JP6161250B2 - Graffiti remover and removal method - Google Patents

Description

  The present invention relates to a graffiti remover and a removal method capable of removing graffiti formed on a building or the like safely and easily for an operator without damaging a base material and a coating film in a lower layer.

  Conventionally, in order to remove graffiti, a method of polishing with sandpaper or a method of spraying an organic solvent such as toluene has been taken. However, the method of polishing with sandpaper not only requires a lot of labor, but also has a problem of scraping and damaging the underlying base material and coating film. The method of spraying organic solvents such as toluene is disadvantageous because organic solvents such as toluene are classified as dangerous materials under the Fire Service Act, there are many regulations in management, and they are harmful to the human body and have problems with work safety. There was a weakness. In addition, when the lower layer is a coating film, it is altered by dissolution and swelling, and when the lower layer is a base material such as a block wall or a stone or a porous coating film, there is a problem in use such as graffiti soaking.

  Patent Document 1 proposes a graffiti and scale remover that can remove graffiti and scale formed on the surface of the coating without dissolving, swelling or damaging the coating. With this remover, there is no abnormality such as dissolution and swelling of the coating film, and the graffiti can be removed cleanly. However, since this remover is mainly composed of a glycol solvent and an organopolysiloxane and does not contain water, it has high flammability. Further, since this removing agent does not consider spraying by spraying, workability is poor when the work area is large.

  In Patent Document 2, only a top coating film formed by applying a room temperature drying paint on the base coating film without removing the base coating film formed by applying the reaction curable coating composition. A film remover that can be removed has been proposed. With this remover, the top coat film can be peeled without damaging the base coat film. However, since this removing agent is mainly composed of alcohol having 2 to 3 carbon atoms, it has high flammability, and an evaporation preventing layer is required when the temperature is high. Although it has been proposed to use a spray as one method of applying the remover, since the remover contains 10 to 60% by weight of inorganic or organic fine particles, spraying by spray is difficult. When the area is large, workability is poor. Further, since this removing agent causes a certain amount of liquid dripping after application, workability on a vertical surface is poor.

JP 2004-107464 A JP 2010-285590 A

  The present invention provides a graffiti removing agent and a removal method that can remove graffiti formed on a building or the like safely and easily to an operator without damaging the underlying substrate and coating film. The task is to do.

  As a result of diligent studies to solve the above problems, the solvent is selected from the group consisting of monovalent and / or dihydric alcohol solvents having a boiling point of 100 ° C. or higher, water, silicon dioxide, organoclay, polyamide neutralized salts, and polyureas. A graffiti remover having a viscosity of 50 to 1500 mPa · s, and a method of removing the graffiti and / or unnecessary coating by spraying the remover with a spray. The present invention has been reached.

That is, the present invention relates to the following.
[1] Contains at least one viscosity modifier selected from the group consisting of monovalent and / or dihydric alcohol solvents having a boiling point of 100 ° C. or higher, water, silicon dioxide, organoclays, neutralized polyamide salts, and polyureas And a graffiti remover having a viscosity adjusted to 50 to 1500 mPa · s.
[2] From a group consisting of 50 to 98% by weight of a monovalent or / and divalent alcohol solvent having a boiling point of 100 ° C. or higher, 1 to 40% by weight of water, silicon dioxide, organoclay, neutralized polyamide salt and polyurea The graffiti removing agent according to [1], comprising 0.2% to 10% (solid content) by weight of at least one viscosity modifier selected.
[3] The graffiti remover according to [1] or [2], containing 0.05% to 2% (solid content) by weight of a substrate wetting agent and / or surfactant.
[4] The graffiti remover according to [3], wherein the substrate wetting agent is a polyether-modified siloxane-based substrate wetting agent.
[5] The graffiti remover according to any one of [1] to [4] is spray-applied so as to have an amount of 10 to 300 g / m ² by spraying, left for 20 seconds to 30 minutes, and then wiped with a cloth or the like. Alternatively, a method of removing graffiti or / and unnecessary coating by washing with water or / and brush.

  According to the present invention, the graffiti formed on the building or the like is safe to the operator without damaging the underlying base material and the coating film, and further without soaking the graffiti and dirt into the ground, and Graffiti removers and removal methods that can be easily removed can be provided.

The present invention will be specifically described below.
The graffiti remover and the removal method of the present invention damage graffiti or / and unnecessary paint films formed on buildings, concrete structures, road signs, guardrails, railway facilities, etc. to the underlying substrate and paint film. And a graffiti remover and a removal method that can be easily removed without causing graffiti and dirt to penetrate into the ground. Examples of the base material include concrete, natural stone, artificial stone, brick, tile, ceramics, glass, metal, plastic, and the like, and many of them are painted with a paint for protecting the base material or aesthetics.

