WO2020129949A1 - Coating film remover and method for removing coating film - Google Patents

Coating film remover and method for removing coating film Download PDF

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Publication number
WO2020129949A1
WO2020129949A1 PCT/JP2019/049314 JP2019049314W WO2020129949A1 WO 2020129949 A1 WO2020129949 A1 WO 2020129949A1 JP 2019049314 W JP2019049314 W JP 2019049314W WO 2020129949 A1 WO2020129949 A1 WO 2020129949A1
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Prior art keywords
coating film
water
viscosity
peeling
agent
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PCT/JP2019/049314
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French (fr)
Japanese (ja)
Inventor
健吾 卜部
環 川元
康学 湊
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日本ペイントホールディングス株式会社
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Publication of WO2020129949A1 publication Critical patent/WO2020129949A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • 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
    • C09D9/00—Chemical paint or ink removers

Definitions

  • the present invention relates to a paint film peeling agent and a paint film peeling method. More specifically, the present invention relates to a coating film peeling agent for removing a coating film formed on a structure made of metal or the like, and a coating film peeling method.
  • the blast method is a method in which air, water, or the like containing an abrasive is blown onto the coating film at high pressure to expose the metal surface under the coating film.
  • the blast method has a problem in that it has an influence on the human body and the environment, noise, and a large amount of waste.
  • Patent Documents 2 and 3 it has been proposed to remove the coating film using an aqueous release agent without using an organic solvent.
  • the method according to Patent Document 2 uses an electrolytic solution containing salt as an aqueous stripping solution, electrolyzes the electrolytic solution to generate a gas, and the coating film is stripped by the generated gas.
  • the stripping solution containing salt causes chlorine and the like to be generated by electrolysis, which is an unfavorable situation.
  • a conductive base material is used as a cathode, an aqueous penetrant is applied onto the coating film, the aqueous penetrant is allowed to penetrate into the coating film, and then the portable electrode is used as an anode.
  • the electrode is brought into contact with the aqueous penetrating agent to conduct electricity, and the coating film is peeled off.
  • JP-A-52-18737 Japanese Unexamined Patent Publication No. 2010-119971 JP, 2005-182024, A
  • the present invention has been made in view of the background art described above, and an object thereof is to provide a water-based coating film peeling agent having a sufficient peeling force and a coating film peeling method.
  • the present inventors have earnestly studied to solve the above problems. Then, when electrolytic treatment is performed using a coating film stripper having a high viscosity at 0.1S ⁇ 1 (low shear viscosity) and a low viscosity at 100S ⁇ 1 (high shear viscosity), oxygen diffusion is suppressed.
  • the inventors have found that radicals are efficiently generated, and the generated radicals destroy the adhesion region at the interface between the coating film and the base material, thereby improving the peeling force of the coating film, and completed the present invention.
  • the present invention is a water-based coating film stripping agent for stripping a coating film formed on a conductive substrate by electrolysis, which contains a water-soluble polymer compound, an electrolyte, and water. It is a water-based coating film release agent having a viscosity at 1S ⁇ 1 of 20 Pa ⁇ s or more and 5000 Pa ⁇ s or less and a viscosity at 100S ⁇ 1 of 0.001 Pa ⁇ s or more and 40 Pa ⁇ s or less.
  • the electric conductivity of the water-based paint remover may be greater than 0.5 mS/cm.
  • the water-soluble polymer compound is an OH group, a COOX group, an SO 3 X group (wherein X represents hydrogen or a cation), and the following (a) to (d): It may have one or more groups selected from the group consisting of the nitrogen-containing groups shown.
  • the water-based paint remover according to any one of claims 1 to 3, wherein in the water-based paint remover, the electrolyte has a molecular weight or a weight average molecular weight of less than 1,000.
  • the conductive base material may be a metal.
  • Still another aspect of the present invention is a method for peeling a coating film formed on a conductive substrate, wherein the coating film is contacted with an aqueous coating film peeling agent, a contact step, the conductive substrate and the aqueous system. It is energized and a coating release agent performs an electrolytic process, comprising an electrolytic process, wherein the water-based coating release agent comprises a water-soluble polymer compound, an electrolyte, and water, and 0.1 S - 1 is a viscosity of 20 Pa ⁇ s or more and 5000 Pa ⁇ s or less, and a viscosity of 100 S ⁇ 1 is 0.001 Pa ⁇ s or more and 40 Pa ⁇ s or less.
  • the water-based coating film peeling agent may have an electric conductivity of more than 0.5 mS/cm.
  • the water-soluble polymer compound is represented by an OH group, a COOX group, an SO 3 X group (wherein X represents hydrogen or a cation), and the following (a) to (d). It may have one or more groups selected from the group consisting of nitrogen-containing groups.
  • the electrolyte may have a molecular weight or a weight average molecular weight of less than 1,000.
  • the conductive base material may be a metal.
  • the water-based coating film release agent of the present invention suppresses the diffusion of oxygen to efficiently generate radicals, and the generated radicals promote the release using a mechanism of destroying the adhesion region at the interface between the coating film and the substrate. Let Therefore, the water-based coating film peeling agent has an improved coating film peeling force.
  • the coating film peeling method using the water-based coating film peeling agent of the present invention in a safe situation, in a short time and with a small coating amount, without causing problems such as human body, environment, noise, waste, etc.
  • the coating film formed on the flexible substrate can be efficiently peeled off.
  • the present invention is a water-based coating film stripping agent for stripping a coating film formed on a conductive substrate by electrolysis, containing a water-soluble polymer compound, an electrolyte, and water, and containing 0.1S ⁇
  • the viscosity of 1 (low shear viscosity) is 20 Pa ⁇ s or more and 5000 Pa ⁇ s or less, and the viscosity at 100 S ⁇ 1 (high shear viscosity) is 0.001 Pa ⁇ s or more and 40 Pa ⁇ s or less. It is an agent.
  • Water-soluble polymer compound as a constituent of water-based coating remover of the present invention, if the viscosity at viscosity and 100S -1 at 0.1 S -1 of the aqueous coating release agent as it can adjust the range It is not particularly limited. For example, one selected from the group consisting of an OH group, a COOX group, a SO 3 X group (wherein X represents hydrogen or a cation), and a nitrogen-containing group represented by the following (a) to (d). A water-soluble compound having the above groups is preferable.
  • the water-soluble polymer compound may be a natural product, a synthetic product, or a mixture thereof.
  • examples thereof include carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC), casein, starch, maltose, trehalose, xanthan gum, guar gum, and modified products thereof.
  • the weight average molecular weight of the water-soluble polymer compound is preferably 1,000 or more, more preferably 5,000 or more, and particularly preferably 10,000 or more. When the weight average molecular weight is less than 1000, a large amount of water-soluble polymer compound must be added to adjust the viscosity of the water-based coating film release agent, which is economically disadvantageous.
  • the electrolyte which is a constituent of the water-based paint remover of the present invention, is a compound composed of a cation and an anion.
  • cations forming the electrolyte hydrogen ions, metal ions such as Li, Na, K, Mg, Ca, Al, Ag, and Fe, imidazolium ion, pyridinium ion, quaternary ammonium ion, and Organic ions such as quaternary phosphonium ions may be mentioned.
  • Examples of anions constituting the electrolyte include hydroxide ion, chloride ion, nitrate ion, sulfate ion, dihydrogen phosphate ion, hydrogen phosphate ion, phosphate ion and the like.
  • Examples of the electrolyte include potassium dihydrogen phosphate, ammonium sulfate, potassium acetate and the like. Further, it is preferably not a chloride ion.
  • the molecular weight of the electrolyte or when the electrolyte has a molecular weight distribution, the weight average molecular weight of the electrolyte is preferably less than 1000, more preferably less than 800, and particularly preferably less than 500.
  • the molecular weight or the weight average molecular weight is 1000 or more, the performance as an electrolyte is poor, and a large amount must be added, which is economically disadvantageous.
  • the aqueous coating film remover of the present invention has a viscosity (low shear viscosity) at 0.1 S ⁇ 1 of 20 Pa ⁇ s or more and 5000 Pa ⁇ s or less. It is preferably 50 Pa ⁇ s or more and 3000 Pa ⁇ s or less, and most preferably 200 Pa ⁇ s or more and 1500 Pa ⁇ s or less.
  • the water-based coating film release agent of the present invention has a viscosity (high shear viscosity) at 100 S ⁇ 1 of 0.001 Pa ⁇ s or more and 40 Pa ⁇ s or less. It is preferably 0.005 Pa ⁇ s or more and 15 Pa ⁇ s or less, and most preferably 0.01 Pa ⁇ s or more and 2 Pa ⁇ s or less.
  • the water-based coating film stripping agent of the present invention has a high low shear viscosity and is a low high shear viscosity coating film stripping agent, so that when electrolytic treatment is carried out, oxygen diffusion is suppressed and radicals are efficiently generated. Will be the situation. Then, the generated radicals destroy the adhesion region at the interface between the coating film and the base material, thereby promoting the peeling of the coating film.
