WO2013151113A1 - Ink composition for coated steel sheet - Google Patents

Ink composition for coated steel sheet Download PDF

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Publication number
WO2013151113A1
WO2013151113A1 PCT/JP2013/060267 JP2013060267W WO2013151113A1 WO 2013151113 A1 WO2013151113 A1 WO 2013151113A1 JP 2013060267 W JP2013060267 W JP 2013060267W WO 2013151113 A1 WO2013151113 A1 WO 2013151113A1
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WO
WIPO (PCT)
Prior art keywords
ink composition
steel sheet
marking
resin
coated steel
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PCT/JP2013/060267
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French (fr)
Japanese (ja)
Inventor
貴之 北口
Original Assignee
株式会社サクラクレパス
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Application filed by 株式会社サクラクレパス filed Critical 株式会社サクラクレパス
Priority to CN201380029648.5A priority Critical patent/CN104334653A/en
Publication of WO2013151113A1 publication Critical patent/WO2013151113A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • 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
    • C09D11/00—Inks
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to an ink composition for coated steel sheet. More specifically, the present invention relates to two layers of upper and lower coatings by a paint applied to a steel sheet, for example, even if a primer coating and a top coating have a marking layer by an ink composition between them.
  • the present invention relates to an ink composition for a coated steel sheet in which the adhesion between the coating films does not decrease, and therefore the upper coating film does not float or peel off at the marking site.
  • the thick steel plate is first subjected to coating as a surface treatment after removing the scale by, for example, shot blasting.
  • the coating of shot blasted steel plate is usually undercoated, and after marking with an ink composition for the purpose of displaying the inspection result of the coating on the undercoat coating film, The top is overcoated.
  • the upper and lower two-layer coating film on which the steel plate has been applied in this way has a marking layer made of an ink composition between the coating film and the components of the ink composition in the marking layer, As a result of some interaction between them, the adhesion between the upper and lower two-layer coating film is reduced at the marking location, and the upper layer coating film may float or peel off from the lower coating layer at the marking location. there were.
  • the present invention has been made in order to solve the above-mentioned problems in the conventional ink composition for coated steel sheet, in which the upper and lower two-layer coating film by the paint applied to the steel sheet surface is marked with the ink composition between them. Even if it has a layer, the adhesion of the upper and lower two-layer coatings does not decrease at the marking location, and therefore the upper coating layer floats or peels off from the lower coating layer at the marking location.
  • An object of the present invention is to provide an ink composition for a coated steel sheet that gives a marking that does not occur.
  • an ink composition for a coated steel sheet comprising an organic solvent, a pigment, a dispersant and a resin, wherein the resin has an acid value of 150 mgKOH / g or less and a glass transition temperature of 0 to 55 ° C.
  • an ink composition for coated steel sheet which is at least one selected from styrene-acrylic resins.
  • the ink composition for coated steel sheet according to the present invention has an adhesive force between the upper and lower two-layer coating films even if the marking layer thereby is provided between the upper and lower two-layer coating films by the paint applied to the steel sheet surface. Therefore, the upper coating film does not float or peel off from the lower coating film at the portion having the marking layer.
  • the undercoating film and the overcoating are applied.
  • the adhesion of the coating film does not decrease at the marking layer, and therefore, the top coating film does not float or peel off from the undercoating film at the marking position.
  • the ink composition for coated steel sheet according to the present invention comprises an organic resin, a pigment, a dispersant, and a resin.
  • the resin has an acid value of 150 mgKOH / g or less and a glass transition temperature in the range of 0 to 55 ° C. -At least one selected from acrylic resins.
  • Such an ink composition according to the present invention forms an undercoating film with an undercoating paint on the surface of a steel sheet, forms an overcoating film with an overcoating paint thereon, and inspects the coating when coating the steel sheet.
  • it is preferably used for marking the surface of the undercoat coating film.
  • the organic solvent used in the coated steel sheet ink composition according to the present invention is not particularly limited, but is preferably at least one selected from the group consisting of alcohols, glycols, glycol ethers and glycol ether esters. Used. Specific examples of such preferred organic solvents include alcohols such as ethanol, isopropyl alcohol, 3-methyl-3-methoxybutanol, 3-methoxy-1-butanol, and the like. For example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol and the like can be mentioned. Examples of glycol ethers include methyl ether, ethyl ether, propyl ether, butyl ether and phenyl ether of the above glycols. Examples of glycol ether esters include acetates of the above glycol ethers.
  • ethanol isopropyl alcohol, 3-methyl-3-methoxybutanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol mono At least one selected from the group consisting of propyl ether, propylene glycol monobutyl ether and dipropylene glycol monomethyl ether is preferably used.
  • the amount of the organic solvent in the ink composition is appropriately determined in relation to the components such as the color pigment, but is usually 25 to 80% by weight based on the weight of the ink composition, preferably It is in the range of 30 to 65% by weight.
  • the amount of the organic solvent is too large, the viscosity of the ink composition is too small, and the amount of outflow from the pen tip is excessive at the time of marking.
  • the amount of the organic solvent is too small, on the contrary, the viscosity of the ink composition is too small and the outflow of the ink composition from the nib is inhibited during marking.
  • the color pigment is not particularly limited, and any pigment may be used as long as it is a pigment conventionally used in a normal ink composition.
  • Specific examples include, for example, inorganic pigments such as carbon black, titanium oxide, cobalt blue, cobalt green, chrome yellow, cadmium red, phthalocyanine blue, phthalocyanine green, monoazo yellow, disazo yellow, quinacridone red, dioxazine violet, DPP red, Mention may be made of organic pigments such as aniline black.
  • colored pigments colored processed powders combining dyes and pigments with resin powders, fluorescent pigments, pigments with natural mica surfaces coated with metal oxides, and synthetic mica surfaces with metal oxides Examples thereof include pearl pigments coated with.
  • the ink composition usually contains such a color pigment in the range of 2 to 35% by weight, preferably in the range of 3 to 20% by weight.
  • the marking has a sufficient coloring power, so that the marking becomes difficult to see.
  • the viscosity of the ink composition is too high and the ink composition hardly flows out from the pen tip during marking.
  • the resin to be used since the resin to be used also has a function of a dispersant, it is not particularly necessary to use a separate dispersant, but if desired, other than the above resin Ordinary dispersants can be used.
  • the dispersant does not include an acrylic resin and a styrene-acrylic resin having an acid value of 150 mgKOH / g or less and a glass transition temperature of 0 to 55 ° C.
  • EFCA-4310 BASF polymer dispersant
  • Solsperse 71000, Solsperse 12000, Solsperse 20000, Solsperse 22000 (above, polymer dispersant manufactured by Lubrizol Corporation) and Disperbyk-185 Big Chemie Japan Co., Ltd.
  • the ink composition for coated steel sheet according to the present invention gives the marking layer adhesiveness to the coating film by the paint and contains a resin as a dispersant for the color pigment.
  • the resin has an acid value of 150 mgKOH / g or less, a glass transition. It is at least one selected from acrylic resins and styrene-acrylic resins having a temperature in the range of 0 to 55 ° C.
  • acrylic in acrylic resin and styrene-acrylic resin means acrylic acid ester (and acrylic acid).
  • acrylic when “acrylic” consists only of acrylic acid ester, that is, acrylic acid is used.
