KR101750441B1 - Surface-protective water-repellent agent for exterior surfaces - Google Patents
Surface-protective water-repellent agent for exterior surfaces Download PDFInfo
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- KR101750441B1 KR101750441B1 KR1020117020003A KR20117020003A KR101750441B1 KR 101750441 B1 KR101750441 B1 KR 101750441B1 KR 1020117020003 A KR1020117020003 A KR 1020117020003A KR 20117020003 A KR20117020003 A KR 20117020003A KR 101750441 B1 KR101750441 B1 KR 101750441B1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
Abstract
It can be easily applied to a surface of a passenger car or other exterior decorative surface and can be easily finished by wiping after application and is excellent in early water repellency with a small amount of application and excellent in stain resistance and weather resistance especially in non- Thereby providing a surface water repellent protective agent. 100 parts by mass of the moisture-curable liquid silicone oligomer A, 0.1 to 40 parts by mass of the curing catalyst B of A, 1 part by mass or more and less than 100 parts by mass of linearly modified polydimethylsiloxane C having both terminal end- Wherein the hydrophobic fine particles D having a diameter of 1 to 50 nm are contained in an amount of 0.1 to 25 parts by mass and further contain at least one or more kinds of silicon-based volatile solvent, hydrocarbon-based volatile solvent and polar group- (B), (C), and (D) in an amount of not more than 500 parts by mass based on 1 part by mass of the total of the components (A), Surface water repellent for.
Description
The protecting agent for external scene of the present invention is excellent in adhesion and has a water repellent effect over a long period of time while having an effect of being easily cleaned when the protective film applied on the surface of the surface material is dirty, Which is particularly excellent in durability and which can protect the appearance of the exterior of the automobile body for a long period of time, Mirror, or a surface that has a function of protecting exterior surfaces of buildings, houses, and other structures such as outer walls of various storage tanks such as petroleum or liquefied gas, and barrier walls or piers of highways, Water-repellent protective agent.
BACKGROUND ART Conventionally, coating agents for external scenes of various structures for applying water repellency to the surfaces of exterior surfaces such as passenger cars and other vehicles, or surfaces of various furniture or wall surfaces of buildings have been developed and used. Among these, a coating agent used for a coating surface of a vehicle such as a passenger car is a wax-type coating agent or an emulsion-type coating agent. Examples of a method and a method for applying such a coating agent include a coating cloth, a sponge, Or by spraying. Of these various types of coating agents, in particular, emulsion type coating agents have been developed in various types due to their convenient use.
There has been proposed a highly water-repellent water-repellent emulsion emulsified from a specific amino-modified silicone oil and a surfactant having excellent properties as a car polish (automobile polish) on the painted surface of an automobile body (see, for example, Patent Document 1 Reference). However, there is a demand for an excellent surface water repellency protection for an external scene due to the initial water repellency, which can be finished simply by wiping after application.
The present invention is also directed to a vehicle coating agent capable of holding a vehicle metal surface, a coated surface, or a resin surface of a vehicle over a long period of time even if the tire is polished and polished, and water repellency and antifouling properties are cleaned. A vehicle coating agent containing both end type reactive silicone oil and having a blending ratio of both end type reactive silicone oil of not less than 25 parts by mass based on 100 parts by mass of the moisture-curable silicone oligomer has been proposed (for example, see Patent Document 2). However, there is a demand for a surface water repellency protection for an external scene, which can be easily finished by wiping after application, further improving initial water repellency and further improving durability after cleaning.
A problem to be solved by the present invention is to provide a coating agent which imparts water repellency to a surface of a surface of an exterior of a passenger car or other vehicle or a surface of various furniture or a wall surface of a building, It is possible to form a coating surface which can be simply finished and has excellent durability, durability, and even more excellent initial water repellency by a small amount of application, and is excellent in stain resistance, gas permeability and weather resistance, Water repellent agent for application to an external scene having excellent durability.
According to a first aspect of the present invention for achieving the above object, in the invention of claim 1, 100 parts by mass of the moisture-curable liquid silicone oligomer A, 0.1 to 40 parts by mass of the curing catalyst B of A, Modified cyclic polydimethylsiloxane C in an amount of not less than 1 part by mass but less than 100 parts by mass and 0.1 to 25 parts by mass of hydrophobic fine particles D having an average particle diameter of 1 to 50 nm and further containing a volatile solvent such as a silicone volatile solvent, Volatile solvent E containing at least one kind of solvent or two or more kinds of solvents and capable of dissolving or dispersing the respective components A, B, C and D at the same time in a total amount of 1 mass of each component of A, B, C and D By mass of the water-repellent protective agent.
In the invention of claim 2, the hydrophobic fine particles D having an average particle diameter of 1 to 50 nm are surface hydrophobicized silica fine particles obtained by subjecting the surface of the hydrophilic silica fine particles to hydrophobic treatment, to be.
In the invention of claim 3, the amount of the linearly modified polydimethylsiloxane C having a silanol group at both terminal groups is less than 25 parts by mass based on 100 parts by mass of the moisture-curable liquid silicone oligomer A. [ Is a surface water repellent for outdoor scenes.
The surface water-repellent protective agent for external scene, which is a means of the present invention, is a coating agent for imparting water repellency by applying the surface water-repellent protective agent to a surface of a surface of an exterior of a passenger car or other automobile or a surface of various furniture or a wall surface of a building, It is possible to finish easily by wiping, so that there is no coating unevenness, the durability of the coating against abrasion at the time of cleaning is particularly excellent, and therefore, the appearance is remarkably good, the initial water repellency is excellent and the stain resistance, cleaning durability and weather resistance The surface water repellent protective agent of the present invention exerts an excellent effect even when it is coated with a coating agent such as a conventional sponge or a polisher or the like. The protective agent is not less than 1 part by mass and not more than 100 parts by mass based on 100 parts by mass of the moisture-curable liquid silicone oligomer as component A And 0.1 to 25 parts by mass of the hydrophobic fine particles as the component D are contained at the same time, unreacted polydimethylsiloxane oil flows out even if washing is carried out repeatedly, so that there is no fear of flashing on the front glass , And the durability effect is maintained. Therefore, the present invention is a surface water repellent agent for an external scene that exhibits an excellent effect not previously available.
With respect to the best mode for carrying out the present invention, the surface water repellent protective agent for external scene related to the means of the present invention will be described with reference to the tables below. The surface water repellent agent for other scenes can be applied to various external scenes. In such a case, the outer surface to be applied may be cleaned and degreased, and then various coating methods such as hand painting using a dedicated sponge, mechanical painting using a polisher or the like, spray painting with an air gun, or immersion coating may be used The surface water repellent protective agent for external scene of the present invention is applied and finished. In addition, when a very good appearance such as an outside scene of a passenger car is required, it is a surface water-repellent protection agent for an external scene which can be wiped off simply by wiping after coating with a surface water-repellent protective agent.
Hereinafter, the main components of the surface water-repellent protective agent for an external scene which is a means of the present invention will be described. One of the A component of the essential components of the present invention according to claim 1, made of a liquid silicone oligomer of the moisture-curable, examples of the silicone oligomer, the chemical formula {(R 1) a-SiO (4-ab) / 2 X b } c, wherein R is a substituted or unsubstituted hydrocarbon group having 1 to 8 carbon atoms, X is a moisture-curable group such as alkoxy, acyl or halogen, and a is 0 to 1. 5, b is a moisture-curable hydrocarbon group-containing silicone oligomer having a moisture-curable group content of 5% or more, c is a value of 3 or more, and has a property of crosslinking and curing by moisture to form a film . Among them, R is preferably an alkyl group such as a methyl group or an ethyl group, particularly a methyl group, and X is preferably an alkoxy group such as a methoxy group, an ethoxy group or an isopropoxy group, particularly a methoxy group. In this case, when a is more than 1.5, the strength of the obtained coating film is insufficient and durability is lowered.
Component A forms a cured coating having a dense crosslinked structure quickly after application by the accelerating action of the curing catalyst of component B, which is one of the essential components, to form a crosslinked coating having excellent weather resistance and excellent resistance to contamination. In order to obtain such an effect satisfactorily, when the component A is 100 parts by mass, the curing catalyst for the component B is 0.1 to 40 parts by mass.
