WO2019022087A1 - Composition pour formation de film de revêtement - Google Patents

Composition pour formation de film de revêtement Download PDF

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Publication number
WO2019022087A1
WO2019022087A1 PCT/JP2018/027752 JP2018027752W WO2019022087A1 WO 2019022087 A1 WO2019022087 A1 WO 2019022087A1 JP 2018027752 W JP2018027752 W JP 2018027752W WO 2019022087 A1 WO2019022087 A1 WO 2019022087A1
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Prior art keywords
film
composition
component
forming
range
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PCT/JP2018/027752
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English (en)
Japanese (ja)
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克彦 岸
学 桐野
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株式会社スリーボンド
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Priority to JP2019532646A priority Critical patent/JP7108199B2/ja
Publication of WO2019022087A1 publication Critical patent/WO2019022087A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • 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
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

Definitions

  • the present invention relates to a film forming composition. More particularly, the present invention relates to a film forming composition capable of obtaining a thin film coating layer for imparting weather resistance, durability, and the like to metal surfaces, painted surfaces, resin surfaces, etc. of automobile bodies and train vehicles in particular. .
  • a composition for forming a solid, semi-solid or liquid film on a coated steel plate of an automobile body or the like for example, a composition obtained by adding a volatile organopolysiloxane oil and a volatile dimethylpolysiloxane to a moisture-curable organopolysiloxane, an organic solvent and a curing catalyst
  • Patent Document 1 Japanese Patent Application Laid-Open No. Hei 10
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2013-194058
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2011-246664 discloses a mixture of moisture-curable silicone oligomers having different viscosities, a hydrolytic curing catalyst selected from a titanium compound and an aluminum compound, a volatilization selected from hydrocarbon compounds and the like. Disclosed is a surface water repellant composition comprising an organic solvent and a perfluoropolyether silane compound. Further, Patent Document 4 (Japanese Patent Application Laid-Open No.
  • Patent Document 5 Japanese Patent Application Laid-Open No. 2008-038049
  • a mixture of silicone oligomers having different viscosities a moisture curing catalyst of a titanium compound, and n-hexane
  • the composition for antifouling film formation which consists of an organic solvent chosen from etc. is disclosed.
  • composition ratio of high viscosity silicone oligomer to low viscosity silicone oligomer is compared with about 1/4 to 1/5.
  • boiling point of the diluent or solvent is not set in an appropriate range. Therefore, there is a problem that it is difficult to form a homogeneous film, and the antifouling performance of the film can not be sufficiently expressed.
  • the film forming composition is also required to have appropriate drying properties.
  • the first embodiment of the present invention includes the following (A) to (C), and the content of the following (A) is 0.35 to 0.58 mass with respect to 1 part by mass of the following (C)
  • the composition for forming a film, which is a part, and the content of the following (B) is 0.05 to 0.15 parts by mass:
  • (A) A mixture of a film-forming component comprising the following (A-1) and (A-2) in a mass ratio of (A-1) / (A-2) 1/26 to 1/36;
  • (A-1) A hydrolyzable group-containing silicone oligomer having a kinematic viscosity at 25 ° C.
  • the present invention also includes the following embodiments.
  • a second embodiment is the film forming composition according to the first embodiment, wherein the boiling point of (C) is in the range of 110 to 155 ° C.
  • the third embodiment is the composition for film formation according to the first or second embodiment, wherein (C) is a saturated aliphatic hydrocarbon solvent.
  • a fourth embodiment is characterized in that the (C) is at least one selected from the group consisting of 2-methyl octane, 3-methyl octane, 4-methyl octane, 4-ethyl heptane, and 2,3-dimethyl heptane And the composition for forming a film according to any one of the first to third embodiments.
  • a fifth embodiment is the film forming composition according to any of the first to fourth embodiments, wherein (B) contains an aluminum alkoxide compound.
  • the sixth embodiment is the film forming composition according to any of the first to fifth embodiments, which is used to form a film on the surface of a steel plate or a coated steel plate.
  • a seventh embodiment is the film-forming composition according to the sixth embodiment, wherein the steel plate or the coated steel plate is a car body of an automobile.
  • the composition for forming a film according to any of the first to fifth embodiments is applied to the surface of a steel plate or a coated steel plate, and the above (C) is applied at normal temperature or under heating environment. It is a method for forming a film, which comprises, after volatilization, further drying or wiping after further water wiping.
  • the ninth embodiment is the film forming method according to the eighth embodiment, wherein the steel plate or the coated steel plate is a car body of an automobile.
  • a tenth embodiment is a cured film obtained by curing the film forming composition according to any one of the first to seventh embodiments.