  • the acid value of the resin is 0, and the acid value of these resins increases as the proportion of acrylic ester in the “acryl” decreases, that is, as the proportion of acrylic acid increases.
  • the reason is not necessarily clear, but at least one selected from an acrylic resin and a styrene-acrylic resin having an acid value and a glass transition temperature in the above-mentioned range between the upper and lower two-layer coating films by the paint applied to the steel sheet.
  • the upper and lower two-layer coating film does not decrease the adhesion between the coating films at the marking layer, and therefore the upper-layer coating film is separated from the lower-layer coating film. Do not float or peel off.
  • the upper and lower two-layer coating film made of the paint applied to the steel plate is the acrylic resin or styrene-acrylic resin in the meantime, the acid value exceeds 150 mgKOH / g or the glass transition temperature is not in the above range.
  • the upper and lower two-layer coating film has a reduced adhesive force between the coating films at the marking layer portion, and the upper-layer coating film has the marking layer. In this place, it floats off or peels off from the underlying coating film.
  • the acrylic resin and the styrene-acrylic resin preferably have a glass transition point of 10 ° C. or higher, and most preferably 15 ° C. or higher.
  • the ink composition for coated steel sheet according to the present invention contains the above resin in a proportion of 3 to 30% by weight, preferably 5 to 20% by weight. When the proportion of the resin is more than 30% by weight, the adhesion of the coating film on the marking is reduced instead.
  • the resin also functions as a dispersant. Therefore, when the proportion of the resin is less than 3% by weight, the effect of suppressing the decrease in the adhesion of the coating film on the marking is poor, and the above-described colored pigments aggregate with each other. Viscosity increases and prevents the ink composition from flowing out of the nib during marking.
  • acrylic resins include, for example, Hiros X-310 (acid value 60 mg KOH / g, glass transition temperature 53 ° C.) manufactured by Seiko PMC Co., Ltd., Mitsubishi Rayon Co., Ltd.
  • Dianal BR-107 (acid value 0 mg KOH / g, glass transition temperature 50 ° C.), Dianal BR-102 (acid value 1 mg KOH / g, glass transition temperature 20 ° C.), etc., and styrene-acrylic resin Examples thereof include Hyros X-1 (acid value 110.5 mgKOH / g, glass transition temperature 52 ° C.) manufactured by Seiko PMC Co., Ltd., BASF Jonkrill 611 (acid value 53 mgKOH / g, glass transition temperature 50 ° C.), etc. Can be mentioned.
  • a resin other than those described above may be included as long as the effect of the ink composition according to the present invention is not impaired.
  • resins include, but are not limited to, ketone resins, xylene resins, rosin esters, hydrogenated rosin esters, terpene phenol resins, alkylphenol resins, and maleic acid resins.
  • the ink composition may contain a preservative, an antifungal agent, an antifoaming agent, a thixotropic agent, and the like, as necessary.
  • the ink composition according to the present invention preferably has a viscosity in the range of 4 to 35 mPa ⁇ s at a temperature of 20 ° C., particularly preferably in the range of 5 to 30 mPa ⁇ s.
  • a viscosity in the range of 4 to 35 mPa ⁇ s at a temperature of 20 ° C., particularly preferably in the range of 5 to 30 mPa ⁇ s.
  • the viscosity is too high, it is difficult for the ink composition to flow out from the nib when writing, and when the viscosity is too low, the ink composition is excessive from the nib when writing, on the contrary, both are preferable. Absent.
  • the ink composition according to the present invention is not particularly limited in its production method, and any method may be used as long as the above-described components can be uniformly dissolved or dispersed. For example, after adding a dispersant and a resin to an organic solvent and heating and dissolving as necessary, a color pigment is added thereto, and the mixture is uniformly stirred and mixed, and if necessary, a dispersion treatment may be performed. .
  • the upper-layer coating film is the lower-layer coating film at the marking location. Therefore, the upper layer coating film does not float or peel off from the lower layer coating film at the location where the marking layer is applied.
  • the shot blast thick steel plate is usually coated with an undercoat, and the undercoat film is marked with an ink composition and then overcoated on the marking layer.
  • the above-mentioned undercoat and topcoat are not particularly limited, but for example, epoxy resin paint has excellent chemical resistance.
  • undercoat and topcoat for steel plates for chemical containers. Is preferably used.
  • the ink composition for coated steel sheet according to the present invention is provided with the marking on the undercoat film of the steel sheet, and even if the top coat is applied thereon, the above-mentioned marking layer is applied to the upper film. Therefore, the upper layer coating film does not float or peel off from the lower layer coating film at the marking site over a long period of time. Therefore, the ink composition according to the present invention is suitably used as an ink composition for marking thick steel plates to be coated as a surface treatment in the manufacture of large structures such as shipbuilding, bridges, pressure vessels, chemical containers and the like. be able to.
  • the physical properties of the ink composition that is, the viscosity, the cross-cut test peel number, and the peel strength were determined as follows.
  • Viscosity Using a standard rotor (1 ° 34 ′ ⁇ R24) with a TVE-25L viscometer (manufactured by Toki Sangyo Co., Ltd.), the viscosity was measured at a temperature of 20 ⁇ 1 ° C. and 20 rpm.
  • the ink composition is applied once on the undercoat film with a marker in the vertical direction, dried for 10 minutes, and then applied once in the horizontal direction. (Marking layer) was formed, and then the coating film was dried at room temperature for 2 days.
  • the above test steel plate is cut with a cutter into the base steel plate at intervals of 3 mm in a grid pattern to make 25 cells, and the surface of the top coat film is covered with cello tape (registered trademark, 18 mm) so as to cover these cells.
  • cello tape registered trademark, 18 mm
  • one end of the cello tape (registered trademark) is kept at a right angle, and the cello tape (registered trademark) is peeled off rapidly. And the number of cells peeled off with the above-mentioned cello tape (registered trademark), that is, the number of peeled film pieces was counted.
  • Color pigment Printex 35 Carbon black color pigment dispersant manufactured by Evonik Degussa Japan Co., Ltd.
  • EFKA-4310 Product made by BASF (comb polymer having basic functional group)
  • Resin High Loss X-1 Styrene-acrylic resin (acid value 110.5 mg / g KOH, glass transition temperature 52 ° C.) manufactured by Seiko PMC Co., Ltd.
  • High loss X-310 Acrylic resin (acid value 60 mg / g KOH, glass transition temperature 53 ° C.) manufactured by Seiko PMC Joncrill 611: BASF styrene-acrylic resin (acid value 53 mg / g KOH, glass transition temperature 50 ° C.)
  • Dianar BR-102 manufactured by Mitsubishi Rayon Co., Ltd. (acid value 1 mg / g KOH, glass transition temperature 20 ° C.)
  • Dianar BR-107 manufactured by Mitsubishi Rayon Co., Ltd.
  • High-loss RS-1191 Styrene-acrylic resin (acid value 280 mg / g KOH, glass transition temperature 128 ° C.) manufactured by Seiko PMC Co., Ltd.
  • Jonkrill 67 BASF styrene-acrylic resin (acid value 213 mg / g KOH, glass transition temperature 73 ° C.)
  • Joncrill 678 BASF styrene-acrylic resin (acid value 215 mg / g KOH, glass transition temperature 85 ° C.)
