JP3786116B2 - Paste graffiti / dirt remover - Google Patents

Description

  This invention is used in public toilets, street poles and other utility poles and buildings, as well as annoying graffiti with paint and magic ink in spray cans, stubborn stains due to tar and paint mist on automobile painted surfaces, leather products such as sofas, etc. Paste graffiti that can effectively remove stains from magic ink, crayons, lipstick, etc. on furniture, furniture and plastic products, stains from chewing gum on the road, etc., and stains from starch and protein adhesives (glue) It relates to a dirt remover.

The graffiti of paints with spray cans (lacquer enamel paint) can be removed by wiping the cloth several times with a mixture of organic solvents and wiped several times. I can't.
On the other hand, in automobiles and leather products, paraffin wax is mixed with various organic solvents, silicon abrasives, etc., and the ointment is removed by a method of wiping it on a cloth. In this case, the role of the wax is to suppress the evaporation of the organic solvent, thereby creating a time for the organic solvent to swell or dissolve the soil substance, thereby contributing to the soil removal. After removing the dirt, a protective film is formed with wax, but it is not effective for removing graffiti with spray can paint.

  In addition, as shown in Patent Document 1, in order to remove graffiti due to paint, a composition containing an organic solvent such as N-methyl-2-pyrrolidone is sprayed on with a spray or the like, and after a short time has elapsed after application. A method of rinsing with water using a sponge or the like (column [0003], right column, page 2) has been proposed.

JP-A-5-5070

Annoying graffiti is written everywhere, and its bases range from coatings, metals, plastics, wood, concrete and block surfaces. Only the graffiti must be removed without damaging these substrates.
More graffiti uses acrylic lacquer enamel paint, which can be dissolved and removed with organic solvents, but if the graffiti is written in public or in a small room, it is flammable. An organic solvent, which is a big danger, cannot be used as it is.

  Therefore, the present invention provides a new form of paste-like graffiti / dirt remover as a product that can remove graffiti safely and environmentally friendly, without damaging the graffiti base and removing graffiti completely. It was made for the purpose of doing.

  As a result of intensive research, the present inventor mixed a powder of a trifluorinated polyurethane resin composition produced according to the production method described in JP-B-2-52942 with a silicone oil having a dimethylpolysiloxane structure and dried. By doing so, the powder surface of the trifluorinated polyurethane resin composition can be modified, and the paste-like product obtained by blending this surface-modified powder with a mixed solvent of various organic solvents is used to remove graffiti and dirt. The present invention has been completed by finding out that it can be effectively used as an agent.

  That is, the pasty graffiti / stain remover according to the present invention is a polymerized fatty acid polyamide resin soluble in an organic solvent obtained by the reaction of a polymerized fatty acid and polyamines, and has a hydroxyl group in the molecular structure and is soluble in an organic solvent. And a reaction cured product obtained by reacting these polymerized fatty acid polyamide resin and polyisocyanate soluble in an organic solvent functioning as a curing agent for the fluororesin in an organic solvent inert to isocyanate groups. 1 to 6 parts by mass of a silicone oil having a dimethylpolysiloxane structure is mixed with 100 parts by mass of the powder of the trifluorinated polyurethane resin composition obtained by pulverizing the powder, and this mixture is dried to obtain three The surface modified powder of the fluoropolyurethane resin composition is mixed with an alcohol solvent, a ketone solvent, an ester solvent, a polyvalent alcohol. And it is characterized in that by blending in a mixed organic solvent of call ether solvent and hydrocarbon solvent.

  A preferable blending ratio of the surface modified powder of the trifluorinated polyurethane resin composition and the mixed organic solvent is 50 to 90 parts by mass of the mixed organic solvent with respect to 40 parts by mass of the surface modified powder of the trifluorinated polyurethane resin composition. The range. By setting the blending ratio in such a range, excellent paste forming properties and graffiti / stain removal properties can be exhibited.

  As the mixed organic solvent, a mixed organic solvent mainly composed of an alcohol solvent, which is a polar solvent having good compatibility with water, is used. By blending, an aqueous paste graffiti / stain remover can be obtained.

