Vehicle coating agent

Abstract

To provide a vehicle coating agent which does not require coating of a substrate agent, and can apply high level flowing property even by single coating.SOLUTION: There is provided a vehicle coating agent including: at least one kind selected from, silicon resin, amino modified silicon, block isocyanate, and a hydrocarbon polymer, where the block isocyanate being emulsified by a cationic surface active agent.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a vehicle coating agent.

Background Art

[0002] In the car wash treatment by a car washing machine, a coating agent containing silicone resin as a main component is used as a vehicle coating agent having a high water splash effect (for example, see Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, the conventional coating agent as described above cannot obtain a sufficient water splash effect with a single coating, and thus it was necessary to apply an undercoat agent having a binder role before applying the coating agent.

[0005] One aspect of the present invention aims to realize a vehicle coating agent that does not require the application of an undercoat agent and can impart high water repellency and water drainage (water runoff) even with a single coating.

Means for Solving the Problems

[0006] In order to solve the above problems, a vehicle coating agent according to one aspect of the present invention includes a silicone resin, an amino-modified silicone, and at least one selected from a blocked isocyanate and a hydrocarbon polymer, and the blocked isocyanate is emulsified with a cationic surfactant.

Effects of the Invention

[0007] According to one aspect of the present invention, it is possible to impart high water repellency and running water property (water drainage property) with a single coating without the need for applying an undercoat agent.

Embodiments for Carrying Out the Invention

[0008] One embodiment of the present invention will be described below, but the present invention is not limited thereto. The present invention is not limited to each configuration described below, and various modifications are possible within the scope shown in the claims. Also, embodiments or examples obtained by combining technical means respectively disclosed in different embodiments or examples are also included in the technical scope of the present invention. Further, unless otherwise specified in this specification, "A to B" representing a numerical range is intended to mean "A or more and B or less".

[0009] In this specification, water repellency refers to the property of repelling water and can be evaluated, for example, by the contact angle. It can be said that the larger the contact angle, the better the water repellency. Also, running water property (also referred to as water drainage property) refers to the property that water droplets easily roll off and can be evaluated, for example, by the sliding angle which is the angle when the water droplets slide. It can be said that the smaller the sliding angle, the better the running water property.

[0010] [1. Vehicle Coating Agent] The vehicle coating agent according to one embodiment of the present invention includes a silicone resin, an amino-modified silicone, and at least one selected from a blocked isocyanate and a hydrocarbon polymer, and the blocked isocyanate is emulsified with a cationic surfactant. Hereinafter, in this specification, the "vehicle coating agent according to one embodiment of the present invention" may be referred to as the "present vehicle coating agent".

[0011] [1.1] Silicone Resin In this specification, the silicone resin is intended to be a resin mainly composed of organopolysiloxane, and includes a silicone oligomer which is an organopolysiloxane with a small molecular weight having a three-dimensional crosslinked structure (for example, having a weight average molecular weight of less than 10,000), and a silicone resin in the narrow sense which is an organopolysiloxane with a large molecular weight having a three-dimensional crosslinked structure (for example, having a weight average molecular weight of 10,000 or more). Note that in this specification, the weight average molecular weight is the molecular weight determined using polystyrene as a standard substance by gel permeation chromatography.

[0012] The silicone resin used in this vehicle coating agent may be one or more selected from a silicone oligomer and a silicone resin in the narrow sense, but it is more preferable to include a silicone resin in the narrow sense, and it is even more preferable to be a silicone resin in the narrow sense. Such a silicone resin in the narrow sense is roughly classified into a straight resin and a silicone-modified organic resin. The former consists only of silicone components. The latter consists of a copolymer of a silicone component and an organic resin. Among them, the straight resin is roughly classified into a DT resin containing D units (R2SiO 2 / 2 ) and T units (RSiO 3 / 2 ) as main constituent units, and an MQ resin (trimethylsiloxysilicate) having M units (R3SiO 1 / 2 ) and Q units (SiO 4 / 2 ) as main constituent units.

[0013] R in the M unit, D unit and T unit is independently a hydrocarbon group having 1 to 15 carbon atoms, more preferably a hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group may be linear, branched, may contain an alicyclic hydrocarbon group, or may contain an aromatic hydrocarbon group. Also, the hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Preferred examples of R include a methyl group, a phenyl group, and the like. It is even more preferable that the silicone resin is an MQ resin having M units and Q units as main constituent units.

[0014] MQ resin (trimethylsiloxysilicic acid) has the general formula (R3SiO 1 / 2 ) X ·(SiO 4 / 2 ) Y (y / x = 0.1 to 0.9). This is made by using water glass as the starting material for Q units (SiO 4 / 2 ) and blocking the ends with trimethylsilyl groups (M units SiO 1 / 2 ).

[0015] The silicone resin may or may not have a functional group in the molecule.

[0016] Also, the silicone resin may be a dispersion, and from the viewpoint of stability during storage, etc., it may be emulsified with surfactants such as cationic surfactants, nonionic surfactants, and amphoteric surfactants.

