JP5679540B2 - Surface water-repellent protective agent for exterior surfaces - Google Patents

Description

The protective agent for an exterior surface of the present invention has an effect of being easily washed when the protective film applied to the surface of the exterior material is soiled, and has excellent adhesion and a water repellent effect over a long period of time. As a result, the appearance of the exterior material can be maintained over a long period of time, and the durability is particularly excellent. The painted surface of a vehicle exterior such as a passenger car, truck, bus, motorcycle, airplane, train or ship, glass surface or The present invention relates to a surface water-repellent protective agent having a function of repelling water and protecting the exterior surface of a vehicle, which is a plastic surface, or an automobile tire, an aluminum wheel, and a mirror.

  Conventionally, coating agents for exterior surfaces of various structures have been developed to apply water repellency by applying them to painted surfaces of exteriors of passenger cars and other vehicles, or surfaces of various furniture and building walls. Has been used. Of these, the coating agents used on the painted surfaces of vehicles such as passenger cars are wax-type coating agents and emulsion-type coating agents. Tools and methods for applying these coating agents include coating fabrics and Some are applied with sponge or suede synthetic leather, others are applied with spray. Among these various types of coating agents, various types of emulsion-type coating agents have been developed for convenience of use.

  A water repellency-imparting emulsion with high water repellency emulsified from a specific amino-modified silicone oil and a surfactant, which has excellent properties as a car polish (automobile polish) on the painted surface of an automobile body has been proposed. (For example, refer to Patent Document 1). However, there is a demand for a surface water-repellent protective agent for exterior surfaces that can be easily finished by wiping after application, and that is superior in initial water repellency.

  Furthermore, moisture-curing silicone oligomers and curing catalysts are used as vehicle coating agents that can maintain the gloss, gloss, water repellency and antifouling properties of metal surfaces, painted surfaces, or resin surfaces of vehicles over a long period of time. And a vehicle coating agent that contains a both-end type reactive silicone oil and the blending ratio of the both-end type reactive silicone oil is 25 parts by mass or more with respect to 100 parts by mass of the moisture-curable silicone oligomer. (For example, refer to Patent Document 2). However, there is a demand for a surface water-repellent protective agent for an exterior surface that can be easily finished by wiping after application, further excellent in initial water repellency, and more excellent in durability after washing.

JP 2004-339305 A JP 2008-75021 A

The problem to be solved by the present invention is a coating agent that is applied to a painted surface of a vehicle exterior such as a passenger car or other vehicle to impart water repellency, and can be easily finished by wiping after application, and is durable or durable. A vehicle with excellent resistance to dirt, washing resistance, weather resistance, etc., especially with excellent durability during washing . It is to provide a surface water-repellent protective agent for application to an exterior surface.

The means of the present invention for solving the above-mentioned problems is that, in the invention of claim 1, 100 parts by mass of the moisture-curable liquid silicone oligomer (A) and 0.1-40 of the curing catalyst (B) of (A). 1 part by mass or more and less than 25 parts by mass of linear modified polydimethylsiloxane (C) having silanol groups at both terminal groups, 0.1 to 10 hydrophobic fine particles (D) having an average particle diameter of 1 to 50 nm .13 parts by mass, further containing at least one or more of a silicone-based volatile solvent, a hydrocarbon-based volatile solvent, and a polar group-containing volatile solvent, and (A), (B), (C ) And (D), the volatile solvent (E) capable of dissolving or dispersing each component is 500 masses with respect to a total of 1 part by mass of each component (A), (B), (C) and (D). Surface water repellency for an exterior surface of a vehicle characterized by containing It is a protective agent.

In the invention of claim 2, the hydrophobic fine particles D having an average particle diameter of 1 to 50 nm are composed of surface-hydrophobized silica fine particles obtained by subjecting the surface of the hydrophilic silica fine particles to a hydrophobic treatment. It is a surface water-repellent protective agent for a vehicle exterior surface of the means.

The surface water-repellent protective agent for exterior surfaces according to the means of the present invention is a coating agent that imparts water repellency by applying to a painted surface of a vehicle exterior such as a passenger car or other automobile, and can be easily finished by wiping after application. There is no unevenness, especially excellent durability of the film against abrasion during cleaning, and therefore, the durability of the appearance is remarkably good, the initial water repellency is excellent, the stain resistance, the cleaning durability and the weather resistance are excellent. The surface water-repellent protective agent of the present invention has an excellent effect such that an excellent coated surface can be formed even when coated with a coating material such as a polisher. The water repellent protective agent is 1 part by mass or more and less than 100 parts by mass with respect to 100 parts by mass of the moisture curable liquid silicone oligomer that is the A component, and the hydrophobic fine particles that are the D component are 0.1 to 25 parts by mass. By containing, there is no fear that unreacted polydimethylsiloxane oil will flow out even if car washing is repeated, and the windshield will not be glaring, and the present invention has heretofore been effective in terms of durability. It is a surface water-repellent protective agent for exterior surfaces that has an excellent effect.

With regard to the best mode for carrying out the present invention, a surface water-repellent protective agent for an exterior surface according to the means of the present invention will be described below with reference to the table. This surface water-repellent protective agent for exterior surfaces can be applied to exterior surfaces of various vehicles . In that case, after washing and degreasing the exterior surface to be applied, various coating methods such as hand-painting with a special sponge, machine coating using a polisher, spray coating with an air gun, immersion coating, etc. The surface water-repellent protective agent for exterior surfaces of the present invention is applied and finished. In addition, when a very good appearance such as an exterior surface of a passenger car is required, the exterior surface can be easily wiped off like car wax by wiping after applying a surface water repellent protective agent. It is a water repellent protective agent.

The main components of the surface water-repellent protective agent for vehicle exterior surfaces according to the means of the present invention will be described below. The component A which is one of the essential components of the invention according to claim 1 is a moisture curable liquid silicone oligomer, and the chemical formula of the silicone oligomer is {(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, halogen, and a is 0 to 0 1.5, b is a value at which the moisture curable group is 5% or more, c is a value of 3 or more, and a moisture curable hydrocarbon group-containing silicone oligomer having a property of forming a film by crosslinking and curing with moisture is preferable. Used for. 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, in the above, when a exceeds 1.5, the strength of the resulting coating is insufficient, and the durability is lowered.

  The component A is one of the essential components, and the curing action of the component B curing catalyst quickly forms a cured film having a dense cross-linked structure immediately after coating, has excellent weather resistance, and excellent stain resistance. A crosslinked film is formed. In order to obtain these effects 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 available from Shin-Etsu Chemical Co., Ltd. KC89S, KR213, KR400, KR401, KR401N, KR500, KR510, KR9218, X-40-2308, X-40-2327, 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 Toshiba Silicone Co., Ltd. XC96-B0446, Toray Dow Corning Co., Ltd. SR2402, AY42-161, AY42-163, AY42-182, AZ-6101, Asahi Kasei Wacker Co., Ltd. SILRES MSE 100, SILICATE
What is marketed by names, such as TES40WN, can illustrate suitably. In addition, KR-400 (containing 10% by mass of aluminum catalyst), KR401 (containing 5% by mass of titanium catalyst), X-40-2327 (containing 5% by mass of phosphoric acid catalyst) of Shin-Etsu Chemical Co., Ltd. Is pre-blended with the B component of the curing catalyst.