  • the low shear viscosity and high shear viscosity of the water-based coating film stripping agent of the present invention are within the above ranges, radicals can be efficiently generated, and as a result, even with a water-based stripping agent, a high stripping force can be obtained. It is possible to realize a coating film peeling agent having.
  • examples of the method for adjusting the viscosity within the above range include a method of dissolving the above water-soluble polymer compound in water.
  • the addition amount (solid content) of the water-soluble polymer compound is 0.
  • the amount is preferably in the range of 5 to 20% by mass, more preferably 1 to 10% by mass. If the amount of the water-soluble polymer compound added is too small, the viscosity of the water-based coating film release agent will not improve, while if it is too large, it will be difficult to apply the water-based film coating release agent on the coating film.
  • the water-based coating film peeling agent of the present invention has the above-mentioned viscosity and has an electric conductivity of more than 0.5 mS/cm.
  • the electric conductivity is more preferably 3 mS/cm or more, further preferably 5 mS/cm or more, and most preferably 10 mS/cm or more.
  • examples of the method for adjusting the electric conductivity within the above range include a method of adding the above-mentioned electrolyte.
  • radicals generated when the aqueous coating film remover of the present invention is electrolytically treated are not particularly limited.
  • a hydroxyl radical, a hydrogen radical, an oxygen radical, etc. are mentioned.
  • the conductive base material on which the coating film to which the water-based coating film peeling agent of the present invention is applied is formed is not particularly limited as long as the electric current is supplied by the power supply from the power supply device.
  • a metal material, a conductive resin material, etc. are mentioned.
  • the metal material forms a large structure such as a bridge or a tank installed outdoors.
  • the metal material is not particularly limited.
  • the shape of the conductive base material there is no particular limitation on the shape of the conductive base material, and for example, a shape including unevenness formed by a flat surface or a curved surface can be sufficiently dealt with.
  • the water-based coating film peeling agent of the present invention may contain any component within the range not departing from the gist of the present invention.
  • Ordinary additives such as an anti-sagging agent, an anti-settling agent, a leveling agent, a surface conditioner, a plasticizer, an antiseptic agent and an antifungal agent may be blended.
  • These optional components may be used alone or in combination of two or more.
  • the coating film peeling method of the present invention is a method of peeling a coating film formed on a conductive substrate by using the above-described aqueous coating film peeling agent of the present invention, which comprises a contact step and an electrolytic treatment step. Including.
  • the contacting step is a step of bringing the coating film formed on the conductive base material into contact with the water-based coating film peeling agent of the present invention.
  • the coating film formed on the conductive substrate is brought into contact with the water-based coating film release agent of the present invention to impregnate the coating film with the water-based coating film release agent.
  • the contact method is not particularly limited, and can be appropriately selected depending on the shape of the conductive base material and the like.
  • a spray method, a brush, a roller or the like preferably, a method of applying a water-based coating film release agent with a thickness of 10 ⁇ m or more to the entire coating film to be released, and forming a film with the water-based coating film release agent, or Examples include a method of immersing a conductive base material having a coating film in a water-based coating film peeling agent.
  • the coating film to be peeled may be contacted in the state as it is, but by forming a defective portion in the coating film in advance and then contacting the aqueous coating film peeling agent with the coating film, the aqueous coating film peeling agent is applied to the coating film.
  • the method of producing the defective portion include a method of making a cut with a knife or the like, a laser cutting, and a hole drilling with a pin.
  • the temperature of the water-based coating film peeling agent when contacting the coating film is not particularly limited, and may be, for example, normal temperature. If the peeling time of the coating film is desired to be shortened, it is possible to heat the coating film at an appropriate temperature before use.
  • the time for bringing the coating film into contact with the water-based coating film peeling agent is not particularly limited, and a time sufficient for impregnating the coating film with the water-based coating film peeling agent may be appropriately set.
  • the electrolytic treatment step is a step in which the conductive base material and the water-based coating film peeling agent are energized to perform electrolytic treatment. Then, by energizing, radicals are generated at the interface between the conductive base material and the coating film.
  • radicals are efficiently generated when electrolytic treatment is performed in the electrolytic treatment step. Then, the generated radicals destroy the adhesion region at the interface between the coating film and the substrate, and promote the peeling of the coating film.
  • the method of energizing the conductive base material and the water-based coating film peeling agent is not particularly limited. Either direct current or alternating current may be applied.
  • the conductive base material on which the coating film is formed is connected to the cathode side of the power supply device, and the counter electrode having conductivity is connected to the anode side of the power supply device.
  • the counter electrode With the counter electrode in contact with the coating film release agent, by energizing between the conductive base material and the counter electrode, the coating film impregnated with the water-based coating film release agent and the conductive base material are energized to generate radicals.
  • the method of generating is mentioned.
  • the distance between the counter electrode and the conductive base material is not particularly limited as long as it can be energized.
  • it is preferably 30 mm or less, further 10 mm or less, and further 5 mm. It is preferably within the range. It is particularly preferably within 3 mm, and most preferably within 1 mm.
  • the power supply device used for energization is not particularly limited as long as it can energize the conductive base material and the water-based coating film peeling agent. It is also possible to use a commercially available power supply device as it is.
  • the applied voltage is not particularly limited. When it is desired to shorten the peeling time of the coating film, a relatively high voltage can be applied while considering safety and the like.
  • the applied voltage is, for example, preferably higher than 2V, more preferably 10 to 30V, and particularly preferably 15 to 25V.
  • the time for energizing is not particularly limited, and may be set to a time sufficient for peeling the coating film. From the viewpoint of workability, it is preferably within 2 hours, more preferably within 1 hour, further within 30 minutes, and further preferably within 10 minutes. Particularly preferably, it is within 3 minutes, and most preferably, within 1 minute.
  • the temperature in the electrolytic treatment step is not particularly limited, and may be performed at room temperature, for example.
  • the material used to form the counter electrode is not particularly limited, but if it is aluminum or carbon, for example, it will be advantageous in terms of cost. Since the counter electrode comes into contact with the water-based coating film release agent, it is preferably formed of a material having corrosion resistance or the like with respect to the water-based film release agent.
  • the shape of the counter electrode is not particularly limited, and can be appropriately selected from plate-like, rod-like, etc. depending on the shape of the conductive base material on which the coating film is formed. Examples of the counter electrode that can be preferably used in the present invention include platinum iron and the like.
  • Example 1 [Preparation of sample plate for coating film peeling] A white coating film (film thickness: about 200 ⁇ m) was formed on the entire surface of a 50 mm ⁇ 70 mm ⁇ 0.8 mm dull steel plate.
  • a paint for forming a white coating film a weak solvent type modified epoxy resin undercoat paint (manufactured by Nippon Paint Co., Ltd., trade name: Hibon 20 Fine HB (milky white)) is used at a drying temperature of 23° C. for a drying period of 7 More than one day and less than one month.
  • the formed white coating film was cut with a cutter knife at intervals of 4 mm to obtain a sample plate for coating film peeling.
  • the viscosity at 0.1S ⁇ 1 (low shear viscosity) is 335 Pa ⁇ s, and the viscosity at 100 S ⁇ 1 (high shear viscosity) is 1.0 Pa ⁇ s,
  • the electric conductivity was 15.1 mS/cm.
  • a power supply device As a power supply device, a constant current power supply device manufactured by Union Electronics Co., Ltd. was used, and a conductive base material was connected to the ⁇ side of the power supply device and a conductive counter electrode was connected to the + side of the power supply device. With the counter electrode in contact with the water-based release agent on the coating film, a voltage was applied between the conductive base material and the counter electrode to energize the film. As the counter electrode, a platinum plate of 20 mm ⁇ 20 mm ⁇ 0.5 mm manufactured by Kita Rika Shokai was used, the distance between the conductive substrate and the counter electrode was set to 1 mm, and a voltage of 20 V was applied for 1 minute. Then, the coating film peeled from the water-based release agent was removed using a spatula.
  • the white paint was sufficiently peeled off.
  • Examples 2 to 24, Comparative Examples 1 to 6 According to the formulation shown in Tables 1 to 4, the water-based coating film release agents used in Examples 2 to 24 and Comparative Examples 1 to 6 were prepared in the same manner as the method for preparing the water-based coating film release agent used in Example 1. Various measurements were performed on the prepared water-based coating film release agent. The measurement results are shown in Tables 1 to 4. Then, using the obtained water-based coating film remover, a contact step and an electrolytic treatment step were carried out in the same manner as in Example 1.
