WO2018151271A1 - Composition de revêtement, et procédé de formation de film protecteur de surface - Google Patents

Composition de revêtement, et procédé de formation de film protecteur de surface Download PDF

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Publication number
WO2018151271A1
WO2018151271A1 PCT/JP2018/005565 JP2018005565W WO2018151271A1 WO 2018151271 A1 WO2018151271 A1 WO 2018151271A1 JP 2018005565 W JP2018005565 W JP 2018005565W WO 2018151271 A1 WO2018151271 A1 WO 2018151271A1
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Prior art keywords
coating composition
formula
epoxy group
silane
epoxy
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PCT/JP2018/005565
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English (en)
Japanese (ja)
Inventor
井上　剛
亮史 樋口
貴司 岩井
亮 高野
山下　文男
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関西ペイント株式会社
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Priority to JP2018526955A priority Critical patent/JP6393016B1/ja
Publication of WO2018151271A1 publication Critical patent/WO2018151271A1/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
    • 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
    • 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
    • B05D7/24—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 for applying particular liquids or other fluent materials
    • 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
    • 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
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F15/00—Flooring
    • E04F15/12—Flooring or floor layers made of masses in situ, e.g. seamless magnesite floors, terrazzo gypsum floors

Definitions

  • the present invention can be easily applied to floor surfaces of various materials such as synthetic resin flooring such as office buildings, commercial facilities and convenience stores, wood flooring, ceramic flooring, metal flooring,
  • the present invention relates to a coating composition and a method for forming a surface protective film, which are capable of protecting the floor surface over a long period of time, and the drying property and the resulting coating film are excellent in scratch resistance and crack resistance.
  • the floor surface of a building has been coated with a resin wax mainly composed of an aqueous emulsion resin for the purpose of improving scratch resistance and gloss.
  • the resin wax is likely to have many scratches and stains on the surface of the coating film due to walking, transportation of materials on a carriage, etc., and the gloss is also reduced in a relatively short period of time, so it is repainted several times a year Work was required and there were problems with maintenance costs and durability. For this reason, a coating agent having high durability against scratches and gloss has been desired.
  • Patent Document 1 discloses a floor coating agent composition mainly composed of a polyorganosiloxane resin having a specific amount of silanol groups. According to such a floor coating composition, it is possible to form a coating film that can exhibit good drying and curing properties at room temperature, but a large amount of organic solvent is used and there is a lot of odor, and it is used in an indoor environment. hard.
  • Patent Document 2 discloses a floor coating agent composition containing an alkoxysilane oligomer, a plasticizer, and a curing catalyst. According to such a floor coating composition, it has a high gloss, excellent scratch resistance, can protect the floor surface over a long period of time, and can easily peel and repaint the coating film as necessary. However, since the drying property is inferior, there is a problem in the paint workability because it is easily scratched immediately after the construction.
  • Patent Document 3 discloses a solvent-free or low-solvent active energy ray-curable composition for floor covering, which has little odor and does not require a drying process after coating or can be completed in a short time.
  • an active energy ray-curable composition a cured coating film excellent in scratch resistance can be formed, but the irradiation apparatus is large and requires capital investment, and preparation before painting may be complicated. There were many problems that could not be done easily.
  • the present invention has been made in view of the above circumstances, and the object of the present invention is that the odor is low, the construction is simple, and the drying property and curability are excellent at room temperature. It is to provide a coating composition having excellent crack resistance.
  • the present invention includes the following aspects.
  • Item 1 (A) an epoxy silane oligomer having an epoxy group and a siloxane bond and having a weight average molecular weight of 500 to 20,000, (B) A colloidal silica having an average primary particle size in the range of 1 to 100 nm, and (C) a coating composition containing a curing catalyst.
  • the epoxy silane oligomer (A) is a hydrolysis condensate (a1) of an epoxy group-containing hydrolyzable silane represented by the following general formula (I) and / or the epoxy group-containing hydrolyzable silane and the following general formula: Item 2.
  • R 1 represents an organic group containing an epoxy group
  • X represents a hydrolyzable group which may be the same or different
  • a represents an integer of 1 to 3.
  • R 2 represents an organic group having no epoxy group
  • X represents a hydrolyzable group which may be the same or different
  • a represents an integer of 0 to 3.
  • Item 1 or Item 2 further comprises 1 to 100 parts by mass of the silane coupling agent (D) having a reactive group based on 100 parts by mass of the total mass of the active ingredients of the component (A) and the component (B).
  • Item 4. The coating composition according to any one of Items 1 to 3, wherein the colloidal silica (B) is acidic colloidal silica.
  • the organic solvent (E) having a solubility in 100 g of water of 5 g or more at 20 ° C. is 5 to 200 parts by mass with respect to 100 parts by mass of the total mass of the active ingredients of the component (A) and the component (B).
  • Item 5 The coating composition according to any one of Items 1 to 4, which contains part by mass.
  • hydrolyzable silane selected from hydrolyzable silanes having no 1-4 functional epoxy groups represented by the general formula (II) and / or hydrolysis of the hydrolyzable silanes Item 6.