The moisture-curable liquid silicone oligomer of component A is a liquid silicone oligomer of KC89S, KR213, KR400, KR401, KR401N, KR500, KR510, KR9218, X-40-2308, X-40-2327 from Shin-Etsu Chemical Co., , X-40-2651, X-40-9225, X-40-9227, X-40-9238, X-40-9247, X-40-9250, X-41-1053, X-41-1056, X -41-1805, X-41-1810, GE XC96-B0446 from Toshiba Silicones, SR2402, AY42-161, AY42-163, AY42-182, AZ from Toray Dow Corning Co., -6101, SILRES MSE 100, SILICATE TES 40 WN from Asahi Chemical Industry Co., Ltd., and the like are suitable and preferable examples. KR-400 (10% by mass of aluminum catalyst), KR401 (5% by mass of titanium catalyst) and X-40-2327 (5% by mass of phosphoric acid catalyst) of Shinetsu Kagaku Co., , And a component of the curing catalyst B is blended in advance.
As the B component used as the curing catalyst for A, an organic metal compound, an acid, an alkali, and the like are used. Examples of the organometallic compound include compounds such as aluminum, titanium, zirconium and tin, and specific examples thereof include diisopropoxy (ethylacetoacetate) aluminum, isopropoxybis (ethylacetoacetate) aluminum, tris (Ethyl acetoacetate) titanium, tetrakis (2-butoxyethyl alcoholate) titanium, dibutoxybis (ethylacetoacetate) zirconium (acetylacetonate) titanium, diisopropoxybis , Dibutyltin dilaurate, dibutyltin bis (octyloxycarbonylmethylthiolate), and the like, and commercially available products include D (trademark) of Shinetsu Kagaku Co., Ltd. -20, D-25, DX-9740 and the like.
Examples of the acid catalyst which is a curing catalyst for the component B include formic acid, acetic acid, oxalic acid, citric acid, trifluoroacetic acid, paratoluenesulfonic acid, hydrochloric acid, sulfuric acid and phosphoric acid. Examples of commercially available products include D- 220, and X-40-2309A. Examples of the alkali catalyst which is a curing catalyst for the component B include sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, ethylamine, diethylamine, triethylamine, butylamine, dibutylamine, tributylamine, ethanolamine, diethanolamine, Amines such as triethanolamine, methyldiethanolamine, dimethylethanolamine, ethylenediamine, triethylenediamine, morpholine, piperidine, diazabicylundecane, aminosilanes, amino-modified silicones, various primary or secondary amines and epoxy groups Containing silane coupling agent, and various organic and inorganic alkali compounds such as disilazane. Commercially available products include KP-390 manufactured by Shin-Etsu Chemical Co., Ltd., and the like.
These B components are preferably added in a range of 0.1 to 40 parts by mass based on 100 parts by mass of the A component. If it is less than this range, a sufficient curing rate can not be obtained, and if it is larger than this range, the pot life (the period of time after the original package is opened, or after the accelerator and other additives are mixed, Not only the workability is lowered but also the physical properties of the cured coating are adversely affected, which is not preferable.
The straight-chain modified polydimethylsiloxane having a silanol group at both terminals, which is a component C as another essential component of the invention according to claim 1, is a compound in which a hydroxyl group directly bonded to a silicon atom is condensed with the component A to form a chemical bond This is an essential component for imparting a water repellent performance to the coating film without decreasing the physical properties of the durable cross-linked cured coating constituted by the component (A). The presence of the silanol groups at both ends improves the reaction probability compared to the modified polysiloxane which is only reactive at one end, whereby the persistence is remarkably improved and the molecules are present on the surface of the film due to the reaction at both terminals It is presumed that water repellency is expressed in a smaller amount.
This component is a straight chain, both terminally modified polydimethylsiloxane having silanol groups at both ends of the chain, and is not particularly limited as long as it is directly or directly soluble in the component A by the following component E, 3000 cs or less. When the viscosity exceeds 3000 cs, the reactivity with the component A is lowered and the water repellency is lowered.
The component C is an essential component for imparting persistent water repellency to the cured coating composed of the component A, but when it is substituted with a non-reactive water repellent such as silicone oil, the component C bleeds out over time, It is difficult to obtain water repellency. On the other hand, by using the composition of the present invention, it is possible not only to have excellent durability of the coating film but also to obtain a strong crosslinked coating which shows excellent water repellency at the beginning and excellent in water repellency.
The amount of the component C is preferably 1 part by mass or more and less than 100 parts by mass with respect to 100 parts by mass of the component A. [ That is, in order to improve the water repellency of the component A, it is preferable to use 1 part by mass or more of the component C with respect to 100 parts by mass of the component A, and furthermore, the strength of the film is not lowered, It is more preferable that the C component does not exceed 25 parts by mass.
Examples of the linearly modified polydimethylsiloxane having a silanol group at both ends of the C component include commercially available dimethylpolysiloxanes such as YF3800, XF3905, YF3057, YF3807, YF3802 and XC-96-723, which are hydroxyl-terminated dimethylpolysiloxanes from GE Toshiba Silicones Are suitably and preferably used.
The hydrophobic fine particles D having an average particle diameter of 1 to 50 nm are used as the D component in the invention according to claim 1. Examples of the hydrophobic fine particles having an average particle diameter of 1 to 50 nm as the D component include polyethylene, polypropylene, alkyl acrylate of polyacrylic acid, polymethacrylic acid alkyl ester, polytetrafluoroethylene, tetrafluoroethylene methyl vinyl ether copolymer, crosslinked polydimethyl Siloxane and the like, and hydrophobized fine particles of inorganic fine particles such as silica, alumina and titania. Among them, surface hydrophobicized silica fine particles are preferable from the viewpoints of difficulty of alteration, easiness of obtaining fine particles, stability of dispersion and the like. The average particle diameter of the hydrophobic fine particles is preferably in the range of 1 to 50 nm. Within this range, the outer appearance of the film on the surface to be treated is not damaged, and the durability of the resulting coating film, particularly the durability against wear during washing, is improved. The effect is also stably expressed. Preferred examples of the particulate silica include Aerosil R104, Aerosil R106, Aerosil R202, Aerosil R711, Aerosil R7200, Aerosil R805, Aerosil R812, Aerosil R8200, Aerosil R972, Room 972 V, Aerosil RX200, Aerosil RX300, Aerosil RX50, Aerosil RY200 and the like are exemplified. The amount of the component (D) used is preferably in the range of 0.1 to 25 parts by mass with respect to 100 parts by mass of the component (A). Within this range, the coating workability is not deteriorated or the appearance of the coating film on the surface to be treated is not damaged, and the durability of the resulting coating film, in particular, the durability against wear during washing is improved. In addition, the effect is stably expressed. If the amount of the component D is less than 0.1 part by mass, the effect is not sufficient. If the amount of the component D is more than 25 parts by mass, the coatability of the coating decreases and the appearance of the resulting coating deteriorates.
The E component in the invention according to claim 1 is at least one component selected from the group consisting of a silicone-based volatile solvent, a hydrocarbon-based volatile solvent, and a polar group-containing volatile solvent, wherein the component A, the component B, the component C, A volatile organic solvent capable of being dispersed is used.
Examples of the silicone based volatile solvent of component E include polydimethylsiloxane oils having a viscosity of 5 mm 2 / s or less, cyclic dimethylsiloxanes such as hexamethylcyclotrisiloxane and octamethylcyclotetrasiloxane, dimethyldimethoxysilane, dimethyldiethoxysilane , And trimethylmethoxysilane. Specific examples thereof include KF96L-0.65 cs, KF96L-1 cs, KF96L-1.5 cs, KF96L-2 cs, KF96L-5 cs, KF994, KF995 TSF405 and TSF3802A of GE Toshiba Silicone Co., and AK0.65 of Asahi Chemical Industry Co., Ltd., and the like.
