WO2007119805A1 - Fluide pour revêtement contenant un ester phosphorique et revêtements anti-réflexion - Google Patents

Fluide pour revêtement contenant un ester phosphorique et revêtements anti-réflexion Download PDF

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Publication number
WO2007119805A1
WO2007119805A1 PCT/JP2007/058120 JP2007058120W WO2007119805A1 WO 2007119805 A1 WO2007119805 A1 WO 2007119805A1 JP 2007058120 W JP2007058120 W JP 2007058120W WO 2007119805 A1 WO2007119805 A1 WO 2007119805A1
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Prior art keywords
film
coating
formula
component
forming
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PCT/JP2007/058120
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English (en)
Japanese (ja)
Inventor
Ryosuke Shimano
Kenichi Motoyama
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Nissan Chemical Industries, Ltd.
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Publication date
Application filed by Nissan Chemical Industries, Ltd. filed Critical Nissan Chemical Industries, Ltd.
Priority to CN2007800122539A priority Critical patent/CN101415789B/zh
Priority to JP2008510995A priority patent/JP5293180B2/ja
Priority to KR1020087024793A priority patent/KR101362627B1/ko
Publication of WO2007119805A1 publication Critical patent/WO2007119805A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4

Definitions

  • Coating liquid for coating formation containing phosphoric ester compound and antireflection film
  • the present invention relates to a coating liquid for forming a film containing polysiloxane and a phosphate ester compound, a film formed therefrom, and a method for producing them. Specifically, a coating liquid for forming a film containing a polysiloxane having an organic group substituted with a fluorine atom in the side chain, a phosphate ester compound having a hydroxyl group, a film formed therefrom, and a method for forming the film About. Furthermore, the present invention relates to the application of the above-mentioned coating liquid for forming a film and an antireflection application of a film formed therefrom.
  • MgF2 fine particle alcohol dispersion formed by reacting magnesium salt or alkoxymagnesium compound as Mg source with fluoride salt as F source, or tetraalkoxy to improve film strength.
  • a liquid containing silane or the like is used as a coating liquid, which is applied onto a glass substrate such as a cathode ray tube, and then heat-treated at 100 to 500 ° C., whereby an antireflection film exhibiting a low refractive index on the substrate.
  • hydrolytic polycondensate such as tetraalkoxysilane, methyltrialkoxysilane, etyltrialkoxysilane, etc.
  • a coating liquid by mixing two or more kinds having different average molecular weights with a solvent such as alcohol.
  • a coating is formed by adding means such as the mixing ratio and relative humidity control during the above mixing, and then heated to create a coating from 1.21 to 1.40.
  • Fluorine-containing silicone with polyfluorocarbon chains such as (CF) C H Si (OCH)
  • a cocondensate liquid is prepared by filtration, and then this liquid is applied onto the lower layer film, 120 to 250 °.
  • a method comprising heating at C is described.
  • the reaction mixture is heated at 40 to 180 ° C. in the absence of water to form a polysiloxane solution, and then a coating solution containing the solution is applied to the substrate surface.
  • a film having a refractive index of 1.28 to 1.38 and a water contact angle of 90 to 115 degrees is disclosed which is formed in close contact with the substrate surface by thermosetting at 450 to 450 ° C. (See Patent Document 4).
  • Patent Document 1 Japanese Patent Laid-Open No. 05-105424
  • Patent Document 2 Japanese Patent Laid-Open No. 06-157076
  • Patent Document 3 Japanese Patent Application Laid-Open No. 61-010043
  • Patent Document 4 Japanese Patent Laid-Open No. 09-208898
  • the present invention has the following gist.
  • the component (A) is a polysiloxane obtained by polycondensation of an alkoxysilane represented by the formula (1) and an alkoxysilane containing the alkoxysilane represented by the formula (2). Coating solution for film formation.
  • R 1 represents a hydrocarbon group having 1 to 5 carbon atoms.
  • R 2 represents an organic group substituted with a fluorine atom
  • R 3 represents a hydrocarbon group having 1 to 5 carbon atoms.
  • R 4 represents an organic group not substituted with a fluorine atom
  • R 5 represents a hydrocarbon group having 1 to 5 carbon atoms
  • n represents an integer of 1 to 3.
  • R 6 represents an organic group having 1 to 20 carbon atoms, and m represents an integer of 1 or 2.
  • a method for forming a coating wherein the coating solution for forming a coating described in any one of 1 to 8 above is applied to a substrate, dried at room temperature to 150 ° C, and then cured from room temperature to 150 ° C. .
  • a coating solution for film formation described in any one of 1 to 8 above is applied to a substrate, dried at room temperature to 150 ° C, and then cured from room temperature to 150 ° C. Forming method.
  • An antireflection film comprising the coating according to 9 or the antireflection film according to 10.