  • the eleventh embodiment is (A-1) a hydrolyzable group-containing silicone oligomer having a kinematic viscosity at 25 ° C. in the range of 100 to 250 mm 2 s ⁇ 1 ; (A-2) a hydrolyzable group-containing silicone oligomer having a kinematic viscosity at 25 ° C. in the range of 21 to 90 mm 2 s ⁇ 1 ; (B) an organoaluminum compound, (C) A method for producing a composition for forming a film, which comprises mixing a hydrocarbon-based organic solvent having a boiling point in the range of 100 to 165 ° C.
  • composition for forming a film is 0.35 to 0.58 parts by mass in total of (A-1) and (A-2) with respect to 1 part by mass of (C). It is a method of producing a composition for forming a film, which comprises 0.05 to 0.15 parts by mass.
  • the composition for forming a film according to the present invention comprises the following (A) to (C), and the content of the following (A) is 0.35 to 0.58 parts by mass with respect to 1 part by mass of the following (C) And the content of the following (B) is 0.05 to 0.15 parts by mass:
  • A) A mixture of a film-forming component comprising the following (A-1) and (A-2) in a mass ratio of (A-1) / (A-2) 1/26 to 1/36;
  • A-1) A hydrolyzable group-containing silicone oligomer having a kinematic viscosity at 25 ° C. in the range of 100 to 250 mm 2 s -1 (A-2) A range of the kinematic viscosity at 25 ° C.
  • a hydrolyzable group-containing silicone oligomer (B) an organoaluminum compound; and (C) a hydrocarbon-based organic solvent having a boiling point in the range of 100 to 165 ° C.
  • the film-forming composition having the above-mentioned constitution has appropriate drying properties and can form a homogeneous film excellent in antifouling properties. Moreover, the composition for film formation has good storability, and is excellent in workability in the wiping step. Furthermore, according to the composition for film formation, a film (film coating layer) having good weather resistance can be formed on a steel plate or a coated steel plate used for a car body of an automobile or the like. And the said coating can have the outstanding water repellency, water repellency, and abrasion resistance.
  • a mixture of film-forming components that contain at a mass ratio of (A-1) A hydrolyzable group-containing silicone oligomer having a kinematic viscosity at 25 ° C. in the range of 100 to 250 mm 2 s -1 (A-2) A range of the kinematic viscosity at 25 ° C. of 21 to 90 mm 2 s -1 And a hydrolyzable group-containing silicone oligomer.
  • hydrolyzable group an alkoxy group, an alkenyloxy group, an acyloxy group, an amino group, an aminooxy group, an oxime group, an amide group and the like can be mentioned.
  • the hydrolyzable group contained in the silicone oligomer is preferably an alkoxy group because of easy handling.
  • a hydrolyzable group-containing silicone oligomer means that a silane compound having a hydrolyzable group is partially hydrolyzed and condensed by a known catalyst such as an acid, a base or an organic tin compound, an organic titanium compound, etc.
  • a catalyst such as an acid, a base or an organic tin compound, an organic titanium compound, etc.
  • it is a polymer obtained by "partial hydrolytic condensation"), which has a hydrolyzable group derived from the above-mentioned silane compound at the molecular chain terminal or side chain, etc., and has a weight average molecular weight of 550 to It is a silicone compound having a linear structure, a branched structure or a three-dimensional network structure having a molecular weight of 20,000.
  • silane compound which has a hydrolysable group for obtaining the said silicone compound (silicone oligomer)
  • polyfunctional alkoxysilane compounds such as a dialkoxysilane compound, a trialkoxysilane compound, a tetraalkoxysilane compound, and monoalkoxysilane Compounds (monofunctional alkoxysilane compounds) can be mentioned.
  • the hydrolyzable group-containing silicone oligomer as the component (A-1) and the component (A-2) is a partial hydrolysis condensate of an alkoxysilane compound represented by the following formula (1).
  • the said partial hydrolysis-condensation product may be obtained by using only 1 type of alkoxysilane compound represented by following formula (1), or it was obtained by combining 2 or more types. It may be one.
  • R 1 and R 2 are each independently an aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, an alicyclic ring having 3 to 10 carbon atoms Group hydrocarbon group or an aromatic hydrocarbon group having 6 to 10 carbon atoms.
  • the substituent is not particularly limited, and examples thereof include an alkyl group, an alkenyl group, an aryl group, a halogen atom, a nitro group, a cyano group, a hydroxy group and a carboxy group. In the above, they are not substituted by the same substituent.
  • a substituted alkyl group is not substituted with an alkyl group.
  • R 1 and R 2 each independently represent a substituent selected from the group consisting of an aliphatic hydrocarbon group having 1 to 5 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms. More preferably each independently a substituent selected from the group consisting of a methyl group, an ethyl group, a propyl group and a phenyl group, particularly preferably each independently a methyl group or a phenyl group is there.
  • x is an integer of 0 to 3.
  • x is preferably an integer of 0 to 2, more preferably 1 or 2.
  • a known hydrolysis catalyst is added to the alkoxysilane compound represented by the above formula (1), and stirring is performed while warming in the presence of water.