Examples of the hydrocarbon-based volatile solvent of the component E include an n-paraffin hydrocarbon solvent, an isoparaffin hydrocarbon solvent, a naphthenic hydrocarbon solvent, or a petroleum oil, a crude oil, IP solvent 1016 (boiling point: 93 to 140 ° C) and 1620 (boiling point: 166 to 202 ° C) (for example) manufactured by Idemitsu Kosan Co., , Isocol 200 (boiling point 95 to 155 ° C) and 300 (boiling point 170 to 189 ° C) manufactured by Nippon Sekiyu Co., Ltd.), 2028 (boiling point 213 to 262 ° C), 2836 (boiling point 277 to 353 ° C) , N-hexane, n-octane, n-decane, n-dodecane, No. 0 solvent L, No. 0 solvent M, No. 0 solvent H (Manufactured by Nippon Sekiyu Co., Ltd.), naphthenic hydrocarbon solvents include cyclohexane, methylcyclohexane, ethylcyclohexane, decalin, Petroleum ether, gasoline, light oil, kerosene, mineral spirit, and tarpaulin, which are mainly used as the oil fractions, the oil fractions, and the oil fractions of the modified or decomposed products, which are mainly composed of L, M, H (all manufactured by Nippon Sekiyu Co., .
Examples of the polar group-containing volatile solvent of the component E include alcohols, glycol ethers, glycol ether esters, ethers, esters, and ketones having a hydroxyl group, an ether group, an ester group, a carbonyl group and a caproxyl group.
Of these, alcohols include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, n- pentanol, neopentyl alcohol, , Isooctanol, n-decanol, n-dodecyl alcohol, cyclopentanol, cyclohexanol and the like.
Examples of the glycol ether and glycol ether ester include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol n-butyl ether, ethylene glycol mono-t-butyl ether, ethylene glycol monohexyl ether , Ethylene glycol mono 2-ethylhexyl ether, ethylene glycol monobenzyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether Diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoethyl ether, diethylene glycol monoethyl ether, Propylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, triethylene glycol mono n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, Butyl ether, propylene glycol mono t-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono n-propyl ether acetate, propylene glycol mono i-propyl ether acetate, propylene glycol mono n-butyl ether Acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono n-propyl ether, dipropylene glycol mono i-propyl ether, dipropylene glycol mono n-butyl ether, dipropylene glycol mono t-butyl Ether, di Dipropylene glycol monoethyl ether acetate, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 3- Methoxy-3-methylbutyl acetate, diethyl ether, di-propyl ether, dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol di Ethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether.
Examples of the esters include ethyl acetate, propyl acetate, butyl acetate, ethylene glycol diacetate, and 1,4-butanediol diacetate.
Examples of the ketone include acetone, methyl ethyl ketone, methyl i-butyl ketone, di-propyl ketone, di-butyl ketone and the like.
Among them, hydrocarbon solvents such as isoparaffin hydrocarbon solvents, n-paraffin hydrocarbon solvents, naphthenic hydrocarbon solvents, kerosene, mineral spirits, and tapen are used alone or in combination, or more in combination with silicon-based volatile solvents . Further, it is preferable to use at least 30 mass% of a solvent having a boiling point of 70 deg. C or higher in the E component. If the solvent having a boiling point of 70 deg. C or higher is less than 30 mass%, the drying becomes excessively quick, and the coating workability or the obtained film appearance deteriorates.
The ratio of the E component to 1 part by mass of the total of the A component, B component, C component and D component is preferably 500 parts by mass or less. When the amount of the component E exceeds 500 parts by mass, the viscosity becomes too low to cause crawling, and the thickness of the film formed by one application becomes too thin, .
The composition may further contain a silicone oil such as polydimethylsiloxane or a modified silicone oil having a functional group such as an epoxy group, an amino group, a mercapto group, an alkoxysilyl group or a vinyl group, or a solid water repellent silicone resin in a small amount Can be added. It is also possible to add an ultraviolet absorber, an ultraviolet stabilizer, an antioxidant, a pigment, a pigment, a flavor, a deodorant, a viscosity adjuster, a stain inhibitor, a wiping property improving agent and the like.
The external surface water-repellent protection agent of the present invention can be applied by spraying with a spray using a hand using a sponge, mechanical painting with a polisher, spraying with an air gun, or an aerosol filled in a pressure-resistant can together with an injection gas. Further, the surface may be further smoothed by, for example, wiping off after application.
The surface water-repellent protective agent for external use of the present invention is excellent in the durability of the coating itself and is excellent in improving the appearance of the external scene. Therefore, the surface water-repellent protective agent of the present invention can be used for a passenger car, a motorcycle, a truck, a bus, a tractor, a combine, A glass surface, a metal surface, or a resin surface of various types of outdoor equipment or structures such as a steel plate (registered trademark), a crane, a house, a building or a bridge, and is preferably used.
Examples 1 to 10 and Comparative Examples 1 to 8 are shown in Tables 1 and 2, respectively, as raw materials for producing the surface water repellent protective agent for external scene of the present invention. The raw materials A, B, C, D and E shown in Tables 1 and 2 were weighed into a stainless steel beaker in a dry box, stirred for about 10 minutes, and then subjected to ultrasonic treatment for 10 minutes, A surface water repellent agent for an external scene, which is a composition of each comparative example, was prepared. Further, the method for preparing the composition is not limited to the above method. In the following Examples and Comparative Examples shown in Tables 1 and 2,% represents mass%. In this case, D1, D2, ..., D9 and D10 were designated as composition No., and H1, H2, ..., H7 and H8 as composition No. in Comparative Examples. Also in Table 1 and in the examples in the text, the composition ratios of KR400 and X-40-2327 are described in advance for component A and component B, respectively.
One
2
5
A
9225
9250
Phenyl
10%
2327
B
C
D
RX300
RY200
R972
E
Other
Immediately
Aminosilane Blend A: 3-Aminopropyltriethoxysilane, IP Solvent 1016, 1620
(Isoparaffin-based solvent manufactured by Idemitsu Kosan Co., Ltd.)
Silicone powder: a mixture of KPM590 manufactured by Shin-Etsu Chemical Co., Ltd. and X-22-1186 at a weight ratio of 1: 1
NAS3: Isoparaffin-based solvent made by Nippon Oil &
PGMAC: Propylene glycol monomethyl ether acetate
A
Bass (wacker)
B
C
D
E
That
outside
Aminosilane Blend A: 3-Aminopropyltriethoxysilane, IP Solvent 1016, 1620
(Isoparaffin-based solvent manufactured by Idemitsu Kosan Co., Ltd.)
Silicone powder: a mixture of KPM590 manufactured by Shin-Etsu Chemical Co., Ltd. and X-22-1186 at a weight ratio of 1: 1
NAS3: Isoparaffin-based solvent made by Nippon Oil &
PGMAC: Propylene glycol monomethyl ether acetate
Example 1
In Composition Example No. D1 of Example 1, 0.86% of a total of 0.43% of KC89S and 0.43% of X-40-9225 of Shinetsu Kagaku Co., Ltd. as a moisture-curable liquid silicone oligomer A, Of a hydroxy-terminated dimethylpolysiloxane XF3905 of Toshiba Silicone Co., Ltd. as a straight chain-modified polydimethylsiloxane C having a silanol group at both terminal ends in an amount of 0.20%, a hydrophobic fine particle having an average particle diameter of 1 to 50 nm D, 0.04% of Aerosil RX300 manufactured by NAPHON Aerosil Co., Ltd., and the subtotal of the components A, B, C, and D is 1.20%. Further, as volatile solvent E, 84.20% of IP solvent 1620 of Idemitsu Kosan Co., Ltd. and 98.80% of 14.60% of propylene glycol monomethyl ether acetate NAS3 of isoparaffin solvent of Nippon Oil Co., %, And the total of the A component, the B component, the C component, the D component, the E component, and others is 100%. Accordingly, in terms of the mass part, 11.63 parts by mass of the B component, 23.26 parts by mass of the C component, and 4.65 parts by mass of the D component are obtained with respect to 100 parts by mass of the A component. Further, the E component was 82.33 parts by mass based on 1 part by mass of the total of the A, B, C, and D components, all of which satisfied the conditions specified in the claims. The appearance of the liquid immediately after the adjustment was good.