  • Jonkrill 682 BASF styrene-acrylic resin (acid value 238 mg / g KOH, glass transition temperature 56 ° C.)
  • Jonkrill 683 BASF styrene-acrylic resin (acid value 160 mg / g KOH, glass transition temperature 75 ° C.)
  • Jonkrill 690 BASF styrene-acrylic resin (acid value 240 mg / g KOH, glass transition temperature 102 ° C.)
  • Hitanol 1140 Alkylphenol resin made by Hitachi Chemical Co., Ltd.
  • Hilac 111 Ketone resin made by Hitachi Chemical Co., Ltd.
  • Example 1 Using the components shown in Table 1 in the amounts shown in Table 1, ink compositions were prepared as described above.
  • Comparative Examples 1-8 Ink compositions were prepared as described above using the components shown in Table 2 in the amounts shown in Table 2.
  • Table 1 and Table 2 show the viscosity, cross-cut test peel number, and coating adhesion for the ink compositions of Examples, and the viscosity, cross-cut test peel number, and coating coating for the ink compositions of Comparative Examples.
  • the adhesion force is shown in Table 2.
  • the coating film according to the comparative example was peeled off from the undercoating film, and the adhesion force due to the marking layer being interposed between the undercoating film and the overcoating film. A decrease was observed.
  • the number of cross-cut test peels in Table 2 is the number of peels of the top coat film from the undercoat film (number of grids).

Abstract

[Problem] To provide an ink composition for a coated steel sheet, whereby, when a marking layer produced from the ink composition is provided between two coating layers (i.e., an upper coating layer and a lower coating layer) each formed from a coating agent and provided on the surface of a steel sheet, it becomes possible to prevent the deterioration of adhesion force of the two coating layers at the marking position and therefore it becomes possible to provide such a marking that the upper coating layer cannot come from the lower coating layer at the marking position or the upper coating layer cannot be delaminated from the lower coating layer at the marking position. (Solution) The present invention provides an ink composition for a coated steel sheet, which comprises an organic solvent, a pigment, a dispersant and a resin, said ink composition being characterized in that the resin comprises an acrylic resin and/or a styrene-acrylic resin each having an acid value of 150 mgKOH/g or less and a glass transition temperature ranging from 0 to 55˚C.

Description

塗装鋼板用インキ組成物Ink composition for painted steel sheet
　本発明は塗装鋼板用インキ組成物に関する。詳しくは、本発明は、鋼板に施された塗料による上下２層の塗膜、例えば、下塗り塗膜と上塗り塗膜がその間にインキ組成物によるマーキング層を有していても、それによって２層の塗膜間の付着力の低下が起こらず、従って、上記上層の塗膜がそのマーキング箇所で浮いたり、剥離したりしない塗装鋼板用インキ組成物に関する。 The present invention relates to an ink composition for coated steel sheet. More specifically, the present invention relates to two layers of upper and lower coatings by a paint applied to a steel sheet, for example, even if a primer coating and a top coating have a marking layer by an ink composition between them. The present invention relates to an ink composition for a coated steel sheet in which the adhesion between the coating films does not decrease, and therefore the upper coating film does not float or peel off at the marking site.
　例えば、厚板鋼板を用いる造船、橋梁、圧力容器、化学薬品容器等の大型構造物の製造においては、材料保管、半製品保管、組立て等が屋外で行われることが多く、しかも、工期が長期にわたることが多いので、厚板鋼板は、事前に何らの表面処理も施さないままでは、上記構造物の製造の間に錆びを生じて劣化する。そこで、そのような経時的な劣化を防止して、耐候性を有するように、厚板鋼板は、例えば、最初にショットブラスト等によってスケールを除去した後、表面処理として塗装が施される。 For example, in the manufacture of large structures such as shipbuilding, bridges, pressure vessels, chemical containers using thick steel plates, material storage, semi-finished product storage, assembly, etc. are often performed outdoors, and the construction period is long. In many cases, the steel plate is deteriorated due to rust during the production of the structure without any surface treatment in advance. Therefore, in order to prevent such deterioration over time and to have weather resistance, the thick steel plate is first subjected to coating as a surface treatment after removing the scale by, for example, shot blasting.
　一例を挙げれば、ショットブラスト厚板鋼板の塗装は、通常、下塗りし、この下塗り塗膜上に塗装の検査結果の表示等を目的として、インキ組成物によるマーキングを施した後、このマーキング層の上に上塗りがされる。しかし、従来、このようにして鋼板がその表面に施された上下２層の塗膜がその間にインキ組成物によるマーキング層を有するとき、上記塗膜とマーキング層中のインキ組成物の成分との間の何らかの相互作用の結果、上記上下２層の塗膜の間の付着力がそのマーキング箇所で低下して、上層の塗膜がマーキング箇所で下層の塗膜から浮いたり、剥がれたりする問題があった。 For example, the coating of shot blasted steel plate is usually undercoated, and after marking with an ink composition for the purpose of displaying the inspection result of the coating on the undercoat coating film, The top is overcoated. However, conventionally, when the upper and lower two-layer coating film on which the steel plate has been applied in this way has a marking layer made of an ink composition between the coating film and the components of the ink composition in the marking layer, As a result of some interaction between them, the adhesion between the upper and lower two-layer coating film is reduced at the marking location, and the upper layer coating film may float or peel off from the lower coating layer at the marking location. there were.
　本発明は、従来の塗装鋼板用インキ組成物における上述した問題を解決するためになされたものであって、鋼板表面に施された塗料による上下２層の塗膜がその間にインキ組成物によるマーキング層を有していても、上記上下２層の塗膜の付着力がそのマーキング箇所で低下を生じず、従って、上記上層の塗膜が上記マーキング箇所で上記下層の塗膜から浮いたり、剥がれたりしないマーキングを与える塗装鋼板用インキ組成物を提供することを目的とする。 The present invention has been made in order to solve the above-mentioned problems in the conventional ink composition for coated steel sheet, in which the upper and lower two-layer coating film by the paint applied to the steel sheet surface is marked with the ink composition between them. Even if it has a layer, the adhesion of the upper and lower two-layer coatings does not decrease at the marking location, and therefore the upper coating layer floats or peels off from the lower coating layer at the marking location. An object of the present invention is to provide an ink composition for a coated steel sheet that gives a marking that does not occur.
　本発明によれば、有機溶媒、顔料、分散剤及び樹脂を含む塗装鋼板用インキ組成物であって、上記樹脂が酸価１５０ｍｇＫＯＨ／ｇ以下、ガラス転移温度０～５５℃の範囲にあるアクリル樹脂及びスチレン－アクリル樹脂から選ばれる少なくとも１種であることを特徴とする塗装鋼板用インキ組成物が提供される。 According to the present invention, there is provided an ink composition for a coated steel sheet comprising an organic solvent, a pigment, a dispersant and a resin, wherein the resin has an acid value of 150 mgKOH / g or less and a glass transition temperature of 0 to 55 ° C. And an ink composition for coated steel sheet, which is at least one selected from styrene-acrylic resins.
