JP2008169361A - Resin surface cleaning agent and resin surface cleaning method - Google Patents

Abstract

Disclosed is a resin surface cleaning agent that can sufficiently and easily remove dirt adhering to a resin surface, particularly a coating film surface, and that is excellent in storage stability and workability.
The resin surface cleaning agent of the present invention is a liquid petroleum hydrocarbon having a boiling point of 150 ° C. or higher at an atmospheric pressure of 0.1 MPa and a flash point of 40 ° C. or higher at an atmospheric pressure of 0.1 MPa. -50% by mass, finely divided metal oxide 3-30% by mass, anionic surfactant 0.1-3% by mass, nonionic surfactant 0.5-10% by mass, amphoteric acrylic polymer 0.1-4 It contains 30% by mass and 30-70% by mass of water.
[Selection figure] None

Description

  The present invention relates to a resin surface cleaning agent and a resin surface cleaning method for removing dirt adhering to a resin surface, particularly a resin coating surface.

Generally, various stains adhere to the resin surface. For example, since resin is difficult to conduct electricity and is likely to generate static electricity, fine particles floating in the air may be adsorbed to form dirt. In addition, outdoors, fine particles floating in the air may be mixed into the rain and adhere to the resin surface to form dirt. Furthermore, when the raindrops adhering to the resin surface are dried, they may become scale marks including fine particles called raindrop marks and form dirt.
Here, examples of the fine particles floating in the air include organic compounds such as oil dust, inorganic compounds such as straw and sand, and composites obtained by combining them.
Dirt (organic dirt) due to organic compound fine particles has high affinity for the resin and adheres specifically. If left for a long time with organic stains attached, it may adhere to the resin surface or penetrate into the resin, causing spots and discoloration, which may impair the appearance.
Dirt due to inorganic compound fine particles (inorganic stain) does not adhere to or penetrate into the resin, but usually the inorganic compound fine particles are harder than the resin, so that the surface of the resin is finely scratched by physical friction due to rubbing or the like. It may be attached.
Contamination due to the fine particles of the composite (composite soil) causes problems with both organic soil and inorganic soil.

In order to prevent the above problem from occurring, usually, for example, measures are taken to clean organic and inorganic stains and fixed matters, stains and scale marks caused by these stains. As a cleaning method, there is widely known a method for cleaning a surface by thinly and uniformly polishing a resin surface to which dirt is attached or a deteriorated resin surface with an inorganic compound, particularly an inorganic oxide.
However, when polished with an inorganic oxide, dirt can be removed effectively and efficiently, but after the polishing treatment, the dirt component and the inorganic oxide used for polishing remain on the resin surface. The remaining inorganic oxide is difficult to remove only by rinsing with running water, and the inorganic oxide that cannot be removed by rinsing causes fine scratches as well as inorganic dirt. In addition, after rinsing, dryness and scale marks are generated by drying, so that the appearance of the resin surface such as gloss and gloss is impaired.
For this reason, in the method of washing by polishing treatment, it is necessary to disperse, dissolve, and extract the dirt with a surfactant, a solvent, etc., and rewash the resin surface, so that the washing operation cannot be said to be simple.

Thus, a method for preventing contamination by surface modification treatment such as coating has been proposed.
For example, in Patent Document 1, a cleaning agent comprising a polyvinylpyrrolidone homo- or copolymer suitable for modifying the outer surface of an automobile body to make it hydrophilic, and making the contact angle between water and the surface less than 50 degrees. Compositions have been proposed. By performing the coating treatment with this cleaning composition, it is possible to suppress the adhesion of dirt, prevent the formation of water drying marks, and clean the surface over a long period of time.
In Patent Document 2, an amphoteric polymer obtained by polymerizing a cationic monomer compound, an anionic monomer compound, and a nonionic hydrophilic monomer compound is used to make ceramics, tiles, glass, etc. A method for treating hard surfaces to impart detergency and hydrophilicity has been proposed. By imparting detergency and hydrophilicity by this method, it is possible to prevent the formation of scale marks and contamination due to drying of water droplets attached to the hard surface.
Patent Document 3 proposes an aqueous composition containing a polybetaine-type polymer for cleaning or rinsing hard surfaces such as ceramics, tiles, glass, metals, melamine, and plastics. According to this aqueous composition, the hard surface can be modified to be hydrophilic, and the adhesion preventing property and adhesion preventing property of the pollutant can be imparted over a long period of time.