  According to the present invention, only the graffiti can be completely removed without damaging the substrate, and furthermore, a safe and environment-friendly pasty graffiti / stain remover can be provided because the organic solvent is not used as it is. .

  When using the graffiti / dirt remover of the present invention, it is only necessary to rub the graffiti or dirt on a cloth, etc. At this time, the graffiti or dirt coating film does not dissolve and disperse, and is put together in a smooth state. Graffiti and dirt can be removed with a brush even on a rough surface such as a block surface.

  In particular, water-based paste graffiti and dirt removers are extremely safe and environmentally friendly because there is no danger of ignition. Furthermore, it can effectively remove water-grafted graffiti and stains that were difficult to remove with solvent-based pastes, as well as the dry state, as well as the resin components of graffiti and stains that dissolve in organic solvents. It is also possible to remove starch and protein adhesive components that dissolve in water.

First Embodiment: Solvent-based Paste Graffiti / Stain Remover Solvent-based paste graffiti / stain remover (hereinafter abbreviated as “graffiti remover”) according to the present invention is a trifluoride polyurethane resin composition. A surface-modifying powder of a trifluorinated polyurethane resin composition obtained by mixing silicone powder having a dimethylpolysiloxane structure at a predetermined ratio as a surface modifier to the powder, and drying the mixture is used as an alcohol. It is obtained by blending in a mixed organic solvent composed of a solvent, a ketone solvent, an ester solvent, a polyhydric alcohol / ether solvent, and a hydrocarbon solvent to obtain a paste.

  The powder of the trifluorinated polyurethane resin composition comprises a polymerized fatty acid polyamide resin soluble in an organic solvent obtained by reaction of a polymerized fatty acid and polyamines, and a fluororesin having a hydroxyl group in the molecular structure and soluble in an organic solvent. And a polyisocyanate soluble in an organic solvent functioning as a curing agent for these polymerized fatty acid polyamide resin and fluororesin in an organic solvent inert to isocyanate groups, and pulverizing the reaction cured product It is a porous powder obtained by this.

  Polymerized fatty acid polyamide resin is obtained by thermally polymerizing unsaturated fatty acids such as oleic acid, linoleic acid, and linolenic acid, and generally called a dimer acid, such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, Ethylenediamine homologues such as pentaethylenehexamine, alkylene diamines such as propylene diamine, tetramethylene diamine and hexamethylene diamine, diamines having aromatic nuclei such as phenylenediamine and xylylenediamine, and other isophorone diamines Polyamide resins obtained by reacting polyamines such as these are used and are dissolved in organic solvents.

The fluororesin has an active hydroxyl group in the molecular structure, has an average molecular weight of 20,000 to 80,000, a fluorine content of 20 to 70% by mass, preferably 30 to 60% by mass, and dissolves in an organic solvent such as xylene. A fluorine-containing copolymer is used.
Polyisocyanate is a conventionally known substance as a curing agent for the above-mentioned polymerized fatty acid polyamide resin and fluororesin, and usually has an isocyanate group content of 5% by mass or more. Such polyisocyanate can be appropriately selected from monomers, dimers, trimers and adducts of aliphatic, cycloaliphatic and aromatic diisocyanates.

  The organic solvent inert to the isocyanate group as the reaction solvent of the three raw materials is an organic solvent that dissolves the three raw materials of the polymerized fatty acid polyamide resin, the hydroxyl group-containing fluororesin, and the polyisocyanate in common and does not react with the polyisocyanate. It means a solvent, and examples thereof include aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, esters such as ethyl acetate and butyl acetate, and ketones such as methyl isobutyl ketone.

  By reacting the three raw materials in an organic solvent, the reaction system is cured within a few minutes. The obtained reaction cured product is slightly elastic and has a bulky Okara-like appearance that feels slightly wetted by the organic solvent to be occluded, but without using a means such as freeze-drying, Using a simple pulverizing means such as a ball mill, dry pulverization can be performed to a fine powder having a particle diameter of about 1 to 100 μm at room temperature.

