CN116144213B - Dispersion comprising inorganic oxide particles and zinc cyanurate particles - Google Patents
Dispersion comprising inorganic oxide particles and zinc cyanurate particles Download PDFInfo
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- CN116144213B CN116144213B CN202310190898.2A CN202310190898A CN116144213B CN 116144213 B CN116144213 B CN 116144213B CN 202310190898 A CN202310190898 A CN 202310190898A CN 116144213 B CN116144213 B CN 116144213B
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- particles
- dispersion
- inorganic oxide
- mass
- coating
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- 239000002245 particle Substances 0.000 title claims abstract description 506
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 title claims abstract description 239
- 239000011701 zinc Substances 0.000 title claims abstract description 221
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 217
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 216
- 229910052809 inorganic oxide Inorganic materials 0.000 title claims abstract description 216
- 239000006185 dispersion Substances 0.000 title claims abstract description 211
- 239000000843 powder Substances 0.000 claims abstract description 138
- 239000007788 liquid Substances 0.000 claims abstract description 99
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 138
- 239000007787 solid Substances 0.000 claims description 125
- 238000007561 laser diffraction method Methods 0.000 claims description 39
- 229910052782 aluminium Inorganic materials 0.000 claims description 29
- 229910044991 metal oxide Inorganic materials 0.000 claims description 22
- 150000004706 metal oxides Chemical class 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 20
- 239000008119 colloidal silica Substances 0.000 claims description 10
- 229910052718 tin Inorganic materials 0.000 claims 2
- 229920005989 resin Polymers 0.000 description 329
- 239000011347 resin Substances 0.000 description 329
- 239000008199 coating composition Substances 0.000 description 244
- 238000000576 coating method Methods 0.000 description 223
- 239000011248 coating agent Substances 0.000 description 215
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 103
- 239000000654 additive Substances 0.000 description 86
- -1 inorganic carbide Inorganic materials 0.000 description 83
- 230000000996 additive effect Effects 0.000 description 82
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 79
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- 238000000034 method Methods 0.000 description 64
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 62
- 239000004925 Acrylic resin Substances 0.000 description 54
- 229920000178 Acrylic resin Polymers 0.000 description 54
- 239000002609 medium Substances 0.000 description 49
- 239000000377 silicon dioxide Substances 0.000 description 46
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- 238000004519 manufacturing process Methods 0.000 description 37
- 239000000463 material Substances 0.000 description 37
- 239000011268 mixed slurry Substances 0.000 description 37
- 238000003756 stirring Methods 0.000 description 31
- 239000011787 zinc oxide Substances 0.000 description 31
- 239000011324 bead Substances 0.000 description 30
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 29
- 239000002131 composite material Substances 0.000 description 27
- 238000001035 drying Methods 0.000 description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 25
- 239000011521 glass Substances 0.000 description 25
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- 150000002148 esters Chemical class 0.000 description 19
- 229910052731 fluorine Inorganic materials 0.000 description 19
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 18
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 18
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- 150000003839 salts Chemical class 0.000 description 10
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- 239000002253 acid Substances 0.000 description 9
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- 239000003960 organic solvent Substances 0.000 description 9
- 229920002554 vinyl polymer Polymers 0.000 description 9
- 239000002023 wood Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 8
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 150000001408 amides Chemical class 0.000 description 8
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 8
- 238000001246 colloidal dispersion Methods 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 239000005038 ethylene vinyl acetate Substances 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 8
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- 229910006404 SnO 2 Inorganic materials 0.000 description 7
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- 238000004438 BET method Methods 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
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- 150000001447 alkali salts Chemical class 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D7/61—Additives non-macromolecular inorganic
-
- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2231—Oxides; Hydroxides of metals of tin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2244—Oxides; Hydroxides of metals of zirconium
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Abstract
The present invention provides a dispersion liquid, which is obtained by dispersing dispersoid particles comprising inorganic oxide particles and zinc cyanurate particles in a liquid medium, wherein the inorganic oxide particles are inorganic oxide powder, the specific surface area of the inorganic oxide powder is 1-800 m 2/g, and the loose bulk density is 0.03-3.0 g/cm 3.
Description
The present application is a divisional application of chinese patent application having a filing date of 2020, 9 and 18, a filing date of 202080064965.0, and a name of "dispersion liquid and coating composition comprising inorganic oxide particles and zinc cyanurate particles".
Technical Field
The present invention relates to a coating composition comprising a coating additive and a resin, a coating film formed from the coating composition, a method for producing the coating composition, and a coating additive added to the coating composition, the coating additive comprising a dispersion comprising inorganic oxide particles and zinc cyanurate particles.
The present invention also relates to a dispersion liquid containing inorganic oxide powder and zinc cyanurate particles among the above-mentioned inorganic oxide particles, and a dispersion liquid containing specific colloidal metal oxide particles and zinc cyanurate particles among the above-mentioned inorganic oxide particles.
Background
Zinc cyanurate is known as an anticorrosive agent for metal surfaces of iron-based metals, and various methods are disclosed for producing the same.
For example, patent document 1 discloses, as a method for producing lead cyanurate and zinc, which are known as corrosion protection agents for metal surfaces, the following production method: pbO or ZnO and cyanuric acid are mixed into paste at 100-180 ℃ and shearing action is applied to the obtained paste at 50-250 ℃.
Patent document 2 discloses an anticorrosive coating material using zinc salts and/or lead salts of organic compounds such as barbituric acid (barbituricacid) and cyanuric acid as an anticorrosive coating agent for metal surfaces based on zinc salts and/or lead salts of organic compounds.
Further, patent document 3 discloses a method for producing needle-like or plate-like basic zinc cyanurate particles by wet-dispersing a mixed slurry containing zinc oxide or basic zinc carbonate, cyanuric acid and water, wherein the needle-like or plate-like basic zinc cyanurate particles have an average particle diameter D 50 to 900nm as measured by a laser diffraction method, a specific surface area of 20m 2/g～100m2/g, and a length ratio (axial ratio) of a major axis to a minor axis of 5 to 25.
Patent document 4 discloses a method for producing a basic zinc cyanurate powder by heat-treating a mixed powder containing zinc oxide, cyanuric acid and water in a closed or open state, and discloses a rust-preventive pigment composition containing the basic zinc cyanurate powder.
In addition to the purpose of coloring the object (surface to be coated), the paint has various effects required for the above-mentioned rust-preventing effect, weather resistance, and the like. For example, corrosion resistance is required for metal base materials (aluminum, iron, etc.), durability, weather resistance, scratch resistance, corrosion resistance, color tone change prevention, etc. are required for resin base materials, wood, etc., and strength improvement, light resistance, etc. are required for glass base materials, silicon base materials, etc.
Prior art literature
Patent document 1: japanese patent laid-open No. 59-031779
Patent document 2: japanese patent laid-open No. 54-123145
Patent document 3: international publication No. 2011/162353
Patent document 4: international publication No. 2016/006585
Disclosure of Invention
It has been known from the past that zinc cyanurate can impart a high corrosion-preventing function to a metal surface. However, zinc cyanurate obtained by the above-described production method has a needle-like or plate-like particle shape and a relatively large particle diameter, and when dispersed in a medium, it becomes a non-uniform slurry, and thus has a problem of difficulty in handling the composition for coating formed by mixing with a resin as a binder.
The present invention has been made in view of the above-described circumstances, and an object of the present invention is to provide a coating composition capable of forming a coating film having high adhesion to a substrate, and to provide a coating composition capable of sufficiently exerting functions such as corrosion resistance of a metal surface and the like possessed by zinc cyanurate, and capable of exerting effects such as improvement in durability, scratch resistance, corrosion resistance of a substrate, and prevention of change in color tone of a substrate (occurrence of appearance failure is less likely to occur) on a PET substrate, wood and the like.
As a result of intensive studies to solve the above problems, the present inventors have found that a coating composition having excellent dispersibility and capable of maintaining a stable dispersion state can be surprisingly obtained by using a dispersion obtained by dispersing both inorganic oxide particles and zinc cyanurate particles as a dispersoid in a liquid medium as a coating additive and compounding the coating additive with a resin component such as a resin emulsion. Further, it has been found that the above-mentioned coating composition can provide a coating film which is excellent in adhesion to a substrate (coated surface), has little cure shrinkage, and is excellent in follow-up property against deformation of the substrate, and thus, in addition to the anticorrosive effect on a metal surface, various functions of the coating composition can be expected: the present invention has been completed by improving the durability, scratch resistance, and corrosion resistance of a substrate, and preventing the effects of color change of the substrate.
That is, as the 1 st aspect of the present invention, there is provided a coating composition comprising a coating additive and a resin, wherein the coating additive comprises a dispersion liquid obtained by dispersing a dispersion particle in a liquid medium, and the dispersion particle comprises an inorganic oxide particle and a zinc cyanurate particle.
In the aspect 2, the coating composition according to the aspect 1 is at least 1 kind selected from the group consisting of aluminum base materials, iron base materials, copper base materials, gold base materials, silver base materials, platinum base materials, mirror materials, glass base materials, silicon base materials, wood, resin films and resin molded products.
The aspect 3 relates to the coating composition according to the aspect 1 or the aspect 2, wherein the resin is in the form of a resin emulsion, which is an oil-in-water emulsion or a water-in-oil emulsion, and is a resin emulsion containing 1 or 2 or more resin components selected from the group consisting of acrylic resins, acrylic-styrene resins, acrylic-silicone (silicone) resins, vinyl acetate resins, styrene resins, olefin resins, ethylene-vinyl acetate resins, ester resins, epoxy resins, phenol resins, amide resins, vinyl alcohol resins, fluorine resins, polyurethane resins, melamine resins, phthalic acid resins, silicone resins, alkyd resins, and vinyl chloride resins as the resin.
The aspect 4 relates to the coating composition according to the aspect 1 or the aspect 2, wherein the resin is in the form of a water-soluble polymer or a colloidal dispersion, and the resin is a water-soluble resin or a colloidal dispersion containing 1 or 2 or more resin components selected from the group consisting of an acrylic resin, an acrylic-styrene resin, an acrylic-silicone resin, a vinyl acetate resin, a styrene resin, an olefin resin, an ethylene-vinyl acetate resin, an ester resin, an epoxy resin, a phenol resin, an amide resin, a vinyl alcohol resin, a fluorine resin, a polyurethane resin, a melamine resin, a phthalic acid resin, a silicone resin, an alkyd resin, and a vinyl chloride resin.
The aspect 5 relates to the coating composition according to any one of aspects 1 to 4, wherein the inorganic oxide particles are oxides of at least 1 atom selected from Si, al, ti, zr, fe, cu, zn, li, na, K, mg, ca, cs, sr, ba, B, ga, Y, nb, mo, in, sn, sb, ta, W, ge, pb, P, as, rb, bi and Ce.
The coating composition according to the aspect 6 is the coating composition according to the aspect 5, wherein the inorganic oxide particles are a composite oxide or a mixed oxide of 2 or more atoms selected from Si, al, ti, zr, fe, cu, zn, li, na, K, mg, ca, cs, sr, ba, B, ga, Y, nb, mo, in, sn, sb, ta, W, ge, pb, P, as, rb, bi and Ce.
The aspect 7 relates to the coating composition according to any one of aspects 1 to 5, wherein the inorganic oxide particles are colloidal oxides of at least 1 atom selected from Si, al, ti, zr, fe, cu, zn, li, na, K, mg, ca, cs, sr, ba, B, ga, Y, nb, mo, in, sn, sb, ta, W, ge, pb, P, as, rb, bi and Ce.
The coating composition according to the aspect 8 is the coating composition according to the aspect 7, wherein the inorganic oxide particles are colloidal composite oxides or colloidal mixed oxides of 2 or more atoms selected from Si, al, ti, zr, fe, cu, zn, li, na, K, mg, ca, cs, sr, ba, B, ga, Y, nb, mo, in, sn, sb, ta, W, ge, pb, P, as, rb, bi and Ce.
The 9 th aspect relates to the coating composition according to any one of the 1 st to 8 th aspects, wherein the primary particles of the zinc cyanurate particles have a major axis of 400nm to 3,000nm and a minor axis of 10nm to 300nm, and the ratio of the major axis to the minor axis is 1.3 to 300, when measured by a transmission electron microscope.
The 10 th aspect relates to the coating composition according to any one of the 1 st to 9 th aspects, wherein the dispersoid particles in the dispersion liquid are particles having an average particle diameter of 80nm to 5,000nm, and the concentration of the solid content of the dispersoid particles in the dispersion liquid is 0.1 to 50 mass%, when measured by a laser diffraction method.
As an 11 th aspect, there is provided the coating composition according to any one of the 1 st to 10 th aspects, wherein the mass ratio of the dispersoid particles in the dispersion liquid is 1: the inorganic oxide particles and zinc cyanurate particles are contained in a proportion of 0.01 to 100, and the solid content concentration of the dispersoid particles in the dispersion is 0.1 to 50 mass%.
The coating composition according to any one of the aspects 1 to 11, wherein the liquid medium is water or an organic solvent.
The coating composition according to any one of the aspects 1 to 12, wherein the ratio of the solid component in the dispersion to the resin is as follows: the mass ratio of the (resin) is 1:0.1 to 20% by mass, and the total amount of solid components in the coating composition is 1 to 70% by mass.
The coating composition according to any one of the aspects 1 to 13, further comprising a slurry of an inorganic oxide powder, wherein the slurry has a solid content concentration of 0.1 to 50% by mass.
As a 15 th aspect, the coating composition according to the 14 th aspect is characterized in that the ratio of the solid content in the dispersion to the solid content in the slurry of the resin and the inorganic oxide powder is as follows: (resin): the mass ratio of (solid component of slurry) was 1:0.1 to 20:0.1 to 1, and the total amount of solid components in the coating composition is 1 to 70 mass%.
The 16 th aspect relates to a coating film of the coating composition according to any one of the 1 st to 15 th aspects, which is formed on at least one substrate selected from the group consisting of an aluminum substrate, an iron-based substrate, a copper-based substrate, a gold-based substrate, a silver-based substrate, a platinum-based substrate, a mirror material, a glass substrate, a silicon substrate, wood, a resin film, and a resin molded product.
In a 17 th aspect, there is provided a coating film of the coating composition according to any one of the 1 st to 15 th aspects, wherein the coating film has a film thickness of 0.1 μm to 100 μm.
The 18 th aspect relates to the coating film according to the 17 th aspect, wherein the coating film is a spin coating film, a bar coating film, a roll coating film, or a dip coating film.
In a 19 th aspect, the method for producing a coating composition according to any one of the 1 st to 15 th aspects comprises a step of mixing a dispersion liquid obtained by dispersing dispersoid particles comprising inorganic oxide particles and zinc cyanurate particles in a liquid medium with a resin using a liquid disperser.
The 20 th aspect relates to the method for producing a coating composition according to the 14 th or 15 th aspect, comprising a step of mixing a dispersion liquid obtained by dispersing dispersoid particles comprising inorganic oxide particles and zinc cyanurate particles in a liquid medium, the resin and the slurry of the inorganic oxide powder using a liquid disperser.
The 21 st aspect relates to the method of the 19 th or 20 th aspect, wherein the liquid disperser is a stirrer, a rotary shear stirrer, a colloid mill, a roll mill, a high-pressure jet disperser, an ultrasonic disperser, a container-driven mill, a medium stirring mill, or a kneader.
The 22 nd aspect relates to the method for producing a coating composition according to any one of the 19 th to 21 th aspects, further comprising a step of mixing the mixed solution of the inorganic oxide particles and the zinc cyanurate particles or the slurry thereof using a pulverizing device, before the step of mixing using the liquid disperser.
In a 23 rd aspect, the method according to the 22 nd aspect is characterized in that the pulverizing device is a ball mill, a bead mill or a sand mill.
The 24 th aspect relates to the method for producing a coating composition according to any one of the 19 th to 21 th aspects, further comprising a step of mixing the pre-pulverized inorganic oxide powder with a mixed solution of zinc cyanurate particles or a slurry thereof using a pulverizing device, before the step of mixing using the liquid disperser.
In view of the 25 th aspect, the present invention relates to a dispersion liquid in which dispersion particles containing inorganic oxide particles and zinc cyanurate particles are dispersed in a liquid medium, wherein the inorganic oxide particles are inorganic oxide powder having a specific surface area of 1 to 800m 2/g and a bulk density of 0.03 to 3.0g/cm 3.
The dispersion according to the 26 th aspect relates to the 25 th aspect, wherein the inorganic oxide powder is an oxide of at least 1 atom selected from Si, al, ti, zr, fe, cu, zn, li, na, K, mg, ca, cs, sr, ba, B, ga, Y, nb, mo, in, sn, sb, ta, W, ge, pb, P, as, rb, bi and Ce.
The 27 th aspect relates to the dispersion of the 25 th or 26 th aspect, wherein the dispersoid particles are particles having an average particle diameter of 200nm to 5,000nm, and the concentration of the solid content of the dispersoid particles in the dispersion is 0.1 to 50% by mass when measured by a laser diffraction method.
In view of point 28, the present invention relates to a dispersion liquid in which dispersion particles containing inorganic oxide particles and zinc cyanurate particles are dispersed in a liquid medium, wherein the inorganic oxide particles are colloidal metal oxide particles excluding particles containing colloidal silica as a main component.
As a 29 th aspect, the dispersion according to the 28 th aspect is characterized in that the colloidal metal oxide particles contain an oxide of at least 1 atom selected from Al, ti, zr, fe, cu, zn, li, na, K, mg, ca, cs, sr, ba, B, ga, Y, nb, mo, in, sn, sb, ta, W, ge, pb, P, as, rb, bi and Ce.
The 30 th aspect relates to the dispersion of the 28 th or 29 th aspect, wherein the dispersoid particles are particles having an average particle diameter of 80nm to 2,000nm, and the concentration of the solid content of the dispersoid particles in the dispersion is 0.1 to 50% by mass when measured by a laser diffraction method.
The present invention also relates to a dispersion liquid containing an inorganic oxide powder and zinc cyanurate particles. That is, the present invention includes the following modes [1] to [21 ].
[1]
A dispersion liquid which is obtained by dispersing in a liquid medium dispersoid particles comprising inorganic oxide powder and zinc cyanurate particles, wherein the specific surface area of the inorganic oxide powder is 1 to 800m 2/g and the bulk density is 0.03 to 3.0g/cm 3.
[2]
The dispersion according to [1], wherein the inorganic oxide powder is an oxide of at least 1 atom selected from Si, al, ti, zr, fe, cu, zn, li, na, K, mg, ca, cs, sr, ba, B, ga, Y, nb, mo, in, sn, sb, ta, W, ge, pb, P, as, rb, bi and Ce.
[3]
The dispersion according to [2], wherein the inorganic oxide powder is a composite oxide or mixed oxide of 2 or more atoms selected from Si, al, ti, zr, fe, cu, zn, li, na, K, mg, ca, cs, sr, ba, B, ga, Y, nb, mo, in, sn, sb, ta, W, ge, pb, P, as, rb, bi and Ce.