In addition, as a method for cleaning organic and inorganic stains, fixed matter, stains and scale marks caused by these, a method of washing the resin surface by dispersing, dissolving and extracting the stain with a surfactant or solvent. Has been proposed. For example, Patent Document 4 proposes a method for cleaning a resin surface with a liquid detergent composition containing a polymeric soap foam enhancer obtained from a quaternary nitrogen-containing monomer or a zwitterionic monomer. Yes.
Special table 2003-524681 gazette Special table 2003-505535 gazette JP-T-2006-514150 JP 2002-309292 A

However, in the methods described in Patent Documents 1 to 4, although dirt and stains fixed on the resin surface can be removed, the actual condition is that the degree of removal is not sufficiently satisfactory. Therefore, there has been a demand for a cleaning agent and a cleaning method that can remove dirt and stains to the same extent as in the polishing treatment with the inorganic compound or the like.
Moreover, since a cleaning agent may be preserve | saved for a long time, it is calculated | required that it is excellent in storage stability. Furthermore, the cleaning agent is easy to spread when the resin surface is applied, can be easily spread, and even if excessively adhered on the resin surface, it can be easily removed by dry wiping or wet wiping or by rinsing with water. There is a need for easy removal. That is, it is required to have excellent workability.

  An object of the present invention is to provide a resin surface cleaning agent that can sufficiently and easily remove dirt adhering to a resin surface, particularly a coating film surface, and that is excellent in storage stability and workability. Furthermore, it aims at providing the washing | cleaning method of the resin surface which can fully and simply remove the stain | pollution | contamination adhering to the resin surface.

  As a result of intensive studies in order to solve the above problems, the present inventors have made use of a cleaning agent in which a specific petroleum hydrocarbon, metal oxide, surfactant, and amphoteric acrylic polymer are combined. It has been found that dirt, stains and scale marks on the surface can be easily removed, and that a clean resin surface can be obtained by rinsing with water. As a result of further investigation based on this finding, the following resin surface cleaning agent and resin surface cleaning method were invented.

[1] A liquid petroleum hydrocarbon having a boiling point of 150 ° C. or higher at an atmospheric pressure of 0.1 MPa and a flash point of 40 ° C. or higher at an atmospheric pressure of 0.1 MPa, a particulate metal oxide 3 -30 mass%, anionic surfactant 0.1-3 mass%, nonionic surfactant 0.5-10 mass%, amphoteric acrylic polymer 0.1-4 mass%, and water 30-70 mass%. A cleaning agent for resin surfaces, comprising:
[2] The resin surface according to [1], wherein the petroleum hydrocarbon has a boiling point of 170 ° C. or higher at a pressure of 0.1 MPa and a flash point of 45 ° C. or higher at a pressure of 0.1 MPa. Cleaning agent,
[3] The resin surface cleaner according to [1] or [2], wherein the petroleum hydrocarbon is a naphthene hydrocarbon,
[4] The particulate metal oxide is at least one metal oxide selected from the group consisting of aluminum oxide, silicon oxide and magnesium oxide, according to any one of [1] to [3] Cleaning agent for resin surface,
[5] The resin surface cleaning agent according to any one of [1] to [4], wherein the fine particle metal oxide has an average particle size of 0.1 to 5 μm.
[6] The resin surface cleaning agent according to any one of [1] to [5], wherein the anionic surfactant is a sulfate ester type anionic surfactant or a sulfonic acid type anionic surfactant,
[7] The resin surface cleaning agent according to any one of [1] to [6], wherein the nonionic surfactant is a polyglycerin ester type nonionic surfactant,
[8] The resin surface cleaning agent according to any one of [1] to [7], wherein the amphoteric acrylic polymer is a betaine-type amphoteric acrylic polymer.

According to the resin surface cleaning agent of the present invention, it is possible to sufficiently remove stains adhering to the resin surface, in particular, the coating film surface formed by the paint for coating. Moreover, even if the detergent for resin surfaces of this invention adheres excessively on the resin surface, it can be easily removed from the resin surface by rinsing with the removed dirt. Therefore, the cleaning operation can be simplified. And the cleaning agent for resin surfaces of this invention is excellent in storage stability and workability.
According to the method for cleaning a resin surface of the present invention, it is possible to sufficiently and easily remove stains adhering to a resin surface, particularly a coating film surface formed by a paint for coating.

(Cleaning agent for resin surface)
The resin surface cleaning agent of the present invention (hereinafter abbreviated as “cleaning agent”) contains petroleum hydrocarbons, particulate metal oxides, anionic surfactants, nonionic surfactants, amphoteric acrylic polymers and water. Is.