Example 2
Composition Example No. 2 of Example 2 contained 5.00% of KC89S, 10.00% of X-40-9225 and 4.75% of X-40-2327 as a moisture-curable liquid silicone oligomer A, 0.50% of D-20 of Shin-Etsu Chemical Co., Ltd. as a curing catalyst B and 0.75% of a total of 0.25% of X-40-2327 as an A-derived component, and a straight chain modified polydimethylsiloxane having a silanol group at both terminal ends C as the hydrophobic fine particles D having a mean particle diameter of 1 to 50 nm and Aerosil R972 of Nippon Aerosil Co., Ltd. as 2.00%, 4.50% of the hydroxy-terminated dimethylpolysiloxane XF3905 of Toshiba Silicone Co., Ltd., , And the subtotal of the C component and the D component is 27.00%. Further, KF96L-0.65 cs of Shin-Etsu Chemical Co., Ltd. as a volatile solvent E was determined to be a total of 73.00% of 5.00% of kerosene and 68.00% of kerosene. Otherwise, the content of A, B, C, And the other 100%. Accordingly, in terms of the mass part, the amount of the component B is 3.80 parts by mass, the content of the component C is 22.78 parts by mass, and the content of the component D is 10.13 parts by mass based on 100 parts by mass of the component A. Furthermore, the E component was 2.70 parts by mass based on 1 part by mass of the total of the A, B, C, and D components, all of which satisfied the conditions specified in the claims. The appearance of the liquid immediately after the adjustment was good.
Example 3
Composition Example No. 3 of Example 3 In the No. D3, a total of 5.50% of X-40-9250 and KR400 of Shinetsu Kagaku Co., Ltd. as moisture-curable liquid silicone oligomer A, 5.50%, and Shinetsu Kagaku The total amount of 0.80% of 0.20% of D-25, 0.10% of DX-9740 and 0.50% of KR400 as an A-derived material, and the total amount of straight chain modified polydimethylsiloxane C having silanol groups ), 0.80% of hydroxy-terminated dimethylpolysiloxane XF3057, and 0.20% of Aerosil RX300 manufactured by Nippon Aerosil Co., Ltd. as hydrophobic fine particles D having an average particle diameter of 1 to 50 nm as component A, component B, component C and component D Is 7.20%. Further, as volatile solvent E, 20.00% of KF96L-0.65 cs of Shinetsu Kagaku Co., Ltd. and 92.80% of 72.80% of isoparaffin solvent NAS3 of Nippon Oil & Component, C component, D component, E component, and the other 100% in total. Accordingly, in terms of the mass part, 14.55 parts by mass of the B component, 12.73 parts by mass of the C component, and 3.64 parts by mass of the D component are contained with respect to 100 parts by mass of the A component. Further, the E component was 12.89 parts by mass based on 1 part by mass of the total of the A, B, C, and D components, all of which satisfied the conditions specified in the claims. The appearance of the liquid immediately after the adjustment was good.
Example 4
In Composition Example No. D4 of Example 4, 5.00% of X-40-9225 and 5.00% of X-40-9250 of Shin-Etsu Chemical Co., Ltd. as a moisture-curable liquid silicone oligomer A were added in a total amount of 10.00% 0.30% of D-20 of Shin-Etsu Chemical Co., Ltd., 0.70% of hydroxy-terminated dimethylpolysiloxane XF3905 of Toshiba Silicone Co., Ltd. and 0.30% of XF3057 as a straight chain modified polydimethylsiloxane C having silanol groups in both terminal groups, Of hydrophobic fine particles D having an average particle diameter of 1 to 50 nm as the hydrophobic fine particles D having a total content of 1.00% and a total content of the components A, B, C and D of 12.10%. Further, as the volatile solvent E, the total amount of 87.80% of KF96L-1 cs, 77.80% of kerosene and 5.00% of propylene glycol monomethyl ether acetate PGMAc of Shin-Etsu Chemical Co., Ltd. was 0.10% , The B component, the C component, the D component, the E component and the other 100% in total. Accordingly, in terms of the mass part, the B component is 3.00 parts by mass, the C component is 10.00 parts by mass, and the D component is 8.00 parts by mass based on 100 parts by mass of the A component. Further, the E component was 7.26 parts by mass based on 1 part by mass of the total of the A, B, C, and D components, all of which satisfied the conditions specified in the claims. The appearance of the liquid immediately after the adjustment was good.
Example 5
Composition Example No. 5 of Example 5 In the No. D5, 3.00% of X-40-9225 of Shin-Etsu Chemical Co., Ltd. as a moisture-curable liquid silicone oligomer A and 5.00% of a total of 2.00% of SIRES MSE 100 of Asahi Kasei Chemical Co., As the catalyst B, 0.30% of D-20 of Shin-Etsu Chemical Co., Ltd., 0.10% of the hydroxy-terminated dimethylpolysiloxane XF3057 of Toshiba Silicone Co., Ltd. as a straight chain modified polydimethylsiloxane C having silanol groups in both terminal groups, As the hydrophobic fine particles D having a particle diameter of 1 to 50 nm, Aerosil RX300 of Nippon Aerosil Co., Ltd. is 0.04%, and the total of A, B, C and D components is 5.44%. Further, as the volatile solvent E, 5.00% of KF96L-0.65 cs of Shinetsu Kagaku Co., 58.56% of IP solvent 1620 of Idemitsu Kosan Co., Ltd., and 30.00% of isoparaffin solvent NAS3 of Nippon Oil Co., And the other components are silicon powder KMP590 1.00% by Shin-Etsu Chemical Co., Ltd., and the total of the components A, B, C, D, E and others is 100%. Accordingly, in terms of the mass part, 6.00 parts by mass of the B component, 2.00 parts by mass of the C component, and 0.80 parts by mass of the D component are contained with respect to 100 parts by mass of the A component. Further, the E component was 17.20 parts by mass based on 1 part by mass of the total of the A, B, C, and D components, all of which satisfied the conditions specified in the claims. The appearance of the liquid immediately after the adjustment was good.
Example 6
Composition Example No. 6 of Example 6 In the No. D6, as the moisture-curable liquid silicone oligomer A, 3.00% of X-40-9250, 0.50% of KR401N and 0.40% of KR400 as a total of 4.40% , 0.20% of D-20 of Shin-Etsu Chemical Co., Ltd. and 0.30% of total of 0.10% of KR400 as an A-derived material, and a straight-chain modified polydimethylsiloxane C having silanol groups in both terminal groups 0.10% of Hydroxyl-terminated dimethylpolysiloxane XF3800, 0.80% of XF3905, 0.10% of YF3057 as a sub-total 1.00%, and 0.10% of Aerosil RX300 of Nippon Aerosil Co., Ltd. as hydrophobic fine particles D having an average particle diameter of 1 to 50 nm , And the subtotal of the A component, the B component, the C component, and the D component is 5.80%. Further, as the volatile solvent E, 5.00% of KF96L-1 cs of Shinetsu Kagaku Co., Ltd. and IP solvent 1620 of Idemitsu Kosan Co., Ltd. were adjusted to a total of 92.80% of 87.80%, and further, silicon of Shinetsu Kagaku Co., 1.00% of powder KMP590 and 0.40% of MQ803TF, and 100% of A, B, C, D, E and others. Accordingly, in terms of the mass part, 6.82 parts by mass of the B component, 22.73 parts by mass of the C component, and 2.27 parts by mass of the D component are obtained with respect to 100 parts by mass of the A component. Furthermore, the E component was 16.00 parts by mass based on 1 part by mass of the total of the A, B, C, and D components, all of which satisfied the conditions specified in the claims. The appearance of the liquid immediately after the adjustment was good.