[4]
The dispersion according to any one of [1] to [3], wherein the primary particles of the zinc cyanurate particles have a major axis of 400nm to 3,000nm and a minor axis of 10nm to 300nm, and the ratio of the major axis to the minor axis is 1.3 to 300, when measured by a transmission electron microscope.
[5]
The dispersion according to any one of [1] to [4], wherein the dispersoid particles are particles having an average particle diameter of 200nm to 5,000nm, and the concentration of the solid content of the dispersoid particles in the dispersion is 0.1 to 50% by mass, when measured by a laser diffraction method.
[6]
The dispersion liquid according to any one of [1] to [5], wherein the mass ratio of the dispersoid particles is 1: the inorganic oxide particles and zinc cyanurate particles are contained in a proportion of 0.01 to 100, and the solid content concentration of the dispersoid particles in the dispersion is 0.1 to 50 mass%.
[7]
The dispersion liquid according to any one of [1] to [6], wherein the liquid medium is water or an organic solvent.
[8]
A coating composition comprising the dispersion of any one of [1] to [7] and a resin.
[9]
The coating composition according to item [8], wherein the resin is in the form of a resin emulsion, which is an oil-in-water emulsion or a water-in-oil emulsion, and which contains, as a resin, 1 or 2 or more resin components selected from the group consisting of an acrylic resin, an acrylic-styrene resin, an acrylic-silicone resin, a vinyl acetate resin, a styrene resin, an olefin resin, an ethylene-vinyl acetate resin, an ester resin, an epoxy resin, a phenol resin, an amide resin, a vinyl alcohol resin, a fluorine resin, a polyurethane resin, a melamine resin, a phthalic acid resin, a silicone resin, an alkyd resin, and a vinyl chloride resin.
[10]
The coating composition according to item [8], wherein the resin is in the form of a water-soluble polymer or a colloidal dispersion, and the resin is a water-soluble resin or a colloidal dispersion containing 1 or more resin components selected from the group consisting of acrylic resins, acrylic-styrene resins, acrylic-silicone resins, vinyl acetate resins, styrene resins, olefin resins, ethylene-vinyl acetate resins, ester resins, epoxy resins, phenol resins, amide resins, vinyl alcohol resins, fluorine resins, polyurethane resins, melamine resins, phthalic acid resins, silicone resins, alkyd resins and vinyl chloride resins.
[11]
The coating composition according to any one of [8] to [10], wherein the ratio of the solid component in the dispersion to the resin is (the solid component in the dispersion): the mass ratio of the (resin) is 1:0.1 to 20% by mass, and the total amount of solid components in the coating composition is 1 to 70% by mass.
[12]
The coating composition according to any one of [8] to [11], further comprising a slurry of an inorganic oxide powder, wherein the slurry has a solid content concentration of 0.1 to 50% by mass.
[13]
The coating composition according to [12], wherein the ratio of the solid content in the dispersion to the solid content in the slurry of the resin and the inorganic oxide powder is (the solid content in the dispersion): (resin): the mass ratio of (solid component of slurry) was 1:0.1 to 20:0.1 to 1, and the total amount of solid components in the coating composition is 1 to 70 mass%.
[14]
A coating film of the coating composition according to any one of [8] to [13], wherein the film thickness is 0.1 μm to 100. Mu.m.
[15]
The coating film according to [14], which is a spin coating film, a bar coating film, a roll coating film or a dip coating film.
[16]
The method for producing a dispersion according to any one of [1] to [7], further comprising a step of mixing the inorganic oxide powder with zinc cyanurate particles or a slurry thereof in a liquid medium using a pulverizer.
[17]
The production method according to item [16], wherein the pulverizing device is a ball mill, a bead mill or a sand mill.
[18]
The method for producing a dispersion according to any one of [1] to [7], further comprising a step of mixing the pre-pulverized inorganic oxide powder with zinc cyanurate particles or a slurry thereof in a liquid medium using a pulverizing device.
[19]
The method for producing a coating composition according to any one of [8] to [13], comprising the step of mixing the dispersion liquid according to any one of [1] to [7] with the resin using a liquid disperser.
[20]
The method for producing a coating composition according to [12] or [13], comprising the step of mixing the dispersion liquid according to any one of [1] to [7], the resin, and the slurry of the inorganic oxide powder using a liquid disperser.
[21]
The method for producing a coating composition according to [19] or [20], wherein the liquid disperser is a stirrer, a rotary shear stirrer, a colloid mill, a roll mill, a high-pressure jet disperser, an ultrasonic disperser, a container-driven mill, a medium stirring mill or a kneader.
Furthermore, the present invention relates to a dispersion comprising specific colloidal metal oxide particles and zinc cyanurate particles. That is, the present invention includes the following modes <1> to <17 >.
<1>
A dispersion liquid is obtained by dispersing, in a liquid medium, dispersoid particles containing colloidal metal oxide particles and zinc cyanurate particles, wherein the colloidal metal oxide particles are colloidal metal oxide particles excluding particles containing colloidal silica as a main component.
<2>
The dispersion according to <1>, wherein the colloidal metal oxide particles comprise an oxide of at least 1 atom selected from Al, ti, zr, fe, cu, zn, li, na, K, mg, ca, cs, sr, ba, B, ga, Y, nb, mo, in, sn, sb, ta, W, ge, pb, P, as, rb, bi and Ce.
<3>
The dispersion according to <2>, wherein the colloidal metal oxide particles comprise a composite oxide or mixed oxide of 2 or more atoms selected from Al, ti, zr, fe, cu, zn, li, na, K, mg, ca, cs, sr, ba, B, ga, Y, nb, mo, in, sn, sb, ta, W, ge, pb, P, as, rb, bi and Ce.
<4>
The dispersion according to any one of <1> to <3>, wherein the primary particles of the zinc cyanurate particles have a major axis of 400nm to 3,000nm and a minor axis of 10nm to 300nm, and the ratio of the major axis to the minor axis is 1.3 to 300, when measured by a transmission electron microscope.
<5>
The dispersion according to any one of <1> to <4>, wherein the dispersoid particles in the dispersion are particles having an average particle diameter of 80nm to 5,000nm, and the concentration of the solid content of the dispersoid particles in the dispersion is 0.1 to 50% by mass when measured by a laser diffraction method.
<6>
The dispersion liquid according to any one of <1> to <5>, wherein the mass ratio of the dispersoid particles is 1: the inorganic oxide particles and zinc cyanurate particles are contained in a proportion of 0.01 to 100, and the solid content concentration of the dispersoid particles in the dispersion is 0.1 to 50 mass%.
<7>
The dispersion according to any one of <1> to <6>, wherein the liquid medium is water or an organic solvent.
<8>
A coating composition comprising the dispersion of any one of <1> to <7> and a resin.
<9>
The coating composition according to <8>, wherein the resin is in the form of a resin emulsion, which is an oil-in-water emulsion or a water-in-oil emulsion, and which contains, as the resin, 1 or 2 or more resin components selected from the group consisting of an acrylic resin, an acrylic-styrene resin, an acrylic-silicone resin, a vinyl acetate resin, a styrene resin, an olefin resin, an ethylene-vinyl acetate resin, an ester resin, an epoxy resin, a phenol resin, an amide resin, a vinyl alcohol resin, a fluorine resin, a polyurethane resin, a melamine resin, a phthalic acid resin, a silicone resin, an alkyd resin and a vinyl chloride resin.
<10>
The coating composition according to <8>, wherein the resin is in the form of a water-soluble polymer or a colloidal dispersion, and the resin is a water-soluble resin or a colloidal dispersion containing 1 or more resin components selected from the group consisting of acrylic resins, acrylic-styrene resins, acrylic-silicone resins, vinyl acetate resins, styrene resins, olefin resins, ethylene-vinyl acetate resins, ester resins, epoxy resins, phenol resins, amide resins, vinyl alcohol resins, fluorine resins, polyurethane resins, melamine resins, phthalic acid resins, silicone resins, alkyd resins and vinyl chloride resins.
<11>
The coating composition according to any one of <8> to <10>, wherein the ratio of the solid component in the dispersion to the resin is (the solid component in the dispersion): the mass ratio of the (resin) is 1:0.1 to 20% by mass, and the total amount of solid components in the coating composition is 1 to 70% by mass.
<12>
A coating film comprising the coating composition according to any one of <8> to <11>, wherein the coating film has a thickness of 0.1 μm to 100. Mu.m.
<13>
The coating film according to <12>, which is a spin coating film, a bar coating film, a roll coating film or a dip coating film.
<14>
The method for producing a dispersion according to any one of <1> to <7>, comprising the step of mixing colloidal metal oxide particles with zinc cyanurate particles or a slurry thereof in a liquid medium using a pulverizer.
<15>
The method according to <14>, wherein the pulverizing device is a ball mill, a bead mill or a sand mill.
<16>
The method for producing a coating composition according to any one of <8> to <11>, comprising the step of mixing the dispersion liquid according to any one of <1> to <7> with the resin using a liquid dispersing machine.
<17>
The method for producing a coating composition according to <16>, wherein the liquid disperser is a stirrer, a rotary shear stirrer, a colloid mill, a roll mill, a high-pressure jet disperser, an ultrasonic disperser, a container-driven mill, a medium stirring mill or a kneader.
In the coating composition of the present invention, zinc cyanurate particles and inorganic oxide particles can be uniformly present in a coating film obtained by applying the composition to a surface to be coated, and a coating film excellent in adhesion and hardness can be obtained.
The coating additive used in the coating composition of the present invention is in the form of a dispersion liquid having high dispersion stability of both inorganic oxide particles and zinc cyanurate particles as dispersoid particles, and has high dispersibility such that no precipitate is observed even when left to stand at room temperature for several days. Further, the coating additive (dispersion liquid) obtained by dispersing the inorganic oxide particles and the zinc cyanurate particles in the liquid medium has the following effects: good stability is maintained even after the composition is mixed with a resin component such as a resin emulsion, and the workability is high in manufacturing a coating composition or the like. In the obtained coating composition, zinc cyanurate particles and inorganic oxide particles are kept in a stable dispersion state, and zinc cyanurate particles and inorganic oxide particles can be uniformly present in a coating film obtained by applying the coating composition to a surface to be coated, whereby the coating film having excellent adhesion can be obtained. Further, when a resin film such as a PET film or a substrate having high transparency such as glass is used, a coating film having excellent adhesion can be obtained while maintaining the transparency of the substrate.
The coating film of the coating composition of the present invention exhibits the functions of corrosion resistance and the like inherent in zinc cyanurate, and the inorganic oxide particles have the functions of hydrophilicity, slipperiness, insulation, thermal conductivity, photocatalytic property and the like, and also have the functions of weather resistance, light resistance, water resistance, scratch resistance, corrosion resistance of a substrate, prevention of change in color tone of a substrate and the like as a coating composition, and can be expected to contribute to prevention of deterioration of a substrate.
Drawings
Fig. 1 is a graph showing an approximate curve obtained from measurement values of Zeta potential (mV) of inorganic oxide particles relative to pH values (pH 2 to 10 (horizontal axis)) of aqueous slurries in which the inorganic oxide powder is silica powder (fumed silica (fumedsilica) a, fumed silica B, silica powder C) or titania powder (titania powder).
Detailed Description
The present invention relates to a coating composition comprising a coating additive and a resin emulsion, the coating additive comprising a dispersion liquid in which dispersoid particles comprising inorganic oxide particles and zinc cyanurate particles are dispersed in a liquid medium.
[ Coating additive ]
The coating additive used in the coating composition of the present invention comprises a dispersion liquid in which dispersion particles comprising inorganic oxide particles and zinc cyanurate particles are dispersed in a liquid medium.
In the case where the coating material additive of the present invention is composed of only a dispersion liquid in which dispersion particles including inorganic oxide particles and zinc cyanurate particles are dispersed in a liquid medium, the dispersion liquid may be treated as the coating material additive, and therefore, in this case, the coating material additive may be interpreted as the dispersion liquid in the following description.
< Inorganic oxide particles >
Examples of the inorganic oxide particles constituting the dispersoid particles include particles of an oxide of at least 1 atom selected from Si, al, ti, zr, fe, cu, zn, li, na, K, mg, ca, cs, sr, ba, B, ga, Y, nb, mo, in, sn, sb, ta, W, ge, pb, P, as, rb, bi and Ce. The particles of the inorganic oxide are particles of an oxide having a valence of 2 to 6, and as the oxide form of these atoms, SiO2、TiO2、Fe2O3、CuO、ZnO、Y2O3、ZrO2、Nb2O5、MoO3、In2O3、SnO2、Sb2O5、Ta2O5、WO3、PbO、Bi2O3、CeO2 and the like can be exemplified. These inorganic oxides may be used alone or in combination of two or more.
As a combination method, there are a method of mixing a plurality of the above inorganic oxides, a method of compounding 2 or more of the above inorganic oxides, or a method of solutionizing 2 or more of the above inorganic oxides at an atomic level. That is, the particles of the inorganic oxide may be particles of an individual oxide selected from 1 atom in the above group of atoms, particles of a composite oxide selected from 2 or more atoms in the same group, or any mixture of these particles (a mixture of individual oxide particles, a mixture of composite oxide particles, a mixture of individual oxide particles and composite oxide particles, or the like, which are collectively referred to as a mixed oxide).
Examples of the composite oxide particles include TiO 2-SnO2 composite oxide particles in which TiO 2 particles and SnO 2 particles are chemically bonded to each other at the interface, snO 2-WO3 composite oxide particles in which SnO 2 particles and WO 3 particles are chemically bonded to each other at the interface, and, SnO 2 particles and SiO 2 particles are chemically bonded to each other at their interfaces to form composite SnO 2-SiO2 composite oxide particles, snO 2 particles, WO 3 particles and SiO 2 particles are composed of SnO 2-WO3-SiO2 composite oxide particles, snO 2 particles, which are chemically bonded to each other at their interfaces, A composite oxide particle of SnO 2-MoO3-SiO2, which is composed of MoO 3 particles and SiO 2 particles having chemical bonds at the interface, a composite oxide particle of Sb 2O5 and SiO 2 particles, which is composed of Sb 2O5-SiO2, which is composed of particles having chemical bonds at the interface, The TiO 2-SnO2-ZrO2 composite oxide particles obtained by forming a solid solution of TiO 2、SnO2 and ZrO 2 at an atomic level are not limited thereto.
The inorganic oxide particles are inorganic oxide powder, colloidal inorganic oxide particles (also referred to as inorganic oxide colloidal particles), or the like, and can be used without any problem in terms of morphology.
Examples of the inorganic oxide powder include powders having a specific surface area of 1 to 800m 2/g and a bulk density of 0.03 to 3.0g/cm 3. Examples thereof include powders having a specific surface area of 10 to 700m 2/g、30～500m2/g、40～300m2/g and a bulk density of 0.03 to 1.0g/cm 3、0.05～0.8m2/g、0.05～0.5m2/g、0.05～0.2m2/g. The bulk density is defined as a ratio of the mass of the powder sample in the non-tap (loose) state to the volume of the powder including a factor of the inter-particle gap volume.
The colloidal inorganic oxide particles may be used in the form of an inorganic oxide sol in which the inorganic oxide particles are dispersed in a liquid medium.
The inorganic oxide particles can be produced by a known method, such as a liquid phase method (hydrolysis method, sol-gel method, hydrothermal method, coprecipitation method, freeze-drying method, etc.), a gas phase method (melting method, spray-drying method, gas phase reaction method (combustion hydrolysis, etc.), etc., by selecting an appropriate production method according to the kind of the inorganic oxide particles.
In the case where the inorganic oxide particles are colloidal inorganic oxide particles, the particles can be produced by a known method (for example, ion exchange method, deflocculation method, hydrolysis method, reaction method (oxidation method), or the like). The colloidal particles thus obtained may be dried and used.
Examples of the ion exchange method include a method of treating an acid salt of the above atom with a hydrogen ion exchange resin, and a method of treating a basic salt of the above atom with a hydroxyl anion exchange resin. Examples of the deflocculation method include a method in which an acid salt of the above atom is neutralized with a base or a method in which a gel obtained by neutralizing a basic salt of the above atom with an acid is washed and then deflocculated with an acid or a base. Examples of the hydrolysis method include a method of hydrolyzing an alkoxide of the above atom, and a method of hydrolyzing a basic salt of the above atom under heating and then removing an unnecessary acid. Examples of the reaction method (oxidation method) include a method of reacting the above-mentioned atomic or inorganic oxide powder with an acid (for example, hydrogen peroxide).
The inorganic oxide particles may be in the form of (surface-treated) modified inorganic oxide particles obtained by coating at least a part of the surface of the inorganic oxide particles with a coating material composed of other inorganic oxide particles with the inorganic oxide particles as a core.
In this case, the inorganic oxide particles to be the coating material may be any of the above inorganic oxides (individual oxides, composite oxides, mixed oxides), and the above known production methods may be appropriately selected for the production method.
The modified inorganic oxide particles may be produced by a conventionally known method, and examples thereof include a method in which the core inorganic oxide particles a and the other inorganic oxide particles B serving as the coating are mixed and heated. In this case, for example, the mixing of the inorganic oxide particles a as cores and the other inorganic oxide particles B as coating materials is performed at a temperature of 0 to 100 ℃, for example, at room temperature to 60 °, and the heating after the mixing may be performed at 70 to 300 ℃, for example.
Among these inorganic oxide particles (in the case of modified inorganic oxide particles, the core inorganic oxide particles) are oxide particles of at least 1 atom selected from Si, al, ti, zr, fe, cu, zn, li, na, K, mg, ca, cs, sr, ba, B, ga, Y, nb, mo, in, sn, sb, ta, W, ge, pb, P, as, rb, bi and Ce, preferably from Si, al, ti, zr, sn, cu and Zn, composite oxide particles of 2 or more atoms selected from the above, or particles of mixed oxides.
The shape of the inorganic oxide particles is not particularly limited, and is, for example, spherical, polyhedral, square, hollow, core-shell, porous, rod-like, plate-like, amorphous, or the like, and is preferably spherical, hollow, core-shell, or porous.
The average particle diameter of the inorganic oxide particles (in the modified inorganic oxide particles, the whole particles are composed of a core and a coating) can be measured by a laser diffraction method or a dynamic light scattering method.
For example, in the case where the inorganic oxide particles are in the form of the inorganic oxide powder, the measurement may be performed by a laser diffraction method in a dispersion liquid obtained by dispersing the powder in an appropriate medium. The average particle diameter of the inorganic oxide powder obtained by the laser diffraction method may be, for example, 500nm to 100. Mu.m, 1.0 μm to 80. Mu.m, or 1.0 μm to 50. Mu.m.
In addition, for example, in the case where the inorganic oxide particles are in the form of colloidal inorganic oxide particles, measurement can be performed by a dynamic light scattering method (DLS method). The average particle diameter of the colloidal inorganic oxide particles obtained by the dynamic light scattering method may be, for example, in the range of 5nm to 500nm, or may be in the range of 5nm to 200nm, or 5nm to 100nm, or 5nm to 50nm, or 3nm to 300nm, 3nm to 200nm, or 3nm to 100 nm.
