s or less, and preferably in the range of 10 to 80 mPa · s. Based on such characteristics, excellent workability and finished appearance can be obtained.

なお、本発明において、上記塗料粘度は、ＡＳＴＭ Ｄ ７４８３−０８「往復ピストンによる液体の絶対粘度（Ｄｙｎａｍｉｃ Ｖｉｓｃｏｓｉｔｙ）および動粘度（Ｋｉｎｅｍａｔｉｃ Ｖｉｓｃｏｓｉｔｙ）測定法」に基づいて、ケンブリッジビスコシティ社製粘度計を使用して測定される粘度の値であり、二酸化炭素塗装装置の噴霧口部位を−１５℃に設定した時の塗料粘度の値である。塗料粘度は、例えば圧力１０ＭＰａで測定することができる。   In the present invention, the viscosity of the paint is measured by using a viscometer manufactured by Cambridge Viscocity, based on ASTM D 7483-08 “Measurement Method of Absolute Viscosity and Kinetic Viscosity of Liquid Using Reciprocating Piston”. It is the value of the viscosity measured by using, and is the value of the viscosity of the paint when the spray port part of the carbon dioxide coating device is set to -15 ° C. The paint viscosity can be measured at a pressure of 10 MPa, for example.

二酸化炭素塗装
本発明の塗料組成物は、二酸化炭素塗装に使用される。二酸化炭素塗装は公知であり、例えば特許文献１及び２に記載されている。 Carbon dioxide coating The coating composition of the present invention is used for carbon dioxide coating. Carbon dioxide coating is known and is described in, for example, Patent Documents 1 and 2.

二酸化炭素塗装は、塗料に二酸化炭素を混合して塗料組成物を調製し、得られた塗料組成物を被塗物に噴霧して塗装する方法である。   Carbon dioxide coating is a method in which carbon dioxide is mixed with paint to prepare a paint composition, and the obtained paint composition is sprayed onto an object to be coated.

塗料組成物に対する二酸化炭素の混合比率は、塗料粘度の観点から、加圧状態において、本発明の塗料組成物の塗料質量１に対して、二酸化炭素質量比率が０．１以上、好ましくは０．２〜１．０の範囲内である。   From the viewpoint of coating viscosity, the mixing ratio of carbon dioxide to the coating composition is such that, in a pressurized state, the carbon dioxide mass ratio is 0.1 or more, preferably 0.00, with respect to the coating mass 1 of the coating composition of the present invention. It is in the range of 2 to 1.0.

塗料に二酸化炭素を混合して塗料組成物を調製する際の条件は当業者が適宜設定することができる。例えば、温度は３０〜７０℃、好ましくは３５〜４５℃とすることができる。圧力は加圧条件で行い、例えば２〜３２ＭＰａ、好ましくは８〜１５ＭＰａである。   Those skilled in the art can appropriately set conditions for preparing a coating composition by mixing carbon dioxide with the coating. For example, the temperature can be 30 to 70 ° C, preferably 35 to 45 ° C. A pressure is performed on pressurization conditions, for example, 2-32 MPa, Preferably it is 8-15 MPa.

本発明の塗料組成物を塗装する際の塗料温度は、塗料粘度の観点から、噴霧時（二酸化炭素塗装装置の噴霧口部位）において、−３０〜５０℃の範囲内であることが好ましく−２０℃〜３０℃の範囲内であることがより好ましい。   The coating temperature when applying the coating composition of the present invention is preferably within the range of −30 to 50 ° C. at the time of spraying (a spray port part of the carbon dioxide coating apparatus) from the viewpoint of the coating viscosity. More preferably, the temperature is in the range of from 30 ° C to 30 ° C.

二酸化炭素塗装を実施するための二酸化炭素塗装装置としては、通常、二酸化炭素塗装に使用されるものを特に制限なく使用することができる。   As the carbon dioxide coating apparatus for carrying out carbon dioxide coating, those usually used for carbon dioxide coating can be used without particular limitation.

本発明の塗料組成物を、二酸化炭素塗装装置を使用して塗装に供する際の二酸化炭素との混合方法は特に制限がなく、例えばインラインミキサー等を用いて公知の方法により行うことができる。   There are no particular limitations on the method of mixing the coating composition of the present invention with carbon dioxide when it is used for coating using a carbon dioxide coating apparatus, and for example, it can be carried out by a known method using an inline mixer or the like.