  Graffiti must be formed with room temperature dry paint such as acrylic lacquer, nitrocellulose lacquer, non-aqueous dispersion type room temperature dry paint, water soluble lacquer, water dispersion (emulsion) type room temperature dry paint, synthetic resin blend paint, marking pen, etc. These graffiti are also targeted in the present invention. In addition, the present invention can also be used for graffiti or / and unnecessary coating films other than these paints.

  The monovalent and / or dihydric alcohol solvent having a boiling point of 100 ° C. or higher in the graffiti removing agent of the present invention is blended because it easily wets the graffiti coating and has an action of swelling it. Examples of the monohydric alcohol solvent include aliphatic alcohols such as butyl alcohol, octyl alcohol and 2-ethylhexyl alcohol, and aromatic alcohols such as benzyl alcohol, 4-methylbenzyl alcohol, 2-ethylbenzyl alcohol and phenethyl alcohol. The dihydric alcohol solvent is selected from the group of mono-, di-, or triethylene glycol, and their methyl, ethyl, propyl, and butyl ethers (where mono ether is a monohydric alcohol). Specifically, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoamyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol Monobenzyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethyl Glycol monohexyl ether, diethylene glycol monobenzyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, trimethylene glycol, triethylene glycol, triethylene glycol Monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetramethylene glycol, tetraethylene glycol, pentamethylene glycol, hexylene glycol, 1,2-butylene glycol, 1,3-butylene glycol Lumpur like. At least one of these is included, but two or more may be used in combination. When using 2 or more types together, the mixed solvent used together needs to have a boiling point of 100 ° C. or more.

  The monovalent and / or dihydric alcohol solvent having a boiling point of 100 ° C. or higher is blended in an amount of 50 to 98% by weight based on the whole graffiti remover. Preferably it is 60 to 95 weight%, More preferably, it is 70 to 90 weight%. From the viewpoint of graffiti removability, 50% by weight or more is preferable, and from the viewpoint of flammability, 98% by weight or less is preferable. When the boiling point is less than 100 ° C., the vapor pressure is high even at room temperature, and the risk of ignition increases. Further, it easily evaporates before penetrating the graffiti coating, and the removal efficiency is significantly reduced. From the viewpoints of safety and workability, the boiling point is more preferably 150 ° C. or higher in the present invention.

  Water in the graffiti remover of the present invention is blended to reduce flammability. Tap water, distilled water, ion exchange water, pure water, etc. may be used.

  Water is blended in an amount of 1 to 40% by weight based on the total graffiti remover. Preferably it is 3-30 weight%, More preferably, it is 5-20 weight%. 1% by weight or more is preferable from the viewpoint of flammability, and 40% by weight or less is preferable from the viewpoint of graffiti removal.

  The viscosity modifier in the graffiti remover of the present invention is blended to impart thixotropic properties. By imparting thixotropy, sprayed graffiti remover does not sag even on graffiti formed on a vertical surface, so removal work can be performed efficiently. As the viscosity modifier, at least one selected from the group consisting of silicon dioxide, organoclay, polyamide neutralized salt, and polyurea viscosity modifier can be used.

As a silicon dioxide-based viscosity modifier, fine particle silica is easily available and easily dispersible, so that it is far superior to other inorganic viscosity modifiers. The fine particle silica may be either a natural product or a synthetic product, but a synthetic silica which is more excellent in dispersibility in a highly polar organic solvent is preferable. In addition, there is no problem with any of the production methods such as a dry method obtained by a gas phase reaction and precipitated silica obtained by a wet method, but the fine particle silica of the dry method has a smaller particle size and is a highly polar organic solvent. It is further preferred because it is excellent in dispersibility in the medium and viscosity adjustment is easy. As a standard for selecting fine-particle silica, an average particle diameter of 10 μm or less and a specific surface area of 100 to 400 m ² / g are preferable. Specific examples of commercially available products include Nipsil E200A, Nipsil E220A of Tosoh Silica Co., Ltd., Silisia 310P of Fuji Silysia Chemical Co., Ltd. Toroyama Co., Ltd. Leoro Seal QS-09, Leoro Seal QS-10, Leoro Seal QS-10L, Leoro Seal QS-102, Leoro Seal QS-20, Leoro Seal QS-20A, Leolo Seal QS-20L, Leoro Seal QS-30, Leolo Seal QS-40, Leolo Seal CP-102, Mizukasil NP-8, Mizukasil P-801, Mizukasil P-802, Mizukas from Mizusawa Chemical Co., Ltd. l P-526, Mizukasil P-802Y, include Mizukasil P-707 and the like.