  • a polysiloxane having an organic group substituted with a fluorine atom as the component (A) in the side chain is obtained.
  • alkoxysilane containing 60 mols of 95 mol% of alkoxysilane represented by formula (1) and 5 to 40 mol% of alkoxysilane represented by formula (2) A solution of polysiloxane (A) obtained by polycondensation of 0.2 to 2 mol of oxalic acid with respect to 1 mol of alkoxy group in an organic solvent at a liquid temperature of 50 to 180 ° C.
  • a phosphate ester compound bonded to a hydroxyl group atom characterized by comprising:
  • R 1 represents a hydrocarbon group having 1 to 5 carbon atoms.
  • R 2 represents an organic group substituted with a fluorine atom
  • R 3 represents a hydrocarbon group having 1 to 5 carbon atoms.
  • the coating liquid for forming a film of the present invention is excellent in storage stability, has a high water contact angle, has good dust wiping property, and can form a stable film without change over time.
  • a coating solution for forming a film exhibiting a low reflectance is useful as a coating solution for forming an antireflection film, and a coating formed using the coating solution should exhibit a low reflectance, a high antifouling property, and a dust wiping property. It is very useful as an antireflection film.
  • the present invention comprises (A) a polysiloxane having a side chain with an organic group substituted with a fluorine atom as a component, and (B) a phosphate ester compound in which a hydroxyl group as a component is bonded to a phosphorus atom.
  • the present invention relates to a coating liquid for forming a film, a film formed therefrom, and a method for producing the same.
  • Component (A) is a polysiloxane having an organic group substituted with a fluorine atom in the side chain.
  • the side chains are mainly those that impart a high water contact angle to the coating, and the side chains are not particularly limited as long as they exhibit antifouling properties.
  • Such an organic group substituted with a fluorine atom is an organic group in which part or all of the hydrogen atoms of an aliphatic group or aromatic group are substituted with fluorine atoms. Specific examples of these are given below.
  • Examples thereof include a trifluoropropyl group, a tridecafluorooctyl group, a heptadecafluorodecyl group, and a pentafluorophenylpropyl group.
  • a perfluoroalkyl group is preferable because a highly transparent film can be easily obtained. More preferably, it is a perfluoroalkyl group having 3 to 15 carbon atoms.
  • a plurality of polysiloxanes having side chains as described above may be used in combination.
  • the method for obtaining a polysiloxane having an organic group substituted with a fluorine atom in the side chain as described above is not particularly limited. In general, it can be obtained by polycondensation of the above-mentioned alkoxysilane having an organic group in the side chain with other alkoxysilane.
  • polysiloxanes obtained by polycondensation of alkoxysilanes represented by formula (1) and alkoxysilanes represented by formula (2) are preferred.
  • R 1 in the formula (1) represents a hydrocarbon group, but since the reactivity is higher when the number of carbon atoms is smaller, a saturated hydrocarbon group having 1 to 5 carbon atoms is preferred, and a methyl group is more preferred. , An ethyl group, a propyl group, and a butyl group.
  • tetraalkoxysilane examples include tetramethoxysilane, tetraeth Examples thereof include xyloxysilane, tetrapropoxysilane, and tetrabutoxysilane, which are readily available as commercial products.
  • At least one of the alkoxysilanes represented by the formula (1) may be used V, but plural kinds may be used as necessary.
  • the alkoxysilane represented by the formula (2) is an alkoxysilane having an organic group substituted with a fluorine atom in the side chain. Accordingly, this alkoxysilane imparts water repellency to the coating film.
  • R 2 in the formula (2) represents an organic group substituted with the above-described fluorine atom, but the number of fluorine atoms of the organic group is not particularly limited.
  • R 3 in the formula (2) represents a hydrocarbon group having 1 to 5 carbon atoms, preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, Butyl group.
  • alkoxysilanes represented by the formula (2) an alkoxysilane in which R 2 is a perfluoroalkyl group is preferred, and more preferably R 2 is an organic group represented by the formula (5). Some anoroxysilanes are preferred.
  • k represents an integer of 0 to 12.
  • alkoxysilane having an organic group represented by the formula (5) include trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorotrimethoxysilane, and tridecafluoro.
  • Examples include loctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, etc.
  • k is an integer of 2 to 12
  • the anti-reflective coating has a fingerprint wiping property. Since it becomes favorable, it is preferable.
  • At least one of the alkoxysilanes represented by the formula (2) may be used as V, but a plurality of types may be used as necessary.