本発明の塗料組成物の塗装に使用する二酸化炭素塗装装置としては、高圧で、二酸化炭素と塗料を均一に混合できる混合器を備え、二酸化炭素と塗料との混合を、例えば、２〜３２ＭＰａの範囲で、十分な二酸化炭素溶解状態を保ちながら、均一で良好な相状態を保持して行うことが可能で、かつ均一な相状態を保持しつつ、噴霧ノズルに供給することができる塗装装置を使用することが好ましい。混合器としては、特に制限されることなく、公知のミキサーを使用することができる。短時間で、二酸化炭素と塗料を均一に混合する観点から、例えば、高圧マイクロ混合器を好適に使用することができる。   The carbon dioxide coating apparatus used for coating the coating composition of the present invention includes a mixer that can uniformly mix carbon dioxide and paint at high pressure, and the mixing of carbon dioxide and paint is, for example, 2 to 32 MPa. A coating apparatus capable of supplying a spray nozzle while maintaining a uniform and good phase state while maintaining a sufficient carbon dioxide-dissolved state in a range. It is preferable to use it. The mixer is not particularly limited, and a known mixer can be used. From the viewpoint of uniformly mixing carbon dioxide and paint in a short time, for example, a high-pressure micromixer can be suitably used.

図１に、使用することができる二酸化炭素塗装の一例を示す。   FIG. 1 shows an example of carbon dioxide coating that can be used.

図１には、
塗料供給源・ポンプからなる塗料ラインと、
CO2供給源・ポンプからなるCO2ラインと、
前記CO2ラインへ付帯するCO2を冷却する熱交換器と、
前記CO2ラインへ付帯する炭酸ガス定量添加部と、
前記塗料ラインと前記炭酸ガス定量添加部の二次側を合流し、混合する混合器と、
前記混合器の二次側の混合ラインと、
前記混合ラインへ付帯する混合物を冷却する熱交換器と、
混合ラインの末端部に接続される噴射ガン
を備えた、二酸化炭素を用いる塗装装置が記載されている。 In FIG.
A paint line consisting of a paint supply source and a pump;
And CO 2 line consisting of CO 2 source pump,
A heat exchanger for cooling CO 2 incidental to the CO 2 line;
A carbon dioxide quantitative addition section attached to the CO 2 line;
A mixer that merges and mixes the secondary side of the paint line and the carbon dioxide quantitative addition section;
A mixing line on the secondary side of the mixer;
A heat exchanger for cooling the mixture incidental to the mixing line;
A coating apparatus using carbon dioxide with a spray gun connected to the end of the mixing line is described.

塗料ラインは、タンクへ充填した塗料を塗料供給源であり、塗料ポンプには空気圧駆動式の定圧ポンプ（例えば、旭サナック(株)製エコポンライト）を使用することができる。塗料ポンプの二次側圧力は、空気駆動圧力を調節して、8〜18MPaとすることができる。   The paint line is a paint supply source of paint filled in a tank, and a pneumatically driven constant pressure pump (for example, Ecoponlite manufactured by Asahi Sunac Co., Ltd.) can be used as the paint pump. The secondary pressure of the paint pump can be adjusted to 8 to 18 MPa by adjusting the air driving pressure.

CO2ラインは、ボンベ・タンクへ充填した炭酸ガスを炭酸ガス供給源であり、炭酸ガスポンプには電気駆動式の定量ポンプ（例えば、日本精密科学(株)ダブルプランジャー無脈流タイプ）を使用することができる。 The CO 2 line is a carbon dioxide gas supply source of carbon dioxide filled in a cylinder tank, and an electric drive type metering pump (for example, double precision non-pulsating flow type of Japan Precision Science Co., Ltd.) is used for the carbon dioxide gas pump. can do.

定量ポンプの二次側圧力は電気回路の操作により、塗料ポンプの二次側圧力以上となるように設定することができる。   The secondary pressure of the metering pump can be set to be equal to or higher than the secondary pressure of the paint pump by operating the electric circuit.

また、定量ポンプの一次側に付帯する炭酸ガスを冷却する熱交換器により、炭酸ガスを気液飽和温度より低い温度とすることができる。   In addition, the carbon dioxide gas can be set to a temperature lower than the gas-liquid saturation temperature by the heat exchanger that cools the carbon dioxide gas attached to the primary side of the metering pump.

炭酸ガス定量添加部は、炭酸ガスがより精密に定量添加できるように、一次圧力調節弁、二次圧力調節弁、流量調節弁、流量検知センサー等を備えることができ、炭酸ガスの定量添加は自動仕切弁の開閉によって行うことができ、具体的には、塗料ライン中の塗料が流れている時に自動仕切弁は開となり、塗料ライン中の塗料が流れていない時に自動仕切弁は閉となる。   The carbon dioxide quantitative addition unit can be equipped with a primary pressure control valve, a secondary pressure control valve, a flow rate control valve, a flow rate detection sensor, etc. so that carbon dioxide can be quantitatively added more precisely. This can be done by opening and closing the automatic gate valve. Specifically, the automatic gate valve is opened when the paint in the paint line is flowing, and the automatic gate valve is closed when the paint in the paint line is not flowing. .

