WO2001012737A1 - Composition de revetement et objet durci - Google Patents

Composition de revetement et objet durci Download PDF

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Publication number
WO2001012737A1
WO2001012737A1 PCT/JP2000/005477 JP0005477W WO0112737A1 WO 2001012737 A1 WO2001012737 A1 WO 2001012737A1 JP 0005477 W JP0005477 W JP 0005477W WO 0112737 A1 WO0112737 A1 WO 0112737A1
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group
component
composition
weight
coating
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PCT/JP2000/005477
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English (en)
Japanese (ja)
Inventor
Kouji Kawahara
Mibuko Shimada
Toshinori Sakagami
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Jsr Corporation
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Publication of WO2001012737A1 publication Critical patent/WO2001012737A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes

Definitions

  • the present invention relates to a coating composition and a cured product. More specifically, an organosilane-based UV-absorbing coating composition containing fine particles or sol of a metal oxide having a specific wavelength of UV-absorbing ability, and a UV-absorbing cured composition obtained therefrom About the body.
  • Optical devices such as a brown tube, a liquid crystal display device, and a plasma display panel have a problem that the liquid crystal and the organic film are deteriorated due to leakage of ultraviolet rays. Also, it is necessary to cut ultraviolet rays on the surface of fluorescent lamps, window glasses of automobiles, eyeglass lenses, and solar cells.
  • the required performance of the UV-absorbing coating film used for these materials is that, even if UV rays are cut, visible light is sufficiently transmitted, transparency is excellent, and adhesion to the substrate is good. For example, the ultraviolet absorption ability does not decrease during the period, and the coating film itself has excellent weather resistance.
  • excellent insulation is an important performance requirement in order not to lower the voltage holding ratio of the device.
  • the present invention has been made in view of the above problems, and has excellent storage stability, and when used as a coating film, has high hardness, excellent weather resistance, light resistance, and transparency, and long-term durability.
  • Organosiloxane-based coating material that has adhesiveness, has semi-permanent UV absorption capability, has insulating properties, high refractive index, and can be formed at low or normal temperature It is intended to provide a hardened body obtained more. Disclosure of the invention
  • R 1 is the same or different when there are two, represents a monovalent organic group having 1 to 15 carbon atoms
  • R 2 is the same or different, an alkyl group having 1 to 5 carbon atoms, Which represents an acyl group or a phenyl group having 1 to 6 carbon atoms, and n is an integer of 0 to 2), a hydrolyzate of the organosilane and a condensate of the organosilane.
  • the present invention relates to a coating composition
  • a coating composition comprising:
  • the above-mentioned coating composition has, as the component (A), a siloxane oligomer having an (A-2) SiO bond and a weight-average molecular weight of 300 to 100,000. And may be contained.
  • the present invention relates to a cured product having a coating film obtained from the coating composition.
  • the coating composition of the present invention comprises the above component (A-1) as a binder, the component (B) comprising a combination of a specific metal oxide having an ultraviolet absorbing ability, and, if necessary, a binder.
  • (A_2) component is the main component, so it has excellent adhesiveness to the substrate, high hardness, excellent long-term durability, UV absorption ability semi-permanently lasting, and insulation Is also excellent It has such characteristics.
  • organosilane (1) an organosilane represented by the above general formula (1), or a hydrolyzate of the organosilane (1) And at least one selected from condensates of organosilane (1), and functions as a binder in the composition of the present invention. That is, the component (A-1) may be only one of these three types, a mixture of any two types, or a mixture containing all three types. Good.
  • the hydrolyzate and the condensate are also collectively referred to as a hydrolyzate and condensate.
  • the hydrolyzate of the organosilane Sila switch (1) is organosilazane switch (1) in two to four ⁇ short without that OR 2 groups are all hydrolyzed included, for example, only one May be hydrolyzed, two or more may be hydrolyzed, or a mixture thereof.
  • the condensate of the organosilane (1) is formed by condensing silanol groups of the hydrolyzate of the organosilane (1) to form a Si-O-Si bond. In the invention, it is not necessary that all of the silanol groups are condensed, and the concept encompasses a mixture of a small amount of condensed silanol groups and a mixture of those having different degrees of condensation. is there.
  • examples of the monovalent organic group having 1 to 15 carbon atoms for R ′ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group.
  • 2-alkyl groups such as ethylhexyl group; acetyl group, propionyl group, butylyl group, valeryl group, benzoyl group, trioiloyl group, Acyl groups such as vinyl group; vinyl group, aryl group, cyclohexyl group, phenyl group, epoxy group, glycidyl group, (meth) acryloxy group, ureide group, amide group And a fluoroacetamide group, an isocyanate group and the like, and substituted derivatives of these groups.