  As the B component used as the curing catalyst for A, an organometallic compound, an acid, an alkali, or the like is used. Examples of the organometallic compound include compounds such as aluminum, titanium, zirconium, and tin. Specifically, di-isopropoxy (ethyl acetoacetate) aluminum, isopropoxybis (ethyl acetoacetate) aluminum, tris (ethyl acetoacetate). Acetate) aluminum, di-isopropoxybis (acetylacetonate) titanium, di-isopropoxybis (ethylacetoacetate) titanium, tetrakis (2-butoxyethyl alcoholate) titanium, dibutoxybis (ethylacetoacetate) zirconium, tetrakis (2- Butoxyethyl alcoholate) zirconium, dibutyltin dilaurate, dibutyltin bis (octyloxycarbonylmethylthiolate), etc. Such as D-20, D-25, DX-9740 of Shin-Etsu Chemical Co., Ltd. are exemplified.

  Examples of the acid catalyst that is a curing catalyst for component B include formic acid, acetic acid, oxalic acid, citric acid, trifluoroacetic acid, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, and phosphoric acid. ) D-220 and X-40-2309A manufactured by the company). Examples of the alkali catalyst that is a curing catalyst for the B component include sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, ethylamine, diethylamine, triethylamine, butylamine, dibutylamine, tributylamine, ethanolamine, diethanolamine, triethanolamine, methyl Diethanolamine, dimethylethanolamine, ethylenediamine, triethylenediamine, morpholine, piperidine, diazabicycloundecane, aminosilanes, amino-modified silicones, reactants of various primary or secondary amines and epoxy group-containing silane coupling agents, disilazane Various organic / inorganic alkaline compounds such as KP-390 manufactured by Shin-Etsu Chemical Co., Ltd. are exemplified.

  These B components are preferably added in the range of 0.1 to 40 parts by mass with respect to 100 parts by mass of the A component. If it is less than this range, a sufficient curing rate cannot be obtained, and if it is more than this range, the pot life (after the original package is opened or after the accelerator and other additives are mixed is effective) Is not preferable because the work period is shortened, workability is lowered, and physical properties of the cured film are adversely affected.

  The linear modified polydimethylsiloxane having silanol groups at both ends, which is a C component which is a further essential component of the invention according to claim 1, is chemically bonded by condensing hydroxyl groups directly bonded to silicon atoms with the A component. Is an essential component for imparting a durable water-repellent performance to the film without deteriorating the physical properties of the durable crosslinked cured film formed by the component A. Due to the presence of silanol groups at both ends, the reaction probability is improved compared to modified polysiloxane reactive only at one end, so that the durability is remarkably improved, and both ends react to form a film. Since it lies on the surface, it is presumed that water repellency is expressed in a smaller amount.

  This component is a linear both-end modified polydimethylsiloxane having silanol groups at both ends of the chain, and is particularly limited as long as it dissolves or decomposes with the A component directly in the A component or by the following E component. None, but those having a viscosity of 3000 cs or less are preferred. When the viscosity exceeds 3000 cs, the reactivity with the component A decreases, and the water repellency durability decreases. Therefore, it is preferable to use it with a low viscosity.

  The C component is an essential component for imparting a durable water repellency to the cured film composed of the A component. However, when replaced with a non-reactive water repellency imparting agent such as silicone oil, the C component bleeds out over time. Long-term water repellency is difficult to obtain. On the other hand, by using the composition of the present invention, it is possible to obtain a strong cross-linked film which not only has excellent durability of the film but also exhibits excellent water repellency at the initial stage and excellent in water repellency.

  The amount of component C used is preferably in the range of 1 to less than 100 parts by weight per 100 parts by weight of component A. That is, in order to improve the water repellency of the A component, it is preferable to use 1 part by mass or more of the C component with respect to 100 parts by mass of the A component. In order to prevent adverse effects due to the out, it is more preferable that the C component does not exceed 25 parts by mass.

  The linear modified polydimethylsiloxane having silanol groups at both ends of the C component is commercially available from GE Toshiba Silicone Corp. as hydroxy-terminated dimethylpolysiloxanes YF3800, XF3905, YF3057, YF3807, YF3802, and XC-96-723. Can be preferably used.

  As the component D in the invention according to claim 1, hydrophobic fine particles D having an average particle diameter of 1 to 50 nm are used. Examples of hydrophobic fine particles having an average particle diameter of 1 to 50 nm of component D include polyethylene, polypropylene, polyacrylic acid alkyl ester, polymethacrylic acid alkyl ester, polytetrafluoroethylene, tetrafluoroethylene / methyl vinyl ether copolymer, and crosslinked poly Examples thereof include organic fine particles such as dimethylsiloxane, and hydrophobized fine particles of inorganic fine particles such as silica, alumina, and titania. Among these, surface-hydrophobized silica fine particles are preferable from the viewpoint of effects such as resistance to alteration, easy availability of fine particles, and dispersion stability. The average particle size of the hydrophobic fine particles is preferably in the range of 1 to 50 nm. Within this range, the appearance of the coating film on the surface to be treated is not impaired, and the durability of the coating film produced, particularly the durability against abrasion during car washing, is improved. In addition, the effect is stably exhibited. As the preferred fine particle silica, Aerosil R104, Aerosil R106, Aerosil R202, Aerosil R711, Aerosil R7200, Aerosil R805, Aerosil R812, Aerosil R8200, Aerosil R972, Aerosil RX200, Aerosil RX300, Aerosil RX50, Aerosil RX50 from Japan Aerosil Examples include RY200. It is preferable to use the D component in a range of 0.1 to 25 parts by mass with respect to 100 parts by mass of the A component. If it is this range, the workability | operativity of application | coating will not be deteriorated, and the external appearance of the film | membrane of the to-be-processed surface will not be impaired, but the durability of the produced | generated film | membrane, especially the abrasion resistance at the time of a car wash is improved. In addition, the effect is stably exhibited. When the amount of D component used is less than 0.1 parts by mass, the effect is not sufficient, and when the amount of D component used exceeds 25 parts by mass, the coating workability is reduced and the appearance of the resulting film is Worse and impractical.

  As E component in the invention which concerns on Claim 1, A component which consists of 1 type, or 2 or more types of a silicone type volatile solvent, a hydrocarbon type volatile solvent, and a polar group containing volatile solvent, B component, C component, D Volatile organic solvents that can dissolve or disperse the components are used.

Examples of the silicone-based volatile solvent of component E include polydimethylsiloxane oil having a viscosity of 5 mm ² / s or less, cyclic dimethylsiloxanes such as hexamethylcyclotrisiloxane and octamethylcyclotetrasiloxane, dimethyldimethoxysilane, and dimethyldiethoxy. Examples thereof include silane, trimethylmethoxysilane, and the like, specifically, KF96L-0.65cs, KF96L-1cs, KF96L-1.5cs, KF96L-2cs, KF96L-5cs, KF994, KF995, GE manufactured by Shin-Etsu Chemical Co., Ltd. Examples thereof include TSF405 and TSF3802A manufactured by Toshiba Silicon Corporation, and AK0.65 manufactured by Asahi Kasei Wacker Corporation.