  • KELZAN AR xanthan gum (manufactured by Sansho Co., Ltd., solid content: 100%)
  • Supergel 200 guar gum (manufactured by Sansho Co., Ltd., solid content: 100%)
  • HEC-SP850 Hydroxyethyl cellulose (manufactured by Daicel Finechem, solid content: 100%)
  • BYK-420 modified urea solution (manufactured by Big Chemie Japan, solid content: 52%)
  • ⁇ L-11 Polyethylene oxide (Meisei Chemical Industry Co., Ltd., solid content: 100%)

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

The present invention provides: an aqueous coating film remover which has sufficient peel strength; and a method for removing a coating film. According to the present invention, radicals are efficiently generated, while suppressing diffusion of oxygen, by performing an electrolysis treatment with use of a coating film remover that has a high viscosity at 0.1 S-1 (low-shear viscosity) and a low viscosity at 100 S-1 (high-shear viscosity), and the adhered region at the interface between a coating film and a base material is destroyed by the thus-generated radicals. Specifically, an aqueous coating film remover according to the present invention has a viscosity at 0.1 S-1 (low-shear viscosity) of from 20 Pa∙s to 5,000 Pa∙s (inclusive) and a viscosity at 100 S-1 (high-shear viscosity) of from 0.001 Pa∙s to 40 Pa∙s (inclusive).

Description

塗膜剥離剤、および塗膜剥離方法Coating film peeling agent and coating film peeling method
　本発明は、塗膜剥離剤、および塗膜剥離方法に関する。さらに詳しくは、金属等からなる構造物等に形成された塗膜を除去するための塗膜剥離剤、および塗膜剥離方法に関する。 The present invention relates to a paint film peeling agent and a paint film peeling method. More specifically, the present invention relates to a coating film peeling agent for removing a coating film formed on a structure made of metal or the like, and a coating film peeling method.
　従来、屋外に設置された橋、タンク等の大型構造物には、耐食性等を付与する目的で、塗膜が形成されている。このような塗膜は、老朽化によってその機能が低下するため、一定期間が経過した後に、新たな塗膜に塗り替える必要がある。 Conventionally, coatings have been formed on large structures such as bridges and tanks installed outdoors to provide corrosion resistance. Since the function of such a coating film deteriorates due to aging, it is necessary to repaint with a new coating film after a certain period of time has passed.
　このとき、古い塗膜は除去する必要があり、その方法としては、主として、ブラスト工法が実施されている。ブラスト工法とは、研削材を含む空気や水等を、高圧にて塗膜に吹きつけて、塗膜の下の金属面を露出させる方法である。しかしながら、ブラスト工法には、人体や環境への影響や、騒音、さらには多量の廃棄物が発生するという問題があった。 At this time, it is necessary to remove the old coating film, and the blasting method is mainly used as the method. The blast method is a method in which air, water, or the like containing an abrasive is blown onto the coating film at high pressure to expose the metal surface under the coating film. However, the blast method has a problem in that it has an influence on the human body and the environment, noise, and a large amount of waste.
　そこで、剥離剤を塗布して塗膜を膨潤・軟化させた後に、用具を用いて除去する方法が提案されている（特許文献１参照）。しかしながら、用いる剥離剤は有機溶媒系であるため、大型構造物に対する大掛かりな塗膜剥離に際しては、引火等による事故が懸念される。 Therefore, there has been proposed a method of applying a release agent to swell and soften the coating film, and then removing the coating film with a tool (see Patent Document 1). However, since the release agent used is an organic solvent type, there is a fear of an accident due to ignition or the like when a large-scale coating film is removed from a large structure.
　これに対して、有機溶剤を使用せず、水系の剥離剤による塗膜剥離も提案されててる（特許文献２および３）。特許文献２による方法は、水系剥離液として、食塩を添加した電解質液を用いて、これを電気分解してガスを発生させ、発生したガスによって塗膜を剥離する。しかしながら、食塩を含む剥離液は、電気分解により塩素等が発生してしまい、好ましくない状況となる。 On the other hand, it has been proposed to remove the coating film using an aqueous release agent without using an organic solvent (Patent Documents 2 and 3). The method according to Patent Document 2 uses an electrolytic solution containing salt as an aqueous stripping solution, electrolyzes the electrolytic solution to generate a gas, and the coating film is stripped by the generated gas. However, the stripping solution containing salt causes chlorine and the like to be generated by electrolysis, which is an unfavorable situation.
　また、特許文献３に記載の方法は、導電性を有する基材を陰極とし、塗膜の上に水性浸透剤を塗布し、水性浸透剤を塗膜に浸透させた後、可搬型電極を陽極として水性浸透剤に電極を接触させて通電し、塗膜を剥離する。 Further, in the method described in Patent Document 3, a conductive base material is used as a cathode, an aqueous penetrant is applied onto the coating film, the aqueous penetrant is allowed to penetrate into the coating film, and then the portable electrode is used as an anode. As an electrode, the electrode is brought into contact with the aqueous penetrating agent to conduct electricity, and the coating film is peeled off.
　しかしながら、特許文献３に記載の方法は、基材と塗膜の界面にて溶存酸素の還元反応が起こり、界面を強アルカリ性にして、塗膜と基材との付着力を低下させて、塗膜を剥離しやすくするものである。このため、その剥離力はいまだ満足できるものではなく、さらなる向上が求められていた。 However, in the method described in Patent Document 3, a reduction reaction of dissolved oxygen occurs at the interface between the base material and the coating film, and the interface is made strongly alkaline to reduce the adhesive force between the coating film and the base material, and the coating is performed. It is intended to facilitate the peeling of the film. Therefore, the peeling force is not yet satisfactory, and further improvement has been required.
特開昭５２－１８７３７号公報JP-A-52-18737 特開２０１０－１１９９７１号公報Japanese Unexamined Patent Publication No. 2010-119971 特開２０１５－１８２０２４号公報JP, 2005-182024, A
　本発明は、上記の背景技術に鑑みてなされたものであり、十分な剥離力を有する水系塗膜剥離剤、および塗膜剥離方法を提供することにある。 The present invention has been made in view of the background art described above, and an object thereof is to provide a water-based coating film peeling agent having a sufficient peeling force and a coating film peeling method.
　本発明者らは、上記課題を解決するため、鋭意検討を行った。そして、０．１Ｓ－１における粘度（低せん断粘度）が高く、１００Ｓ－１における粘度（高せん断粘度）が低い塗膜剥離剤を用いて電解処理を実施すれば、酸素の拡散が抑制されてラジカルが効率よく発生し、発生したラジカルにより、塗膜と基材との界面における密着領域が破壊されて、塗膜の剥離力を向上できることを見出し、本発明を完成させるに至った。 The present inventors have earnestly studied to solve the above problems. Then, when electrolytic treatment is performed using a coating film stripper having a high viscosity at 0.1S −1 (low shear viscosity) and a low viscosity at 100S −1 (high shear viscosity), oxygen diffusion is suppressed. The inventors have found that radicals are efficiently generated, and the generated radicals destroy the adhesion region at the interface between the coating film and the base material, thereby improving the peeling force of the coating film, and completed the present invention.
　すなわち、本発明は、導電性基材に形成された塗膜を電解により剥離するための水系塗膜剥離剤であって、水溶性高分子化合物と、電解質と、水と、を含み、０．１Ｓ－１における粘度が、２０Ｐａ・ｓ以上５０００Ｐａ・ｓ以下であり、１００Ｓ－１における粘度が、０．００１Ｐａ・ｓ以上４０Ｐａ・ｓ以下である、水系塗膜剥離剤である。 That is, the present invention is a water-based coating film stripping agent for stripping a coating film formed on a conductive substrate by electrolysis, which contains a water-soluble polymer compound, an electrolyte, and water. It is a water-based coating film release agent having a viscosity at 1S −1 of 20 Pa·s or more and 5000 Pa·s or less and a viscosity at 100S −1 of 0.001 Pa·s or more and 40 Pa·s or less.
　前記水系塗膜剥離剤は、電導度が、０．５ｍＳ／ｃｍより大きくてもよい。 The electric conductivity of the water-based paint remover may be greater than 0.5 mS/cm.
　前記水系塗膜剥離剤において、前記水溶性高分子化合物は、ＯＨ基、ＣＯＯＸ基、ＳＯ３Ｘ基（式中、Ｘは、水素またはカチオンを表す）、および下記（ア）～（エ）で示される窒素含有基からなる群より選択される１種以上の基を有していてもよい。 In the water-based coating film release agent, the water-soluble polymer compound is an OH group, a COOX group, an SO 3 X group (wherein X represents hydrogen or a cation), and the following (a) to (d): It may have one or more groups selected from the group consisting of the nitrogen-containing groups shown.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　前記水系塗膜剥離剤において、前記電解質は、分子量または重量平均分子量が１０００未満である、請求項１～３いずれかに記載の水系塗膜剥離剤。 The water-based paint remover according to any one of claims 1 to 3, wherein in the water-based paint remover, the electrolyte has a molecular weight or a weight average molecular weight of less than 1,000.
　前記水系塗膜剥離剤において、前記導電性基材は、金属であってもよい。 In the above water-based paint remover, the conductive base material may be a metal.