塗料ライン中の塗料の流れの有無は、図示しない流量センサーや圧力センサーなどの検知手段によって検知し、塗料の流れの有無にあわせて、塗料中の炭酸ガスの重量比率が常に一定になるようすることができる。   The presence or absence of paint flow in the paint line is detected by a detection means such as a flow sensor or pressure sensor (not shown), and the weight ratio of carbon dioxide in the paint is always constant according to the presence or absence of paint flow. be able to.

混合器は、塗料ラインと炭酸ガスラインのそれぞれ末端が接続され、塗料の流れのある場合に効率よく炭酸ガスが一定重量比率となるように二重管方式など迅速混合が可能な構造とすることができる。   The mixer shall have a structure that allows quick mixing such as a double pipe system so that the ends of the paint line and the carbon dioxide line are connected and the carbon dioxide gas is efficiently in a certain weight ratio when there is a paint flow. Can do.

混合器の二次側の混合ラインへは混合物を所定の温度へ冷却する熱交換器があり、冷熱は混合ラインの外面から伝達されても内面から伝達されてもよく、二重管方式など良好な洗浄性が得られるような滞留部の少ない構造が好ましい。   There is a heat exchanger that cools the mixture to a predetermined temperature in the mixing line on the secondary side of the mixer, and cold heat may be transmitted from the outer surface or the inner surface of the mixing line, such as a double pipe system is good A structure having a small number of staying portions so that a good cleaning property can be obtained is preferable.

また、混合ラインの末端部に接続される噴射ガンの一次側にはインライン型粘度センサー（例えば、Cambridge Viscosity社製）と温度センサー（例えば、山里産業株式会社製熱電対）をさらに備えることができ、混合物が冷却され、所定の粘度と温度であることの確認に用いることができる。   Further, an in-line viscosity sensor (for example, manufactured by Cambridge Viscosity) and a temperature sensor (for example, a thermocouple manufactured by Yamazato Sangyo Co., Ltd.) can be further provided on the primary side of the spray gun connected to the end of the mixing line. The mixture is cooled and can be used to confirm that it has a predetermined viscosity and temperature.

本発明の二酸化炭素塗装において、被塗物としては、例えば、冷延鋼板、黒皮鋼板、合金化亜鉛メッキ鋼板、電気亜鉛メッキ鋼板等、またこれらを素材とする建設機械、産業機械等を挙げることができる。これらは必要に応じて、ショットブラスト、表面調整、表面処理などを施したものであってもよい。   In the carbon dioxide coating of the present invention, examples of the article to be coated include cold rolled steel sheet, black leather sheet, alloyed galvanized steel sheet, electrogalvanized steel sheet and the like, and construction machines and industrial machines made of these materials. be able to. These may be subjected to shot blasting, surface adjustment, surface treatment, and the like as necessary.

塗装膜厚は、通常、乾燥膜厚に基づき、１０μｍ〜１５０μｍ、好ましくは３０μｍ〜８０μｍの範囲内であることが適している。   The coating film thickness is usually 10 μm to 150 μm, preferably 30 μm to 80 μm based on the dry film thickness.

塗膜の乾燥及び硬化は、塗膜形成成分の樹脂等に応じた適正な条件で行うことができる。具体的には、常温〜１６０℃で、１０〜１２０分間、或いは数時間、数日間乾燥して硬化させることにより、硬化させることができる。   The coating film can be dried and cured under appropriate conditions according to the resin of the coating film forming component. Specifically, it can be cured by drying and curing at room temperature to 160 ° C. for 10 to 120 minutes or for several hours for several days.

以下、製造例、実施例及び比較例により、本発明をさらに詳細に説明するが、本発明はこれに限定されるものではない。各例中の「部」は質量部、「％」は質量％に基づくものである。   Hereinafter, the present invention will be described in more detail with reference to Production Examples, Examples, and Comparative Examples, but the present invention is not limited thereto. “Part” in each example is based on mass part, and “%” is based on mass%.