[Petroleum hydrocarbons]
Petroleum hydrocarbons contained in the cleaning agent are liquid hydrocarbons obtained by fractionating from petroleum or by reforming petroleum, having a boiling point of 150 ° C. or higher and a flash point of 40 ° C. or higher. Petroleum hydrocarbon. When the boiling point is less than 150 ° C. or the flash point is less than 40 ° C., the dirt cannot be removed or the storage stability is lowered. Here, both the boiling point and flash point in the present invention are values measured under the pressure of 0.1 MPa.
In addition, petroleum hydrocarbons preferably have a boiling point of 170 ° C. or higher and a flash point of 45 ° C. or higher, and a boiling point of 200 ° C. or higher because dirt and stains on the resin surface can be more easily washed away. More preferably, the flash point is 50 ° C. or higher. The boiling point is preferably 330 ° C. or lower, and the flash point is preferably 200 ° C. or lower. This is because it is difficult to obtain those whose boiling point and flash point exceed the upper limit.
Specifically, the petroleum hydrocarbon is preferably a naphthene hydrocarbon because dirt and stains on the resin surface can be more easily washed away. Among naphthenic hydrocarbons, naphthenic hydrocarbons having 9 to 15 carbon atoms are preferable.
Also preferred are mixtures of alicyclic hydrocarbons and aliphatic hydrocarbons.

  Specific examples of petroleum-based hydrocarbons include kerosene, light oil, and commercially available “Exor D-80” and “Exor D-110” (trade names, manufactured by ExxonMobil).

  The content of petroleum hydrocarbons in the cleaning agent is 7 to 50% by mass, preferably 10 to 40% by mass, and more preferably 15 to 35% by mass. When the content of the petroleum hydrocarbon is 7 to 50% by mass, organic stains and stains on the resin surface can be efficiently scraped off. On the other hand, if the content of petroleum hydrocarbon is less than 7% by mass, a sufficient cleaning effect cannot be obtained, and if it exceeds 50% by mass, a cleaning effect can be obtained, but resin (coating film) May swell or dissolve.

[Fine particle metal oxide]
The fine particles in the fine metal oxide are particles having an average particle diameter (primary average diameter) of 0.05 to 10 μm. When the average particle size is 0.05 to 10 μm, dirt, stains, and scale marks on the resin surface can be efficiently scraped without damaging the resin surface. On the other hand, if the average particle diameter of the particulate metal oxide exceeds 10 μm, the resin surface may be damaged. If the average particle diameter is less than 0.05 μm, handling is difficult, and dirt cannot be efficiently rubbed off.
The average particle diameter (primary average diameter) of the particulate metal oxide is preferably 0.1 to 5 μm because dirt, stains, and scale marks on the resin surface can be more efficiently washed away. More preferably, it is 5-2 micrometers.

  Examples of the metal oxide include aluminum oxide, silicon oxide, magnesium oxide, cerium oxide, magnesium oxide, chromium oxide, zirconium oxide, titanium oxide, zinc oxide, calcium oxide, kaolin, activated clay, silica stone, and diatom. Examples include soil, talc, zeolite, bentonite and the like. These fine particle metal oxides may be used alone or in combination of two or more. Among the metal oxides, at least one metal oxide selected from the group consisting of aluminum oxide, silicon oxide, and magnesium oxide is preferable because dirt, stains, and scale marks on the resin surface can be more efficiently cleaned and removed.

  The content of the particulate metal oxide in the cleaning agent is 3 to 30% by mass, preferably 5 to 25% by mass, and more preferably 10 to 20% by mass. When the compounding amount of the particulate metal oxide is 3 to 30% by mass, it is possible to efficiently scrape dirt, stains and scale marks on the resin surface. On the other hand, if the content of the particulate metal oxide is less than 3% by mass, a sufficient cleaning effect cannot be obtained, and if it exceeds 30% by mass, a cleaning effect can be obtained. The load increases.

[Anionic surfactant]
The anionic surfactant is not particularly limited, and examples thereof include fatty acid soaps, carboxylates such as polyoxyalkylene alkyl ether acetates and polyoxyalkylene alkenyl ether acetates, alkyl sulfate esters, alkenyl sulfate esters, and polyoxyalkylenes. Alkyl ether sulfates, polyoxyalkylene alkenyl ether sulfates, sulfated oils, sulfated fatty acid esters, sulfated fatty acids, sulfated olefins such as sulfated olefins, alkylbenzenesulfonates, alkylnaphthalenesulfonates, α- Sulfone such as olefin sulfonate, paraffin sulfonate, Igepon T-type, sulfosuccinic acid diester salt, polyoxyalkylene alkyl sulfonate, polyoxyalkylene alkenyl sulfonate Such as salts, and the like. These anionic surfactants may be used individually by 1 type, and may use 2 or more types together.
Among these anionic surfactants, since the storage stability of the cleaning agent can be increased, a carboxylate type, sulfate ester type or sulfonate type anionic surfactant of polyoxyalkylene alkyl (or alkenyl) ether is provided. A sulfate ester type or sulfonate type anionic surfactant is more preferable. Among the sulfate ester type or sulfonate type anionic surfactants, in particular, polyoxyalkylene alkyl ether sulfate ester salt, polyoxyalkylene alkenyl ether sulfate ester salt, polyoxyalkylene alkyl sulfonate salt, polyoxyalkylene alkenyl ester Sulfonate is preferred.