  • R 1 is a substituent in the substituted derivative of R 1, for example, a halogen atom, rather also substituted unsubstituted amino group, a hydroxyl group, Melka flop preparative group, Lee Seo Shiana over preparative group, glycidyl Dokishi group, 3 , 41-epoxycyclohexyl group, (meth) acryloxy group, ureido group, ammonium base, ketoester group and the like.
  • the carbon number of R 1 composed of these substituted derivatives is 15 or less including the carbon atoms in the substituent.
  • two R 1 are present in the general formula (1), they may be the same or different from each other.
  • Examples of the alkyl group having 1 to 5 carbon atoms for R 2 include a methyl group, an ethyl group, an n_propyl group, an i_propyl group, an n_butyl group, a sec-butyl group, and a t_ Examples include butyl group, n-pentyl group and the like, and examples of the acetyl group having 1 to 6 carbon atoms include acetyl group, propylionyl group, butylyl group, valeryl group, and propyl group. Groups and the like.
  • a plurality of R 2 in the general formula (1) may be the same or different from each other.
  • organosilanes (1) include tetramethylsilicone, tetratradecylsilane, tetraquinone, n-propoxysilane, tetraquinone, i-propoxysilane, Tetra-alkoxysilanes such as tetra-n-butoxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and methyltriethoxysilane; n — Proprietary trimethoxysilane, n — Propyltriethoxysilane, i — Proprietary triethoxysilane, i — Propyltriethoxysilane Sicilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysi
  • trialkoxysilanes and dialkoxysilanes are preferred, and examples of trialkoxysilanes include methyltrimethoxysilane and methyltriethoxysilane.
  • dialkoxysilanes dimethyldimethoxysilane and dimethylethoxysilane are preferred.
  • Organosilane (1) is used as it is or as a hydrolyzate and Z or a condensate.
  • Hydrolyzate of organosilane (1) When used as Z and Z or a condensate, they can be used as the component (A-1) by hydrolysis and condensation in advance, but as described later, organosilanes When (1) is mixed with the remaining components to prepare a composition, by adding an appropriate amount of water, the organosilane (1) is hydrolyzed and condensed, and (A_l ) Component.
  • the following component (A-2) may be used in combination as the component (A).
  • the component (A-2) is a siloxane oligomer having a SiO bond and a weight-average molecular weight of 300 to 100,000. Even when used alone, two or more components are used. It may be a mixture.
  • the ratio of ⁇ to S i in the S i O bond is usually in the range of 0.5 to 2, and as a single oligomer, one (bifunctional oligomer) and one of 1.5 There are two types (trifunctional oligomers) and two types (tetrafunctional oligomers). Among them, siloxane oligomers having a ratio of 0 to S S of 1.5 are preferred.
  • a condensate of chlorosilane or a condensate of alkoxysilane is preferably used.
  • the terminal functional group of the siloxane is a hydroxyl group, a halogen atom or an organic group having 1 to 15 carbon atoms, and may be partially hydrolyzed / condensed.
  • halogen atom examples include fluorine and chlorine.
  • Examples of the organic group having 1 to 15 carbon atoms include a methyl group, an ethyl group, an ⁇ -propyl group, an i-propyl group, an n-butyl group, an i_butyl group, a sec_butyl group, t_butyl, n—hexyl, n—heptyl, n—octyl, n_nonyl, n—decyl, undecyl, dodecyl, tridecyl, tetra Alkyl groups such as radyl, hexadecyl, heptadecyl, octadecyl, and 2-ethylhexyl; Acetyl group, propionyl group, petryl group, valeryl group, benzoyl group, trioil group and other acyl groups; methoxy group, ethoxy group, propoxy group, butoxy group and other alkoxyl groups
  • substituent in the substituted derivative examples include a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, 4_ Epoxycyclohexyl group, (meth) acryloxy group, ureido group, ammonium base, ketoester group and the like.
  • the weight average molecular weight of the (A-2) component is from 300 to 100,000, particularly preferably from 600 to 500,000. If it is less than 300, the flexibility of the obtained coating film is insufficient. On the other hand, if it exceeds 100,000, the obtained coating composition has poor storage stability. Not good.
  • the proportion of the (A-1) component to the (A-2) component used is the (A-1) component
  • the siloxane oligomer is usually co-, hydrolyzed, and condensed with the organosilane (1). You.
  • the amount of water used for hydrolysis / condensation of the organosilane (1) and the siloxane oligomer is usually 0 to 1 mol of the total of the organosilane (1) and the siloxane oligomer. It is about 3 to 3 moles, preferably about 0.4 to 2 moles.
  • the hydrolysis / condensation reaction at this time that is, the reaction in the preparation of the composition of the present invention, is carried out at a temperature of 30 to 80 ° (: preferably 40 to 70 ° C, a reaction time of 0.5 It is about 10 to 10 hours, preferably about 1 to 7 hours.