  The proportion of the three raw materials used is preferably 40 to 70% by mass of the polymerized fatty acid polyamide resin, 5 to 30% by mass of the hydroxyl group-containing fluororesin, and 15 to 50% by mass of the polyisocyanate from the viewpoint of pulverization of the reaction cured product. .

As a surface modifier for the powder raw material of the trifluorinated polyurethane resin composition produced by the method as described above, in the present invention, a dimethylpolysiloxane structure comprising a siloxane bond (Si—O—Si) and a methyl group Use silicone oil with There are various varieties of silicone oil having different molecular weight distributions, and the viscosity increases as the molecular weight increases. In the present invention, those having a viscosity in the range of 30 to 100 mm ² / s (25 ° C.) Can be preferably used from the viewpoints of retention on the surface and separation between the powders after surface modification.

  The ratio of silicone oil, which is a surface modifier added to the powder raw material of the trifluorinated polyurethane resin composition, is 1 to 6 parts by mass of silicone oil with respect to 100 parts by mass of the powder raw material.

  When the blending amount of the silicone oil is less than 1 part by mass, the surface cannot be effectively modified, and when it exceeds 6 parts by mass, the compatibility of the powder after the surface modification with the mixed organic solvent is deteriorated, and the paste It is difficult to form.

  When the raw material powder of the trifluorinated polyurethane resin composition is modified with the silicone oil as the surface modifier, the silicone oil is mixed with the raw material powder of the trifluorinated polyurethane resin composition so as to have a predetermined ratio. . In order to improve the impregnation property of the surface modifier with respect to the raw material powder, a solvent such as butyl acetate may be added to this mixture as needed for viscosity adjustment. Next, this mixture is dried under reduced pressure to remove the solvent, and the dried product is lightly loosened and separated into powder, whereby a surface-modified powdery trifluorinated polyurethane resin composition can be obtained.

  The surface modified powder of the polyurethane trifluoride resin composition thus formed is a powder that easily absorbs the organic solvent, and the absorption amount of the organic solvent varies depending on the particle size of the powder, but the particle size is 10 to 100 μm. In the case of, it was found that an organic solvent having a mass ratio of 2 times or more was absorbed. And the surface modification powder of the trifluoride polyurethane resin composition which absorbed the organic solvent will be in a paste state by general manual stirring, and can be used as a graffiti remover.

  As the mixed organic solvent to be blended with the surface modified powder of the trifluorinated polyurethane resin composition, a mixed organic solvent comprising an alcohol solvent, a ketone solvent, an ester solvent, a polyhydric alcohol / ether solvent and a hydrocarbon solvent is used. use.

As the alcohol solvent, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, methyl isobutyl carbinol and the like can be used.
As the ketone solvent, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, or the like can be used.
Examples of the ester solvent that can be used include methyl acetate, ethyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, cellosolve acetate, butylcellosolve acetate, methoxybutyl acetate, and 2-ethylbutyl acetate.
Examples of the polyhydric alcohol / ether solvent include methyl cellosolve, cellosolve, butyl cellosolve, methoxybutanol, propylene glycol monomethyl ether, and dioxane.
As the hydrocarbon solvent, for example, n-hexane, mineral spirit, toluene, xylene, cyclohexane and the like can be used.

  The mixing ratio of the five kinds of organic solvents described above is 30 to 70 parts by weight of an alcohol solvent, 10 to 20 parts by weight of a ketone solvent, 10 to 10 parts by weight of an ester solvent, since the scrubbing / stain removal property and the aromaticity peculiar to organic solvents To 20 parts by mass, 10 to 20 parts by mass of a polyhydric alcohol / ether solvent, and 5 to 20 parts by mass of a hydrocarbon solvent.

