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] This invention relates to a vehicle coating agent. [Background technology]

[0002] In car washes using automatic car washes, coating agents primarily composed of silicone resin are used as vehicle coating agents with high water-repellent properties (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2019-182937 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] However, conventional coating agents, as mentioned above, do not provide sufficient water repellency with a single application, so it was necessary to apply a primer that acts as a binder before applying the coating agent.

[0005] One aspect of the present invention aims to provide a vehicle coating agent that does not require the application of a primer and can impart a high degree of water repellency and water flow (water drainage) even with a single application. [Means for solving the problem]

[0006] To solve the above problems, a vehicle coating agent according to one aspect of the present invention comprises a silicone resin, an amino-modified silicone, and at least one selected from blocked isocyanates and hydrocarbon polymers, wherein 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 a high degree of water repellency and water flow (water drainage) even with a single application, without the need to apply a primer. [Modes for carrying out the invention]

[0008] One embodiment of the present invention is described below, but the present invention is not limited thereto. The present invention is not limited to the configurations described below, and various modifications are possible within the scope of the claims. Embodiments or examples obtained by combining the technical means disclosed in different embodiments or examples are also included in the technical scope of the present invention. Unless otherwise specified herein, "A to B" representing a numerical range is intended to mean "A or greater 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. A larger contact angle indicates better water repellency. Furthermore, fluidity (also called drainage) refers to the property of water droplets rolling off easily and can be evaluated, for example, by the sliding angle, which is the angle at which a water droplet slides down. A smaller sliding angle indicates better fluidity.

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

[0011] [1.1] Silicone resin In this specification, the silicone resin is intend to be a resin mainly composed of organopolysiloxane, including silicone oligomers (for example, those with a weight-average molecular weight of less than 10,000) which are organopolysiloxanes with a small molecular weight having a three-dimensional cross-linked structure, and silicone resins in a narrow sense which are organopolysiloxanes with a large molecular weight having a three-dimensional cross-linked structure (for example, those with 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 silicone oligomers and silicone resins in a narrow sense, but it is more preferable to contain a silicone resin in a narrow sense, and it is even more preferable to be a silicone resin in a narrow sense. Such silicone resins in a narrow sense are roughly classified into straight resins and silicone-modified organic resins. The former consists only of silicone components. The latter consists of a copolymer of a silicone component and an organic resin. Among them, straight resins are roughly classified into DT resins containing D units (R2SiO 2 / 2 ) and T units (RSiO 3 / 2 ) as main structural units, and MQ resins (trimethylsiloxysilicic acid) containing M units (R3SiO 1 / 2 ) and Q units (SiO 4 / 2 ) as main structural units.

[0013] R in the M unit, D unit and T unit is, independently of each other, 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, etc. It is even more preferable that the silicone resin is an MQ resin having M units and Q units as main structural 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 prepared using water glass as the starting material for the Q unit (SiO 4 / 2 ) and blocking the ends with trimethylsilyl groups (M unit 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 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, etc.

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

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

[0020] As the silicone resin, commercially available silicone resins can be used. Examples of commercially available silicone resins include those commercially available as dispersions of silicone resins, such as DOWSIL TMExamples include 593 Fluid (manufactured by Dow Toray Industries, Inc.) and X-52-8005 (manufactured by Shin-Etsu Chemical Co., Ltd.). Additionally, commercially available silicone resins include BELSIL TMS803 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) and DOWSIL. TM Examples include MQ-1600Resin (manufactured by Dow Toray Industries, Inc.).

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

[0022] [1.2] Aminomodified silicones Examples of amino-modified silicones include modified silicone oils in which at least one amino group is introduced to the terminal and / or side chains of a dimethyl silicone skeleton.