When the anionic surfactant has an alkyl group or alkenyl group, the alkyl group or alkenyl group preferably has 8 or more carbon atoms, more preferably 12 to 22 carbon atoms, and more preferably 16 to 20 carbon atoms. It is particularly preferred. When the alkyl group or alkenyl group has 8 or more carbon atoms, the storage stability of the cleaning agent can be further increased.
When the anionic surfactant has a polyoxyalkylene group, examples of the polyoxyalkylene group include a polyoxyethylene group. Moreover, since the storage stability of a washing | cleaning agent can be made higher, it is preferable that the repeating unit of oxyethylene is 10 or less, and it is more preferable that it is 2-6.

  The content of the anionic surfactant in the cleaning agent is 0.1 to 3% by mass, preferably 0.2 to 2% by mass, and more preferably 0.5 to 1.5% by mass. . When the content of the anionic surfactant is 0.1 to 3% by mass, it is possible to efficiently remove stains and stains on the resin surface and maintain the storage stability of the cleaning agent. On the other hand, if the content of the anionic surfactant is less than 0.1% by mass, a sufficient cleaning effect and storage stability of the cleaning agent cannot be obtained, and if it exceeds 3% by mass, the cleaning effect is Although obtained, the resin (coating film) may swell or dissolve.

[Nonionic surfactant]
The nonionic surfactant is not particularly limited, and examples thereof include polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl ester, polyoxyalkylene alkenyl ester, sucrose ester and span. Of fatty acids such as polyhydric alcohol fatty acid esters such as glycerin ester, glycerin ester, polyglycerin ester, polyhydric alcohol fatty acid ester alkylene oxide adduct such as tweens, alkylamine alkylene oxide adduct, fatty acid amide alkylene oxide adduct, and hardened castor oil. Examples include polyalkylene glycol types such as alkylene oxide adducts and polypropylene glycol ethylene oxide adducts. These nonionic surfactants may be used individually by 1 type, and may use 2 or more types together.

  Of these nonionic surfactants, since the storage stability of the cleaning agent can be increased, sucrose esters, spans, glycerin esters, and polyglycerin esters are preferable, and polyglycerin esters (polyglycerin esters) are more preferable. Type nonionic surfactant). Furthermore, among polyglycerin esters, polyglycerin obtained by reacting tetraglycerin or more, in particular pentaglycerin to pentadecaglycerin, and a fatty acid having an alkyl group or an alkenyl group having 10 to 22 carbon atoms, particularly 12 to 20 carbon atoms. Glycerin esters are preferred. The polyglycerol ester may be a monoester, a diester, or a triester.

  Examples of the polyglycerin ester type nonionic surfactant include “Decalyn 1-M” (decaglycerin myristic acid monoester), “Hexaglyn 1-L” (hexaglycerin lauric acid monoester), and “Hexaglyn 1-SV”. (Hexaglycerin stearic acid monoester), “Decalyn 2-ISV” (decaglycerin isostearic acid diester) [both trade names, manufactured by Nikko Chemicals Co., Ltd.]] and the like are commercially available.

  The content of the nonionic surfactant in the cleaning agent is 0.5 to 10% by mass, preferably 2 to 9% by mass, and more preferably 3 to 8% by mass. When the content of the nonionic surfactant is 0.5 to 10% by mass, the resin surface can be efficiently soiled and stained, and the storage stability of the cleaning agent can be maintained. When the blending amount of the nonionic surfactant is less than 0.5% by mass, a sufficient cleaning effect and storage stability of the cleaning agent cannot be obtained, and when it exceeds 10% by mass, a cleaning effect can be obtained. There is a risk of swelling or dissolving the resin (coating film).