　また別の本発明は、導電性基材に形成された塗膜を剥離する方法であって、前記塗膜を水系塗膜剥離剤に接触させる、接触工程と、前記導電性基材と前記水系塗膜剥離剤とを通電させて電解処理を行う、電解処理工程と、を含み、前記水系塗膜剥離剤は、水溶性高分子化合物と、電解質と、水と、を含み、０．１Ｓ－１における粘度が、２０Ｐａ・ｓ以上で５０００Ｐａ・ｓ以下あり、１００Ｓ－１における粘度が、０．００１Ｐａ・ｓ以上４０Ｐａ・ｓ以下である、塗膜剥離方法である。 Still another aspect of the present invention is a method for peeling a coating film formed on a conductive substrate, wherein the coating film is contacted with an aqueous coating film peeling agent, a contact step, the conductive substrate and the aqueous system. It is energized and a coating release agent performs an electrolytic process, comprising an electrolytic process, wherein the water-based coating release agent comprises a water-soluble polymer compound, an electrolyte, and water, and 0.1 S - 1 is a viscosity of 20 Pa·s or more and 5000 Pa·s or less, and a viscosity of 100 S −1 is 0.001 Pa·s or more and 40 Pa·s or less.
　前記塗膜剥離方法において、前記水系塗膜剥離剤は、電導度が、０．５ｍＳ／ｃｍより大きくてもよい。 In the coating film peeling method, the water-based coating film peeling agent may have an electric conductivity of more than 0.5 mS/cm.
　前記塗膜剥離方法において、前記水溶性高分子化合物は、ＯＨ基、ＣＯＯＸ基、ＳＯ３Ｘ基（式中、Ｘは、水素またはカチオンを表す）、および下記（ア）～（エ）で示される窒素含有基からなる群より選択される１種以上の基を有していてもよい。 In the coating film peeling method, the water-soluble polymer compound is represented by an OH group, a COOX group, an SO 3 X group (wherein X represents hydrogen or a cation), and the following (a) to (d). It may have one or more groups selected from the group consisting of nitrogen-containing groups.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　前記塗膜剥離方法において、前記電解質は、分子量または重量平均分子量が１０００未満であってもよい。 In the coating film peeling method, the electrolyte may have a molecular weight or a weight average molecular weight of less than 1,000.
　前記塗膜剥離方法において、前記導電性基材は、金属であってもよい。 In the coating film peeling method, the conductive base material may be a metal.
　本発明の水系塗膜剥離剤は、酸素の拡散を抑制してラジカルを効率よく発生させ、発生したラジカルにより、塗膜と基材との界面における密着領域を破壊するメカニズムを用いて剥離を進行させる。このため、塗膜の剥離力が向上した水系塗膜剥離剤となる。 The water-based coating film release agent of the present invention suppresses the diffusion of oxygen to efficiently generate radicals, and the generated radicals promote the release using a mechanism of destroying the adhesion region at the interface between the coating film and the substrate. Let Therefore, the water-based coating film peeling agent has an improved coating film peeling force.
　また、剥離剤を用いた電解処理であるため、ブラスト工法による、人体や環境、騒音、廃棄物等の問題を発生させず、さらに、水系剥離剤であるため、有機溶剤が原因となる引火等による事故を回避することができる。さらに、上記のメカニズムにより、水系であっても剥離力の高い塗膜剥離剤となる。 Also, since it is an electrolytic treatment using a stripping agent, it does not cause problems such as human body, environment, noise, and waste due to the blasting method.Furthermore, since it is a water-based stripping agent, it causes ignition due to organic solvent It is possible to avoid an accident caused by. Further, by the above mechanism, it becomes a coating film peeling agent having a high peeling force even in an aqueous system.
　したがって、本発明の水系塗膜剥離剤を用いた塗膜剥離方法は、人体や環境、騒音、廃棄物等の問題を発生させることなく、安全な状況で、短時間かつ少ない塗布量で、導電性基材に形成された塗膜を、効率よく剥離することができる。 Therefore, the coating film peeling method using the water-based coating film peeling agent of the present invention, in a safe situation, in a short time and with a small coating amount, without causing problems such as human body, environment, noise, waste, etc. The coating film formed on the flexible substrate can be efficiently peeled off.
　＜水系塗膜剥離剤＞
　本発明は、導電性基材に形成された塗膜を電解により剥離するための水系塗膜剥離剤であって、水溶性高分子化合物と、電解質と、水と、を含み、０．１Ｓ－１における粘度（低せん断粘度）が、２０Ｐａ・ｓ以上５０００Ｐａ・ｓ以下であり、１００Ｓ－１における粘度（高せん断粘度）が、０．００１Ｐａ・ｓ以上４０Ｐａ・ｓ以下である、水系塗膜剥離剤である。 <Water-based paint remover>
The present invention is a water-based coating film stripping agent for stripping a coating film formed on a conductive substrate by electrolysis, containing a water-soluble polymer compound, an electrolyte, and water, and containing 0.1S − The viscosity of 1 (low shear viscosity) is 20 Pa·s or more and 5000 Pa·s or less, and the viscosity at 100 S −1 (high shear viscosity) is 0.001 Pa·s or more and 40 Pa·s or less. It is an agent.
　［水溶性高分子化合物］
　本発明の水系塗膜剥離剤の構成成分となる水溶性高分子化合物は、水系塗膜剥離剤の０．１Ｓ－１における粘度と１００Ｓ－１における粘度とを上記範囲に調整できるものであれば、特に限定されるものではない。例えば、ＯＨ基、ＣＯＯＸ基、ＳＯ３Ｘ基（式中、Ｘは、水素またはカチオンを表す）、および下記（ア）～（エ）で示される窒素含有基からなる群より選択される１種以上の基を有する、水溶性化合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000005
 [Water-soluble polymer compound]
Water-soluble polymer compound as a constituent of water-based coating remover of the present invention, if the viscosity at viscosity and 100S -1 at 0.1 S -1 of the aqueous coating release agent as it can adjust the range It is not particularly limited. For example, one selected from the group consisting of an OH group, a COOX group, a SO 3 X group (wherein X represents hydrogen or a cation), and a nitrogen-containing group represented by the following (a) to (d). A water-soluble compound having the above groups is preferable.
Figure JPOXMLDOC01-appb-C000005
　水溶性高分子化合物は、天然物でも合成物でもあるいはそれらの混合物あってもよい。例えば、カルボキシメチルセルロース（ＣＭＣ）、ヒドロキシエチルセルロース（ＨＥＣ）、カゼイン、でんぷん、マルトース、トレハロース、キサンタンガム、グァーガムや、これらを変性したもの等を挙げることができる。 The water-soluble polymer compound may be a natural product, a synthetic product, or a mixture thereof. Examples thereof include carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC), casein, starch, maltose, trehalose, xanthan gum, guar gum, and modified products thereof.
　水溶性高分子化合物の重量平均分子量は、１０００以上であることが好ましく、５０００以上であることがさらに好ましく、１００００以上であることが特に好ましい。重量平均分子量が１０００未満の場合には、水系塗膜剥離剤の粘度を調整するにあたり、水溶性高分子化合物を多量に添加しなければならなくなり、経済的に不利である。 The weight average molecular weight of the water-soluble polymer compound is preferably 1,000 or more, more preferably 5,000 or more, and particularly preferably 10,000 or more. When the weight average molecular weight is less than 1000, a large amount of water-soluble polymer compound must be added to adjust the viscosity of the water-based coating film release agent, which is economically disadvantageous.
　［電解質］
　本発明の水系塗膜剥離剤の構成成分となる電解質は、陽イオンと陰イオンから構成される化合物である。電解質を構成する陽イオンとしては、水素イオン、そして、Ｌｉ、Ｎａ、Ｋ、Ｍｇ、Ｃａ、Ａｌ、Ａｇ、Ｆｅ等の金属イオンに加え、イミダゾリウムイオン、ピリジニウムイオン、第四級アンモニウムイオン、および第四級ホスホニウムイオン等の有機イオンが挙げられる。電解質を構成する陰イオンとしては、水酸化物イオン、塩化物イオン、硝酸イオン、硫酸イオン、リン酸二水素イオン、リン酸水素イオン、リン酸イオン等が挙げられる。電解質としては、例えば、リン酸二水素カリウム、硫酸アンモニウム、酢酸カリウム等が挙げられる。さらに、塩化物イオンでないことが好ましい。 [Electrolytes]
The electrolyte, which is a constituent of the water-based paint remover of the present invention, is a compound composed of a cation and an anion. As the cations forming the electrolyte, hydrogen ions, metal ions such as Li, Na, K, Mg, Ca, Al, Ag, and Fe, imidazolium ion, pyridinium ion, quaternary ammonium ion, and Organic ions such as quaternary phosphonium ions may be mentioned. Examples of anions constituting the electrolyte include hydroxide ion, chloride ion, nitrate ion, sulfate ion, dihydrogen phosphate ion, hydrogen phosphate ion, phosphate ion and the like. Examples of the electrolyte include potassium dihydrogen phosphate, ammonium sulfate, potassium acetate and the like. Further, it is preferably not a chloride ion.