As described above, the inorganic oxide particles may be used in the form of colloidal inorganic oxide particles, and the inorganic oxide particles may be dispersed in a liquid medium to form an inorganic oxide sol, and as the concentration of the inorganic oxide in the inorganic oxide sol, a concentration in the range of 0.1 to 40 mass%, or 0.1 to 20 mass%, or 0.1 to 10 mass% may be used.
As the liquid medium, a medium used in a dispersion liquid described later, that is, an aqueous medium such as water, an organic solvent such as an alcohol, a glycol, an ester, a ketone, a nitrogen-containing solvent, an aromatic solvent, or a mixed solvent of an organic solvent and water, or the like can be used.
The inorganic oxide particles may be commercially available ones, and examples thereof include, but are not limited to, the following.
Examples of the commercial products of the inorganic oxide powder include AEROSIL (registered trademark) series (silica), aeroxin Alu series (alumina), aeroxin TiO 2 series (titania), aeroxin STX series (titanium oxide (core) -silica (shell) composite, manufactured by AEROSIL (registered trademark); cab-O-SIL (registered trademark) series (silica) and SpectrAl (registered trademark) series (alumina) manufactured by Cabot corporation; CIKNanoTek (registered trademark) NanoTek (alumina, titania, tin oxide, zirconia, zinc oxide, copper oxide); sylysia (registered trademark) series (silica) of the fuji silicon chemistry (ltd); reolosil (registered trademark) series (registered trademark) from Deshan, EXCELICA (registered trademark) series (silica), and HDK (registered trademark) series (silica) from WACKER SILICONE (Inc.); AKP (registered trademark) series (alumina) manufactured by sumitomo chemical corporation; taimicron series (alumina) manufactured by Daming chemical industry Co., ltd; DISPLAL (registered trademark) series, DISPLAL (registered trademark) series (alumina) manufactured by Sasol corporation; titanium oxide and zinc oxide manufactured by Sakai chemical industry Co., ltd; titanium oxide, zinc oxide and tin oxide are produced by stone raw products (strain); zirconia manufactured by first rare element chemical industry Co., ltd; zirconia manufactured by new japanese electric works, etc.
Examples of commercial products of colloidal inorganic oxide particles include Snowtex (registered trademark) (silica sol) ST-N-40, ST-XS, ST-OXS, ST-S, T-OS, ST-30, ST-O, ST-N, ST-C, ST-30L, ST-OL, ST-OYL, ST-ZL, etc., alumina sol 100 (AS-100), same 200 (AS-200), same 520-A (AS-520A 0) (a water dispersion of alumina), nanoUse (registered trademark) (zirconia sol) ZR-30BS, same ZR-30AH, ZR-40BL, same ZR-30AL, etc.; CIKNanoTek (registered trademark) of the product NanoTek (aluminum oxide, titanium oxide, tin oxide, zirconium oxide, zinc oxide, copper oxide, solvent dispersion); titanium oxide sol produced by Shicheng (Inc.), SN-100D (antimony doped tin oxide water dispersion sol), etc.; silicadoll (registered trademark) manufactured by the chemical industry, japan, inc; ADELITE (registered trademark) AT series manufactured by ADEKA, inc.; a catalyst S series (registered trademark) manufactured by Nissan catalyst chemical Co., ltd.; quartron (registered trademark) manufactured by Hibiscus chemical industry Co., ltd; titanium oxide manufactured by Tayca, inc.; alumina sol manufactured by Chuanmin FINECHEMICALS (ltd.); needral (aqueous cerium oxide dispersion) manufactured by Kagaku chemical Co., ltd; the solar volatile catalyst is formulated into Cataloid (registered trademark) A series (alumina water dispersion sol) and Neosunveil (registered trademark) PW (titania water dispersion sol) manufactured by Kabushiki Kaisha.
When the inorganic oxide particles are in the form of inorganic oxide powder or in the form of a mixture of inorganic oxide powder and inorganic oxide colloidal particles, inorganic nitride, inorganic oxynitride, inorganic sulfide, inorganic hydride, inorganic carbide, inorganic chloride, (poorly soluble) inorganic hydroxide, poorly soluble organic polymer particles, organic polymer-coated inorganic powder, inorganic fibers (glass fibers), or inorganic clay mineral powder may be used instead of the inorganic oxide powder, and these powders and inorganic oxide powder may be used in combination.
The inorganic powder may contain at least 1 atom selected from Si, al, ti, zr, fe, cu, zn, li, na, K, mg, ca, cs, sr, ba, B, ga, Y, nb, mo, in, sn, sb, ta, W, ge, pb, P, as, rb, bi, ce, which is various atoms listed in the inorganic oxide powder (inorganic oxide particles).
The specific surface area, bulk density, shape, and average particle diameter of these powders may be those exemplified as the inorganic oxide powder.
< Zinc cyanurate particles >
Cyanuric acid is a tribasic acid and acid, neutral and basic salts can be produced by reaction with divalent zinc. For example, when the molar ratio of (zinc oxide)/(cyanuric acid) is 1.0, an acid salt corresponding to Zn (C 3N3O3 H) is formed. When the molar ratio of (zinc oxide)/(cyanuric acid) was 1.5, a neutral salt corresponding to Zn 3(C3N3O3)2 was formed. When the molar ratio of (zinc oxide)/(cyanuric acid) was 2.5, a basic salt corresponding to Zn 3(C3N3O3)2.2 ZnO was formed. These salts may contain water of crystallization, for example, 1 water salt, 2 water salt, 3 water salt may be formed.
In the present invention, zinc cyanurate particles having a molar ratio of (zinc oxide)/(cyanuric acid) of 1.0 to 5.0 can be used.
The zinc source may be zinc oxide or basic zinc carbonate, and the molar ratio in terms of zinc oxide may be used in the above molar ratio. For example, 2 kinds of zinc oxide manufactured by Sakai chemical industries, ltd.
Among them, basic salts are preferably used in the present invention, and Zn 3(C3N3O3)2·2ZnO·3H2 O can be used, for example.
In the present invention, it is preferable to use zinc cyanurate particles having a needle-like or plate-like elongated particle shape, wherein the length of the major axis of the primary particles is 400nm to 3,000nm and the length of the minor axis of the primary particles is 10nm to 300nm, and the length ratio (major axis/minor axis) of the major axis to the minor axis is 1.3 to 300, when measured by observation with a transmission electron microscope. As the zinc cyanurate particles, particles having a specific surface area of, for example, 10m 2/g～100m2/g can be used.
For example, zinc cyanurate particles having a major axis length of 400nm to 1,000nm, or 400nm to 800nm, or 400nm to 600nm of primary particles, a minor axis length of 10nm to 300nm, or 10nm to 90nm, or 30nm to 90nm of primary particles, and a length ratio (major axis/minor axis) of the major axis to the minor axis of 1.3 to 100 at this time can be preferably used. Further, the length ratio of the major axis to the minor axis may be any combination selected from 1.3 or 4.4 of the lower limit value and 12, 20, 80 or 100 of the upper limit value.
For example, zinc cyanurate particles having a major axis length of primary particles of 1,000nm to 3,000nm, or 2,000nm to 3,000nm, a minor axis length of primary particles of 80 nm to 300nm, or 100nm to 300nm, and a length ratio (major axis/minor axis) of the major axis to the minor axis of 3.3 to 37.5 can be preferably used. Further, the length ratio of the major axis to the minor axis may be any combination selected from 3.3 of the lower limit value, 20 of the upper limit value, and 37.5.
The zinc cyanurate particles may be dispersed in pure water, and the average particle diameter of the zinc cyanurate particles in the aqueous dispersion may be measured by using a laser diffraction particle size distribution measuring apparatus (for example, trade name SALD-7500nano, manufactured by shimadzu corporation).
The zinc cyanurate particles in the aqueous dispersion have an average particle diameter of 80nm to 20,000nm, as measured by a laser diffraction method.
As a method for producing zinc cyanurate particles, there are 2 production methods, namely, a method for producing a slurry in which a raw material is dispersed in water and a method for producing a solid phase in which a raw material is in a powder state.
The method for producing a slurry in which raw materials are subjected to a liquid phase reaction in a water-dispersed state is, for example, the following method: zinc oxide or basic zinc carbonate, cyanuric acid and water are prepared at a concentration of 0.1 to 10.0 mass% of cyanuric acid concentration, and the mixed slurry is wet-dispersed at a temperature of 5 to 55 ℃ using a liquid disperser, whereby a reaction and dispersion of the product are carried out to obtain a slurry (dispersion) of zinc cyanurate particles.
Further, cyanuric acid dissolved in water reacts rapidly with zinc oxide and basic zinc carbonate to promote particle growth, so zinc cyanurate particles as a product tend to become large. Therefore, the reaction is preferably carried out at 55℃or less or 45℃or less.
The wet dispersion is performed using a dispersion medium. By performing wet dispersion using a dispersion medium, mechanical energy generated by collision of the dispersion medium can cause mechanochemical reaction of cyanuric acid with at least one selected from zinc oxide and basic zinc carbonate. The mechanochemical reaction is a chemical reaction in which zinc oxide, basic zinc carbonate, and cyanuric acid are chemically reacted by applying mechanical energy thereto from various aspects by collision of a dispersion medium.
Examples of the dispersion medium include stabilized zirconia beads, silica glass beads, soda lime glass beads, alumina beads, and mixtures thereof. In view of contamination caused by the dispersion medium being broken by collision of the dispersion medium with each other, glass beads or stabilized zirconia beads are preferably used as the dispersion medium. The size of the dispersion medium may be, for example, 0.1 to 10mm in diameter, and preferably 0.5 to 2.0mm in diameter. When the diameter of the dispersion medium is less than 0.1mm, collision energy between the pulverization media is small, and mechanochemical reaction tends to be weakened. In addition, if the diameter of the dispersion medium is larger than 10mm, collision energy between the dispersion media becomes excessive, and the dispersion medium breaks up to cause more pollution, which is not preferable.
The apparatus (pulverizing apparatus) for wet dispersion using the dispersion medium is not particularly limited as long as it is an apparatus capable of causing mechanochemical reaction of zinc oxide and/or basic zinc carbonate with cyanuric acid by adding the mixed slurry to a container into which the dispersion medium is charged and then agitating to collide the dispersion medium with zinc oxide, basic zinc carbonate and/or cyanuric acid. Examples of the method include a ball mill, a bead mill, and a sand mill such as a sand mill (AIMEX, manufactured by Kagaku Kogyo Co., ltd.), apexMill ((Kyowa Kagaku Kogyo Co., ltd.), attritor mill (manufactured by Japanese coke industry Co., ltd.), and a pearl mill (AshizawaFinetech, manufactured by Kogyo Co., ltd.), and the number of revolutions, reaction time, etc. of a device for stirring the dispersion medium may be appropriately adjusted in accordance with a desired particle size, etc.
In the obtained zinc cyanurate particle dispersion, the zinc cyanurate particles are contained in the dispersion (slurry) as a solid component thereof in the range of 0.10 to 50 mass%, 0.1 to 20 mass%, 0.1 to 10 mass%, or 0.1 to 5 mass%.
In order to reduce the particle size of the obtained zinc cyanurate particles, the zinc cyanurate particles may be subjected to a pulverization treatment step using the above pulverization treatment apparatus. The rotation speed, reaction time, etc. of the device for stirring the dispersion medium may be appropriately adjusted in accordance with the desired particle diameter, etc.
The zinc cyanurate particles obtained by this production method have a major axis length of 100nm to 800nm, a minor axis length of 10nm to 60nm, a length ratio (major axis/minor axis) of 5 to 25, and an average particle diameter of 80nm to 900nm when measured by a laser diffraction method, for example, when measured by observation with a transmission electron microscope. The specific surface area of the zinc cyanurate particles obtained by drying the aqueous slurry of zinc cyanurate particles at 110℃was 10m 2/g～100m2/g.
In addition, the raw materials in powder state solid phase reaction production method, for example, in the closed or open under 30 ~ 300 ℃ heating treatment method, the mixed powder is composed of mesh 1,000 μm sieve residues below 1% zinc oxide, cyanuric acid and water, zinc oxide relative to cyanuric acid mole ratio is 2 ~ 3, and mixed powder water content is 9 ~ 18 mass%.
The obtained zinc cyanurate particles contain about 10% by mass of water, and therefore, are subjected to a heat treatment under open conditions to remove water and form zinc cyanurate particles having a water content of less than 1.0% by mass (commercially available as, for example, trade name StarFine manufactured by Nikko chemical Co., ltd.) and can be used in a dispersion (paint additive) described later. In the case of industrial mass production, the heat treatment is preferably performed using a powder mixer having a mixing unit and a heating unit. Specific examples thereof include a heated reaction tank capable of stirring and mixing in an open or closed type, such as a vibration dryer, a henschel mixer, luo Dige mixer (LoedigeMixer), a Nauta conical screw mixer, and a rotary kiln.
In order to reduce the particle size of the obtained zinc cyanurate particles, the zinc cyanurate particles may be subjected to a pulverization treatment step using the above pulverization treatment apparatus. The rotation speed, reaction time, etc. of the device for stirring the dispersion medium may be appropriately adjusted in accordance with the desired particle diameter, etc.
In the zinc cyanurate particles obtained by the production method, for example, the screen residue having a mesh size of 400 μm is less than 10% by mass, the length of the major axis of the primary particles is 400nm to 3,000nm and the length of the minor axis of the primary particles is 10nm to 300nm when measured by a transmission electron microscope, the length ratio (major axis/minor axis) of the major axis to the minor axis is 1.3 to 300, and the average particle diameter when measured by a laser diffraction method is 0.5 μm to 20 μm. The specific surface area of the obtained zinc cyanurate particles is, for example, 10m 2/g～100m2/g.
The surface charge of the obtained zinc cyanurate particles has a negative charge in the aqueous system at a pH value in the range of 3 to 10. Therefore, the aqueous anticorrosive paint can be obtained stably, with good dispersibility in water in the acidic to alkaline region, and good compatibility with synthetic resins, emulsions, and the like when preparing the aqueous anticorrosive paint (paint composition, and the like).
< Method for producing dispersion (coating additive) >)
The method for producing the dispersion is not particularly limited, and the dispersion can be obtained, for example, by a step of mixing inorganic oxide particles with zinc cyanurate particles or a slurry thereof in a liquid medium using a pulverizing device. When the inorganic oxide particles are inorganic oxide particles, they may be subjected to a pre-pulverization treatment, and mixed with zinc cyanurate or a slurry thereof in a liquid medium using a pulverizing device to form a dispersion.
As a device for mixing inorganic oxide particles and zinc cyanurate particles to obtain a dispersion, i.e., a coating additive, the same device (pulverizing device, dispersion medium) as that for wet dispersion of zinc cyanurate using the above-mentioned dispersion medium can be used, specifically, A ball mill, a bead mill, a sand mill, etc. such as a sand mill (manufactured by AIMEX Co., ltd.), apexMill ((manufactured by Guangdong Metal & machinery Co., ltd.), attritor mill (manufactured by Japanese coke Co., ltd.), and a pearl mill (manufactured by Ashizawa Finetech Co., ltd.) may be used.
In the dispersion (coating additive) obtained by dispersing the obtained dispersion particles comprising the inorganic oxide particles and zinc cyanurate particles in a liquid medium, the average particle diameter of the dispersion particles when measured by a laser diffraction method may be, for example, 80nm to 5,000nm, 80nm to 2,000nm, 200nm to 5,000nm, 80nm to 1,000nm or 10nm to 500nm.
In the case where the inorganic oxide particles are in the form of an inorganic oxide powder, the average particle diameter of the dispersoid particles when measured by a laser diffraction method in a dispersion liquid obtained by dispersing the dispersoid particles containing the obtained inorganic oxide powder and zinc cyanurate particles in a liquid medium may be, for example, 200nm to 5,000nm, 300nm to 5,000nm, 1,000nm to 3,000 or 1,000nm to 2,000nm.
In the dispersion (coating additive), the inorganic oxide particles and the zinc cyanurate particles are in the form of inorganic oxides: the mass ratio of zinc cyanurate may be, for example, 1:0.01 to 100, 1:0.1 to 10 or 1:1 to 10. In the dispersion (coating additive), the concentration of the solid component (solid component of the dispersion particles) obtained by adding the inorganic oxide particles and the zinc cyanurate particles together may be, for example, 0.1 to 50 mass%, 0.1 to 30 mass%, 0.1 to 20 mass%, or 0.1 to 10 mass%.
The type B viscosity of the dispersion (coating additive) may be, for example, 1 to 500 mPas, 5 to 500 mPas, 10 to 300 mPas, or 50 to 300 mPas.
Further, since zinc cyanurate is dissolved in an acidic liquid, when zinc cyanurate particles and inorganic oxide particles are mixed, it is preferable to perform a mixing operation (wet grinding treatment) of these particles by adjusting the pH of the liquid to be alkaline to neutral. In addition, the Zeta potential (Zeta potential) of the zinc cyanurate particles is-10 mV to-1 mV when the pH value is alkaline to neutral.
In addition, when inorganic oxide particles having an isoelectric point in the pH range of 5 to 12 and having a Zeta potential of-80 mV to +80mV are used to obtain the above dispersion, the pH is adjusted so that the pH range is-5 mV to-80 mV, whereby a dispersion excellent in dispersibility can be obtained.
Or when the dispersion is obtained, the dispersion having excellent dispersibility can be obtained by using inorganic oxide particles having no isoelectric point at a pH of 5 to 12 and having a Zeta potential of-5 mV to-50 mV in the pH range.
When inorganic oxide particles having no isoelectric point at a pH of 5 to 12 and having a Zeta potential of +5mV to +80mV in the pH range are mixed with zinc cyanurate particles to obtain the above dispersion, the concentration of the dispersoid particles containing the inorganic oxide particles and the cyanuric acid particles is adjusted to 0.1 to 20 mass% or 0.1 to 10 mass%, whereby a dispersion excellent in dispersibility can be obtained.
For example, in the case where the inorganic oxide particles mixed with the zinc cyanurate particles are silica powder in the form of inorganic oxide powder, the concentration of the dispersoid particles containing the silica powder and the zinc cyanurate particles is 0.1 to 20% by mass, and the mass ratio of silica to zinc cyanurate (silica: zinc cyanurate) is adjusted to 1: and 0.1 to 10, and mixing the materials. In the case of titanium oxide powder, when the titanium oxide powder is mixed with zinc cyanurate particles in a region closer to the alkaline point than the isoelectric point, the concentration of dispersoid particles including titanium oxide powder and zinc cyanurate particles is 0.1 to 20% by mass, and the mass ratio of titanium oxide to zinc cyanurate (titanium oxide: zinc cyanurate) is adjusted to 1:0.1 to 10, wherein in the case of an alumina powder, when the alumina powder is mixed with zinc cyanurate particles in an acidic region closer to the isoelectric point, the concentration of dispersoid particles comprising the alumina powder and zinc cyanurate particles is 0.1 to 10% by mass, and the mass ratio of alumina to zinc cyanurate (alumina: zinc cyanurate) is adjusted to 1:1 to 10, wherein in the case of the zirconia powder, when the zirconia powder is mixed with the zinc cyanurate particles in a region closer to the isoelectric point than the isoelectric point, the concentration of the dispersoid particles containing the zirconia powder and the zinc cyanurate particles is 0.1 to 20% by mass, and the mass ratio of the zirconia to the zinc cyanurate (zirconia: zinc cyanurate) is adjusted to 1:0.1 to 10, and respectively carrying out mixing operation.