  As organoclays, clay minerals such as chain minerals such as natural minerals montmorillonite (bentonite), hectorite, saponite, layered clay minerals, sepiolite, and long fibrous clay minerals such as palygorskite, which are classified as smectites. Organic treatments can be mentioned. The organic treatment is generally performed using an alkyl quaternary ammonium compound, and the dispersibility of the obtained organoclay is enhanced by hydrophobizing the surface of the clay mineral. More preferable as a viscosity modifier in terms of dispersibility and viscosity expression is US Pat. No. 6,036,765 obtained by organic treatment of sepiolite or a combination of clay minerals having different crystal structures such as palygorskite and smectite. The organoclay described. Product examples of the viscosity modifier include BENTONE LT, BENAQUA 4000 (Elementis Specialties), Optigel CK, Optigel LX, Garamite 1958 (Rockwood Additives) and the like.

  Polyamide neutralized salt-based viscosity modifier is obtained by neutralizing a polyamide obtained by reacting a carboxylic acid and a diamine with a base compound. Generally, dimer acid (fatty acid dimer) and primary are used. A salt of a compound obtained by a reaction of an amine with a diamine compound is applicable, and preferably an anti-settling agent for water-based paints disclosed in JP-A-10-310726. More preferably, the neutralizing agent is an amine compound. Specific examples of commercially available products include ASA TW121, ASA TW-122, ASA TW-123, ASA TW-124, Enomoto Kasei Co., Ltd. DISPARON AQ-580, DISPARON AQ-600, DISPARON AQ-607, DISPARON AQ-610, DISPARON AQ-630, DISPARON AQ-870, DISPARON AQH-800, etc. are listed.

  The polyurea viscosity modifier is a viscosity modifier obtained by reaction of a monoisocyanate or diisocyanate compound with a primary or secondary polyamine, and is present as 0.01 to 50 μm particles in the solution of the present invention. Specific examples of commercially available products include BYK-410, BYK-411, BYK-420, BYK-425, and BYK-428 manufactured by Big Chemie.

  The viscosity modifier is blended in an amount of 0.2 to 10 (solid content) weight% of the entire graffiti remover. Preferably it is 0.5-9 (solid content) weight%, More preferably, it is 1-8 (solid content) weight%. From the viewpoint of thixotropic properties, 0.2 (solid content) or more is preferable, and from the viewpoint of sprayability by spraying, 10 (solid content) or less is preferable. Moreover, in this invention, a viscosity needs to be adjusted to 50-1500 mPa * s, Preferably it is 80-1000 mPa * s, More preferably, it is 100-500 mPa * s. If it is less than 50 mPa · s, it will easily drip when applied, and it will be difficult to soak into the graffiti coating, making it impossible to obtain a sufficient effect. If it exceeds 1500 mPa · s, spray coating becomes extremely difficult. The viscosity in the present invention is a value obtained by measurement at 60 rpm (25 ° C.) with a B-type viscometer.

  In the graffiti remover of the present invention, other aqueous viscosity modifiers, for example, cellulose viscosity modifiers, polycarboxylic acid viscosity modifiers, and urethane-associative viscosity modifiers may be blended. When the ratio is high, in the case of a cellulose-based viscosity modifier, separation and precipitation may occur during storage, and the polycarboxylic acid-based viscosity modifier and the urethane-associated viscosity modifier may have poor viscosity development.

  In the graffiti remover of the present invention, a substrate wetting agent may be blended. The base material wetting agent functions to increase the wettability of the graffiti remover to the base material and improve the graffiti removal property. As the substrate wetting agent, any of a nonionic surfactant and an anionic surfactant can be used, but a nonionic surfactant having little influence on a metal material or the like is preferable. Nonionic surfactants include higher alcohol ether surfactants such as polyoxyethylene alkyl ether, styrenated phenol surfactants such as polyoxyethylene styrenated phenyl ether, sorbitan fatty acid esters, polyoxyethylene olein. Examples include ether / ester surfactants such as acid esters and polyoxyethylene polyoxypropylene block polymers. 8-16 is preferable for HLB (Hydrophile-Lipophile Balance) of these surfactants.