  • polysiloxane (A) is a polycondensation of alkoxysilanes represented by formula (1) and formula (2) and other alkoxysilanes represented by formula (3) and Z or formula (6). It can also be made.
  • the alkoxysilanes represented by the formulas (1) and (2) either the alkoxysilane represented by the formula (3) or the alkoxysilane represented by the formula (6) is used alone. You may use both together.
  • R 4 represents an organic group not substituted with a fluorine atom
  • R 5 is a hydrocarbon having 1 to 5 carbon atoms.
  • N represents an integer of 1 to 3;
  • R 7 represents a hydrocarbon group having 1 to 5 carbon atoms
  • R 8 represents an organic chain having 1 to 20 carbon atoms.
  • the alkoxysilane of the formula (3) is an alkoxysilane having 1, 2 or 3 organic groups and 1, 2 or 3 alkoxy groups, wherein R 4 is substituted with a fluorine atom.
  • R 5 in formula (3) is a hydrocarbon group having 1 to 5 carbon atoms each. When n is 1 or 2, R 5 is generally the same in many cases, but in the present invention, R 5 may be the same or different.
  • R 4 in the formula (3) is an organic group having 1 to 20 carbon atoms, preferably an organic group having 1 to 15 carbon atoms. When n is 2 or 3, in general, R 4 is often the same, but in the present invention, R 4 may be the same or different.
  • alkoxysilanes represented by formula (3) are not limited to these.
  • methacrylonitrile trimethoxysilane methacrylonitrile trimethoxysilane, .gamma.-methacryloxypropyl triethoxysilane, gamma - ⁇ laid trimethoxysilane, I - ureidopropyltriethoxysilane
  • dialkoxysilanes such as ethoxysilane, dimethyldimethoxysilane, and dimethyljetoxysilane.
  • R 5 in the formula (3) is a force that is a hydrocarbon group having 1 to 5 carbon atoms, preferably a saturated hydrocarbon group having 1 to 4 carbon atoms, more preferably a saturated carbon group having 1 to 3 carbon atoms. It is a hydrogen group.
  • the alkoxysilane represented by the formula (3) can be used in a plurality of types as required.
  • the alkoxysilane of the formula (6) is a hydrocarbon group in which R 7 has 1 to 5 carbon atoms, preferably a saturated hydrocarbon group having 1 to 4 carbon atoms, and more A saturated hydrocarbon group having 1 to 3 carbon atoms is preferred.
  • R 7 is often the same, but in the present invention, R 7 may be the same or different.
  • R 8 is an organic chain having 1 to 20 carbon atoms, and the structure is not particularly limited, and may include cyclic structures such as double bonds, triple bonds, and phenyl groups, and branched structures. Moreover, you may contain hetero atoms, such as nitrogen, oxygen, and fluorine.
  • the R 8 moiety contains a perfluoroalkyl chain ( It is preferable to use an alkoxysilane having an organic chain as in 7).
  • a specific example of an alkoxysilane having a structure in which R 8 in formula (6) is an organic chain containing a perfluoroalkyl chain represented by formula (7) is 1,6-bis. (Trimethoxysilylethyl) dodecafluoro hexane, 1,6-bis (triethoxysilylethyl) dodecafluoro hexane, and the like.
  • the component (A) used in the present invention is usually represented by the formula (3) and the formula (6) as necessary, essentially including the alkoxysilane represented by the formula (1) and the formula (2).
  • the ratio of the alkoxysilane used is not particularly limited as long as it is a homogeneous solution in a solvent obtained by polycondensation of one or both of the alkoxysilanes.
  • the alkoxysilane represented by the formula (2) is 5 mol% or more with respect to the total amount of alkoxysilane used to obtain the component (A), a film having a water contact angle of 80 ° or more is obtained. When it is 40 mol% or less, the formation of gels and foreign substances can be suppressed, and it is easy to obtain a homogeneous solution of component (A)!
  • the amount of the alkoxysilane of formula (1) is, (A) in the total amount of Al Kokishishiran used for obtaining the component, 60 mole 0/0 Power et al Mashi 95 mol% Ca children! /,.
  • alkoxysilane represented by the formula (3) When only the alkoxysilane represented by the formula (3) is used in combination, it is preferably 0 to 35 mol% in the total amount of alkoxysilane used to obtain the component (A). When only the alkoxysilane represented by the formula (6) is used in combination, 0 to 20 mol% is preferable in the total amount of alkoxysilane used to obtain the component (A).
  • the total amount (A) component of the alkoxysilane represented by formula (3) and formula (6) is The total amount of alkoxysilanes used to obtain the component (A) is 0 to 35 mol% in the total amount of alkoxysilanes used to obtain the component (A). Preferably it is 0 to 15 mol% in quantity! /.
  • the method for condensing the polysiloxane that is component (A) used in the present invention is not particularly limited.
  • hydrolysis and condensation of an alkoxysilane in an alcohol solvent is used.
  • the hydrolysis' condensation reaction may be either partial hydrolysis or complete hydrolysis.
  • complete three-necked water splitting theoretically, it is sufficient to cover 0.5 times mole of water of all alkoxy groups in the alkoxysilane, but usually an excess amount of water is more than 0.5 times mole.