In addition, for example, in the case where the inorganic oxide particles mixed with the zinc cyanurate particles are alumina sol in the form of colloidal oxide particles [ metal oxide particles (metal oxide sol) ] and when the inorganic oxide particles are mixed with the zinc cyanurate particles in an acidic region than the isoelectric point, the concentration of the dispersed particles including the alumina particles and the zinc cyanurate particles is 0.1 to 20% by mass, and the mass ratio of the alumina to the zinc cyanurate (alumina: zinc cyanurate) is adjusted to 1:1 to 10, and mixing the materials. In the case of the zirconia sol, when the zirconia sol is mixed with zinc cyanurate particles in a region closer to the alkaline point than the isoelectric point, the concentration of the dispersed particles including the zirconia particles and the zinc cyanurate particles is 0.1 to 30 mass%, and the mass ratio of the zirconia to the zinc cyanurate (zirconia: zinc cyanurate) is adjusted to 1:0.1 to 10, wherein in the case of a titania sol, when the titania sol is mixed with zinc cyanurate particles in a basic region closer to the isoelectric point, the concentration of dispersoid particles comprising titania particles and zinc cyanurate particles is 0.1 to 30 mass%, and the mass ratio of titania to zinc cyanurate (titania: zinc cyanurate) is adjusted to 1:0.1 to 10, wherein in the case of a tin oxide sol, when the tin oxide sol is mixed with zinc cyanurate particles in a region closer to the isoelectric point than the isoelectric point, the concentration of dispersoid particles comprising tin oxide particles and zinc cyanurate particles is 0.1 to 30% by mass, and the mass ratio of tin oxide to zinc cyanurate (tin oxide: zinc cyanurate) is adjusted to 1:0.1 to 10, and respectively carrying out mixing operation.
In the dispersion (coating additive) obtained by dispersing the dispersion particles containing the obtained inorganic oxide particles and zinc cyanurate particles in a liquid medium, the liquid medium may be selected from an aqueous medium and an organic solvent, and the aqueous medium may be replaced with the organic solvent by evaporation using a rotary evaporator or the like.
The aqueous medium may be water.
As the organic solvent, alcohols, glycols, esters, ketones, nitrogen-containing solvents, aromatic solvents can be used. Examples of the solvent include organic solvents such as methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, acetone, methyl ethyl ketone, dimethylformamide, N-methyl-2-pyrrolidone, toluene, xylene, and dimethylethane. In addition, a reactive diluent solvent containing polyethylene glycol, silicone oil, a vinyl group or an epoxy group having radical polymerization, or the like may be used.
Furthermore, the surface of the inorganic oxide particles may also be treated with a silane coupling agent such as tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxydiphenylsilane, N-propyltrimethoxysilane, N-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, octyltriethoxysilane, trimethylmonoethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-epoxypropoxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, N-2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-epoxypropoxypropylmethyltriethoxysilane, 3-glycidoxypropyl silane, 3-methacryloxypropylamino-N-2- (3-methoxy) amino-ethyl) -amino-propyl silane, 3-glycidoxypropylsilane, 3-acryloxypropyl trimethoxysilane, vinyl triethoxysilane, 3-isocyanatopropyl triethoxysilane, hexamethyldisilazane, and the like.
Furthermore, the object of the present invention comprises: the dispersion liquid in which the dispersion liquid containing inorganic oxide particles and zinc cyanurate particles is dispersed in a liquid medium is a system in which the inorganic oxide particles are the inorganic oxide powder. That is, the object of the present invention is a dispersion in which dispersoid particles containing inorganic oxide powder having a specific surface area of 1 to 800m 2/g and a bulk density of 0.03 to 3.0g/cm 3 and zinc cyanurate particles are dispersed in a liquid medium.
As described above, the inorganic oxide powder is a powder of an oxide of at least 1 atom selected from Si, al, ti, zr, fe, cu, zn, li, na, K, mg, ca, cs, sr, ba, B, ga, Y, nb, mo, in, sn, sb, ta, W, ge, pb, P, as, rb, bi and Ce.
The inorganic oxide powder and zinc cyanurate particles contained in the present dispersion, the types and average particle diameters thereof, the production method (apparatus, procedure, etc.), the mixing ratio in the dispersion, the types of liquid media, and the like are as described above in the description of the inorganic oxide particles, the cyanuric acid particles, and the like.
The average particle diameter, solid content concentration, and method of producing the dispersion of the present dispersion are also as described above. Preferably, the dispersoid particles are particles having an average particle diameter of 200nm to 5,000nm, and the concentration of the solid content of the dispersoid particles in the dispersion is 0.1 to 50% by mass, as measured by a laser diffraction method.
The dispersion may be mixed with a resin emulsion described later to produce a coating composition.
Furthermore, the object of the present invention also includes: the inorganic oxide particles in which dispersoid particles including inorganic oxide particles and zinc cyanurate particles are dispersed in the dispersion are colloidal metal oxide particles excluding particles mainly composed of colloidal silica.
That is, the present invention is directed to a dispersion in which dispersoid particles including colloidal metal oxide particles and zinc cyanurate particles are dispersed in a liquid medium, the colloidal metal oxide particles excluding particles mainly composed of colloidal silica.
Among the above colloidal inorganic oxide particles, the above colloidal metal oxide particles are particles containing colloidal silica as a main component, that is, particles containing at least 1 atom selected from Al, ti, zr, fe, cu, zn, li, na, K, mg, ca, cs, sr, ba, B, ga, Y, nb, mo, in, sn, sb, ta, W, ge, pb, P, as, rb, bi and Ce.
The colloidal metal oxide particles contained in the present dispersion are described in the description of the inorganic oxide particles except that particles mainly composed of colloidal silica are excluded from the colloidal inorganic oxide particles, and the types, average particle diameters, production methods, proportions in the dispersion, and the like thereof are described in the description of the inorganic oxide particles. The type of zinc cyanurate particles, the average particle diameter, the production method (apparatus, procedure, etc.), the mixing ratio in the dispersion, the type of the liquid medium, and the like are also as described above.
The average particle diameter, solid content concentration, and method of producing the dispersion of the present dispersion are also as described above. Preferably, the dispersoid particles are particles having an average particle diameter of 80nm to 2,000nm, and the concentration of the solid content of the dispersoid particles in the dispersion is 0.1 to 50% by mass, as measured by a laser diffraction method.
The colloidal particles containing no colloidal silica as a main component contained in the colloidal metal oxide particles include colloidal particles composed of only silica (SiO 2) and colloidal particles containing silica as a main component (for example, a proportion of 50 mass%) constituting the particles, and these particles are excluded in this embodiment. However, silica may be contained as a component of the composite oxide particles and as a component of the coating material to be mentioned in the modified inorganic oxide particles, and in this case, the silica content may be more than 0 mass% and 30 mass% or less with respect to the composite oxide particles and the modified inorganic oxide particles.
The dispersion may be mixed with a resin emulsion described later to produce a coating composition.
[ Resin ]
Examples of the resin used in the coating composition of the present invention include 1 or 2 or more resins selected from the group consisting of acrylic resins, acrylic-styrene resins, acrylic-silicone resins, vinyl acetate resins, styrene resins, olefin resins (vinyl resins, propylene resins), ethylene-vinyl acetate resins, ester resins, epoxy resins, phenol resins, amide resins, vinyl alcohol resins, fluorine resins, polyurethane resins, melamine resins, phthalic acid resins, silicone resins, alkyd resins, and vinyl chloride resins.
Further, for example, the "acrylic resin" refers to a resin having a structure derived from an acrylic acid ester (and a methacrylic acid ester) in the resin, and may have a structure derived from another polymerizable compound in the resin. As an example, an acrylic resin in which a polysiloxane is compounded (referred to as "acrylic resin (polysiloxane compounding)") and an acrylic resin having a structure derived from vinyl acetate (referred to as "acetic acid-acrylic resin") can be classified as acrylic resins. In addition, there are resins having structures derived from epoxy and from ester (referred to as "epoxy-ester resins"), which can be classified as epoxy resins and ester resins, but are classified as epoxy resins in the present specification.
For example, "acrylic-styrene resin" may be described as "styrene-acrylic resin", and may be regarded as a synonym when the names of the resins before and after the substitution are made.
[ Morphology of resin ]
In general, examples of the form (classification) of the resin component used in the coating material include water-soluble polymers (also simply referred to as water-soluble polymers and water-soluble resins) and water-dispersible polymers. Examples of the form of the water-dispersible polymer include colloidal dispersion and resin emulsion, and examples of the resin emulsion include oil-in-water emulsion and water-in-oil emulsion. The resin composition of the present invention may be used in various forms as described above, and various resins as described above may be used as the resin component.
In general, water-soluble polymers having a particle size of, for example, 0.01 μm or less and a molecular weight of 10 3～104 are used for coating compositions to give films having high gloss and are used for applications requiring high-temperature sintering. The colloidal dispersion has a particle diameter of 0.01 to 0.1 μm and a molecular weight of 10 4～106, and can give a coating film having high gloss when used in a coating composition, and is used for applications requiring high-temperature sintering and applications requiring normal-temperature drying. The resin emulsion has a particle size of, for example, 0.05 μm or more, a molecular weight of 10 3 or more, and a high drying property of the coating composition, and can give a coating film having high water resistance, and is used for applications requiring sintering and applications requiring normal-temperature drying.
The form of the resin may be appropriately selected according to the application of the coating composition, and from the viewpoint of stabilization and handling of the coating composition, it is preferable to use it in the form of a resin emulsion, and more preferably in the form of an oil-in-water resin emulsion (also referred to as an aqueous resin emulsion).
Among them, an aqueous resin emulsion having a pH of 7 to 10 or 3 to 6.5, a solid content (ratio of resin components) of 30 to 65% by mass in the resin emulsion, and a viscosity of about 20 to 20,000 mPas can be exemplified as a preferable resin emulsion.
Examples of the acrylic resin emulsion include trade names Movinyl DM772, movinyl 6520, movinyl 6530 (the above is an anionic resin emulsion) manufactured by Japan Coating Resin, and trade names VONCOAT-418 EF manufactured by DIC (ltd); examples of the acrylic (polysiloxane complex) resin emulsion which can be classified as an acrylic resin emulsion include CERANATE WHW-822 manufactured by DIC (incorporated); as the acetic acid-acrylic resin emulsion which can be classified as the acrylic resin emulsion as well, VONCOAT CF-2800 manufactured by DIC (Inc.) and the like are mentioned.
Examples of the acrylic-styrene resin emulsion include trade names Movinyl DM and Movinyl 749E, LDM6740 (the above is an anionic resin emulsion) manufactured by Japan Coating Resin, and VONCOAT CG-8680 manufactured by DIC, etc.
Examples of the acrylic-silicone resin emulsion include LDM7523 (anionic resin emulsion) manufactured by Japan Coating Resin, and VONCOAT SA-6360 manufactured by DIC.
Examples of the vinyl acetate resin emulsion include a product name Movinyl (nonionic resin emulsion) manufactured by Japan Coating Resin, a product name POLYSOLS-65 manufactured by Showa electric, inc.
Examples of the ethylene-vinyl acetate resin emulsion include a product name Movinyl E (nonionic resin emulsion) manufactured by Japan Coating Resin (ltd).
Examples of the ester resin emulsion include Elitel KA-3556 manufactured by Unitika < Co., ltd.
Examples of the epoxy resin emulsion include those sold under the trade names EPICLON H-502-42W manufactured by DIC Co., ltd; examples of the epoxy-ester resin emulsion that can be classified as an epoxy resin emulsion include WATERSOL EFD-5530 manufactured by DIC corporation.
Examples of the olefin (vinyl) resin emulsion include PE-381 manufactured by Kagaku chemical Co., ltd.
As the fluorine-based emulsion, SIFCLEARF-104 manufactured by E-TEC, inc. and the like are mentioned.
Examples of the polyurethane resin emulsion include trade names HYDRAN HW-171 manufactured by DIC (incorporated herein by reference) and trade names NeoRez R-967 manufactured by DSM Coating Resins.
As the alkyd resin emulsion, WATERSOL S-118 manufactured by DIC (Kagaku Kogyo Co., ltd.) and the like are mentioned.
As the vinyl chloride resin emulsion, vinyblan VE-701 manufactured by Nissan chemical industries, ltd.
Among the above-mentioned resin emulsions, preferable examples include acrylic resin emulsions, acrylic-styrene resin emulsions, acrylic-silicone resin emulsions, vinyl acetate resin emulsions, epoxy resin emulsions, and urethane resin emulsions.
The coating composition of the present invention may further contain a slurry of an inorganic oxide powder.
Examples of the inorganic oxide powder used in the slurry include particles in powder form among inorganic oxide particles used in the coating additive. The atomic species of the inorganic oxide particles used for the coating additive (dispersion) may be the same as or different from the atomic species of the inorganic oxide powder used for the slurry, and 1 or more kinds of the inorganic oxide powder used for the slurry may be used. In addition, the medium used for the slurry may be the same medium as the liquid medium used for the dope additive.
The slurry may be prepared by mixing the inorganic oxide powder with a liquid medium using a liquid dispersing machine described later, and may be mixed using a pulverizing device similar to the above-described device for wet dispersion of zinc cyanurate using a dispersing medium, or may be used in combination.
The slurry of the inorganic oxide powder may have a solid content concentration of 0.1 to 50% by mass, for example, 0.1 to 30% by mass or 0.1 to 20% by mass.
The above-mentioned coating composition can be prepared such that the ratio of the solid component in the dispersion (coating additive) to the solid component in the slurry of the resin (resin component in emulsion in the case of resin emulsion) and the inorganic oxide powder is as follows: (resin component in emulsion in the case of resin emulsion)): the mass ratio of (solid components in the slurry) was 1:0.1 to 20:0 to 1, for example 1:0.1 to 15:0 to 1 or 1:0.1 to 10:0 to 0.5, and the proportion of the total solid content in the coating composition is 1 to 70% by mass, 1 to 50% by mass, or 1 to 30% by mass. In the case of a slurry containing an inorganic oxide powder, the lower limit of the ratio of the solid content in the slurry may be 0.1 to the solid content (mass ratio) 1 in the dispersion (coating additive).
The coating composition of the present invention can be obtained by subjecting the inorganic oxide particles, zinc cyanurate particles (coating additive), and the resin (for example, resin emulsion or the like) and, when used, the slurry of the inorganic oxide powder to a step of mixing using a liquid disperser.
Examples of the liquid dispersing machine used for producing the coating composition include a stirrer, a rotary shear type stirrer, a colloid mill, a roll mill, a high-pressure jet type dispersing machine, an ultrasonic dispersing machine, a container-driven type mill, a medium stirring mill, and a kneader.
The stirrer is the simplest dispersing device, and can disperse the object by the speed fluctuation near the stirring blade and the collision against the stirring blade.
The rotary shear mixer is a device that disperses a target object by passing through a narrow gap between a high-speed rotary blade and an outer cylinder, and can disperse the target object by a shear flow and a speed variation in the gap.
The colloid mill may disperse the object by a shear flow in a narrow gap between a high-speed rotating disk and a fixed disk.
The roll mill may disperse the object by using shearing force and compression force of gaps between 2 or 3 rotating rolls.
The high-pressure jet dispenser may disperse the target by jetting the treatment liquid at a high pressure so as to collide with the fixing plate and the treatment liquid with each other.
The ultrasonic disperser can disperse the target object by ultrasonic vibration.
The container-driven mill is a device for dispersing a target object by collision and friction of a medium (ball) inserted into a fixed container, and includes a rotary mill, a vibration mill, and a planetary mill.
The medium stirring mill is a device for dispersing a target by collision force and shearing force of a medium using balls or beads as a medium, and examples thereof include Attritor mills and bead mills.
The coating composition obtained by mixing the inorganic oxide particles, the dispersion of zinc cyanurate particles (coating additive) and the resin (slurry of inorganic oxide powder when used) can be produced, for example, at a pH of 7 to 10. Further, by adding ammonia water as an alkaline component in a proportion of 100ppm to 10,000ppm, the pH can be adjusted to a range of 10 to 11. The coating composition mixed with a resin (for example, a resin emulsion) having a pH of 3 to 6.5 can be produced in a range of pH 3 to 6.5. When the inorganic oxide particles and the zinc cyanurate particles are mixed (when preparing the dispersion liquid), the dispersion liquid is preferably adjusted to be alkaline to neutral, and the coating composition can be produced and used under alkaline to acidic conditions.
[ Other additives ]
The coating composition of the present invention may contain, in addition to the dispersion of the inorganic oxide particles and zinc cyanurate particles and the resin (slurry of the inorganic oxide powder when used), additives conventionally used in conventional coatings (compositions), for example, a catalyst for curing, a pigment, a leveling agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a plasticizer, a surfactant, and the like, which are used in the art, in addition to the conventional coating composition, in a range not impairing the effect of the present invention.
In the coating composition of the present invention, for example, when it is desired to further improve the hardness of the coating film, a curing agent, a thickener, a dispersant, a defoaming agent may be added as optional components, and the content of the inorganic oxide particles may be appropriately adjusted (increased), the resin type of the resin emulsion may be selected from fluorine-based, epoxy-based and the like (or these resin types may be mixed together), and the composition and the compounding ingredients may be appropriately adjusted according to the purpose.
The type B viscosity of the coating composition may be, for example, 10 mPas to 100 mPas. In addition, depending on the application of the coating composition and the substrate, for example, in the case where it is desired to increase the film thickness, a resin type of high viscosity (for example, a resin type as a resin emulsion) may be selected, and the viscosity may be increased by adding a thickener.
[ Applicable site ]
The surface to be coated, that is, the coated surface of the coating composition of the present invention is not particularly limited, and examples thereof include aluminum substrates, iron substrates, copper substrates, gold substrates, silver substrates, platinum substrates, mirror materials, glass substrates, silicon substrates, wood, resin films, and resin molded articles.
For these substrates, a coating composition may be applied and dried, and subjected to an appropriate curing treatment (heat curing/photo curing) to form a coating film. The film thickness of the coating film of the coating composition also varies depending on the viscosity of the coating composition, and may be set to a range of 0.1 μm to 100 μm, for example. The coating film is not particularly limited as long as it has a hardness to such an extent that no defects occur in the processing step of the base material, and the hardness thereof can be appropriately set according to the type of the substrate.
Examples of the coating method include spin coating, bar coating, roll coating, dip coating, and the like, and spin coating, bar coating, roll coating, and dip coating can be obtained by these methods.
Hereinafter, examples of applications of the respective substrates, preferred types of resins in the coating composition, and drying conditions after the substrate is coated are exemplified, but the present invention is not limited thereto.