塗料組成物の製造
製造例
１．脂肪酸変性アクリル樹脂塗料の作成
製造例１−１．脂肪酸変性アクリル樹脂溶液（１）の製造
温度計、サーモスタット、撹拌装置、還流冷却器、窒素導入管及び滴下装置を備えた反応容器にキシレン４５部を仕込み１１５℃に昇温後、スチレン３０部、メチルメタクリレート４６部、グリシジルメタクリレート２４部、キシレン１５部及びｔ−ブチルパーオキシオクトエート２．０部の混合物を４時間かけて滴下し、滴下終了後１時間熟成した。 Manufacture of paint compositions
Production Example 1 Preparation of fatty acid-modified acrylic resin paint Production Example 1-1. Production of fatty acid-modified acrylic resin solution (1) 45 parts of xylene were charged in a reaction vessel equipped with a thermometer, a thermostat, a stirring device, a reflux condenser, a nitrogen introduction tube and a dropping device, and the temperature was raised to 115 ° C. A mixture of 46 parts of methyl methacrylate, 24 parts of glycidyl methacrylate, 15 parts of xylene and 2.0 parts of t-butyl peroxyoctoate was added dropwise over 4 hours, followed by aging for 1 hour after completion of the addition.

その後さらにキシレン１０部及び大豆油脂肪酸４３部を加え、反応温度を１４０℃に昇温し５時間熟成した。さらにキシレン５５部を加え、固形分５４％の脂肪酸変性アクリル樹脂溶液（１）を得た。得られた脂肪酸変性アクリル樹脂溶液は水酸基価が６６ｍｇＫＯＨ/ｇ、酸価が０．１５ｍｇＫＯＨ/ｇであった。   Thereafter, 10 parts of xylene and 43 parts of soybean oil fatty acid were added, and the reaction temperature was raised to 140 ° C. and aged for 5 hours. Further, 55 parts of xylene was added to obtain a fatty acid-modified acrylic resin solution (1) having a solid content of 54%. The obtained fatty acid-modified acrylic resin solution had a hydroxyl value of 66 mgKOH / g and an acid value of 0.15 mgKOH / g.

製造例１−２．脂肪酸変性アクリル樹脂溶液（２）の製造
温度計、サーモスタット、撹拌装置、還流冷却器、窒素導入管及び滴下装置を備えた反応容器にｎ−ブタノール４５部を仕込み１１５℃に昇温後、スチレン３０部、メチルメタクリレート４６部、グリシジルメタクリレート２４部、ｎ−ブタノール１５部及びｔ−ブチルパーオキシオクトエート２．０部の混合物を４時間かけて滴下し、滴下終了後１時間熟成した。 Production Example 1-2. Production of fatty acid-modified acrylic resin solution (2) 45 parts of n-butanol was charged in a reaction vessel equipped with a thermometer, thermostat, stirring device, reflux condenser, nitrogen inlet tube and dropping device, and the temperature was raised to 115 ° C., followed by styrene 30 A mixture of 4 parts of methyl methacrylate, 46 parts of methyl methacrylate, 24 parts of glycidyl methacrylate, 15 parts of n-butanol and 2.0 parts of t-butyl peroxyoctoate was added dropwise over 4 hours, followed by aging for 1 hour after completion of the addition.

その後さらにｎ−ブタノール１０部及び大豆油脂肪酸４３部を加え、反応温度を１４０℃に昇温し５時間熟成した。さらにｎ−ブタノール５５部を加え、固形分５４％の脂肪酸変性アクリル樹脂溶液（２）を得た。得られた脂肪酸変性アクリル樹脂溶液は水酸基価が６６ｍｇＫＯＨ/ｇ、酸価が０．１５ｍｇＫＯＨ/ｇであった。   Thereafter, 10 parts of n-butanol and 43 parts of soybean oil fatty acid were added, and the reaction temperature was raised to 140 ° C. and aged for 5 hours. Further, 55 parts of n-butanol was added to obtain a fatty acid-modified acrylic resin solution (2) having a solid content of 54%. The obtained fatty acid-modified acrylic resin solution had a hydroxyl value of 66 mgKOH / g and an acid value of 0.15 mgKOH / g.

製造例１−３．顔料分散ペーストＮｏ．１の製造例
製造例１−１で得た固形分５４％の脂肪酸変性アクリル樹脂溶液（１）を１００部（固形分５４部）、モナーク１３００（注２）３部、ＬＡＫＡＢＡＲ ＳＦ（注３）５０部、ＺＩＮＣ ＰＨＯＳＰＨＡＴＥ ＰＺ２０（注４）２０部、ミズカシルＰ−５２６（注５）５０部を配合し、キシレンで固形分を調整し、ボールミルに仕込み６時間攪拌することによって、固形分６５％の顔料分散ペーストを得た。 Production Example 1-3. Pigment dispersion paste No. Production Example 1 100 parts of fatty acid-modified acrylic resin solution (1) having a solid content of 54% obtained in Production Example 1-1 (54 parts of solid content), 3 parts of Monarch 1300 (Note 2), LAKABAR SF (Note 3) 50 parts, 20 parts of ZINC PHOSPHATE PZ20 (Note 4) and 50 parts of Mizukasil P-526 (Note 5) were mixed, the solid content was adjusted with xylene, charged into a ball mill, and stirred for 6 hours to obtain a solid content of 65%. A pigment dispersion paste was obtained.