  • Item 7 Among the components (F), at least a part of the component includes a tetrafunctional hydrolyzable silane represented by the following general formula (III) and / or a hydrolyzed condensate (G) of the hydrolyzable silane.
  • Item 7. A coating composition according to Item 6.
  • the epoxy silane oligomer (A) is a mixture of an epoxy group-containing hydrolyzable silane represented by the formula (I) and a hydrolyzable silane having no epoxy group represented by the formula (II).
  • Item 8. The coating composition according to any one of Items 1 to 7, which is a decomposition condensate (a2).
  • the epoxy silane oligomer (A) is a mixture of an epoxy group-containing hydrolyzable silane represented by the formula (I) and a hydrolyzable silane having no epoxy group represented by the formula (II).
  • the coating composition according to any one of Items 1 to 8, wherein the former / the latter (molar ratio) is in the range of 99/1 to 55/45.
  • Item 10 The coating composition according to any one of Items 1 to 9, further comprising water (H).
  • Item 11 A method for forming a surface protective film, comprising a step of applying the coating composition according to any one of Items 1 to 10 as a top coat on a surface of a substrate and drying it.
  • Item 12 A method for forming a surface protective film on a floor surface, comprising a step of applying the coating composition according to any one of Items 1 to 10 as a top coat on a floor surface and drying it.
  • the coating composition of the present invention has little odor, is easy to construct, has excellent drying and curing properties at room temperature, and the resulting coating film has excellent scratch resistance and crack resistance.
  • the composition of the present invention has good water dilution stability and can be cured without requiring a special device in the curing process, so that the construction is simple and the coating workability is excellent.
  • the coating composition of the present invention when applied to a substrate surface, for example, a floor surface, the floor surface can be protected over a long period of time.
  • the coating composition of the present invention comprises (A) an epoxy silane oligomer having a weight average molecular weight in the range of 500 to 20,000, (B) colloidal silica having an average primary particle diameter in the range of 1 to 100 nm, and (C ) It contains a curing catalyst.
  • Epoxysilane oligomer (A) contained in the coating composition of the present invention is a compound having an epoxy group and a siloxane bond in the molecule and having a weight average molecular weight in the range of 500 to 20,000. is there.
  • the epoxy silane oligomer (A) is, for example, a hydrolysis condensate (a1) of an epoxy group-containing hydrolyzable silane represented by the following general formula (I) and / or the epoxy group-containing hydrolyzable silane: It may be a hydrolysis condensate (a2) of a mixture with a hydrolyzable silane represented by the following general formula (II) having no epoxy group.
  • R 1 represents an organic group containing an epoxy group
  • X represents a hydrolyzable group which may be the same or different
  • a represents an integer of 1 to 3.
  • R 2 represents an organic group having no epoxy group
  • X represents a hydrolyzable group which may be the same or different
  • a represents an integer of 0 to 3.
  • organic group containing an epoxy group represented by R 1 examples include a glycidoxy group such as a glycidoxypropyl group, a (3,4-epoxycyclohexyl) methyl group, and a (3,4-epoxycyclohexyl) ethyl group. 3,4-epoxycyclohexyl group and the like.
  • X is a hydrolyzable group, and examples thereof include an alkoxy group, an acetoxy group, an oxime group, an aminoxy group, a halogen atom, etc., and an easily available alkoxy group having 1 to 6 carbon atoms is preferable. From the viewpoint of reaction rate, a methoxy group is preferred.
  • Examples of the epoxy group-containing hydrolyzable silane represented by the general formula (I) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyldimethoxy.
  • the epoxy silane oligomer (A) may be a hydrolysis condensate (a2) of a mixture of the hydrolyzable silane represented by the formula (I) and the hydrolyzable silane represented by the following formula (II). Good.
  • R 2 represents an organic group having no epoxy group
  • X represents a hydrolyzable group which may be the same or different
  • a represents an integer of 0 to 3.
  • the organic group having no epoxy group is preferably a monovalent organic group having 1 to 18 carbon atoms from the viewpoint of scratch resistance, which may be linear or branched, and is a urethane bond, ester bond or ether bond. Or may be substituted with halogen such as fluorine.
  • the hydrolyzable silane having no epoxy group represented by the general formula (II) for example, the a is an integer of 0 to 3, monofunctional, difunctional, trifunctional Or a tetrafunctional hydrolyzable silane.
  • Monofunctional, difunctional, trifunctional or tetrafunctional hydrolyzable silanes may be used in combination of two or more as required.
  • the weight average molecular weight of the epoxysilane oligomer (A) is 500 to 20,000, preferably 600 to 10,000, and more preferably 600 to 4000 from the viewpoints of drying property and crack resistance.
  • the epoxy equivalent of the epoxysilane oligomer (A) is usually 130 (g / eq) or more, preferably 150 (g / eq) or more, and 180 (g / eq) from the viewpoint of water dilution stability and curability.
  • the above is more preferable, 1,000 (g / eq) or less is preferable, and 800 (g / eq) or less is more preferable.
