WO2007102514A1 - Liquide de revêtement pour la formation d'un film de revêtement, procédé de production de celui-ci, film de revêtement formé à partir de celui-ci et élément antireflet - Google Patents

Liquide de revêtement pour la formation d'un film de revêtement, procédé de production de celui-ci, film de revêtement formé à partir de celui-ci et élément antireflet Download PDF

Info

Publication number
WO2007102514A1
WO2007102514A1 PCT/JP2007/054350 JP2007054350W WO2007102514A1 WO 2007102514 A1 WO2007102514 A1 WO 2007102514A1 JP 2007054350 W JP2007054350 W JP 2007054350W WO 2007102514 A1 WO2007102514 A1 WO 2007102514A1
Authority
WO
WIPO (PCT)
Prior art keywords
polysiloxane
coating
film
group
solution
Prior art date
Application number
PCT/JP2007/054350
Other languages
English (en)
Japanese (ja)
Inventor
Yoshihiro Tani
Kenichi Motoyama
Original Assignee
Nissan Chemical Industries, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nissan Chemical Industries, Ltd. filed Critical Nissan Chemical Industries, Ltd.
Priority to JP2008503878A priority Critical patent/JP5382310B2/ja
Priority to CN200780008121.9A priority patent/CN101395238B/zh
Priority to KR1020087021635A priority patent/KR101334496B1/ko
Publication of WO2007102514A1 publication Critical patent/WO2007102514A1/fr

Links

Classifications

    • 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
    • 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
    • G02B1/14—Protective coatings, e.g. hard 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds

Definitions

  • Coating liquid for coating formation manufacturing method thereof, coating film thereof, and antireflection material
  • the present invention relates to a coating liquid for forming a film containing polysiloxane, a method for producing the same, a film formed from the coating liquid, and an antireflection material having the film.
  • Patent Document 1 discloses an alcohol dispersion of MgF fine particles produced by reacting a magnesium salt or an alkoxymagnesium compound as an Mg source with a fluoride salt as an F source, or an improvement in film strength.
  • a solution containing tetraalkoxysilane and the like is used as a coating solution, which is applied on a glass substrate and heat-treated at a temperature of 100 to 500 ° C to form an antireflection film exhibiting a low refractive index on the substrate.
  • Patent Document 2 discloses a hydrolytic polycondensate such as tetraalkoxysilane, which is a coating liquid obtained by mixing two or more types having different average molecular weights and a solvent such as alcohol.
  • a coating film is prepared by adding means such as mixing ratio at the time of mixing and control of relative humidity.
  • the coating is obtained by heating at a temperature of 250 ° C. or higher, and has a refractive index of 1.21 to: 1.40, and has a thickness of 60 to 160 nm with micropits or irregularities having a diameter of 50 to 200 nm.
  • the coating is formed on a glass substrate to produce a low reflection glass.
  • Patent Document 3 discloses a low reflectance glass comprising glass, a lower layer film having a high refractive index formed on the surface thereof, and an upper layer film having a low refractive index formed on the surface thereof.
  • the upper film is formed by using a fluorine-containing silicone compound having a polyfluorocarbon chain such as CF (CF) CH Si (OCH), and a silane coupling agent such as Si ( ⁇ CH) at 5 to 90% by mass.
  • CF CF
  • OCH silane coupling agent
  • Si ⁇ CH
  • Patent Document 4 discloses a silicon compound represented by Si (OR), CF (CF) CH CH
  • a coating solution in which a polysiloxane solution is produced by heating a reaction mixture contained in a specific ratio at a temperature of 40 to 180 ° C. in the absence of water.
  • a coating solution By applying this coating solution to the surface of the substrate and thermosetting at a temperature of 80 to 450 ° C, a film having a refractive index of 1.28 to 1.38 and a water contact angle of 90 to 115 degrees is formed. It has been done.
  • 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 antireflection film as described above is used in various display devices and the like, but is used in recent years as display devices such as liquid crystal and plasma are becoming larger, lighter, and thinner.
  • Antireflective substrates, particularly antireflective films tend to reduce the film thickness for the purpose of weight reduction and high transparency, and there is a problem that damage caused by heat increases. For this reason, there is an increasing demand for a coating solution for forming a thermosetting film that can be cured at a relatively low temperature, which can obtain an antireflection substrate by a low-temperature treatment that does not damage the film. It was. However, it is desired that the curing temperature of the conventional low-refractive index coating as described above is further lowered even if it is not sufficiently low.
  • the object of the present invention is to provide a coating solution that is excellent in storage stability, can be sufficiently cured by low-temperature heat treatment, and can form a coating film having a low refractive index and excellent scratch resistance.
  • Another manufacturing method a coating obtained from the coating solution, and an antireflection application using the coating.
  • the gist of the present invention is as described below.
  • polysiloxane (A) which is a polysiloxane having an organic group having a fluorine atom, and at least one of polysiloxane (B) and monoamine compound (C) represented by formula (1), Coating solution for film formation in which they are dissolved in organic solvent (D).
  • R 2 , R 3 and R 4 each independently represent a hydrogen atom or a saturated hydrocarbon group having 1 to 5 carbon atoms, and n represents an integer of 2 or more.
  • R 5 is an organic group having a fluorine atom
  • R 6 represents a hydrocarbon group having 1 to 5 carbon atoms.
  • R 7 is a hydrogen atom or an organic group having 1 to 20 carbon atoms having no fluorine atom
  • R 8 is a hydrocarbon group having 1 to 5 carbon atoms
  • m represents an integer of 0 to 3.
  • the value obtained by converting the total amount of all the silicon atoms of polysiloxane (A) or polysiloxane (A) and polysiloxane (B) into silicon dioxide is 0.5 to 15% by mass in the coating solution.
  • Polysiloxane (B) contains 0.05 to 0.55 mol of all silicon atoms of polysiloxane (B) with respect to 1 mol of all atoms of polysiloxane (A). Coating solution for forming a film according to -7.
  • the monoamine compound (C) is derived from the amino group in the monoamine compound (C) with respect to 1 mol of the total amount of all the atoms of the polysiloxane (A) or the polysiloxane (A) and the polysiloxane (B).
  • the inorganic acid or organic acid is 0 ⁇ 01 ⁇ 2.5 mol per 1 mol of polysiloxane (A) or the total amount of all the silicon atoms of polysiloxane (A) and polysiloxane (B).
  • a low refractive index film obtained by heating and curing the coating liquid for forming a film according to the above:!
  • An antireflection material wherein the low refractive index coating according to 11 above is formed on the surface of a substrate having a higher refractive index.
  • the coating solution for forming a film described in the above:! ⁇ 10 is applied to a substrate, dried at a temperature of 20 ⁇ : 100 ° C for 10 seconds to 6 minutes, and then cured at a temperature of 20 ⁇ 70 ° C.
  • a method for forming a low refractive index film is applied to a substrate, dried at a temperature of 20 ⁇ : 100 ° C for 10 seconds to 6 minutes, and then cured at a temperature of 20 ⁇ 70 ° C.