製造例１−４．顔料分散ペーストＮｏ．２〜Ｎｏ．3の製造例
表１の配合内容とする以外は、製造例１−３と同様にして、顔料分散ペーストＮｏ．２〜Ｎｏ．３を得た。 Production Example 1-4. Pigment dispersion paste No. 2-No. Production Example 3 in the same manner as in Production Example 1-3 except that the blending contents shown in Table 1 were used. 2-No. 3 was obtained.

なお、各表に記載の配合内容における数字は質量部に基づく配合量を表す。   In addition, the number in the mixing | blending content of each table | surface represents the compounding quantity based on a mass part.

２．ウレタン塗料の作成
製造例２−１．アクリル樹脂溶液の製造
酢酸ブチル１１３部、スチレン４１．６部、ｎ−ブチルアクリレート６．９部、イソブチルメタクリレート１９部、プラクセルＦＭ−３（注１）１５部、２−ヒドロキシエチルメタクリレート１７部、アクリル酸０．５部、ジ−ｔｅｒｔ−ブチルハイドロパーオキサイド８部を窒素ガス下で１１０℃において反応させ、酸価３．９ｍｇＫＯＨ／ｇ、水酸基価９４．９ｍｇＫＯＨ／ｇ、重量平均分子量１１，０００のアクリル樹脂の溶液を得た。 2. Production of urethane paint Production Example 2-1. Production of acrylic resin solution 113 parts of butyl acetate, 41.6 parts of styrene, 6.9 parts of n-butyl acrylate, 19 parts of isobutyl methacrylate, 15 parts of Plaxel FM-3 (Note 1), 17 parts of 2-hydroxyethyl methacrylate, acrylic 0.5 parts of acid and 8 parts of di-tert-butyl hydroperoxide were reacted at 110 ° C. under nitrogen gas to give an acid value of 3.9 mgKOH / g, a hydroxyl value of 94.9 mgKOH / g, and a weight average molecular weight of 11,000. An acrylic resin solution was obtained.

（注１）プラクセルＦＭ−３：ダイセル化学工業株式会社製、商品名、２−ヒドロキシエチルアクリレートのε−カプロラクトン変性ビニルモノマー。   (Note 1) Plaxel FM-3: Daicel Chemical Industries, Ltd., trade name, ε-caprolactone-modified vinyl monomer of 2-hydroxyethyl acrylate.

製造例２−２．顔料分散ペーストＮｏ．4の製造例
製造例２−１で得た固形分６０％のアクリル樹脂溶液を１００部（固形分６０部）、モナーク１３００を５部、ＬＡＫＡＢＡＲ ＳＦを１００部、ミズカシルＰ−５２６を１０部配合し、酢酸ブチルで固形分を調整し、ボールミルに仕込み６時間攪拌することによって、固形分６０％の顔料分散ペーストを得た。 Production Example 2-2. Pigment dispersion paste No. 4 Production Example 100 parts of 60% solid acrylic resin solution obtained in Production Example 2-1 (60 parts solids), 5 parts Monarch 1300, 100 parts LAKABAR SF, 10 parts Mizukacil P-526 The solid content was adjusted with butyl acetate, charged into a ball mill and stirred for 6 hours to obtain a pigment dispersion paste having a solid content of 60%.

製造例２−３．顔料分散ペーストＮｏ．５の製造例
表２の配合内容とする以外は、製造例２−１と同様にして、顔料分散ペーストＮｏ．５を得た。 Production Example 2-3. Pigment dispersion paste No. Production Example 5 In the same manner as in Production Example 2-1, except for the contents shown in Table 2, pigment dispersion paste No. 5 was used. 5 was obtained.

（注２）モナーク１３００：キャボットコーポレーション社製、商品名、カーボンブラック
（注３）ＬＡＫＡＢＡＲ（ラカバール）ＳＦ：ＬＡＫＡＶＩＳＵＴＨ（ラカヴィッシュ）社製、商品名、硫酸バリウム粉末
（注４）ＺＩＮＣ ＰＨＯＳＰＨＡＴＥ ＰＺ２０：ＳＮＣＺ社製、商品名、防錆顔料
（注５）ミズカシルＰ−５２６：水澤化学社製、商品名、シリカ。 (Note 2) Monarch 1300: Cabot Corporation, trade name, carbon black (Note 3) LAKABAR (SF) SF: LAKAVISSU, trade name, barium sulfate powder (Note 4) ZINC PHOSPHATE PZ20: SNCZ Product name, anti-corrosion pigment (Note 5) Mizukasil P-526: Product name, silica, manufactured by Mizusawa Chemical.