  • the weight average molecular weight is determined based on the retention time (retention capacity) measured using a gel permeation chromatograph (GPC) by the retention time (retention capacity) of a standard polystyrene having a known molecular weight measured under the same conditions. It is the value calculated
  • HEC-8120GPC (trade name, manufactured by Tosoh Corporation) is used as a gel permeation chromatograph
  • TSKgel G4000HXL”, “TSKgel G3000HXL”, “TSKgel G2500HXL” and “TSKgel” are used as columns.
  • G2000HXL (trade name, all manufactured by Tosoh Corporation), using a differential refractometer as the detector, mobile phase: tetrahydrofuran, measurement temperature: 40 ° C, flow rate: 1 mL / min Can be measured below.
  • the component (A) epoxysilane oligomer can be obtained by combining a production method used for producing a general organosilane oligomer with a conventionally known chemical reaction. .
  • a production method used for producing a general organosilane oligomer with a conventionally known chemical reaction.
  • it can be manufactured using the following manufacturing method.
  • a method of producing an epoxysilane oligomer as component (A) by performing a hydrolysis-condensation reaction in the presence of water and a catalyst is a method of producing an epoxysilane oligomer as component (A) by performing a hydrolysis-condensation reaction in the presence of water and a catalyst.
  • the epoxy silane oligomer (A) is a hydrolysis condensate (a1) of an epoxy group-containing hydrolyzable silane represented by the general formula (I), particularly from the viewpoint of scratch resistance. And / or the hydrolysis condensate (a2) of a mixture of the epoxy group-containing hydrolyzable silane and the hydrolyzable silane having no epoxy group represented by the general formula (II) is preferable.
  • the hydrolysis condensate (a2) of a mixture of the epoxy group-containing hydrolyzable silane represented by the formula (I) and the hydrolyzable silane having no epoxy group represented by the general formula (II) is preferable.
  • the epoxysilane oligomer (A) is the hydrolyzed compound (a2), it is represented by the epoxy group-containing hydrolyzable silane represented by the formula (I) and the formula (II).
  • the ratio of the hydrolyzable silane having no epoxy group is preferably in the range of 99/1 to 55/45 as the former / the latter (molar ratio), and in the range of 85/15 to 60/40. More preferably, the adjustment is performed by
  • the hydrolysis condensate (a1) and the hydrolysis condensate (a2) may be used in combination.
  • the hydrolysis condensation reaction in the production method of the epoxysilane oligomer (A) used in the present invention employs, for example, conditions in the range of pH 1 to 7.5, preferably pH 2 to 7, in the presence of the catalyst. Good. By making it react in the said pH area
  • the catalyst is not particularly limited as long as it can be adjusted to the pH range, and for example, formic acid, acetic acid, propionic acid, oxalic acid, citric acid, maleic acid, benzoic acid, malonic acid, glutaric acid,
  • examples include organic acids such as toluenesulfonic acid or inorganic acids such as hydrogen fluoride, hydrochloric acid, nitric acid, phosphoric acid and sulfuric acid, or solid acid catalysts such as cation exchange resins having a carboxylic acid group or a sulfonic acid group on the surface. .
  • the amount of the catalyst used is not particularly limited, but if it is too much, there are problems such as high cost and gelation during synthesis and storage, and if it is too little, the reaction may be slow.
  • the amount of the catalyst used is suitably in the range of 0.1 to 20 parts by mass, preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the hydrolyzable silane compounded as a starting material.
  • an organic solvent may be used. It is preferable to use an organic solvent from the viewpoint of preventing gelation and adjusting the viscosity during production.
  • organic solvent examples include alcohols such as methanol, ethanol and isopropanol, aromatic compounds such as toluene and xylene, ketones such as acetone, and esters such as ethyl acetate can be used.
  • the reaction temperature during the hydrolysis condensation is usually 0 to 200 ° C., preferably 10 to 190 ° C., more preferably 10 to 120 ° C. Although this reaction can be carried out regardless of pressure, a pressure range of 0.02 to 0.2 MPa is preferable, and a pressure range of 0.08 to 0.15 MPa is particularly preferable. The reaction is usually completed in about 1 to 15 hours.
  • the alcohol, solvent, and catalyst generated by the reaction may be removed from the mixed solution after hydrolysis condensation by a known method.
  • the obtained product may be further purified by removing the catalyst by various purification methods such as washing, column separation, and adsorption by a solid adsorbent according to the purpose. From the viewpoint of efficiency, it is preferable to remove the alcohol and catalyst generated by the reaction by washing with water.
  • the structure of the epoxy silane oligomer changes depending on the condensation ratio of the hydrolyzable group of the hydrolyzable silane, but the product obtained by this production method contains Si—OH groups of 100 % -Condensed complete cage structure, linear, branched, ladder structure, incomplete cage structure and / or random condensate epoxy silane oligomer with remaining Si—OH groups may be included.
  • the epoxy silane oligomer which is the component (A) obtained by this production method may be any of the complete cage structure, linear chain, branched chain, ladder structure, incomplete cage structure and / or random condensate. Good.