  • the amount of water used in the above reaction can be appropriately selected as desired, but is usually 0.1 to 2.5 moles of all alkoxy groups in the alkoxysilane.
  • hydrolysis' acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid; ammonia, methylamine, ethylamine, ethanolamine, triethylamine, etc. for the purpose of promoting the condensation reaction; Alkali; metal salts such as hydrochloric acid, sulfuric acid, or nitric acid are used as catalysts.
  • the amount of the catalyst used in the reaction is preferably about 0.05 times the molar amount of all alkoxy groups in the alkoxysilane.
  • the heating temperature and the heating time can be appropriately selected according to need.
  • the reaction system is set to 50 to 180 ° C., and several tens of power can be obtained in a sealed container or under reflux so that the liquid does not evaporate or volatilize. Done for tens of hours.
  • methods such as heating and stirring for 24 hours at 50 ° C. and heating and stirring for 8 hours under reflux can be mentioned.
  • a method of heating a mixture of alkoxysilane, solvent and oxalic acid can be mentioned. Specifically, after adding oxalic acid to alcohol in advance to obtain an alcohol solution of oxalic acid, the solution and alkoxysilane are mixed and heated. In this case, the amount of oxalic acid is generally set to 0.2 mol, such as 0.2 force, with respect to 1 mol of all alkoxy groups of alkoxysilane.
  • the heating in this method can be performed at a liquid temperature of 50 to 180 ° C, and preferably, for example, in a sealed container or under reflux for several tens of hours for several tens of hours so that the liquid does not evaporate or volatilize. Done.
  • a plurality of alkoxysilanes when a plurality of alkoxysilanes are used, a plurality of alkoxysilanes may be mixed and used in advance, or a plurality of alkoxysilanes may be added sequentially.
  • the concentration obtained by converting the total amount of silicon atoms of the prepared alkoxysilane into SiO is 20 quality. Generally, the amount is not more than%.
  • Solvents used for polycondensation of alkoxysilanes include alkoxysilanes represented by formula (1) and formula (2) and, if necessary, alkoxysilanes represented by formula (3) and formula (6). If it melt
  • alcohols are produced by the polycondensation reaction of alkoxysilanes, and therefore, alcohols and organic solvents having good compatibility with alcohols are used.
  • organic solvent examples include alcohols such as methanol, ethanol, propanol, and butanol; ethylene glycol monomethyl ether, ethylene glycol monoremonoethylenoatenore, diethyleneglycolenomonomethinoreatenore, diethylene
  • examples include ethers such as glycol monoethyl ether; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.
  • the component (B) used in the present invention is a phosphate ester compound having a hydroxyl group.
  • a phosphate ester compound having one or two hydroxyl groups bonded to a phosphorus atom in one molecule is preferable.
  • the phosphate compound represented by the formula (4) is preferable.
  • R 6 in the formula (4) may include a cyclic structure such as a force double bond, a triple bond, and a phenol group, which is an organic group having 1 to 20 carbon atoms, and a branched structure. It may also contain heteroatoms such as nitrogen and oxygen.
  • the carbon number of R 6 is 21 or more, the compatibility with polysiloxane (A) may be insufficient, or the storage stability of the coating solution may not be sufficiently obtained. Twenty organic groups are preferred.
  • a case of 10 is more preferable because it can suppress an increase in reflectance, and a case of 1 to 6 carbon atoms is preferable because there is almost no increase in reflectance.
  • M in the formula (4) is an integer of 1 or 2, but when m is 0, the compound of the formula (4) becomes a phosphate ester compound having no hydroxyl group, and is an antistatic effect that is an effect of the present invention. It is difficult to obtain an effect.
  • the compound of formula (4) represents phosphoric acid, and the coating formed due to insufficient affinity with polysiloxane (A) may become unstable and whiten over time. Therefore, a compound that has antistatic properties while maintaining the stability of the coating, and thereby exhibits dust wiping properties, which is the effect of the present invention, is a phosphorous having both a hydroxyl group in which m is 1 or 2 and an alkyl ester moiety. It is an acid ester compound. Many hydroxyl groups! Since the antistatic effect is so strong that m is 2, particularly when m is 2, the effect of the present invention can be achieved with a small amount.
  • di-n-butyl phosphate isolated diester
  • phenol phosphate also known as phosphoric acid monophenyl ester, monoester isolated
  • phosphoric acid diphenyl also known as phosphoric acid diphenyl ester
  • diesters isolated product hexyl phosphoric acid 2
  • E Ji Le phosphate -