　電解質の分子量、または電解質が分子量分布を持つ場合には電解質の重量平均分子量は、１０００未満であることが好ましく、８００未満であることがさらに好ましく、５００未満であることが特に好ましい。分子量または重量平均分子量が１０００以上の場合には、電解質としての性能が劣るため、多量に添加しなければならなくなり、経済的に不利である。 The molecular weight of the electrolyte, or when the electrolyte has a molecular weight distribution, the weight average molecular weight of the electrolyte is preferably less than 1000, more preferably less than 800, and particularly preferably less than 500. When the molecular weight or the weight average molecular weight is 1000 or more, the performance as an electrolyte is poor, and a large amount must be added, which is economically disadvantageous.
　［粘度］
　本発明の水系塗膜剥離剤は、０．１Ｓ－１における粘度（低せん断粘度）が、２０Ｐａ・ｓ以上５０００Ｐａ・ｓ以下である。５０Ｐａ・ｓ以上３０００Ｐａ・ｓ以下であることが好ましく、２００Ｐａ・ｓ以上１５００Ｐａ・ｓ以下であることが最も好ましい。 [viscosity]
The aqueous coating film remover of the present invention has a viscosity (low shear viscosity) at 0.1 S −1 of 20 Pa·s or more and 5000 Pa·s or less. It is preferably 50 Pa·s or more and 3000 Pa·s or less, and most preferably 200 Pa·s or more and 1500 Pa·s or less.
　また、本発明の水系塗膜剥離剤は、１００Ｓ－１における粘度（高せん断粘度）が、０．００１Ｐａ・ｓ以上４０Ｐａ・ｓ以下である。０．００５Ｐａ・ｓ以上１５Ｐａ・ｓ以下であることが好ましく、０．０１Ｐａ・ｓ以上２Ｐａ・ｓ以下であることが最も好ましい。 Further, the water-based coating film release agent of the present invention has a viscosity (high shear viscosity) at 100 S −1 of 0.001 Pa·s or more and 40 Pa·s or less. It is preferably 0.005 Pa·s or more and 15 Pa·s or less, and most preferably 0.01 Pa·s or more and 2 Pa·s or less.
　本発明の水系塗膜剥離剤は、低せん断粘度が高く、高せん断粘度が低い塗膜剥離剤であるため、電解処理を実施した際には、酸素の拡散を抑制し、ラジカルが効率よく発生する状況となる。そして、発生したラジカルにより、塗膜と基材との界面における密着領域を破壊することで、塗膜の剥離を進行させる。 The water-based coating film stripping agent of the present invention has a high low shear viscosity and is a low high shear viscosity coating film stripping agent, so that when electrolytic treatment is carried out, oxygen diffusion is suppressed and radicals are efficiently generated. Will be the situation. Then, the generated radicals destroy the adhesion region at the interface between the coating film and the base material, thereby promoting the peeling of the coating film.
　本発明の水系塗膜剥離剤の低せん断粘度および高せん断粘度が上記の範囲にあれば、ラジカルを効率よく発生させることができ、その結果、水系の剥離剤であっても、高い剥離力を有する塗膜剥離剤を実現することができる。 When the low shear viscosity and high shear viscosity of the water-based coating film stripping agent of the present invention are within the above ranges, radicals can be efficiently generated, and as a result, even with a water-based stripping agent, a high stripping force can be obtained. It is possible to realize a coating film peeling agent having.
　本発明の水系塗膜剥離剤において、粘度を上記の範囲とする方法としては、例えば、上述した水溶性高分子化合物を水に溶解させる方法が挙げられる。 In the water-based paint remover of the present invention, examples of the method for adjusting the viscosity within the above range include a method of dissolving the above water-soluble polymer compound in water.
　本発明の水系塗膜剥離剤において、水溶性高分子化合物によって粘度を調整する場合には、水溶性高分子化合物の添加量（固形分量）は、水系塗膜剥離剤全体に対して、０．５～２０質量％の範囲とすることが好ましく、１～１０質量％とすることがより好ましい。水溶性高分子化合物の添加量があまり少ないと、水系塗膜剥離剤の粘度が向上せず、一方で、あまり多いと、水系塗膜剥離剤を塗膜上に塗装することが困難となる。 When the viscosity of the water-based coating film release agent of the present invention is adjusted by the water-soluble polymer compound, the addition amount (solid content) of the water-soluble polymer compound is 0. The amount is preferably in the range of 5 to 20% by mass, more preferably 1 to 10% by mass. If the amount of the water-soluble polymer compound added is too small, the viscosity of the water-based coating film release agent will not improve, while if it is too large, it will be difficult to apply the water-based film coating release agent on the coating film.
　［電導度］
　本発明の水系塗膜剥離剤は、上記の粘度を有し、かつ、電導度が、０．５ｍＳ／ｃｍより大きいことが好ましい。電導度は、３ｍＳ／ｃｍ以上であることがより好ましく、５ｍＳ／ｃｍ以上であることがさらに好ましく、１０ｍＳ／ｃｍ以上であることが最も好ましい。 [conductivity]
It is preferable that the water-based coating film peeling agent of the present invention has the above-mentioned viscosity and has an electric conductivity of more than 0.5 mS/cm. The electric conductivity is more preferably 3 mS/cm or more, further preferably 5 mS/cm or more, and most preferably 10 mS/cm or more.
　本発明の水系塗膜剥離剤において、電導度を上記の範囲とする方法としては、例えば、前記の電解質を加える方法が挙げられる。 In the water-based coating film stripping agent of the present invention, examples of the method for adjusting the electric conductivity within the above range include a method of adding the above-mentioned electrolyte.
　［ラジカル種］
　本発明の水系塗膜剥離剤を電解処理した際に発生するラジカルは、特に限定されるものではない。例えば、ヒドロキシラジカル、水素ラジカル、酸素ラジカル等が挙げられる。 [Radical species]
The radicals generated when the aqueous coating film remover of the present invention is electrolytically treated are not particularly limited. For example, a hydroxyl radical, a hydrogen radical, an oxygen radical, etc. are mentioned.
　［導電性基材］
　本発明の水系塗膜剥離剤を適用する塗膜が形成された導電性基材は、電源装置からの電力の供給により電流が流れるものであれば、特に限定されるものではない。例えば、金属材、導電性樹脂材等が挙げられる。 [Conductive substrate]
The conductive base material on which the coating film to which the water-based coating film peeling agent of the present invention is applied is formed is not particularly limited as long as the electric current is supplied by the power supply from the power supply device. For example, a metal material, a conductive resin material, etc. are mentioned.
　本発明においては、特に、屋外に設置された橋、タンク等の大型構造物を形成している金属材であることが好ましい。金属材としては、特に限定されるものではない。例えば、鉄材、冷延鋼板、熱延鋼板、ステンレス、電気亜鉛めっき鋼板、溶融亜鉛めっき鋼板、亜鉛－アルミニウム合金系めっき鋼板、亜鉛－鉄合金系めっき鋼板、亜鉛－マグネシウム合金系めっき鋼板、亜鉛－アルミニウム－マグネシウム合金系めっき鋼板、アルミニウム系めっき鋼板、アルミニウム－シリコン合金系めっき鋼板、錫系めっき鋼板等が挙げられる。 In the present invention, it is particularly preferable that the metal material forms a large structure such as a bridge or a tank installed outdoors. The metal material is not particularly limited. For example, iron material, cold rolled steel sheet, hot rolled steel sheet, stainless steel, electrogalvanized steel sheet, hot dip galvanized steel sheet, zinc-aluminum alloy-based steel sheet, zinc-iron alloy-based steel sheet, zinc-magnesium alloy-based steel sheet, zinc- Examples thereof include aluminum-magnesium alloy-based plated steel sheet, aluminum-based plated steel sheet, aluminum-silicon alloy-based plated steel sheet, tin-based plated steel sheet and the like.
　また、導電性基材の形状に特に制限はなく、例えば、平面や曲面で形成されたる凹凸等を含む形状であっても、十分に対応することができる。 Also, there is no particular limitation on the shape of the conductive base material, and for example, a shape including unevenness formed by a flat surface or a curved surface can be sufficiently dealt with.