Example 7
In Composition Example No. D7 of Example 7, 0.50% of X-40-9225 of Shinetsu Kagaku Co., 1.00% of X-40-9250, and 6.00% of KR400 as a moisture-curable liquid silicone oligomer A, , 0.50% of KR400 as an A-derived component as a curing catalyst B, 0.50% of a hydroxyl-terminated dimethylpolysiloxane XF3905 and 0.50% of YF3057 as straight-chain modified polydimethylsiloxane C having a silanol group in both terminal groups, Of hydrophobic fine particles D having an average particle diameter of 1 to 50 nm as a sub-total of 1.00% and Aerosil RY200 of Nippon Aerosil Co., Ltd. as 0.60%, and the total of A, B, C and D components is 8.10%. Further, as volatile solvent E, 20.00% of KF96L-0.65 cs of Shinetsu Kagaku Co., Ltd. and 90.80% of isoparaffin-based solvent NAS3 of 70.80% of Shin-Etsu Chemical Co., Ltd. 1.00% of silicone powder KMP590 and 0.10% of KF96-20 cs, and 100% of A, B, C, D, E and others in total. Accordingly, in terms of the mass part, 8.33 parts by mass of the B component, 16.67 parts by mass of the C component, and 10.00 parts by mass of the D component are obtained with respect to 100 parts by mass of the A component. Further, the E component was 11.21 parts by mass based on 1 part by mass of the total of the A, B, C and D components, all of which satisfied the conditions specified in the claims. The appearance of the liquid immediately after the adjustment was good.
Example 8
Composition Example No. 8 of Example 8 In the composition No. D8, 12.00% of X-40-9225 of Shinetsu Kagaku Co., Ltd., 1.00% of X-40-9250, 1.00% of KR401N as a moisture-curable liquid silicone oligomer A, A total of 15.00% of SIRES MSE 100 of Wakaku as a curing catalyst B, 0.30% of D-25 of Shin-Etsu Chemical Co., Ltd. as a curing catalyst B, (Manufactured by Nippon Aerosil Co., Ltd.) as the hydrophobic fine particles D having an average particle diameter of 1 to 50 nm and a total of 1.00% of 0.10% of the hydroxyl terminated dimethylpolysiloxane YF3800, 0.40% of XF3905, 0.40% of YF3057 and 0.10% of YF3807, Of 0.20%, and the subtotal of the components A, B, C, and D is 16.50%. Further, KF96L-0.65 cs of KF96-500 cs (so-called silicone oil) of Shin-Etsu Chemical Co., Ltd. (so-called silicone oil) was used as the volatile solvent E, and the content of KF96L-0.65 cs and kerosene of 68.45% %, And the total of the A component, the B component, the C component, the D component, the E component, and others is 100%. Accordingly, in terms of the mass part, the B component is 2.00 parts by mass, the C component is 6.67 parts by mass, and the D component is 1.33 parts by mass based on 100 parts by mass of the A component. Further, the E component was 5.06 parts by mass based on 1 part by mass of the total of the A, B, C, and D components, all satisfying the conditions defined in the claims. The appearance of the liquid immediately after the adjustment was good.
Example 9
Composition Example No. 9 of Example 9 In the composition No. D9, 3.40% of X-40-9250, 0.40% of KR401N and 0.90% of KR400 as a moisture-curable liquid silicone oligomer A were added in a total amount of 4.40% , 0.20% of D-20 of Shin-Etsu Chemical Co., Ltd. and 0.30% of total of 0.10% of KR400 as an A-derived material, and a straight-chain modified polydimethylsiloxane C having silanol groups in both terminal groups , 0.30% of hydroxy terminated dimethylpolysiloxane XF3800, 2.64% of XF3905, 0.33% of YF3057, and 0.10% of Aerosil RX300 of Nippon Aerosil Co., Ltd. as hydrophobic fine particles D having an average particle diameter of 1 to 50 nm , And the subtotal of the A component, the B component, the C component, and the D component is 8.10%. 5.00% of KF96L-1 cs of Shinetsu Kagaku Co., Ltd. and 85.50% of IP solvent 1620 of Idemitsu Kosan Co., Ltd. were used as the volatile solvent E in the subtotal 90.50%. In addition, silicon powder of Shinetsu Kagaku Co., KMP590 1.00%, and MQ803TF 0.40%, which are 100% in total of the components A, B, C, D, E and others. Accordingly, the amount of the component B is 6.82 parts by mass, the content of the component C is 75.00 parts by mass, and the content of the component D is 2.27 parts by mass with respect to 100 parts by mass of the A component. Further, the E component was 11.17 parts by mass based on 1 part by mass of the total of the A, B, C and D components, all of which satisfied the conditions specified in the claims. The appearance of the liquid immediately after the adjustment was good.
Example 10
Composition Example No. 10 of Example 10 contained 3.40% of X-40-9250, 0.40% of KR401N and 0.90% of KR400 as a moisture-curable liquid silicone oligomer A, 4.40% of a total of 4.40% , 0.20% of D-20 of Shin-Etsu Chemical Co., Ltd. and 0.30% of total of 0.10% of KR400 as an A-derived material, and a straight-chain modified polydimethylsiloxane C having silanol groups in both terminal groups 0.40% of hydroxy-terminated dimethylpolysiloxane XF3800, 3.36% of XF3905, 0.42% of YF3057 as a hydrophobic fine particle D having an average of 4.20% and a mean particle diameter of 1 to 50 nm, and 0.10% of Aerosil RX300 of Nippon Aerosil Co., Ltd. , And the subtotal of the A component, the B component, the C component, and the D component is 9.00%. 5.00% of KF96L-1 cs of Shinetsu Kagaku Co., Ltd. and IP solvent 1620 of Idemitsu Kosan Co., Ltd. were used as a volatile solvent E, with a total of 89.60% of 84.60% as a volatile solvent E, and a silicon powder of Shinetsu Kagaku Co., KMP590 1.00%, and MQ803TF 0.40%, which are 100% in total of the components A, B, C, D, E and others. Therefore, in terms of the mass part, 6.82 parts by mass of the B component, 95.45 parts by mass of the C component, and 2.27 parts by mass of the D component are obtained with respect to 100 parts by mass of the A component. Further, the E component was 9.96 parts by mass based on 1 part by mass of the total of the A, B, C, and D components, all of which satisfied the conditions specified in the claims. The appearance of the liquid immediately after the adjustment was good.
(Comparative Example 1)
In Composition Example No. H1 of Comparative Example 1, a total of 0.050% of 0.040% of KC89S and 0.010% of X-40-9225 of Shinetsu Kagaku Co., Ltd. as a moisture-curable liquid silicone oligomer A, 0.001% of D-20 in the formula (1), 0.001% of a hydroxyl-terminated dimethylpolysiloxane YF3800 of Toshiba Silicone Co., Ltd. as a linear-chain-modified polydimethylsiloxane C having silanol groups in both terminal groups and an average particle diameter of 1 to 50 nm As the hydrophobic fine particles D, 0.001% of Aerosil RX300 manufactured by Nippon Aerosil Co., Ltd., and the sub-total of A component, B component, C component and D component is 0.053%. Further, as volatile solvent E, 5.00% of KF96L-1 cs of Shin-Etsu Chemical Co., Ltd., 94.947% of kerosene was 99.947% of the total, and the other components were 0%, and the contents of A component, B component, C component, D component, E component And the other 100%.
Therefore, in terms of the mass part, 2.00 parts by mass of the B component, 2.00 parts by mass of the C component, and 2.00 parts by mass of the D component are obtained with respect to 100 parts by mass of the A component. Furthermore, the E component was 1886 parts by mass based on 1 part by mass of the total amount of the A, B, C, and D components, and deviated from the conditions specified in claim 1. Also, the appearance of the liquid immediately after the adjustment was good.
(Comparative Example 2)
In Composition Example No. H2 of Comparative Example 2, 2.00% of KC89S of Shinetsu Kagaku Co., Ltd., 4.00% of total of 2.00% of X-40-9250 was used as a moisture-curable liquid silicone oligomer A, , 0.30% of D-20 in the cross-linking agent, 0.001% of a hydroxyl-terminated dimethylpolysiloxane YF3800 of Toshiba Silicone Co., Ltd. as a straight chain modified polydimethylsiloxane C having silanol groups in both terminal groups and an average particle diameter of 1 to 50 nm As the hydrophobic fine particles D, 0.100% of Aerosil RX300 manufactured by Nippon Aerosil Co., Ltd., and the subtotal of the components A, B, C, and D is 4.501%. Further, as volatile solvent E, 15.00% of KF96L-0.65 cs of Shinetsu Kagaku Co., Ltd., 75.50% of isoparaffin solvent NAS3 of Nippon Oil Co., Ltd., and 95.50% of propylene glycol monomethyl ether acetate PGMAc of 5.00% , And the other components are 0%, and the total of the components A, B, C, D, and E is 100%. Accordingly, in terms of the mass part, the B component is 10.00 parts by mass, the C component is 0.0251 parts by mass, and the D component is 2.50 parts by mass based on 100 parts by mass of the A component. Further, the E component was 21.22 parts by mass based on 1 part by mass of the total of the A, B, C, and D components, and the C component slightly deviated from the conditions specified in claim 3. Furthermore, the appearance of the liquid immediately after the adjustment was good.