  Examples of E component hydrocarbon volatile solvents include n-paraffin hydrocarbon solvents, isoparaffin hydrocarbon solvents, naphthene hydrocarbon solvents, or petroleum fractions and residual oils mainly composed of these. Or the fraction of a decomposition product etc. are illustrated, As an isoparaffin-type hydrocarbon solvent, isohexane, isooctane, isononane, isodecane, 1016 (boiling point 93-140 degreeC) of IP solvent made from Idemitsu Kosan Co., Ltd., 1620 (boiling point 166- 202 ° C.) (for Examples), 2028 (boiling point 213 to 262 ° C.), 2836 (boiling point 277 to 353 ° C.), Isosol 200 (boiling point 95 to 155 ° C.), 300 (boiling point 170 to 189 ° C.) ° C.), 400 (boiling point 206-257 ° C.), n-paraffin hydrocarbon solvent, n-hexane, n-octane, -Decane, n-dodecane, No. 0 solvent L, No. 0 solvent M, No. 0 solvent H (all manufactured by Nippon Petrochemical Co., Ltd.), cyclohexane, methylcyclohexane, ethylcycloxan, decalin as naphthenic hydrocarbon solvents, Naphthezol L, M, and H (all manufactured by Nippon Petrochemical Co., Ltd.) are mainly petroleum fractions, residual oil reforming or cracked fractions such as petroleum ether, gasoline, light oil, and kerosene. , Mineral spirits, and terpenes.

  Examples of the polar group-containing volatile solvent of component E include alcohols having a hydroxyl group, an ether group, an ester group, a carbonyl group, a caproxyl group, glycol ethers, glycol ether esters, ethers, esters, and ketones.

  Among these, as alcohols, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, n-pentanol, neopentyl alcohol, n-hexanol, n-octanol , Isooctanol, n-decanol, n-dodecy alcohol, cyclopentanol, cyclohexanol and the like.

  Next, as glycol ether and glycol ether ester, 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 mono n-propyl ether, Ethylene glycol mono n-butyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene 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, propylene glycol mono i-propyl ether, propylene glycol mono n-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, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, tripropylene glycol monomethyl ether, tripropylene glycol Monoethyl ether, 3-methoxy-1-pro Panol, 3-methoxy-1-butanol, 3-methoxybutyl acetate, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, diethyl ether, di-propyl ether, dibutyl ether, ethylene Examples include glycol dimethyl ether, ethylene glycol diethyl 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 ketones include acetone, methyl ethyl ketone, methyl i-butyl ketone, di i-propyl ketone, and di i-butyl ketone.

  Among these, hydrocarbon solvents such as isoparaffin hydrocarbon solvents, n-paraffin hydrocarbon solvents, naphthene hydrocarbon solvents, kerosene, mineral spirits, and terpenes are used alone or in combination, or silicone volatiles. It is preferable to use it in combination with a solvent. Further, it is preferable to use 30% by mass or more of a solvent having a boiling point of 70 ° C. or higher in the E component. When the solvent having a boiling point of 70 ° C. or more is less than 30% by mass, drying is too fast, and the coating workability and the obtained film appearance are deteriorated.

  The ratio of the E component to the total of 1 part by mass 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 and it is easy to repel, and in one application, the thickness of the formed film may be too thin and the performance may not be achieved. It is not preferable from the viewpoint of workability.

  In order to further improve the initial water repellency, the present composition further includes a silicone oil such as polydimethylsiloxane, a modified silicone oil having a functional group such as an epoxy group, an amino group, a mercapto group, an alkoxysilyl group, and a vinyl group. A small amount of solid water-repellent silicone resin can be added. In addition, ultraviolet absorbers, ultraviolet stabilizers, antioxidants, pigments, dyes, fragrances, deodorants, viscosity modifiers, repellency inhibitors, wiping improvers, and the like can also be added.

The surface water-repellent protective agent for vehicle exterior of the present invention can be applied by hand coating using a sponge or the like, mechanical coating by a polisher, spraying by an air gun, or spraying as an aerosol filled in a pressure can with a spray gas. Further, after application, the surface may be further smoothed by wiping or the like as necessary.

The surface water-repellent protective agent for vehicle exterior of the present invention has particularly high durability of the coating itself, and is excellent in the effect of improving the appearance of the exterior surface, so passenger cars, motorcycles, trucks, buses, tractors, combines, It can be particularly suitably used for airplanes, trains, ships, forklifts, Yumbo (registered trademark), painted surfaces of crane exteriors, glass surfaces, metal surfaces, resin surfaces, and the like.

  Examples 1 to 10 and Comparative Examples 1 to 8 are shown in Table 1-1 and Table 1-2 for raw materials for producing the surface water-repellent protective agent for exterior surfaces of the present invention. The raw materials A, B, C, D and E shown in Table 1-1 and Table 1-2 are weighed in a stainless beaker in a dry box, stirred for about 10 minutes, and then sonicated for 10 minutes. Thus, a surface water-repellent protective agent for exterior surfaces, which is a composition of each example and each comparative example, was prepared. In addition, the preparation method of a composition is not limited to the said method. In Examples and Comparative Examples shown in Table 1-1 and Table 1-2 below,% indicates mass%. In this case, the composition No. D1, D2,..., D9, and D10. H1, H2,..., H7, H8, respectively. In addition, regarding the composition ratio of KR400 and X-40-2327 in Examples in Table 1-1 and in the text, the composition ratio was previously classified into the A component and the B component.

  Composition Example No. 1 of Example 1 In D1, 0.86% of Shin-Etsu Chemical KC89S (0.43%) and X-40-9225 (0.43%) as moisture-curing liquid silicone oligomer A, and 0.83% as curing catalyst B, Shin-Etsu Chemical Co., Ltd. As a linear modified polydimethylsiloxane C having silanol groups at both end groups, 0.10% of D-20 of Toshiba Silicone Co., Ltd. hydroxy-terminated dimethylpolysiloxane XF3905 is 0.20%, and the average particle diameter is 1 to Aerosil RX300 of Nippon Aerosil Co., Ltd. is 0.04% as hydrophobic fine particles D of 50 nm, and the subtotal of A component, B component, C component and D component is 1.20%. Furthermore, as volatile solvent E, 84.20% of IP Solvent 1620 of Idemitsu Kosan Co., Ltd. and NAS3 of propylene glycol monomethyl ether acetate of isoparaffinic solvent of Nippon Oil & Fats Co., Ltd. are 14.60%, 98.80%, etc. Is 0%, which is 100% in total of A component, B component, C component, D component, E component and others. Accordingly, in terms of parts by mass, the A component is 100 parts by mass, the B component is 11.63 parts by mass, the C component is 23.26 parts by mass, and the D component is 4.65 parts by mass. Furthermore, the E component was 82.33 parts by mass with respect to 1 part by mass of the subtotal of the A component, B component, C component, and D component, and all satisfied the conditions specified in the claims. The liquid appearance immediately after the adjustment was good and good.