　本発明による塗装鋼板用インキ組成物は、それによるマーキング層を鋼板表面に施された塗料による上下２層の塗膜の間に有せしめても、上記上下２層の塗膜の間の付着力を低下させず、従って、上記上層の塗膜は上記マーキング層を有する箇所で下層の塗膜から浮いたり、剥がれたりしない。 The ink composition for coated steel sheet according to the present invention has an adhesive force between the upper and lower two-layer coating films even if the marking layer thereby is provided between the upper and lower two-layer coating films by the paint applied to the steel sheet surface. Therefore, the upper coating film does not float or peel off from the lower coating film at the portion having the marking layer.
　例えば、鋼板の表面の下塗り塗料による下塗り塗膜上に本発明によるインキ組成物にてマーキングを施し、更に、そのマーキング層の上に上塗り塗料による上塗り塗膜を施しても、下塗り塗膜と上塗り塗膜は上記マーキング層の箇所で相互の付着力が低下せず、従って、上塗り塗膜は上記マーキング箇所で下塗り塗膜から浮いたり、剥がれたりしない。 For example, even if the surface of the steel sheet is coated with the ink composition according to the present invention on the undercoating film of the present invention, and further the overcoating film is coated on the marking layer with the overcoating film, the undercoating film and the overcoating are applied. The adhesion of the coating film does not decrease at the marking layer, and therefore, the top coating film does not float or peel off from the undercoating film at the marking position.
　本発明による塗装鋼板用インキ組成物は、有機溶媒、顔料、分散剤及び樹脂を含み、上記樹脂が酸価が１５０ｍｇＫＯＨ／ｇ以下、ガラス転移温度が０～５５℃の範囲にあるアクリル樹脂及びスチレン－アクリル樹脂から選ばれる少なくとも１種であるものである。 The ink composition for coated steel sheet according to the present invention comprises an organic resin, a pigment, a dispersant, and a resin. The resin has an acid value of 150 mgKOH / g or less and a glass transition temperature in the range of 0 to 55 ° C. -At least one selected from acrylic resins.
　本発明によるこのようなインキ組成物は、鋼板の表面に下塗り塗料による下塗り塗膜を形成し、その上に上塗り塗料による上塗り塗膜を形成して、鋼板を塗装する際に、その塗装の検査結果を表示する等を目的として、上記下塗り塗膜の表面にマーキングを施すために好ましく用いられる。 Such an ink composition according to the present invention forms an undercoating film with an undercoating paint on the surface of a steel sheet, forms an overcoating film with an overcoating paint thereon, and inspects the coating when coating the steel sheet. For the purpose of displaying the result, etc., it is preferably used for marking the surface of the undercoat coating film.
（有機溶媒）
　本発明による塗装鋼板用インキ組成物において用いられる有機溶媒は、特に限定されるものではないが、アルコール類、グリコール類、グリコールエーテル類及びグリコールエーテルエステル類よりなる群から選ばれる少なくとも１種が好ましく用いられる。このような好ましい有機溶剤の具体例としては、アルコール類として、例えば、エタノール、イソプロピルアルコール、３－メチル－３－メトキシブタノール、３－メトキシ－１－ブタノール等を挙げることができ、グリコール類として、例えば、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール等を挙げることができ、グリコールエーテル類として、例えば、上記グリコール類のメチルエーテル、エチルエーテル、プロピルエーテル、ブチルエーテル、フェニルエーテル等を挙げることができ、グリコールエーテルエステル類として、例えば、上記グリコールエーテル類のアセテート等を挙げることができる。 (Organic solvent)
The organic solvent used in the coated steel sheet ink composition according to the present invention is not particularly limited, but is preferably at least one selected from the group consisting of alcohols, glycols, glycol ethers and glycol ether esters. Used. Specific examples of such preferred organic solvents include alcohols such as ethanol, isopropyl alcohol, 3-methyl-3-methoxybutanol, 3-methoxy-1-butanol, and the like. For example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol and the like can be mentioned. Examples of glycol ethers include methyl ether, ethyl ether, propyl ether, butyl ether and phenyl ether of the above glycols. Examples of glycol ether esters include acetates of the above glycol ethers.
　本発明においては、特に、これらのなかでも、エタノール、イソプロピルアルコール、３－メチル－３－メトキシブタノール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテール及びジプロピレングリコールモノメチルエーテルよりなる群から選ばれる少なくとも１種が好ましく用いられる。 In the present invention, in particular, among these, ethanol, isopropyl alcohol, 3-methyl-3-methoxybutanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol mono At least one selected from the group consisting of propyl ether, propylene glycol monobutyl ether and dipropylene glycol monomethyl ether is preferably used.
　本発明において、インキ組成物における上記有機溶媒の量は、着色顔料等の成分との関係において適宜に定められるが、インキ組成物の重量に基づいて、通常、２５～８０重量％、好ましくは、３０～６５重量％の範囲である。有機溶媒の量が多すぎるときは、インキ組成物の粘度が小さすぎて、マーキングに際して、ペン先からの流出量が過多になる。しかし、有機溶媒量が少なすぎるときは、反対に、インキ組成物の粘度が小さすぎて、マーキングに際して、ペン先からのインキ組成物の流出が阻害される。 In the present invention, the amount of the organic solvent in the ink composition is appropriately determined in relation to the components such as the color pigment, but is usually 25 to 80% by weight based on the weight of the ink composition, preferably It is in the range of 30 to 65% by weight. When the amount of the organic solvent is too large, the viscosity of the ink composition is too small, and the amount of outflow from the pen tip is excessive at the time of marking. However, when the amount of the organic solvent is too small, on the contrary, the viscosity of the ink composition is too small and the outflow of the ink composition from the nib is inhibited during marking.
（顔料）
　本発明によるインキ組成物において、着色顔料は、特に限定されるものではなく、従来、通常のインキ組成物に用いられている顔料であれば、いずれでも用いられる。具体例として、例えば、カーボンブラック、酸化チタン、コバルトブルー、コバルトグリーン、クロムイエロー、カドミウムレッド等の無機顔料、フタロシアニンブルー、フタロシアニングリーン、モノアゾイエロー、ジスアゾイエロー、キナクリドンレッド、ジオキサジンバイオレット、ＤＰＰレッド、アニリンブラック等の有機顔料を挙げることができる。 (Pigment)
In the ink composition according to the present invention, the color pigment is not particularly limited, and any pigment may be used as long as it is a pigment conventionally used in a normal ink composition. Specific examples include, for example, inorganic pigments such as carbon black, titanium oxide, cobalt blue, cobalt green, chrome yellow, cadmium red, phthalocyanine blue, phthalocyanine green, monoazo yellow, disazo yellow, quinacridone red, dioxazine violet, DPP red, Mention may be made of organic pigments such as aniline black.
　また、上記以外にも、着色顔料として、染料や顔料を樹脂粉体と組み合わせた着色加工粉体、蛍光顔料、天然マイカの表面を金属酸化物で被覆した顔料、合成マイカの表面を金属酸化物で被覆したパール顔料等をも挙げることができる。 In addition to the above, as colored pigments, colored processed powders combining dyes and pigments with resin powders, fluorescent pigments, pigments with natural mica surfaces coated with metal oxides, and synthetic mica surfaces with metal oxides Examples thereof include pearl pigments coated with.