  • a co-hydrolyzed condensate (hydrolyzate and Z or a condensate thereof) obtained by co-hydrolyzing and condensing the component (A-1) and the component (A-2) ) Is usually from 500 to 100,000, preferably from 600 to 800,000, and more preferably from 1,000 to 100,000. It is about 50, 000.
  • component (A) examples include MKC silicate manufactured by Mitsubishi Chemical Corporation, ethyl silicate manufactured by Colcoat, and silicone manufactured by Toray Dow Corning. Resin, silicone resin manufactured by Toshiba Silicone Co., Ltd., silicone resin manufactured by Shin-Etsu Chemical Co., Ltd., hydroxyl-containing polydimethylsiloxane manufactured by Dow Corning Asia Ltd., There are silicone oligomers and the like manufactured by Nipponika Co., Ltd., and these may be used as they are or after being condensed.
  • the component (A) can be used alone or in combination of two or more.
  • the component (B) in the composition of the present invention comprises fine particles of a metal oxide containing titanium oxide, zirconium oxide and tin oxide and Z or sol, and has an ultraviolet absorbing ability.
  • the ultraviolet absorbing ability of the component (B) makes it possible to obtain the ultraviolet absorbing ability of the coating film without substantially impairing the coating film performance. It is possible to prevent deterioration of organic substances due to ultraviolet rays.
  • (B) component for example, titanium dioxide emissions (T i 0 2), oxidized zirconium two ⁇ beam (Z r ⁇ 2) and tin oxide (S n 0 2), a solid solution in the respective metal oxides three mixtures Or an alloy of three metals consisting of titanium, zirconium and tin, or a composite of a metal oxide obtained by oxidizing a solid solution, and is particularly limited. Not done.
  • the component (B) used in the composition of the present invention is, for example, a ternary solid solution of a Ti_Zr-Sn-based metal oxide (colloid).
  • the Zr content and the Sn content are each 1% by weight to 89% by weight.
  • the component (B) may be present in the form of a powder composed of fine particles, an aqueous sol in which the fine particles are dispersed in water, a solvent sol in which a polar solvent such as methyl alcohol or a nonpolar solvent such as toluene is dispersed.
  • a solvent-based sol it may be further diluted with water or a solvent depending on the dispersibility of the ternary fine particles.
  • the average particle diameter of these ternary fine particles is preferably as small as possible from the viewpoint of ultraviolet absorbing ability, preferably 0.5 m or less, particularly preferably 0.1 lizm or less.
  • the component (B) By atomizing the component (B), it is possible to absorb an ultraviolet ray having a wavelength of 300 nm or less by 80% or more, and to provide a semi-permanent ultraviolet absorber without deterioration. In addition, because of its good uniform dispersibility, it has excellent coating properties such as transparency and storage stability.
  • the composition can be obtained. Surfactants, dispersing agents, coupling agents, and the like are added to these fine particle sols for the purpose of improving dispersibility and storage stability and preventing photocatalytic activity, and surface treatment is performed by these. Ivy is also preferably used.
  • the solid content concentration is preferably 60% by weight or less, and more preferably 50% by weight or less. This solid content concentration is usually adjusted by the amount of the water.
  • the component (A) may be added after preparing the composition comprising the component (A) and other additives described below, or the method of the present invention may be added. It can be added during the preparation of the composition to hydrolyze and condense the organosilane, siloxane and the like constituting the component (A) in the presence of the component (B).
  • the component (B) is added during the preparation of the composition, the semiconductor compound in the component (B) can be co-condensed with the component (A), and the dispersibility of the component (B) can be improved.
  • the component (B) is an aqueous sol, it is preferable to add it during the preparation of the composition. Also, when the viscosity in the system increases due to the incorporation of the component (D) described later, (B) It is preferred to add the components during the preparation of the composition.
  • the component (B) can be used alone or in combination of two or more.
  • the amount of the component (B) used is generally 0.5 to 500 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the hydrolyzed condensate of the component (A). 0 parts by weight.
  • the amount of the component (B) is too small, the effect of the present invention is hardly exhibited due to insufficient ultraviolet absorbing ability.
  • the amount is too large, the amount of the obtained coating composition is reduced. Film forming ability Inferior, cracking or peeling may occur.
  • composition of the present invention contains the above-mentioned components (A) and (B) as essential components, and in some cases, contains optional components described below.
  • Water and Z or an organic solvent are used to mix and adjust the total solids concentration of the composition.
  • the other role of water and organic or organic solvents is to make them applicable to a variety of coating methods, and to further improve the strength and dispersion stability and storage stability of the composition. I can do it.
  • Water is also used for hydrolysis and condensation of the component (A) as described above.
  • the organic solvent used for adjusting the total solid content of the composition is not particularly limited as long as the above components can be uniformly mixed. Examples thereof include alcohols, aromatic hydrocarbons, and ethers. , Ketones, esters and the like.
  • alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec_butyl alcohol. T-butyl alcohol, n-hexyl alcohol, n-octyl alcohol, ethylene glycol, diethyl glycol, triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, Examples thereof include diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene monomethyl ether acetate, and diacetone alcohol.
  • aromatic hydrocarbons include benzene, toluene, xylene, etc.
  • ethers include tetrahydrofuran and dioxane, and ketones.
  • esters include acetate, methylethylketone, methylisobutylketone, diisobutylketone, and the like.
  • Specific examples of the esters include ethyl acetate, propyl acetate, and butyl acetate. And propylene carbonate.
  • organic solvents can be used alone or in combination of two or more.
  • composition of the present invention may further contain the following components (C) to (D) as optional components.
  • the component (C) is a catalyst that promotes the hydrolysis-condensation reaction of the organosilane (1) and the component (A_2).
  • the curing speed of the resulting coating film is increased, and the polysiloxane produced by the polycondensation reaction of the organosilane component and the siloxane component used.
  • Crosslinking of the coating progresses, and a coating film having excellent strength and long-term durability can be obtained, and the coating film can be made thicker and the coating operation can be easily performed.
  • Examples of such a component (C) include an acidic compound, an alkaline compound, a metal salt, an amine compound, an organometallic compound and / or a partial hydrolyzate thereof (hereinafter, an organometallic compound and Z or a portion thereof). Hydrolysates are collectively referred to as “organometallic compounds, etc.”).
  • Examples of the acidic compound include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, alkitanic acid, p-toluenesulfonic acid, and phthalic acid, and preferably acetic acid.
  • alkaline compound examples include sodium hydroxide and potassium hydroxide, and are preferably sodium hydroxide.
  • metal salts examples include alkali metal salts such as naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminate, and carbonic acid.
  • amine compound for example, ethylenediamine, Kisamethylenediamine, diethylamine, triethylenetetramine, tetraethylenepentamine, pyridine, pyrazine, m-phenyleneamine, p-phenyleneamine MIN, ETHANOLAMINE, TRIETHYLAMINE, 3-AMINOPROPYL TRIMETHYXYLAN, 3—AMINOPROPYL'TRIETOXYLAN, 3— (2-AMINOETHYL) Aminopropyl trimethoxysilane, 3 — (2—aminoethyl) monoaminopropyl triethoxysilane, 3 — (2—aminoethyl) monoaminopropyl methyl ⁇ Dimethoxysilane, 3-anilinopropyl-trimethoxysilane, alkylamine salts, quaternary ammonium salts, and as a curing agent for example, ethylenediamine, Kis
  • organometallic compound (2) examples include a compound represented by the following general formula (2) (hereinafter referred to as “organometallic compound (2)”), a compound having 1 to 1 carbon atoms bonded to the same tin atom.
  • organometallic compounds examples include organometallic compounds of tin (IV) having 1 to 2 alkyl groups of 0 (hereinafter referred to as “organotin compounds”), and partial hydrolysates of these compounds.
  • M represents zirconium, titanium or aluminum
  • R 3 and R 4 are the same or different and are ethyl, n-propyl, i-propyl, n-butyl, sec_butyl
  • a monovalent hydrocarbon group having 1 to 6 carbon atoms such as a group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, phenyl group, etc.
  • R 5 represents R 3 and
  • a methoxy group, an ethoxy group, an n_propoxy group, a ⁇ -propoxy group, an n-butoxy group, sec — represents an alkoxyl group having 1 to 16 carbon atoms such as a butoxy group, a t-butoxy group, a lauryloxy group, a stearyloxy group, and r and s are integers
  • organometallic compound (2) examples include:
  • organometallic compounds (2) and their partial hydrolysates tri-n-butoxy-ethyl acetate-zirconium, di-i-propoxy-bis (acetyl acetate) titanium, di-i Aluminum propoxy-ethyl acetate acetate, aluminum tris (ethyl acetate acetate), or partial hydrolysates of these compounds are preferred.
  • organotin compound examples include:
  • Carboxylic acid type organotin compounds such as;
  • Mercaptide-type organotin compounds such as;
  • Chloride-type organotin compounds such as;
  • the component (C) can be used alone or as a mixture of two or more kinds, and can also be used as a mixture with a zinc compound or another reaction retarder.
  • the component (C) may be blended at the time of preparing the composition, or may be blended with the composition at the stage of forming a coating film. It may be blended at both stages of formation.
  • the amount of the component (C) used is usually from 0 to 100 parts by weight based on 100 parts by weight of the total amount of the above-mentioned organosilanes (1) and (A-2) in cases other than organometallic compounds. 0 parts by weight, preferably from 0.01 to 80 parts by weight, and more preferably from 0.1 to 50 parts by weight.
  • the component (D) has the following general formula (3)
  • R 4 and R 5 have the same meanings as R 4 and R 5 in the above general formulas of the organometallic compound (2), respectively. And at least one member selected from the group consisting of carboxylic acid compounds, dihydroxy compounds, amide compounds, and oxyaldehyde compounds.