[0017] Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyhydric alcohol fatty acid ester, polyoxyethylene polyhydric alcohol fatty acid ester, polyoxyethylene fatty acid ester, polyglycerin fatty acid ester, alkylamine oxide, etc. and these can be used.

[0018] Examples of the cationic surfactant include quaternary ammonium salts, alkylamine salts, and ethylene oxide adducts thereof, etc. and these can be used.

[0019] Examples of the amphoteric surfactant include fatty acid amidopropyl betaine, imidazoline derivatives, etc. and these can be used.

[0020] As the silicone resin, commercially available silicone resins can be used. As commercially available silicone resins, those commercially available as dispersions of silicone resins include DOWSIL TMExamples include 593 Fluid (manufactured by Dow Corning Toray Co., Ltd.), X-52-8005 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. Also, as commercially available products of silicone resin alone, there are BELSIL TMS803 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), DOWSIL TM MQ-1600Resin (manufactured by Dow Corning Toray Co., Ltd.), etc.

[0021] The silicone resin described above may be used alone or in combination of two or more kinds.

[0022] [1.2] Amino-modified silicone Examples of the amino-modified silicone include modified silicone oils in which at least one or more amino groups are introduced at the ends and / or side chains of the dimethyl silicone skeleton.

[0023] The at least one or more amino groups can be introduced as an amino group and / or an amino group-containing organic group that binds to the silicon atom constituting the dimethyl silicone skeleton. Examples of the amino group-containing organic group include -R 1 NH2 (where R 1 is an alkylene group.), etc. of the monoamine type organic group, -R 2 NHR 3 NH2 (where R 2 and R 3 are each independently an alkylene group.), etc. of the diamine type organic group, etc. R 1 , R 2 and R 3 are hydrocarbon groups, which may be linear, branched, may contain an alicyclic hydrocarbon group, or may contain an aromatic hydrocarbon group. Also, the hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Preferred examples of R 1 , R 2 and R 3 include a methylene group, an ethylene group, a propylene group, a phenyl group, etc.

[0024] The amino group and / or the amino group-containing organic group may be introduced at the terminal and / or the side chain of the dimethyl silicone skeleton. In other words, as the amino-modified silicone, the amino group and / or the amino group-containing organic group may be a side chain type amino-modified silicone introduced into the side chain, a both ends type amino-modified silicone introduced into both ends, a single end type amino-modified silicone introduced into one end, a both ends and side chain type amino-modified silicone introduced into both ends and the side chain, a single end and side chain type amino-modified silicone introduced into one end and the side chain, and the like.

[0025] In one embodiment of the present invention, the amino-modified silicone may be a modified silicone oil in which at least one or more amino groups are introduced at the terminal and / or the side chain of a skeleton in which silicone chains and polyoxyalkylene are alternately and linearly bonded.

[0026] The amino-modified silicone may further have other functional groups and / or functional group-containing organic groups other than the amino group and / or the amino group-containing organic group. When having other functional groups and / or functional group-containing organic groups, these groups may be present in a part of the side chain or at the terminal of the main chain of the amino-modified silicone. Examples of other functional groups or functional group-containing organic groups that may be present in a part of the side chain or at the terminal of the main agent include a phenyl group, a polyether group, an epoxy group, a hydroxyl group, and the like.

[0027] Further, the amino-modified silicone may be a dispersion liquid and may be emulsified by a surfactant such as a nonionic surfactant, a cationic surfactant, or an amphoteric surfactant.

[0028] Examples of the nonionic surfactant that can be used include polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyhydric alcohol fatty acid ester, polyoxyethylene polyhydric alcohol fatty acid ester, polyoxyethylene fatty acid ester, polyglycerin fatty acid ester, alkylamine oxide, and the like.

[0029] As the cationic surfactant, for example, quaternary ammonium salts, alkylamine salts, and ethylene oxide adducts thereof can be used.

[0030] As the amphoteric surfactant, for example, fatty acid amide propyl betaine, alkyl imidazoline, etc. can be used.

[0031] The surfactant may be used alone or in combination of two or more.

[0032] As the amino-modified silicone, commercially available amino-modified silicones can be used. Examples of commercially available amino-modified silicones include KF-880 (manufactured by Shin-Etsu Chemical Co., Ltd.), DOWSIL TM 3705 (manufactured by Dow Corning Toray Co., Ltd.), etc.

[0033] The amino-modified silicone may be used alone or in combination of two or more of the aforementioned amino-modified silicones.

[0034] In one embodiment of the present invention, the amino equivalent of the amino-modified silicone is preferably 300 g / mol to 7000 g / mol, more preferably 1000 g / mol to 3000 g / mol. If the amino equivalent of the amino-modified silicone is 7000 g / mol or less, it is preferable because the adsorptivity to the coated surface of the vehicle coating agent is excellent. Further, if the amino equivalent is 300 g / mol or more, there is an advantage that the reactivity is not too strong and yellowing of the film does not occur. The amino equivalent of the amino-modified silicone can be obtained by dividing the weight average molecular weight of the amino-modified silicone by the number of nitrogen atoms contained in the amino-modified silicone.