　本発明によれば、インキ組成物は、このような着色顔料を、通常、２～３５重量％の範囲で含み、好ましくは、３～２０重量％の範囲で含む。インキ組成物における着色顔料の量が２重量％よりも少ないときは、マーキングが十分な着色力をもたなので、マーキングが見え難くなる。しかし、インキ組成物における着色顔料の量が３５重量％よりも多いときは、インキ組成物の粘度が高すぎて、マーキングに際して、ペン先からインキ組成物が流出し難くなる。 According to the present invention, the ink composition usually contains such a color pigment in the range of 2 to 35% by weight, preferably in the range of 3 to 20% by weight. When the amount of the color pigment in the ink composition is less than 2% by weight, the marking has a sufficient coloring power, so that the marking becomes difficult to see. However, when the amount of the color pigment in the ink composition is more than 35% by weight, the viscosity of the ink composition is too high and the ink composition hardly flows out from the pen tip during marking.
（分散剤）
　後述するように、本発明のインキ組成物においては、用いる樹脂も、分散剤の機能を有しているので、特に別に分散剤を用いる必要はないが、しかし、所望ならば、上記樹脂以外に、通常の分散剤を用いることができる。但し、本発明においては、分散剤には、酸価１５０ｍｇＫＯＨ／ｇ以下、ガラス転移温度０～５５℃の範囲にあるアクリル樹脂及びスチレン－アクリル樹脂は含まないものとする。 (Dispersant)
As will be described later, in the ink composition of the present invention, since the resin to be used also has a function of a dispersant, it is not particularly necessary to use a separate dispersant, but if desired, other than the above resin Ordinary dispersants can be used. However, in the present invention, the dispersant does not include an acrylic resin and a styrene-acrylic resin having an acid value of 150 mgKOH / g or less and a glass transition temperature of 0 to 55 ° C.
　従って、本発明においては、例えば、ＥＦＣＡ－４３１０（ＢＡＳＦ製高分子分散剤）、ソルスパース７１０００、ソルスパース１２０００、ソルスパース２００００、ソルスパース２２０００（以上、ルーブリゾール・コーポレーション製高分子分散剤）やＤｉｓｐｅｒｂｙｋ－１８５（ビック・ケミー・ジャパン（株）製）等を用いることができる。 Accordingly, in the present invention, for example, EFCA-4310 (BASF polymer dispersant), Solsperse 71000, Solsperse 12000, Solsperse 20000, Solsperse 22000 (above, polymer dispersant manufactured by Lubrizol Corporation) and Disperbyk-185 ( Big Chemie Japan Co., Ltd.) can be used.
（樹脂）
　本発明による塗装鋼板用インキ組成物は、マーキング層に塗料による塗膜への接着性を与えると共に、着色顔料の分散剤として、樹脂を含み、この樹脂は、酸価１５０ｍｇＫＯＨ／ｇ以下、ガラス転移温度０～５５℃の範囲にあるアクリル樹脂及びスチレン－アクリル樹脂から選ばれる少なくとも１種である。 (resin)
The ink composition for coated steel sheet according to the present invention gives the marking layer adhesiveness to the coating film by the paint and contains a resin as a dispersant for the color pigment. The resin has an acid value of 150 mgKOH / g or less, a glass transition. It is at least one selected from acrylic resins and styrene-acrylic resins having a temperature in the range of 0 to 55 ° C.
　本発明において、アクリル樹脂及びスチレン－アクリル樹脂における「アクリル」はアクリル酸エステル（及びアクリル酸）を意味し、これらの樹脂において、「アクリル」がアクリル酸エステルのみからなるとき、即ち、アクリル酸を含まないときは、樹脂の酸価は０であり、「アクリル」におけるアクリル酸エステルの割合が減少するにつれて、即ち、アクリル酸の割合が増えるにつれて、これらの樹脂の酸価は大きくなる。 In the present invention, “acrylic” in acrylic resin and styrene-acrylic resin means acrylic acid ester (and acrylic acid). In these resins, when “acrylic” consists only of acrylic acid ester, that is, acrylic acid is used. When not included, the acid value of the resin is 0, and the acid value of these resins increases as the proportion of acrylic ester in the “acryl” decreases, that is, as the proportion of acrylic acid increases.
　理由は必ずしも明らかではないが、鋼板に施された塗料による上下２層の塗膜がその間に上述した範囲の酸価とガラス転移温度を有するアクリル樹脂及びスチレン－アクリル樹脂から選ばれる少なくとも１種を含むインキ組成物によるマーキング層を有するとき、上下２層の塗膜は、上記マーキング層の箇所において、塗膜間の付着力が低下せず、従って、上記上層の塗膜は下層の塗膜から浮いたり、剥がれたりしない。 The reason is not necessarily clear, but at least one selected from an acrylic resin and a styrene-acrylic resin having an acid value and a glass transition temperature in the above-mentioned range between the upper and lower two-layer coating films by the paint applied to the steel sheet. When having the marking layer by the ink composition to be included, the upper and lower two-layer coating film does not decrease the adhesion between the coating films at the marking layer, and therefore the upper-layer coating film is separated from the lower-layer coating film. Do not float or peel off.
　しかし、鋼板に施された塗料による上下２層の塗膜がその間に上記アクリル樹脂やスチレン－アクリル樹脂であっても、酸価が１５０ｍｇＫＯＨ／ｇを超えるか、又はガラス転移温度が上記範囲にないものを含むインキ組成物によるマーキング層を有するときは、上下２層の塗膜は、上記マーキング層の箇所において、塗膜間の付着力が低下して、上記上層の塗膜は、上記マーキング層の箇所において、下層の塗膜から浮いたり、剥がれたりする。 However, even if the upper and lower two-layer coating film made of the paint applied to the steel plate is the acrylic resin or styrene-acrylic resin in the meantime, the acid value exceeds 150 mgKOH / g or the glass transition temperature is not in the above range. When having a marking layer made of an ink composition containing an object, the upper and lower two-layer coating film has a reduced adhesive force between the coating films at the marking layer portion, and the upper-layer coating film has the marking layer. In this place, it floats off or peels off from the underlying coating film.
　特に、本発明によれば、アクリル樹脂及びスチレン－アクリル樹脂は、ガラス転移点が１０℃以上であることが好ましく、１５℃以上であることが最も好ましい。 In particular, according to the present invention, the acrylic resin and the styrene-acrylic resin preferably have a glass transition point of 10 ° C. or higher, and most preferably 15 ° C. or higher.
　本発明による塗装鋼板用インキ組成物は、上記樹脂を３～３０重量％、好ましくは、５～２０重量％の割合で含む。上記樹脂の割合が３０重量％よりも多いときは、マーキング上の塗膜の付着性を却って低下させる。 The ink composition for coated steel sheet according to the present invention contains the above resin in a proportion of 3 to 30% by weight, preferably 5 to 20% by weight. When the proportion of the resin is more than 30% by weight, the adhesion of the coating film on the marking is reduced instead.
　本発明によるインキ組成物において、上記樹脂は、分散剤としても機能している。従って、上記樹脂の割合が３重量％よりも少ないときは、マーキング上の塗膜の付着性の低下を抑制する効果に乏しいうえに、前述した着色顔料が相互に凝集するので、インキ組成物の粘度が高まり、マーキング時、ペン先からのインキ組成物の流出を阻害する。 In the ink composition according to the present invention, the resin also functions as a dispersant. Therefore, when the proportion of the resin is less than 3% by weight, the effect of suppressing the decrease in the adhesion of the coating film on the marking is poor, and the above-described colored pigments aggregate with each other. Viscosity increases and prevents the ink composition from flowing out of the nib during marking.