  • a method of causing partial hydrolytic condensation can be mentioned, but it is not limited thereto.
  • x is 0 or 1
  • an alkoxy represented by (OR 2 ) in the side chain It will have a group.
  • the main skeleton of the polymer does not have a linear structure, and a branched structure or a three-dimensional crosslinked body is formed, partially contain an alkoxy group represented by (OR 2 ) in the structure. It becomes.
  • the said alkoxysilane compound may contain the thing whose x is 2 or 3 in said Formula (1), However
  • the alkoxy group is effectively effective in the structure of a component (A-1) and a component (A-2)
  • x is preferably 0 or 1 in order to add to
  • x since a polymer can not be formed only by the alkoxysilane compound in which x is 3, when x includes an alkoxysilane compound in which x is 3, x is in the range of 0 to 2 In combination, partial hydrolytic condensation is performed.
  • component (A-1) contains in the mixture as component (A) is a hydrolyzable group-containing silicone oligomer having a viscosity at 25 ° C. in the range of 100 to 250 mm 2 s ⁇ 1 .
  • viscosity is dynamic viscosity (mm 2 s -1 ) at 25 ° C., which is measured by a viscosity measurement method according to JIS Z 8803: 2011.
  • the kinematic viscosity can be measured by a single cylindrical rotational viscometer (B-type viscometer).
  • the description concerning the "hydrolyzable group-containing silicone oligomer" is as described above.
  • the component (A-1) is a component necessary for expressing its function in the cured film by the composition for forming a film of the present invention, and is used to form a film in concert with the component (A-2) described later. It is presumed to be a component that contributes and mainly acts on the antifouling performance. Therefore, according to the composition for film formation which concerns on this invention, it is thought that the homogeneous film excellent in antifouling property can be formed. The above mechanism is based on speculation, and its correctness does not affect the technical scope of the present invention.
  • the viscosity of the hydrolyzable group-containing silicone oligomer used as the component (A-1) can be controlled by those skilled in the art according to the molecular weight (weight-average molecular weight) and the composition of the oligomer.
  • the weight average molecular weight of the hydrolyzable group-containing silicone oligomer used as the component (A-1) is not particularly limited, but is preferably 5,000 or more and 20,000 or less, and is preferably 7,000 or more and 14,000 or less More preferable.
  • the value measured by the gel permeation chromatography which uses a polystyrene as a standard substance shall be employ
  • the measurement conditions are as follows; “Measurement condition” Column: TSKgel (registered trademark) SuperMultipore HZ-M (manufactured by Tosoh Corporation) Flow rate: 0.35 mL / min Column temperature: 40 ° C.
  • Eluent THF Sample: Measured by dissolving 0.1% by mass of oligomer relative to 100 g of THF.
  • composition of the hydrolyzable group-containing silicone oligomer used as the component (A-1) is preferably a partial hydrolysis condensate of the alkoxysilane compound represented by the above formula (1).
  • the preferred form of the alkoxysilane compound is as described above.
  • a synthetic product or a commercially available product can be used as long as it is a silicone oligomer having each of the above-mentioned properties.
  • a commercially available product for example, X-40-9250 (Shin-Etsu Chemical Co., Ltd., kinematic viscosity at 25 ° C. is 160 mm 2 s ⁇ 1 , and in the above formula (1), R 1 and R 2 are both methyl groups.
  • X-40-9250 Shin-Etsu Chemical Co., Ltd., kinematic viscosity at 25 ° C. is 160 mm 2 s ⁇ 1
  • R 1 and R 2 are both methyl groups.
  • a partial hydrolytic condensate obtained from a mixture of alkoxysilane compounds where x 1 or 2
  • X-40-9225 Shin-Etsu Chemical Co., Ltd., dynamic viscosity at 25 ° C.
  • partial hydrolysis condensate of the alkoxysilane compound R 1 is a methyl group or a phenyl group, R 2 is a methyl group), XR31-B2 33 (Momentive Performance Materials Japan LLC, Ltd., dynamic viscosity 220 mm 2 s -1 at 25 ° C., the above formula (1), R 1 is methyl group or phenyl group, R 2 is a methyl group
  • XR31-B2 33 Momentive Performance Materials Japan LLC, Ltd., dynamic viscosity 220 mm 2 s -1 at 25 ° C.
  • Component (A-2) contained in the mixture as component (A) is a hydrolyzable group-containing silicone oligomer having a viscosity at 25 ° C. in the range of 21 to 90 mm 2 s ⁇ 1 .
  • viscosity is dynamic viscosity (mm 2 s -1 ) at 25 ° C., which is measured by a viscosity measurement method according to JIS Z 8803: 2011.
  • the kinematic viscosity can be measured by a single cylindrical rotational viscometer (B-type viscometer).
  • the description concerning the "hydrolyzable group-containing silicone oligomer" is as described above.