  • the content of the component (B) is such that the phosphorus atom of the component (B) is 0.01 mol or more with respect to 1 mol of the total amount of silicon atoms in the component (A). preferable. More preferably, it is 0.1 mol or more, and particularly preferably 0.15 mol or more. When the amount is less than 0.01 mol, it may be difficult to obtain good dust wiping properties, which is the effect of the present invention. On the other hand, even if it exceeds 0.45 mol, the effect of dust wiping is hardly improved, so 0.45 mol or less is preferable. When used in an antireflection film, the amount is more preferably 0.4 mol or less, and particularly preferably 0.25 mol or less.
  • the coating liquid for forming a film of the present invention is usually in a solution state in which the component (A), the component (B), and other components described later as required are dissolved in a solvent.
  • the (C) solvent used in the present invention is not particularly limited as long as it can uniformly dissolve the component (A), the component (B), and other components described later as required.
  • an organic solvent Usually an organic solvent.
  • solvents include alcohols such as methanol, ethanol, propanol, butanol and diacetone alcohol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethylene glycol, propylene glycol and hexylene glycol.
  • Glycols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl enore ethere, ethylene glycol monobutino ree enore, ethenorecanolitol, butyl carbitol, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, Ethers such as propylene glycol monobutyl ether and tetrahydrofuran; esters such as methyl acetate, ethyl acetate, and ethyl lactate Etc.
  • Ethers such as propylene glycol monobutyl ether and tetrahydrofuran
  • esters such as methyl acetate, ethyl acetate, and ethyl lactate Etc.
  • a plurality of solvents may be used.
  • the component (A) and other components other than the component (B), for example, inorganic fine particles, fillers, leveling agents, surface modification Components such as an agent and a surfactant may be contained.
  • Examples of the inorganic fine particles include metal oxide fine particles, metal double oxide fine particles, and magnesium fluoride fine particles.
  • metal oxides examples include silica, alumina, titanium oxide, zirconium oxide, tin oxide, and zinc oxide.
  • metal double oxides include ITO, copper, silver, and zinc antimonate. Etc.
  • hollow silica fine particles, porous silica fine particles, and the like can also be exemplified.
  • Such inorganic fine particles may be either powder or colloidal solution, but those of colloidal solution are preferable because they are easy to handle.
  • This colloidal solution may be a dispersion of inorganic fine particle powder in a dispersion medium or a commercially available colloidal solution.
  • the inclusion of inorganic fine particles makes it possible to impart the surface shape of the formed cured film and other functions.
  • the inorganic fine particles preferably have an average particle diameter of 0.001 force to 0.2 m, and more preferably 0.001 force to 0.1 m.
  • the average particle size of the inorganic fine particles exceeds 0.2 ⁇ , the transparency of the cured film formed by the prepared coating liquid may be lowered.
  • the dispersion medium for the inorganic fine particles examples include water and organic solvents.
  • the colloidal solution is preferably adjusted to ⁇ or pKa from 2 to 10, more preferably from 3 to 7.
  • Examples of the organic solvent used for the dispersion medium of the colloidal solution include alcohols such as methanol, ethanol, propanol, and butanol; glycols such as ethylene glycol; ketones such as methyl ethyl ketone and methyl isobutyl ketone; toluene, Aromatic hydrocarbons such as xylene; Amides such as dimethylformamide, dimethylacetamide, and N methylpyrrolidone; Esters such as ethyl acetate, butyl acetate, and ⁇ -butyroratatone; Ethylene glycol monopropyl ether, tetrahydrofuran, 1,4 dioxane And ethers such as Of these, alcohols and ketones are preferred. These organic solvents can be used alone or in admixture of two or more as a dispersion medium.
  • the method for preparing the coating liquid for forming a film of the present invention is not particularly limited.
  • the components (A) and (B) may be in a uniform solution state.
  • the component (A) is polycondensed in a solvent, and thus is obtained in a solution state. Therefore, a method of using the solution containing the component (A) (hereinafter referred to as the solution of the component (A)) as it is and mixing it with the component (B) is simple.
  • the solution of component (A) may be concentrated, diluted by adding a solvent, or replaced with another solvent, and then mixed with component (B).
  • the solvent can be added after mixing the solution of component (A) and component (B).
  • the component (B) may be dissolved in the solvent (C) and then mixed with the solution (A).
  • the SiO equivalent concentration in the coating solution is preferably from 0.5 to 15% by mass.
  • SiO equivalent concentration is lower than 0.5% by mass, it is desirable to apply it once.
  • the solvent used for dilution, substitution or the like may be the same solvent as used for the polycondensation of alkoxysilane described above, or may be a different solvent.
  • the solvent is not particularly limited as long as the compatibility with the component (A) and the component (B) is not impaired, and one kind or a plurality of kinds can be arbitrarily selected and used.