Let us consider the process of graffiti removal in solvent-based paste graffiti removers. When the graffiti remover is attached to the cloth and used to remove the graffiti, the graffiti film does not dissolve and disperse, unlike the case where only the solvent is used to remove the graffiti. Therefore, even if the surface is extremely uneven, such as a block surface, the dirt is not dispersed and can be removed neatly by using a brush together.
This phenomenon is caused specifically by the surface modified powder of the trifluorinated polyurethane resin composition surface modified with silicone oil. The mixed organic solvent contained in the graffiti remover dissolves the resin component of the graffiti paint film. At the same time, the silicone oil, which does not dissolve in this resin component, deprives the organic solvent with good compatibility, so the resin component of the coating film cannot be dissolved and becomes a gel (swelled state) and a coherent shape (gelation of graffiti coating film) It is presumed that

  Moreover, what is necessary is just to mix | blend the compounding ratio in the surface modification powder and mixed organic solvent of a trifluoride polyurethane resin composition in a preferable range from a viewpoint of paste formation property and the removability of graffiti and dirt. Generally, as can be seen from the experimental results of Example 2 described later, 50 to 90 parts by mass of the mixed organic solvent may be blended with 40 parts by mass of the surface modified powder of the trifluorinated polyurethane resin composition. preferable.

Second Embodiment: Aqueous Paste Graffiti / Dirt Remover While the first embodiment is a solvent-based paste graffiti remover, the aqueous paste graffiti remover according to the second embodiment is Water is added to the solvent-based paste graffiti remover according to the first embodiment and stirred to form an emulsion.

  The amount of water to be blended is 1 to 2.5 times that of the mixed organic solvent in the solvent-based paste-like graffiti remover, so that an emulsion can be easily formed even by general manual stirring. Such a bulky paste can be obtained.

  In addition, as the mixed organic solvent in the aqueous paste graffiti remover, an organic solvent having a main component of an alcohol solvent which is a polar solvent having good compatibility with water is used for blending water. In particular, in order to provide a bulky paste-forming property such as soft cream, it is preferable that the alcohol-based solvent is contained in the mixed organic solvent in an amount of 50% or more by mass.

  This water-based paste graffiti remover has water as the main component, but is not compatible with water or oil, silicone oil, non-polar solvent (hydrocarbon solvent) that does not dissolve in water, well soluble in water An appropriate amount of a polar solvent (mainly alcoholic or ketone-based) is blended to form an emulsion and form a paste. Note that the graffiti and dirt resin components to be removed correspond to the “oil” mentioned here.

  Here, let us consider the process of removing graffiti etc. in an aqueous paste graffiti remover. First, an aqueous paste graffiti remover is applied from above the graffiti coating, so that each component in the graffiti remover quickly starts to wet and penetrate into the graffiti coating. The main compatible groups forming the graffiti remover emulsion are “silicone oil and non-polar solvent” and “water and polar solvent”. The smaller the surface tension, the greater the penetration force, and the silicone oil and the nonpolar solvent quickly wet and permeate the resin component of the graffiti coating and the interface (attachment surface) between the substrate and the graffiti coating. Water and polar solvents wet and permeate in a follow-up manner, and especially organic solvents such as ketones and esters in polar solvents have a large resin component dissolving power. It moves into the resin component and further promotes swelling and dissolution of the resin component.

Silicone oil does not dissolve with the resin component of the graffiti paint film, so it wets and penetrates, but it is left in the form as it is, and this phenomenon causes the resin component of the graffiti paint film to be gelled and not dispersed. It can be considered that it plays a role to summarize. Silicone oil also helps protect the graffiti substrate.
On the other hand, the “silicone oil and nonpolar solvent” and “water and polar solvent” forming the emulsion cover the outside of the graffiti coating film due to the influence of water with a large surface tension, and the volatility in the graffiti remover It is considered that the organic solvent has a function of suppressing volatilization of the organic solvent and supporting the permeation / dissolution and swelling / gelation of the graffiti coating into the resin component.

  When graffiti and dirt were removed with an aqueous paste graffiti remover, the resin component of the graffiti coating film and the amount of water that did not dissolve the silicone oil increased, so the graffiti coating gelation property was higher than that of the solvent paste graffiti remover. Appears prominently. Moreover, it is possible to remove adhesive (glue) components such as starch and proteins that dissolve in water together with the resin component that dissolves in the organic solvent.