  • Component (A-2) is presumed to be a main component in forming a cured film with the composition for film formation of the present invention, and a component contributing mainly to the formation of a homogeneous film. Therefore, according to the composition for film formation which concerns on this invention, it is thought that a homogeneous film can be formed.
  • Component (A-2) can also contribute to the stain resistance and weatherability of the film.
  • the hydrolyzable group-containing silicone oligomer having a kinematic viscosity of less than 21 mm 2 s -1 or more than 90 mm 2 s -1 is used, the compatibility with the component (A-1) becomes poor, and the film formability decreases. Also, the stain resistance and the weather resistance decrease.
  • the above mechanism is based on speculation, and its correctness does not affect the technical scope of the present invention.
  • the viscosity of the hydrolyzable group-containing silicone oligomer used as the component (A-2) can be controlled by those skilled in the art according to the molecular weight (weight-average molecular weight) and the composition of the oligomer.
  • the weight average molecular weight of the hydrolyzable group-containing silicone oligomer used as the component (A-2) is not particularly limited, but is preferably 1,000 or more and less than 5,000, preferably 1,500 or more and 2,500 or less. More preferable.
  • composition of the hydrolyzable group-containing silicone oligomer used as the component (A-2) is preferably a partial hydrolysis condensate of the alkoxysilane compound represented by the above formula (1).
  • the preferred form (structure) of the alkoxysilane compound is as described above.
  • component (A-2) synthetic or commercially available products can be used as long as they are silicone oligomers having the above-mentioned respective properties.
  • R 1 is Partial hydrolytic condensation product of an alkoxysilane compound in which a methyl group or a phenyl group
  • R 2 is a methyl group
  • X-40-9246 Shin-Etsu Chemical Co., Ltd., kinematic viscosity at 25 ° C.
  • partial hydrolysis condensate of R 1, alkoxysilane compounds R 2 are a methyl group
  • TSR165 produced by Momentive performance Materials Japan LLC, Ltd., dynamic viscosity 80 mm 2 s -1 at 25 ° C.
  • partial hydrolysis of the alkoxysilane compound R 1 is a methyl group or a phenyl group
  • R 2 is a methyl group (Condensates) etc. can be mentioned, These may be used independently and may use multiple types together.
  • the mass ratio of the component (A-1) / (A-2) is in the range of 1/26 to 1/36.
  • the composition for film formation Wettability to a substrate preferably, steel plate or coated steel plate
  • the mass ratio of (A-1) / (A-2) is more preferably in the range of 1/27 to 1/35, and 1/28 to 1/1.
  • the range of 30 is particularly preferable.
  • the content of the component (A) in the composition for film formation of the present invention is 1 mass of the component (C) described later It is in the range of 0.35 to 0.58 parts by mass with respect to parts.
  • the content of the component (A) exceeds 0.58 parts by mass, the film forming ability and the antifouling property to the substrate (preferably, a steel plate or a coated steel plate) at the time of forming the film forming composition as a film decreases. Also, the wettability and the weather resistance are lowered.
  • the content of the component (A) is less than 0.35 parts by mass, the film forming ability and the antifouling property of the film become insufficient.
  • the reason for this is considered to be that film defects occur due to too little or too much film-forming component. Therefore, by setting the content of the component (A) in the composition for forming a film of the present invention in the above range, the film forming ability is excellent, and the antifouling property, the wettability and the weatherability of the film are improved.
  • the content of the component (A) is more preferably 0.38 to 0.50 parts by mass with respect to 1 part by mass of the component (C) to more easily obtain such effects.
  • the range of 40 to 0.48 parts by mass is particularly preferred.
  • Component (B) contained in the composition for film formation of the present invention is an organoaluminum compound.
  • the organoaluminum compound as the component (B) is known as a condensation reaction catalyst, and the hydrolyzable group (preferably, Si-OR 2 ) contained in the component (A) is used as a moisture in the air Or the like to cause a condensation reaction.
  • the film forming composition according to the present invention has an excellent film forming ability.
  • the composition for film formation which concerns on this invention can form a film with a favorable weather resistance by using not a metal compound other than but an organoaluminum compound as a condensation reaction catalyst.
  • the reason is that by using the organoaluminum compound, the condensation reaction of hydrolyzable groups contained in the component (A) can be advanced at an appropriate rate, and a uniform film can be formed. Conceivable.
  • organoaluminum compound as the component (B) known substances used as a condensation reaction catalyst can be used.