[0023] The aforementioned at least one amino group may be introduced as an amino group and / or an amino group-containing organic group that bonds to a silicon atom constituting the dimethylsilicone skeleton. The aforementioned amino group-containing organic group may be -R 1 NH2(here, R 1 It is an alkylene group. ) Monoamine-type organic groups such as -R 2 NHR 3 NH2(here, R 2 and R 3 Each of these is an alkylene group independently. Examples include diamine-type organic groups such as ). 1 , R 2 and R 3 R is a hydrocarbon group, which may be linear, branched, contain an alicyclic hydrocarbon group, or contain an aromatic hydrocarbon group. Furthermore, the hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. 1 , R 2 and R 3 Preferred examples include methylene groups, ethylene groups, propylene groups, phenyl groups, and the like.

[0024] The amino group and / or the amino group-containing organic group may be introduced into the terminals and / or side chains of the dimethyl silicone skeleton. In other words, examples of amino-modified silicones include side-chain type amino-modified silicones in which the amino group and / or the amino group-containing organic group is introduced into the side chains, double-ended type amino-modified silicones in which the amino group is introduced into both terminals, single-ended type amino-modified silicones in which the amino group is introduced into one terminal, double-ended side-chain type amino-modified silicones in which the amino group is introduced into both terminals and side chains, and single-ended side-chain type amino-modified silicones in which the amino group is introduced into one terminal and side chains.

[0025] In one embodiment of the present invention, the amino-modified silicone may be a modified silicone oil in which at least one amino group is introduced to the terminals and / or side chains of a skeleton in which silicone chains and polyoxyalkylene are alternately linked in a linear fashion.

[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. If other functional groups and / or functional group-containing organic groups are present, these groups may be located on part of the side chain or at the end of the main chain of the amino-modified silicone. Examples of other functional groups or functional group-containing organic groups that may be present on part of the side chain or at the end of the main component include phenyl groups, polyether groups, epoxy groups, hydroxyl groups, and the like.

[0027] Furthermore, the amino-modified silicone may be in the form of a dispersion, or it may be emulsified with a surfactant such as a nonionic surfactant, a cationic surfactant, or an amphoteric surfactant.

[0028] Examples of nonionic surfactants that can be used include polyoxyethylene alkyl ethers, polyoxyalkylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyhydric alcohol fatty acid esters, polyoxyethylene polyhydric alcohol fatty acid esters, polyoxyethylene fatty acid esters, polyglycerin fatty acid esters, alkylamine oxides, and the like.

[0029] Examples of cationic surfactants that can be used include quaternary ammonium salts, alkylamine salts, and ethylene oxide adducts thereof.

[0030] Examples of the aforementioned amphoteric surfactants include fatty acid amidopropyl betaine and alkylimidazoline.

[0031] The aforementioned surfactant may be used individually or in combination of two or more types.

[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.) and DOWSIL. TM Examples include 3705 (manufactured by Dow Toray Industries, Inc.).

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

[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, and more preferably 1000 g / mol to 3000 g / mol. A amino equivalent of 7000 g / mol or less is preferable because it provides excellent adsorption of the vehicle coating agent to the coated surface. Furthermore, a amino equivalent of 300 g / mol or more has the advantage of not causing yellowing of the film because the reactivity is not too strong. The amino equivalent of the amino-modified silicone can be determined 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] Furthermore, the kinematic viscosity of the amino-modified silicone at 25°C is 200 mm². 2 / s~5000mm 2 It is preferable that it be / s, 500mm 2 / s~3000mm 2 It is more preferable that the kinematic viscosity is 5000 mm². 2 If the kinematic viscosity is less than or equal to 200 mmHg, it is preferable because when this vehicle coating agent is sprayed onto the vehicle surface, for example, using a car wash machine, stains and / or unevenness are less likely to occur, and it does not hinder the water flow characteristic of silicone resin. 2 A kinematic viscosity of / s or higher prevents the film from becoming too thin. Therefore, it is preferable because it does not cause a decrease in water flow due to a thin film. The kinematic viscosity of amino-modified silicone at 25°C can be measured by known methods 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 be within the aforementioned range. Note that the kinematic viscosity refers to the kinematic viscosity of the amino-modified silicone itself and is not intended to refer to the kinematic viscosity of the solution or dispersion.