[Amotropic acrylic polymer]
The amphoteric acrylic polymer is a polymer having an ethylenically unsaturated group polymer chain as a main chain and an anionic group and a cationic group in the side chain.
Examples of the amphoteric acrylic polymer include a copolymer of a cationic monomer and an anionic monomer, or an acrylic monomer or a methacrylic monomer having a betaine group, a sulfobetaine group, or a phosphobetaine group. A homopolymer or a copolymer may be mentioned.
Moreover, an amphoteric acrylic polymer may be used individually by 1 type, and may use 2 or more types together.

  As a copolymer of a cationic monomer and an anionic monomer, for example, a cationic monomer such as diallyldimethylammonium chloride as disclosed in JP-T-2003-505535, a carboxylic acid, Examples thereof include a copolymer obtained by copolymerization with a metal salt (anionic monomer) of a monoethylenically unsaturated monomer having sulfonic acid, sulfuric acid, phosphonic acid or phosphoric acid. Here, specific examples of the monoethylenically unsaturated monomer having carboxylic acid, sulfonic acid, sulfuric acid, phosphonic acid or phosphoric acid include acrylic acid, methacrylic acid, α-ethacrylic acid, β, β-dimethylacrylic. Acid, methylenemalonic acid, vinylacetic acid, allylacetic acid, ethylideneacetic acid, propylideneacetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, N-methacryloylalanine, N-acryloylhydroxyglycine, sulfoacrylic acid Propyl, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl methacrylate, styrene sulfonic acid, vinyl sulfonic acid, vinyl phosphonic acid, sulfoethyl acrylate, sulfonoethyl acrylate, phosphopropyl acrylate, phosphonopropyl acrylate, methacrylate Acid sulfoethyl, Suruhonoechiru methacrylate, sulfopropyl, like methacrylate sulfo Bruno propyl.

  Moreover, as a homopolymer or copolymer (betaine type amphoteric acrylic polymer) of an acrylic monomer or a methacrylic monomer having a betaine group, a sulfobetaine group or a phosphobetaine group, for example, JP-T-2006-514150 Or a homopolymer or copolymer of a monomer having a betaine group, a sulfobetaine group or a phosphobetaine group, or a copolymer with a monomer copolymerizable with these monomers, as disclosed in .

  Examples of monomers having a betaine group, a sulfobetaine group or a phosphobetaine group include sulfopropyldimethylammonioethyl methacrylate, sulfoethyldimethylammonioethyl methacrylate, sulfobutyldimethylammonioethyl methacrylate, sulfohydroxypropyl methacrylate Acrylic acid or dialkyl ammonium methacrylate methacrylate such as dimethylammonioethyl, sulfopropyldimethylammoniopropylacrylamide, sulfopropyldimethylammoniopropylmethacrylamide, sulfohydroxypropyldimethylammoniopropylmethacrylamide, sulfopropyldiethylammonioethylmethacrylate , Alkyls of dialkyl ammonium alkyl acrylamide or methacrylamide Sulfonates or phosphonates; sulfobetaines derived from piperazine, 2-vinyl-1- (3-sulfopropyl) pyridinium betaine, 4-vinyl-1- (3-sulfopropyl) pyridinium betaine, 1-vinyl- Heterocyclic betaine monomers such as 3- (3-sulfopropyl) imidazolium betaine; dialkylammonium alkylallyl compounds such as sulfopropylmethyl diallylammonium betaine or hydroxyalkyl sulfonates or phosphonates; dialkylammonium alkylstyrenes Alkyl or hydroxyalkyl sulfonates or phosphonates; betaines derived from ethylenically unsaturated anhydrides and dienes; cyclic amines such as ((dicyanoethanolate) ethoxy) dimethylammoniopropylmethacrylamide Betaine, etc. resulting from the tar and the like.

Among amphoteric acrylic polymers, the storage stability and rinsing properties of the cleaning agent can be increased, so that acrylic monomers having a betaine group or homopolymers or copolymers of methacrylic monomers are preferred, and having a sulfobetaine group. A homopolymer or copolymer of an acrylic monomer or a methacrylic monomer (polysulfobetaine type amphoteric acrylic polymer) is more preferable.
As the betaine type amphoteric acrylic polymer, “MIRAPOLE SURF S 500”, “MIRAPOLE SURF S 200” (trade name, manufactured by Rhodia Nikka Co., Ltd.) and the like are commercially available.