[0035] Also, the kinematic viscosity of the amino-modified silicone at 25°C is 200 mm 2 / s to 5000 mm 2 / s, preferably 500 mm 2 / s~3000 mm 2 It is more preferably / s. If the kinematic viscosity is 5000 mm 2 / s or less, when the vehicle coating agent is spray-applied using, for example, a car wash machine, stains and / or unevenness are less likely to occur on the vehicle surface, and it is preferable because it does not become a factor inhibiting the water flow property, which is a characteristic of the silicone resin. Further, if the kinematic viscosity is 200 mm 2 / s or more, the film does not become too thin. Therefore, it is preferable because it does not cause a decrease in the water flow property due to the thin film. The kinematic viscosity of the amino-modified silicone at 25°C can be measured by a known method described in JIS K 2283:2000 (Ubbelohde viscometer), etc.

[0036] When using a combination of multiple types of amino-modified silicones as the amino-modified silicone, it is preferable that the kinematic viscosity of the mixture is within the above range. Note that the kinematic viscosity is the kinematic viscosity of the amino-modified silicone itself and does not intend the kinematic viscosity of a solution or dispersion.

[0037] [1.3] Block isocyanate The block isocyanate used in the vehicle coating agent is not particularly limited as long as it is obtained by previously reacting the active isocyanate group in the polyisocyanate compound with a blocking agent to inactivate it.

[0038] The polyisocyanate compound is a compound having two or more isocyanate groups per molecule, and examples thereof include various polyisocyanate compounds such as diisocyanate compounds, triisocyanate compounds, tetraisocyanate compounds, pentaisocyanate compounds, and hexaisocyanate compounds. A more specific example of the polyisocyanate includes aromatic polyisocyanates such as tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI); aliphatic isocyanates such as hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI).

[0039] The blocking agent is not particularly limited. For example, alcohols such as methanol, ethanol, 2-propanol, 2-methoxyethanol; phenols such as phenol, methylphenol, n-propylphenol, iso-propylphenol, iso-butylphenol, t-butylphenol, octylphenol, nonylphenol; active methylenes such as dimethyl malonate, diethyl malonate, methyl acetoacetate, acetylacetone; mercaptans such as butyl mercaptan, dodecyl mercaptan; acid amides such as acetanilide, acetic acid amide, ε-caprolactam, δ-valerolactam, γ-butyrolactam; acid imides such as succinimide, maleimide; imidazoles such as imidazole, 2-methylimidazole; ureas such as urea, thiourea; oximes such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime; amines such as diphenylamine, diisopropylamine, aniline; imines such as ethyleneimine, polyethyleneimine; pyrazoles such as pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole; sodium bisulfite and the like can be mentioned.

[0040] The polyisocyanate compound constituting the blocked isocyanate used in this vehicle coating agent may be of one kind or a combination of multiple kinds. Also, the blocking agent may be of one kind or a combination of multiple kinds.

[0041] The blocked isocyanate used in this vehicle coating agent is emulsified with a cationic surfactant. As the cationic surfactant, for example, quaternary ammonium salts, alkylamine salts, and ethylene oxide adducts thereof can be used. More specific examples of the cationic surfactant include, for example, Lipocard 2HT-75, Leomix T-50, Liposcard C / 12 (Lion Corporation) and the like.

[0042] Since the blocked isocyanate is a non-adsorptive substance, adsorption by a cationic surfactant is essential. By using a blocked isocyanate emulsified with a cationic surfactant as the blocked isocyanate, when the vehicle coating agent is spray-coated, ionic adsorption of the blocked isocyanate onto the coated surface becomes possible. As a result, the blocked isocyanate forms a film on the coated surface together with the silicone resin contained in the vehicle coating agent. Since the silicone resin has a three-dimensional and high-density cross-linked network-like three-dimensional structure, the water repellency increases due to the orientation of CH3 groups on the surface of the film. On the other hand, since the blocked isocyanate has weaker water repellency than the silicone resin with CH3 groups oriented on the surface, a slight difference in water repellency is expected to occur between the silicone resin and the blocked isocyanate on the film surface. Since water droplet slippage is promoted by the formation of a composite surface film having a continuous gradient from a region with strong water repellency to a region with weak water repellency on the same surface, it is presumed that the coating film formed from the silicone resin and the blocked isocyanate is likely to exhibit flowing water properties.

[0043] [1.4] Hydrocarbon polymer The hydrocarbon polymer used in the vehicle coating agent is at least one selected from the group consisting of urethane resins, polyolefin resins, acrylic resins, and fluorine resins. The hydrocarbon polymer may be acid-modified.