  • the method for mixing the other components described above is not particularly limited, either at the same time as component (A) and component (B) or after mixing components (A) and (B). ! ⁇ .
  • a coating solution for forming a coating comprising (A) component and 0.01 to 0.45 mol of phosphorus atoms in component (B) with respect to 1 mol of the total amount of silicon atoms in component (A).
  • a coating liquid for forming a coating film comprising the above [1] and inorganic fine particles.
  • a coating forming coating solution containing at least one selected from the group consisting of the above [1] or [2] and a filler, a leveling agent, a surface modifier, and a surfactant.
  • the coating liquid for forming a film of the present invention can be applied to a substrate and thermally cured to obtain a desired film.
  • a known or well-known method can be adopted as the coating method.
  • dip coating method, flow coating method, spin coating method, flexographic printing method, ink jet coating method, spray coating method, bar coating method, gravure roll coating method, roll coating method, blade coating method, air doctor one coating method, air knife Methods such as a coating method, a wire doctor coating method, a reverse coating method, a transfer roll coating method, a micro gravure coating method, a kiss coating method, a cast coating method, a slot orifice coating method, a calendar coating method, and a die coating method can be employed.
  • examples of the substrate used include known or well-known substrates such as plastic, glass, and ceramics.
  • Plastics include polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, triacetyl cellulose And plates and films of diacetyl cellulose and acetate butyrate cellulose.
  • the coating film formed on the substrate may be thermally cured as it is at a room temperature force of 450 ° C, preferably 40 to 450 ° C, but prior to this, preferably in the temperature range of room temperature to 150 ° C, preferably After drying in the temperature range of 10 ° C to 150 ° C, heat curing may be performed. In this case, the time required for drying is preferably 10 seconds to 10 minutes.
  • the time required for thermosetting can be appropriately selected according to the desired film properties, but is usually 1 hour to 10 days. When a low curing temperature is selected, it is easy to obtain a film having sufficient scratch resistance by increasing the curing time.
  • the curing temperature of the coating film is from room temperature to 150 ° C in consideration of the heat resistance of the substrate.
  • the temperature is preferably 10 ° C to 150 ° C.
  • the coating film of the present invention thus obtained has a feature that the water contact angle is 80 ° or more, and the dust wiping property is excellent. Power!
  • the coating film formed by the present invention having a low reflectance can be suitably used particularly as a low refractive index layer for antireflection applications.
  • the coating of the present invention is used for antireflection applications, the surface of a substrate having a refractive index higher than that of the coating of the present invention, such as ordinary glass or TAC (triacetylcellulose) film, is used.
  • TAC triacetylcellulose
  • this base material can be easily converted into a base material having an antireflection function.
  • the coating of the present invention is effective even when used as a single coating on the substrate surface, but it can also be used as an antireflection laminate in which a coating is formed on a lower coating having a high refractive index. It is valid.
  • the film thickness obtained by substituting 1 for b is 104 nm
  • the film thickness obtained by substituting 2 for b is 312 nm.
  • the thickness of the coating film formed on the substrate can be adjusted by the film thickness at the time of coating,
  • the coating of the present invention has the characteristics of low reflectance. Therefore, it can be suitably used in fields where light reflection prevention is desired, such as glass cathode ray tubes; displays for televisions, computers, car navigation systems, mobile phones, etc .; mirrors with glass surfaces; glass showcases.
  • light reflection prevention such as glass cathode ray tubes; displays for televisions, computers, car navigation systems, mobile phones, etc .; mirrors with glass surfaces; glass showcases.
  • n BuOH n Butinoreare no Reno 1 (1 Butanore)
  • PA phosphoric acid
  • PhPA Phenylphosphoric acid (also known as phosphoric acid monophenyl ester, isolated monoester)
  • DdPA Mono n dodecyl phosphate (also known as mono n dodecyl phosphate, isolated mono ester)
  • TMePA Trimethyl phosphate (also known as trimethyl phosphate, triester isolate)
  • the residual alkoxysilane monomer in the polysiloxane (A) solution was measured by gas chromatography (hereinafter referred to as GC). GC measurements were made by Shimadzu GC— 1
  • Polysiloxane (A) solutions (P2 to P11) were obtained in the same manner as in Synthesis Example 1 with the compositions shown in Table 1. At that time, as in Synthesis Example 1, a mixture of a plurality of types of alkoxysilanes (hereinafter referred to as monomers) was used. When the obtained polysiloxane (A) solutions (P2 to P11) were measured by GC, no monomer was detected.