  • the content of the epoxy silane oligomer (A) is, for example, 20 to 80 mass from the viewpoint of crack resistance and scratch resistance with respect to 100 mass parts of the active ingredient of the epoxy silane oligomer (A) and colloidal silica (B). Parts, preferably 25 to 60 parts by mass, more preferably 30 to 60 parts by mass.
  • colloidal silica (B) contained in the coating composition of the present invention is characterized in that the average primary particle diameter is in the range of 1 to 100 nm from the viewpoint of improving scratch resistance.
  • the average primary particle diameter is a median diameter (d50) of a volume-based particle size distribution measured by a dynamic light scattering method, and is measured using, for example, a nanotrack particle size distribution measuring apparatus manufactured by Nikkiso Co., Ltd. Can do.
  • Colloidal silica is obtained by dispersing silica fine particles in a dispersion medium.
  • a dispersion medium water; alcohol solvents such as methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol; polyhydric alcohol solvents such as ethylene glycol; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, etc. Polyhydric alcohol derivatives; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol; monomers such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and tetrahydrofurfuryl acrylate.
  • a water-soluble solvent such as water, methanol, ethanol, etc., especially water as a dispersion medium is preferable from the viewpoint of stability when applied to the coating composition.
  • colloidal silica using water as a dispersion medium examples include acidic colloidal silica and basic colloidal silica.
  • the acidic colloidal silica is not particularly limited.
  • commercially available products such as Snowtex AK, Snowtex O, Snowtex O-40, Snowtex OL, Snowtex OUP, Snowtex OXS, Snowtex OYL (above, trade names) Manufactured by Nissan Chemical Industries, Snowtex is a registered trademark), Adelite AT-20Q (trade name, manufactured by ADEKA, Adelite is a registered trademark), and the like.
  • the basic colloidal silica is not particularly limited.
  • commercially available products such as Snowtex C, Snowtex N, Snowtex NXS (trade name, manufactured by Nissan Chemical Industries, Snowtex is a registered trademark), Adelite AT- 20, Adelite AT-20N (above, trade name, manufactured by ADEKA, Adelite is a registered trademark), and the like.
  • the colloidal silica using a water-soluble solvent as a dispersion medium is not particularly limited.
  • commercially available products include MA-ST-M, IPA-ST, EG-ST, PGM-ST (trade names, Nissan Chemical Industries, Ltd.). Manufactured) and the like.
  • colloidal silicas may be used alone or in combination of two or more.
  • a method of using two or more kinds of colloidal silica in combination specifically, for example, an acidic colloidal silica having an average primary particle diameter of 10 to 15 nm and an acidic colloidal silica having an average primary particle diameter of 20 to 25 nm are mixed in a mass ratio ( The former / the latter) are preferably used in combination within the range of 10/90 to 70/30, acidic colloidal silica having an average primary particle diameter of 20 to 25 nm and acidic colloidal having an average primary particle diameter of 50 to 80 nm.
  • silica is used in combination so that the mass ratio (the former / the latter) is preferably 10/90 to 60/40.
  • the colloidal silica can contain inorganic fine particles other than silica fine particles such as alumina sol, titania sol, and ceria sol.
  • the average primary particle diameter of the colloidal silica (B) is preferably 1 to 100 nm, more preferably 8 to 50 nm, and particularly preferably 10 to 50 nm from the viewpoints of transparency and hardness of the cured coating film.
  • the colloidal silica is preferably an acidic colloidal silica in view of the stability of the coating composition and the appearance of the coating film.
  • the content of the colloidal silica (B) is, for example, 20 with respect to 100 parts by mass of the total mass of the active ingredients of the epoxysilane oligomer (A) and the colloidal silica (B) from the viewpoint of the hardness and scratch resistance of the resulting coating. It is ⁇ 80 parts by mass, preferably 40 to 75 parts by mass, and more preferably 40 to 70 parts by mass.
  • (C) Curing catalyst The present invention contains a curing catalyst from the viewpoint of curability of the coating composition.
  • the curing catalyst is not particularly limited as long as it can hydrolyze and condense a compound having a hydrolyzable group to promote curability, and the catalyst exemplified in the section for producing the epoxysilane oligomer (A).
  • organic tin compounds such as diacetyltin diacetate, dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, diacetyltin dioctoate, tin octylate, dibutyltin diacetate, dibutyltin dioctylate; aluminum trimethoxide, tris ( Acetylacetonate) aluminum, aluminum tri-n-butoxide, aluminum tris (acetylacetone), aluminum tris (acetoacetate ethyl), aluminum diisopropoxy (acetoacetate ethyl), aluminum acetylacetate Organoaluminum compounds such as nitrates
  • Organic zinc compounds such as cobalt acid; boric acid, trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, triphenyl borate, tri (4-chlorophenyl) borate, trihexafluoroisopropyl borate, etc.
  • Boric acid compounds such as boric acid esters; alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, cesium hydroxide; tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxy Ammonium hydroxide such as tetrabutylammonium fluoride; amines such as diethylamine and triethylamine; monoethanolamine, triethanolamine, N-methyldiethanol Examples include ethanolamines such as noramine, and strong base tertiary amine compounds such as DBU.