Aluminum substrates are used for applications such as building materials, home appliances, and interior panels.
Examples of the type of the resin in the preferable coating composition for the aluminum substrate include acrylic resins (including acrylic (silicone composite) resins, acetic acid-acrylic resins, and the like), acrylic-styrene resins, acrylic-silicone resins, vinyl acetate resins, olefin resins (vinyl resins, and the like), ester resins, epoxy resins (including epoxy-ester resins, and the like), fluorine resins, polyurethane resins, alkyd resins, vinyl chloride resins, and the like.
The drying conditions may be 200 to 300 ℃ (heat drying).
The iron-based substrate includes not only a substrate composed of only iron (Fe), but also a substrate containing iron (Fe) and other elements (carbon (C), silicon (Si), manganese (Mn), chromium (Cr), molybdenum (Mo), phosphorus (P), sulfur (S), tungsten (W), vanadium (V), nickel (Ni), aluminum (Al), niobium (Nb), nitrogen (N), and the like).
The iron-based base material is used for, for example, building materials, structures, home appliances, machines, etc. (steel sheet type: stainless steel sheet, mild steel sheet, galvanized steel sheet, electromagnetic steel sheet, etc.).
Examples of the type of resin in the preferable coating composition for the iron-based substrate include acrylic resins (also including acrylic (silicone composite) resins, acetic acid-acrylic resins, and the like), acrylic-styrene resins, acrylic-silicone resins, vinyl acetate resins, styrene resins, olefin resins (vinyl resins, and the like), ester resins, epoxy resins, fluorine resins, polyurethane resins, alkyd resins, and the like.
The drying conditions may be 20℃to 400℃and may be normal temperature drying or heat drying.
Copper-based/silver-based substrates also include substrates that have been surface treated with a metal.
Copper-based and silver-based substrates are used for applications such as electronic materials (substrates, wires, bonding wires), electromagnetic wave shields, wires, and the like.
Examples of the type of resin in the coating composition preferably used for the copper-based/silver-based substrate include acrylic resins (also including acrylic (silicone composite) resins, acetic acid-acrylic resins, etc.), acrylic-styrene resins, vinyl acetate resins, styrene resins, olefin resins (vinyl resins, acrylic resins, etc.), phenol resins, epoxy resins, fluorine resins, polyurethane resins, etc.
Further, examples of the drying/curing conditions include curing by ultraviolet irradiation, electron beam irradiation, and curing by thermal polymerization (40 to 230 ℃).
Gold-based substrates also include substrates that have been surface treated with metal.
Gold-based substrates are used for electronic materials (ICs, LSIs, bonding wires for transistors) and the like.
Examples of the type of resin in the coating composition preferably used for the gold-based substrate include acrylic resins, styrene resins, olefin resins (vinyl resins, propylene resins, etc.), epoxy resins, fluorine resins, and the like.
Further, examples of the drying/curing conditions include curing by ultraviolet irradiation, electron beam irradiation, and curing by thermal polymerization (40 to 80 ℃).
Platinum-based substrates also include substrates that have been surface treated with a metal.
Platinum-based substrates are used for applications such as sensors, electrodes, catalysts, and the like.
The resin type in the preferable coating composition for platinum-based base material includes fluorine-based resin, polyurethane-based resin, and the like.
The drying condition may be 100℃to 400℃and the drying may be performed by heating.
The mirror material is used for mirrors and the like.
Examples of the type of resin in the coating composition preferably used for the mirror material include acrylic resins, phenolic resins, alkyd resins, ester resins, epoxy resins, and urethane resins.
The drying condition may be 150 to 200 ℃ (heat drying).
Glass substrates are used in smart phones, solar cells, semiconductors, building materials, windows, and other applications.
Examples of the type of resin in the preferred coating composition for glass substrates include acrylic resins, phenolic resins, fluorine resins, epoxy resins, silicone resins, and the like.
The drying condition may be 80℃to 400℃and the drying may be performed by heating.
Silicone substrates are used for solar cells, semiconductors, and the like.
Examples of the type of resin in the preferred coating composition for the silicone base material include acrylic resins, ester resins, urethane resins, styrene resins, amide resins, vinyl alcohol resins, and vinyl acetate resins.
Further, examples of the drying/curing conditions include curing by ultraviolet irradiation, electron beam irradiation, and curing by thermal polymerization (100 to 300 ℃).
Wood is used for building materials, furniture and the like.
Examples of the type of resin in the preferable coating composition for wood include acrylic resins (including acetic acid-acrylic resins and the like), acrylic-styrene resins, vinyl acetate resins, olefin resins (vinyl resins and the like), phenol resins, ester resins, epoxy resins, fluorine resins, polyurethane resins, silicone resins, alkyd resins and the like.
The drying conditions may be 20 to 50℃or 20 to 100℃for drying by heating.
Examples of the resin type in the resin film/resin molded article include epoxy, melamine, polyurethane, polyimide, polyamideimide, polyethylene, polypropylene, teflon (registered trademark) (polytetrafluoroethylene), acrylic, acrylonitrile Styrene (AS), acrylonitrile Butadiene Styrene (ABS), polyvinyl chloride, polycarbonate, polyester, PET, and cycloolefin.
Resin films/resin molded articles are used for smart phones, agricultural films, electronic materials (substrates and seals), and the like.
Examples of the type of resin in the preferred coating composition for the resin film/resin molded article include acrylic resins (also including acrylic (silicone composite) resins, acetic acid-acrylic resins, and the like), acrylic-styrene resins, vinyl acetate resins, styrene resins, olefin resins (vinyl resins, acrylic resins, and the like), phenol resins, epoxy resins, polyurethane resins, fluorine resins, alkyd resins, and the like.
The drying/curing conditions include ultraviolet irradiation, electron beam irradiation, and thermal polymerization (40 to 80 ℃) and may be set to 40 to 60 ℃ by heat drying.
The coating composition comprising a resin (e.g., a resin emulsion) and a dispersion containing particles of an inorganic oxide powder and zinc cyanurate particles dispersed in a liquid medium, and a coating composition comprising a resin (e.g., a resin emulsion) and a dispersion containing particles of a colloidal metal oxide other than particles containing colloidal silica as a main component and zinc cyanurate particles dispersed in a liquid medium, can be used as the resin (type of resin, form of resin), the ratio of the components in the composition, the method (apparatus, order, etc.) for producing the composition, other components, additives, and applicable sites, respectively, to those exemplified in the coating composition.
Examples
The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples.
The components used in the dispersion and the coating composition were prepared by the following steps, and the average particle diameters of the inorganic oxide particles and the dispersoid particles, the specific surface area of the inorganic oxide powder, the loose bulk density, the Zeta potential, and the viscosity of the coating composition were measured.
(1) The following inorganic oxide particles were prepared.
Colloidal silica: aqueous carbon dioxide silica sol (trade name SnowtexST-N-40, manufactured by Nissan chemical Co., ltd., specific surface area 122.5m 2/g by BET method, pH 9.4, solid content 40.4% by mass, and average particle diameter 34.5nm by dynamic light scattering method)
Silica powder: fumed silica A (product name: AEROSIL (registered trademark) 300, manufactured by AEROSIL (Co., ltd.) of Japan) and specific surface area 253.2m 2/g by BET method)
Silica powder: fumed silica B (product name: AEROSIL (registered trademark) 50 manufactured by AEROSIL (Co., ltd.) and specific surface area 45.8m 2/g by BET method)
Silica powder: silica powder C (specific surface area 229.7m 2/g by BET method and trade name Sylysia380 manufactured by Fuji silicon Co., ltd.)
Titanium dioxide powder: titanium dioxide powder (Sakai chemical industry Co., ltd., trade name R-25, specific surface area 44.2m 2/g by BET method and surface treatment by Al 2O3)
Aqueous alumina sol (colloidal alumina) (trade name AS-200, manufactured by Nissan chemical Co., ltd., pH 4.6, solid content 10.3% by mass, and average particle diameter of 244nm by dynamic light scattering)
Aqueous zirconia sol (colloidal zirconia) (trade name NanoUse (registered trademark) ZR-30BS, manufactured by Nissan chemical Co., ltd., pH 9.8, solid content 30.5 mass%, and average particle diameter of 60.2nm by dynamic light scattering method)
Aqueous titanium dioxide sol (colloidal titanium dioxide)
126.2G of pure water was charged into a1 liter vessel, and 17.8g of metastannic acid (15 g in terms of SnO 2), 284g of titanium tetraisopropoxide (80 g in terms of TiO 2), 84g of oxalic acid dihydrate (70 g in terms of oxalic acid) and 438g of a 35 mass% tetraethylammonium hydroxide aqueous solution were added with stirring. In the obtained mixed solution, the molar ratio of oxalic acid to titanium atoms was 0.78, and the molar ratio of tetraethylammonium hydroxide to titanium atoms was 1.04. 950g of the mixed solution was kept at 80℃for 2 hours, and then depressurized to 580Torr and kept for 2 hours to prepare a titanium mixed solution. The pH value of the prepared titanium mixed solution was 4.7, the conductivity was 27.2mS/cm, and the TiO 2 concentration was 8.4 mass%.
950G of the above titanium mixed solution and 950g of pure water were put into a 3 liter glass-lined autoclave vessel, and subjected to hydrothermal treatment at 140℃for 5 hours. After cooling to room temperature, the taken out solution after the hydrothermal treatment is a light milky aqueous titanium dioxide sol. The pH value of the obtained aqueous titanium dioxide sol was 3.9, the conductivity was 19.7mS/cm, the TiO 2 concentration was 4.2 mass%, tetraethylammonium hydroxide was 4.0 mass%, oxalic acid was 1.8 mass%, and the dynamic light scattering particle size was 16nm.
Aqueous tin oxide sol (tin oxide sol)
37.5Kg of oxalic acid ((COOH) 2·2H2 O) was dissolved in 220kg of pure water, placed in a GL container of 0.5m 3, heated to 70℃with stirring, and then 150kg of 35% hydrogen peroxide and 75kg of metallic tin powder (manufactured by Kaisha Metal Co., ltd., AT-SnNO N, containing 99.7% SnO 2) were added. The hydrogen peroxide and the metallic tin are added alternately for 15 times. 10kg of 35% hydrogen peroxide was added first, followed by 5kg of metallic tin. This operation is repeated after waiting for the completion of the reaction (10 to 15 minutes).
The time required for the addition was 2.5 hours, and after the addition was completed, the reaction was completed by heating for 1 hour while maintaining the liquid temperature at 90 ℃. The hydrogen peroxide to metallic tin ratio was H 2O2/Sn molar ratio 2.44. The specific gravity of the obtained aqueous tin oxide was 1.22, the pH was 1.49, snO 2 was 26.1 mass%, the oxalic acid concentration from the charge was 7.6 mass%, and the molar ratio of (COOH) 2/SnO2 was 0.47.
The particle diameter of the tin oxide colloid is 10-15 nm under an electron microscope, and the tin oxide colloid is spherical particles with good dispersibility. 230kg of tin dioxide sol was dispersed in 1100kg of water, then 3.0kg of isopropylamine was added thereto, then, the liquid was passed through a column filled with a hydroxyl type anion exchange resin, thereby making it alkaline, and then the sol was heat-cured at 90 ℃ and passed again through a column filled with an anion exchange resin, thereby obtaining 1431kg of an alkaline aqueous tin oxide sol. The obtained sol was a stable and very high transparent tin dioxide sol having a specific gravity of 1.034, a pH of 11.33, a SnO 2 content of 4.04 mass%, an isopropylamine content of 0.21 mass% and a dynamic light scattering particle diameter of 20 nm.
(2) Zinc cyanurate particles (CA particles) were prepared.
Zinc cyanurate particles a: trade name Starfine (registered trademark) manufactured by Nissan chemical Co., ltd. (average particle diameter measured by laser diffraction method is 1.7 μm, major axis of primary particles observed by transmission electron microscope is 400-600 nm, minor axis is 50-70 nm, major axis/minor axis ratio is 5.7-12, specific surface area is 15m 2/g, and molar ratio of (zinc oxide)/(cyanuric acid) conversion is 2.5)
Zinc cyanurate particles B: trade name Starfine (registered trademark) manufactured by Nissan chemical Co., ltd. (average particle diameter of 55 μm measured by laser diffraction method, major axis of primary particles observed by a laser electron microscope: 1,000 to 2,000nm, minor axis: 100 to 300nm, major axis/minor axis ratio of 3.3 to 20, specific surface area of 10m 2/g, and molar ratio of (zinc oxide)/(cyanuric acid) conversion of 2.5)
(3) An oil-in-water type resin emulsion was prepared.
Acrylic resin emulsion: DIC (product name VONCOAT-418 EF), resin concentration 55.5 mass% and pH 7.3
Acrylic-styrene resin emulsion a: DIC trade name VONCOAT CG-8680, resin concentration 50.0 mass% and pH 8.4
Acrylic-styrene resin emulsion B: japan Coating Resin, trade name Movinyl DM-60, resin concentration 48.3% by mass and pH 7.5
Acrylic (silicone composite) resin emulsion: DIC (product name CERANATE WHW-822, resin concentration 35.0 mass% and pH 8.1)
Acrylic-silicone resin emulsion: japan Coating Resin (available from Kabushiki Kaisha), trade name LDM7523, resin concentration 47.2% by mass and pH 8.0
Polyurethane resin emulsion a: DIC (product name) HM-171, resin concentration of 35.8 mass% and pH 8.2
Polyurethane resin emulsion B: DSM Coating Resins, trade name NeoRez R-967, resin concentration 39.7 mass% and pH 8.0
Epoxy resin emulsion: DIC (trade name EPICLON H-502-42W, resin concentration 39.3 mass% and pH 9.1)
Epoxy-ester resin emulsion: DIC (product name of Watersol EFD-5530, resin concentration 37.0% by mass and pH 9.1)
Alkyd resin emulsion: DIC (product name Watersol S-118, resin concentration 60.0 mass% and pH 9.2)
Acetic acid-acrylic resin emulsion: DIC (product name VONCOAT CF-2800), resin concentration 50.0 mass% and pH 4.7
Vinyl acetate resin emulsion: zhaokogawa electric product, trade name Polysol S-65, resin concentration 50.5 mass% and pH 5.0
Vinyl chloride resin emulsion: trade name Vinyblan VE-701 manufactured by Nissan chemical industry Co., ltd., resin concentration of 30.9 mass% and pH value of 7.7
Olefin-based (vinyl-based) resin emulsion: trade name PE-381, resin concentration 50.0% by mass, pH 8.0 manufactured by Kagaku chemical Co., ltd
Fluorine-based resin emulsion: manufactured by ETEC corporation, trade name SIFCLEARF-104, resin concentration 46.8 mass% and pH 7.8
Ester resin emulsion: unitika Co., ltd., trade name ElitelKA-3556, resin concentration 29.2 mass% and pH 8.0
(4) An inorganic oxide powder slurry is prepared.
(4-1) Preparation of fumed silica A slurry
50G of fumed silica A and 450g of pure water were placed in a 500ml polypropylene vessel, and the mixture was stirred by a stirrer equipped with turbine blades to prepare a mixed slurry (SiO 2 concentration: 10 mass%). Next, 150g of the slurry A and 180g of glass beads having a diameter of 0.7 to 1.0mm were placed in a 250ml polypropylene vessel, and the vessel was placed on a ball mill rotary table having a rotation speed of 165rpm, and wet-pulverized for 30 hours to obtain a fumed silica A slurry.
(4-2) Preparation of titanium dioxide powder slurry
50G of titanium dioxide powder and 450g of pure water were placed in a 500ml polypropylene vessel, and the mixture was stirred by a stirrer equipped with turbine blades to prepare a mixed slurry (TiO 2 concentration: 10 mass%). Next, 150g of the slurry and 180g of glass beads having a diameter of 0.7 to 1.0mm were placed in a 250ml polypropylene vessel, and the vessel was placed on a ball mill rotary table having a rotation speed of 165rpm, and wet-pulverized for 30 hours to obtain a titania powder slurry.
(4-3) Preparation of fumed silica B slurry
50G of fumed silica B and 450g of pure water were placed in a 500ml polypropylene vessel, and the mixture was stirred by a stirrer equipped with turbine blades to prepare a mixed slurry (SiO 2 concentration: 10 mass%). Next, 150g of the slurry and 180g of glass beads having a diameter of 0.7 to 1.0mm were placed in a 250ml polypropylene vessel, and the vessel was placed on a ball mill rotary table having a rotation speed of 165rpm, and wet-pulverized for 30 hours to obtain a fumed silica B slurry.
(4-4) Preparation of silica powder C slurry
50G of silica powder C and 450g of pure water were placed in a 500ml polypropylene vessel, and a mixed slurry (SiO 2 concentration: 10 mass%) was prepared while stirring the mixture with a stirrer equipped with turbine blades. Next, 150g of the slurry and 180g of glass beads having a diameter of 0.7 to 1.0mm were placed in a 250ml polypropylene vessel, and the vessel was placed on a ball mill rotary table having a rotation speed of 165rpm, and wet-pulverized for 30 hours to obtain a silica powder C slurry.
(5) The average particle diameter of the inorganic oxide particles was measured in the following order.
(5-1) Measuring the average particle diameter of the colloidal inorganic oxide particles by a dynamic light scattering method.
After diluting the dispersion of colloidal inorganic oxide particles with pure water, the dynamic light scattering measurement device was used to measure the dispersion of colloidal inorganic oxide particles by using the parameters of each inorganic oxide: the measurement was performed by a light scattering instrument Zetasizer manufactured by Malvern InstrumentsLtd.
(5-2) The average particle diameter of the inorganic oxide powder (silica powder, titania powder) was measured by a laser diffraction method.
After dispersing the inorganic oxide powder in pure water to form a dispersion, measurement was performed using the trade name SALD-7500nano manufactured by Shimadzu corporation. Here, as the substituted value of the refractive index, [1.45 to 0.00i ] is used in the case of the silica powder, and [2.55 to 0.00i ] is used in the case of the titania powder.
(6) The specific surface area and bulk density of the inorganic oxide powder (silica powder, titania powder) among the inorganic oxide particles were measured.
(6-1) Specific surface area
An appropriate amount of inorganic oxide powder was added to a quartz measurement unit, and the mixture was dried at 300℃for 1 hour, and the specific surface area was measured by the BET method using Monosorb manufactured by Yuasa Ionics.
(6-2) Bulk Density
Bulk density was measured using a Powder Tester PT-X manufactured by Mikroot Co., ltd. The inorganic oxide Powder was placed in a sieve of a Powder Tester PT-X, and the Powder was dropped through a chute while vibrating, and the density when it was received in a 100cm 3 container was measured.
(6-3) Zeta potential measurement
1G of an inorganic oxide powder was added to 100g of pure water, and the mixture was dispersed by a magnetic stirrer to obtain an inorganic oxide powder slurry, which was then added to a measuring unit in an appropriate amount, and the Zeta potential was measured by an electrophoretic light scattering method using ELSZ-2000, manufactured by tsukamurella electronics (ltd).