Graffiti wet with water was difficult to remove with solvent-based paste graffiti remover, but with water-based paste graffiti remover, it immediately became familiar with graffiti and dirt, similar to the removal of graffiti and dirt in the dry state. Can be removed.
Furthermore, water-based pastes have no flash point and are safe and environmentally friendly.

  Based on the above, the water-based paste graffiti remover does not hurt the graffiti base and can be used for both wet and dry stains. Besides graffiti with paint and ink, starch, protein, etc. Can also be used as a universal graffiti / stain remover.

  Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1: [Examination of amount of surface modifier added]
100 parts by mass of a xylene solution (non-volatile content 70%) of a polymerized fatty acid polyamide resin (manufactured by Fuji Kasei Kogyo Co., Ltd., trade name “Tomide 215-X”) obtained by condensation of dimer acid and polyethylene polyamine, a hydroxyl group-containing fluororesin (three Hexamethylene diisocyanate trimer in a slightly yellow transparent solution in which 20 parts by mass of xylene solution (non-volatile content 50%) of xylene solution (trade name “Lumiflon LF100”) manufactured by Asahi Glass Co., Ltd. and 10 parts by mass of xylene are mixed. 50 parts by mass of xylene solution (non-volatile content: 75%) was added in several portions while stirring at room temperature in an open state. An exothermic reaction occurred immediately, the reaction system was cured, and the temperature was about 60 ° C. The reaction took several minutes. The produced reaction-cured product had a slightly yellowish brown, bulky Okara shape with slight elasticity. This was pulverized with a magnetic ball mill for about 30 hours and then sieved to obtain 100 parts by mass of white raw material powder of a trifluorinated polyurethane resin composition. This raw material powder was a powder having a particle size in the range of 10 to 100 μm.

Next, the product name “KF96-50” (Viscosity: 50 mm ² / s (25 ° C.), non-volatile content: 100%) manufactured by Shin-Etsu Chemical Co., Ltd. as a silicone oil as a surface modifier is added to 100 parts by mass of the raw material powder. In the range of 0.5 to 8 parts by mass, and further mixed with a solvent containing butyl acetate as a main component for viscosity adjustment to improve impregnation, and the mixture is dried under reduced pressure. Thus, the surface modification of the raw material powder trifluoride polyurethane resin composition was performed.

  Regarding the surface modified powder of the trifluorinated polyurethane resin composition obtained above, the results of evaluating “powder separability”, “compatibility with mixed organic solvent” and “gelability of graffiti coating” Table 1 shows.

  For evaluation of “powder separability”, the surface modified powder of the trifluorinated polyurethane resin composition obtained after drying under reduced pressure was loosened with a fingertip, and the return state of the powder was observed. When the state of the powder easily returned to the state before the surface modification, it was evaluated as “◯”.

  “Compatibility with mixed organic solvent” means whether or not the surface modified powder of the trifluorinated polyurethane resin composition is mixed with the mixed organic solvent and absorbed and absorbed easily It is a guideline. Since this compatibility is substantially the compatibility between the silicone oil as the surface modifier and the mixed organic solvent, the compatibility between the silicone oil and the mixed organic solvent was evaluated. As the mixed organic solvent, 50 parts by weight of ethanol and 30 parts by weight of isopropanol as an alcohol solvent, 10 parts by weight of methyl isobutyl ketone as an acetone solvent, 10 parts by weight of butyl acetate and 10 parts by weight of 2-ethylbutyl acetate as an ester solvent, A mixed organic solvent containing 10 parts by mass of butyl cellosolve as a polyhydric alcohol / ether solvent and 5 parts by mass of xylene as a hydrocarbon solvent was used. The compatibility was evaluated as ◯ if there was compatibility, △ if turbidity appeared, and x if phase separation occurred.

  The “gelability of graffiti coating” is 70 mass parts of mixed organic solvent having the same composition as that used in the evaluation of “compatibility with mixed organic solvent” in 40 parts by mass of the surface modified powder of the trifluorinated polyurethane resin composition. The parts were mixed to prepare a solvent-based graffiti remover, and the degree of gelation of the graffiti film when the graffiti film by the acrylic lacquer enamel paint was actually removed was evaluated. When the coating film did not dissolve and became a smooth gelled state, it was evaluated as ◯, when partially dissolved, Δ when it was dissolved without gelation.