  • the said curing catalyst may be used independently and may use 2 or more types together.
  • phosphoric acid compounds and organotin compounds are preferable from the viewpoints of drying property, scratch resistance, and water dilution stability.
  • Examples of the phosphoric acid compound include orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphorous acid, polyphosphoric acid, phosphonic acid, methanephosphonic acid, benzenephosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, and phosphinic acid.
  • An alkali metal salt or an ammonium salt of these phosphoric acid compounds include orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphorous acid, polyphosphoric acid, phosphonic acid, methanephosphonic acid, benzenephosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, and phosphinic acid.
  • An alkali metal salt or an ammonium salt of these phosphoric acid compounds include orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphorous acid, polyphosphoric acid, phosphonic acid, methanephosphonic acid, benzenephosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid
  • the content of the curing catalyst (C) is 0.1 to 30 parts by mass, preferably 0.5 to the total mass of 100 parts by mass of the active ingredients of the epoxysilane oligomer (A) and colloidal silica (B). It is preferably adjusted within a range of ⁇ 20 parts by mass.
  • the coating composition of this invention may contain a silane coupling agent (D).
  • a silane coupling agent (D) By containing the silane coupling agent (D), the dispersibility of the colloidal silica (B) in the coating composition is improved, and the coating film appearance such as scratch resistance and glossiness is improved, which is particularly preferable.
  • limit especially as a silane coupling agent (D) The silane coupling agent which has a reactive group is suitable.
  • the reactive group is not particularly limited as long as it is a functional group that does not cause aggregation in the coating composition and can react at room temperature, and specifically includes an epoxy group, a hydroxyl group, an amino group, a ureido group, and a mercapto group. , Vinyl group, (meth) acryloyl group or isocyanate group.
  • silane coupling agent (D) examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyldisilane.
  • Glycidoxy group-containing silane coupling agent such as ethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) methyltriethoxysilane, 2- (3,4-epoxycyclohexyl) )
  • Epoxy group-containing silane coupling agents such as (3,4-epoxycyclohexyl) group-containing silane coupling agents such as ethyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) methyldimethoxysilane; Aminoethyl) aminopropyl Amino group-containing silane coupling agents such as methoxysilane, 3-aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropy
  • silane coupling agent a ureido group-containing silane coupling agent and a glycidoxy group-containing silane coupling agent are preferable from the viewpoint of the stability of the coating composition and scratch resistance.
  • the content of the epoxy silane oligomer (A) and the colloidal silica (B) is from the viewpoint of coating film appearance and scratch resistance. 1 to 100 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the total active ingredients.
  • the coating composition of the present invention may be solventless or may contain an organic solvent.
  • the organic solvent (E) By containing the organic solvent (E), the compatibility between the epoxysilane oligomer (A) and the colloidal silica (B) can be improved, which is particularly preferable.
  • the organic solvent any appropriate solvent can be used as long as it dissolves the hydrolyzable silane compound and can be dissolved even after the hydrolysis condensation reaction proceeds.
  • organic solvent examples include alcohol solvents such as methanol, ethanol, butanol, methyl isobutyl carbinol, 2-ethyl hexanol and benzyl alcohol; ketone solvents such as acetone and methyl isobutyl ketone; ethyl acetate, butyl acetate, methyl benzoate, Ester solvents such as methyl propionate; ether solvents such as cyclohexanone, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monotertiary butyl ether, propylene glycol monomethyl ether, isopropyl glycol; diethylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methoxy 3- glycol ether-based solvents such as methyl-1-butanol, aromatic hydrocarbon solvents include
  • the solubility (20 ° C.) of the organic solvent in water 5 g / 100 g or more of water is preferable.
  • the epoxysilane oligomer (A) and colloidal silica (B), a hydrolyzable silane described below and / or its When blending the hydrolyzed condensate (F) and the silane silane coupling agent (D), it is preferably 20 g / water 100 g or more, more preferably 50 g / water 100 g or more, from the viewpoint of improving their compatibility. .
  • organic solvents it is selected from butanol, 3-methoxy-3-methyl-1-butanol, and ethylene glycol monotertiary butyl ether from the viewpoint of coating workability and compatibility. It is preferable to use at least one kind.
  • the content is from the viewpoint of coating film appearance and coating workability, the epoxysilane oligomer (A) component and the colloidal silica (B) component.
  • the total mass of the active ingredients is, for example, 5 to 200 parts by mass, preferably 10 to 50 parts by mass, based on 100 parts by mass.
  • the coating composition of the present invention comprises 1 to 4 functional hydrolyzable silanes. You may contain the at least 1 sort (s) of hydrolyzable silane chosen from these, and / or its hydrolysis-condensation product (F).
  • the hydrolysis-condensation product of the hydrolysable silane represented by the said general formula (II) can be used conveniently.
  • methyltrimethoxysilane is particularly preferable from the viewpoint of drying properties.
  • the coating composition of the present invention contains at least one hydrolyzable silane selected from the hydrolyzable silanes having no 1 to 4 functional epoxy groups and / or their hydrolyzed condensates (F).