  Composition Example No. 2 of Example 2 In D2, as moisture curable liquid silicone oligomer A, Shin-Etsu Chemical Co., Ltd. KC89S was 5.00%, X-40-9225 was 10.00%, and X-40-2327 was 4.75%, for a total of 19.75. %, Shin-Etsu Chemical Co., Ltd.'s D-20 as 0.50% and X-40-2327 as A-derived component as 0.25%, totaling 0.75%, both end groups having silanol groups As the linear modified polydimethylsiloxane C having a hydroxy-terminated dimethylpolysiloxane XF3905 of Toshiba Silicone Co., Ltd., 4.50%, and as the hydrophobic fine particles D having an average particle diameter of 1 to 50 nm, Aerosil R972 of Nippon Aerosil Co., Ltd. At 0.000%, the subtotal of component A, component B, component C and component D is 27.00%. Furthermore, as the volatile solvent E, KF96L-0.65cs of Shin-Etsu Chemical Co., Ltd. is 5.00% and kerosene 68.00%, a total of 73.00%, the others are 0%, A component, B component, C The total of the component, D component, E component and others is 100%. Therefore, in terms of parts by mass, the A component is 100 parts by mass, the B component is 3.80 parts by mass, the C component is 22.78 parts by mass, and the D component is 10.13 parts by mass. Furthermore, the E component was 2.70 parts by mass with respect to 1 part by mass of the subtotal of the A component, B component, C component, and D component, all satisfying the conditions specified in the claims. The liquid appearance immediately after the adjustment was good and good.

  Composition Example No. In D3, Shin-Etsu Chemical Co., Ltd. used X-50-9250 of Shinetsu Chemical Co., Ltd. as 1.00% and KR400 as 4.50% as moisture curable liquid silicone oligomer A, and 5.50% as curing catalyst B Shin-Etsu Chemical Co., Ltd. A linear modified poly having 0.20% of D-25, 0.10% of DX-9740, and 0.50% of KR400 as a component derived from A, 0.80% in total, and having silanol groups at both terminal groups As the dimethylsiloxane C, 0.70% of the hydroxy-terminated dimethylpolysiloxane XF3057 of Toshiba Silicone Co., and 0.20% of Aerosil RX300 of Nippon Aerosil Co., Ltd. as the hydrophobic fine particles D having an average particle diameter of 1 to 50 nm, A The subtotal of component, B component, C component and D component is 7.20%. Furthermore, as a volatile solvent E, Shin-Etsu Chemical Co., Ltd. KF96L-0.65cs is 20.00%, Nippon Oil & Fats Co.'s isoparaffin solvent NAS3 is 72.80%, 92.80%, and others are 0%. The total of A component, B component, C component, D component, E component and others is 100%. Therefore, in terms of parts by mass, the A component is 100 parts by mass, the B component is 14.55 parts by mass, the C component is 12.73 parts by mass, and the D component is 3.64 parts by mass. Furthermore, the E component was 12.89 parts by mass with respect to 1 part by mass of the subtotal of the A component, B component, C component, and D component, all satisfying the conditions specified in the claims. The liquid appearance immediately after the adjustment was good and good.

  Composition Example No. 4 of Example 4 In D4, Shin-Etsu Chemical Co., Ltd. X-40-9225 is 5.00% and X-40-9250 is 5.00% as a moisture-curing liquid silicone oligomer A. As a linear modified polydimethylsiloxane C having 0.30% D-20 of Chemical Co., Ltd. and silanol groups at both terminal groups, 0.70% of hydroxy-terminated dimethylpolysiloxane XF3905 of Toshiba Silicone Co., Ltd. and XF3057 As a hydrophobic fine particle D having a total particle size of 1.00% and an average particle diameter of 1 to 50 nm, Aerosil RY200 of Nippon Aerosil Co., Ltd. is 0.80%, and the components A, B, C and D The subtotal is 12.10%. Furthermore, as a volatile solvent E, KF96L-1cs of Shin-Etsu Chemical Co., Ltd. is 5.00%, kerosene 77.80% and propylene glycol monomethyl ether acetate PGMAc is 5.00% for a total of 87.80%, and others are MQ803TF. 0.10%, which is 100% in total of the A component, B component, C component, D component, E component and others. Therefore, in terms of parts by mass, the A component is 100 parts by mass, 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. Furthermore, the E component was 7.26 parts by mass with respect to 1 part by mass of the subtotal of the A component, B component, C component, and D component, all satisfying the conditions specified in the claims. The liquid appearance immediately after the adjustment was good and good.

  Composition Example No. 5 of Example 5 In D5, the moisture-curing liquid silicone oligomer A is Xue-9225 of Shin-Etsu Chemical Co., Ltd., 3.00%, and SIRES MSE 100 of Asahi Kasei Wacker is 2.00%, for a total of 5.00%. Shin-Etsu Chemical Co., Ltd. D-20 0.30%, Toshiba Silicone Co., Ltd. hydroxy-terminated dimethylpolysiloxane XF3057 0.10% as linear modified polydimethylsiloxane C having silanol groups at both end groups, Aerosil RX300 of Nippon Aerosil Co., Ltd. is 0.04% as hydrophobic fine particles D having an average particle diameter of 1 to 50 nm, and the subtotal of A component, B component, C component and D component is 5.44%. Furthermore, as volatile solvent E, Shinetsu Chemical Co., Ltd. KF96L-0.65cs is 5.00%, Idemitsu Kosan Co., Ltd. IP solvent 1620 is 58.56%, and Nippon Oil & Fats Co., Ltd.'s isoparaffinic solvent NAS3. 30.00% subtotal 93.56%, others are 1.00% of Shin-Etsu Chemical Co., Ltd. silicone powder KMP590, A component, B component, C component, D component, E component and other total 100 %. Therefore, in terms of parts by mass, the A component is 100 parts by mass, the B component is 6.00 parts by mass, the C component is 2.00 parts by mass, and the D component is 0.80 parts by mass. Furthermore, the E component was 17.20 parts by mass with respect to 1 part by mass of the subtotal of the A component, B component, C component, and D component, and all satisfied the conditions specified in the claims. The liquid appearance immediately after the adjustment was good and good.

  Composition Example No. 6 of Example 6 In D6, as a moisture-curable liquid silicone oligomer A, X40-9250 of Shin-Etsu Chemical Co., Ltd. is 3.00%, KR401N is 0.50% and KR400 is 0.90%, a total of 4.40%. Linear modified polydimethyl having 0.20% D-20 from Shin-Etsu Chemical Co., Ltd. as catalyst B and 0.10% KR400 as the component derived from A, 0.30% in total, and having silanol groups at both terminal groups Hydrophobic siloxane C, 0.10% of hydroxy-terminated dimethylpolysiloxane XF3800, 0.80% of XF3905 and 0.10% of YF3057, average particle size of 1-50 nm Aerosil RX300 from Nippon Aerosil Co., Ltd. as fine particles D is 0.10%, and the subtotal of A component, B component, C component and D component is 5.80% . Furthermore, as a volatile solvent E, KF96L-1cs of Shin-Etsu Chemical Co., Ltd. is 5.00% and IP Solvent 1620 of Idemitsu Kosan Co., Ltd. is 87.80%, a total of 92.80%, and others are Shin-Etsu Chemical Co., Ltd. 1.00% of the silicone powder KMP590 and 0.40% of MQ803TF, and the total of the A component, B component, C component, D component, E component and others is 100%. Therefore, in terms of parts by mass, the A component is 100 parts by mass, the B component is 6.82 parts by mass, the C component is 22.73 parts by mass, and the D component is 2.27 parts by mass. Furthermore, the E component was 16.00 parts by mass with respect to 1 part by mass of the subtotal of the A component, B component, C component, and D component, and all satisfied the conditions specified in the claims. The liquid appearance immediately after the adjustment was good and good.