  • Such a component (D) is preferably used in combination when an organometallic compound or the like is used as the component (C).
  • the component (D) acts as a stability improver for the composition. That is, the component (D) coordinates with a metal atom such as the above-mentioned organometallic compound to promote the condensation reaction of the above-mentioned component (A) by the organometallic compound or the like. It is presumed that by appropriately controlling the composition, it is possible to further improve the storage stability of the obtained composition.
  • component (D) examples include acetylaceton, methyl acetate acetate, ethyl acetate acetate, acetate acetate-n-propyl, acetate acetate-i-propyl, ⁇ -acetate.
  • Examples include amide, triethanolamine, dimethyldalioxime, dithizone, methionine, and salicylaldehyde. Of these, ace
  • the component (D) may be used alone or in combination of two or more.
  • the amount of the component (D) to be used is generally 2 mol or more, preferably 3 to 20 mol, per 1 mol of the organometallic compound in the organometallic compound or the like. In this case, if the amount of the component (D) is less than 2 mol, the effect of improving the storage stability of the obtained composition tends to be insufficient.
  • the component (E) in the present invention is silica and / or alumina, preferably silica fine particles and Z or alumina fine particles dispersed in water or an organic solvent. Includes silica sol and aluminum nasol. The average particle size of these fine particles is preferably 500 // m or less, more preferably 20 Om or less.
  • the above (E) The effect of the composition of the present invention is to improve the flexibility of the cured coating film and increase the critical thickness.
  • Examples of the component (E) include silica, for example, Snowtex, isopropanol silica gel, and methanol gel (manufactured by Nissan Chemical Industries, Ltd.); Catloid, Oscar [manufactured by Catalysis Chemical Industry Co., Ltd.]; Ludox (manufactured by Dupont, USA); Nalcoag (manufactured by Nalco Chemical Company, USA).
  • Examples of the alumina include, for example, Aluminum Nasol—100, Nissan Chemical Industries, Ltd. Aluminum Nasol—200, Aluminum Nasol—520, and Aluminum Naxos by Degussa West Germany. C.
  • the component (E) can be used alone or in combination of two or more.
  • the amount of the component (E) used in the composition is usually 5 to 500 parts by weight, based on 100 parts by weight of the total amount of the organosilane (1) and the component (A-2). Parts by weight, preferably between 10 and 400 parts by weight, more preferably between 15 and 300 parts by weight.
  • a filler can be separately added and dispersed in the composition of the present invention in order to color the obtained coating film and increase the film thickness.
  • composition of the present invention may contain, if desired, a known dehydrating agent such as methyl orthoformate, methyl orthoacetate, tetraethoxysilane, etc .; Polyoxyethylene alkyl phenyl ether, Polyoxyethylene fatty acid ester, Polycarboxylic acid type polymer surfactant, Polycarbonate, Polyphosphate, Polyacrylate, Polyamide ester salt And dispersants such as polyethylene glycol; methylcellulose, ethylcellulose, hydroxyshethylcellulose, hydroxypropylcellulose, and hydroxypropylmethylcellulose.
  • a known dehydrating agent such as methyl orthoformate, methyl orthoacetate, tetraethoxysilane, etc .
  • Polyoxyethylene alkyl phenyl ether Polyoxyethylene fatty acid ester
  • Polycarboxylic acid type polymer surfactant Polycarbonate, Polyphosphate, Polyacrylate, Polyamide ester salt
  • dispersants such as polyethylene glycol; methylcellulose,
  • Thickeners such as celluloses such as cellulose, castor oil derivatives, and phyllosilicates; ammonium carbonate, ammonium hydrogen carbonate, ammonium nitrite, sodium borohydride, calcium azide, etc.
  • Inorganic blowing agents azo compounds such as azobisisobutyronitrile, hydrazine compounds such as diphenylsulfone-1,3'-disulfohydrazine, semicarbazide compounds, triazole compounds,
  • organic foaming agents such as roso compounds
  • other additives such as surfactants, silane coupling agents, titanium coupling agents, and dyes can be added.
  • the composition of the present invention may contain a metal oxide having an ultraviolet absorbing ability other than the component (B) for the purpose of increasing the ultraviolet absorbing ability.
  • a metal oxide having ultraviolet absorbing ability for example, Z n O, can and this the like C e 0 2, existing forms of these metals oxides, (B) a component of the present invention The same is true. Further, these metal oxides may form a complex with the metal oxide constituting the component (B).
  • Tyke TTO manufactured by Ishihara Sangyo Co., Ltd., ZW-143, ZW-513C, ZS-300, ZS_300 manufactured by Sumitomo Osaka Cement Co., Ltd. 303, ZnO — 100, ZnO—200, Z—NOUVE manufactured by Mitsui Mining & Smelting Co., Ltd., Needlar manufactured by Taki Chemical Co., Ltd., Nippon Inorganic Chemical Industry Co., Ltd. ) Made by CERIGUARD and HiCera Super K29.