  • organic aluminum compound examples include aluminum salt compounds such as aluminum octylate, aluminum triacetate and aluminum tristearate, aluminum alkoxide compounds such as aluminum trimethoxide, aluminum triethoxide, aluminum triaryl oxide, and aluminum triphenoxide, Aluminum methoxybis (ethylacetoacetate), aluminum methoxybis (acetylacetonate), aluminum ethoxybis (ethylacetoacetate), aluminum ethoxybis (acetylacetonate), aluminum isopropoxybis (ethylacetoacetate), aluminum isopropoxybis (Methyl acetoacetate), aluminum isopropoxy bis (t-butyl ace Acetate), aluminum butoxy bis (ethyl acetoacetate), aluminum dimethoxy (ethyl aceto acetate), aluminum dimethoxy (acetyl acetonate), aluminum diethoxy (ethyl aceto acetate), aluminum diethoxy (acetyl acetonate), aluminum diis
  • condensation reaction of the hydrolyzable group contained in the component (A) can be advanced at an appropriate speed, a uniform film can be formed, and the component (A) can be improved from the viewpoint of improving the weather resistance and the like.
  • B) preferably contains an aluminum alkoxide compound.
  • a well-known commercial item can be used as an organoaluminum compound as a component (B),
  • DX-9740 A mixture of an aluminum alkoxide compound
  • CAT-AC A mixture of an aluminum alkoxide compound
  • W aluminum chelate A
  • W aluminum chelate D
  • ALCH aluminum diisopropoxy (ethylacetoacetate)
  • ALCH-TR aluminum tris (ethylacetoacetate)
  • the content of the component (B) in the present invention (the total amount of two or more organic aluminum compounds, if used) is 0.05 to 0.15 mass per 1 mass part of the component (C) described later
  • the scope of the department When the content of the component (B) exceeds 0.15 parts by mass, the reactivity of the entire resin becomes too high, and the film forming ability at the time of forming the film forming composition into a film decreases, as a result, Also, the weather resistance and the color fastness can not be made appropriate.
  • the content of the component (B) is less than 0.05 parts by mass, the reactivity is insufficient, so that the curability at the time of film formation is reduced, and it can not be used for an appropriate usable time .
  • the content of the component (B) in the composition for forming a film of the present invention in the above range, the film forming ability and the drying property (curability) become good, and the weather resistance and the color fastness Improve.
  • the content of the component (B) is more preferably in the range of 0.06 to 0.14 parts by mass with respect to 1 part by mass of the component (C) to more easily obtain such effects. It is particularly preferable to set the range from .08 to 0.12 parts by mass.
  • the component (C) contained in the film-forming composition of the present invention is a hydrocarbon-based organic solvent having a boiling point in the range of 100 to 165 ° C.
  • the hydrocarbon-based organic solvent as the component (C) is a component necessary for uniformly dissolving and diluting the component (A) and the component (B) to form a thin film.
  • the boiling point of the component (C) exceeds 165 ° C., not only the film forming ability and the drying property (curing property) are lowered, but also the wettability can not be made appropriate.
  • the boiling point of the component (C) is less than 100 ° C., the film forming ability is reduced.
  • the boiling point of the component (C) in the composition for forming a film of the present invention in the above range, the film forming ability and the drying property (curing property) become good, and the wettability is improved.
  • the reason for this is that the boiling point is in the above-mentioned temperature range, so that the volatility of the film-forming composition becomes appropriate when forming a film, and the components (A) and (B) are not required mutually It is considered that this is because the action can be suppressed. Therefore, according to the film forming composition of the present invention, a dense film can be formed.
  • the boiling point of the component (C) is more preferably in the range of 110 to 155 ° C., and particularly preferably in the range of 120 to 150 ° C.
  • the hydrocarbon-based organic solvent contained in the film-forming composition of the present invention contains a solvent (hydrocarbon solvent) substantially consisting of only a hydrocarbon compound.
  • the hydrocarbon solvent may be either an aliphatic hydrocarbon solvent or an aromatic hydrocarbon solvent.
  • the aliphatic hydrocarbon solvent may have any of linear structure, branched structure and cyclic structure, and the aliphatic hydrocarbon solvent may have unsaturated bond.
  • Particularly preferred components (C) in the present invention are saturated aliphatic hydrocarbon solvents.
  • the component (C) includes other solvents having a boiling point in the above temperature range, for example, a hydrocarbon solvent having one or more of halogen and various organic functional groups, as long as the function of the present invention is not impaired. It may be When component (C) contains such hydrocarbon solvents, the content is preferably less than 25%, more preferably less than 15%, and less than 10% based on the total amount of component (C). Is particularly preferred, and substantially 0% is most preferred. That is, it is preferable that the component (C) substantially consists of only a hydrocarbon solvent. Furthermore, it is more preferable that the component (C) consists essentially of a saturated aliphatic hydrocarbon solvent.
  • the boiling point may not be single temperature by the reason of containing 2 or more types of solvents as a component (C).
  • a solvent having a distillation start temperature (initial boiling point) and a distillation end temperature (dry point) in the above ranges is considered to correspond to the component (C) in the present invention.