  Composition Example No. 7 in Example 7 In D7, the moisture curable liquid silicone oligomer A was Xeoku Chemical Co., Ltd. X-40-9225 0.50%, X-40-9250 1.00% and KR400 4.50%, a total of 6.00. %, KR400 as a component derived from A as a curing catalyst B, 0.50%, and linear-modified polydimethylsiloxane C having silanol groups at both terminal groups, and hydroxy-terminated dimethylpolysiloxane XF3905 from Toshiba Silicone Co. 50% and YF3057 0.50% subtotal 1.00%, and Aerosil RY200 of Nippon Aerosil Co., Ltd. as hydrophobic fine particles D having an average particle diameter of 1 to 50 nm is 0.60%. A component, B component, C The subtotal of component and D component is 8.10%. Furthermore, as a volatile solvent E, KF96L-0.65cs from Shin-Etsu Chemical Co., Ltd. is 20.00% and NAS3 of isoparaffin solvent from Nippon Oil & Fats Co., Ltd. is 70.80%, a total of 90.80%. Silicone powder KMP590 of Shin-Etsu Chemical Co., Ltd. is 1.00% and KF96-20cs is 0.10%, and the total of A component, B component, C component, D component, E component and others is 100%. Therefore, in terms of parts by mass, the A component is 100 parts by mass, the B component is 8.33 parts by mass, the C component is 16.67 parts by mass, and the D component is 10.00 parts by mass. Furthermore, the E component was 11.21 parts by mass with respect to 1 part by mass of the subtotal of the A component, B component, C component, and D component, all satisfying the conditions specified in the claims. The liquid appearance immediately after the adjustment was good and good.

  Composition Example No. 8 in Example 8 In D8, Shin-Etsu Chemical Co., Ltd. X-40-9225 is 12.00%, X-40-9250 is 1.00%, KR401N is 1.00%, and Asahi Kasei Wacker's SIRES as moisture-curable liquid silicone oligomer A As a linear modified polydimethylsiloxane C having MSE 100 of 1.00%, 15.00% in total, D-25 of Shin-Etsu Chemical Co., Ltd. as curing catalyst B, 0.30%, and silanol groups at both terminal groups 0.10% of hydroxy-terminated dimethylpolysiloxane YF3800, 0.40% of XF3905, 0.40% of YF3057 and 0.10% of YF3807 of Toshiba Silicone Co., Ltd. Aerosil R972 of Nippon Aerosil Co., Ltd. is 0.20% as hydrophobic fine particle D of 50 nm, A component, B component, C component and And the D component subtotal is 16.50%. Further, as volatile solvent E, Shin-Etsu Chemical Co., Ltd. KF96L-0.65cs is 15.00% and kerosene is 68.45%, a total of 83.45%, others are Shin-Etsu Chemical KF96-500cs (so-called Silicone oil) is 0.05%, and the total of A component, B component, C component, D component, E component and others is 100%. Therefore, in terms of parts by mass, component A is 100 parts by mass, component B is 2.00 parts by mass, component C is 6.67 parts by mass, and component D is 1.33 parts by mass. Furthermore, the E component was 5.06 parts by mass with respect to 1 part by mass of the subtotal of the A component, B component, C component, and D component, all satisfying the conditions specified in the claims. The liquid appearance immediately after the adjustment was good and good.

  Composition Example No. 8 in Example 9 In D9, as moisture curable liquid silicone oligomer A, XE-40-9250 of Shin-Etsu Chemical Co., Ltd. is 3.00%, KR401N is 0.50%, and KR400 is 0.90%, a total of 4.40%. Linear modified polydimethyl having 0.20% D-20 from Shin-Etsu Chemical Co., Ltd. as catalyst B and 0.10% KR400 as the component derived from A, 0.30% in total, and having silanol groups at both terminal groups Hydrophobic with an average particle size of 1-50 nm, with a total of 3.30% of hydroxy-terminated dimethylpolysiloxane XF3800, 2.64% of XF3905, and 0.33% of YF3057 as siloxane C. The fine particle D is Aerosil RX300 of Nippon Aerosil Co., Ltd. at 0.10%, and the subtotal of A component, B component, C component and D component is 8.10% . Furthermore, Shin-Etsu Chemical Co., Ltd. KF96L-1cs is 5.00% and Idemitsu Kosan Co., Ltd. IP Solvent 1620 is 85.50%, a total of 90.50%. Others are Shin-Etsu Chemical Co., Ltd. 1.00% of the silicone powder KMP590 and 0.40% of MQ803TF, and the total of the A component, B component, C component, D component, E component and others is 100%. Therefore, in terms of parts by mass, the A component is 100 parts by mass, the B component is 6.82 parts by mass, the C component is 75.00 parts by mass, and the D component is 2.27 parts by mass. Furthermore, the E component was 11.17 parts by mass with respect to 1 part by mass of the subtotal of the A component, B component, C component, and D component, all satisfying the conditions specified in the claims. The liquid appearance immediately after the adjustment was good and good.

  Composition Example No. 10 of Example 10 In D10, as a moisture-curable liquid silicone oligomer A, X40-9250 of Shin-Etsu Chemical Co., Ltd. is 3.00%, KR401N is 0.50%, and KR400 is 0.90%, a total of 4.40%. Linear modified polydimethyl having 0.20% D-20 from Shin-Etsu Chemical Co., Ltd. as catalyst B and 0.10% KR400 as the component derived from A, 0.30% in total, and having silanol groups at both terminal groups Hydrophobic with an average particle size of 1 to 50 nm as a siloxane C, a subtotal of 4.20% of hydroxy-terminated dimethylpolysiloxane XF3800 of Toshiba Silicone Co., Ltd., 3.36% of XF3905 and 0.42% of YF3057 Aerosil RX300 from Nippon Aerosil Co., Ltd. as fine particle D is 0.10%, and the subtotal of A component, B component, C component and D component is 9.00% That. Furthermore, as the volatile solvent E, Shin-Etsu Chemical Co., Ltd. KF96L-1cs is 5.00% and Idemitsu Kosan Co., Ltd. IP solvent 1620 is 84.60%, a total of 89.60%, and others are Shin-Etsu Chemical Co., Ltd. 1.00% of the silicone powder KMP590 and 0.40% of MQ803TF, and the total of the A component, B component, C component, D component, E component and others is 100%. Therefore, in terms of parts by mass, the A component is 100 parts by mass, the B component is 6.82 parts by mass, the C component is 95.45 parts by mass, and the D component is 2.27 parts by mass. Furthermore, the E component was 9.96 parts by mass with respect to 1 part by mass of the subtotal of the A component, B component, C component, and D component, and all satisfied the conditions specified in the claims. The liquid appearance immediately after the adjustment was good and good.