  • the coating solution for forming a film was prepared by mixing the phosphate compound (B) and the solvent into the polysiloxane (A) solution. Using this coating solution, the storage stability and the film were evaluated as follows.
  • a solvent was mixed with the polysiloxane (A) solution to prepare a coating solution.
  • the storage stability and coating film shown below were evaluated in the same manner as in the Examples.
  • Comparative Example 6 the coating solution using PA instead of the phosphoric acid ester compound (B) in the example was used, and in Comparative Example 7, the coating solution using TMoePA was evaluated. .
  • the PZSi molar ratio in Table 3 represents the molar ratio of the phosphorus atom of the phosphate ester compound (B) to the silicon atom of the polysiloxane (A).
  • the prepared coating-forming coating solution was applied to a triacetyl cellulose (hereinafter referred to as TAC) film (film thickness of 80 m, reflectance at a wavelength of 550 nm of 4.5%) subjected to the treatment described below to a wire bar (No. 3) was applied to form a coating film. Then, it was left at room temperature for 1 minute, dried for 5 minutes at a temperature of 100 ° C using a clean oven, and then cured at a temperature of 40 ° C for 3 days.
  • TAC triacetyl cellulose
  • the TAC film used at that time was immersed for 3 minutes in a 5% by weight potassium hydroxide (KOH) aqueous solution of a TAC film with a hard coat (film thickness 80 ⁇ m) manufactured by Nippon Paper Industries Co., Ltd. heated to 40 ° C. After alkaline treatment, clean with pure water, then immerse in 0.5% by weight aqueous sulfuric acid (H2S04) at room temperature for 30 seconds and finally clean with pure water, and then in an oven at 70 ° C for 1 hour It is a dried film.
  • KOH potassium hydroxide
  • H2S04 aqueous sulfuric acid
  • the obtained coating film was evaluated for water contact angle, magic wiping property, fingerprint wiping property, HAZE, transmittance, reflectance, surface resistance, triboelectric charge index, and dust wiping property. These evaluation methods are as follows, and the evaluation results are shown in Tables 4 and 5.
  • the fingerprint was attached to the coated surface, it was wiped off with a tissue paper, and the level of wiping was visually evaluated according to the following criteria.
  • ⁇ The oil can be wiped off, but a fingerprint mark remains.
  • the UV reflectance measuring device MPC-3100 is installed on the spectrophotometer UV-3100PC manufactured by Shimadzu Corporation. Connected and measured in wavelength range 400-800nm. The reflectance at a wavelength of 550 nm and an incident angle of 5 ° was measured.
  • the surface resistance value was measured using a digital insulation meter DSM-8103 manufactured by Toa DDK Corporation. At that time, a sample that was left in an environment of 23 ° C and 50% relative humidity for 3 hours or more was used.
  • Kanebo-type Kanebo-type friction band voltage measuring device EST-8 with a Western blanket (for muslin JIS L 0803) as a friction cloth, leave it for 3 hours or more in an environment of 23 ° C and 50% relative humidity. After the sample coating surface was rubbed 10 times, the surface voltage was measured for 60 seconds. The triboelectric charging index IFC (integrated value of the charged voltage time curve) obtained as a result of this evaluation was used to evaluate the chargeability of the coating (the smaller the value, the better the ability to wipe off dust that is difficult to charge). This evaluation method is based on JIS L 1094.
  • the tissue paper was torn finely on the coated surface and paper dust was adhered to the coated surface, and then wiped off with a tissue paper.
  • the level of wiping was visually evaluated according to the following criteria. ⁇ : Remove 70% or more of dust adhered before wiping ⁇ : Remove 40 to 70% of dust adhered before wiping X: Almost no wiping
  • Example 1 0. 2 0. 2 94. 7 1. 4 10 11 0. 01 ⁇ Example 2 0. 2 0. 2 95. 0 1. 5 10 12 0. 08 ⁇ Example 3 0. 2 0. 2 94. 4 1. 5 10 12 0. 12 ⁇ Example 4 0. 2 0. 2 94. 7 1. 4 10 13 0. 20 ⁇ Example 5 0. 2 0. 2 94. 5 1. 5 10 12 0. 02 ⁇ Example 6 0 2 0. 2 94. 6 1. 5 10 11 0. 00 ⁇ Example 7 0. 2 0. 2 94. 0 1. 8 10 13 0. 05 ⁇ Example 8 0. 2 0. 2 93. 0 1.
  • Comparative Example 6 had a high water contact angle and good dust wiping properties, as in the Example, but the HAZE value increased after 1 week and was stable as in Examples 1 to 20. A film could not be obtained.
  • the coating liquid for forming a film of the present invention is excellent in storage stability, has a high water contact angle, has good dust wiping properties, and can form a stable film without change over time.
  • those showing a low reflectance are useful as coating solutions for forming an antireflection film, and are formed using them.
  • the coated film is very useful as an antireflection film.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Paints Or Removers (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Silicon Polymers (AREA)