The Zeta potential was measured by using an automatic titrator (ELSZ-PT manufactured by Katsuka electronics Co., ltd.) and using 0.1mol/L hydrochloric acid (manufactured by Kanto Chemie Co., ltd.) and 0.1mol/L sodium hydroxide (manufactured by Kanto Chemie Co., ltd.) as titration reagents, and adjusting the pH of the inorganic oxide powder slurry to a range of 2 to 10. The measurement results are shown in Table 1.
(7) The average particle diameter of the dispersoid particles was measured by a laser diffraction method.
The dispersion liquid containing the inorganic oxide particles and the zinc cyanurate particles was diluted with pure water, and then measured using a trade name SALD-7500nano manufactured by Shimadzu corporation. Here, 1.70-0.2i is used as the substitution value of the refractive index.
(8) The type B viscosity of the coating composition was measured according to the following method.
The coating composition was poured into a 100mL resin container, and measured with a type B viscometer (BII type viscometer available from DONGMACHINS Co., ltd.) using a No.2 rotor.
Example 1
99G of an aqueous silica sol and 261g of pure water were placed in a 500ml polypropylene vessel, and 40g of zinc cyanurate particles A were added while stirring them by a stirrer equipped with turbine blades, whereby a mixed slurry (SiO 2 concentration 10.0 mass% and zinc cyanurate concentration 10.0 mass%) was prepared. Next, 150g of the mixed slurry and 180g of glass beads having a diameter of 0.7 to 1.0mm were placed in a 250ml polypropylene vessel, and the vessel was placed on a ball mill rotary table having a rotation speed of 165rpm, wet-pulverized for 30 hours to obtain a dispersion 1, which was used as a coating additive 1. Further, after the paint additive 1 was left to stand at room temperature for 12 hours, no sedimentation layer was visually confirmed, and it was confirmed that a good dispersion state was maintained.
The solid content (silica+zinc cyanurate) of the obtained coating additive 1 was 20% by mass, and the average particle diameter thereof was 135nm as measured by a laser diffraction method.
42.7G of pure water, 0.5g of 28% NH 3, 29.5g of the coating additive and 99.6g of an acrylic resin emulsion (trade name: VONCOAT40-418 EF) were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 1 hour to obtain a coating composition 1.
The resulting coating composition 1 had a solid content concentration of 35.5% by mass, a pH of 9.1 and a type B viscosity of 21 mPas.
Example 2
16G of fumed silica A and 344g of pure water were placed in a 500ml polypropylene vessel, and 40g of zinc cyanurate particles A were added thereto while stirring them by a stirrer equipped with turbine blades, to prepare a mixed slurry (SiO 2 concentration 4.0 mass%, zinc cyanurate concentration 10.0 mass%). Next, 150g of the mixed slurry and 180g of glass beads having a diameter of 0.7 to 1.0mm were placed in a 250ml polypropylene vessel, and the vessel was placed on a ball mill rotary table having a rotation speed of 165rpm, and wet-pulverized for 30 hours to obtain a dispersion 2 as a coating additive 2. Further, after the paint additive 2 was left to stand at room temperature for 12 hours, no sedimentation layer was visually confirmed, and it was confirmed that a good dispersion state was maintained.
The resulting coating additive 2 had a solid content (silica+zinc cyanurate) of 14 mass%, a pH of 6.3 and an average particle diameter of the dispersoid particles measured by a laser diffraction method of 306nm.
24.9G of pure water, 0.5g of 28% NH 3, 29.5g of the coating additive 2, 17.7g of 10 mass% fumed silica slurry wet-pulverized for 30 hours by a ball mill, and 99.6g of an acrylic resin emulsion (trade name: VONCOAT40-418 EF) were added to a 250ml polypropylene container, and stirred with a stirrer equipped with turbine blades for 2 hours, to obtain a coating composition 2.
The solid content concentration of the obtained coating composition 2 was 35.5% by mass, the pH was 8.9 and the type B viscosity was 56 mPas.
Example 3
16G of titanium dioxide powder and 344g of pure water were placed in a 500ml polypropylene vessel, and 40g of zinc cyanurate particles A were added while stirring them by a stirrer equipped with turbine blades, to prepare a mixed slurry (TiO 2 concentration 4.0 mass%, zinc cyanurate concentration 10.0 mass%). Next, 150g of the mixed slurry and 180g of glass beads having a diameter of 0.7 to 1.0mm were placed in a 250ml polypropylene vessel, and the vessel was placed on a ball mill rotary table having a rotation speed of 165rpm, and wet-pulverized for 30 hours to obtain a dispersion 3, which was used as a coating additive 3. Further, after the paint additive 3 was left to stand at room temperature for 12 hours, no sedimentation layer was visually confirmed, and it was confirmed that a good dispersion state was maintained.
The resulting coating additive 3 had a solid content (titanium dioxide+zinc cyanurate) of 14 mass%, a pH of 6.2 and an average particle diameter of the dispersoid particles as measured by a laser diffraction method of 1,458 nm.
24.9G of pure water, 0.5g of 28% NH 3, 29.5g of the coating additive 3, 17.7g of a 10 mass% titanium dioxide powder slurry wet-pulverized for 30 hours by a ball mill, and 99.6g of an acrylic resin emulsion (trade name: VONCOAT40-418 EF) were added to a 250ml polypropylene container, and stirred by a stirrer equipped with turbine blades for 2 hours to obtain a coating composition 3.
The resulting coating composition 3 had a solid content concentration of 35.5% by mass, a pH of 9.3 and a type B viscosity of 71 mPas.
Comparative example 1
336G of pure water was placed in a 500ml polypropylene vessel, and 64g of zinc cyanurate particles A was added thereto while stirring the mixture by a stirrer equipped with turbine blades, to prepare a zinc cyanurate particle A slurry (zinc cyanurate concentration: 16.0 mass%).
53.8G of pure water, 0.5g of 28% NH 3, 18.4g of zinc cyanurate particle A slurry (solid content 16 mass%) and 99.6g of an acrylic resin emulsion (trade name: VONCOAT40-418 EF) were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 2 hours, to obtain comparative coating composition 1.
The solid content concentration of the comparative coating composition 1 was 33.8% by mass, the pH was 9.6, and the type B viscosity was 27 mPas.
Comparative example 2
336G of pure water was placed in a 500ml polypropylene vessel, and 64g of zinc cyanurate particles A was added thereto with stirring by a stirrer equipped with turbine blades, to prepare a zinc cyanurate particle A slurry (concentration of zinc cyanurate: 16.0 mass%). Subsequently, 150g of a slurry of zinc cyanurate particles A and 180g of glass beads having a diameter of 0.7 to 1.0mm were placed in a 250ml polypropylene vessel, and the vessel was placed on a rotary table of a ball mill having a rotation speed of 165rpm and wet-pulverized for 48 hours to obtain comparative dispersion 2 (zinc cyanurate dispersion).
The average particle diameter of the comparative dispersion 2 obtained was 1,592nm as measured by the laser diffraction method.
53.8G of pure water, 0.5g of 28% NH 3, 18.4g of the above-mentioned zinc cyanurate dispersion (solid content 16 mass%) and 99.6g of an acrylic resin emulsion (trade name: VONCOAT40-418 EF) were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 2 hours, to obtain comparative coating composition 2.
The solid content concentration of the comparative coating composition 2 was 33.8% by mass, the pH was 9.5, and the type B viscosity was 25 mPas.
Reference example 1
16G of fumed silica A and 344g of pure water were placed in a 500ml polypropylene vessel, and 40g of zinc cyanurate particles A were added thereto while stirring them by a stirrer equipped with turbine blades, to prepare a mixed slurry (SiO 2 concentration 4.0 mass%, zinc cyanurate concentration 10.0 mass%).
The pH of the resulting mixed slurry was 6.3, and the average particle diameter measured by a laser diffraction method was 11,245nm.
41.5G of pure water, 0.5g of 28% NH 3, 29.5g of the mixed slurry, 1.8g of fumed silica A and 99.6g of an acrylic resin emulsion (trade name: VONCOAT40-418 EF) were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 2 hours, to obtain a reference coating composition 1.
The obtained reference coating composition 1 had a solid content concentration of 35.5% by mass, a pH of 8.6 and a type B viscosity of 450 mPas.
Reference example 2
16G of fumed silica A and 344g of pure water were placed in a 500ml polypropylene vessel, and 40g of zinc cyanurate particles A were added and mixed with stirring by a stirrer equipped with turbine blades to obtain a mixed slurry (reference dispersion) (SiO 2 concentration 4.0 mass%, concentration of zinc cyanurate 10.0 mass%).
The solid content (silica+zinc cyanurate) of the resultant mixed slurry (reference dispersion 2) was 14% by mass, and the average particle diameter of the dispersoid particles measured by the laser diffraction method was 11,245nm.
24.9G of pure water, 0.5g of 28% NH 3, 29.5g of the above mixed slurry (reference dispersion 2) and 99.6g of an acrylic resin emulsion (trade name: VONCOAT40-418 EF) were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 1 hour to obtain reference coating composition 2.
The obtained reference coating composition 2 had a solid content concentration of 38.5% by mass, a pH of 8.6 and a type B viscosity of 450 mPas.
Example 4
The coating composition 1 produced in the same manner as in example 1 was diluted with pure water so that the solid content concentration was 22 mass%, to obtain a coating composition 4 having a solid content concentration of 22.0 mass% and a pH value of 9.1.
Reference example 3
The reference coating composition 1 produced in the same manner as in reference example 1 was diluted with pure water so that the solid content concentration was 22 mass%, to obtain a reference coating composition 3 having a solid content of 22.0 mass% and a pH value of 8.6.
Example 5
16G of fumed silica B and 344g of pure water were placed in a 500ml polypropylene vessel, and 40g of zinc cyanurate particles A were added thereto while stirring them by a stirrer equipped with turbine blades, to prepare a mixed slurry (SiO 2 concentration 4.0 mass%, zinc cyanurate concentration 10.0 mass%). Next, 150g of the mixed slurry and 180g of glass beads having a diameter of 0.7 to 1.0mm were placed in a 250ml polypropylene vessel, and the vessel was placed on a ball mill rotary table having a rotation speed of 165rpm, and wet-pulverized for 30 hours to obtain a dispersion 5. After the dispersion 5 was allowed to stand at room temperature for 12 hours, no sedimentation layer was visually confirmed, and it was confirmed that a good dispersion state was maintained.
The resulting dispersion 5 had a solid content (silica+zinc cyanurate) of 14% by mass, a pH of 6.3 and an average particle diameter of the dispersoid particles of 1,707nm as measured by a laser diffraction method. The resulting dispersion 5 was used as the coating additive 5.
24.9G of pure water, 0.5g of 28% NH 3, 29.5g of the coating additive 5, 17.7g of 10 mass% fumed silica B slurry wet-pulverized for 30 hours by a ball mill, and 99.6g of an acrylic resin emulsion (trade name: VONCOAT40-418 EF) emulsion were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 2 hours, to obtain a coating composition 5.
The solid content concentration of the obtained coating composition 5 was 35.5% by mass, the pH was 9.3 and the type B viscosity was 17 mPas.
Example 6
16G of silica powder C and 344g of pure water were placed in a 500ml polypropylene vessel, and 40g of zinc cyanurate particles A were added while stirring them by a stirrer equipped with turbine blades, to obtain a mixed slurry (SiO 2 concentration 4.0 mass%, zinc cyanurate concentration 10.0 mass%). Next, 150g of the mixed slurry and 180g of glass beads having a diameter of 0.7 to 1.0mm were placed in a 250ml polypropylene vessel, and the vessel was placed on a ball mill rotary table having a rotation speed of 165rpm, and wet-pulverized for 30 hours to obtain a dispersion 6. After the dispersion 6 was allowed to stand at room temperature for 12 hours, no sedimentation layer was visually confirmed, and it was confirmed that a good dispersion state was maintained.
The resulting dispersion 6 had a solid content (silica+zinc cyanurate) of 14% by mass, a pH of 6.3 and an average particle diameter of the dispersoid particles of 1,204nm as measured by a laser diffraction method. The resulting dispersion 6 was used as a coating additive 6.
24.9G of pure water, 0.5g of 28% NH 3, 29.5g of the coating additive 6, 17.7g of 10 mass% silica powder C slurry wet-pulverized for 30 hours by a ball mill, and 99.6g of an acrylic resin emulsion (trade name: VONCOAT40-418 EF) were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 2 hours to obtain a coating composition 6.
The solid content concentration of the obtained coating composition 6 was 35.5% by mass, the pH was 9.0 and the type B viscosity was 45 mPas.
Example 7
112.5G of an aqueous alumina sol and 101.3g of pure water were placed in a 500ml polypropylene vessel, and 11.3g of zinc cyanurate particles A were added thereto while stirring them by a stirrer equipped with turbine blades, whereby a mixed slurry (Al 2O3.1 mass% and zinc cyanurate 5 mass%) was prepared. Next, 150g of the mixed slurry and 180g of glass beads having a diameter of 0.5 to 0.7mm were placed in a 250ml polypropylene vessel, and the vessel was placed on a ball mill rotary table having a rotation speed of 165rpm and wet-pulverized for 30 hours to obtain a dispersion 7. After the dispersion 7 was allowed to stand at room temperature for 12 hours, no sedimentation layer was visually confirmed, and it was confirmed that a good dispersion state was maintained.
The resulting dispersion 7 had a solid content (alumina+zinc cyanurate) of 10.1 mass% and an average particle diameter of the dispersoid particles as measured by a laser diffraction method of 112nm. The resulting dispersion 7 was used as a coating additive 7.
13.1G of pure water, 0.5g of 28% NH 3, 59.1g of the above-mentioned coating additive 7 and 99.6g of an acrylic resin emulsion (trade name: VONCOAT40-418 EF) were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 1 hour to obtain a coating composition 7.
The resulting coating composition 7 had a solid content concentration of 35.5% by mass, a pH of 6.2 and a type B viscosity of 100 mPas.
Example 8
150G of an aqueous zirconia sol and 53.5g of pure water were placed in a 500ml polypropylene vessel, and 22.5g of zinc cyanurate particles A were added thereto while stirring them by a stirrer equipped with turbine blades, whereby a mixed slurry (ZrO 2 concentration 20.2 mass% and zinc cyanurate concentration 10 mass%) was prepared. Next, 150g of the mixed slurry and 180g of glass beads having a diameter of 0.5 to 0.7mm were placed in a 250ml polypropylene vessel, and the vessel was placed on a ball mill rotary table having a rotation speed of 165rpm, and wet-pulverized for 30 hours to obtain a dispersion 8. After the dispersion 8 was allowed to stand at room temperature for 12 hours, no sedimentation layer was visually confirmed, and it was confirmed that a good dispersion state was maintained.
The resulting dispersion 8 had a solid content (zirconium dioxide+zinc cyanurate) of 30.2% by mass and an average particle diameter of the dispersoid particles measured by a laser diffraction method of 53nm. The resulting dispersion 8 was used as a coating additive 8.
42.7G of pure water, 0.5g of 28% NH 3, 29.5g of the above-mentioned coating additive 8 and 99.6g of an acrylic resin emulsion (trade name: VONCOAT40-418 EF) were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 1 hour to obtain a coating composition 8.
The resulting coating composition 8 had a solid content concentration of 37.3% by mass, a pH of 9.1 and a type B viscosity of 20 mPas.
Example 9
200G of an aqueous titania sol and 2.5g of pure water were placed in a 500ml polypropylene vessel, and 22.5g of zinc cyanurate particles A were added thereto while stirring them by a stirrer equipped with turbine blades, whereby a mixed slurry (TiO 2 concentration 3.7 mass% and zinc cyanurate concentration 10 mass%) was prepared. Next, 150g of the mixed slurry and 180g of glass beads having a diameter of 0.5 to 0.7mm were placed in a 250ml polypropylene vessel, and the vessel was placed on a ball mill rotary table having a rotation speed of 165rpm and wet-pulverized for 30 hours to obtain a dispersion 9. After the dispersion 9 was allowed to stand at room temperature for 12 hours, no sedimentation layer was visually confirmed, and it was confirmed that a good dispersion state was maintained.
The resulting dispersion 9 had a solid content (titanium dioxide+zinc cyanurate) of 13.7 mass% and an average particle diameter of the dispersoid particles measured by a laser diffraction method of 151nm. The resulting dispersion 9 was used as a coating additive 9.
30.5G of pure water, 0.5g of 28% NH 3, 29.5g of the above-mentioned coating additive 9 and 111.8g of acrylic-styrene resin emulsion B (trade name MovinylDM-60) were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 1 hour to obtain a coating composition 9.
The resulting coating composition 9 had a solid content concentration of 34.1% by mass, a pH of 9.8 and a type B viscosity of 22.8 mPas.
Example 10
201.5G of an aqueous tin oxide sol and 1.0g of pure water were placed in a 500ml polypropylene vessel, and 22.5g of zinc cyanurate particles A were added while stirring them by a stirrer equipped with turbine blades, whereby a mixed slurry (SnO 2 concentration of 3.6 mass%, zinc cyanurate concentration of 10 mass%) was prepared. Next, 150g of the mixed slurry and 180g of glass beads having a diameter of 0.5 to 0.7mm were placed in a 250ml polypropylene vessel, and the vessel was placed on a ball mill rotary table having a rotation speed of 165rpm, and wet-pulverized for 30 hours to obtain a dispersion 10. After the dispersion 10 was left to stand at room temperature for 12 hours, no sedimentation layer was visually confirmed, and it was confirmed that a good dispersion state was maintained.
The resulting dispersion 10 had a solid content (tin oxide+zinc cyanurate) of 13.6 mass% and an average particle diameter of the dispersoid particles as measured by a laser diffraction method of 91nm. The resulting dispersion 10 was used as the coating additive 10.
30.5G of pure water, 0.5g of 28% NH 3, 29.5g of the above-mentioned coating additive 10 and 111.8g of acrylic-styrene resin emulsion B (trade name MovinylDM-60) were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 1 hour to obtain a coating composition 10.
The resulting coating composition 10 had a solid content concentration of 34.1% by mass, a pH of 9.8 and a type B viscosity of 21 mPas.
Comparative example 4
336G of pure water was placed in a 500ml polypropylene vessel, and 64g of zinc cyanurate particles A were added thereto while stirring them by a stirrer having turbine blades, whereby a zinc cyanurate slurry (concentration of zinc cyanurate: 16.0 mass%) was prepared.
42.7G of pure water, 0.5g of 28% NH 3, 19.4g of an aqueous zirconia sol, 18.5g of a zinc cyanurate slurry (solid content 16 mass%) and 99.6g of an acrylic resin emulsion (trade name: VONCOAT-418 EF) were added to a vessel made of 250ml of polypropylene, and stirred with a stirrer equipped with turbine blades for 2 hours, to obtain comparative coating composition 4.
The solid content concentration of the comparative coating composition 4 was 35.5% by mass, the pH was 9.4 and the type B viscosity was 13 mPas.