実施例
塗料組成物の製造
塗料組成物Ｎｏ．１
製造例１−１で得た脂肪酸変性アクリル樹脂溶液（１）を８５部、並びに製造例１−３で得た顔料分散ペーストＮｏ．１を２７２部、５％オクチル酸コバルトを０．５部、５％オクチル酸亜鉛を１．５部、フローレンＡＣ−３００（注６）を０．５部、キシレンを１６部配合し、固形分６０質量％に調整し、塗料組成物Ｎｏ．１を得た。 Examples Production of paint composition Paint composition no. 1
85 parts of the fatty acid-modified acrylic resin solution (1) obtained in Production Example 1-1 and the pigment dispersion paste No. 1 obtained in Production Example 1-3. 1 part 272 parts, 5% cobalt octylate 0.5 parts, 5% zinc octylate 1.5 parts, Floren AC-300 (Note 6) 0.5 parts, xylene 16 parts, The coating composition No. was adjusted to 60 mass%. 1 was obtained.

塗料組成物Ｎｏ．２
表３の配合内容とする以外は、塗料組成物Ｎｏ．１と同様にして、固形分６０質量％の塗料組成物Ｎｏ．２を得た。 Coating composition No. 2
Except for the content of Table 3, the coating composition No. In the same manner as in coating composition No. 1 having a solid content of 60% by mass. 2 was obtained.

塗料組成物Ｎｏ．３
製造例２−１で得たアクリル樹脂溶液を３３部、スミジュールＮ３３００（注７）を２０部（固形分）、並びに製造例２−２で得た顔料分散ペーストＮｏ．４を２９３部、ＢＹＫ−４１０（注８）０．８部、フローレンＡＣ−３００を０．５部、酢酸ブチルを３０部配合し、固形分６０質量％に調整し、塗料組成物Ｎｏ．３を得た。 Coating composition No. 3
33 parts of the acrylic resin solution obtained in Production Example 2-1, 20 parts (solid content) of Sumidur N3300 (Note 7), and pigment dispersion paste No. 1 obtained in Production Example 2-2. No. 4 was mixed with 293 parts, BYK-410 (Note 8) 0.8 part, Florene AC-300 0.5 part, and butyl acetate 30 parts, adjusted to a solid content of 60% by mass. 3 was obtained.

（注６）フローレンＡＣ−３００：共栄社化学株式会社、商品名、消泡剤
（注７）スミジュールＮ３３００：住化バイエルウレタン社製、商品名、ヘキサメチレンジイソシアネートのイソシアヌレート体、固形分１００％、ＮＣＯ当量１９３、
（注８）ＢＹＫ−４１０：ビックケミー（株）社製、商品名、ウレタンウレア系レオロジーコントロール剤。 (Note 6) Florene AC-300: Kyoeisha Chemical Co., Ltd., trade name, antifoaming agent (Note 7) Sumijour N3300: manufactured by Sumika Bayer Urethane Co., Ltd., trade name, isocyanurate of hexamethylene diisocyanate, solid content 100% , NCO equivalent 193,
(Note 8) BYK-410: manufactured by Big Chemie Co., Ltd., trade name, urethane urea rheology control agent.

塗料組成物Ｎｏ．４
表３の配合内容とする以外は、塗料組成物Ｎｏ．３と同様にして、固形分６０質量％の塗料組成物Ｎｏ．４を得た。 Coating composition No. 4
Except for the content of Table 3, the coating composition No. In the same manner as in No. 3, the coating composition no. 4 was obtained.

塗料組成物Ｎｏ．５
製造例１−１で得た脂肪酸変性アクリル樹脂溶液（１）を８５部、並びに製造例１−４で得た顔料分散ペーストＮｏ．３を２７２部、５％オクチル酸コバルトを０．５部、５％オクチル酸亜鉛を１．５部、フローレンＡＣ−３００を０．５部、ｎ−ブタノールを１６部配合し、固形分６０質量％に調整し、塗料組成物Ｎｏ．５を得た。 Coating composition No. 5
85 parts of the fatty acid-modified acrylic resin solution (1) obtained in Production Example 1-1 and the pigment dispersion paste No. obtained in Production Example 1-4. 3 272 parts, 0.5% cobalt octylate 0.5 parts, 5% zinc octylate 1.5 parts, fluorene AC-300 0.5 parts, n-butanol 16 parts, solid content 60 mass %, And the coating composition No. 5 was obtained.