  As can be seen from Table 1, the “powder separability” is the same as in Experiment No. 1 to 6 could be easily pulverized, but it was necessary to satisfy both “compatibility with mixed organic solvent” and “gelability of graffiti coating film”. It is necessary for the graffiti remover of the present invention that the silicone oil be 1 to 6 parts by mass with respect to 100 parts by mass. Experiment No. No. 2 “gelability of graffiti coating” partly dissolves graffiti coating. In the case of No. 5, turbidity was observed in “compatibility with mixed organic solvent”, but it could be used as a graffiti remover.

Example 2: [Examination of blending amount of mixed organic solvent in solvent-based paste remover]
Except for mixing 3 parts by weight of the silicone oil as the surface modifier with respect to 100 parts by mass of the raw material powder of the trifluorinated polyurethane resin composition, the same as in Example 1,
A surface modified powder of a trifluorinated polyurethane resin composition was produced.

  In 40 mass parts of the surface modified powder of this trifluorinated polyurethane resin composition, the mixed organic solvent having the same composition as that used in the evaluation of “compatibility with mixed organic solvent” in Example 1 is in the range of 40 to 100 mass parts. Mixing in the proportions shown in Table 2, a solvent-based paste graffiti remover was prepared in the same manner as in Example 1. “Powder to solvent ratio” in Table 2 is a value obtained by dividing the mass of the mixed organic solvent by the mass of the surface modified powder.

Table 2 shows the results of evaluating the “paste forming ability” and “graffiti removing ability” of the solvent-based paste graffiti remover obtained above and measuring the “flash point”.
The “paste formability” is based on visual observation. A mixture of a predetermined amount of a mixed organic solvent mixed with the surface-modified powder of the polyurethane trifluoride resin composition and mixed by manual stirring becomes a paste state. When it was stable even after the lapse of time, it was marked with ◯, when the paste was slightly separated, it was marked with △, and when separation was obvious or when it was not pasted, it was marked with x.

  “Graffiti removability” means that the graffiti remover is attached to the cloth in the process of removing the graffiti film (width 40 mm, length 50 mm) formed with the acrylic lacquer enamel red spray paint on the white baked steel sheet. Spread out from above and scrape with cloth after 20 seconds. If the graffiti coating can be completely removed within 30 seconds, mark as ○. The case where removal was not possible within 2 seconds was marked with x.

  The “flash point” was measured using a tag-closed flash point measuring device that complies with the flash point measurement test of the dangerous goods class 4 of the Fire Service Act.

  As can be seen from Table 2, “Graffiti removability” is an experiment no. It was good in all of 7-13, and "flash point" showed 20-23 degreeC.

  The evaluation of “paste formability” is an experiment to find an appropriate blending ratio of the surface modified powder and the mixed organic solvent. As can be seen from Table 2, the “powder to solvent ratio” is 1.00 (equivalent). Experiment No. No paste was formed in Experiment No. 7, but the “powder to solvent ratio” was in the range of 1.25 to 2.00. In 8-11, good paste formability was obtained. Experiment No. with a “powder to solvent ratio” of 2.25. No. 12, a slight separation of the paste state was observed, but the graffiti removal property was good and there was no problem in practical use. From these results, it can be seen that 50 to 90 parts by mass of the mixed organic solvent is an appropriate mixing ratio with respect to 40 parts by mass of the surface modified powder of the trifluorinated polyurethane resin composition.

Example 3: [Examination of the amount of water in the water-based paste remover]
The surface-modified powder of the same trifluorinated polyurethane resin composition used in Example 2 and the mixed organic solvent were mixed in the ratio shown in Table 3, and pure water was mixed in the ratio shown in Table 3, An aqueous paste graffiti remover was prepared. The “solvent to water ratio” in Table 3 is a value obtained by dividing the mass of pure water by the mass of the mixed organic solvent.