[0037] [1.3] Blocked isocyanates The blocked isocyanate used in this vehicle coating agent is not particularly limited, as long as the active isocyanate group in the polyisocyanate compound has been deactivated by reacting it with the blocking agent beforehand.

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

[0039] The aforementioned blocking agents are not particularly limited, but examples include: alcohols such as methanol, ethanol, 2-propanol, and 2-methoxyethanol; phenols such as phenol, methylphenol, n-propylphenol, iso-propylphenol, iso-butylphenol, t-butylphenol, octylphenol, and nonylphenol; active methylene compounds such as dimethyl malonate, diethyl malonate, methyl acetoacetate, and acetylacetone; mercaptans such as butyl mercaptan and dodecyl mercaptan; acetanilide, acetate amide, ε-caprolactam, δ-valerolactam, and γ-butyrolamine. Examples include acid amides such as kutam; acid imides such as succinimide and maleimide; imidazoles such as imidazole and 2-methylimidazole; ureas such as urea and thiourea; oximes such as formaldehyde oxime, acetaldehyde oxime, acetooxime, methyl ethyl ketoxime, cyclohexanone oxime, acetophenone oxime, and benzophenone oxime; amines such as diphenylamine, diisopropylamine, and aniline; imines such as ethyleneimine and polyethyleneimine; pyrazoles such as pyrazole, 3-methylpyrazole, and 3,5-dimethylpyrazole; and sodium bisulfite.

[0040] The polyisocyanate compound constituting the blocking isocyanate used in this vehicle coating agent may be one type or a combination of multiple types. Similarly, the blocking agent may be one type or a combination of multiple types.

[0041] The blocked isocyanate used in this vehicle coating agent is emulsified with a cationic surfactant. Examples of cationic surfactants include quaternary ammonium salts, alkylamine salts, and their ethylene oxide adducts. More specific examples of cationic surfactants include Lipocard 2HT-75, Rheomix T-50, and Liposocard C / 12 (Lion Corporation).

[0042] Since blocked isocyanates are non-adsorbent substances, adsorption by cationic surfactants is essential. By using blocked isocyanates emulsified with cationic surfactants, ion adsorption of the blocked isocyanates to the coated surface becomes possible when the vehicle coating agent is spray-applied. As a result, the blocked isocyanates, together with the silicone resin contained in the vehicle coating agent, form a film on the coated surface. Because silicone resin has a three-dimensional, high-density crosslinked network structure, the orientation of CH3 groups on the surface of the film increases water repellency. On the other hand, since blocked isocyanates have weaker water repellency than silicone resin with oriented CH3 groups on its surface, a slight difference in water repellency between the silicone resin and blocked isocyanates on the film surface is expected. Since water droplet sliding is promoted by the formation of a composite surface film with a continuous gradient from areas of strong water repellency to areas of weak water repellency on the same surface, it is presumed that the coating film formed from silicone resin and blocked isocyanates will exhibit easier water flow.

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

[0044] For example, acid-modified polyolefin resins are lipophilic and, due to the acid modification, possess adsorbent properties. Therefore, acid-modified polyolefin resins have excellent adhesion and readily adsorb with silicone resin, forming a film on the coated surface together with the silicone resin contained in this vehicle coating agent. Because silicone resin has a three-dimensional, high-density crosslinked network structure, CH3 groups are oriented on the surface of the film. Simultaneously, since polyolefins also have CH3 groups in their polymer backbone, it is expected that the density of CH3 groups oriented on the surface of the film will increase. It is presumed that the water-repellent CH3 groups will form a uniform and smooth coating film without gaps, promoting the water droplet sliding effect and thus making it easier for water to flow. It is presumed that urethane resins, acrylic resins, and fluororesins will also be more likely to exhibit water flow through a similar mechanism.

[0045] The hydrocarbon polymer may be added as a dispersion, or it may be emulsified with 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 with a polyisocyanate. A more specific example of a urethane resin is 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.

[0047] Commercially available urethane resins can be used as the urethane resin. Examples of commercially available urethane resins that are sold as dispersions include Superflex 650, Superflex E-2000 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adekabon Titer HUX-210, and Adekabon Titer HUX-895 (manufactured by ADEKA Corporation).