[0044] For example, an acid-modified polyolefin resin is lipophilic and has adsorptivity due to being acid-modified. Therefore, the acid-modified polyolefin resin has excellent adhesion and is easily complex-adsorbed with the silicone resin. Thus, together with the silicone resin contained in the vehicle coating agent, it forms a film on the surface to be coated. Since the silicone resin has a three-dimensional and highly crosslinked network-like three-dimensional structure, while the CH3 groups are oriented on the surface of the film, and at the same time the polyolefin also has CH3 groups in the polymer backbone, it is expected that the density of the CH3 groups oriented on the surface of the film will increase. Since the water-repellent CH3 groups form a uniform and smooth coating film without gaps, the water droplet sliding effect is promoted, so it is presumed that the running water property is likely to be exhibited. For urethane resins, acrylic resins, and fluorine resins, it is presumed that the running water property is likely to be exhibited by the same mechanism.

[0045] The hydrocarbon polymer may be added as a dispersion, and may be emulsified by a surfactant such as a nonionic surfactant, a cationic surfactant, or an amphoteric surfactant.

[0046] (Urethane resin) The urethane resin is not particularly limited as long as it is a polyurethane resin obtained by reacting a polyol and a polyisocyanate. As a more specific example of the urethane resin, a polyurethane resin obtained by reacting a polyol such as polypropylene glycol or polyester polyol with a polyisocyanate such as diphenylmethane diisocyanate or tolylene diisocyanate can be mentioned.

[0047] As the urethane resin, a commercially available urethane resin can be used. Examples of commercially available urethane resins include those commercially available as a dispersion of urethane resins, such as Superflex 650 and Superflex E-2000 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.); Adeka Bon Titer HUX-210 and Adeka Bon Titer HUX-895 (manufactured by Adeka Corporation).

[0048] (Polyolefin resin) Examples of the polyolefin resin include polyethylene, polypropylene, ethylene-propylene copolymer, and the like.

[0049] The polyolefin resin is preferably an acid-modified polyolefin resin. Examples of the acid-modified polyolefin resin include acid-modified polypropylene resin, acid-modified polyethylene resin, etc. From the viewpoint of better water flowability, acid-modified polypropylene resin is more preferable.

[0050] Preferable examples of the acid-modified polyolefin include modified polymers obtained by copolymerizing (e.g., graft copolymerizing) a polyolefin with an unsaturated carboxylic acid or its derivative. Examples of the unsaturated carboxylic acid or its derivative include unsaturated carboxylic acids such as maleic acid and fumaric acid, their acid anhydrides, their esters, or their metal salts.

[0051] As the polyolefin resin, commercially available polyolefin resins can be used. Examples of the commercially available polyolefin resin as a dispersion of polyolefin resin include Hi-Tech P-5060P (manufactured by Toho Chemical Industry Co., Ltd.). Examples of the polyolefin resin commercially available alone include LICOCENE MA6252 GR (manufactured by Clariant Plastics & Coatings).

[0052] (Acrylic resin) Examples of the acrylic resin include poly(meth)acrylic acid, poly(meth)acrylic acid ester, polyacrylamide, ethylene-acrylic acid copolymer, and the like.

[0053] In this specification, the term "(meth)acrylic acid" is intended to mean both acrylic acid and methacrylic acid. Examples of the poly(meth)acrylate ester include (meth)acrylate esters with alcohols having an alkyl group with 1 to 18 carbon atoms, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, glycidyl (meth)acrylate, allyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and the like.

[0054] As the acrylic resin, commercially available acrylic resins can be used. Examples of commercially available acrylic resins include those commercially available as dispersion liquids of acrylic resins, such as Polystron 1280 (manufactured by Arakawa Chemical Industries, Ltd.).

[0055] (Fluororesin) Examples of fluororesins include polytetrafluoroethylene, poly(chlorotrifluoroethylene), and the like.

[0056] As the fluororesin, commercially available fluororesins can be used. Examples of commercially available fluororesins include those commercially available as dispersion liquids of fluororesins, such as Rubron LDW-410 (manufactured by Daikin Industries, Ltd.).

[0057] [1.5] Other Components This vehicle coating agent preferably contains water. Water can function as a medium for uniformly dispersing and diluting the above-mentioned respective components contained in this vehicle coating agent. The content of water contained in this vehicle coating agent is not particularly limited. Further, this vehicle coating agent can be appropriately diluted with a car wash machine and used.

[0058] The water used in the vehicle coating agent is more preferably water containing no impurities so as not to affect the respective components. For example, distilled water, ion-exchanged water, tap water, etc. can be preferably used.

[0059] In one embodiment of the present invention, the silicone resin, the amino-modified silicone, the blocked isocyanate, and the hydrocarbon polymer can be mixed as an aqueous emulsion. The vehicle coating agent may contain water derived from these aqueous emulsions.

[0060] In addition, the aqueous emulsions of the silicone resin, the amino-modified silicone, the blocked isocyanate, and the hydrocarbon polymer may contain a surfactant. Therefore, the vehicle coating agent may contain a surfactant derived from these aqueous emulsions.