  The content of the amphoteric acrylic polymer in the cleaning agent is preferably 0.1 to 4% by mass, more preferably 0.2 to 3% by mass, and 0.5 to 2% by mass. Particularly preferred. When the content of the amphoteric acrylic polymer is 0.1 to 4% by mass, it is possible to efficiently remove stain components and stains on the surface of the resin, and the cleaning agent component does not remain. A clean resin surface is obtained. On the other hand, if the content of the amphoteric acrylic polymer is less than 0.1% by mass, the sufficient cleaning effect and the detergency of the cleaning agent component, particularly the particulate metal oxide may be lowered. If it exceeds 1, the storage stability of the cleaning agent becomes low, and the cleaning agent tends to be difficult to extend at the time of construction, so that a sufficient cleaning effect may not be obtained.

  As a result of investigations by the present inventors, it has been found that the cleaning agent can clean and remove dirt, stains and scale marks adhering to the resin surface, particularly the coating film surface. Further, it has been found that this cleaning agent can be removed from the resin surface by rinsing with running water together with the removed dirt component even when it adheres excessively to the resin surface. Therefore, according to the said washing | cleaning agent, stain | pollution | contamination can be removed sufficiently and simply, and the clean resin surface can be obtained. Moreover, the said cleaning agent is excellent in storage stability and workability.

(Resin surface cleaning method)
The resin surface cleaning method of the present invention is a method of cleaning the resin surface using the above-described cleaning agent.
As a specific example of the method for cleaning the resin surface, for example, the cleaning agent is spread on the resin surface with a sponge, cloth or the like, and then lightly rubbed. Thereafter, rinsing with running water and, if necessary, dry wiping or wet wiping to remove excess cleaning agent can be mentioned. Further, if necessary, a polishing machine such as a polisher or a sand grinder can be used.
Examples of the resin surface to which this cleaning method is applied include, for example, a resin coating film formed by a paint for coating and a surface of a resin molded product in an automobile body.

  According to this method for cleaning the resin surface, dirt adhering to the resin surface, particularly the coating film surface, can be easily removed, and the resin surface can be discolored, altered, eroded or swollen by rinsing with the removed dirt. And can be easily removed from the resin surface. Such a method is useful as a pretreatment for a function-imparting process on the resin surface.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further, this invention is not limited at all by these Examples.

Example 1
In a 1000 mL mixing container, “Exol D-80” which is a petroleum hydrocarbon (trade name, manufactured by ExxonMobil, boiling point of 200 to 250 ° C. (about 225 ° C.) at a pressure of 0.1 MPa, flash point of 77 ° C. or more) 300 g, anionic surfactant polyoxyethylene (4 mol) oleyl ether sodium sulfate 30 g (non-volatile content 30 mass%), non-ionic surfactant “NIKKOL DECAGLLY 1-M” (trade name, Nikko Chemicals Co., Ltd.) ), 60 g of decaglycerin myristic acid monoester, nonvolatile content 100% by mass), and heated to 60-70 ° C. and mixed with stirring. In this, 240 g of hot water of about 60 ° C. was added in 20 divided portions, and the mixture was stirred and mixed with a strong shearing force to obtain an emulsion.
In a separate 1000 mL mixing container, 170 g of water and 50 g of “MIRAPOLE SURF S 500” (trade name, manufactured by Rhodia Nikka Co., Ltd., nonvolatile content 20% by mass), which is a betaine-type amphoteric acrylic polymer, Stir and mix. Into this, 150 g of aluminum oxide having an average particle diameter of 1 μm was gradually added and mixed by stirring to obtain a dispersion. And the said emulsion was added to this dispersion, and it stirred and mixed, and obtained 1000g of cleaning agents.

The obtained cleaning agent was evaluated by the following method. The evaluation results are shown in Table 1.
[Resin articles for evaluation]
For the evaluation of the cleaning agent, as a resin article, a bonnet ("Life" repair / replacement bonnet (black), manufactured by Honda Motor Co., Ltd.) or a test cationic electrodeposition coating plate (70 mm × 150mm), manufactured by Testpiece Co., Ltd., JIS G 3141 (SPCC SD), two-component urethane paint for automobile repair (BC base coat, D800 Deltron Clear, D841 Medium MS Hardener, Multi Thinner, PPG Japan Co., Ltd.) The coating film of the painting board which painted is used.

[Evaluation of separation resistance]
The cleaning agent was allowed to stand at 50 ° C. for one week, and the presence or absence of oil floating on the liquid surface was visually observed to evaluate separation resistance. The separation resistance is one of storage stability indexes, and the smaller the change, the better the storage stability.
○: There was no change in the liquid level.
Δ: Oil droplets were observed on the liquid surface.
Δ ×: A slight oil layer was present on the liquid surface.
X: It had an oil layer on the liquid surface.