ｎ−ブタノールは比重、蒸発速度及び溶解性パラメーターが、（０．８１、０．４７、１１．３）であり、本発明の有機溶媒（Ａ）に該当しない。かっこ内記載は、（比重、蒸発速度、溶解性パラメーター）の順である。   n-butanol has a specific gravity, an evaporation rate and a solubility parameter of (0.81, 0.47, 11.3), and does not fall under the organic solvent (A) of the present invention. The description in parentheses is in the order of (specific gravity, evaporation rate, solubility parameter).

下記「試験板の作製及び評価」に従って試験に供した結果を表４及び表５に示す。   Tables 4 and 5 show the results subjected to the test in accordance with the following “production and evaluation of test plate”.

評価結果
試験板の作成及び評価
実施例１〜１０、比較例１〜４ 試験板（１）
リン酸亜鉛処理化成処理を施した冷延鋼板（７０ｍｍ×３００ｍｍ×２．０ｍｍ）に上記の製造例にて得た塗料組成物Ｎｏ．１、ＮＯ．２またはＮｏ．５を用いて、乾燥膜厚７０μｍとなるように、図１に記載の塗装機を用いて塗装した。用いた塗料組成物、塗装機の条件は表４のように設定して試験板を作成した。 Evaluation Results Creation and Evaluation of Test Plates Examples 1 to 10, Comparative Examples 1 to 4 Test plate (1)
The coating composition No. obtained in the above production example on a cold-rolled steel sheet (70 mm × 300 mm × 2.0 mm) subjected to zinc phosphate treatment. 1, NO. 2 or No. 5 was applied using the coating machine shown in FIG. 1 so that the dry film thickness was 70 μm. Test plates were prepared by setting the coating composition used and the conditions of the coating machine as shown in Table 4.

次に、温度２０℃、湿度６０％に調整された恒温室内に３０分間放置して試験板を得た。   Next, it was left for 30 minutes in a temperature-controlled room adjusted to a temperature of 20 ° C. and a humidity of 60% to obtain a test plate.

実施例１１〜２０、比較例５〜６ 試験板（２）
リン酸亜鉛処理化成処理を施した冷延鋼板（７０ｍｍ×３００ｍｍ×２．０ｍｍ）に乾燥膜厚が２０μｍとなるように電着塗装を施し、焼付け乾燥して電着塗装板を得た。次いで上記製造例にて得た塗料組成物Ｎｏ．３、Ｎｏ．４を用いて、乾燥膜厚５０μｍとなるように、上記記載の塗装機を用いて塗装した。
用いた塗料組成物、塗装機の条件は表5のように設定して塗装した。 Examples 11-20, Comparative Examples 5-6 Test plate (2)
A cold-rolled steel sheet (70 mm × 300 mm × 2.0 mm) subjected to zinc phosphate treatment was subjected to electrodeposition coating so that the dry film thickness was 20 μm, and baked and dried to obtain an electrodeposition coated plate. Subsequently, coating composition No. obtained in the said manufacture example. 3, no. 4 was applied using the coating machine described above so that the dry film thickness was 50 μm.
The coating composition used and the conditions of the coating machine were set as shown in Table 5 and applied.

次に、電気熱風乾燥機を用いて、８０℃で３０分加熱乾燥して各試験板を得た。   Next, each test plate was obtained by heating and drying at 80 ° C. for 30 minutes using an electric hot air dryer.

塗料粘度：塗料粘度は、ＡＳＴＭ Ｄ ７４８３−０８に基づき、二酸化炭素塗装装置の噴霧口部位（噴射ガンの一次側）に備えたケンブリッジビスコシティ社製粘度計を使用して測定した。二酸化炭素塗装装置の噴霧口部位を−１５℃に設定し、圧力１０ＭＰａで測定した。   Paint Viscosity: The paint viscosity was measured using a viscometer manufactured by Cambridge Viscocity Co., Ltd. provided at the spray port part (primary side of the spray gun) of the carbon dioxide coating device based on ASTM D 7473-08. The spray port part of the carbon dioxide coating apparatus was set to −15 ° C., and measurement was performed at a pressure of 10 MPa.

仕上がり外観：得られた各試験板の仕上り外観を目視で評価した：
○は、平滑性が良好で問題なし
△は、ワキ、チリ肌等の仕上り性の低下がやや見られる、
×は、ワキ、チリ肌等の仕上り性の低下が大きい。 Finished appearance: The finished appearance of each test plate obtained was visually evaluated:
○ indicates smoothness and no problem. △ indicates a slight decrease in finish such as armpit and dust skin.
X indicates a large decrease in finish such as armpit and dust skin.