  • an organic ultraviolet absorber such as salicylic acid, benzophenone, benzotriazole, cyanoacrylate, and triazine.
  • examples of the ultraviolet stabilizer include piperidine.
  • the coating composition of the present invention includes a coating of the composition.
  • a repelling agent can be blended to further improve the properties.
  • leveling agents a fluorine-based leveling agent (trade name; the same applies hereinafter) is, for example, BM10 from BM-CHEMIE. 0, BM 1100; F-Chemicals Co., Ltd.'s F-772, F-C 7777; Kyoeisha Chemical Co., Ltd.'s Flourance Series; Sumitomo Sri-Jam's FC series; Fluonal TF series of Toho Chemical Co., Ltd., and the like.
  • silicone-based repelling agents include BYK Chemical's BYK series.
  • S shmegomann S shmego series F-Chemicals F-force 30, F-force 31, F-force 34, F-force 35, F-force 36 , F 39, F 83, F 86, F 88, etc.
  • peling agent examples include Carfinol manufactured by Nissin Chemical Industry Co., Ltd .; and Emargen and Homogenol manufactured by Kao Corporation.
  • the finish of the coating film is improved and the appearance of the coating film is improved, and the coating film can be uniformly applied.
  • the amount of leveling agent used is preferably from 0.01 to 5% by weight, more preferably from 0.02 to 3% by weight, based on the total composition.
  • the repelling agent As a method of blending the repelling agent, it may be blended at the time of preparing the composition, or may be blended with the composition at the stage of forming the coating film. You may mix
  • the method of mixing the components is not particularly limited, but the components (C) and (D) are used. In this case, it is preferable to obtain a mixture of the components (A) to (E) excluding the component (D), and then add the component (D) to the mixture.
  • the above-mentioned organosilane (1) and The siloxane oligomer may be subjected to a hydrolysis / condensation reaction in an organic solvent in the presence of water and the above component (C).
  • organic solvent include those used for adjusting the total solid concentration of the composition.
  • the organic solvent can be removed to obtain the composition of the present invention.
  • the total solid content of the composition of the present invention is preferably 50% by weight or less, and is appropriately adjusted depending on the purpose of use. For example, when the purpose is to impregnate the base material for forming a thin film, it is usually 1 to 30% by weight, and when it is used for the purpose of forming a thick film, it is usually 10 to 50% by weight. Or 20 to 45% by weight. If the total solid content of the composition exceeds 50% by weight, storage stability tends to decrease.
  • the coating composition of the present invention preferably has a total solid content concentration of 1 to 30% by weight, but is appropriately adjusted according to the type of the base material, the coating method, the coating film thickness and the like. .
  • Suitable substrates for using the composition of the present invention include, for optical device applications, glass such as float glass and soda glass; polyethylene terephthalate, polybutylene terephthalate, and the like.
  • a transparent substrate made of plastic such as polyethersulfone or polycarbonate can be used.
  • the substrate is not limited to these, and may be a metal such as iron, aluminum, or stainless steel; cement, concrete, ALC, flexible board, mortar, plate, gypsum, ceramics, or the like.
  • Inorganic ceramics materials such as phenolic resin, resin, phenolic resin, epoxy resin, acrylic resin, polyester, polyethylene, polypropylene, and ABS resin (acrylonitrile-butadiene) —Styrene resin), thermoplastic norbo Plastic molded products such as linen resin; plastic films such as polyethylene, polypropylene, polyvinyl alcohol, polyurethane, and polyimid; wood, paper, etc. Can be mentioned.
  • these substrates can be subjected to a surface treatment in advance for the purpose of adjusting the base, improving the adhesion, filling the porous substrate, smoothing, and patterning. .
  • thermoplastic norbornane resin examples include at least one tetracyclododecene derivative represented by the following general formula (4) or the above tetracyclododecene derivative.
  • A, B, C and D each represent a hydrogen atom or a monovalent organic group, and m represents an integer of 0 to 4.
  • a primer may be used in the coating composition of the present invention, if necessary.
  • the type of primer is not particularly limited as long as it has an action of improving the adhesion between the substrate and the composition, and is selected according to the type of the substrate and the purpose of use. Primers can be used alone or in combination of two or more.
  • primers examples include alkyd resin, amino alkyd resin, epoxy resin, polyester, acryl resin, urethane resin, fluorine resin, and acryl silicone resin.
  • these primers can be provided with various functional groups when adhesion between the substrate and the coating film under severe conditions is required.
  • a functional group examples include a hydroxyl group, a hydroxyl group, a carbonyl group, an amide group, an amine group, a glycidyl group, an alkoxysilyl group, an ether bond, and an ester bond. it can. Further, the primer may be blended with an ultraviolet absorber, an ultraviolet stabilizer and the like.