  • the content can be appropriately adjusted in terms of the balance of scratch resistance and crack resistance, but is 1 to 40% by weight, preferably 35 to 40% by weight based on the total amount of active ingredients of the coating composition. 30% by mass.
  • the coating composition of the present invention is a tetrafunctional hydrolyzable silane in at least a part of the component (F). And / or a hydrolysis condensate (G) thereof.
  • the general formula (III) is a tetrafunctional hydrolyzable silane, specifically, tetraalkoxysilane such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraphenoxysilane; A halosilane etc. can be mentioned.
  • the hydrolysis-condensation product of the tetrafunctional hydrolyzable silane preferably has an average condensation degree of 2 to 15, and the silica remaining as silica when the organosilicate compound is baked at 900 ° C.
  • a condensate obtained by condensing until the weight fraction falls within the range of 20 to 60% by mass is preferable.
  • the hydrolysis condensate may contain a branched or cyclic structure condensate.
  • the said average condensation degree can be calculated
  • the content thereof is scratch resistance, drying property, and crack resistance. From the viewpoint of balance, it is preferably in the range of 1 to 20% by mass, preferably 1.5 to 15% by mass, based on the total amount of active ingredients of the coating composition.
  • an active ingredient means the residue remove
  • the amount of the active ingredient can be determined from the heating residue when the mixture or composition containing the solvent is dried in a hot air dryer at 105 ° C. for 3 hours to volatilize the solvent.
  • the coating composition of the present invention may contain water (H). By containing water, drying can be promoted during the formation of the coating film. Moreover, the viscosity of a coating composition can be adjusted suitably by diluting later with water at the time of coating, and coating workability
  • the coating composition of the present invention can contain water in the composition, and water can be used instead of an organic solvent in the dilution operation at the painting stage. There is little risk of harming the surrounding sanitary environment, and safety is high.
  • any water can be used.
  • tap water, ion exchange water, and pure water are preferably used.
  • the content of water (H) can be adjusted as appropriate within a range that takes into consideration the finish of the coating composition of the present invention and the repellency during coating.
  • the amount added can be, for example, in the range of 1 to 30% by mass relative to the total amount of active ingredients of the coating composition before dilution.
  • the coating composition of the present invention is a curing catalyst other than the above-mentioned curing catalyst, pigments such as RTV rubber, coloring pigment, extender pigment, glittering pigment, dye, matting agent, aggregate, Resin particles, surface modifiers, viscosity modifiers, antifoaming agents, antibacterial agents, antifungal agents, flame retardants, antifogging agents, plasticizers, slip agents, dehydrating agents, UV absorbers, light stabilizers, metal oxides Fine particles, metal powders, antioxidants, surfactants, film-forming aids, thickeners, antistatic agents, water repellency imparting agents, additives such as fibers; cross-linking agents such as isocyanate compounds and melamine resins; resin emulsions , Resin components such as wax emulsions; modifiers such as acrylic resins, fluororesins, and various organically modified silicone oils can be appropriately blended.
  • pigments such as RTV rubber, coloring pigment, extender pigment, glittering pigment, dye, matting agent,
  • the coating composition of the present invention may be a one-component composition or a multi-component composition of two or more components.
  • the epoxysilane oligomer (A) is used as the first component
  • the curing catalyst (C) is used as the second component
  • the other components are distributed to any one of them.
  • a third liquid containing can be prepared individually, and all liquids can be mixed and used immediately before use.
  • Components (D) to (H) and other additives such as pigment dispersants, anti-settling agents, antifoaming agents, antioxidants, ultraviolet absorbers, and the like are appropriately included in any of the first to third liquids. be able to.
  • the compatibility may be improved by mixing the colloidal silica (B) and the curing catalyst (C) after being previously dispersed.
  • the coating composition obtained as described above is applied to the surface of the substrate, applied as a top coat, and dried to form a coating that protects the surface of the substrate.
  • the substrate surface is not particularly limited.
  • the field of application of the above material is not particularly limited as long as it is a field for the purpose of protecting the surface of the base material.
  • machinery ships, vehicles, aircraft, civil engineering, architecture, anticorrosion, ink, and other general industries Field and so on.
  • the coating composition of the present invention can be applied using a coating means known per se, and examples thereof include a method of spreading the coating composition on the surface to be coated with a mop, sponge, cloth or the like.
  • rollers, air sprays, airless sprays, ricin guns, universal guns, brushes, dip coats, roll coaters, brush coats, and the like can be appropriately selected according to the type of substrate, use, etc. from the coating method.
  • the coating composition of the present invention can be applied multiple times within a range that does not impair the appearance of the coating film. Furthermore, the excess after coating can be wiped off as necessary.
  • the formed coating film can be dried at room temperature, it may be dried by heating or forcedly depending on the composition of the coating composition used, the coating environment, and the like.
  • a coating film can be obtained by drying in an environment of 5 to 45 ° C.
  • the relative humidity during coating (hereinafter sometimes abbreviated as RH) is preferably 70% or less, particularly preferably 60% or less.
  • the drying time at room temperature is 1 hour or longer, preferably 1 day or longer, and more preferably 3 days or longer.