Example 11
99G of an aqueous silica sol and 261g of pure water were placed in a 500ml polypropylene vessel, and 32g of zinc cyanurate particles A and 8g of cyanuric acid powder (manufactured by Nippon chemical Co., ltd.) were added to change the molar ratio of (zinc oxide)/(cyanuric acid) of zinc cyanurate particles A to 1.5 while stirring them with a stirrer equipped with turbine blades, to prepare a mixed slurry (SiO 2 concentration 10 mass% and zinc cyanurate concentration 10 mass%). Next, 150g of the mixed slurry and 180g of glass beads having a diameter of 0.7 to 1.0mm were placed in a 250ml polypropylene vessel, and the vessel was placed on a ball mill rotary table having a rotation speed of 165rpm, and wet-pulverized for 30 hours to obtain a dispersion 11, which was used as a coating additive 11. Further, after the paint additive 11 was left to stand at room temperature for 12 hours, no sedimentation layer was visually confirmed, and it was confirmed that a good dispersion state was maintained.
The solid content (silica+zinc cyanurate) of the obtained coating additive 11 was 20% by mass, and the average particle diameter measured by a laser diffraction method was 78nm.
42.7G of pure water, 0.5g of 28% NH 3, 29.5g of the coating additive 11 and 99.6g of an acrylic resin emulsion (trade name: VONCOAT40-418 EF) were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 1 hour to obtain a coating composition 11.
The resulting coating composition 11 had a solid content concentration of 35.5% by mass, a pH of 9.0 and a type B viscosity of 20 mPas.
Example 12
99G of an aqueous silica sol and 261g of pure water were placed in a 500ml polypropylene vessel, and 26.8g of zinc cyanurate particles A and 13.2g of zinc oxide (2 kinds of zinc oxide manufactured by Kagaku Co., ltd.) were added to change the molar ratio of (zinc oxide)/(cyanuric acid) of zinc cyanurate particles A to 4.5 in a state of stirring with a stirrer equipped with turbine blades, whereby a mixed slurry (SiO 2 concentration 10 mass%, zinc cyanurate concentration 10 mass%) was prepared. Next, 150g of the mixed slurry and 180g of glass beads having a diameter of 0.7 to 1.0mm were placed in a 250ml polypropylene vessel, and the vessel was placed on a ball mill rotary table having a rotation speed of 165rpm, and wet-pulverized for 30 hours to obtain a dispersion 12 as a coating additive 12. Further, after the paint additive 12 was left to stand at room temperature for 12 hours, no sedimentation layer was visually confirmed, and it was confirmed that a good dispersion state was maintained.
The solid content (silica+zinc cyanurate) of the obtained coating additive 12 was 20% by mass, and the average particle diameter measured by a laser diffraction method was 157nm.
42.7G of pure water, 0.5g of 28% NH 3, 29.5g of the coating additive 12 and 99.6g of an acrylic resin emulsion (trade name: VONCOAT40-418 EF) were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 1 hour to obtain a coating composition 12.
The resulting coating composition 12 had a solid content concentration of 33.8% by mass, a pH of 9.1 and a type B viscosity of 21 mPas.
Example 13
99G of an aqueous silica sol and 261g of pure water were placed in a 500ml polypropylene vessel, and 40g of zinc cyanurate particles B were added while stirring them by a stirrer equipped with turbine blades, to prepare a mixed slurry (SiO 2 concentration 10.0 mass%, zinc cyanurate concentration 10.0 mass%). Next, 150g of the mixed slurry and 180g of glass beads having a diameter of 0.7 to 1.0mm were placed in a 250ml polypropylene vessel, and the vessel was placed on a ball mill rotary table having a rotation speed of 165rpm, and wet-pulverized for 30 hours to obtain a dispersion 13 as a coating additive 13. Further, after the paint additive 13 was left to stand at room temperature for 12 hours, no sedimentation layer was visually confirmed, and it was confirmed that a good dispersion state was maintained.
The solid content (silica+zinc cyanurate) of the obtained coating additive 13 was 20% by mass, and the average particle diameter measured by a laser diffraction method was 134nm.
42.7G of pure water, 0.5g of 28% NH 3, 29.5g of the coating additive 1 and 99.6g of an acrylic resin emulsion (trade name: VONCOAT40-418 EF) were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 1 hour to obtain a coating composition 1.
The resulting coating composition 13 had a solid content concentration of 33.8% by mass, a pH of 9.1 and a type B viscosity of 19 mPas.
Comparative example 3
85.4G of pure water and 114.6g of an acrylic resin emulsion (trade name: 40-418 EF) were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 1 hour to obtain comparative coating composition 3.
The solid content concentration of the comparative coating composition 3 was 31.8% by mass, the pH was 9.6, and the type B viscosity was 17 ma.s.
Example 14
32.2G of pure water, 29.3g of the above-mentioned coating additive 1 and 110.6g of an acrylic-styrene resin emulsion A (trade name VONCOATCG-8680) were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 1 hour to obtain a coating composition 14.
The resulting coating composition 14 had a solid content concentration of 35.5% by mass, a pH of 7.4 and a type B viscosity of 50 mPas.
Example 15
28.4G of pure water, 29.3g of the above-mentioned coating additive 1 and 114.5g of an acrylic-styrene resin emulsion B (trade name MovinylDM-60) were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 1 hour to obtain a coating composition 15.
The resulting coating composition 15 had a solid content concentration of 35.5% by mass, a pH of 7.9 and a type B viscosity of 25 mPas.
Example 16
29.3G of the coating additive 1 and 158g of an acrylic (silicone composite) resin emulsion (trade name CERANATEWHW-822) were added to a 250ml polypropylene container, and stirred with a stirrer equipped with a stirrer for 1 hour to obtain a coating composition 16.
The resulting coating composition 16 had a solid content concentration of 32.7% by mass, a pH of 7.9 and a type B viscosity of 31 mPas.
Example 17
25.8G of pure water, 29.3g of the above-mentioned coating additive 1 and 117.2g of an acrylic-silicone resin emulsion (trade name MovinylLDM 7523) were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 1 hour to obtain a coating composition 17.
The resulting coating composition 17 had a solid content concentration of 35.5% by mass, a pH of 7.7 and a type B viscosity of 20 mPas.
Example 18
29.3G of the above-mentioned coating additive 1 and 154.5g of polyurethane-based resin emulsion A (trade name HYDRANHW-171) were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 1 hour to obtain a coating composition 18.
The resulting coating composition 18 had a solid content concentration of 33.3% by mass, a pH of 8.4 and a type B viscosity of 16 mPas.
Example 19
3.7G of pure water, 29.3g of the above-mentioned coating additive 1 and 139.3g of polyurethane-based resin emulsion B (trade name NeoRezR-967) were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 1 hour to obtain a coating composition 19.
The resulting coating composition 19 had a solid content concentration of 35.5% by mass, a pH of 8.4 and a type B viscosity of 19 mPas.
Example 20
2.3G of pure water, 29.3g of the above-mentioned coating additive 1 and 140.7g of an epoxy resin emulsion (trade name EPICLONH-502-42W) were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 1 hour to obtain a coating composition 20.
The resulting coating composition 20 had a solid content concentration of 35.5% by mass, a pH of 9.2 and a type B viscosity of 197 mPas.
Example 21
29.3G of the above-mentioned coating additive 1 and 149.5g of an epoxy-ester resin emulsion (trade name WATERSOLEFD-5530) were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 1 hour to obtain a coating composition 21.
The resulting coating composition 21 had a solid content concentration of 34.2% by mass, a pH of 8.8 and a type B viscosity of 32 mPas.
Example 22
50.7G of pure water, 29.3g of the coating additive 1 and 92.2g of alkyd-based resin emulsion (trade name WATERSOLS-118) were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 1 hour, to obtain a coating composition 22.
The resulting coating composition 22 had a solid content concentration of 35.5% by mass, a pH of 8.8 and a type B viscosity of 678 mPa.s.
Example 23
32.2G of pure water, 29.3g of the above-mentioned coating additive 1 and 110.6g of an acetic acid-acrylic resin emulsion (trade name VONCOATCF-2800) were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 1 hour to obtain a coating composition 23.
The resulting coating composition 23 had a solid content concentration of 35.5% by mass, a pH of 5.6 and a type B viscosity of 65 mPas.
Example 24
33.4G of pure water, 29.3g of the above-mentioned coating additive 1 and 109.5g of a vinyl acetate-based resin emulsion (trade name POLYSOLS-65) were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 1 hour to obtain a coating composition 24.
The resulting coating composition 24 had a solid content concentration of 35.5% by mass, a pH of 7.2 and a type B viscosity of 14 mPas.
Example 25
26.5G of pure water, 21.3g of the above-mentioned coating additive 1 and 130.0g of a vinyl chloride-based resin emulsion (trade name VinyblanVE-701) were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 1 hour to obtain a coating composition 25.
The resulting coating composition 25 had a solid content concentration of 25.0% by mass, a pH of 7.8 and a type B viscosity of 8.0 mPas.
Example 26
32.3G of pure water, 29.3g of the above-mentioned coating additive 1 and 110.6g of an olefin-based resin emulsion (trade name: PE-381) were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 1 hour to obtain a coating composition 26.
The resulting coating composition 26 had a solid content concentration of 35.5% by mass, a pH of 7.8 and a type B viscosity of 58 mPas.
Example 27
24.7G of pure water, 29.3g of the above-mentioned coating additive 1 and 118.2g of a fluororesin emulsion (trade name SIFCLEARF-104) were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 1 hour to obtain a coating composition 27.
The resulting coating composition 27 had a solid content concentration of 35.5% by mass, a pH of 8.2 and a type B viscosity of 6.0 mPas.
Example 28
17.8G of pure water, 20.1g of the above-mentioned coating additive 1 and 130.0g of an ester-based resin emulsion (trade name ElitelKA-3556) were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 1 hour to obtain a coating composition 28.
The resulting coating composition 28 had a solid content concentration of 25.0% by mass, a pH of 8.3 and a type B viscosity of 29 mPas.
Comparative example 5
128.3G of pure water and 71.7g of an acrylic resin emulsion (trade name: 40-418 EF) were added to a 250ml polypropylene vessel, and stirred with a stirrer equipped with turbine blades for 1 hour, to obtain comparative coating composition 5.
The solid content concentration of the comparative coating composition 5 was 19.9% by mass, the pH was 9.0, and the type B viscosity was 11 mPas.
Comparative example 6
Comparative coating composition 1 prepared in the same manner as in comparative example 1 was diluted with pure water so that the solid content concentration was 22 mass%, to obtain comparative coating composition 6 having a solid content concentration of 22.0 mass%.
The solid content concentration of the comparative coating composition 6 thus obtained was 22.0% by mass, the pH was 8.9 and the type B viscosity was 15 mPas.
Comparative example 7
Comparative coating composition 1 prepared in the same manner as in comparative example 2 was diluted with pure water so that the solid content concentration was 22 mass%, to obtain comparative coating composition 7 having a solid content concentration of 22.0 mass%.
The solid content concentration of the comparative coating composition 7 was 22.0% by mass, the pH was 8.9, and the type B viscosity was 18 mPas.
Example 29
The coating composition 15 produced in the same manner as in example 15 was diluted with pure water so that the solid content concentration was 22% by mass, to obtain a coating composition 29 having a solid content concentration of 22.0% by mass, a pH of 7.9 and a type B viscosity of 25 mPas.
Example 30
The coating composition 16 produced in the same manner as in example 16 was diluted with pure water so that the solid content was 22% by mass, to obtain a coating composition 30 having a solid content of 22.0% by mass, a pH of 7.9 and a B-type viscosity of 31mpa·s.
Example 31
The coating composition 18 produced in the same manner as in example 18 was diluted with pure water so that the solid content concentration was 22% by mass, to obtain a coating composition 31 having a solid content concentration of 22.0% by mass, a pH value of 8.4 and a B-type viscosity of 16mpa·s.
Example 32
The coating composition 20 produced in the same manner as in example 20 was diluted with pure water so that the solid content concentration was 22% by mass, to obtain a coating composition 32 having a solid content concentration of 22.0% by mass, a pH value of 9.2 and a B-type viscosity of 197mpa·s.
Example 33
The coating composition 22 produced in the same manner as in example 22 was diluted with pure water so that the solid content was 22% by mass, to obtain a coating composition 33 having a solid content of 22.0% by mass, a pH of 8.8 and a B-type viscosity of 678mpa·s.
Example 34
The coating composition 23 produced in the same manner as in example 23 was diluted with pure water so that the solid content was 22% by mass, to obtain a coating composition 34 having a solid content of 22.0% by mass, a pH of 6.3 and a type B viscosity of 30 mPas.
Example 35
The coating composition 24 produced in the same manner as in example 24 was diluted with pure water so that the solid content was 22% by mass, to obtain a coating composition 35 having a solid content of 22.0% by mass, a pH of 7.4 and a type B viscosity of 11 mPas.
Example 36
The coating composition 26 produced in the same manner as in example 26 was diluted with pure water so that the solid content was 22% by mass, and a coating composition 36 having a solid content of 22.0% by mass, a pH of 7.5 and a type B viscosity of 46 mPas was obtained.
Example 37
The coating composition 27 produced in the same manner as in example 27 was diluted with pure water so that the solid content was 22% by mass, to obtain a coating composition 37 having a solid content of 22.0% by mass, a pH of 7.9 and a type B viscosity of 5 mPas.
The coating compositions 1 to 3 of examples 1 to 3 and examples 5 to 28, the coating compositions 5 to 28, the comparative coating compositions 1 to 4 of comparative examples 1 to 4, and the reference coating compositions 1 to 2 of reference examples 1 to 2 were used to evaluate the coating and film coating of the aluminum sheet in the following order.
The coating compositions 4, 29 to 37, and 37 of example 4, comparative coating compositions 5 to 7 of comparative examples 5 to 7, and reference coating composition 3 of reference example 3 were used to evaluate the coating and film coating of PET film in the following order.
Examples 38 to 46
The coating compositions 1, 15, 16, 18, 20, 23, 24, 26, 27 of examples 1, 15, 16, 18, 20, 23, 24, 26, 27 were used to evaluate the coating and film coating of Cu plates in the following order.
Comparative examples 8 to 10
The coating and film evaluation of Cu plates were performed in the following order using comparative coating compositions 3, 1, and 2 of comparative examples 3, 1, and 2.
Examples 47 to 53
Using the coating compositions 1, 16, 18, 20, 22, 26, 27 of examples 1, 16, 18, 22, 26, 27, coating of SUS plates and evaluation of coating films were performed in the following order.
Comparative examples 11 to 13
The coating and the film evaluation of the SUS plate were performed in the following order using comparative coating compositions 3, 1, and 2 of comparative examples 3, 1, and 2.
Examples 54 to 63
The coating compositions 1, 15, 16, 18, 20, 22 to 24, 26, 27 of examples 1, 15, 16, 18, 20, 22 to 24, 26, 27 were used to apply and evaluate the coating film of the mild steel sheet in the following order.
Comparative example 14, 15
The coating and film evaluation of the mild steel sheet were performed in the following order using comparative coating compositions 1 and 2 of comparative examples 1 and 2.
Examples 64 to 73
The coating compositions 1, 15, 16, 18, 20, 22 to 24, 26, 27 of examples 1, 15, 16, 18, 20, 22 to 24, 26, 27 were used to apply and evaluate the coating film of the galvanized steel sheet in the following order.
Comparative examples 16 and 17
The coating and the film evaluation of the galvanized steel sheet were performed in the following order using the comparative coating compositions 1 and 2 of comparative examples 1 and 2.
Examples 74 to 82
The coating compositions 1, 15, 18, 20, 22 to 24, 26, 27 of examples 1, 15, 18, 20, 22 to 24, 26, 27 were used to evaluate the coating and film coating of fir boards in the following order.
Comparative examples 18 to 20
The coating and film evaluation of the fir board were performed in the following order using comparative coating compositions 3, 1,2 of comparative examples 3, 1, 2.
(9) The coated aluminum sheet was prepared as follows.
An aluminum plate (manufactured by Wako Co., ltd., JIS model A1050P) having a plate thickness of 0.5mm and dimensions of 70mm wide by 150mm long was used.
(Coating method)
Coating compositions 1 to 3, 5 to 28, comparative coating compositions 1 to 4 and reference coating compositions 1 to 2 were applied to the surface of an aluminum sheet at a rate of 2 m/min by bar coating, and baked in an electric furnace set at 230℃for 30 seconds to obtain an aluminum sheet with a coating film. The specific method of bar coating is as follows.
Stick coating: each coating composition was applied dropwise to an aluminum plate, and the coating was carried out at a wet coating film thickness of 61. Mu.m using an RDS.24 bar coater.
(10) The coated film substrate (PET) was prepared as follows.
A PET film (trade name CosmoShineA4100, manufactured by Toyobo Co., ltd.) which had a thickness of 100 μm and had dimensions of 297mm wide by 420mm long and was subjected to a bonding treatment was used.
(Coating method)
Coating compositions 4, coating compositions 29 to 37, comparative coating compositions 5 to 7 and reference coating composition 3 were applied to the easy-to-join layer of PET film at a rate of 2 m/min by bar coating, and dried on a hot plate set at 60℃for 5 minutes to obtain a PET film with a coating film. The specific method of bar coating is as follows.
Stick coating: each coating composition was dropped onto a PET film, and the coating was performed at a wet coating film thickness of 4.6. Mu.m, using a No.2 bar coater.
(11) The coated Cu plate was prepared as follows.
A Cu plate (manufactured by Wako Co., ltd., JIS type C1220P) having a plate thickness of 0.5mm and dimensions of 100mm wide by 365mm long was used.
(Coating method)
Coating compositions 1, 15, 16, 18, 20, 23, 24, 26, 27 and comparative coating compositions 1 to 3 were applied to the surface of a Cu plate at a rate of 2m/min by bar coating, and baked in an electric furnace set at 230 ℃ for 30 seconds to obtain a Cu substrate with a coating film. The specific method of bar coating is as follows.
Stick coating: each coating composition was dropped onto a copper plate, and the coating was carried out at a wet coating film thickness of 61. Mu.m using an RDS.24 bar coater.
(12) Coated SUS plates were prepared as follows.
SUS plate (SUS 430 manufactured by Wako Co., ltd., JIS) having a plate thickness of 0.5mm and a size of 100mm wide by 300mm long was used.
(Coating method)
Coating compositions 1, 16, 18, 20, 22, 26, 27 and comparative coating compositions 1 to 3 were applied to the surface of SUS plates at a rate of 2 m/min by bar coating, and baked in an electric furnace set at 230 ℃ for 30 seconds to obtain SUS plates with coating films. The specific method of bar coating is as follows.
Stick coating: each coating composition was dropped onto SUS plate, and coated with 61 μm of wet coating film thickness using RDS.24 bar coater.
(13) The coated mild steel sheet was prepared as follows.
A mild steel sheet (JIS type SPCC bright steel sheet manufactured by TP technical Co., ltd.) having a sheet thickness of 0.8mm and a dimension of 70mm wide by 150mm long was used.