  • a solution of an organic solvent of polysiloxane (A), at least one of polysiloxane (B) and monoamine compound (C), and organic solvent (D) are mixed.
  • the manufacturing method of the coating liquid for film formation is described.
  • the coating liquid for forming a film of the present invention has excellent storage stability, for example, a film that is sufficiently cured by heat treatment at a temperature of 20 to 70 ° C. and low temperature and excellent in scratch resistance. Can be provided.
  • the film obtained from the coating liquid for forming a film of the present invention can be suitably used for an antireflection material such as an antireflection film.
  • the mechanism of why the coating film formed from the coating solution has the above excellent characteristics is not necessarily clear, but is estimated as follows.
  • the coating liquid contains a combination of fluorine-containing polysiloxane (A) and at least one of hydrocarbon-based polysiloxane (B) and monoamine compound (C).
  • A fluorine-containing polysiloxane
  • B hydrocarbon-based polysiloxane
  • C monoamine compound
  • the coating liquid for forming a film of the present invention (also simply referred to as a coating liquid in the present invention) is represented by polysiloxane (A), which is a polysiloxane having an organic group having a fluorine atom, and the formula (1).
  • R ⁇ R 2, R 3 and R 4 each independently represent a hydrogen atom or a saturated hydrocarbon group having 1 to 5 carbon atoms, n represents an integer of 2 or more.
  • the polysiloxane (A) used in the present invention is a polysiloxane having an organic group having a fluorine atom.
  • the organic group having a fluorine atom is an organic group bonded to a silicon atom of the polysiloxane main chain and partially or entirely substituted with a fluorine atom.
  • the organic group having a fluorine atom is not particularly limited as long as it has a fluorine atom unless the effects of the present invention are impaired.
  • an alkyl group in which part or all of the hydrogen atoms are substituted with fluorine atoms, an alkyl group having an ether bond in which some or all of the hydrogen atoms are substituted with fluorine atoms, and the like are preferable.
  • the number of fluorine atoms of the organic group is not particularly limited. More preferred is a perfluoroalkyl group, and still more preferred is an organic group represented by the formula (4).
  • organic group represented by the formula (4) examples include trifluoropropyl group, tridecafluorooctyl group, heptadecafluorodecinole group and the like.
  • the polysiloxane (A) may have one or more organic groups having fluorine atoms.
  • the organic group having a fluorine atom of polysiloxane (A) is reduced from 0.:! To 0.4 mol with respect to 1 mol of all the silicon atoms of polysiloxane (A), thereby further reducing the reflectance. Because it is possible, it is preferred. Further, 0.05 to 25.25 mol is preferable because the hardness of the coating can be further increased.
  • the polysiloxane (A) of the present invention has an organic group other than the organic group having a fluorine atom. It may be bonded to a silicon atom of the polysiloxane main chain.
  • the organic group is an organic group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, having no fluorine atom.
  • Examples of such an organic group having no fluorine atom include a saturated hydrocarbon group having a linear or branched structure; an aromatic group having a benzene ring; a glycidyl group, an amino group, a ureido group, or a bur group. Or an organic group having an ether bond or an ester bond.
  • Specific examples thereof include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, heptyl group, octyl group, dodecyl group, hexadecyl group, octadecyl group, phenyl group, bur group, ⁇ -aminopropyl.
  • the amount of the organic group is not particularly limited as long as it does not impair the effects of the present invention, but the polysiloxane ( ⁇ ) has no fluorine atom.
  • the amount is preferably from 0 ⁇ 01 to 0.75 mol per 1 mol of all the silicon atoms. In such a range, a coating with a water contact angle of 90 ° or more can be obtained, and a homogeneous polysiloxane solution can easily be obtained. Also, the case of 0 ⁇ 01-0.7 mol is preferable because the hardness of the coating can be further increased.
  • the method for obtaining such a polysiloxane ( ⁇ ) is not particularly limited, but polysiloxanes obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the following formula (2) are preferred.
  • R 5 is an organic group having a fluorine atom
  • R 6 represents a hydrocarbon group having 1 to 5 carbon atoms.
  • the alkoxysilane represented by the formula (2) imparts water repellency to the film. It is.
  • R 5 in the formula (2) represents an organic group having a fluorine atom, but is not particularly limited as long as it is an organic group having a fluorine atom.
  • R 5 is preferably an alkyl group in which some or all of the hydrogen atoms are substituted with fluorine atoms, or an alkyl group having an ether bond in which some or all of the hydrogen atoms are substituted with fluorine atoms. .
  • Fluorine atom of this organic group The number of is also not particularly limited.
  • R 5 is an organic group having a fluorine atom, preferably an organic group having 1 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and particularly preferably 3 to 8 carbon atoms. Such alkoxysilanes are preferred because they are readily available.
  • R 6 represents a hydrocarbon group having 1 to 5 carbon atoms, and a saturated hydrocarbon group is particularly preferred.
  • lower alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group are preferred because they are readily available as commercial products.
  • R 6 may be the same or different.
  • an alkoxysilane in which R 5 is an organic group represented by the formula (4) is preferred.