  • the dry film thickness can be appropriately adjusted depending on the substrate to be applied and the coating environment, but is generally 1 to 1,000 ⁇ m, preferably 5 to 500 ⁇ m, in order to obtain sufficient scratch resistance.
  • the present invention also provides a method for improving the scratch resistance and finish of the floor surface by coating the floor surface with the coating composition as a top coat.
  • this floor surface is a general floor material, for example, ceramic floor materials such as ceramic siding boards, ceramics, porcelain tiles, metal floor materials such as iron, aluminum, metal siding, And wood-based flooring such as natural wood and plywood, synthetic resin-based flooring such as polyvinyl chloride resin, and the like, and those having an old coating film on the surface are also included.
  • ceramic floor materials such as ceramic siding boards, ceramics, porcelain tiles
  • metal floor materials such as iron, aluminum, metal siding
  • wood-based flooring such as natural wood and plywood
  • synthetic resin-based flooring such as polyvinyl chloride resin, and the like, and those having an old coating film on the surface are also included.
  • the dry film thickness of the coating composition can be adjusted as appropriate depending on the substrate to be applied and the coating environment, but in order to obtain sufficient scratch resistance, it is generally 1 to 50 ⁇ m per coating.
  • the thickness is preferably 1 to 30 ⁇ m.
  • the coating composition of the present invention can be applied on the surface of the base coating formed after previously applying a base coating on the surface of the substrate.
  • the undercoat paint can be appropriately selected according to the type and state of the substrate surface, and is not particularly limited.
  • an acrylic resin an acrylic silicone resin, a fluorine resin, polyvinyl acetate Paints and books containing resin binders such as resin, polyolefin resin, silicone resin, polyurethane resin, epoxy resin, phenol resin, polyester resin, alkyd resin, melamine resin, biodegradable resin, etc.
  • An inorganic coating agent other than the invention may be used.
  • These paints and coating agents may be solventless, water-based or solvent-based.
  • it can also apply several times in the range which does not impair a coating-film external appearance.
  • the coating for forming the undercoat can be performed using a coating method known per se.
  • a coating method such as roller, air spray, airless spray, lysine gun, universal gun, brush, roll coater, etc. It can be appropriately selected and used according to the application. Drying of the formed undercoat film is most preferably performed at room temperature, but heating drying or forced drying can be performed depending on the type of the undercoat paint or the coating environment.
  • the dry film thickness can be appropriately adjusted depending on the substrate to be applied and the coating environment, but it is generally from 0.5 to 1,000 ⁇ m, preferably from 5 to 1,000 ⁇ m, in order to obtain a sufficient finish at the time of top coat coating.
  • Part and % indicate “part by mass” and “% by mass” unless otherwise specified.
  • the epoxy equivalent is the number of grams of resin containing 1 gram equivalent of an epoxy group measured by a method based on JIS K7236: 2001.
  • the heating residue (active ingredient) was 80%.
  • the weight average molecular weight was 1,100 and the epoxy equivalent was 183 g / eq.
  • KBM-403 trade name, manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltrimethoxysilane, molecular weight 236.34.
  • the heating residue (active ingredient) was 72%.
  • the weight average molecular weight was 1,000 and the epoxy equivalent was 230 g / eq.
  • KBM-13 trade name, Shin-Etsu Chemical Co., Ltd., methyltrimethoxysilane, molecular weight 136.22.
  • KBM-22 trade name, Shin-Etsu Chemical Co., Ltd., dimethyldimethoxysilane, molecular weight 120.2.
  • coating composition 62.5 parts of epoxysilane oligomer (A-1) obtained in Production Example 1 (50 parts as an active ingredient), 125 parts of Snowtex O-40 (Note 4) (50 parts as an active ingredient), phosphorus as a curing catalyst A solution obtained by dissolving 2 parts of an acid in 10 parts of ion-exchanged water was mixed and stirred with a disper until uniform to obtain a coating composition (KP-1).
  • Example 2 to 21, Comparative Examples 1 to 5 coating compositions (KP-2) to (KP-26) were obtained in the same manner as in Example 1, except that the composition of each component was changed to the composition shown in Tables 1 to 3.
  • the blending amounts in Tables 1 to 3 indicate the amounts of active ingredients for the components (A), (B), (C), (D), (F), and (G), and the obtained coating
  • the results of various evaluations described below for the compositions are also shown in Tables 1 to 3.
  • S Agglomerates are not observed in the diluted composition, and it is transparent.
  • A Aggregates are not observed in the diluted composition, but slightly cloudy.
  • B Aggregates and obvious cloudiness occur in the diluted composition.
  • C The diluted composition aggregates and solidifies.
  • Test item 2. Appearance of coating film: Each coating composition is applied to a 2 mm thick glass plate (150 ⁇ 70 mm) with an applicator so that the dry film thickness is 10 ⁇ m, and dried for 24 hours under conditions of an air temperature of 23 ° C. and a humidity of 50% RH. Obtained. The appearance of the coating film was visually evaluated for each test plate.