(Coating method)
Coating compositions 1, 15, 16, 18, 20, 22 to 24, 26, 27 and comparative coating compositions 1,2 were applied to the surface of a mild steel sheet at a rate of 2 m/min by bar coating, and baked in an electric furnace set at 230℃for 30 seconds to obtain a mild steel sheet with a coating film. The specific method of bar coating is as follows.
Stick coating: each coating composition was applied dropwise to a mild steel sheet, and the resulting steel sheet was coated with a wet coating film having a thickness of 61. Mu.m, using an RDS.24 bar coater.
(14) The coated galvanized steel sheet was prepared as follows.
Galvanized steel sheets having a sheet thickness of 6mm and dimensions of 70mm wide by 150mm long ((product of STANDARDTESTPIECE, JIS type SS400, hot dip galvanization (without chemical conversion treatment)).
(Coating method)
The coating compositions 1, 15, 16, 18, 20, 22 to 24, 26, 27 and the comparative coating compositions 1,2 were applied to the surface of a galvanized steel sheet at a speed of 2 m/min by bar coating, and baked in an electric furnace set at 230℃for 30 seconds to obtain a galvanized steel sheet with a coating film. The specific method of bar coating is as follows.
Stick coating: each coating composition was applied dropwise to a galvanized steel sheet, and the resulting steel sheet was coated with a wet coating film having a thickness of 61. Mu.m, using an RDS.24 bar coater.
(15) The coated wood was prepared as follows.
A fir board (manufactured by STANDARDTESTPIECE, kagaku Kogyo, R.H., 4-sided planer) having a thickness of 5mm and a size of 100 mm. Times.150 mm was used.
(Coating method)
Coating the coating compositions 1, 15, 18, 20, 22, 23, 24, 26 and 27 and comparative coating compositions 1 to 3 on the surface of the fir board substrate by brushing, drying at 80 ℃ for 3 minutes to form a first layer, wherein the coating amount after drying reaches 30g/m 2. Then, the same coating composition as that used for the first layer was applied to the surface of the first layer so that the coating amount after drying reached 70g/m 2, and dried at 80℃for 10 minutes, thereby obtaining a fir board with a coating film having a two-layer structure.
(16) Appearance test of coated aluminum plate, coated Cu plate, coated SUS plate, coated mild steel plate, coated galvanized steel plate, coated fir board and coated PET film
For each of the coated aluminum plate, coated Cu plate, coated SUS plate, coated mild steel plate, coated galvanized steel plate, coated fir plate and coated PET film, the area of the portion where the coating film was formed with respect to the area of the aluminum plate, cu plate, SUS plate, mild steel plate, galvanized steel plate, fir plate or PET film was visually observed and evaluated based on the following evaluation criteria.
< Evaluation criteria >
Good: more than 90% of the coating film formation area was observed.
Slightly bad: 50 to 89% of the coating film formation area was observed.
Poor: 10 to 49% of the coating film formation area was observed.
(17) Pencil hardness test
With reference to JISK5600, pencil hardness was measured according to the following method for each of the coated aluminum plate, the coated Cu plate, the coated SUS plate, the coated mild steel plate, the coated galvanized steel plate, and the coated PET film.
The pencil hardness at the time of peeling of the coating film was measured by pressing and moving a pencil lead made by Hi-uni company, mitsubishi pencil (Inc.) onto the surface of the coating film using a hand-press pencil-stroke hardness tester manufactured by An Tian polishing machine (Inc.).
Further, it is desirable that the pencil hardness is 3B or more when an aluminum base material is used, 5B or more when a copper base material is used, 3B or more when an iron base material (SUS, mild steel sheet, galvanized steel sheet) is used, and 6B or more when a PET film is used.
< Criterion for determination >
[ Soft ]6B, 5B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H [ hard ]
(18) Adhesion test by Cross cutting method
Regarding the respective coated aluminum plates, coated Cu plates, coated SUS plates, coated soft steel plates, coated galvanized steel plates, coated fir plates, and coated PET films, JISK5600 as a reference, adhesion (adhesiveness) of the coating films obtained by the cross cutting method to the substrates (aluminum plates, PET films, cu plates, SUS plates, soft steel plates, galvanized steel plates, fir plates) was evaluated according to the following methods.
100 Lattice patterns were cut at 1mm intervals on the coated surface, and the tape was brought into contact with 20mm so as to cover the lattice portions. Then, the tape was peeled off by grasping the tape end and pulling the tape off in a manner of reliably pulling off the tape in 0.5 to 1.0 seconds, and whether or not peeling occurred in the coating film and the number thereof (number of checkered) were visually checked, and evaluated according to the following judgment criteria.
< Criterion for determination >
A: the number of the unpeeled chessboards is more than 90
B: the number of unpeeled chessboards is 60 or more and less than 90
C: the number of unpeeled chessboards is 40 or more and less than 60
D: the number of the chessboards which are not peeled off is less than 40
(19) HAZE assay
The HAZE measurement was performed on a PET film with a coating film by using NDH-5000 manufactured by Nippon electric color industry Co., ltd.) using a measurement method according to JISK 7105.
The results obtained are summarized in tables 1 to 7.
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As shown in Table 1[ tables 1-1 to 1-4], according to the present invention, a coating film having a hardness of about 3B or more and excellent adhesion to a substrate can be formed on the whole aluminum plate substrate.
Specifically, as shown in [ tables 1 to 1] and [ tables 1 to 2] (examples 1 to 3, and examples 5 to 10), even when various silica powders, colloidal alumina, colloidal zirconia, colloidal titania, and tin oxide sols are used, a coating film which is formed on the whole of an aluminum plate substrate and has excellent adhesion to the substrate can be formed.
As shown in [ tables 1 to 3] (examples 11 to 13), even when the particle size of the zinc cyanurate particles and the (zinc oxide)/(zinc cyanurate) conversion molar ratio of the zinc cyanurate particles were changed, a coating film having a hardness of 2B or more and excellent adhesion to the substrate could be formed on the whole of the aluminum plate substrate.
As shown in tables 1 to 4 and tables 1 to 5 (examples 14 to 21 and examples 22 to 28), according to the present invention, when various resin emulsions are used, it is possible to form a coating film having both hardness and adhesion to an aluminum plate substrate as a whole.
On the other hand, in both of comparative example 1 in which zinc cyanurate slurry and resin emulsion were mixed and comparative example 2 in which zinc cyanurate slurry was wet-pulverized to form a dispersion and mixed with resin emulsion, the appearance (poor) and adhesion (D) of the coating film were much worse than those of the examples without using inorganic oxide powder. In the case of comparative example 3, which is a resin emulsion alone, the coating film appearance was good, but the adhesion was evaluated as D. In addition, when colloidal metal oxide particles and zinc cyanurate were simply mixed without forming a dispersion (comparative example 4), the coating film appearance was good but the adhesion (C) was poor.
In reference examples 1 and 2, in which the average particle diameter of the dispersoid measured by the laser diffraction method was a value exceeding 10,000nm, the appearance (poor) and adhesion (D) of the coating film were both significantly worse than those of the examples.
As shown in table 2[ tables 2-1 to 2-3] (example 4, example 29 to example 33, and example 34 to example 37), according to the present invention, when various resin emulsions are used, it is possible to form a coating film having a hardness of 2B or more and excellent adhesion to a substrate on the whole PET substrate. Further, according to the present invention, since a significant increase in the HAZE value is suppressed, adhesion to a substrate can be improved without significantly impairing the transparency of a PET substrate.
On the other hand, in both the case of comparative example 5 in which the zinc cyanurate slurry and the resin emulsion were mixed and the case of comparative example 6 in which the zinc cyanurate slurry was wet-pulverized to form a dispersion and mixed with the resin emulsion, the appearance (poor) and the adhesion (D) of the coating film were much worse than those of the examples. In the case of comparative example 4, which is a resin emulsion alone, the coating film appearance was good, but the adhesion was evaluated as D.
In addition, in reference example 3, in which the average particle diameter size of the dispersoid measured by the laser diffraction method was a value exceeding 10,000nm, in the dispersion liquid containing the inorganic oxide powder and the zinc cyanurate particles, the appearance (poor) and the adhesion (C) of the coating film were both much worse than those of the examples.
As shown in table 3[ tables 3-1 to 3-2] (examples 38 to 40, and examples 41 to 46), according to the present invention, a coating film having a hardness of 5B or more and excellent adhesion to a substrate can be formed on the entire Cu plate substrate.
On the other hand, in the case where the inorganic oxide particles were not used, although the appearance of the coating film was good in comparative example 8, the adhesion was evaluated as D, and in both the case of comparative example 9 in which the zinc cyanurate slurry and the resin emulsion were mixed and comparative example 10 in which the zinc cyanurate slurry was wet-pulverized to form a dispersion and the dispersion was mixed with the resin emulsion, the coating film appearance (poor) and the adhesion (D (comparative example 9), B (comparative example 10)) were both much worse than those of the examples.
As shown in table 4[ tables 4-1 to 4-2] (examples 47 to 49, examples 50 to 53), according to the present invention, a coating film having a hardness of 3B or more and excellent adhesion to a substrate can be formed on the entire SUS plate substrate.
On the other hand, in the case where the inorganic oxide particles were not used, in comparative example 11, which was only a resin emulsion, although the appearance of the coating film was good, the adhesion was evaluated as D, and in the case of comparative example 12, in which zinc cyanurate slurry and a resin emulsion were mixed, and comparative example 13, in which zinc cyanurate slurry was wet-pulverized to form a dispersion, and mixed with a resin emulsion, both the appearance (poor) and the adhesion (D) of the coating film were much worse than those of the examples.
As shown in table 5[ tables 5-1 to 5-2] (examples 54 to 56, and examples 57 to 63), according to the present invention, a coating film having a hardness of 3B or more and excellent adhesion to a base material can be formed on the whole mild steel sheet base material.
On the other hand, in the case where the inorganic oxide particles were not used, comparative example 14 in which zinc cyanurate slurry and resin emulsion were mixed and comparative example 15 in which zinc cyanurate slurry was wet-pulverized to form a dispersion and mixed with resin emulsion were the results of much poorer coating film appearance (poor) and adhesion (D) than in the examples.
As shown in Table 6[ tables 6-1 to 6-2] (examples 64 to 67, and examples 68 to 73), according to the present invention, a coating film having a hardness of HB or more and excellent adhesion to a substrate can be formed on the whole of a galvanized steel sheet substrate.
On the other hand, when the inorganic oxide particles were not used, the comparative example 16 in which the zinc cyanurate slurry was mixed with the resin emulsion and the comparative example 17 in which the zinc cyanurate slurry was wet-pulverized to form a dispersion and mixed with the resin emulsion were both the appearance (poor) and the adhesion (C (comparative example 16), B (comparative example 17)) of the coating film were much worse than those of the examples.
As shown in table 7[ tables 7-1 to 7-2] (examples 74 to 76, and examples 77 to 82), according to the present invention, a coating film which is formed on the entire wood and has excellent adhesion to a substrate can be formed.
On the other hand, when the inorganic oxide particles were not used, only comparative example 18 in which the resin emulsion and comparative example 20 in which the zinc cyanurate slurry was wet-pulverized to form a dispersion and mixed with the resin emulsion had good coating film appearance, but the coating film appearance was poor, and comparative example 19 in which the zinc cyanurate slurry was mixed with the resin emulsion had much poorer coating film appearance (poor) and adhesion (C) than in the examples.
Fig. 1 is a graph showing an approximation curve obtained from measurement values of Zeta potential (mV) of inorganic oxide particles with respect to pH values (pH 2 to 10 (horizontal axis)) of aqueous slurries in which the inorganic oxide powder is silica powder (fumed silica a, fumed silica B, silica powder C) or titania powder (titania powder).
As shown in fig. 1, the inorganic oxide particles used in the present example: the silica powder (fumed silica A, fumed silica B, silica powder C) and the titania powder (titania powder) each have no isoelectric point at pH5 to pH12 and have a Zeta potential of-5 mV to-50 mV in the pH range.
As described above, it was confirmed that the use of the coating additives 1 (fumed silica a), 2 (fumed silica B), 3 (silica powder C) and 4 (titania powder) of these powders all gave inorganic oxide particles having no isoelectric point at pH5 to pH12 but having Zeta potential of-5 mV to-50 mV in the pH range, and that no sedimentation layer was visually confirmed after standing at room temperature for 12 hours, and that a good dispersion state was maintained, and that a dispersion liquid having excellent dispersibility was obtained.
Claims (4)
1. A dispersion liquid comprising a liquid medium and dispersed therein dispersoid particles comprising inorganic oxide particles and zinc cyanurate particles,
The inorganic oxide particles are inorganic oxide powder,
The specific surface area of the inorganic oxide powder is 1-800 m 2/g, the loose bulk density is 0.03-3.0 g/cm 3,
The inorganic oxide particles are inorganic oxide particles which have isoelectric points at pH values of 5-12 and have Zeta potentials of-80 mV to +80mV in the pH range, or inorganic oxide particles which do not have isoelectric points at pH values of 5-12 and have Zeta potentials of-5 mV to-50 mV in the pH range by adjusting the pH value,
The inorganic oxide powder is an oxide of at least 1 atom selected from Si, al, ti and Sn.
2. The dispersion according to claim 1, wherein the dispersoid particles have an average particle diameter of 200 to 5,000nm, and the concentration of the solid content of the dispersoid particles in the dispersion is 0.1 to 50% by mass, when measured by a laser diffraction method.
3. A dispersion liquid comprising a liquid medium and dispersed therein dispersoid particles comprising inorganic oxide particles and zinc cyanurate particles,
The inorganic oxide particles are colloidal metal oxide particles excluding particles mainly composed of colloidal silica,
The inorganic oxide particles are inorganic oxide particles which have isoelectric points at pH values of 5-12 and have Zeta potentials of-80 mV to +80mV in the pH range, or inorganic oxide particles which do not have isoelectric points at pH values of 5-12 and have Zeta potentials of-5 mV to-50 mV in the pH range by adjusting the pH value,
The colloidal metal oxide particles comprise an oxide of at least 1 atom selected from Al, ti and Sn.
4. The dispersion according to claim 3, wherein the dispersed particles have an average particle diameter of 80nm to 2,000nm, and the concentration of the solid content of the dispersed particles in the dispersion is 0.1 to 50% by mass, when measured by a laser diffraction method.
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| CN202310190898.2A CN116144213B (en) | 2019-09-20 | 2020-09-18 | Dispersion comprising inorganic oxide particles and zinc cyanurate particles |
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| JP2019171647 | 2019-09-20 | ||
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| JP2019-171646 | 2019-09-20 | ||
| JP2019-171645 | 2019-09-20 | ||
| JP2019171645 | 2019-09-20 | ||
| CN202310190898.2A CN116144213B (en) | 2019-09-20 | 2020-09-18 | Dispersion comprising inorganic oxide particles and zinc cyanurate particles |
| PCT/JP2020/035605 WO2021054471A1 (en) | 2019-09-20 | 2020-09-18 | Dispersion liquid containing inorganic oxide particles and zinc cyanurate particles, and coating composition |
| CN202080064965.0A CN114402043B (en) | 2019-09-20 | 2020-09-18 | Dispersion and coating composition comprising inorganic oxide particles and zinc cyanurate particles |
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| CN202310190980.5A Pending CN116285692A (en) | 2019-09-20 | 2020-09-18 | Coating composition, method for producing same, and coating film |
| CN202310190898.2A Active CN116144213B (en) | 2019-09-20 | 2020-09-18 | Dispersion comprising inorganic oxide particles and zinc cyanurate particles |
| CN202080064965.0A Active CN114402043B (en) | 2019-09-20 | 2020-09-18 | Dispersion and coating composition comprising inorganic oxide particles and zinc cyanurate particles |
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| CN202310190980.5A Pending CN116285692A (en) | 2019-09-20 | 2020-09-18 | Coating composition, method for producing same, and coating film |
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| CN202080064965.0A Active CN114402043B (en) | 2019-09-20 | 2020-09-18 | Dispersion and coating composition comprising inorganic oxide particles and zinc cyanurate particles |
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| KR (1) | KR20220062563A (en) |
| CN (3) | CN116285692A (en) |
| TW (1) | TW202126759A (en) |
| WO (1) | WO2021054471A1 (en) |
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| CN116285692A (en) * | 2019-09-20 | 2023-06-23 | 日产化学株式会社 | Coating composition, method for producing same, and coating film |
| WO2022210051A1 (en) * | 2021-04-01 | 2022-10-06 | 日産化学株式会社 | Organic solvent dispersion containing colloidal silica particles and zinc cyanurate particles, and production method thereof |
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| CN106700811A (en) * | 2016-12-20 | 2017-05-24 | 铜陵市经纬流体科技有限公司 | Aerogel hybrid microsphere grafted silicon composite coating and preparation method thereof |
| CN114402043B (en) * | 2019-09-20 | 2023-06-30 | 日产化学株式会社 | Dispersion and coating composition comprising inorganic oxide particles and zinc cyanurate particles |
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| DE3224766A1 (en) * | 1982-07-02 | 1984-01-05 | Henkel KGaA, 4000 Düsseldorf | METHOD FOR PRODUCING LEAD AND ZINC CYANURATES |
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| EP2599782B1 (en) * | 2010-06-24 | 2015-01-07 | Nissan Chemical Industries, Ltd. | Basic zinc cyanurate fine particles, and method for producing same |
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2020
- 2020-09-18 CN CN202310190980.5A patent/CN116285692A/en active Pending
- 2020-09-18 CN CN202310190898.2A patent/CN116144213B/en active Active
- 2020-09-18 CN CN202080064965.0A patent/CN114402043B/en active Active
- 2020-09-18 WO PCT/JP2020/035605 patent/WO2021054471A1/en active Application Filing
- 2020-09-18 KR KR1020227011462A patent/KR20220062563A/en unknown
- 2020-09-18 TW TW109132411A patent/TW202126759A/en unknown
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| CN103695916A (en) * | 2013-11-29 | 2014-04-02 | 明光市留香泵业有限公司 | Water-soluble antifouling antirust liquid and preparation method thereof |
| CN105177551A (en) * | 2015-09-16 | 2015-12-23 | 马鞍山杰创塑胶科技有限公司 | Fluorine-modified aluminum profile rare earth silane treating fluid and preparing method thereof |
| CN106700811A (en) * | 2016-12-20 | 2017-05-24 | 铜陵市经纬流体科技有限公司 | Aerogel hybrid microsphere grafted silicon composite coating and preparation method thereof |
| CN114402043B (en) * | 2019-09-20 | 2023-06-30 | 日产化学株式会社 | Dispersion and coating composition comprising inorganic oxide particles and zinc cyanurate particles |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114402043B (en) | 2023-06-30 |
| WO2021054471A1 (en) | 2021-03-25 |
| KR20220062563A (en) | 2022-05-17 |
| JPWO2021054471A1 (en) | 2021-03-25 |
| CN116144213A (en) | 2023-05-23 |
| CN116285692A (en) | 2023-06-23 |
| TW202126759A (en) | 2021-07-16 |
| CN114402043A (en) | 2022-04-26 |
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