[Evaluation of sedimentation resistance]
After leaving the cleaning agent at 50 ° C. for one week, the presence or absence of sedimentation of the particulate metal oxide was visually observed to evaluate the sedimentation resistance. Sedimentation resistance is one of the storage stability indicators, and the smaller the sediment, the better the storage stability.
○: No sediment was observed on the bottom.
○ △: Slightly deposited on the bottom.
(Triangle | delta): It had a soft sediment on the bottom face.
X: The bottom had a hard sediment.

[Evaluation of redispersibility]
When the fine particle metal oxide settled by leaving the cleaning agent at 50 ° C. for one week, the redispersibility of the precipitate was visually evaluated with stirring. The redispersibility is one of the storage stability indexes, and the easier the redispersion, the better the storage stability.
○: The sediment was redispersed. Or there was no sediment.
X: The sediment was not redispersed.

[Evaluation of the elongation of cleaning agents]
First, tap water was poured over the hood to wash away dust and sand. About 5 mL of the cleaning agent was taken in a sponge dipped in tap water and lightly wiped back and forth several times so as to gently wipe the bonnet, and the cleaning agent was spread on the bonnet surface. The elongation of the cleaning agent at that time was visually evaluated. In addition, the extendability of a cleaning agent is one of the indexes of workability, and the longer it is, the better the workability is.
○: It had an extension.
Δ: Slightly extended.
X: It did not have extension.

[Evaluation of cleaning agent removal]
In order to remove the white powder generated by drying the cleaning agent after the cleaning agent was spread on the bonnet surface in order to evaluate the extensibility of the cleaning agent, it was wiped dry or wet. The removal property of the cleaning agent was evaluated based on how much time it took to wipe off the white powder. In addition, the removability of a cleaning agent is one of the indexes of workability, and the easier it is to remove, the better the workability.
○: The white powder was easily removed without sticking.
Δ: It took time, but the white powder could be removed.
X: The white powder adhered and could not be removed.

[Contact angle]
After degreasing the painted plate (70 mm x 150 mm) with normal hexane, take about 3 mL of cleaning agent in a sponge and reciprocate several times so that the surface of the painted plate is lightly wiped. It was. Thereafter, the surface of the coated plate was rinsed with tap water, and gently washed with a sponge. The contact angle with water on the surface of the coated plate after natural drying was measured using a FACE contact angle measuring device (Kyowa Interface Science Instruments Co., Ltd.).
By comparing the amount of change with the contact angle of water (initial contact angle: 89 degrees) on the surface of the paint plate after degreasing with normal hexane, the dirt state on the paint plate surface and the residual state of the cleaning agent Can be estimated.
The amount of change is in the range of ± 2 degrees or less: It is estimated that the surface is clean with no impurities on the surface.
The amount of change is in the range of more than ± 2 degrees and less than ± 10 degrees: it is estimated that the surface has oily soil or inorganic soil due to insufficient cleaning, and the cleaning agent component remains.
Change amount is ± 10 degrees or more: It is estimated that the surface is adsorbed with an oily or hydrophilic compound.

[Evaluation of stain removability]
A contaminated coated plate was prepared by applying asphalt dissolved in hexane to a coated plate (70 mm × 150 mm), drying and adhering it, and then heat-treating at 80 ° C. for 10 minutes. Next, the cleaning agent was spread on the surface of the contaminated coated plate by reciprocating several times with a sponge having about 3 mL of the cleaning agent. After drying, the surface of the painted plate was rinsed with tap water, and the detergent was washed away while gently stroking with a sponge, followed by natural drying. The condition of the surface of the coated plate after natural drying was visually evaluated.
○: Dirt on the painted plate surface was removed.
○ △: Dirt on the painted plate surface was almost removed.
Δ: Some dirt remained on the surface of the painted plate.
X: Dirt was not removed at all.

[Evaluation of rinse removal]
About 3 mL of the cleaning agent was taken on a sponge, spread on the surface of a painted plate (70 mm × 150 mm), and dried. Next, the white powder generated by drying the cleaning agent was rinsed off by simply rinsing with water, and the degree to which the white powder remained on the painted plate surface was visually evaluated.
○: White powder was removed.
X: White powder was not removed.

Examples 2 to 13 and Comparative Examples 1 to 7
Example 1 except that the blends of petroleum hydrocarbon, anionic surfactant, nonionic surfactant, amphoteric acrylic polymer, particulate metal oxide and water were changed as shown in Tables 1 to 3 respectively. By operating in the same manner, the cleaning agents of Examples 2 to 13 and Comparative Examples 1 to 7 were obtained. The obtained cleaning agent was evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 1-3.