  • any of the compositions includes a brush, an all-over-one roll, an all-over flowco, an all-over spinco, an ultrasonic coater, (Micro) Use of gravure cups, etc., date coating, sink coating, spraying, screen process, electrodeposition, steaming and the like.
  • the composition of the present invention can be applied by previously applying an undercoat to the substrate.
  • the coating composition of the present invention has a dry film thickness of about 0.01 to 20 ⁇ m when applied once and about 0.02 to 40 wm when applied twice. Can be formed.
  • the film thickness can be adjusted according to the application. Then, the film is dried at room temperature or by heating at a temperature of about 30 to 200 ° C., usually for about 0.5 to 60 minutes to dry the coating film. Film) can be formed.
  • the coating composition of this invention in addition to being excellent in storage stability and coating film appearance, adhesion, and weather resistance, it is also excellent in electrical insulation, high in hardness, and has ultraviolet absorption ability. However, it is possible to prevent deterioration of the organic base and the substrate.
  • the cured film obtained by the composition of the present invention has an ultraviolet absorbing ability semi-permanently, and is capable of integrating ultraviolet light having a specific wavelength of 190 to 350 nm, particularly 200 to 320 nm. Can cut about 70-100%, Excellent absorption capacity.
  • the coating composition of the present invention also has excellent electrical insulation properties, it can be used for a liquid crystal display element, a liquid crystal protective film of a projection television, an ultraviolet light cut film formed on the surface of a back plate of a plasma display panel, or the like. It is suitable for use in electronic material applications, such as UV cut films on the inner surface of heat pipes, sealing materials for light emitting diodes (LEDs), and coating materials for EPROM windows. In addition, it can also be suitably used as an ultraviolet light coating material for automotive window glass, eyeglass lenses, solar cells and the like.
  • the measurement was carried out by gel permeation chromatography (GPC) under the following conditions.
  • Tetrahydrofuran was used as a solvent, and was prepared by dissolving 1 g of sample in 100 cc of tetrahydrofuran.
  • Standard polystyrene Standard polystyrene manufactured by Pressure Chemical Co., USA was used.
  • composition to which the curing accelerator was not added was sealed and stored in a polyethylene bottle at room temperature for 3 months, and the presence or absence of gelation was visually determined. For those that do not cause gelation, measure the viscosity with a BM viscometer manufactured by Tokyo Keiki Co., Ltd., and if the change rate is within 20%, no change ( ⁇ ) The thing was changed (X).
  • Each composition was applied on a quartz glass so as to have a dry film thickness of 10, and then the transmittance of visible light was measured and evaluated according to the following criteria.
  • ⁇ ; transmittance is 90% or more
  • ⁇ ; transmittance is 80% or more and less than 90%
  • ⁇ : transmittance is 70% or more and less than 80%
  • Each composition was applied on quartz glass to a dry film thickness of 1 m, baked at 200 for 30 minutes, and then using a high resistance meter manufactured by Heureett Packard. The surface specific resistance was measured.
  • composition (I_a) is applied to a quartz glass plate by Barco overnight, and is heated and dried at 200 ° C for 30 minutes to obtain hardness, ultraviolet absorption, transparency, and insulation. A test piece for a sex test was obtained. Table 1 shows the storage stability evaluation results and various evaluation results of the test specimens for each composition.
  • compositions (I_b) to (Ig) having a solid content of 20% and the preparation of each test piece were performed in the same manner as in Example 1. went. However, the post-addition component in each Example was added after cooling to room temperature after completion of the reaction. Tables 1 and 2 show the evaluation results of storage stability of each composition and various evaluation results of each test piece.
  • Example 1 2 3 4 Composition name I-a I-b I-c I-d Formulation (parts)
  • HIT-32M (* 3) 200 200 200 200 200 Ion exchange water 20 20 20 20 20 20
  • the composition is applied to a quartz glass plate by spin coating at 500 rpm for 20 seconds, and is dried by heating at 200 rpm for 30 minutes.
  • a test piece for a sex test was obtained.
  • Table 4 shows the evaluation results of the storage stability of the composition and various evaluation results of the test pieces.
  • the Mw of the composition is the Mw obtained by removing the component (B) from the obtained composition by filtration.
  • a — 1 tetrafunctional oligomer having a terminal alkoxysilyl group, M w; 5 0 0.
  • a — 2 trifunctional oligomer having a terminal alkoxysilyl group, M w; 35,000.
  • a-3 trifunctional oligomer having a terminal hydroxyl group, Mw: 8,000
  • a — 4 Bifunctional oligomer having a terminal alkoxysilyl group and a Zoxyalkylene group, Mw: 5,000.
  • HIT32M manufactured by Nissan Chemical Industries, Ltd., methanol dispersion, solid concentration: 30%.