  In addition, substrate wetting agents such as acetylene diol-based substrate wetting agents, acetylene-modified siloxane-based substrate wetting agents, polyether-modified siloxane-based wetting agents, fluorine-containing substrate wetting agents and the like can also be suitably used. Specific product names of acetylenic diol base wetting agents include Surfynol 104, Surfynol 504, Surfynol MD-20, Surfynol DF-110D, TEGO Wet520 manufactured by Evonik Degussa, manufactured by Air Products. Specific product names of acetylene-modified siloxane-based wetting agents include Surfynol DF-66 manufactured by Air Products, polyether-modified siloxane-based and fluorine-containing substrate wetting agents, and Big Chemie BYK-307, BYK-345, BYK-346, BYK-348, BYK-3455, manufactured by the company, TEGO Wet250, TEGO Wet260, TEGO Wet280, TEGO Twin4000, TEGO Twin4100, manufactured by Evonik Degussa Company Chemical POLYFLOW KL-100 Co., Ltd., Polyflow KL-600, include POLYFLOW KL-700 and the like. Among the above-mentioned substrate wetting agents, polyether-modified siloxane-based substrate wetting agents are suitable from the viewpoint of improving the wettability of the graffiti remover of the present invention to the substrate.

  The base material wetting agent or / and the surfactant is blended in an amount of 0.05 to 2 (solid content) wt% of the entire graffiti removing agent. Preferably it is 0.08-1.5 (solid content) weight%, More preferably, it is 0.1-1 (solid content) weight%. From the viewpoint of substrate wettability, 0.05 (solid content) weight% or more is preferable, and 2 (solid content) weight% or less is preferable.

  Furthermore, various additives such as rust preventives, antioxidants, ultraviolet absorbers, colorants, fragrances and the like may be appropriately added to the graffiti remover in the present invention as necessary.

  The graffiti remover of the present invention is a combination of the above-mentioned components, but each component used has relatively low volatility, so there is little composition fluctuation and stable and good graffiti removal effect is exhibited. it can. Moreover, since the graffiti removing agent of the present invention does not contain a component that has a great influence on the human body, it is safe for work.

The graffiti remover of the present invention is spray-applied on an object such as graffiti by spraying so that the amount of the graffiti remover is 10 to 300 g / m ² , left for 20 seconds to 30 minutes, and then wiped with a cloth or / and washed with water or A method of removing graffiti or unnecessary coating by brush cleaning is preferred. Here, spray is an aerosol spray that is sprayed using a compressed gas such as a trigger spray that is used for application of detergents, a manual sprayer that is used for spraying chemicals, or a spray-type lacquer spray. If spray coating is possible, it can be used without problems. The trigger spray ejects the liquid in the container by pulling the trigger lever, and is commercially available at a relatively low cost.

The graffiti remover of the present invention can also be applied by a method other than spraying, and examples thereof include a method such as application with a brush / roller or soaking in a sponge or the like. However, in any method other than spraying, there is no problem when the area is small, but it is not preferable in terms of work efficiency when work in a large area or limited time is unavoidable. The graffiti remover of the present invention is most suitable for use in a general household by a commercially available trigger spray method, and is spray applied so that the amount is 10 to 300 g / m ² , preferably 50 to 200 g / m ^2. However, after spraying, the liquid is not dripped, and after being left for 20 seconds to 30 minutes, graffiti or the like can be easily removed by wiping with a cloth or the like and / or washing with water and / or brush. As a method for removing graffiti on a porous surface, the most efficient removal method is washing with high-pressure water after applying the graffiti remover.

  Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

[Example 1]
Diethylene glycol monobutyl ether (trade name: Buticenol 20, manufactured by Kyowa Hakko Chemical Co., Ltd., boiling point 230 ° C.) 82.2 parts, 10.0 parts of tap water, fine particle silica (trade name: Leolosil QS-102, manufactured by Tokuyama Corporation, solid A removal agent A was prepared by mixing and stirring 6.8 parts of a rust inhibitor (trade name: Thiolite C-560R13, manufactured by Chiyoda Chemical Co., Ltd.). The viscosity at 25 ° C. was 900 mPa · s. Viscosity was measured using VISCOMETER TV-20 (manufactured by Toki Sangyo Co., Ltd.) with an H3 rotor at 60 rpm for 1 minute.

[Example 2]
A remover B was prepared by mixing and stirring 0.5 parts of a surfactant (trade name: Ricanon UA-5012, manufactured by Shin Nippon Rika Co., Ltd.) with the remover A of Example 1. The viscosity at 25 ° C. was 800 mPa · s.