[0048] (Polyolefin resin) Examples of polyolefin resins include polyethylene, polypropylene, and ethylene-propylene copolymers.

[0049] The polyolefin resin is preferably an acid-modified polyolefin resin. Examples of acid-modified polyolefin resins include acid-modified polypropylene resin and acid-modified polyethylene resin, but from the viewpoint of superior water flow properties, acid-modified polypropylene resin is more preferable.

[0050] A preferred example of an acid-modified polyolefin is a modified polymer 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 aforementioned polyolefin resin, commercially available polyolefin resins can be used. Examples of commercially available polyolefin resins include Hi-Tec P-5060P (manufactured by Toho Chemical Industry Co., Ltd.), which is sold as a dispersion of polyolefin resin. Examples of commercially available polyolefin resins sold as a standalone product include LICOCENE MA6252 GR (manufactured by Clariant Plastics & Coatings).

[0052] (Acrylic resin) Examples of acrylic resins include poly(meth)acrylic acid, poly(meth)acrylic acid esters, polyacrylamide, and ethylene-acrylic acid copolymers.

[0053] In this specification, "(meth)acrylic acid" refers to both acrylic acid and methacrylic acid. Examples of the poly(meth)acrylic acid ester include (meth)acrylic acid esters with alcohols having an alkyl group having 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 that are sold as dispersions include Polystron 1280 (manufactured by Arakawa Chemical Industries, Ltd.).

[0055] (Fluorine-based resin) Examples of fluoropolymer resins include polytetrafluoroethylene and polychlorotrifluoroethylene.

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

[0057] [1.5] Other ingredients This vehicle coating agent preferably contains water. Water can function as a medium for uniformly dispersing and diluting the aforementioned components contained in this vehicle coating agent. The amount of water contained in this vehicle coating agent is not particularly limited. Furthermore, this vehicle coating agent can be used after being appropriately diluted in a car wash machine.

[0058] The water used in this vehicle coating agent is preferably free of impurities so as not to affect the aforementioned components. For example, distilled water, deionized water, tap water, etc., can be suitably used.

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

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

[0061] In addition to the above-mentioned components, this vehicle coating agent may further contain, as necessary, low-temperature stabilizers, emulsifying stabilizers, preservatives, pH adjusters, rust inhibitors, silicone oil, organic acids, inorganic acids, etc., as neutralizers for amino-modified silicones, to the extent that they do not impede the effects of the present invention. Note that silicone oil is not included in the silicone resin of this disclosure, which is a resin mainly composed of organopolysiloxane.

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

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

[0064] A content of 1% by mass or more of amino-modified silicone is preferable because it allows the coating agent to adhere sufficiently to the vehicle surface. On the other hand, a content of 15% by mass or less of amino-modified silicone is preferable because it is less likely to cause unevenness on the vehicle surface. Therefore, it is preferable because it does not hinder the water flow of the silicone resin.

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

[0066] A silicone resin content of 1% by mass or more is preferable because it allows the coating agent to exhibit sufficient water flow. On the other hand, a silicone resin content of 20% by mass or less is preferable because it results in a uniform film and reduces the likelihood of unevenness occurring on the vehicle surface.

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

[0068] If the content of blocked isocyanate is 0.1% by mass or more, it is preferable because the blocked isocyanate participates in film formation on the vehicle surface, resulting in a slight difference in water repellency between the film surface and the silicone resin. This creates a composite surface film with a continuous gradient from areas of strong water repellency to areas of weak water repellency on the same surface, resulting in sufficient water flow. On the other hand, if the content of 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 hinder the water flow of the silicone resin.

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

[0070] A cationic surfactant content of 0.1% by mass or more is preferable because it allows the coating agent (blocked isocyanate) to adsorb sufficiently to the vehicle surface. If the cationic surfactant content is 10% by mass or less, the hydrophilicity of the cationic surfactant itself does not become too pronounced, thus less likely to hinder the water-flowing properties of the silicone resin.