　［任意の成分］
　本発明の水系塗膜剥離剤には、本発明の主旨を逸脱しない範囲において、任意の成分が配合されていてもよい。例えば、合成樹脂、ゴム、架橋剤、架橋促進剤、酸化防止剤、紫外線防止剤、顔料、顔料分散剤、染料、滑剤、発泡剤、難燃剤、消泡剤、造膜助剤、凍結防止剤、タレ防止剤、沈降防止剤、レベリング剤、表面調整剤、可塑剤、防腐剤、防カビ剤等の通例の添加剤等が配合されていてもよい。なお、これらの任意の成分は、１種単独でも、または２種以上を組み合わせて用いてもよい。 [Arbitrary ingredients]
The water-based coating film peeling agent of the present invention may contain any component within the range not departing from the gist of the present invention. For example, synthetic resins, rubbers, cross-linking agents, cross-linking accelerators, antioxidants, UV inhibitors, pigments, pigment dispersants, dyes, lubricants, foaming agents, flame retardants, defoamers, film-forming aids, anti-freezing agents. Ordinary additives such as an anti-sagging agent, an anti-settling agent, a leveling agent, a surface conditioner, a plasticizer, an antiseptic agent and an antifungal agent may be blended. These optional components may be used alone or in combination of two or more.
　＜塗膜剥離方法＞
　本発明の塗膜剥離方法は、上記した本発明の水系塗膜剥離剤を用いて、導電性基材に形成された塗膜を剥離する方法であり、接触工程と、電解処理工程と、を含む。 <Coating film peeling method>
The coating film peeling method of the present invention is a method of peeling a coating film formed on a conductive substrate by using the above-described aqueous coating film peeling agent of the present invention, which comprises a contact step and an electrolytic treatment step. Including.
　［接触工程］
　接触工程は、導電性基材に形成された塗膜に、本発明の水系塗膜剥離剤に接触させる工程である。接触工程では、導電性基材に形成された塗膜に本発明の水系塗膜剥離剤に接触させることにより、塗膜に水系塗膜剥離剤を含浸させる。 [Contact process]
The contacting step is a step of bringing the coating film formed on the conductive base material into contact with the water-based coating film peeling agent of the present invention. In the contacting step, the coating film formed on the conductive substrate is brought into contact with the water-based coating film release agent of the present invention to impregnate the coating film with the water-based coating film release agent.
　接触の方法は、特に限定されるものではなく、導電性基材の形状等によって、適宜選択することができる。例えば、スプレー法や刷毛、ローラー等を用いて、好ましくは、剥離する塗膜全体に１０μｍ以上の厚みで水系塗膜剥離剤を塗布し、水系塗膜剥離剤による被膜を形成する方法、あるいは、水系塗膜剥離剤に、塗膜を有する導電性基材を浸漬させる方法等が挙げられる。 The contact method is not particularly limited, and can be appropriately selected depending on the shape of the conductive base material and the like. For example, using a spray method, a brush, a roller or the like, preferably, a method of applying a water-based coating film release agent with a thickness of 10 μm or more to the entire coating film to be released, and forming a film with the water-based coating film release agent, or Examples include a method of immersing a conductive base material having a coating film in a water-based coating film peeling agent.
　なお、剥離したい塗膜は、そのままの状態で接触させてもよいが、塗膜に予め欠陥部分を作製し、その後に水系塗膜剥離剤を接触させることで、塗膜に水系塗膜剥離剤を十分に含浸させることが可能となる。欠陥部分を作製する方法としては、例えば、ナイフ等で切れ目を付与する方法、レーザーによるカット、ピンによる孔あけ等が挙げられる。 The coating film to be peeled may be contacted in the state as it is, but by forming a defective portion in the coating film in advance and then contacting the aqueous coating film peeling agent with the coating film, the aqueous coating film peeling agent is applied to the coating film. Can be sufficiently impregnated. Examples of the method of producing the defective portion include a method of making a cut with a knife or the like, a laser cutting, and a hole drilling with a pin.
　また、塗膜と接触させる際の水系塗膜剥離剤の温度は、特に限定されるものではなく、例えば、常温としてもよい。なお、塗膜の剥離時間を短くしたい場合には、適当な温度に加温して用いることも可能である。 The temperature of the water-based coating film peeling agent when contacting the coating film is not particularly limited, and may be, for example, normal temperature. If the peeling time of the coating film is desired to be shortened, it is possible to heat the coating film at an appropriate temperature before use.
　塗膜を水系塗膜剥離剤に接触させる時間についても、特に限定されるものではなく、塗膜に水系塗膜剥離剤を含浸させるに十分な時間を、適宜設定すればよい。 The time for bringing the coating film into contact with the water-based coating film peeling agent is not particularly limited, and a time sufficient for impregnating the coating film with the water-based coating film peeling agent may be appropriately set.
　［電解処理工程］
　電解処理工程は、導電性基材と水系塗膜剥離剤とを通電させて電解処理を行う工程である。そして、通電により、導電性基材と塗膜との界面に、ラジカルを発生させる。 [Electrolysis process]
The electrolytic treatment step is a step in which the conductive base material and the water-based coating film peeling agent are energized to perform electrolytic treatment. Then, by energizing, radicals are generated at the interface between the conductive base material and the coating film.
　本発明の塗膜剥離方法においては、電解処理工程にて電解処理を実施した際に、ラジカルが効率よく発生する。そして、発生したラジカルにより、塗膜と基材との界面における密着領域を破壊して、塗膜の剥離を進行させる。 In the coating film peeling method of the present invention, radicals are efficiently generated when electrolytic treatment is performed in the electrolytic treatment step. Then, the generated radicals destroy the adhesion region at the interface between the coating film and the substrate, and promote the peeling of the coating film.
　導電性基材と水系塗膜剥離剤とを通電させる方法は、特に限定されるものではない。直流通電であっても、交流通電であってもよい。例えば、直流通電によって電解処理を実施する場合には、電源装置の陰極側に塗膜が形成された導電性基材を接続し、電源装置の陽極側に導電性を有する対極を接続し、水系塗膜剥離剤に対極を接触させた状態で、導電性基材と対極との間に通電することで、水系塗膜剥離剤が含浸した塗膜と導電性基材とを通電させ、ラジカルを発生させる方法が挙げられる。 The method of energizing the conductive base material and the water-based coating film peeling agent is not particularly limited. Either direct current or alternating current may be applied. For example, in the case of carrying out the electrolytic treatment by applying a direct current, the conductive base material on which the coating film is formed is connected to the cathode side of the power supply device, and the counter electrode having conductivity is connected to the anode side of the power supply device. With the counter electrode in contact with the coating film release agent, by energizing between the conductive base material and the counter electrode, the coating film impregnated with the water-based coating film release agent and the conductive base material are energized to generate radicals. The method of generating is mentioned.
　対極と導電性基材との距離は、通電可能であれば特に限定されるものではなく、例えば、剥離時間を短くしたい場合には３０ｍｍ以内であることが好ましく、さらには１０ｍｍ以内、さらには５ｍｍ以内であることが好ましい。３ｍｍ以内であることがとりわけ好ましく、１ｍｍ以内であることが最も好ましい。 The distance between the counter electrode and the conductive base material is not particularly limited as long as it can be energized. For example, when it is desired to shorten the peeling time, it is preferably 30 mm or less, further 10 mm or less, and further 5 mm. It is preferably within the range. It is particularly preferably within 3 mm, and most preferably within 1 mm.
　また、通電に用いる電源装置としては、導電性基材と水系塗膜剥離剤とを通電できるものであれば、特に限定されるものではない。市販の電源装置をそのまま使用することも可能である。 The power supply device used for energization is not particularly limited as long as it can energize the conductive base material and the water-based coating film peeling agent. It is also possible to use a commercially available power supply device as it is.
　また、印加する電圧についても特に限定されるものではない。塗膜の剥離時間を短くしたい場合には、安全性等に考慮しつつ、比較的高い電圧を印加することができる。印加する電圧は、例えば、２Ｖより大きいことが好ましく、１０～３０Ｖであることがさらに好ましく、１５～２５Ｖであることが特に好ましい。 Also, the applied voltage is not particularly limited. When it is desired to shorten the peeling time of the coating film, a relatively high voltage can be applied while considering safety and the like. The applied voltage is, for example, preferably higher than 2V, more preferably 10 to 30V, and particularly preferably 15 to 25V.
　通電する時間については、特に限定されるものではなく、塗膜を剥離するのに十分な時間を設定すればよい。作業性の観点からは、２時間以内であることが好ましく、さらには１時間以内、さらには３０分以内、さらには１０分以内であることが好ましい。３分以内であることがとりわけ好ましく、１分以内であることが最も好ましい。 The time for energizing is not particularly limited, and may be set to a time sufficient for peeling the coating film. From the viewpoint of workability, it is preferably within 2 hours, more preferably within 1 hour, further within 30 minutes, and further preferably within 10 minutes. Particularly preferably, it is within 3 minutes, and most preferably, within 1 minute.
　電解処理工程における温度は、特に限定されるものではなく、例えば、常温で実施してもよい。なお、塗膜の剥離時間を短くしたい場合には、適当な温度に加温して実施することも可能である。 The temperature in the electrolytic treatment step is not particularly limited, and may be performed at room temperature, for example. In addition, when it is desired to shorten the peeling time of the coating film, it is also possible to perform heating by heating to an appropriate temperature.