Abstract

La présente invention a pour objet un fluide pour revêtement filmogène dont la stabilité au stockage est excellente et qui permet d'obtenir un film présentant un angle de contact très élevé avec l'eau et d'excellentes propriétés dépoussiérantes. La présente invention a également pour objet des films formés à partir du fluide ; les procédés de production des films et du fluide ; et des revêtements anti-réflexion fabriqués en utilisant le fluide. La présente invention concerne spécifiquement un fluide pour revêtement filmogène qui comprend (A) un polysiloxane comportant des groupements organiques fluorés sous forme de chaînes latérales et (B) un ester phosphorique comportant un groupement hydroxy attaché à l'atome de phosphore ; des films formés à partir du fluide ; et les procédés de production des films et du fluide.
PCT/JP2007/058120 2006-04-13 2007-04-12 Fluide pour revêtement contenant un ester phosphorique et revêtements anti-réflexion WO2007119805A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN2007800122539A CN101415789B (zh) 2006-04-13 2007-04-12 含有磷酸酯化合物的被膜形成用涂布液及防反射膜
JP2008510995A JP5293180B2 (ja) 2006-04-13 2007-04-12 リン酸エステル化合物を含有する被膜形成用塗布液及び反射防止膜
KR1020087024793A KR101362627B1 (ko) 2006-04-13 2007-04-12 인산에스테르 화합물을 함유하는 피막 형성용 도포액 및 반사 방지막

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JP2006-110725 2006-04-13

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Cited By (3)

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CN102559035A (zh) * 2011-11-28 2012-07-11 东莞大宝化工制品有限公司 一种双重干燥的uv喷涂亚光面漆及其制备方法
WO2013161829A1 (fr) * 2012-04-27 2013-10-31 旭硝子株式会社 Produit d'hydrolyse-condensation partielle, agent répulsif de l'encre, composition de résine photosensible de type négatif, film durci, cloison de séparation et élément optique
JP2015534652A (ja) * 2012-08-31 2015-12-03 ハネウェル・インターナショナル・インコーポレーテッド 高耐久性反射防止被覆

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101647537B1 (ko) * 2009-05-01 2016-08-10 닛산 가가쿠 고교 가부시키 가이샤 규소계 액정 배향제, 액정 배향막 및 액정 표시 소자
TWI490254B (zh) 2013-12-31 2015-07-01 Ind Tech Res Inst 無機鈍化塗料、其形成方法、及所形成之無機鈍化保護膜

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JPH01299847A (ja) * 1988-05-27 1989-12-04 Fuji Photo Film Co Ltd セルロースエステルフイルム
JPH09208898A (ja) * 1995-12-01 1997-08-12 Nissan Chem Ind Ltd 低屈折率及び撥水性を有する被膜
JPH10120445A (ja) * 1996-10-18 1998-05-12 Sony Corp 表示装置用フィルター及び表示装置
JP2001019939A (ja) * 1999-07-12 2001-01-23 Kureha Chem Ind Co Ltd 近赤外光吸収性組成物及び近赤外光吸収剤
WO2002074828A1 (fr) * 2001-03-21 2002-09-26 Hoya Corporation Objets moules transparents, element optique, lentilles plastiques, et leurs procedes de production

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TW376408B (en) * 1995-12-01 1999-12-11 Nissan Chemical Ind Ltd Coating film having water repellency and low refractive index
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JPH01299847A (ja) * 1988-05-27 1989-12-04 Fuji Photo Film Co Ltd セルロースエステルフイルム
JPH09208898A (ja) * 1995-12-01 1997-08-12 Nissan Chem Ind Ltd 低屈折率及び撥水性を有する被膜
JPH10120445A (ja) * 1996-10-18 1998-05-12 Sony Corp 表示装置用フィルター及び表示装置
JP2001019939A (ja) * 1999-07-12 2001-01-23 Kureha Chem Ind Co Ltd 近赤外光吸収性組成物及び近赤外光吸収剤
WO2002074828A1 (fr) * 2001-03-21 2002-09-26 Hoya Corporation Objets moules transparents, element optique, lentilles plastiques, et leurs procedes de production

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102559035A (zh) * 2011-11-28 2012-07-11 东莞大宝化工制品有限公司 一种双重干燥的uv喷涂亚光面漆及其制备方法
CN102559035B (zh) * 2011-11-28 2014-05-07 东莞大宝化工制品有限公司 一种双重干燥的uv喷涂亚光面漆及其制备方法
WO2013161829A1 (fr) * 2012-04-27 2013-10-31 旭硝子株式会社 Produit d'hydrolyse-condensation partielle, agent répulsif de l'encre, composition de résine photosensible de type négatif, film durci, cloison de séparation et élément optique
JPWO2013161829A1 (ja) * 2012-04-27 2015-12-24 旭硝子株式会社 部分加水分解縮合物、撥インク剤、ネガ型感光性樹脂組成物、硬化膜、隔壁および光学素子
JP2015534652A (ja) * 2012-08-31 2015-12-03 ハネウェル・インターナショナル・インコーポレーテッド 高耐久性反射防止被覆

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KR20080109839A (ko) 2008-12-17
TWI473864B (zh) 2015-02-21
CN101415789B (zh) 2012-08-08
KR101362627B1 (ko) 2014-02-21
CN101415789A (zh) 2009-04-22
JP5293180B2 (ja) 2013-09-18
JPWO2007119805A1 (ja) 2009-08-27

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