Table 3 shows the results of evaluating the “bulky paste forming property” and “graffiti removing property” of the solvent-based paste graffiti remover obtained above and measuring the “flash point”.
“Bulk paste formability” is an experiment to find an appropriate blending amount of water, and after mixing and stirring the surface modified powder, the mixed organic solvent, and water, it is judged as ○ if a bulky paste is formed. When formed, it was set as Δ, and when separation was observed, it was marked as x.
“Graffiti removability” and “flash point” were evaluated or measured in the same manner as in Example 2.

As shown in Table 3, “Graffiti removability” is shown in Experiment No. It was favorable in all of 14-19. On the other hand, for “flash point”, experiment No. In the case where the water ratio is small as in FIG. 14, the ignition is instantaneously performed at a temperature of less than 40 ° C. From 15 to 19, the flash point could not be measured, and it was found that the flammability was low.
In addition, “bulky paste forming property” indicates that the “solvent to water ratio” of Experiment Nos. 1.00 and 2.00. 15 and 16 were the best. In addition, in Experiment No. with a “solvent to water ratio” of 2.50. In Nos. 17 and 19, the formation of a bulky paste was conducted in Experiment No. Although it was slightly inferior to 15 and 16, the graffiti removal property was good, the flash point could not be measured, and the flammability was low. On the other hand, Experiment No. with a small amount of water in the mixed organic solvent. In 14, it is difficult to form a bulky paste, and some flammability is recognized, so it is not preferable.
From these results, in order to obtain an aqueous paste graffiti remover excellent in terms of “bulky paste forming property”, “graffiti removal property” and “flash point”, the mass ratio of the mixed organic solvent is 1-2. It turns out that the mixing | blending of water 5 times, preferably 1 to 2.0 times is an appropriate blending ratio.

Example 4
Experiment No. 3 in Example 3 An experiment was carried out in which the aqueous paste-like graffiti remover obtained in 16 was attached to a cloth to actually remove the following graffiti and dirt.
・ Black color of acrylic lacquer enamel for car repair written on the signboard ・ Red color of acrylic lacquer enamel for car repair written on the block ・ ・ Turp pitch and paint mist on the painted surface of passenger cars ・ Written on leather sofa Magic ink black ・ Dustless chalk white written on transparent acrylic plate ・ Chewing gum applied on painted steel plate ・ Ripstick and crayon written on furniture ・ Remaining protein adhesive on signboard As a result, chewing gum and protein type The removal of the adhesive required some aging time, but others could be easily removed. From this, it was confirmed that the aqueous paste graffiti / stain remover according to the present invention can effectively remove many kinds of graffiti and stains as described above.

Claims (3)

  Polymerized fatty acid polyamide resin soluble in organic solvent obtained by reaction of polymerized fatty acid and polyamines, fluororesin having a hydroxyl group in the molecular structure and soluble in organic solvent, and these polymerized fatty acid polyamide resin and fluororesin A trifluorinated polyurethane resin composition obtained by reacting a polyisocyanate soluble in an organic solvent functioning as a curing agent in an organic solvent inert to isocyanate groups and crushing the reaction cured product 1 to 6 parts by mass of a silicone oil having a dimethylpolysiloxane structure is mixed with 100 parts by mass of the powder of the product, and the surface-modified powder of the trifluorinated polyurethane resin composition obtained by drying the mixture is used as an alcohol. Mixed solvents, ketone solvents, ester solvents, polyhydric alcohol / ether solvents and hydrocarbon solvents Pasty graffiti, dirt off agent of solvent type, characterized in that by blending in an organic solvent.   The solvent-based paste form according to claim 1, wherein 50 to 90 parts by mass of the mixed organic solvent is blended with 40 parts by mass of the surface modified powder of the trifluorinated polyurethane resin composition. Graffiti / dirt remover.   A mixed organic solvent containing an alcohol solvent as a main component is used as the mixed organic solvent in claim 1 or 2, and 1 to 2.5 times as much water is blended by mass with respect to the mixed organic solvent. A water-based paste-like graffiti / dirt remover.