  • the hydrocarbon solvent as the component (C) is not particularly limited as long as it has a boiling point in the above range. Specifically, n-octane (boiling point 126 ° C.), 2-methyl octane (also called isononane, boiling point 143 ° C.), 3-methyl octane (boiling point 144 ° C.), 4-methyl octane (boiling point 142 ° C.) Ethyl heptane (boiling point 141 ° C), 2,3-dimethylheptane (boiling point 140 ° C), 1,3,5-trimethylcyclohexane (boiling point 140 ° C), 1,2,4-trimethylcyclohexane (boiling point 145 ° C), cyclooctane (Boiling point 149 ° C), 1,1,3,5-tetramethylcyclohexane (boiling point 129 °
  • Component (C) preferably contains at least one selected from the group consisting of 2-methyl octane, 3-methyl octane, 4-methyl octane, 4-ethyl heptane, and 2,3-dimethyl heptane.
  • additives can be added as long as the properties of the composition are not impaired.
  • additives include, for example, reactive or non-reactive silicone oils, alkoxysilane compounds, adhesion promoters such as silane coupling agents, anti-aging agents, anti-rust agents, coloring agents, surfactants, rheology control Agents, ultraviolet light absorbers, infrared light absorbers, fluorescent agents, abrasives, perfumes, fillers and the like, and components can be selected according to the purpose.
  • composition for film formation which concerns on this invention can be manufactured by mixing each said component by a predetermined
  • the composition for forming a film includes mixing (A-1) and (A-2) with respect to 1 part by mass of the (C). In total, 0.35 to 0.58 parts by mass, 0.05 to 0. Comprising 5 parts by weight, the production method of the coating composition is provided.
  • the order of addition of each of the above components, the method of addition, and the like are not particularly limited. Also, the mixing method and mixing time are not particularly limited, and methods known to those skilled in the art can be used. In addition, the description in the section of the above-mentioned [composition for film formation] is used for explanation concerning the desirable composition ratio (mass ratio) of each component in the above-mentioned manufacturing method, the kind of compound, structure, etc.
  • composition for film formation of the present invention can be applied to substrates of various metals, glasses, ceramics, resins and the like.
  • application to coated steel plates, coated steel plates, and glass surfaces is preferable, and in particular to painted steel plates used in exteriors of automobiles (also referred to as automobile exterior steel plates in this specification).
  • Use is preferred.
  • the preferable form of this invention is a form by which the said composition for film formation is used in order to form a film in the surface of a steel plate or a coated steel plate.
  • a further preferable mode is a mode in which the steel plate or the coated steel plate is a car body of an automobile.
  • the film formation method by the composition for film formation is provided.
  • the composition for forming a film is coated on the surface of a steel plate or a coated steel plate (preferably a car body of an automobile), and the component (C) is volatilized under normal temperature or heating environment After that, it is possible to further dry or wipe after further water wiping. That is, after volatilization of the component (C), only dry wiping may be performed, or water wiping may be performed before dry wiping.
  • “normal temperature” refers to a temperature in a room temperature environment in which the temperature is not adjusted by air conditioning or the like, and means about 15 to 25 ° C.
  • the term "heating environment” refers to an environment heated by air conditioning, a heater (heat ray irradiation means) or the like, a constant temperature environment (for example, standing in a constant temperature chamber) set to a high temperature. Refers to an environment above room temperature, above ° C.
  • a method may be adopted in which the composition for forming a film is applied to the surface of a steel plate or a coated steel plate, and after the water is wiped, it is wiped dry (that is, the construction method of the latter) After applying the composition for film formation to the surface of a steel plate or a coated steel plate, a method of performing only dry wiping (namely, the former application method) may be adopted.
  • a cured film having good properties can be obtained by any of the above methods.
  • the composition for film formation and the film formation method according to the present invention are characterized in that the workability at the time of application is excellent.
  • the application means (coating method of the composition for film formation) at the time of film formation of the said film formation method is not specifically limited, For example, hand-painting using the fiber which impregnated the said composition, brushing, Any appropriate application means such as machine coating using an automatic machine can be used.
  • the following method is suitably used. That is, according to a preferred embodiment of the film forming method of the present invention, the film forming composition according to the present invention is impregnated with an appropriate amount of fibers such as dried sponge and waste and is impregnated with the film forming composition by hand.
  • the method involves thinly spreading the surface of a steel plate or a coated steel plate (base material) and volatilizing volatile components by forced drying using natural drying or a dryer or the like.
  • the component (A) which is a reaction component contained in the composition for film formation contacts the moisture in air, and a hydrolysis reaction advances with the effect
  • crosslinking and curing are performed on a steel plate or a coated steel plate (base material) to form a resin-like cured product.
  • the cured product can be spread by drying with a dry cloth or the like to form a uniform cured coating layer.
  • the conventionally known film forming method requires a post-process such as a process of performing surface treatment with a treatment liquid for wiping separately and then performing dry wiping with a dry cloth at the time of construction.
  • a post-process such as a process of performing surface treatment with a treatment liquid for wiping separately and then performing dry wiping with a dry cloth at the time of construction.