(Comparative Example 1)
Composition Example No. 1 of Comparative Example 1 In H1, 0.050% of Shin-Etsu Chemical Co., Ltd. KC89S and 0.040% of X-40-9225 are used as moisture-curable liquid silicone oligomer A, and 0.050% in total, and Shin-Etsu Chemical Co., Ltd. as curing catalyst B As a linear modified polydimethylsiloxane C having 0.001% D-20 and silanol groups at both terminal groups, 0.001% of hydroxy-terminated dimethylpolysiloxane YF3800 manufactured by Toshiba Silicones Co., Ltd. has an average particle diameter of 1 to Aerosil RX300 of Nippon Aerosil Co., Ltd. is 0.001% as hydrophobic fine particles D of 50 nm, and the subtotal of A component, B component, C component and D component is 0.053%. Furthermore, as a volatile solvent E, KF96L-1cs of Shin-Etsu Chemical Co., Ltd. is 5.00% and kerosene is 94.947%, a total of 99.947%, the others are 0%, A component, B component, C component , D component, E component, and others are 100% in total.
Therefore, in terms of parts by mass, component A is 100 parts by mass, component B is 2.00 parts by mass, component C is 2.00 parts by mass, and component D is 2.00 parts by mass. Further, the E component was 1886 parts by mass with respect to 1 part by mass of the subtotal of the A component, B component, C component, and D component, which was outside the conditions defined in claim 1. The liquid appearance immediately after the adjustment was good and good.

(Comparative Example 2)
Composition Example No. In H2, the moisture-curable liquid silicone oligomer A is 2.00% of Shin-Etsu Chemical Co., Ltd. KC89S and 2.00% of X-40-9250, a total of 4.00%, and Shin-Etsu Chemical Co., Ltd. as the curing catalyst B. As a linear modified polydimethylsiloxane C having a silanol group at both end groups of 0.40%, a silicone-terminated hydroxy-terminated dimethylpolysiloxane YF3800 of 0.001%, an average particle diameter of 1 to Aerosil RX300 manufactured by Nippon Aerosil Co., Ltd. is 0.100% as hydrophobic fine particles D of 50 nm, and the subtotal of A component, B component, C component and D component is 4.501%. Further, as volatile solvent E, Ketsushin Chemical Co., Ltd. KF96L-0.65cs is 15.00%, Nippon Oil & Fats Co., Ltd. isoparaffin solvent NAS3 is 75.50% and propylene glycol monomethyl ether acetate PGMAc is 5.00. % Is 95.50%, the others are 0%, and the total of A component, B component, C component, D component, E component and others is 100%. Therefore, in terms of parts by mass, the A component is 100 parts by mass, 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. Furthermore, the E component is 21.22 parts by mass with respect to 1 part by mass of the A component, B component, C component, and D component, and the C component slightly deviates from the conditions defined in claim 3. It was. The liquid appearance immediately after the adjustment was good and good.

(Comparative Example 3)
Composition Example No. of Comparative Example 3 In H3, as moisture curable liquid silicone oligomer A, X-40-9225 of Shin-Etsu Chemical Co., Ltd. is 1.00%, X-40-9250 is 1.00%, and SIRES MSE 100 of Asahi Kasei Wacker is 1.00% 3.00% of total, D-20 of Shin-Etsu Chemical Co., Ltd. as the curing catalyst B, 0.001%, and hydroxy of the Toshiba Silicone Co., Ltd. as linear modified polydimethylsiloxane C having silanol groups at both terminal groups The terminal dimethylpolysiloxane YF3800 is 0.20%, the average particle size is 1 to 50 nm of hydrophobic fine particles D, and Aerosil RX300 of Nippon Aerosil Co., Ltd. is 0.05%. A component, B component, C component and D component The subtotal is 3.251%. Furthermore, as volatile solvent E, Shinetsu Chemical Co., Ltd. KF96L-0.65cs is 5.00%, Idemitsu Kosan Co., Ltd. IP Solvent 1620 is 81.749%, and Nippon Oil & Fats Co., Ltd. is an isoparaffin solvent NAS3. The subtotal of 10.00% is 96.749%, the others are 0%, and the total of A component, B component, C component, D component, E component and others is 100%. Therefore, in terms of parts by mass, component A is 100 parts by mass, component B is 0.03 parts by mass, component C is 6.67 parts by mass, and component D is 1.67 parts by mass. Furthermore, the E component was 29.76 parts by mass with respect to 1 part by mass of the subtotal of the A component, B component, C component, and D component, and the B component was outside the conditions defined in claim 1. The liquid appearance immediately after the adjustment was good and good.

(Comparative Example 4)
Composition Example No. of Comparative Example 4 In H4, as moisture curable liquid silicone oligomer A, KC89S of Shin-Etsu Chemical Co., Ltd. is 1.00%, X-40-9225 is 1.00%, X-40-9250 is 1.00%, and KR400 is 0.00. 90% total 3.90%, curing catalyst B KR400 as A-derived content, 0.10%, linear modified polydimethylsiloxane C having silanol groups at both terminal groups as the hydroxy terminal of Toshiba Silicone Co., Ltd. Dimethylpolysiloxane YF3800 5.00% and XF3905 1.00%, Aerosil RX300 of Nippon Aerosil Co., Ltd. as 0.01% of hydrophobic fine particles D having an average particle diameter of 1 to 50 nm, A component, B component, The subtotal of C component and D component is 10.01%. In addition, Shin-Etsu Chemical Co., Ltd. KF96L-0.65cs is 10.00%, KF96L-1cs is 5.00%, and kerosene is 73.69%. Silicon powder KMP590 of 1.00%, KF96-20cs of Shin-Etsu Chemical Co., Ltd. is 0.30, A component, B component, C component, D component, E component and other total 100% is there. Therefore, in terms of parts by mass, the A component is 100 parts by mass, the B component is 2.56 parts by mass, the C component is 153.85 parts by mass, and the D component is 0.26 parts by mass. Further, the E component was 8.86 parts by mass with respect to 1 part by mass of the subtotal of the A component, B component, C component, and D component, and the C component deviated from the conditions defined in claim 1. The liquid appearance immediately after the adjustment was good and good.