In addition, the abbreviation in a table | surface represents the following.
Petroleum hydrocarbon 1: "Exol D-80"
Petroleum hydrocarbon 2: Petroleum hydrocarbon having a boiling point of about 257 ° C. at a pressure of 0.1 MPa and a flash point of about 117 ° C. Petroleum hydrocarbon 3: Boiling point of about 182 ° C. and a flash point of about 37 ° C. at a pressure of 0.1 MPa Petroleum hydrocarbons Anionic surfactant 1: Polyoxyethylene (4 mol) oleyl ether sodium sulfate (non-volatile content 30% by mass)
Anionic surfactant 2: polyoxyethylene (4 mol) sodium lauryl ether acetate (nonvolatile content 30% by mass)
Nonionic surfactant 1: “NIKKOL DECAGLYN 1-M”, decaglycerin myristic acid monoester (non-volatile content: 100% by mass)
Nonionic surfactant 2: “Hexaglyn 1-L” (hexaglycerin lauric acid monoester) (non-volatile content: 100% by mass)
Nonionic surfactant 3: “Decalyn 2-ISV” (decaglycerin isostearic acid diester) (non-volatile content: 100% by mass)
Amphoteric acrylic polymer: “MIRAPOLE SURF S 500” (non-volatile content 20% by mass)

The cleaning agents of Examples 1 to 13 containing specific amounts of petroleum hydrocarbons, particulate metal oxides, anionic surfactants, nonionic surfactants, amphoteric acrylic polymers and water are excellent in storage stability and workability. It was excellent. In addition, according to the cleaning agents of Examples 1 to 13, it was possible to obtain a clean resin surface by being excellent in soil removability, preventing residue such as soiling by simple rinsing.
On the other hand, the cleaning agents of Comparative Examples 1 and 2 in which an anionic surfactant and a nonionic surfactant are not used in combination have low storage stability and workability. No resin surface was obtained.
As with Comparative Examples 1 and 2, the cleaning agent of Comparative Example 3 containing no petroleum-based hydrocarbons has low storage stability and workability, and dirt remains even after rinsing, resulting in a clean resin surface. It was not obtained.
In the cleaning agent of Comparative Example 4 in which no particulate metal oxide was blended, the stain removability was low.
In the cleaning agent of Comparative Example 5 in which the amphoteric acrylic polymer was not blended, the workability was low and the rinsing removability was low. In particular, the particulate metal oxide remained and a clean resin surface could not be obtained.
In addition, the cleaning agent of Comparative Example 6 in which the content of the amphoteric acrylic polymer exceeded 4% by mass had low storage stability and workability. Furthermore, the contact angle becomes small and it seems that the amphoteric acrylic polymer is adhered.
In the cleaning agent of Comparative Example 7 containing a petroleum hydrocarbon having a flash point of less than 40 ° C., the storage stability and workability were low.

Claims (9)

7-50% by mass of a liquid petroleum hydrocarbon having a boiling point of 150 ° C. or higher at an atmospheric pressure of 0.1 MPa and a flash point of 40 ° C. or higher at an atmospheric pressure of 0.1 MPa,
3 to 30% by weight of fine metal oxide,
Anionic surfactant 0.1-3 mass%,
Nonionic surfactant 0.5-10 mass%,
0.1 to 4% by weight of amphoteric acrylic polymer,
And 30-70% by mass of water,
A resin surface cleaning agent comprising:   The cleaning agent for resin surface according to claim 1, wherein the boiling point of petroleum hydrocarbon at a pressure of 0.1 MPa is 170 ° C or higher and the flash point at a pressure of 0.1 MPa is 45 ° C or higher. .   3. The resin surface cleaning agent according to claim 1 or 2, wherein the petroleum hydrocarbon is a naphthene hydrocarbon.   The resin surface cleaning agent according to any one of claims 1 to 3, wherein the particulate metal oxide is at least one metal oxide selected from the group consisting of aluminum oxide, silicon oxide and magnesium oxide. .   5. The resin surface cleaning agent according to claim 1, wherein the fine particle metal oxide has an average particle size of 0.1 to 5 [mu] m.   The resin surface cleaning agent according to any one of claims 1 to 5, wherein the anionic surfactant is a sulfate ester type anionic surfactant or a sulfonic acid type anionic surfactant.   The resin surface cleaning agent according to claim 1, wherein the nonionic surfactant is a polyglycerin ester type nonionic surfactant.   The resin surface cleaning agent according to any one of claims 1 to 7, wherein the amphoteric acrylic polymer is a betaine-type amphoteric acrylic polymer.   A method for cleaning a resin surface, wherein the resin surface is cleaned using the resin surface cleaning agent according to claim 1.