　用いる対極を形成する材料としては、特に限定されるものではないが、例えば、アルミニウムやカーボン等であれば、コスト面で有利となる。なお、対極は、水系塗膜剥離剤と接触するため、水系塗膜剥離剤に対して耐腐食性等を有する材料から形成されることが好ましい。対極の形状としても、特に限定されるものではなく、塗膜が形成されている導電性基材の形状によって、板状、棒状等、適宜選択することができる。本発明において好ましく用いることができる対極としては、例えば、白金コテ等を挙げることができる。 The material used to form the counter electrode is not particularly limited, but if it is aluminum or carbon, for example, it will be advantageous in terms of cost. Since the counter electrode comes into contact with the water-based coating film release agent, it is preferably formed of a material having corrosion resistance or the like with respect to the water-based film release agent. The shape of the counter electrode is not particularly limited, and can be appropriately selected from plate-like, rod-like, etc. depending on the shape of the conductive base material on which the coating film is formed. Examples of the counter electrode that can be preferably used in the present invention include platinum iron and the like.
　以下、実施例等によって本発明をさらに詳細に説明するが、本発明はこれらによって限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples and the like, but the present invention is not limited thereto.
　＜測定・評価方法＞
　実施例および比較例においては、調製した水系塗膜剥離剤について、以下の方法で各種測定を実施した。 <Measurement and evaluation methods>
In the examples and comparative examples, various measurements were performed on the prepared water-based coating film release agents by the following methods.
　［高せん断粘度］
　アントンパール社製、応力制御型レオメーター（型式；ＭＣＲ３０２）を用いて、以下の条件で定常流測定を実施し、測定開始１２００秒後の測定データを、高せん断粘度とした。
　　治具：５０ｍｍコーンプレート
　　ギャップ：０．０９９ｍｍ
　　せん断速度：１００ｓ－１
　　測定温度：２３℃ [High shear viscosity]
A steady flow measurement was performed under the following conditions using a stress control rheometer (model: MCR302) manufactured by Anton Paar Co., and the measurement data 1200 seconds after the start of measurement was taken as the high shear viscosity.
Jig: 50mm cone plate Gap: 0.099mm
Shear rate: 100s -1
Measurement temperature: 23 ℃
　［低せん断粘度］
　アントンパール社製、応力制御型レオメーター（型式；ＭＣＲ３０２）を用いて、以下の条件で定常流測定を実施し、測定開始１２００秒後の測定データを、低せん断粘度とした。
　　治具：５０ｍｍコーンプレート
　　ギャップ：０．０９９ｍｍ
　　せん断速度：０．１ｓ－１
　　測定温度：２３℃ [Low shear viscosity]
Using a stress control rheometer (model: MCR302) manufactured by Anton Paar, steady flow measurement was carried out under the following conditions, and the measurement data 1200 seconds after the start of measurement was taken as the low shear viscosity.
Jig: 50mm cone plate Gap: 0.099mm
Shear rate: 0.1s -1
Measurement temperature: 23 ℃
　［電導度］
　堀場製作所社製、卓上型電気伝導率計（型式：ＬＡＱＵＡ　ＤＳ－７１）を用いて、測定温度２５℃で測定を行い、測定開始１２０秒後の測定データを、電導度とした。 [conductivity]
Using a tabletop electric conductivity meter (model: LAQUA DS-71) manufactured by HORIBA, Ltd., measurement was carried out at a measurement temperature of 25° C., and the measurement data 120 seconds after the start of measurement was taken as the electric conductivity.
　＜実施例１＞
　［塗膜剥離用サンプル板の作製］
　５０ｍｍ×７０ｍｍ×０．８ｍｍのダル鋼板の全面に、白色塗膜（膜厚：約２００μｍ）を形成した。白色塗膜を形成する塗料としては、弱溶剤形変性エポキシ樹脂下塗り塗料（日本ペイント社製、商品名：ハイボン２０ファインＨＢ（ミルキーホワイト））を用いて、乾燥温度２３℃にて、乾燥期間７日以上１か月未満とした。形成した白色塗膜に、カッターナイフにて４ｍｍ間隔でカットを入れ、これを塗膜剥離用サンプル板とした。 <Example 1>
[Preparation of sample plate for coating film peeling]
A white coating film (film thickness: about 200 μm) was formed on the entire surface of a 50 mm×70 mm×0.8 mm dull steel plate. As a paint for forming a white coating film, a weak solvent type modified epoxy resin undercoat paint (manufactured by Nippon Paint Co., Ltd., trade name: Hibon 20 Fine HB (milky white)) is used at a drying temperature of 23° C. for a drying period of 7 More than one day and less than one month. The formed white coating film was cut with a cutter knife at intervals of 4 mm to obtain a sample plate for coating film peeling.
　［水系塗膜剥離剤の調製］
　イオン交換水５０ｇに、リン酸二水素カリウム１．３ｇ、ＫＥＬＺＡＮ　ＡＲ（キサンタンガム）１．８ｇを混合し、水系塗膜剥離剤を作製した。 [Preparation of water-based paint remover]
Ion-exchanged water (50 g) was mixed with potassium dihydrogen phosphate (1.3 g) and KELZAN AR (xanthan gum) (1.8 g) to prepare a water-based coating film peeling agent.
　得られた水系塗膜剥離剤の粘度は、０．１Ｓ－１における粘度（低せん断粘度）が３３５Ｐａ・ｓであり、１００Ｓ－１における粘度（高せん断粘度）が１．０Ｐａ・ｓであり、電導度は１５．１ｍＳ／ｃｍであった。 Regarding the viscosity of the obtained water-based coating film peeling agent, the viscosity at 0.1S −1 (low shear viscosity) is 335 Pa·s, and the viscosity at 100 S −1 (high shear viscosity) is 1.0 Pa·s, The electric conductivity was 15.1 mS/cm.
　［接触工程］
　得られた水系塗膜剥離剤（温度２５℃）を、塗膜剥離用サンプル板に、刷毛にて、塗膜全面を覆うように５ｍｍの厚みで塗装した。 [Contact process]
The obtained water-based paint film peeling agent (temperature: 25° C.) was applied to a paint film peeling sample plate with a brush to a thickness of 5 mm so as to cover the entire surface of the paint film.
　［電解処理工程］
　電源装置として、ユニオン電子工業社製、定電流電源装置を用いて、電源装置の－側に導電性基材を接続し、電源装置の＋側に導電性を有する対極を接続した。塗膜上の水系剥離剤に対極を接触させた状態で、導電性基材と対極との間に電圧を印加し、通電させた。対極としては、北側理化商会製、２０ｍｍ×２０ｍｍ×０．５ｍｍの白金プレートを用いて、導電性基材と対極の距離を１ｍｍにし、２０Ｖの電圧を１分間、印加した。その後、ヘラを用いて水系剥離剤と剥離した塗膜を除去した。 [Electrolysis process]
As a power supply device, a constant current power supply device manufactured by Union Electronics Co., Ltd. was used, and a conductive base material was connected to the − side of the power supply device and a conductive counter electrode was connected to the + side of the power supply device. With the counter electrode in contact with the water-based release agent on the coating film, a voltage was applied between the conductive base material and the counter electrode to energize the film. As the counter electrode, a platinum plate of 20 mm×20 mm×0.5 mm manufactured by Kita Rika Shokai was used, the distance between the conductive substrate and the counter electrode was set to 1 mm, and a voltage of 20 V was applied for 1 minute. Then, the coating film peeled from the water-based release agent was removed using a spatula.
　［剥離評価］
　白色塗膜の剥離状況について、目視にて評価を実施した。評価基準を以下に示す。◎、〇、△が合格、×が不合格である。
　　◎　：剥離面積１００％
　　〇　：剥離面積７０％以上１００％より小さい
　　△　：剥離面積３０％以上７０％より小さい
　　×　：剥離面積３０％より小さい [Peeling evaluation]
The state of peeling of the white coating film was visually evaluated. The evaluation criteria are shown below. ⊚, ○, and △ are pass, and x is fail.
◎: 100% peeled area
◯: Peeling area 70% or more and less than 100% Δ: Peeling area 30% or more and less than 70% ×: Peeling area less than 30%
　実施例１の水系塗膜剥離剤によれば、白色塗膜は十分に剥離されていた。 According to the water-based paint remover of Example 1, the white paint was sufficiently peeled off.
　＜実施例２～２４、比較例１～６＞
　表１～表４に示される配合処方に従って、実施例１で用いた水系塗膜剥離剤の調製方法と同様にして、実施例２～２４および比較例１～６で用いる水系塗膜剥離剤を調製し、調製した水系塗膜剥離剤について各種測定を実施した。測定結果を、表１～表４に示す。続いて、得られた水系塗膜剥離剤を用いて、実施例１と同様にして、接触工程と電解処理工程を実施した。 <Examples 2 to 24, Comparative Examples 1 to 6>
According to the formulation shown in Tables 1 to 4, the water-based coating film release agents used in Examples 2 to 24 and Comparative Examples 1 to 6 were prepared in the same manner as the method for preparing the water-based coating film release agent used in Example 1. Various measurements were performed on the prepared water-based coating film release agent. The measurement results are shown in Tables 1 to 4. Then, using the obtained water-based coating film remover, a contact step and an electrolytic treatment step were carried out in the same manner as in Example 1.