[0061] In addition to the above components, the vehicle coating agent may further contain, as necessary, a low-temperature stabilizer, an emulsion stabilizer, a preservative, a pH adjuster, a rust inhibitor, silicone oil, an organic acid, an inorganic acid, etc. as a neutralizing agent for the amino-modified silicone, within a range that does not hinder the effects of the present invention. Note that the silicone oil is not included in the silicone resin of the present disclosure which is a resin mainly composed of organopolysiloxane.

[0062] [1.6] Vehicle coating agent The vehicle coating agent includes the silicone resin, at least one selected from the amino-modified silicone, the blocked isocyanate, and the hydrocarbon polymer, and the blocked isocyanate only needs to be emulsified with a cationic surfactant.

[0063] The content ratio of the solid content of the amino-modified silicone to the total mass of the vehicle coating agent is preferably 1% by mass to 15% by mass, and more preferably 1% by mass to 10% by mass, for example, when the water content is 75% by mass.

[0064] If the content ratio of the amino-modified silicone is 1% by mass or more, it is preferable because the coating agent can be sufficiently adsorbed to the vehicle surface. On the other hand, if the content ratio of the amino-modified silicone is 15% by mass or less, unevenness is less likely to occur on the vehicle surface. Therefore, it is preferable because it is less likely to inhibit the water repellency of the silicone resin.

[0065] The content ratio of the solid content of the silicone resin to the total mass of the vehicle coating agent is preferably 1% by mass to 20% by mass, more preferably 1% by mass to 10% by mass, for example, when the water content is 75% by mass.

[0066] If the content ratio of the silicone resin is 1% by mass or more, it is preferable because the coating agent exhibits sufficient water repellency. On the other hand, if the content ratio of the silicone resin is 20% by mass or less, the film becomes uniform and unevenness is less likely to occur on the vehicle surface, so it is preferable.

[0067] The content ratio of the solid content of the blocked isocyanate to the total mass of the vehicle coating agent is preferably 0.1% by mass to 10% by mass, more preferably 0.1% by mass to 5% by mass, for example, when the water content is 75% by mass.

[0068] If the content ratio of the blocked isocyanate is 0.1% by mass or more, the blocked isocyanate participates in the film formation on the vehicle surface, and a slight difference in water repellency occurs between the blocked isocyanate and the silicone resin on the film surface, so it is preferable. As a result, a composite surface film having a continuous gradient from a region with strong water repellency to a region with weak water repellency is formed on the same surface, and sufficient water repellency is exhibited. On the other hand, if the content ratio of the blocked isocyanate is 10% by mass or less, unevenness is less likely to occur on the vehicle surface. Therefore, it is preferable because it is less likely to inhibit the water repellency of the silicone resin.

[0069] The content ratio of the solid of the cationic surfactant that emulsifies the blocked isocyanate to the total mass of the vehicle coating agent is preferably 0.1 mass% to 10 mass%, more preferably 0.1 mass% to 5 mass% when the water content is 75 mass%, for example.

[0070] If the content ratio of the cationic surfactant is 0.1 mass% or more, it is preferable because the coating agent (blocked isocyanate) can be sufficiently adsorbed to the vehicle surface. If the content ratio of the cationic surfactant is 10 mass% or less, the hydrophilicity of the cationic surfactant itself will not be strongly expressed, so it is difficult to inhibit the water flow property, which is a characteristic of the silicone resin.

[0071] The content ratio of the solid of the hydrocarbon polymer to the total mass of the vehicle coating agent is preferably 0.1 mass% to 10 mass%, more preferably 0.1 mass% to 5 mass% when the water content is 75 mass%, for example.

[0072] If the content ratio of the hydrocarbon polymer is 0.1 mass% or more, the coating agent participates in the film formation on the vehicle surface and forms a uniform film. Therefore, it is preferable because the water flow property, which is a characteristic of the silicone resin, is expressed. On the other hand, if the content ratio of the hydrocarbon polymer is 10 mass% or less, the film of the coating agent becomes uniform and it is difficult for unevenness to occur on the vehicle surface, so it is preferable.

[0073] [2. Manufacturing Method of Vehicle Coating Agent] The manufacturing method of the vehicle coating agent is not particularly limited, and it may include the step of mixing the above-mentioned components, and usually, the methods commonly used in the art can be appropriately adopted.

[0074] [3. Use of Vehicle Coating Agent] This vehicle coating agent can be suitably used as a coating agent for vehicles such as automobiles and railway vehicles.

[0075] In particular, since the present vehicle coating agent does not require the application of a primer and can impart high water repellency and water runoff even with a single application, the present vehicle coating agent and the coating agent containing the same can be suitably used as a one-component vehicle coating agent for single application with an automatic car wash.

[0076] <Summary> One embodiment of the present invention includes the following configurations.

[0077] [1] It includes a silicone resin, an amino-modified silicone, and at least one selected from a blocked isocyanate and a hydrocarbon polymer. The blocked isocyanate is emulsified with a cationic surfactant, and the vehicle coating agent.