[Example 3]
The removing agent A of Example 1 was mixed and stirred with 0.5 part of a polyether-modified siloxane-based substrate wetting agent (trade name: TEGO Wet280, manufactured by Evonik Degussa) to prepare a removing agent C. The viscosity at 25 ° C. was 800 mPa · s.

[Example 4]
Diethylene glycol monobutyl ether (trade name: Buticenol 20, Kyowa Hakko Chemical Co., Ltd., boiling point 230 ° C.) 81.0 parts, tap water 8.0 parts, polyamide amine salt (trade name: Disparon AQ-600, Enomoto Kasei Co., Ltd. Manufactured, solid content 20%) 10.0 parts, polyether-modified siloxane-based substrate wetting agent (trade name: TEGO Twin 4100, manufactured by Evonik Degussa) 0.5 part, rust preventive (trade name: Thiolite C-560R13 , Manufactured by Chiyoda Chemical Co., Ltd.) was mixed and stirred to prepare remover D. The viscosity at 25 ° C. was 250 mPa · s.

[Example 5]
Diethylene glycol monobutyl ether (trade name: Buticenol 20, Kyowa Hakko Chemical Co., Ltd., boiling point 230 ° C.) 81.0 parts, tap water 8.0 parts, polyamide amine salt (trade name: Disparon AQ-600, Enomoto Kasei Co., Ltd. Manufactured, solid content 20%) 10.0 parts, surfactant (trade name: Ricanon UA-5012, manufactured by Shin Nippon Rika Co., Ltd.) 0.5 part, rust preventive (trade name: Thiolite C-560R13, Chiyoda Chemical) (Product made from Co., Ltd.) 0.5 part was mixed and stirred, and the removal agent E was produced. The viscosity at 25 ° C. was 250 mPa · s.

[Example 6]
Diethylene glycol monobutyl ether (trade name: Buticenol 20, manufactured by Kyowa Hakko Chemical Co., Ltd., boiling point 230 ° C.) 67.0 parts, 20.0 parts of tap water, fine particle silica (trade name: Leolosil QS-102, manufactured by Tokuyama Corporation, solid 4.0 parts, polyamidoamine salt (trade name: Disparon AQ-600, manufactured by Enomoto Kasei Co., Ltd., solid content 20%) 8.0 parts, surfactant (trade name: Neugen TDS-100, A remover F was prepared by mixing and stirring 0.5 parts of Daiichi Kogyo Seiyaku Co., Ltd.) and 0.5 parts of a rust inhibitor (trade name: Thiolite C-560R13, manufactured by Chiyoda Chemical Co., Ltd.). The viscosity at 25 ° C. was 500 mPa · s.

[Example 7]
Diethylene glycol monobutyl ether (trade name: Buticenol 20, manufactured by Kyowa Hakko Chemical Co., Ltd., boiling point 230 ° C.) 67.0 parts, 20.0 parts of tap water, fine particle silica (trade name: Leolosil QS-102, manufactured by Tokuyama Corporation, solid 4.0 parts), polyamide amine salt (trade name: Disparon AQ-600, manufactured by Enomoto Kasei Co., Ltd., solid content 20%) 8.0 parts, polyether-modified siloxane-based wetting agent (trade name) : TEGO Twin 4100, manufactured by Evonik Degussa Co., Ltd.) 0.5 parts, and a rust inhibitor (trade name: Thiolite C-560R13, manufactured by Chiyoda Chemical Co., Ltd.) 0.5 parts were mixed and stirred to prepare remover G. The viscosity at 25 ° C. was 500 mPa · s.

[Example 8]
Diethylene glycol monobutyl ether (trade name: Butisenol 20, Kyowa Hakko Chemical Co., Ltd., boiling point 230 ° C.) 82.2 parts, tap water 11.8 parts, organoclay (trade name: Garamite 1958, Rockwood Additives Ltd., solid content 100 parts) 5.0 parts, surfactant (trade name: Ricanon UA-5012, manufactured by Shin Nippon Rika Co., Ltd.) 0.5 part, rust preventive (trade name: Thiolite C-560R13, manufactured by Chiyoda Chemical Co., Ltd.) Remover H was prepared by mixing and stirring 0.5 parts. The viscosity at 25 ° C. was 950 mPa · s.