　上述したような酸価とガラス転移温度を有する樹脂として、アクリル樹脂としては、例えば、星光ＰＭＣ（株）製ハイロスＸ－３１０（酸価６０ｍｇＫＯＨ／ｇ、ガラス転移温度５３℃）、三菱レイヨン（株）製ダイヤナールＢＲ－１０７（酸価０ｍｇＫＯＨ／ｇ、ガラス転移温度５０℃）、ダイヤナールＢＲ－１０２（酸価１ｍｇＫＯＨ／ｇ、ガラス転移温度２０℃）等を挙げることができ、スチレン－アクリル樹脂としては、例えば、星光ＰＭＣ（株）製ハイロスＸ－１（酸価１１０．５ｍｇＫＯＨ／ｇ、ガラス転移温度５２℃）、ＢＡＳＦ製ジョンクリル６１１（酸価５３ｍｇＫＯＨ／ｇ、ガラス転移温度５０℃）等を挙げることができる。 As the resin having an acid value and a glass transition temperature as described above, acrylic resins include, for example, Hiros X-310 (acid value 60 mg KOH / g, glass transition temperature 53 ° C.) manufactured by Seiko PMC Co., Ltd., Mitsubishi Rayon Co., Ltd. Dianal BR-107 (acid value 0 mg KOH / g, glass transition temperature 50 ° C.), Dianal BR-102 (acid value 1 mg KOH / g, glass transition temperature 20 ° C.), etc., and styrene-acrylic resin Examples thereof include Hyros X-1 (acid value 110.5 mgKOH / g, glass transition temperature 52 ° C.) manufactured by Seiko PMC Co., Ltd., BASF Jonkrill 611 (acid value 53 mgKOH / g, glass transition temperature 50 ° C.), etc. Can be mentioned.
　本発明においては、本発明によるインキ組成物の効果を阻害しない範囲において、上述した以外の樹脂を含んでいてもよい。そのような樹脂として、限定されるものではないが、例えば、ケトン樹脂、キシレン樹脂、ロジンエステル、水添ロジンエステル、テルペンフェノール樹脂、アルキルフェノール樹脂、マレイン酸樹脂等を挙げることができる。 In the present invention, a resin other than those described above may be included as long as the effect of the ink composition according to the present invention is not impaired. Examples of such resins include, but are not limited to, ketone resins, xylene resins, rosin esters, hydrogenated rosin esters, terpene phenol resins, alkylphenol resins, and maleic acid resins.
（その他の添加剤）
　本発明によれば、インキ組成物は、必要に応じて、防腐剤、防黴剤、消泡剤、チキソトロピー性付与剤等を含んでいてもよい。 (Other additives)
According to the present invention, the ink composition may contain a preservative, an antifungal agent, an antifoaming agent, a thixotropic agent, and the like, as necessary.
（粘度）
　本発明によるインキ組成物は、通常、温度２０℃において、粘度が４～３５ｍＰａ・ｓの範囲にあることが好ましく、特に、５～３０ｍＰａ・ｓの範囲にあることが好ましい。粘度が余りに高いときは、筆記に際して、ペン先からインキ組成物が流出し難くなり、粘度が低すぎるときは、反対に、筆記に際して、ペン先からインキ組成物が過多になるので、いずれも好ましくない。 (viscosity)
In general, the ink composition according to the present invention preferably has a viscosity in the range of 4 to 35 mPa · s at a temperature of 20 ° C., particularly preferably in the range of 5 to 30 mPa · s. When the viscosity is too high, it is difficult for the ink composition to flow out from the nib when writing, and when the viscosity is too low, the ink composition is excessive from the nib when writing, on the contrary, both are preferable. Absent.
（製造）
　本発明によるインキ組成物は、その製造方法において特に限定されるものではなく、上述した成分を均一に溶解させ、又は分散させることができれば、どのような方法によってもよい。例えば、有機溶媒に分散剤と樹脂を加え、必要に応じて加熱して、溶解させた後、これに着色顔料を加えて、均一に攪拌、混合し、必要に応じて、分散処理すればよい。 (Manufacturing)
The ink composition according to the present invention is not particularly limited in its production method, and any method may be used as long as the above-described components can be uniformly dissolved or dispersed. For example, after adding a dispersant and a resin to an organic solvent and heating and dissolving as necessary, a color pigment is added thereto, and the mixture is uniformly stirred and mixed, and if necessary, a dispersion treatment may be performed. .
　鋼板の表面に施された塗料による上下２層の塗膜がその間に本発明のインキ組成物によるマーキング層を有していても、上層の塗膜は、そのマーキングの箇所において、下層の塗膜への付着力が低下せず、従って、上層の塗膜は、上記マーキング層が施されている箇所において、下層の塗膜から浮いたり、剥離したりしない。 Even if the upper and lower two-layer coating film by the paint applied to the surface of the steel sheet has a marking layer by the ink composition of the present invention between them, the upper-layer coating film is the lower-layer coating film at the marking location. Therefore, the upper layer coating film does not float or peel off from the lower layer coating film at the location where the marking layer is applied.
　例えば、前述したように、ショットブラスト厚板鋼板の塗装は、通常、下塗りし、この下塗り塗膜上にインキ組成物によるマーキングを施した後、このマーキング層の上に上塗りされる。本発明において、上記下塗り塗料及び上塗り塗料は、特に限定されるものではないが、例えば、エポキシ樹脂塗料は耐薬品性にすぐれているので、例えば、化学薬品容器用の鋼板の下塗り塗料及び上塗り塗料に好適に用いられる。 For example, as described above, the shot blast thick steel plate is usually coated with an undercoat, and the undercoat film is marked with an ink composition and then overcoated on the marking layer. In the present invention, the above-mentioned undercoat and topcoat are not particularly limited, but for example, epoxy resin paint has excellent chemical resistance. For example, undercoat and topcoat for steel plates for chemical containers. Is preferably used.
　本発明による塗装鋼板用インキ組成物は、上述したように、鋼板の下塗り塗膜の上にマーキングを施し、その上に上塗り塗装を施しても、上層の塗膜は、上記マーキング層が施されている箇所における付着力が低下しないので、長期間にわたって、上層の塗膜はマーキングの箇所で下層の塗膜からの浮きや剥離を生じない。従って、本発明によるインキ組成物は、造船、橋梁、圧力容器、化学薬品容器等の大型構造物の製造において、表面処理として塗装が施される厚板鋼板のマーキング用インキ組成物として好適に用いることができる。 As described above, the ink composition for coated steel sheet according to the present invention is provided with the marking on the undercoat film of the steel sheet, and even if the top coat is applied thereon, the above-mentioned marking layer is applied to the upper film. Therefore, the upper layer coating film does not float or peel off from the lower layer coating film at the marking site over a long period of time. Therefore, the ink composition according to the present invention is suitably used as an ink composition for marking thick steel plates to be coated as a surface treatment in the manufacture of large structures such as shipbuilding, bridges, pressure vessels, chemical containers and the like. be able to.
　以下に実施例を挙げて本発明を説明するが、本発明はこれら実施例により何ら限定されるものではない。 Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.
　インキ組成物の物性、即ち、粘度、碁盤目試験剥離数及び剥離強度は、下記のようにして求めた。 The physical properties of the ink composition, that is, the viscosity, the cross-cut test peel number, and the peel strength were determined as follows.