[0078] [2] The hydrocarbon polymer according to [1], wherein the hydrocarbon polymer is at least one selected from the group consisting of a urethane-based resin, a polyolefin-based resin, an acrylic-based resin, and a fluorine-based resin.

[0079] [3] The vehicle coating agent according to [2], wherein the polyolefin-based resin is an acid-modified polypropylene resin.

[0080] [4] The vehicle coating agent according to any one of [1] to [3], wherein the amino equivalent of the amino-modified silicone is 300 g / mol to 7000 g / mol.

[0081] [5] The vehicle coating agent according to any one of [1] to [4], wherein the kinematic viscosity of the amino-modified silicone is 200 mm 2 / s to 5000 mm 2 / s.

[0082] [6] A one-component vehicle coating agent containing the vehicle coating agent according to any one of [1] to [5] for single application with an automatic car wash.

Examples

[0083] Hereinafter, an embodiment of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[0084] [Example 1: Production of a coating agent containing a silicone resin, an amino-modified silicone, and a blocked isocyanate emulsified with a cationic surfactant] 10 parts by mass of an amino-modified silicone (KF-880, manufactured by Shin-Etsu Chemical Co., Ltd.) and 3 parts by weight of a polyoxyethylene alkyl ether were mixed, and then 60 parts by mass of ion-exchanged water was added and stirred for emulsification to obtain an amino-modified silicone emulsion. Next, in a separate container, 2 parts by mass of a blocked isocyanate (SC-8B, manufactured by Aika Industries Co., Ltd., non-volatile content 67% by mass) and 1 part by mass of a quaternary ammonium salt (Lipcard 2HT-75, manufactured by Lion Corporation, non-volatile content 75% by mass) were mixed, and 8 parts by mass of ion-exchanged water was added and stirred for emulsification to obtain an emulsion of the blocked isocyanate. The total amount of the obtained emulsion of the blocked isocyanate was added to the aforementioned amino-modified silicone emulsion, and further 16 parts by mass of a silicone resin (X-52-8005, manufactured by Shin-Etsu Chemical Co., Ltd., non-volatile content 58% by mass, aqueous emulsion) was added and stirred and dispersed. Then, the pH was adjusted to 5 to 7 with citric acid, and the obtained composition was used as a vehicle coating agent (1).

[0085] [Comparative Example 1: Production of a coating agent containing a silicone resin, an amino-modified silicone, and a blocked isocyanate emulsified with an amphoteric surfactant] Instead of mixing 2 parts by mass of blocked isocyanate (manufactured by Aika Kogyo Co., Ltd., SC-8B, non-volatile content 67% by mass) and 1 part by mass of quaternary ammonium salt (manufactured by Lion Corporation, Lipocard 2HT-75, non-volatile content 75% by mass), adding 8 parts by mass of ion-exchanged water and performing stirring and emulsification, 2 parts by mass of blocked isocyanate (manufactured by Aika Kogyo Co., Ltd., SC-8B, non-volatile content 67% by mass) and 4 parts by mass of fatty acid amide propyl betaine (manufactured by Kawaken Fine Chemicals Co., Ltd., Softazoline LPB, non-volatile content 30% by mass) were mixed, and 14 parts by mass of ion-exchanged water was added and stirring and emulsification were performed. A composition was prepared by performing the same operations as in Example 1 except that an emulsion of blocked isocyanate thus obtained was used, and it was designated as Comparative Vehicle Coating Agent (1).

[0086] [Comparative Example 2: Production of a Coating Agent Containing a Silicone Resin, an Amino-Modified Silicone, and a Blocked Isocyanate Emulsified with a Nonionic Surfactant] Instead of mixing 2 parts by mass of blocked isocyanate (manufactured by Aika Kogyo Co., Ltd., SC-8B, non-volatile content 67% by mass) and 1 part by mass of quaternary ammonium salt (manufactured by Lion Corporation, Lipocard 2HT-75, non-volatile content 75% by mass), adding 8 parts by mass of ion-exchanged water and performing stirring and emulsification, 2 parts by mass of blocked isocyanate (manufactured by Aika Kogyo Co., Ltd., SC-8B, non-volatile content 67% by mass) and 1 part by mass of polyoxyethylene alkyl ether were mixed, and 8 parts by mass of ion-exchanged water was added and stirring and emulsification were performed. A composition was prepared by performing the same operations as in Example 1 except that an emulsion of blocked isocyanate thus obtained was used, and it was designated as Comparative Vehicle Coating Agent (2).

[0087] [Example 2: Production of a Coating Agent Containing a Silicone Resin, an Amino-Modified Silicone, and a Polyolefin-Based Resin] 10 parts by mass of amino-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd., KF-880) and 3 parts by weight of polyoxyethylene alkyl ether were mixed, and then 67 parts by mass of ion-exchanged water was added and stirred for emulsification to obtain an amino-modified silicone emulsion. Next, 4 parts by mass of an acid-modified polypropylene resin (manufactured by Toho Chemical Industry Co., Ltd., Hi-Tech P-5060P, non-volatile content 40% by mass, aqueous dispersion) was added to the obtained amino-modified silicone emulsion and stirred. Thereafter, 16 parts by mass of a silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd., X-52-8005, non-volatile content 58% by mass, aqueous emulsion) was further added, and after stirring and dispersing, the pH was adjusted to 5 - 7 with citric acid, and the obtained composition was used as a vehicle coating agent (2).