  • these subsequent steps may be carried out, but according to the film forming method of the present invention, it is possible to immediately make homogeneity by carrying out only the dry wiping treatment with a dry cloth after solvent evaporation. A cured film can be obtained. That is, the film forming method according to the present invention is extremely excellent in workability.
  • a cured film obtained by curing the film forming composition.
  • the cured film formed using the film-forming composition is excellent in antifouling property and is a uniform (uniform) film.
  • the said cured film is excellent in a weather resistance, and can have favorable water repellency.
  • the cured film according to the present invention is preferably in the form of a thin film, and the film thickness thereof is preferably approximately 0.001 to 100 ⁇ m, more preferably 0.002 to 75 ⁇ m, and more preferably 0.01 to 50 ⁇ m. It is even more preferable if it is present, and particularly preferably 0.05 to 10 ⁇ m.
  • the film thickness of a cured film being in the said range, favorable antifouling property and weather resistance can be exhibited, and it is excellent also in the workability at the time of construction. Further, by setting the film thickness in the above range, the water repellency, the water sliding property and the abrasion resistance can be improved.
  • each film formation composition (Hereinafter, it is also only called a "composition") respectively prepared by the Example and the comparative example using the following method.
  • the uncured liquid composition on the application surface is homogeneously present on the test piece, and the location where the composition is not present (in a so-called repelling state) is less than 10% of the entire application surface.
  • a certain item was accepted (in the table, it was written as "o”).
  • the other state was made into rejection (it described with "x" in the table
  • the cured film on the surface to be coated is a uniform cured film without unevenness, and the portion where the cured product is in the state of so-called repellence, dents or spots is less than 10% of the surface to be coated. It passed (it was written as " ⁇ " in the table). Moreover, the other state was made into rejection (it described with "x" in the table
  • the uniform coating film was not formed in the coating-film surface, what measured the wettability evaluation as rejection (x) touched the location where wetting exists, and measured.
  • A is highly dry but has a short pot life at the time of construction, which is not preferable from the viewpoint of workability.
  • C is not preferable because the drying time is long. Therefore, in the present invention, the evaluation of B is particularly preferable in view of the balance between the pot life at the time of construction and the drying property.
  • composition [Preparation of composition] The following were used as the raw material contained in each composition of an Example and a comparative example. Each component was weighed so as to obtain the mass described in the following table, and mixed by a three-one motor of Shinto Kagaku Co., Ltd. for 15 minutes at 25 ° C. to obtain a composition. In addition, the unit of each component in the following table
  • surfaces is a "mass part.”
  • (A-2) Hydrolyzable group-containing silicone oligomer having a kinematic viscosity at 25 ° C. in the range of 21 to 90 mm 2 s -1 and its comparative component KR-500: in), neither R 1, R 2 is a methyl group, partially hydrolyzed condensate of the alkoxysilane compound is x 1 or 2, the weight-average molecular weight of about 1,50 ⁇ 2,500,25 is 25 mm 2 s -1 Etsu Chemical Co., Ltd. Comparative kinematic viscosity at ° C.
  • KR-400 In the formula (1), both R 1, R 2 is a methyl group Partial hydrolysis condensate of alkoxysilane compound (Curing catalyst is included in the product), Dynamic viscosity at 25 ° C is 1.2 mm 2 s -1 Shin-Etsu Chemical Co., Ltd. (In addition, the composition containing the raw material B) not added) ⁇ Comparison (2) KC-89S: Partial hydrolysis condensate of an alkoxysilane compound in which R 1 and R 2 in the above formula (1) are both methyl groups, and the kinematic viscosity at 25 ° C. is 5 mm 2 s -1 Shin-Etsu Chemical Industry Co., Ltd.
  • Comparison (3) X-40-9225 Partial hydrolysis condensate of alkoxysilane compound in which R 1 and R 2 are both methyl groups in the above formula (1), dynamic viscosity at 25 ° C. 100 mm 2 s -1 manufactured by Shin-Etsu Chemical Co., Ltd.
  • compositions containing the respective components (A) to (C) in the predetermined composition ratio according to the present invention in Examples 1 to 8 in Table 1 have good film forming ability and antifouling properties. Also, it was confirmed that the drying property of the range suitable for construction was also held. Furthermore, the composition according to the present invention was good in wettability, weather resistance and color fastness.
  • Comparative Examples 1 to 5 in Table 2 In the composition using a hydrocarbon-based organic solvent having a boiling point outside the specific range of the present invention instead of (C) of the present invention, all have film forming ability It was inadequate. In particular, in Comparative Examples 4 and 5 in which the boiling range exceeds the upper limit of the range of the present invention, the wettability is also poor, and the drying property is not suitable for construction. Moreover, in Comparative Examples 1 and 2 in which the boiling range is less than the lower limit of the range of the present invention, the drying property is not suitable for construction.