(Comparative Example 3)
In Composition Example No. H3 of Comparative Example 3, 1.00% of X-40-9225, 1.00% of X-40-9250 and 1.00% of SIRES MSE 100 of Asahi Kasei Wakka were used as the moisture-curable liquid silicone oligomer A As a curing catalyst B, 0.001% of D-20 of Shin-Etsu Chemical Co., Ltd. as a curing catalyst, and 0.001% of a D-20 of Shinetsu Kagaku Co., Ltd. as a straight chain modified polydimethylsiloxane C having a silanol group in both terminal groups. The hydrophobic fine particles D having 0.20% of the terminal dimethylpolysiloxane YF3800 and the hydrophobic fine particles D having an average particle diameter of 1 to 50 nm were mixed with 0.05% of Aerosil RX300 manufactured by Nippon Aerosil Co., Ltd. The sub-components of the components A, B, C and D were 3.251 %to be. Further, as volatile solvent E, 5.00% of KF96L-0.65 cs of Shinetsu Kagaku Co., 81.749% of IP solvent 1620 of Idemitsu Kosan Co., Ltd., and 10.00% of isoparaffin solvent NAS3 of Nippon Oil Co., 96.749%, and the others are 0%, and the total of the A component, the B component, the C component, the D component, the E component and others is 100%. Accordingly, in terms of the mass part, the B component is 0.03 parts by mass, the C component is 6.67 parts by mass, and the D component is 1.67 parts by mass based on 100 parts by mass of the A component. Furthermore, the E component was 29.76 parts by mass based on 1 part by mass of the total of the A, B, C, and D components, and the B component deviated from the conditions defined in claim 1. Also, the appearance of the liquid immediately after the adjustment was good.
(Comparative Example 4)
In Composition Example No. H4 of Comparative Example 4, 1.00% of KC89S, 1.00% of X-40-9225, 1.00% of X-40-9250 and 0.90 of KR400 as a moisture-curable liquid silicone oligomer A %, 3.90% as a curing catalyst B, 0.10% of KR400 as an A-derived component, 5.00% of a hydroxyl-terminated dimethylpolysiloxane YF3800 of Toshiba Silicone Co., Ltd. as a linearly modified polydimethylsiloxane C having a silanol group in both terminal groups, And 0.01% of Aerosil RX300 manufactured by Nippon Aerosil Co., Ltd. as hydrophobic fine particles D having an average particle diameter of 1 to 50 nm and XF3905 of 1.00%, and the subtotal of the components A, B, C and D was 10.01% . Further, as the volatile solvent E, KF96L-0.65 cs, KF96L-1 cs and kerosene of Shinetsu Kagaku Co., Ltd. were changed to 10.00%, 5.00% and 73.69%, respectively, to 88.69% of total amount, and silicone powder KMP590 of Shinetsu Kagaku And the total amount of the components A, B, C, D, E, and other components is 100%, with KF96-20 cs of 0.00 and Shin-Etsu Chemical Co., Ltd. being 0.30. Accordingly, in terms of the mass part, the amount of the component B is 2.56 parts by mass, the content of the component C is 153.85 parts by mass, and the content of the component D is 0.26 parts by mass based on 100 parts by mass of the component A. Furthermore, the E component was 8.86 parts by mass based on 1 part by mass of the total of the A, B, C, and D components, and the C component deviated from the conditions defined in claim 1. Also, the appearance of the liquid immediately after the adjustment was good.
(Comparative Example 5)
In Composition Example No. H5 of Comparative Example 5, 0.50% of X-40-9225 of Shinetsu Kagaku Co., 0.50% of X-40-9250 and 1.90% of X-40-2327 were used as the moisture-curable liquid silicone oligomer A, , 3.90% of D-20 of Shin-Etsu Chemical Co., Ltd. as a curing catalyst B and 3.10% of X-40-2327 of 0.10% as an A-derived component in a total amount of 3.10% As the modified polydimethylsiloxane C, 0.20% of hydroxy-terminated dimethylpolysiloxane YF3800 of Toshiba Silicone Co., Ltd., 0.020% of Aerosil RX300 of Nippon Aerosil Co., Ltd. as hydrophobic fine particles D having an average particle diameter of 1 to 50 nm, A The subtotal of the components B, C, and D is 6.22%. Further, as the volatile solvent E, IP solvent 1620 of Idemitsu Kosan Co., Ltd. was added in an amount of 0.00% and kerosene 72.68% was added to the total amount of 92.68%. In addition, silicone powder KMP590 1% and KF96-500 cs (product of Shinetsu Kagaku Co., Silicone oil) 0.10%, and the total of the components A, B, C, D, E and others is 100%. Accordingly, in terms of the mass part, the amount of the component B is 106.90 parts by mass, the amount of the component C is 6.90 parts by mass, and the amount of the component D is 0.69 parts by mass based on 100 parts by mass of the component A. Further, the E component was 14.90 parts by mass based on 1 part by mass of the total of the A, B, C, and D components, and the B component deviated from the conditions defined in claim 1. Also, the appearance of the liquid immediately after the adjustment was good.
(Comparative Example 6)
In Composition Example No. H6 of Comparative Example 6, 0.50% of X-40-9225 of Shinetsu Kagaku Co., 4.1% of X-40-9250 and 5.50% of KR400 of 0.9% as moisture-curable liquid silicone oligomer A, 0.10% of KR400 as the A-derived component as the curing catalyst B, 0% of the linearly modified polydimethylsiloxane C having a silanol group at both ends and a hydrophobic particle D having an average particle diameter of 1 to 50 nm, ) Is 0.20%, and the subtotal of the components A, B, C, and D is 5.80%. Further, as volatile solvent E, 15.00% of KF96L-0.65 cs of Shinetsu Kagaku Co., Ltd. and 76.0% of isoparaffin-based solvent of Nippon Oil Co., Ltd. were changed to 91.70% of the total, and further, the silicon of Shinetsu Kagaku Co., 1% of powder KMP590 and 1.50% of KF96-500cs (silicone oil), and the total of 100% of A, B, C, D, E and others. Accordingly, in terms of the mass part, 1.82 parts by mass of the B component, 0 parts by mass of the C component, and 3.64 parts by mass of the D component are obtained with respect to 100 parts by mass of the A component. Furthermore, the E component was 15.81 parts by mass based on 1 part by mass of the total of the A, B, C, and D components, and deviated from the conditions defined in claims 1 and 3. In addition, the appearance of the liquid immediately after the adjustment was good.
(Comparative Example 7)
In Composition Example No. H7 of Comparative Example 7, 12.00% of X-40-9225 from Shin-Etsu Chemical Co., Ltd., 1.00% of X-40-9250 was used as the moisture-curable liquid silicone oligomer A, SIRES MSE 100 of Asahi Kasei Chemical Co., Having a silanol group at both terminal ends, and 0.60% of D-25 of Shinetsu Kagaku Co., Ltd. as a curing catalyst B as a curing catalyst B in the total amount of 1.00% and 1.00% of KR401N of Shinetsu Kagaku Co., 0.20% of the hydroxy-terminated dimethylpolysiloxane YF3800 of Toshiba Silicone Co., Ltd., and 5.00% of Aerosil RY200 of Nippon Aerosil Co., Ltd. as the hydrophobic fine particles D having an average particle diameter of 1 to 50 nm as the dimethylsiloxane C, The subtotal of the components B, C, and D is 20.80%. Further, as the volatile solvent E, 10.00% of KF96L-0.65 cs of Shin-Etsu Chemical Co., Ltd. and 69.20% of kerosene were used as the subtotal 79.20% as the volatile solvent E. Other contents of the components A, B, C, D and E And the other 100%. Accordingly, in terms of the mass part, the amount of the component B is 4.00 parts by mass, the content of the component C is 1.33 parts by mass, and the content of the component D is 33.33 parts by mass based on 100 parts by mass of the component A. Further, the E component was 3.81 parts by mass based on 1 part by mass of the total of the A, B, C, and D components, and the D component deviated from the conditions defined in claim 1. In addition, the appearance of the liquid immediately after the adjustment was good.