(Comparative Example 5)
Composition Example No. In H5, as moisture-curable liquid silicone oligomer A, X-40-9225 of Shin-Etsu Chemical Co., Ltd. is 0.50%, X-40-9250 is 0.50%, and X-40-2327 is 1.90%. 2.90% of the total, 3.00% of Shin-Etsu Chemical Co., Ltd. D-20 as the curing catalyst B and 0.10% of X-40-2327 as the A-derived component, 3.10%, both ends As a linear modified polydimethylsiloxane C having a silanol group as a linear modified polydimethylsiloxane C of Toshiba Silicone Co., Ltd., hydroxy-terminated dimethylpolysiloxane YF3800 is 0.20% and hydrophobic fine particles D having an average particle diameter of 1 to 50 nm are used as Nippon Aerosil Co., Ltd. ) Aerosil RX300 is 0.020%, and the subtotal of A component, B component, C component and D component is 6.22%. Furthermore, as a volatile solvent E, IP solvent 1620 of Idemitsu Kosan Co., Ltd. is 0.00%, and kerosene is 72.68%, a total of 92.68%, and others are silicon powder KMP590 of Shin-Etsu Chemical Co., Ltd. 1% And KF96-500cs (silicone oil) is 0.10%, and the total of A component, B component, C component, D component, E component and others is 100%. Therefore, in terms of parts by mass, the A component is 100 parts by mass, the B component is 106.90 parts by mass, the C component is 6.90 parts by mass, and the D component is 0.69 parts by mass. Further, the E component was 14.90 parts by mass with respect to 1 part by mass of the subtotal of the A component, B component, C component, and D component, and the B component was outside the conditions defined in claim 1. The liquid appearance immediately after the adjustment was good and good.

(Comparative Example 6)
Composition Example No. of Comparative Example 6 In H6, as the moisture curable liquid silicone oligomer A, X-40-9225 of Shin-Etsu Chemical Co., Ltd. was 0.50%, X-40-9250 was 4.1%, and KR400 was 0.9%, totaling 5.50. %, KR400 as the origin of A as a curing catalyst B, 0.10%, linear modified polydimethylsiloxane C having silanol groups at both end groups, 0%, hydrophobic fine particles D having an average particle diameter of 1 to 50 nm As a result, Aerosil RY200 of Nippon Aerosil Co., Ltd. is 0.20%, and the subtotal of the A component, B component, C component and D component is 5.80%. Furthermore, as a volatile solvent E, Shin-Etsu Chemical Co., Ltd. KF96L-0.65cs is 15.00%, and Nippon Oil &Fats's isoparaffinic solvent NAS3 is 76.0%, a total of 91.70%. Chemical Co., Ltd. silicon powder KMP590 1% and KF96-500cs (silicone oil) 1.50%, A component, B component, C component, D component, E component and other total 100%. Therefore, in terms of parts by mass, the A component is 100 parts by mass, the B component is 1.82 parts by mass, the C component is 0 parts by mass, and the D component is 3.64 parts by mass. Further, the E component was 15.81 parts by mass with respect to 1 part by mass of the subtotal of the A component, B component, C component, and D component, which was outside the conditions defined in claims 1 and 3. The liquid appearance immediately after the adjustment was good and good.

(Comparative Example 7)
Composition Example No. In H7, X-40-9225 of Shin-Etsu Chemical Co., Ltd. is 12.00%, X-40-9250 is 1.00% and SIRES MSE 100 of Asahi Kasei Wacker is 1.00% as moisture curable liquid silicone oligomer A In addition, 1.00% of KR401N of Shin-Etsu Chemical Co., Ltd. is 15.00% in total, D-25 of Shin-Etsu Chemical Co., Ltd. is 0.60% as a curing catalyst B, and linear chain having silanol groups at both terminal groups As modified polydimethylsiloxane C, 0.20% of hydroxy-terminated dimethylpolysiloxane YF3800 manufactured by Toshiba Silicone Co., Ltd. and 5.00% Aerosil RY200 manufactured by Nippon Aerosil Co., Ltd. as hydrophobic fine particles D having an average particle diameter of 1 to 50 nm. , A component, B component, C component and D component subtotal is 20.80%. Further, as volatile solvent E, Shin-Etsu Chemical Co., Ltd. KF96L-0.65cs is 10.00% and kerosene is 69.20%, a total of 79.20%, the others are 0%, A component, B component, The total of C component, D component, E component and others is 100%. Therefore, in terms of parts by mass, the A component is 100 parts by mass, the B component is 4.00 parts by mass, the C component is 1.33 parts by mass, and the D component is 33.33 parts by mass. Furthermore, the E component was 3.81 parts by mass with respect to 1 part by mass of the subtotal of the A component, B component, C component, and D component, and the D component was outside the conditions defined in claim 1. The liquid appearance immediately after the adjustment was good and good.

(Comparative Example 8)
Composition Example No. In H8, the moisture-curing liquid silicone oligomer A is 3.80% X-40-9250 of Shin-Etsu Chemical Co., Ltd. and 1.80% of KR400, a total of 4.80%, and Shin-Etsu Chemical Co., Ltd. is the curing catalyst B. As a linear modified polydimethylsiloxane C having silanol groups at both terminal groups, a total of 0.50% of D-20 of 0.30% and KR400 of A-derived content of 0.20%, Toshiba Silicone Corp. Hydroxy-terminated dimethylpolysiloxane XF3905 of 0.30% and YF3057 of 0.20%, hydrophobic fine particles D having an average particle diameter of 1 to 50 nm are 0%, and a subtotal of A component, B component, C component and D component Is 5.80%. Furthermore, as a volatile solvent E, Shin-Etsu Chemical Co., Ltd. KF96L-0.65cs is 20.00% and kerosene is 73.20%, a total of 93.20%. Others are Shin-Etsu Chemical Co., Ltd. silicon powder KMP590. 0.000%, and the total of A component, B component, C component, D component, E component and others is 100%. Therefore, in terms of parts by mass, component A is 100 parts by mass, component B is 10.42 parts by mass, component C is 10.42 parts by mass, and component D is 0 part by mass. Furthermore, the E component was 16.07 parts by mass with respect to 1 part by mass of the subtotal of the A component, B component, C component, and D component, and the D component deviated from the conditions defined in claim 1. The liquid appearance immediately after the adjustment was good and good.

  The surface water-repellent protective agent prepared in the range of the compositions of Examples and Comparative Examples in Table 1-1 and Table 1-2 above was applied to a test specimen by spraying with an air gun and a coating method using a special sponge. After the time curing, each of the appearance, initial gloss, initial contact angle, initial sliding angle, stain resistance, washing resistance and weather resistance was evaluated for Examples 1 to 10 and Comparative Examples 1 to 8. These results are shown in Table 2.

  In addition, the prepared surface water repellent protective agent for each exterior surface is filled into a glass bottle, and after sealing and left at 45 ° C. for 3 months, the appearance is evaluated, and a performance test is performed again for those having no problem in appearance. The storage stability was evaluated.

  A urethane-coated iron plate was prepared by the following application method. That is, SPCC steel sheet (general cold rolled steel sheet) degreased with Nippon Paint Co., Ltd.'s two-component curable urethane paint with isopropyl alcohol and then with petroleum-based solvent, with white stain resistance and other black color. It was painted by air gun spraying and baked at 100 ° C. for 2 hours for adjustment to obtain a urethane coated iron plate. A special degreasing agent was sprayed uniformly on the surface of this urethane-coated iron plate with a pump spray, and the degreasing work was performed by immediately wiping with a special cloth. Next, the surface water-repellent protective agent for exterior surfaces shown in Table 1-1 and Table 1-2 is applied to the degreased clean surface by hand-coating with a special sponge, or a low-pressure air gun is applied. Using it, it was uniformly coated on the degreased surface and dried. Immediately after drying, excess polymer was wiped off with a cloth exclusively for wiping to smooth the surface. In any case, after initial curing at 25 ° C., initial evaluation was performed.