[Example 9]
Diethylene glycol monobutyl ether (trade name: Butisenol 20, Kyowa Hakko Chemical Co., Ltd., boiling point 230 ° C.) 82.2 parts, tap water 11.8 parts, organoclay (trade name: Garamite 1958, Rockwood Additives Ltd., solid content 100 parts) 5.0 parts, polyether-modified siloxane base wetting agent (trade name: TEGO Twin4100, manufactured by Evonik Degussa) 0.5 part, rust inhibitor (trade name: Thiolite C-560R13, Chiyoda Chemical Co., Ltd.) A remover I was prepared by mixing and stirring 0.5 part of the product. The viscosity at 25 ° C. was 950 mPa · s.

[Example 10]
Diethylene glycol monobutyl ether (trade name: Butisenol 20, Kyowa Hakko Chemical Co., Ltd., boiling point 230 ° C.) 82.2 parts, tap water 11.8 parts, organoclay (trade name: Garamite 1958, Rockwood Additives Ltd., solid content 100 parts) 5.0 parts, polyether-modified siloxane base wetting agent (trade name: BYK-307, manufactured by Big Chemie) 0.5 part, rust inhibitor (trade name: Thiolite C-560R13, Chiyoda Chemical Co., Ltd.) (Product made) 0.5 part was mixed and stirred, and the removal agent J was produced. The viscosity at 25 ° C. was 950 mPa · s.

[Example 11]
Diethylene glycol monobutyl ether (Brand name: Buticenol 20, Kyowa Hakko Chemical Co., Ltd., boiling point 230 ° C.) 50.0 parts, 39.0 parts tap water, Polyamide amine salt (Brand name: Disparon AQ-600, Enomoto Kasei Co., Ltd.) Manufactured, solid content 20%) 10.0 parts, surfactant (trade name: Ricanon UA-5012, manufactured by Shin Nippon Rika Co., Ltd.) 0.5 part, rust preventive (trade name: Thiolite C-560R13, Chiyoda Chemical) (Made by Co., Ltd.) 0.5 parts was mixed and stirred to prepare remover K. The viscosity at 25 ° C. was 350 mPa · s.

[Comparative Example 1]
Isopropyl alcohol (trade name: IPA, manufactured by Ando Parachemy Co., Ltd., boiling point 82 ° C.) 80.0 parts, 10.0 parts of tap water, polyamide amine salt (trade name: Disparon AQ-600, manufactured by Enomoto Kasei Co., Ltd., solid Min. 20%) 10.0 parts, 0.5 parts surfactant (trade name: Ricanon UA-5012, manufactured by Shin Nippon Chemical Co., Ltd.), rust inhibitor (trade name: Thiolite C-560R13, manufactured by Chiyoda Chemical Co., Ltd.) ) 0.5 part was mixed and stirred to prepare remover L. The viscosity at 25 ° C. was 200 mPa · s.

[Comparative Example 2]
Diethylene glycol monobutyl ether (trade name: Butisenol 20, Kyowa Hakko Chemical Co., Ltd., boiling point 230 ° C.) 80.0 parts, 9.0 parts of tap water, polyacryl emulsion viscosity modifier (trade name: Primal ASE-60, Dow -Corning (formerly Rohm & Haas), solid content 28% 10.0 parts, surfactant (trade name: Ricanon UA-5012, Shin Nippon Rika Co., Ltd.) 0.5 part, rust inhibitor (product) Name: Thiolite C-560R13, manufactured by Chiyoda Chemical Co., Ltd.) 0.5 parts was mixed and stirred to prepare remover M. The viscosity at 25 ° C. was 30 mPa · s.

[Comparative Example 3]
Diethylene glycol monobutyl ether (trade name: Buticenol 20, manufactured by Kyowa Hakko Chemical Co., Ltd., boiling point 230 ° C.) 70.0 parts, 7.0 parts of tap water, fine particle silica (trade name: Leolosil QS-102, manufactured by Tokuyama Corporation, solid Min. 100%) 8.0 parts, Polyamide amine salt (trade name: Disparon AQ-600, manufactured by Enomoto Kasei Co., Ltd., solid content 20%) 15.0 parts, surfactant (trade name: Ricanon UA-5012, Remover N was prepared by mixing and stirring 0.5 parts of Shin Nippon Rika Co., Ltd.) and 0.5 parts of a rust inhibitor (trade name: Thiolite C-560R13, manufactured by Chiyoda Chemical Co., Ltd.). The viscosity at 25 ° C. was 2000 mPa · s.