[0088] [Example 3: Production of a coating agent containing a silicone resin, an amino-modified silicone, and a polyolefin resin] A composition was prepared in the same manner as in Example 2, except that 4 parts by mass of an acid-modified polyethylene resin (manufactured by Toho Chemical Industry Co., Ltd., Hi-Tech E-6500, non-volatile content 35% by mass, aqueous dispersion) was added instead of 4 parts by mass of the acid-modified polypropylene resin (manufactured by Toho Chemical Industry Co., Ltd., Hi-Tech P-5060P, non-volatile content 40% by mass, aqueous dispersion), and it was used as a vehicle coating agent (3).

[0089] [Example 4: Production of a coating agent containing a silicone resin, an amino-modified silicone, and a urethane resin] A composition was prepared in the same manner as in Example 2, except that 3 parts by mass of a urethane resin (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Superflex E-2000, non-volatile content 50% by mass, aqueous dispersion) was added instead of 4 parts by mass of the acid-modified polypropylene resin (manufactured by Toho Chemical Industry Co., Ltd., Hi-Tech P-5060P, non-volatile content 40% by mass, aqueous dispersion), and it was used as a vehicle coating agent (4).

[0090] [Example 5: Production of a coating agent containing a silicone resin, an amino-modified silicone, and an acrylic resin] Instead of 4 parts by mass of the acid-modified polypropylene resin (manufactured by Toho Chemical Industry Co., Ltd., High-Tech P-5060P, non-volatile content 40% by mass, aqueous dispersion), 5 parts by mass of an acrylic resin (manufactured by Arakawa Chemical Industries, Ltd., Polystron 1250, non-volatile content 20% by mass, aqueous dispersion) was added, and the same operations as in Example 2 were performed to prepare a composition, which was used as the vehicle coating agent (5).

[0091] [Example 6: Production of a coating agent containing a silicone resin, an amino-modified silicone, and a fluororesin] Instead of 4 parts by mass of the acid-modified polypropylene resin (manufactured by Toho Chemical Industry Co., Ltd., High-Tech P-5060P, non-volatile content 40% by mass, aqueous dispersion), 5 parts by mass of a fluororesin (manufactured by Daikin Industries, Ltd., Rubron LDW-410, non-volatile content 30% by mass, aqueous dispersion) was added, and the same operations as in Example 2 were performed to prepare a composition, which was used as the vehicle coating agent (6).

[0092] [Comparative Example 3: Production of a coating agent containing a silicone resin, an amino-modified silicone, and a wax] Instead of 4 parts by mass of the acid-modified polypropylene resin (manufactured by Toho Chemical Industry Co., Ltd., High-Tech P-5060P, non-volatile content 40% by mass, aqueous dispersion), 4 parts by mass of paraffin wax (manufactured by Gohsei Chemical Industry Co., Ltd., Daisit EY, non-volatile content 30% by mass, aqueous dispersion) was added, and the same operations as in Example 2 were performed to prepare a composition, which was used as the comparative vehicle coating agent (3).

[0093] [Comparative Example 4: Production of a coating agent containing a silicone resin, an amino-modified silicone, and a wax] Instead of 4 parts by mass of the acid-modified polypropylene resin (manufactured by Toho Chemical Industry Co., Ltd., High-Tech P-5060P, non-volatile content 40% by mass, aqueous dispersion), 4 parts by mass of carnauba wax (manufactured by BYK, AQUACER 581, non-volatile content 30% by mass, aqueous dispersion) was added, and the same operations as in Example 2 were performed to prepare a composition, which was used as the comparative vehicle coating agent (4).

[0094] [Comparative Example 5] A composition was prepared by performing the same operations as in Example 1 except that an emulsion of blocked isocyanate was not added, and it was used as Comparative Vehicle Coating Agent (5).

[0095] [Evaluation of Vehicle Coating Agents Produced in Examples and Comparative Examples by Laboratory Tests] The surface on the coating side of a 90 mm × 120 mm cationic electrodeposition coating plate was washed with a detergent (Mentup G, manufactured by Daifuku Co., Ltd.) until it was completely wet with water. Next, a solution obtained by diluting the vehicle coating agents produced in the examples and comparative examples 150-fold by mass with tap water was used to perform spray coating on the coating surface of the washed coating plate. The coating plate subjected to spray coating was washed with water and dried to obtain a test piece. The water repellency on the coating surface of the test piece where spray coating was performed was visually evaluated, and the sliding angle and contact angle were measured. Also, for the coating plate without vehicle coating agent application where spray coating of the vehicle coating agent was not performed, the water repellency on the coating surface was visually evaluated, and the sliding angle and contact angle were measured.