  • Comparative Examples 6 to 10 A composition using a hydrolyzable group-containing silicone oligomer having a viscosity outside the specific range of the present invention in place of (A-2) of the present invention is other than drying property and color resistance. In all the characteristics of the above, the result was inferior, and it was not for practical use. Comparative Examples 11 to 13: Any composition using a condensation reaction catalyst other than organic aluminum instead of the present invention (B) is poor in film forming ability and weatherability, and has problems in color fastness. There were many things.
  • Comparative Examples 14 to 17 The content of (A) (content to 1 mass of the component (C)) is included in the specific range of the present invention, but the composition ratio of (A-1) to (A-2) is In the composition containing the mixture out of the specific range of the present invention, the film forming ability and / or the antifouling property was poor, and the wettability was also poor. Comparative Examples 18 and 19: In a composition whose content of (B) (content to 1 mass of the component (C)) is outside the specific range of the present invention, the content is sufficiently sufficient in Comparative Example 18 where the content is less than the lower limit. Cure speed was not obtained. Therefore, the drying property was in a range not suitable for construction.
  • Comparative Example 19 in which the content exceeds the upper limit, the film forming ability is poor, and the weather resistance and the color fastness are also poor.
  • Comparative Examples 20 and 21 The composition having the content of (A) (content with respect to 1 mass of the component (C)) outside the specific range of the present invention is poor in film forming ability and antifouling property, and further, Some were poor in wettability and weatherability.
  • composition for film formation of the present invention has excellent characteristics of the film after curing. And, the composition for film formation of the present invention can be suitably used particularly for forming a thin film coating for giving protection performance to a metal surface, a painted surface or a resin surface of a car body of a car or a train car. It is useful.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

L'invention concerne une composition pour formation de film de revêtement qui contient les composants (A) à (C) suivants, la teneur en composant (A) étant comprise entre 0,35 et 0,58 partie en masse, et la teneur en composant (B) étant comprise entre 0,05 et 0,15 partie en masse : (A) mélange de composants de formation de film de revêtement comprenant (A-1) et (A-2) tels que ci-dessous, selon un rapport en masse tel que （Ａ－１）／（Ａ－２）＝１／２６～１／３６, （Ａ－１) étant un oligomère de silicone comprenant un groupe hydrolysable de viscosité cinématique à 25°C se trouvant dans une plage de １００ à ２５０ｍｍ２ｓ－１, et (A-2) étant un oligomère de silicone comprenant de viscosité cinématique à 25°C se trouvant dans une plage de ２１ à ９０ｍｍ２ｓ－１ ; (B) composé aluminium organique ; et (C) solvant organique à base d'hydrocarbure de point d'ébulition compris entre 100 et 165°C. L'invention fournit une composition pour formation de film de revêtement qui permet de former un film de revêtement uniforme ayant des propriétés de séchage adéquate, et se révélant excellent en termes de propriétés antisalissure.
PCT/JP2018/027752 2017-07-25 2018-07-24 Composition pour formation de film de revêtement WO2019022087A1 (fr)

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Cited By (1)

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WO2020188918A1 (fr) * 2019-03-18 2020-09-24 株式会社スリーボンド Composition d'agent de revêtement durcissable et film de revêtement durci

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JP6528930B2 (ja) * 2014-12-22 2019-06-12 株式会社スリーボンド コーティング剤組成物
KR102395402B1 (ko) * 2016-04-26 2022-05-09 가부시끼가이샤 쓰리본드 경화성 조성물
WO2020188918A1 (fr) * 2019-03-18 2020-09-24 株式会社スリーボンド Composition d'agent de revêtement durcissable et film de revêtement durci

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JP2008094971A (ja) * 2006-10-12 2008-04-24 Soft99 Corporation 自動車ガラス用撥水性コーティング剤
JP2011246664A (ja) * 2010-05-31 2011-12-08 Kobe Gosei Kk 外装面用の表面撥水保護剤
JP2016141748A (ja) * 2015-02-03 2016-08-08 株式会社ソフト９９コーポレーション 塗装面用表面保護剤
JP2017082207A (ja) * 2015-10-30 2017-05-18 大阪ガスケミカル株式会社 塗料組成物および塗膜
JP2017115087A (ja) * 2015-12-25 2017-06-29 ライオン株式会社 繊維用撥水剤

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Publication number Priority date Publication date Assignee Title
WO2020188918A1 (fr) * 2019-03-18 2020-09-24 株式会社スリーボンド Composition d'agent de revêtement durcissable et film de revêtement durci
JPWO2020188918A1 (fr) * 2019-03-18 2020-09-24
CN113453886A (zh) * 2019-03-18 2021-09-28 三键有限公司 固化性涂敷剂组合物以及固化被膜
CN113453886B (zh) * 2019-03-18 2023-04-18 三键有限公司 固化性涂敷剂组合物以及固化被膜

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