粘度
　ＴＶＥ－２５Ｌ型粘度計（東機産業（株）製）で標準ロータ（１°３４‘×Ｒ２４）を用い、温度２０±１℃で２０ｒｐｍの条件下に測定した。 Viscosity Using a standard rotor (1 ° 34 ′ × R24) with a TVE-25L viscometer (manufactured by Toki Sangyo Co., Ltd.), the viscosity was measured at a temperature of 20 ± 1 ° C. and 20 rpm.
碁盤目試験剥離数
　試験用鋼板（日本テストパネル（株）製ＳＳ４００（両面ショットブラスト鋼板、３．２×７０×１５０ｍｍ）に下塗り塗料（ＮＫＭコーティングス（株）製エポマリンＰＣ１００下塗り）を約３．１ｇ（乾燥塗膜厚さ約１２５μｍ）塗布した後、室温で２日間乾燥して、下塗り塗膜を形成した。 Number of cross-cut test peeling steel plate for test (SS400 (double-sided shot blast steel plate, 3.2 × 70 × 150 mm) manufactured by Nippon Test Panel Co., Ltd.) undercoat (appromarin PC100 undercoat manufactured by NKM Coatings Co., Ltd.) After 1 g (dry film thickness of about 125 μm) was applied, it was dried at room temperature for 2 days to form an undercoat film.
　この後、この下塗り塗膜の上にマーカーにてインキ組成物を縦方向に１回塗布し、１０分間乾燥させた後、横方向に１回塗布して、インキ組成物によるべた塗りの塗膜（マーキング層）を形成し、この後、この塗膜を室温で２日間乾燥させた。 Thereafter, the ink composition is applied once on the undercoat film with a marker in the vertical direction, dried for 10 minutes, and then applied once in the horizontal direction. (Marking layer) was formed, and then the coating film was dried at room temperature for 2 days.
　このように乾燥させた上記インキ組成物のべた塗り塗膜上に上塗り塗料（ＮＫＭコーティングス（株）製エポマリンＰＣ１００上塗り）を約３．２ｇ（乾燥塗膜厚さ約１２５μｍ）塗布した後、室温で２日間乾燥して、上塗り塗膜を形成し、かくして、試験用塗装鋼板を準備した。 About 3.2 g (dry coating film thickness: about 125 μm) of the top coating material (Epomarin PC100 top coating manufactured by NKM Coatings Co., Ltd.) was applied on the solid coating film of the ink composition thus dried, and then room temperature was applied. And dried for 2 days to form a top coat film, thus preparing a test coated steel sheet.
　上記試験用塗装鋼板にカッターで素地鋼板に達する切り込みを３ｍｍ間隔で碁盤目状に入れて、２５個の桝目を作り、これらの桝目を覆うように上塗り塗膜の表面にセロテープ（登録商標、１８ｍｍ幅、ニチバン（株）製）を貼り付けて、１分間放置した。 The above test steel plate is cut with a cutter into the base steel plate at intervals of 3 mm in a grid pattern to make 25 cells, and the surface of the top coat film is covered with cello tape (registered trademark, 18 mm) so as to cover these cells. A width, manufactured by Nichiban Co., Ltd.) was pasted and left for 1 minute.
　次いで、セロテープ（登録商標）の一方の端部を直角に保ち、これを急速に引き剥がして、上記マーキング層を有する下塗り塗膜と上塗り塗膜からなる塗膜がいずれの層で上記セロテープ（登録商標）と共に剥離したかを調べると共に、上記セロテープ（登録商標）と共に剥がれた桝目の数、即ち、剥がれた塗膜片の数を数えた。 Next, one end of the cello tape (registered trademark) is kept at a right angle, and the cello tape (registered trademark) is peeled off rapidly. And the number of cells peeled off with the above-mentioned cello tape (registered trademark), that is, the number of peeled film pieces was counted.
塗膜の付着性
　サンドペーパー（粒度５００）で試験用塗装鋼板とドリー（円筒形の引張り端）の両面を磨き、アルコールで両方の表面を洗浄した。次いで、エポキシ樹脂接着剤で試験用塗装鋼板にドリーを固定し、２日間放置して接着剤を硬化させた。付着性試験機（エルコメーター（株）製Ｆ１０６－２）のドリー爪でドリーを挟み、試験機のハンドルを一定に速度で回して、ドリーに引張り力を加え、塗膜又は接着剤層が剥がれたときの値を読み取って、塗膜の付着力とした。 Adhesion of the coating film Both surfaces of the test coated steel plate and the dolly (cylindrical tensile end) were polished with sandpaper (particle size 500), and both surfaces were washed with alcohol. Then, the dolly was fixed to the test coated steel plate with an epoxy resin adhesive, and left for 2 days to cure the adhesive. Hold the dolly with the dolly of the adhesion tester (Elcomometer Co., F106-2), turn the handle of the tester at a constant speed, apply tensile force to the dolly, and the coating or adhesive layer will peel off. The value at the time of reading was read as the adhesion of the coating film.
　また、表１及び表２に記載した各成分の詳細は以下のとおりである。 The details of each component described in Tables 1 and 2 are as follows.
着色顔料
　プリンテックス３５：エボニックデグサジャパン（株）製カーボンブラック
着色顔料分散剤
　ＥＦＫＡ－４３１０：ＢＡＳＦ製（塩基性官能基を有する櫛形高分子） Color pigment Printex 35: Carbon black color pigment dispersant manufactured by Evonik Degussa Japan Co., Ltd. EFKA-4310: Product made by BASF (comb polymer having basic functional group)
樹脂
　ハイロスＸ－１：星光ＰＭＣ（株）製スチレン－アクリル樹脂（酸価１１０．５ｍｇ／ｇＫＯＨ、ガラス転移温度５２℃）
　ハイロスＸ－３１０：星光ＰＭＣ（株）製アクリル樹脂（酸価６０ｍｇ／ｇＫＯＨ、ガラス転移温度５３℃）
　ジョンクリル６１１：ＢＡＳＦ製スチレン－アクリル樹脂（酸価５３ｍｇ／ｇＫＯＨ、ガラス転移温度５０℃）
　ダイヤナールＢＲ－１０２：三菱レイヨン（株）製（酸価１ｍｇ／ｇＫＯＨ、ガラス転移温度２０℃）
　ダイヤナールＢＲ－１０７：三菱レイヨン（株）製（酸価０ｍｇ／ｇＫＯＨ、ガラス転移温度５０℃）
　ハイロスＲＳ－１１９１：星光ＰＭＣ（株）製スチレン－アクリル樹脂（酸価２８０ｍｇ／ｇＫＯＨ、ガラス転移温度１２８℃）
　ジョンクリル６７：ＢＡＳＦ製スチレン－アクリル樹脂（酸価２１３ｍｇ／ｇＫＯＨ、ガラス転移温度７３℃）
　ジョンクリル６７８：ＢＡＳＦ製スチレン－アクリル樹脂（酸価２１５ｍｇ／ｇＫＯＨ、ガラス転移温度８５℃）
　ジョンクリル６８２：ＢＡＳＦ製スチレン－アクリル樹脂（酸価２３８ｍｇ／ｇＫＯＨ、ガラス転移温度５６℃） Resin High Loss X-1: Styrene-acrylic resin (acid value 110.5 mg / g KOH, glass transition temperature 52 ° C.) manufactured by Seiko PMC Co., Ltd.