(Comparative Example 8)
Composition Example of Comparative Example 8 In No. H8, 3.80% of X-40-9250 of Shinetsu Kagaku Co., Ltd. and 4.80% of KR400 of 4.80% as a moisture-curable liquid silicone oligomer A, 0.30% of D-20 in the formula (1), and 0.50% of a total of 0.50% of KR400 as the A-derived material in an amount of 0.20%. As the linearly modified polydimethylsiloxane C having silanol groups in both terminal groups, 0.30% of polysiloxane XF3905, 0.20% of YF3057, and 0% of hydrophobic fine particles D having an average particle diameter of 1 to 50 nm. The subtotal of the components A, B, C and D is 5.80%. Further, KF96L-0.65 cs of KF96L-0.65 cs and 73.60% kerosene of Shinetsu Kagaku Co., Ltd. as a volatile solvent E were added to the total amount of 93.20%, and silicon oil KMP590 1.00% of Shinetsu Kagaku Co., Component, C component, D component, E component, and the other 100% in total. Accordingly, in terms of the mass part, 10.42 parts by mass of the B component, 10.42 parts by mass of the C component, and 0 parts by mass of the D component are obtained with respect to 100 parts by mass of the A component. Furthermore, with respect to 1 part by mass of the total of the A, B, C, and D components, the E component was 16.07 parts by mass, and the D component deviated from the conditions specified in claim 1. In addition, the appearance of the liquid immediately after the adjustment was good.
The surface water repellent protective agent prepared in the ranges of the compositions of the examples and comparative examples in the above Tables 1 and 2 was applied to a test body by spraying with an air gun and a sponge application method and cured for a predetermined time, , Initial contact angle, initial slip angle, stain resistance, gas permeability and weather resistance were evaluated for Examples 1 to 10 and Comparative Examples 1 to 8. These results are shown in Tables 3 and 4, respectively.
Further, the surface water repellent protective agent for each external scene prepared was charged in a glass bin and sealed. After sealing for 3 months at 45 캜, the external appearance was evaluated. The storage stability was evaluated.
10
sponge
sponge
Workability
Dropout angle
The urethane-coated steel sheet was made by the following application method. That is, the SPCC steel sheet (general cold rolled steel sheet) obtained by degreasing the two-component curing type urethane paint made by Nippon Paint Co., Ltd. with isopropyl alcohol and then with a petroleum solvent was used as the white stain resistance, And baked at 100 DEG C for 2 hours to prepare a urethane-coated iron plate. A degreasing operation was carried out by spraying uniformly a special degreasing agent on the surface of the urethane-coated steel plate, wiping off immediately, and wiping with a special cloth. Subsequently, the degreased clean surface was uniformly hand painted with a dedicated sponge for the surface water repellent protective agent for external scene described in Tables 1 and 2 or applied uniformly on the degreased surface using a low-pressure air gun and dried . Immediately after drying, the excess polymer (polymer) was wiped with a cloth for cleaning only and the surface was smoothed. In either case, an initial evaluation was performed after one day of curing at 25 ° C.
After curing at 25 占 폚 for 2 weeks, an inverse model test was carried out using a cleaning liquid diluted 50 times with neutral car shampoo by the method specified in JIS K5400. After the surface was washed 5,000 times with a brush, the remaining water droplets were lightly pressed and absorbed with paper, and then tap water was applied to the surface, and the water repellency was generally protected by the naked eye. And those markedly deteriorated were evaluated as?. Furthermore, the test piece was fixed to the exposure test bench by the method specified in JIS K 2396, and the outdoor exposure test was performed for 3 months. After that, the surface was washed, washed with water and wiped with a neutral car shampoo diluted 50 times, Water was applied and evaluated visually. A " indicates that the water repellency is generally maintained, and " " indicates that the water repellency is maintained rather than the uncoated surface but is clearly lower than that at the initial stage. After 2 weeks of curing at 25 占 폚, the carbon black powder was uniformly dispersed on the surface, maintained at 50 占 폚 for 2 hours, cleaned with neutral car-shampoo, and the surface thereof was observed for contamination resistance test. The clear surface was rated as?, The clearness was almost clear but the slight black contamination remained, and the clear black contamination remained.
As a result of these tests, it was found that the spread of the liquid in Example 10 was worse than that in the Examples slightly different from those in Example 10, and that there was a slight unevenness in the degree of visibility in Examples 9 and 10 Except for this, the embodiment of the present invention was good in both the application with the dedicated sponge and the application with the air gun. On the other hand, in Comparative Example 5, Comparative Example 5 had a poor wiping sound after drying and poor appearance, and Comparative Example 7 also had bad appearance due to unevenness of application at the time of spraying and poor leveling property thereafter. In Comparative Example 2, there was almost no improvement in the contact angle of the surface due to appearance-free construction. For these three examples, no further evaluation was performed. Further, in Comparative Example 4, the spread of the liquid was slightly poor, and a slight uneven appearance was recognized.
In the stain resistance, in Examples 1 and 10, only good results were obtained, and the remaining Examples 2 to 9 were excellent. On the other hand, Comparative Examples 1, 3 and 4 and Comparative Example 6 were good in the comparative example and Comparative Example 8 was excellent in the good.
In the present invention, Examples 1 and 5, 8, 9 and 10 were good in the Examples, and the remaining Examples 2 to 4 and 6 and 7 were excellent. On the other hand, in the comparative examples, all were poor.
In the case of the weather resistance, Example 1 was good in Example 1, but the other Examples 2 to 10 were excellent in ⊚. On the other hand, in Comparative Example 4, Comparative Example 4 was good and Comparative Example 8 was good, but Comparative Examples 1, 3, and 6 were poor.
As described above, in Examples 1 to 8 of the present invention, excellent stain resistance, gas resistance and weather resistance as well as excellent appearance were obtained, and a favorable appearance without coating unevenness was obtained, and a strong film having excellent durability against car wash It can be formed. Also in Examples 9 and 10, it was found that a strong film excellent in durability, gas-resistance and weatherability as well as excellent in durability against washing, there was. On the contrary, in Comparative Examples 1 to 8, none of the three points of stain resistance, resistance to weather, and weather resistance were excellent.
Further, the surface water repellent protective composition of the present invention and the composition of the comparative example are coated and cured on the painted surface of the automobile loop to improve the initial gloss and water repellency, and the effect on the front window glass caused by the rainwater flowing from the roof due to the subsequent rainfall Respectively.
First, five compact cars of each maker of black metallic paint within three years from the registration of the new car were prepared, and polishing was carried out using a non-silicon compound in all five loops, (Oil content) was removed. Water and oil were removed from the front window glass using a commercially available strong oil film remover. Water repellent protective compositions D1, D6 and D7 shown as Examples 11 to 13 in Table 5, and compositions H4 and H6 in Comparative Examples 9 to 10 as Comparative Examples 9 to 10 were used in the same application method as Tables 3 and 4, After curing for about 20 hours in the room adjusted to about 25 캜 by an air-conditioner, the initial gloss and water repellency of the applied surface were visually evaluated and confirmed to be all good. Also compositions D1, D6 and D7, and H4 and H6 are the same compositions as those of Table 1 and Tables 3 and 4.
Then, while the wiper was operated by hanging the engine from the car wash, the water was continuously poured in a shower state for 30 minutes so that about 10 L of tap water flowed from the rear of the loop toward the front window glass in one minute by using a watering hose. Thereafter, the glass state of the front window was immediately observed, and the presence or absence of flashing due to adhesion of the oil film was visually evaluated as sparkling property. The results are shown in Table 5. In this evaluation, " ⊚ " indicates that no glare was hardly observed on the front window glass surface, and " Good " Moreover, x is defined as a clear glare.