二酸化炭素を希釈剤とする塗装において、良好な塗装作業性を有し、かつ仕上り外観にも優れた塗膜を得ることができる塗料組成物を提供することができる。   In the coating using carbon dioxide as a diluent, it is possible to provide a coating composition that can provide a coating film having good coating workability and excellent finished appearance.

Claims (7)

二酸化炭素塗装に使用するための塗料組成物であって、該塗料は、塗膜形成成分と有機溶媒とを含有し、該有機溶媒は、
蒸発速度が酢酸ブチルを1としたとき０．０８〜０．８、
溶解性パラメーターが８．０（ｃａｌ／ｃｍ3）0.5〜１０．５（ｃａｌ／ｃｍ3）0.5、
比重が０．９５以下である有機溶媒（Ａ）を、有機溶媒の総量に対して８０質量％以上含有する、
圧力２〜３２ＭＰａ、塗料質量１に対する二酸化炭素質量比率が０．１以上である二酸化炭素の混合比率の範囲内で二酸化炭素と混合して、塗料温度を−３０〜５０℃として二酸化炭素塗装に用いるための塗料組成物。 A coating composition for use in carbon dioxide coating, wherein the coating contains a film-forming component and an organic solvent,
The evaporation rate is 0.08 to 0.8 when butyl acetate is 1.
Solubility parameter is 8.0 (cal / cm 3 ) 0.5 to 10.5 (cal / cm 3 ) 0.5 ,
Containing 80% by mass or more of the organic solvent (A) having a specific gravity of 0.95 or less based on the total amount of the organic solvent ;
Mixing with carbon dioxide within the range of the mixing ratio of carbon dioxide having a pressure of 2 to 32 MPa and a carbon dioxide mass ratio of 0.1 or more with respect to the coating mass 1, the coating temperature is set to −30 to 50 ° C. and used for carbon dioxide coating. Paint composition for. 塗膜形成成分として、アルキド樹脂、アクリル樹脂、脂肪酸変性アクリル樹脂、ウレタン樹脂、エポキシ樹脂、ポリエステル樹脂、アクリルシリコン樹脂、フッ素樹脂、メラミン樹脂から選ばれる少なくとも１種を含有する請求項１に記載の塗料組成物。   The coating film forming component according to claim 1, comprising at least one selected from alkyd resins, acrylic resins, fatty acid-modified acrylic resins, urethane resins, epoxy resins, polyester resins, acrylic silicon resins, fluororesins, and melamine resins. Paint composition. 塗料質量の総量に対して、有機溶媒（Ａ）を５〜９０質量％含有する、請求項１又は２に記載の塗料組成物。   The coating composition of Claim 1 or 2 which contains 5-90 mass% of organic solvents (A) with respect to the total amount of coating-material mass. 有機溶媒（Ａ）の溶解性パラメーターが８．３（ｃａｌ／ｃｍ3）0.5〜１０．２（ｃａｌ／ｃｍ3）0.5である、請求項１〜３のいずれか１項に記載の塗料組成物。 The coating composition according to any one of claims 1 to 3 , wherein the solubility parameter of the organic solvent (A) is 8.3 (cal / cm 3 ) 0.5 to 10.2 (cal / cm 3 ) 0.5 . . 有機溶媒（Ａ）の比重が０．９２以下である、請求項１〜４のいずれか１項に記載の塗料組成物。 The coating composition according to any one of claims 1 to 4 , wherein the specific gravity of the organic solvent (A) is 0.92 or less. 塗料質量１に対する二酸化炭素質量比率が０．２〜０．５、かつ、塗料温度を−１５℃として測定する塗料粘度が、１００ｍＰａ・s以下である、請求項１〜５のいずれか１項に記載の塗料組成物。 Carbon dioxide weight ratio is 0.2 to 0.5 for the coating mass 1, and viscosity of the coating composition to measure the coating temperature of -15 ° C. is not more than 100 mPa · s, in any one of claims 1 to 5 The coating composition as described. 被塗物に、二酸化炭素塗装装置により、塗料温度を−３０〜５０℃として、
圧力２〜３２ＭＰａ、塗料質量１に対する二酸化炭素質量比率が０．１以上である二酸化炭素の混合比率の範囲内で請求項１〜６のいずれか１項に記載の塗料組成物と二酸化炭素とを混合した塗料組成物を噴霧して塗装することを特徴とする塗装方法。 The coating temperature is set to −30 to 50 ° C. on the object by a carbon dioxide coating device.
The coating composition according to any one of claims 1 to 6 and carbon dioxide within a range of a mixing ratio of carbon dioxide having a pressure of 2 to 32 MPa and a carbon dioxide mass ratio of 0.1 or more with respect to the coating mass 1. A coating method, characterized by spraying the mixed coating composition.
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