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

[0072] If the hydrocarbon polymer content is 0.1% by mass or more, the coating agent participates in film formation on the vehicle surface, resulting in a uniform film. Therefore, it is preferable because the water-flowing properties characteristic of silicone resin are exhibited. On the other hand, if the hydrocarbon polymer content is 10% by mass or less, the coating agent film becomes uniform, and unevenness is less likely to occur on the vehicle surface, which is also preferable.

[0073] [2. Manufacturing method of vehicle coating agent] The manufacturing method for this vehicle coating agent is not particularly limited and only requires the inclusion of a step of mixing the aforementioned components, and any method commonly used in this field can be appropriately adopted.

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

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

[0076] <Summary> One embodiment of the present invention includes the following configuration:

[0077] [1] comprising a silicone resin, an amino-modified silicone, and at least one selected from blocked isocyanates and hydrocarbon polymers, The aforementioned blocked isocyanate is emulsified with a cationic surfactant, and is a vehicle coating agent.

[0078] [2] The vehicle coating agent according to [1], wherein the hydrocarbon polymer is at least one selected from the group consisting of urethane resins, polyolefin resins, acrylic resins, and fluororesins.

[0079] [3] The vehicle coating agent according to [2], wherein the polyolefin 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 kinematic viscosity of the amino-modified silicone is 200 mm 2 / s~5000mm 2 A vehicle coating agent described in any of [1] to [4], which is / s.

[0082] A one-component vehicle coating agent containing any of the vehicle coating agents described in [6][1] to [5], for single application in an automatic car wash machine. [Examples]

[0083] One embodiment of the present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited thereto.

[0084] [Example 1: Production of a coating agent containing silicone resin, amino-modified silicone, and blocked isocyanate emulsified with a cationic surfactant] Ten parts by mass of amino-modified silicone (Shin-Etsu Chemical Co., Ltd., KF-880) and three parts by mass of polyoxyethylene alkyl ether were mixed, and then 60 parts by mass of ion-exchanged water was added and the mixture was stirred to emulsify and obtain an amino-modified silicone emulsion. Next, in a separate container, two parts by mass of blocked isocyanate (Aica Kogyo Co., Ltd., SC-8B, non-volatile content 67% by mass) and one part by mass of quaternary ammonium salt (Lion Corporation, Lipocard 2HT-75, non-volatile content 75% by mass) were mixed, and eight parts by mass of ion-exchanged water was added and the mixture was stirred to emulsify and obtain a blocked isocyanate emulsion. The entire amount of the obtained blocked isocyanate emulsion was added to the aforementioned amino-modified silicone emulsion, and then 16 parts by mass of silicone resin (Shin-Etsu Chemical Co., Ltd., X-52-8005, non-volatile content 58% by mass, aqueous emulsion) was added, and the mixture was stirred and dispersed. The pH was then adjusted to 5-7 with citric acid, and the resulting composition was designated as vehicle coating agent (1).

[0085] [Comparative Example 1: Production of a coating agent containing silicone resin, amino-modified silicone, and blocked isocyanate emulsified with an amphoteric surfactant] A composition was prepared by performing the same procedure as in Example 1, except that instead of mixing 2 parts by mass of blocked isocyanate (manufactured by Aica 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), and adding 8 parts by mass of ion-exchanged water and stirring to emulsify, an emulsion of blocked isocyanate was used, obtained by mixing 2 parts by mass of blocked isocyanate (manufactured by Aica Kogyo Co., Ltd., SC-8B, non-volatile content 67% by mass) and 4 parts by mass of fatty acid amidopropyl betaine (manufactured by Kawaken Fine Chemical Co., Ltd., Softazolin LPB, non-volatile content 30% by mass), and adding 14 parts by mass of ion-exchanged water and stirring to emulsify, and this was used as comparative vehicle coating agent (1).