[Comparative Example 4]
70.0 parts of diethylene glycol monobutyl ether (trade name: butisenol 20, manufactured by Kyowa Hakko Chemical Co., Ltd., boiling point 230 ° C.), 10.0 parts of tap water, 3% hexylethylcellulose solution (trade name: HEC AW-15F, Sumitomo Seiki) 20.0 parts dissolved in tap water to make 3% aqueous solution), 0.5 parts surfactant (trade name: Ricanon UA-5012, manufactured by Shin Nippon Rika Co., Ltd.), rust inhibitor (Product name: Thiolite C-560R13, manufactured by Chiyoda Chemical Co., Ltd.) 0.5 parts was mixed and stirred to prepare remover O. The viscosity at 25 ° C. was 60 mPa · s.

[Comparative Example 5]
Diethylene glycol monobutyl ether (trade name: Buticenol 20, manufactured by Kyowa Hakko Chemical Co., Ltd., boiling point 230 ° C.) 70.0 parts, 10.0 parts of tap water, fatty acid polyamide (trade name: Tikuzol W-300, manufactured by Kyoeisha Chemical Co., Ltd., Solid content 25%) 20.0 parts, polyether-modified siloxane-based wetting agent (trade name: TEGO Twin 4100, manufactured by Evonik Degussa) 0.5 part, rust preventive (trade name: Thiolite C-560R13, Chiyoda A remover P was prepared by mixing and stirring 0.5 parts of Chemical Co., Ltd.). The viscosity at 25 ° C. was 70 mPa · s.
Table 1 shows the components, viscosity, and stability (appearance) of the above removers AP.

<Stability appearance evaluation>
Appearance change over time (after 1 day) was evaluated. The evaluation criteria are as follows. A: No change. X: Aggregation sedimentation of a viscosity modifier etc. is seen.

The blending components are as follows.
Monovalent or / and dihydric alcohol solvent 1: Diethylene glycol monobutyl ether (trade name: Buticenol 20, manufactured by Kyowa Hakko Chemical Co., Ltd., boiling point 230 ° C.)
Monovalent or / and dihydric alcohol solvent 2: isopropyl alcohol (trade name: IPA, manufactured by Ando Parachemy Corporation, boiling point 82 ° C.)
Viscosity modifier 1: fine particle silica (trade name: Leolosil QS-102, manufactured by Tokuyama Corporation, solid content 100%)
Viscosity modifier 2: Polyamide amine salt (trade name: Disparon AQ-600, manufactured by Enomoto Kasei Co., Ltd., solid content 20%)
Viscosity modifier 3: Organoclay (trade name: Garamite 1958, manufactured by Rockwood Additives Ltd., solid content 100%)
Viscosity modifier 4: Polyacryl emulsion viscosity modifier (trade name: Primal ASE-60, manufactured by Dow Corning (formerly Rohm & Haas), solid content 28%)
Viscosity modifier 5: 3% hexylethylcellulose solution (trade name: HEC AW-15F, manufactured by Sumitomo Seika Co., Ltd. dissolved in tap water to make a 3% aqueous solution)
Viscosity modifier 6: Fatty acid polyamide (trade name: Chixol W-300, manufactured by Kyoeisha Chemical Co., Ltd., solid content 25%)
Surfactant 1: Product name: Ricanon UA-5012, manufactured by Shin Nippon Rika Co., Ltd. Surfactant 2: Product name: Neugen TDS-100, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Base material wetting agent 1: Polyether-modified siloxane Base material wetting agent (trade name: TEGO Wet280, manufactured by Evonik Degussa)
Base material wetting agent 2: Polyether-modified siloxane base material wetting agent (trade name: TEGO Twin 4100, manufactured by Evonik Degussa)
Base material wetting agent 3: Polyether-modified siloxane base material wetting agent (trade name: BYK-307, manufactured by Big Chemie)
Rust inhibitor: Brand name: Thiolite C-560R13, manufactured by Chiyoda Chemical Co., Ltd.

The removal agent was evaluated as follows, and the results are shown in Table 2.
<Drip sag resistance evaluation>
The remover was applied to the tin plate with a 300 μm and 200 μm gap thickness blade, and the plate was quickly stood vertically and evaluated for sag after 5 minutes. The evaluation criteria are as follows. A: No sagging even at 300 μm. ○: Slight sagging at 300 μm, but no sagging at 200 μm. Δ: Slight sagging is observed at 200 μm. X: Overall sagging is observed at 200 μm.