High loss X-310: Acrylic resin (acid value 60 mg / g KOH, glass transition temperature 53 ° C.) manufactured by Seiko PMC
Joncrill 611: BASF styrene-acrylic resin (acid value 53 mg / g KOH, glass transition temperature 50 ° C.)
Dianar BR-102: manufactured by Mitsubishi Rayon Co., Ltd. (acid value 1 mg / g KOH, glass transition temperature 20 ° C.)
Dianar BR-107: manufactured by Mitsubishi Rayon Co., Ltd. (acid value 0 mg / g KOH, glass transition temperature 50 ° C.)
High-loss RS-1191: Styrene-acrylic resin (acid value 280 mg / g KOH, glass transition temperature 128 ° C.) manufactured by Seiko PMC Co., Ltd.
Jonkrill 67: BASF styrene-acrylic resin (acid value 213 mg / g KOH, glass transition temperature 73 ° C.)
Joncrill 678: BASF styrene-acrylic resin (acid value 215 mg / g KOH, glass transition temperature 85 ° C.)
Jonkrill 682: BASF styrene-acrylic resin (acid value 238 mg / g KOH, glass transition temperature 56 ° C.)
　ジョンクリル６８３：ＢＡＳＦ製スチレン－アクリル樹脂（酸価１６０ｍｇ／ｇＫＯＨ、ガラス転移温度７５℃）
　ジョンクリル６９０：ＢＡＳＦ製スチレン－アクリル樹脂（酸価２４０ｍｇ／ｇＫＯＨ、ガラス転移温度１０２℃）
　ヒタノール１１４０：日立化成工業（株）製アルキルフェノール樹脂
　ハイラック１１１：日立化成工業（株）製ケトン樹脂 Jonkrill 683: BASF styrene-acrylic resin (acid value 160 mg / g KOH, glass transition temperature 75 ° C.)
Jonkrill 690: BASF styrene-acrylic resin (acid value 240 mg / g KOH, glass transition temperature 102 ° C.)
Hitanol 1140: Alkylphenol resin made by Hitachi Chemical Co., Ltd. Hilac 111: Ketone resin made by Hitachi Chemical Co., Ltd.
実施例１
　表１に示す成分を表１に示す量で用いて、前述したようにして、インキ組成物を調製した。 Example 1
Using the components shown in Table 1 in the amounts shown in Table 1, ink compositions were prepared as described above.
実施例２～１３
　表１及び表２に示す成分を表１及び表２に示す量で用いて、前述したようにして、インキ組成物を調製した。 Examples 2 to 13
Using the components shown in Tables 1 and 2 in the amounts shown in Tables 1 and 2, ink compositions were prepared as described above.
比較例１～８
　表２に示す成分を表２に示す量で用いて、前述したようにして、インキ組成物を調製した。 Comparative Examples 1-8
Ink compositions were prepared as described above using the components shown in Table 2 in the amounts shown in Table 2.
　実施例のインキ組成物について、粘度、碁盤目試験剥離数及び塗膜の付着力を表１及び表２に示し、比較例のインキ組成物について、粘度、碁盤目試験剥離数及び塗膜の付着力を表２に示す。 Table 1 and Table 2 show the viscosity, cross-cut test peel number, and coating adhesion for the ink compositions of Examples, and the viscosity, cross-cut test peel number, and coating coating for the ink compositions of Comparative Examples. The adhesion force is shown in Table 2.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１及び表２に示すように、実施例による塗膜は、付着性試験において、下塗り塗膜が剥離し、下塗り塗膜と上塗り塗膜との間における剥離は見られなかった。即ち、下塗り塗膜と上塗り塗膜との間にマーキング層が介在しても、下塗り塗膜と上塗り塗膜との間の付着力の低下はみられなかった。 As shown in Tables 1 and 2, in the coating test according to the example, the undercoat film was peeled off in the adhesion test, and peeling between the undercoat film and the topcoat film was not observed. That is, even when a marking layer was interposed between the undercoat film and the topcoat film, no decrease in the adhesion force between the undercoat film and the topcoat film was observed.
　また、碁盤目試験においても、剥離数は０であって、下塗り塗膜と上塗り塗膜との間の付着力の低下はみられなかった。 Also, in the cross cut test, the number of peels was 0, and no decrease in the adhesion between the undercoat film and the topcoat film was observed.
　これに対して、比較例による塗膜は、碁盤目試験において、上塗り塗膜が下塗り塗膜から剥離して、下塗り塗膜と上塗り塗膜との間にマーキング層が介在することによる付着力の低下が認められた。表２における碁盤目試験剥離数はすべて、下塗り塗膜からの上塗り塗膜の剥離数（桝目数）である。
  On the other hand, in the cross-cut test, the coating film according to the comparative example was peeled off from the undercoating film, and the adhesion force due to the marking layer being interposed between the undercoating film and the overcoating film. A decrease was observed. The number of cross-cut test peels in Table 2 is the number of peels of the top coat film from the undercoat film (number of grids).

Claims (2)

  1. 　有機溶媒、顔料、分散剤及び樹脂を含む塗装鋼板用インキ組成物であって、上記樹脂が酸価１５０ｍｇＫＯＨ／ｇ以下、ガラス転移温度０～５５℃の範囲にあるアクリル樹脂及びスチレン－アクリル樹脂から選ばれる少なくとも１種であることを特徴とする塗装鋼板用インキ組成物。 An ink composition for a coated steel sheet comprising an organic solvent, a pigment, a dispersant and a resin, wherein the resin is an acrylic resin and a styrene-acrylic resin having an acid value of 150 mgKOH / g or less and a glass transition temperature of 0 to 55 ° C. An ink composition for coated steel sheet, which is at least one selected.
  2. 　有機溶媒がエタノール、イソプロピルアルコール、３－メチル－３－メトキシブタノール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテール及びジプロピレングリコールモノメチルエーテルよりなる群から選ばれる少なくとも１種である請求項１に記載の塗装鋼板用インキ組成物。 Organic solvent is ethanol, isopropyl alcohol, 3-methyl-3-methoxybutanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether The ink composition for coated steel sheets according to claim 1, which is at least one selected from the group consisting of dipropylene glycol monomethyl ether.
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JPH0570724A (en) * 1991-02-25 1993-03-23 Dainippon Ink & Chem Inc Ink for jet printer
JPH09217019A (en) * 1996-02-13 1997-08-19 Dainippon Ink & Chem Inc Production of pigment composition and aqueous coloring solution containing pigment composition produced by the method
JPH10212432A (en) * 1997-01-30 1998-08-11 Marktec Corp Paint for on-demand type dot printer
JPH11152424A (en) * 1997-11-25 1999-06-08 Dainippon Ink & Chem Inc Production of aqueous pigment dispersion and aqueous colored liquid
JP2002121484A (en) * 2000-10-13 2002-04-23 Marktec Corp Heat-resistant coating for dot printing
JP2002322400A (en) * 2001-04-26 2002-11-08 Shachihata Inc Oily ink for use in steel material
JP2009052030A (en) * 2007-07-27 2009-03-12 Seiren Co Ltd Ink set for ink jet, ink jet coloring process and colored product for outdoor

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