[0086] [Comparative Example 2: Production of a coating agent containing silicone resin, amino-modified silicone, and blocked isocyanate emulsified with a nonionic surfactant] A composition was prepared by performing the same procedure as in Example 1, except that instead of mixing 2 parts by mass of blocked isocyanate (manufactured by Aica 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), and adding 8 parts by mass of ion-exchanged water and stirring to emulsify, an emulsion of blocked isocyanate was used, which was obtained by mixing 2 parts by mass of blocked isocyanate (manufactured by Aica Kogyo Co., Ltd., SC-8B, non-volatile content 67% by mass) and 1 part by mass of polyoxyethylene alkyl ether, and adding 8 parts by mass of ion-exchanged water and stirring to emulsify. This was used as comparative vehicle coating agent (2).

[0087] [Example 2: Production of a coating agent containing silicone resin, amino-modified silicone, and polyolefin resin] Ten parts by mass of amino-modified silicone (Shin-Etsu Chemical Co., Ltd., KF-880) and three parts by mass of polyoxyethylene alkyl ether were mixed, and then 67 parts by mass of ion-exchanged water was added and stirred to emulsify, obtaining an amino-modified silicone emulsion. Next, four parts by mass of acid-modified polypropylene resin (Toho Chemical Industry Co., Ltd., Hi-Tec P-5060P, 40% by mass of non-volatile content, aqueous dispersion) was added to the obtained amino-modified silicone emulsion and stirred. Then, sixteen parts by mass of silicone resin (Shin-Etsu Chemical Co., Ltd., X-52-8005, 58% by mass of non-volatile content, aqueous emulsion) was added and stirred to disperse, and the pH was adjusted to 5-7 with citric acid, and the resulting composition was designated as vehicle coating agent (2).

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

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

[0090] [Example 5: Production of a coating agent containing silicone resin, amino-modified silicone, and acrylic resin] A composition was prepared by performing the same procedure as in Example 2, except that 5 parts by mass of acrylic resin (Polistron 1250, manufactured by Arakawa Chemical Industries, Ltd., 20% by mass of non-volatile content, aqueous dispersion) was added instead of 4 parts by mass of acid-modified polypropylene resin (Hi-Tec P-5060P, manufactured by Toho Chemical Industry Co., Ltd., 40% by mass of non-volatile content, aqueous dispersion). This was used to prepare vehicle coating agent (5).

[0091] [Example 6: Production of a coating agent containing silicone resin, amino-modified silicone, and fluororesin] A composition was prepared by performing the same procedure as in Example 2, except that 5 parts by mass of fluoropolymer resin (Daikin Industries, Ltd., Rubron LDW-410, 30% by mass of non-volatile content, aqueous dispersion) was added instead of 4 parts by mass of acid-modified polypropylene resin (Toho Chemical Industry Co., Ltd., Hi-Tec P-5060P, 40% by mass of non-volatile content, aqueous dispersion). This was used as vehicle coating agent (6).

[0092] [Comparative Example 3: Production of a coating agent containing silicone resin, amino-modified silicone, and wax] A composition was prepared by performing the same procedure as in Example 2, except that 4 parts by mass of paraffin wax (Daijit EY, manufactured by Go-o Chemical Industry Co., Ltd., 30% by mass of non-volatile content, aqueous dispersion) was added instead of 4 parts by mass of acid-modified polypropylene resin (Hi-Tec P-5060P, manufactured by Toho Chemical Industry Co., Ltd., 40% by mass of non-volatile content, aqueous dispersion), and this was designated as comparative vehicle coating agent (3).

[0093] [Comparative Example 4: Production of a coating agent containing silicone resin, amino-modified silicone, and wax] A composition was prepared by performing the same procedure as in Example 2, except that 4 parts by mass of carnauba wax (BYK, AQUACER581, 30% by mass of non-volatile content, aqueous dispersion) was added instead of 4 parts by mass of acid-modified polypropylene resin (Toho Chemical Industry Co., Ltd., Hi-Tec P-5060P, 40% by mass of non-volatile content, aqueous dispersion), and this was designated as comparative vehicle coating agent (4).

[0094] [Comparative Example 5] A composition was prepared by performing the same procedure as in Example 1, except that a blocked isocyanate emulsion was not added, and this was designated as comparative vehicle coating agent (5).