  • S Specular gloss is 80 or more
  • A Specular gloss is 70 or more and less than 80
  • B Specular gloss is 50 or more and less than 70
  • C Specular gloss is less than 50.
  • S Drying time of touch is less than 15 minutes
  • Test item 6. Crack resistance: Each coating composition was applied to a 2 mm thick glass plate (150 ⁇ 70 mm) with an applicator so that the dry film thickness was 15 ⁇ m, and dried for 24 hours under conditions of an air temperature of 23 ° C. and a humidity of 50% RH. Then, it was further heat-dried (forced drying) for 1 hour with a dryer at 80 ° C. to obtain a test plate. The appearance of the coating film was visually evaluated for each test plate.
  • Paint workability “Eco-cation sealer transparent” as a primer on a composition vinyl floor tile (trade name “P tile P-60”, manufactured by Tajima) of 305 ⁇ 305 ⁇ 2 mm (water-based cationic emulsion-based undercoat composition manufactured by Kansai Paint Co., Ltd.) was coated so that the coat-weight 40 g / m 2, temperature 23 ° C., were those dried for 24 hours under the conditions of humidity of 50% RH and the coated plate.
  • the ease of application when each coating composition was spread to a dry film thickness of 10 ⁇ m using a floor mop was evaluated according to the following criteria.
  • the coating composition of each example has (A) an epoxy silane oligomer having an epoxy group and a siloxane bond and a weight average molecular weight of 500 to 20,000, and (B) an average primary particle size. Because it contains colloidal silica in the range of 1 to 100 nm and (C) a curing catalyst, it is easy to coat because of its excellent water dilution stability and coating workability, and drying and curing at room temperature. In addition, the obtained coating film is excellent in scratch resistance and crack resistance. Furthermore, it has little odor and high gloss. On the other hand, since the coating composition of each comparative example does not satisfy all the above requirements, it simultaneously satisfies water dilution stability, coating film appearance, glossiness, drying property, scratch resistance, crack resistance, and painting workability. I could't.

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

Abstract

L'invention a pour objet de fournir une composition de revêtement dont la mauvaise odeur est faible, qui est facile à travailler, qui se révèle excellente en termes de propriétés de séchage et de durcissement à température ambiante, et qui est telle qu'un film de revêtement qu'elle permet d'obtenir est doté d'excellentes propriétés de résistance aux éraflures et aux fissures. Plus particulièrement, l'invention concerne une composition de revêtement qui comprend (A) un oligomère époxy-silane de masse moléculaire moyenne en poids comprise entre 500 et 20000 possédant un groupe époxy et une liaison silane, (B) une silice colloïdale de diamètre moyen de particule primaire compris dans une plage de 1 à 100nm, et (C) un catalyseur de durcissement.
PCT/JP2018/005565 2017-02-16 2018-02-16 Composition de revêtement, et procédé de formation de film protecteur de surface WO2018151271A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200062658A (ko) * 2018-11-27 2020-06-04 한국전기연구원 전도성 페이스트용 기판접착소재 및 이의 제조방법

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7011397B2 (ja) * 2017-03-24 2022-01-26 大日本塗料株式会社 塗料組成物
JP7026009B2 (ja) * 2018-06-28 2022-02-25 大日本塗料株式会社 構造物の塗装方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008285502A (ja) * 2007-04-19 2008-11-27 Mitsubishi Rayon Co Ltd 活性エネルギー線硬化性組成物および成形体
JP2010163584A (ja) * 2009-01-16 2010-07-29 Kyushu Hi-Tech:Kk 化学床保護用可撓性付与常温硬化型無機質コーティング剤
JP2010188604A (ja) * 2009-02-18 2010-09-02 Fujifilm Corp 複層フィルム及びその製造方法
JP2015175151A (ja) * 2014-03-14 2015-10-05 シーバイエス株式会社 床用コーティング剤組成物およびそれを用いた床構造体
JP2016210670A (ja) * 2015-05-11 2016-12-15 株式会社九州ハイテック メンテナンスフリー型石材タイル及びそのコーティング剤並びにそのタイルの製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008285502A (ja) * 2007-04-19 2008-11-27 Mitsubishi Rayon Co Ltd 活性エネルギー線硬化性組成物および成形体
JP2010163584A (ja) * 2009-01-16 2010-07-29 Kyushu Hi-Tech:Kk 化学床保護用可撓性付与常温硬化型無機質コーティング剤
JP2010188604A (ja) * 2009-02-18 2010-09-02 Fujifilm Corp 複層フィルム及びその製造方法
JP2015175151A (ja) * 2014-03-14 2015-10-05 シーバイエス株式会社 床用コーティング剤組成物およびそれを用いた床構造体
JP2016210670A (ja) * 2015-05-11 2016-12-15 株式会社九州ハイテック メンテナンスフリー型石材タイル及びそのコーティング剤並びにそのタイルの製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200062658A (ko) * 2018-11-27 2020-06-04 한국전기연구원 전도성 페이스트용 기판접착소재 및 이의 제조방법
KR102542110B1 (ko) 2018-11-27 2023-06-09 한국전기연구원 전도성 페이스트용 기판접착소재 및 이의 제조방법

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