In Examples 11 to 13, there was no problem in the front window glass because there was no glare, and the visual field remained good. On the other hand, in any of Examples 9 to 10, a glare was felt on the front window glass. The reason for this is that in the composition H4 of Comparative Example 9, the value of C / A x 100, which is the amount of the component C used for the component A, is 153.85, and the amount of the component C relative to 100 parts by weight of the component A exceeds 25 parts by mass Out of the unreacted component in the C component. On the other hand, in the composition H6 of Comparative Example 10, there is no water repellency imparting agent for component C, and since it is substituted by KF96-500 cs which is a non-reactive water repellency imparting agent silicone oil, flashing occurs.
Claims (3)
100 parts by mass of the moisture-curable liquid silicone oligomer (A), 0.1 to 40 parts by mass of the curing catalyst (B) of (A), 1 part by mass of linearly modified polydimethylsiloxane (C) having silanol groups in both terminal groups (D) having an average particle diameter of 1 to 50 nm in an amount of 0.1 to 10.13 parts by mass, and further containing at least one or more species of a silicon-based volatile solvent, a hydrocarbon-based volatile solvent and a polar group-containing volatile solvent (A), (B), (C) and (D), which can dissolve or disperse the components (A), (B), D) in an amount of not more than 500 parts by mass based on 1 part by mass of the total amount of each component.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JPJP-P-2009-047422 | 2009-02-28 | ||
| JP2009047422A JP5679540B2 (en) | 2009-02-28 | 2009-02-28 | Surface water-repellent protective agent for exterior surfaces |
| PCT/JP2010/053096 WO2010098448A1 (en) | 2009-02-28 | 2010-02-26 | Surface-protective water-repellent agent for exterior surfaces |
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| KR20110121693A KR20110121693A (en) | 2011-11-08 |
| KR101750441B1 true KR101750441B1 (en) | 2017-06-23 |
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| KR1020117020003A KR101750441B1 (en) | 2009-02-28 | 2010-02-26 | Surface-protective water-repellent agent for exterior surfaces |
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| JP (1) | JP5679540B2 (en) |
| KR (1) | KR101750441B1 (en) |
| CN (1) | CN102333832B (en) |
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| JP5682095B2 (en) * | 2011-05-18 | 2015-03-11 | スリーボンドファインケミカル株式会社 | Coating layer and coating layer forming method |
| JP6051389B2 (en) * | 2012-09-25 | 2016-12-27 | 石原ケミカル株式会社 | Coating agent for painted surfaces of vehicle bodies |
| JP6074655B2 (en) * | 2012-09-26 | 2017-02-08 | 石原ケミカル株式会社 | Coating agent for painted surfaces of vehicles |
| JP6125275B2 (en) * | 2013-02-28 | 2017-05-10 | 株式会社ソフト９９コーポレーション | Coating agent and application method thereof |
| JP6438783B2 (en) * | 2015-02-03 | 2018-12-19 | 株式会社ソフト９９コーポレーション | Surface protectant for painted surface |
| JP6844986B2 (en) * | 2015-10-30 | 2021-03-17 | 大阪ガスケミカル株式会社 | Paint composition and coating |
| WO2017187874A1 (en) * | 2016-04-26 | 2017-11-02 | 株式会社スリーボンド | Curable composition |
| CN106318203A (en) * | 2016-08-25 | 2017-01-11 | 无锡卡秀堡辉涂料有限公司 | Titanium-polymer moisture-cured organosilicone high-temperature-resistant coating |
| CN106967536B (en) * | 2017-03-29 | 2019-04-02 | 东北石油大学 | Sandstones mother oil displacement tests rock core oil washing agent and preparation method thereof |
| JP7137081B2 (en) * | 2017-06-15 | 2022-09-14 | 株式会社スリーボンド | Surface treatment method and composition for surface treatment |
| JP6403080B1 (en) * | 2017-08-22 | 2018-10-10 | 大阪ガスケミカル株式会社 | Coating composition and method for producing coating film |
| JP7104708B2 (en) * | 2017-08-22 | 2022-07-21 | 大阪ガスケミカル株式会社 | Curable Compositions and Their Applications |
| JP6953339B2 (en) * | 2018-03-22 | 2021-10-27 | 信越化学工業株式会社 | Water repellent composition |
| JP7328520B2 (en) * | 2018-08-07 | 2023-08-17 | 株式会社スリーボンド | Curable composition |
| KR20210095656A (en) * | 2018-12-19 | 2021-08-02 | 피피지 인더스트리즈 오하이오 인코포레이티드 | Ambient-curable, high-temperature protective coating |
| RU2711456C1 (en) * | 2019-05-28 | 2020-01-17 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Пензенский государственный университет архитектуры и строительства" | Composition for anti-icing coating |
| DE102019134728A1 (en) | 2019-12-17 | 2021-06-17 | OSRAM Opto Semiconductors Gesellschaft mit beschränkter Haftung | OPTICAL COMPONENT, OPTOELECTRONIC SEMICONDUCTOR COMPONENT AND METHOD FOR MANUFACTURING AN OPTICAL COMPONENT |
| KR102481985B1 (en) * | 2020-08-18 | 2022-12-29 | 주식회사 엠팸 | Coating composition for solar panel |
| JP2022096138A (en) * | 2020-12-17 | 2022-06-29 | 株式会社ソフト９９コーポレーション | Glass water repellent agent |
| CN112694836A (en) * | 2020-12-22 | 2021-04-23 | 曹加月 | Waterproof coating for high-speed rail and preparation method thereof |
| CN113004788B (en) * | 2021-02-19 | 2022-07-26 | 3M中国有限公司 | Surface finishing composition |
| CN113046026B (en) * | 2021-04-07 | 2023-03-24 | 山西大同大学 | Chlorine-free low-corrosivity coal antifreezing solution |
| KR102586496B1 (en) * | 2022-08-21 | 2023-10-06 | 김현철 | vehicle polish |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007301773A (en) | 2006-05-09 | 2007-11-22 | Nof Corp | Surface material and its manufacturing method |
| JP2008075021A (en) * | 2006-09-22 | 2008-04-03 | Soft99 Corporation | Coating agent for vehicles |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5548245A (en) * | 1978-10-03 | 1980-04-05 | Toray Silicone Co Ltd | Silicone resin composition |
| JP3599358B2 (en) * | 1993-08-06 | 2004-12-08 | ジーイー東芝シリコーン株式会社 | Composition for coating |
| JPH0913018A (en) * | 1995-07-03 | 1997-01-14 | Nippon Sheet Glass Co Ltd | Composition for water-repellent coating film and water-repellent glass |
| JP3374368B2 (en) * | 1996-12-24 | 2003-02-04 | 松下電工株式会社 | Resin composition for adhesion reducing coating and painted product using the same |
| JP2002241695A (en) * | 2000-12-15 | 2002-08-28 | Dow Corning Toray Silicone Co Ltd | Water-repellent silicone coating agent composition |
| JP2003253207A (en) * | 2002-02-28 | 2003-09-10 | Dow Corning Toray Silicone Co Ltd | Curable silicone resin composition for coating |
| JP2013093081A (en) * | 2011-10-26 | 2013-05-16 | Dainippon Printing Co Ltd | Method for designing circuit board, method for manufacturing circuit board, circuit board, substrate for suspension, suspension, suspension with element, and hard disk drive |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007301773A (en) | 2006-05-09 | 2007-11-22 | Nof Corp | Surface material and its manufacturing method |
| JP2008075021A (en) * | 2006-09-22 | 2008-04-03 | Soft99 Corporation | Coating agent for vehicles |
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| JP5679540B2 (en) | 2015-03-04 |
| CN102333832B (en) | 2014-02-19 |
| JP2010202717A (en) | 2010-09-16 |
| WO2010098448A1 (en) | 2010-09-02 |
| CN102333832A (en) | 2012-01-25 |
| KR20110121693A (en) | 2011-11-08 |
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