  Further, after curing at 25 ° C. for 2 weeks, a model test for car wash resistance was performed using a cleaning solution obtained by diluting a neutral car shampoo with water 50 times by the method defined in JIS K 5400. After reciprocating 5000 times with a brush, the surface is rinsed with water, the remaining water droplets are lightly pressed against the paper and blotted, then tap water is applied to the surface and the water repellency is generally maintained visually as ◎, Retained but markedly marked as ◯. Furthermore, after performing the outdoor exposure test for 3 months after fixing the test piece to the exposure test stand by the method prescribed in JIS K 2396, the surface was washed with a neutral car shampoo diluted 50 times, washed with water, and wiped off with water. Later, water was applied to make a visual evaluation. The case where the water repellency was generally maintained was evaluated as ◎, and the case where the water repellency was maintained from the non-constructed surface but was clearly reduced compared to the initial level was evaluated as ◯. Also, after curing for 2 weeks at 25 ° C., the surface is uniformly sprinkled with carbon black powder, kept at 50 ° C. for 2 hours, washed with a neutral car shampoo, and then observed on the surface for stain resistance. A test was conducted. A sample with a clean surface was marked with ◎, a sample that was almost clean but with a slight black stain remaining was marked with ◯, and a sample with clearly black stain left was marked with ×.

  As a result of these tests, by using the composition of the present invention, the elongation of the liquid in Example 10 was slightly worse than that in other examples, and the extent that there was no problem in appearance in Examples 9 and 10. Except for the slight unevenness, the example of the present invention was good in both application with a special sponge and application with an air gun. On the other hand, in Comparative Example, Comparative Example 5 has poor wiping property after drying and poor appearance, and Comparative Example 7 also has poor appearance due to severe coating unevenness during spraying and poor leveling afterwards. It was. Moreover, although the comparative example 2 did not have a problem on an external appearance, the improvement of the contact angle of the surface by construction was hardly seen. These three cases were not evaluated further. Furthermore, in Comparative Example 4, the elongation of the liquid was slightly poor, and some unevenness was observed in appearance.

  In terms of stain resistance, in Examples, only Examples 1 and 10 were good, and the remaining Examples 2 to 9 were all excellent and excellent. On the other hand, in Comparative Examples, Comparative Examples 1, 3, 4 and Comparative Example 6 were good in ◯ and only Comparative Example 8 was excellent in ◎.

  As for car wash resistance, in Examples, Examples 1, 5, 8, 9, and 10 were good, and the remaining Examples 2 to 4, 6, and 7 were all excellent and excellent. On the other hand, in the comparative example, all were bad with x.

  In terms of weather resistance, in Example, Example 1 was excellent in ◯, but the remaining Examples 2 to 10 were all excellent in ◎. On the other hand, in Comparative Example, Comparative Example 4 was good in ○ and Comparative Example 8 was good in ◎, but the remaining Comparative Examples 1, 3, and 6 were all x and bad.

  As described above, in Examples 1 to 8 of the present invention, all of the stain resistance, the washing resistance and the weather resistance are excellent with ◎ or ○, and a preferable appearance without coating unevenness is obtained. It was found that a strong film excellent in the thickness can be formed on the surface. In Examples 9 and 10 as well, although slight unevenness is seen in the appearance, all of the stain resistance, the washing resistance and the weather resistance are excellent with ◎ or ◯, and a strong coating particularly excellent in car washing durability is provided on the surface. It was found that can be formed. On the other hand, in Comparative Examples 1 to 8, none of the three points of stain resistance, car wash resistance and weather resistance were excellent.

  Further, the surface water-repellent protective agent composition of the present invention and the composition of the comparative example were applied and cured on the painted surface of the roof of an automobile, and then the roof was subjected to subsequent rain to the one with good initial gloss and water repellency. The effect of rainwater flowing from the windshield on the windshield was investigated.

  First, for the survey, we prepared five compact cars from each manufacturer of black metallic paint within three years from the registration of the new car. All five cars were polished with non-silicone compound and degreased. Oil was removed, and scale and oil were removed using a commercially available strong oil film remover on the front window glass. Using the compositions D1, D6 and D7 of the surface water-repellent protective agent shown as Examples 11 to 13 in Table 3 and the compositions H4 and H6 of Comparative Examples shown as Comparative Examples 9 to 10, the same coating method as Table 2 After applying to the roof only and curing for about 20 hours in a room adjusted to about 25 ° C with an air conditioner, the initial gloss and water repellency of the coated surface are visually evaluated to confirm that both are good. confirmed. In addition, D1, D6 and D7 of composition, and H4 and H6 are the same compositions as those of Table 1 and Table 2.

  Next, at the car wash, with the engine running and the wiper operating, using a watering hose, about 10 liters of tap water per minute flows from the back of the roof in the direction of the windshield for 30 minutes. Continued to pour water. Thereafter, the state of the front window glass was immediately observed, and the presence / absence of glare due to the adhesion of the oil film was visually evaluated as glare. The results are shown in Table 3. In this evaluation, the case where almost no glare was observed on the surface of the front window glass was rated as ◎, and the case where slight glare was observed but there was no problem in ensuring visibility was rated as ○. Furthermore, the thing with which glare is clearly recognized was set as x.

In Examples 11 to 13, there was no glare in the front window glass, and there was no problem, and the visibility remained good. On the other hand, in Comparative Examples 9 to 10, glare was felt on the front window glass in any of the examples. The reason is that in the composition H4 of Comparative Example 9, the value of C / A × 100, which is the amount of the C component used relative to the A component, is 153.85, and the C component with respect to 100 parts by mass of the A component greatly increases 25 parts by mass. This is due to the bleeding out of the unreacted component of the C component. On the other hand, in the composition H6 of Comparative Example 10, there is no C component water repellency imparting agent, and this is replaced with KF96-500cs which is a non-reactive water repellency imparting agent silicone oil. Is.

Claims (2)

Moisture-curable liquid silicone oligomer (A) 100 parts by mass, (A) curing catalyst (B) 0.1-40 parts by mass, linear modified polydimethylsiloxane (C) having silanol groups at both terminal groups 1 to less than 25 parts by weight, 0.1 to 10.13 parts by weight of hydrophobic fine particles (D) having an average particle diameter of 1 to 50 nm, and a silicone-based volatile solvent, a hydrocarbon-based volatile solvent, A volatile solvent (E) containing at least one or more polar group-containing volatile solvents and capable of dissolving or dispersing each component of (A), (B), (C) and (D) , (A), (B), (C) and a surface water-repellent protective agent for vehicle exterior surfaces, containing 500 parts by mass or less with respect to 1 part by mass in total of each component . Mean hydrophobic fine particle size 1 to 50 nm (D) is of vehicles according to claim 1, characterized in that it consists of surface-hydrophobicized silica fine particles obtained by the hydrophobic treatment on the surface of the hydrophilic silica particles Surface water-repellent protective agent for exterior surfaces.