  • HIT30M Nissan Chemical Industries, Ltd., methanol dispersion, solid content concentration 30%.
  • Silica sol i-Propyl alcohol dispersion, solid concentration 30%.
  • UV absorption rate (%) 99 98 99 98 surface resistivity (10 '5 ⁇ ⁇ cm) 1. 2 3.0 2.0 1. 5 visible light transmittance ⁇ ⁇ ⁇ ⁇ Table 5
  • Example 1 2 1 3 1 4 1 5 Formulation (parts)
  • UV absorption rate (%) 98 98 98 98 98 surface resistivity (10 '5 ⁇ ⁇ cm) 1. 9 1. 9 2.0 2.0 visible light transmittance ⁇ ⁇ ⁇ ⁇ Table 6
  • the coating composition of the present invention has excellent storage stability and, when formed into a coating film, has high hardness, excellent weather resistance, light resistance, and transparency, has long-term durability adhesion, and has an ultraviolet absorbing ability.
  • the cured product of the present invention is excellent in both ultraviolet absorbing ability and visible light transmittance, excellent in weather resistance, light resistance, transparency, has long-term durability adhesion, and has excellent insulating properties.
  • ultraviolet shielding films for optical devices such as plasma display panels, coating materials for EPROM windows, LCD protective films for projection televisions, etc. It can be suitably used for various purposes, such as materials and ultraviolet cut-coat materials for automobile windows.

Abstract

L'invention concerne une composition de revêtement renfermant : au moins un élément sélectionné dans le groupe comprenant des organosilanes représentés par la formule générale (R1)nSi(OR2)4-n (dans laquelle R1 représente un groupe organique monovalent en C¿1-15?, et lorsque 2 R?1¿ sont présents, ceux-ci sont identiques ou différents; les R2 sont identiques ou différents et chacun représente alkyle en C¿1-5?, acyle en C1-6 ou phényle; et n est un nombre entier compris entre 0 et 2), des hydrolysats et des condensats de ces organosilanes; et de fines particules et/ou un sol d'oxyde métallique contenant du titane, du zirconium et des métaux à base d'étain. La composition renferme en outre un oligomère de siloxane possédant des liaisons SiO et un poids moléculaire moyen de 300 à 100000. La composition de revêtement permet d'obtenir une matière de revêtement d'organosilane qui présente une excellente stabilité au stockage et forme un film de revêtement possédant d'excellentes propriétés d'aspect, d'adhérence et de résistance aux intempéries, etc., présentant une dureté élevée et une capacité d'absorption des ultraviolets, et capable de prévenir la détérioration d'une couche primaire ou d'un substrat.
PCT/JP2000/005477 1999-08-16 2000-08-16 Composition de revetement et objet durci WO2001012737A1 (fr)

Applications Claiming Priority (2)

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JP22990999 1999-08-16
JP11/229909 1999-08-16

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001081466A1 (fr) * 2000-04-20 2001-11-01 Dsm N.V. Composition de resine durcissable, film durci et produit composite
CN103201049A (zh) * 2010-11-11 2013-07-10 日本曹达株式会社 使用有机薄膜形成用固体物或油状物的有机薄膜叠层体制造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998039253A1 (fr) * 1997-03-03 1998-09-11 Nissan Chemical Industries, Ltd. Procede de production de sols de composites, de composition de revetement et d'elements optiques
JPH10324846A (ja) * 1997-05-26 1998-12-08 Seiko Epson Corp コーティング用組成物、積層体及び眼鏡レンズ
JP2000063754A (ja) * 1998-08-20 2000-02-29 Nissan Chem Ind Ltd コーティング組成物及び光学部材

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998039253A1 (fr) * 1997-03-03 1998-09-11 Nissan Chemical Industries, Ltd. Procede de production de sols de composites, de composition de revetement et d'elements optiques
JPH10324846A (ja) * 1997-05-26 1998-12-08 Seiko Epson Corp コーティング用組成物、積層体及び眼鏡レンズ
JP2000063754A (ja) * 1998-08-20 2000-02-29 Nissan Chem Ind Ltd コーティング組成物及び光学部材

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001081466A1 (fr) * 2000-04-20 2001-11-01 Dsm N.V. Composition de resine durcissable, film durci et produit composite
US7122253B2 (en) 2000-04-20 2006-10-17 Dsm N.V. Curable resin composition, cured film, and composite product
CN103201049A (zh) * 2010-11-11 2013-07-10 日本曹达株式会社 使用有机薄膜形成用固体物或油状物的有机薄膜叠层体制造方法
CN103201049B (zh) * 2010-11-11 2016-01-20 日本曹达株式会社 使用有机薄膜形成用固体物或油状物的有机薄膜叠层体制造方法
US9309416B2 (en) 2010-11-11 2016-04-12 Nippon Soda Co., Ltd. Process for producing organic thin film laminate using solid or oily material for organic thin film formation applications

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