[0096] (Visual Evaluation) The test piece was tilted at 45° with respect to the horizontal direction so that the coating surface was on the upper surface, and tap water was sprayed onto the coating surface using a hand spray, and the state of the water droplets was visually observed. The water repellency of the coating surface was evaluated according to the following evaluation criteria. The results are shown in Table 1. 〇: The shape of the water droplet is round, the flow rate of the water droplet is fast, and the amount of remaining water is small. △: The shape of the water droplet is round, but the flow rate of the water droplet is slightly slow, and there is slightly more remaining water. ×: The shape of the water droplet is non-uniform, the flow rate of the water droplet is slow, and the amount of remaining water is large.

[0097] (Measurement of Sliding Angle) For the test pieces, the sliding angle of water was measured using a fully automatic contact angle meter DMo-702 (manufactured by Kyowa Interface Science Co., Ltd.). Specifically, a syringe filled with ion-exchanged water was fixed, and 50 μL of ion-exchanged water was dropped onto the test piece placed horizontally so that the painted surface was on the upper surface. Then, the test plate was gradually tilted, and the angle of the test piece (sliding angle) when the water droplet began to slide downward was measured. The measurement was performed 5 times, and the average value was taken as the sliding angle. The results are shown in Table 1.

[0098] (Measurement of Contact Angle) For the test pieces, the contact angle of water was measured using a fully automatic contact angle meter DMo-702 (manufactured by Kyowa Interface Science Co., Ltd.). Specifically, a syringe filled with ion-exchanged water was fixed, and 2.0 μL of ion-exchanged water was dropped onto the test piece placed horizontally so that the painted surface was on the upper surface, and the contact angle was measured. The measurement was performed 10 times, and the average value was taken as the contact angle. The results are shown in Table 1.

[0099] [Table 1]

[0100] [Evaluation of Vehicle Coating Agents Manufactured in Examples and Comparative Examples by On-Vehicle Tests] The surface of the vehicle coating of the actual vehicle was washed using a cleaning agent (Ment-Up G, manufactured by Daifuku Co., Ltd.) until it was completely wetted with water. Next, a vehicle coating agent manufactured in the examples and comparative examples was mounted on a portal car wash, and a liquid automatically diluted 150 times by mass with tap water was applied to the surface of the washed vehicle coating. The vehicle to which the vehicle coating agent was applied was washed with water and dried. The water runoff property on the surface of the vehicle to which the vehicle coating agent was applied was visually evaluated. Also, the water runoff property of the surface of the vehicle to which the vehicle coating agent was not applied was visually evaluated. The evaluation criteria are the same as those in the laboratory test. The results are shown in Table 1.

[0101] (Summary) As shown in Table 1, the painted surfaces coated with the coating agents of Examples 1 to 6, which contain a silicone resin, an amino-modified silicone, and a blocked isocyanate, a polyolefin resin, a urethane resin, an acrylic resin, or a fluororesin emulsified with a cationic surfactant, were compared with the painted surfaces without the vehicle coating agent applied, the painted surfaces coated with the coating agents of Comparative Examples 3 and 4 containing a silicone resin, an amino-modified silicone, and a wax, and the painted surfaces coated with the coating agent of Comparative Example 5 containing only a silicone resin and an amino-modified silicone. In both the laboratory test and the actual vehicle test, they were excellent in water repellency and water runoff properties.

[0102] Also, the painted surfaces coated with the coating agents of Comparative Examples 1 and 2 using a blocked isocyanate emulsified with an amphoteric surfactant and a nonionic surfactant, respectively, were inferior in water repellency and water runoff properties compared to the painted surface coated with the coating agent of Example 1 using a blocked isocyanate emulsified with a cationic surfactant.

Industrial Applicability

[0103] The present invention can be used for vehicle coating agents, particularly vehicle coating agents used for car washing treatment with a car washing machine.

Claims

1. A vehicle coating agent comprising a silicone resin, an amino-modified silicone, and at least one selected from a blocked isocyanate and a hydrocarbon polymer, wherein the blocked isocyanate is emulsified with a cationic surfactant.

2. The vehicle coating agent according to Claim 1, wherein the hydrocarbon polymer is at least one selected from the group consisting of a urethane resin, a polyolefin resin, an acrylic resin, and a fluororesin.

3. The vehicle coating agent according to Claim 2, wherein the polyolefin resin is an acid-modified polypropylene resin.

4. The vehicle coating agent according to Claim 1, wherein the amino equivalent of the amino-modified silicone is 300 g / mol to 7000 g / mol.

5. The kinematic viscosity of the amino-modified silicone is 200 mm ２ / s to 5000 mm ２ / s, and the vehicle coating agent according to claim 1.

6. A one-component vehicle coating agent containing the vehicle coating agent according to any one of Claims 1 to 5 and for single application by an automatic car wash.

Images