　実施例および比較例で用いた配合成分を、以下に示す。
　・過酸化水素（富士フイルム和光純薬社製、濃度３０％）
　・リン酸２水素カリウム（富士フイルム和光純薬社製、固形分：１００％）
　・硫酸アンモニウム（富士フイルム和光純薬社製、固形分：１００％）
　・酢酸カリウム（富士フイルム和光純薬社製（固形分：１００％）
　・ＫＥＬＺＡＮ　ＡＲ：キサンタンガム（三晶株式会社製、固形分：１００％）
　・ｓｕｐｅｒｇｅｌ　２００：グァーガム（三晶株式会社製、固形分：１００％）
　・ＨＥＣ－ＳＰ８５０：ヒドロキシエチルセルロース（ダイセルファインケム社製、固形分：１００％）
　・ＢＹＫ－４２０：変性ウレア溶液（ビックケミー・ジャパン社製、固形分：５２％）
　・Ｌ－１１：ポリエチレンオキサイド（明成化学工業社製、固形分：１００％） The ingredients used in the examples and comparative examples are shown below.
・Hydrogen peroxide (Fujifilm Wako Pure Chemical Industries, concentration 30%)
・Potassium dihydrogen phosphate (Fuji Film Wako Pure Chemical Industries, Ltd., solid content: 100%)
・Ammonium sulfate (manufactured by Fuji Film Wako Pure Chemical Industries, solid content: 100%)
・Potassium acetate (Fujifilm Wako Pure Chemical Industries, Ltd. (solid content: 100%)
KELZAN AR: xanthan gum (manufactured by Sansho Co., Ltd., solid content: 100%)
・Supergel 200: guar gum (manufactured by Sansho Co., Ltd., solid content: 100%)
HEC-SP850: Hydroxyethyl cellulose (manufactured by Daicel Finechem, solid content: 100%)
BYK-420: modified urea solution (manufactured by Big Chemie Japan, solid content: 52%)
・L-11: Polyethylene oxide (Meisei Chemical Industry Co., Ltd., solid content: 100%)
　［剥離評価］
　実施例２～２４および比較例１～６について、実施例１と同様にして、白色塗膜の剥離状況を目視にて評価した。結果を、表１～表４に示す。 [Peeling evaluation]
With respect to Examples 2 to 24 and Comparative Examples 1 to 6, the peeling condition of the white coating film was visually evaluated in the same manner as in Example 1. The results are shown in Tables 1 to 4.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009

Claims (10)

  1. 　導電性基材に形成された塗膜を電解により剥離するための水系塗膜剥離剤であって、
    　水溶性高分子化合物と、電解質と、水と、を含み、
    　０．１Ｓ－１における粘度が、２０Ｐａ・ｓ以上５０００Ｐａ・ｓ以下であり、
    　１００Ｓ－１における粘度が、０．００１Ｐａ・ｓ以上４０Ｐａ・ｓ以下である、水系塗膜剥離剤。     A water-based coating film peeling agent for electrolytically peeling a coating film formed on a conductive substrate,
    Including a water-soluble polymer compound, an electrolyte, and water,
    The viscosity at 0.1S −1 is 20 Pa·s or more and 5000 Pa·s or less,
    A water-based coating film remover having a viscosity at 100 S −1 of 0.001 Pa·s or more and 40 Pa·s or less.
  2. 　電導度が、０．５ｍＳ／ｃｍより大きい、請求項１に記載の水系塗膜剥離剤。 The water-based paint remover according to claim 1, which has an electric conductivity of more than 0.5 mS/cm.
  3. 　前記水溶性高分子化合物は、ＯＨ基、ＣＯＯＸ基、ＳＯ３Ｘ基（式中、Ｘは、水素またはカチオンを表す）、および下記（ア）～（エ）で示される窒素含有基からなる群より選択される１種以上の基を有する、請求項１または２に記載の水系塗膜剥離剤。
    Figure JPOXMLDOC01-appb-C000001
         The water-soluble polymer compound is a group consisting of an OH group, a COOX group, an SO 3 X group (in the formula, X represents hydrogen or a cation), and a nitrogen-containing group represented by the following (a) to (d). The water-based paint stripping agent according to claim 1 or 2, which has one or more groups selected from the following.
    Figure JPOXMLDOC01-appb-C000001
  4. 　前記電解質は、分子量または重量平均分子量が１０００未満である、請求項１～３いずれかに記載の水系塗膜剥離剤。 The water-based paint remover according to any one of claims 1 to 3, wherein the electrolyte has a molecular weight or a weight average molecular weight of less than 1000.
  5. 　前記導電性基材は、金属である、請求項１～４いずれかに記載の水系塗膜剥離剤。 The water-based paint remover according to any one of claims 1 to 4, wherein the conductive base material is a metal.
  6. 　導電性基材に形成された塗膜を剥離する方法であって、
    　前記塗膜を水系塗膜剥離剤に接触させる、接触工程と、
    　前記導電性基材と前記水系塗膜剥離剤とを通電させて電解処理を行う、電解処理工程と、を含み、
    　前記水系塗膜剥離剤は、水溶性高分子化合物と、電解質と、水と、を含み、
    　０．１Ｓ－１における粘度が、２０Ｐａ・ｓ以上で５０００Ｐａ・ｓ以下あり、
    　１００Ｓ－１における粘度が、０．００１Ｐａ・ｓ以上４０Ｐａ・ｓ以下である、塗膜剥離方法。     A method of peeling a coating film formed on a conductive substrate,
    A step of contacting the coating film with an aqueous coating film release agent,
    Conducting electrolytic treatment by energizing the conductive base material and the water-based coating film release agent, including an electrolytic treatment step,
    The water-based coating film release agent contains a water-soluble polymer compound, an electrolyte, and water,
    The viscosity at 0.1 S −1 is 20 Pa·s or more and 5000 Pa·s or less,
    The coating film peeling method, wherein the viscosity at 100 S −1 is 0.001 Pa·s or more and 40 Pa·s or less.
  7. 　前記水系塗膜剥離剤は、電導度が、０．５ｍＳ／ｃｍより大きい、請求項６に記載の塗膜剥離方法。 The coating film peeling method according to claim 6, wherein the water-based coating film peeling agent has an electric conductivity of more than 0.5 mS/cm.
  8. 　前記水溶性高分子化合物は、ＯＨ基、ＣＯＯＸ基、ＳＯ３Ｘ基（式中、Ｘは、水素またはカチオンを表す）、および下記（ア）～（エ）で示される窒素含有基からなる群より選択される１種以上の基を有する、請求項６または７に記載の塗膜剥離方法。
    Figure JPOXMLDOC01-appb-C000002
         The water-soluble polymer compound is a group consisting of an OH group, a COOX group, an SO 3 X group (in the formula, X represents hydrogen or a cation), and a nitrogen-containing group represented by the following (a) to (d). The coating film peeling method according to claim 6 or 7, which has one or more groups selected from the following.
    Figure JPOXMLDOC01-appb-C000002
  9. 　前記電解質は、分子量または重量平均分子量が１０００未満である、請求項６～８いずれかに記載の水系塗膜剥離方法。 The method for stripping an aqueous coating film according to any one of claims 6 to 8, wherein the electrolyte has a molecular weight or a weight average molecular weight of less than 1000.
  10. 　前記導電性基材は、金属である、請求項６～９いずれかに記載の塗膜剥離方法。 The coating film peeling method according to any one of claims 6 to 9, wherein the conductive base material is a metal.
PCT/JP2019/049314 2018-12-20 2019-12-17 Coating film remover and method for removing coating film WO2020129949A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06114842A (en) * 1992-10-02 1994-04-26 Mitsui Petrochem Ind Ltd Film removing method
JPH11209665A (en) * 1998-01-30 1999-08-03 Nippon Cb Chemical Kk Coating film release agent
JP2000044849A (en) * 1998-07-30 2000-02-15 Nisshin Oil Mills Ltd:The Paint remover containing high viscous xanthane gum
JP2015182024A (en) * 2014-03-25 2015-10-22 Ｊｆｅエンジニアリング株式会社 Peeling method of coating film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06114842A (en) * 1992-10-02 1994-04-26 Mitsui Petrochem Ind Ltd Film removing method
JPH11209665A (en) * 1998-01-30 1999-08-03 Nippon Cb Chemical Kk Coating film release agent
JP2000044849A (en) * 1998-07-30 2000-02-15 Nisshin Oil Mills Ltd:The Paint remover containing high viscous xanthane gum
JP2015182024A (en) * 2014-03-25 2015-10-22 Ｊｆｅエンジニアリング株式会社 Peeling method of coating film

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