<Evaluation of sprayability>
The removal agent was sprayed onto the vertical surface of the concrete block by a trigger spray (trade name: Canyon Spray CHS-3AN, manufactured by Canyon Co., Ltd.), and the suitability was evaluated. The evaluation criteria for dischargeability are as follows. A: Discharge without any problem. ○: A small amount of material to be discharged. Δ: Discharge does not occur after a while. X: Not discharged at all. Moreover, the evaluation criteria of atomization property are as follows. A: Atomized without any problem. ○: A small amount of atomized material. X: It does not atomize at all.

<Graffiti removal evaluation 1>
Lacquer spray (trade name: Camper Lacquer Spray A (red), manufactured by Campehapio Co., Ltd.) was applied to the tin plate and dried for 24 hours. Stand this object so that the coated surface is vertical, apply 100 g / m ² of remover to the coated surface by trigger spray, leave it at room temperature for 30 seconds, wipe it off with a cotton cloth, and remove the coating film. Visually evaluated. The evaluation criteria are as follows. A: Complete removal. ○: Almost removed, but slightly disappeared. Δ: A portion is not removed and remains. X: Almost no removal

<Graffiti removal evaluation 2>
A lacquer spray (trade name: Camper Lacquer Spray A (red), manufactured by Campehapio Co., Ltd.) was applied to a slate plate coated with a building exterior paint and dried for 24 hours. Stand this object so that the coated surface is vertical, apply 200 g / m ² of remover to the coated surface by trigger spray, leave it at room temperature for 2 minutes, wipe it off with a cotton cloth, and remove the coating film. Visually evaluated. The evaluation criteria are as follows. A: Complete removal. ○: Almost removed, but slightly disappeared. Δ: A portion is not removed and remains. X: Almost no removal At the same time, the influence on the ground was visually evaluated. The evaluation criteria are as follows. A: No effect. X: Elution or peeling of the coating film is observed.

<Graffiti removal evaluation 3>
Apply lacquer spray (trade name: lacquer spray (black, blue, silver, yellow, red), made by Konan Shoji Co., Ltd.) to concrete blocks and leave it outdoors for 40 days. I let you. Stand this object so that the coated surface is vertical, apply 300 g / m ² of remover to the coated surface by trigger spray, leave it at room temperature for 5 minutes, 10 minutes, and 20 minutes. Wipe with a waste cloth and a high pressure washer made by Karcher (ordinary discharge pressure 6 MPa, normal discharge water amount 280 L / h) were subjected to high pressure water washing for about 1 minute, and the removability of the coating film was visually evaluated. The evaluation criteria are as follows. A: Complete removal. ○: Almost removed, but slightly disappeared. Δ: A portion is not removed and remains. X: Almost no removal

  The examples of the present invention were excellent in sag resistance, could be sprayed by spraying, could completely remove the lacquer spray coating assuming graffiti, and had no effect on the underlying coating. Comparative Example 3 could not be sprayed with a spray, and Comparative Example 1 was remarkably inferior in penetrability / removability to the graffiti coating and had an effect on the underlying coating. In Comparative Examples 2, 4 and 5, sufficient viscosity was not obtained, so that the liquid was easily dripped and the graffiti removal property was inferior.

  According to the graffiti remover and the removal method of the present invention, a graffiti formed on a building made of concrete, natural stone, artificial stone, brick, tile, ceramics, glass, metal, plastic, etc. It is safe for the operator and can be easily removed without damaging the substrate and the coating film.

Claims (5)

Contains a glycol ether solvent having a hydroxyl group with a boiling point of 100 ° C. or higher, water, and at least one viscosity modifier selected from the group consisting of silicon dioxide, organoclay, neutralized polyamide and polyurea, and has a viscosity of 50 to 50 Graffiti remover containing no chlorinated alkane adjusted to 1500 mPa · s. Glycol ether solvent having a hydroxyl group with a boiling point of 100 ° C. or higher 50 to 98% by weight, water 1 to 40% by weight, and at least one viscosity selected from the group consisting of silicon dioxide, organoclay, neutralized polyamide and polyurea The graffiti remover according to claim 1, comprising 0.2% to 10% (solid content) by weight of a modifier.   The graffiti remover according to claim 1 or 2, comprising 0.05 to 2 (solid content) wt% of a substrate wetting agent or / and a surfactant.   4. The graffiti remover according to claim 3, wherein the base material wetting agent is a polyether-modified siloxane base material wetting agent. The graffiti remover according to any one of claims 1 to 4 is spray-applied so as to have an amount of 10 to 300 g / m ² by spraying, left for 20 seconds to 30 minutes, and then wiped with a cloth or / and washed with water or A method of removing graffiti or / and unnecessary coating by brush cleaning.