[0095] [Laboratory testing evaluation of vehicle coating agents manufactured in the examples and comparative examples] The painted surface of a 90mm x 120mm cationic electrodeposition coated board was cleaned using a cleaning agent (Daifuku Co., Ltd., Mente-Up G) until it was completely wet. Next, the vehicle coating agent prepared in the examples and comparative examples was diluted 150 times by mass with tap water and spray-applied to the painted surface of the cleaned board. The spray-coated board was then washed with water and dried to create a test specimen. The water flow on the spray-coated surface of the test specimen was visually evaluated, and the sliding angle and contact angle were measured. In addition, the water flow on the painted surface of uncoated boards (those without spray application of the vehicle coating agent) was also visually evaluated, and the sliding angle and contact angle were measured.

[0096] (Visual evaluation) The test specimen was tilted at a 45° angle to the horizontal so that the painted surface was facing upwards. Tap water was then sprayed onto the painted surface using a hand sprayer, and the behavior of the water droplets was visually observed. The water flow properties of the painted surface were evaluated according to the following criteria. The results are shown in Table 1. ○: The water droplets are round in shape, flow quickly, and leave little residue. △: The water droplets are round, but the flow rate is somewhat slow, leaving a slight residue. ×: The shape of the water droplets is uneven, the water droplets flow slowly, and a lot of water remains.

[0097] (Measurement of the angle of fall) The water sliding angle of the test specimen was measured using a fully automatic contact angle meter DMo-702 (manufactured by Kyowa Interface Science Co., Ltd.). Specifically, a syringe filled with deionized water was fixed in place, and 50 μL of deionized water was dropped onto the test specimen, which was placed horizontally with the painted surface facing upwards. The test plate was then gradually tilted, and the angle of the test specimen (sliding angle) at which the water droplet began to slide downwards was measured. Five measurements were taken, and the average value was taken as the sliding angle. The results are shown in Table 1.

[0098] (Measurement of contact angle) The contact angle of water was measured for the test specimens using a fully automatic contact angle meter DMo-702 (manufactured by Kyowa Interface Science Co., Ltd.). Specifically, a syringe filled with deionized water was fixed in place, and 2.0 μL of deionized water was dropped onto the test specimen, which was placed horizontally with the painted surface facing upwards, 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 the examples and comparative examples through actual vehicle testing] The surface of the painted vehicle was cleaned using a cleaning agent (Daifuku Co., Ltd., Mente-Up G) until it was completely wet. Next, the vehicle coating agents manufactured in the examples and comparative examples were loaded into a gantry-type car wash machine, and the solution, automatically diluted 150 times by mass with tap water, was applied to the cleaned surface of the vehicle's painted surface. The vehicle coated with the vehicle coating agent was washed with water and dried. The water flow on the surface of the vehicle coated with the vehicle coating agent was visually evaluated. The water flow on the surface of the vehicle that had not been coated with the vehicle coating agent was also visually evaluated. The evaluation criteria were the same as in the laboratory test. The results are shown in Table 1.

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

[0102] Furthermore, the painted surfaces coated with the coating agents of Comparative Examples 1 and 2, which used blocked isocyanates emulsified with amphoteric and nonionic surfactants, respectively, exhibited inferior water repellency and water flow properties compared to the painted surfaces coated with the coating agent of Example 1, which used blocked isocyanates emulsified with cationic surfactants. [Industrial applicability]

[0103] This invention can be used in vehicle coating agents, particularly those used in car washes.

Claims

1. comprising an organopolysiloxane having a three-dimensional crosslinked structure, an amino-modified silicone, and a blocked isocyanate, The aforementioned blocked isocyanate is emulsified with a cationic surfactant, and is a vehicle coating agent.

2. 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.

3. The kinematic viscosity of the amino-modified silicone is 200 mm². ２ / s ~ 5000mm ２ A vehicle coating agent according to claim 1, wherein the value is / s.

4. A one-component vehicle coating agent comprising the vehicle coating agent described in any one of claims 1 to 3, for single application using an automatic car wash machine.

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