  • alkoxysilane in which R 5 is an organic group represented by the formula (4) include trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluoro Citryltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane and the like.
  • At least one of the alkoxysilanes represented by the formula (2) may be used, but a plurality of types may be used as necessary.
  • the polysiloxane (A) used in the present invention can be obtained by using an alkoxysilane represented by the formula (2) and an alkoxysilane represented by the formula (3) in combination. At that time, a plurality of alkoxysilanes represented by the formula (3) may be used.
  • R 7 is a hydrogen atom or an organic group having 1 to 20 carbon atoms that does not have a fluorine atom, is a hydrocarbon group having 1 to 5 carbon atoms, and m represents an integer of 0 to 3.
  • R 8 represents a hydrocarbon group, but a saturated hydrocarbon group having 1 to 5 carbon atoms is preferable because the reactivity is higher when the number of carbon atoms is smaller. More preferred are a methyl group, an ethyl group, a propyl group, and a butyl group.
  • the alkoxysilane represented by formula (3) represents tetraalkoxysilane. Specific examples thereof include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, which are easily available as commercial products.
  • the alkoxysilane represented by the formula (3) has 1 to 20 carbon atoms in which R 7 does not have a hydrogen atom or a fluorine atom, preferably 1 ⁇ :
  • R 7 may be the same or different from each other.
  • Examples of the organic group having 1 to 20 carbon atoms not having a fluorine atom include a saturated hydrocarbon group having a linear or branched structure, an aromatic group having a benzene ring, a glycidyl group, an amino group, a urea group, or a vinyl group. Or an organic group having an ether bond or an ester bond.
  • [0021] in the formula (3) is a hydrocarbon group having 1 to 5 carbon atoms. when m is 1 or 2, but is generally preferred if R 8 are the same, in the present invention, R 8 may be the same or have different from one, respectively.
  • the polysiloxane ( ⁇ ) used in the present invention can be obtained by polycondensation of an alkoxysilane containing the alkoxysilane represented by the formula (2), preferably 5 to 40 mol% in the total alkoxysilane.
  • an alkoxysilane containing the alkoxysilane represented by the formula (2) preferably 5 to 40 mol% in the total alkoxysilane.
  • the amount of the alkoxysilane represented by the formula (3) used in combination is preferably 60 to 95 mol% in the total alkoxysilane, in other words, 1 mol of the alkoxysilane represented by the formula (2). In contrast, 1 ⁇ 5 to 19 mol is preferred.
  • the amount of the alkoxysilane m is 0, 20-90 mole 0/0 Gayori if more reduce the reflectance of 20 to 95 mol% is preferred instrument particularly coating in the total alkoxysilane preferable.
  • the polysiloxane (A) for example, an alkoxysilane represented by the formula (2), an alkoxysilane in which m in the formula (3) is 0, and, if necessary, a formula (3)
  • Examples thereof include a method in which at least one alkoxysilane having m of 1 to 3 and an organic solvent are heated and polycondensed in the presence of oxalic acid. Specifically, after adding oxalic acid to alcohol in advance to obtain an alcohol solution of oxalic acid, the above-mentioned various alkoxysilanes are mixed while the solution is heated.
  • the amount of the oxalic acid is preferably 0.2 to 2 moles per 1 mole of the total alkoxy group content of the alkoxysilane used.
  • the above heating can be performed at a liquid temperature of preferably 0 to 180 ° C., and is preferably performed under reflux in a vessel equipped with a reflux pipe so that the liquid does not evaporate or volatilize. It is carried out for about 10 to 10 hours.
  • alkoxysilanes When a plurality of types of alkoxysilanes are used, they may be mixed as a mixture in which alkoxysilanes are mixed in advance, or a plurality of types of alkoxysilanes may be mixed in sequence.
  • SiO concentration the concentration of all alkoxy atoms in the charged alkoxysilane in terms of oxide
  • Preferably it is heated in the range of 4 to 15% by mass.
  • concentration range By selecting an arbitrary concentration within such a concentration range, it is possible to suppress gel formation and obtain a homogeneous polysiloxane-containing solution.
  • polymerization solvent An organic solvent used for polycondensation of alkoxysilane (hereinafter also referred to as polymerization solvent).
  • organic solvent (D) Is not particularly limited as long as it dissolves the alkoxysilane represented by formula (2) and formula (3), but the use of organic solvent (D) is preferred.
  • alcohols are produced by the polycondensation reaction of alkoxysilanes, and therefore alcohols and organic solvents having good compatibility with alcohols are used.
  • polymerization solvent examples include methanol, ethanol, propanol, and ⁇ -buta
  • alcohols such as diols, glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether.
  • a plurality of the above organic solvents may be mixed and used.
  • the polysiloxane (B) contained in the coating solution of the present invention is at least one polysiloxane represented by the formula (1).
  • R 2 , R 3 and R 4 each independently represent a hydrogen atom or a saturated hydrocarbon group having 1 to 5 carbon atoms, and n represents an integer of 2 or more, preferably 2 to 50.
  • R 2 , R 3 and R 4 each independently represent a hydrogen atom or a saturated hydrocarbon group having 1 to 5 carbon atoms, but specific examples of the saturated hydrocarbon group having 1 to 5 carbon atoms Examples include methyl, ethyl, propyl, butyl and the like.
  • the polysiloxane (B) is not particularly limited as long as it is at least one polysiloxane represented by the formula (1). That is, it may be a mixture of a plurality of polysiloxanes represented by the formula (1).
  • n is preferably an integer of 2 or more, more preferably an integer of 3 to 50. More preferably, it is 4-30.
  • the method for obtaining the polysiloxane (B) used in the present invention is not particularly limited.
  • it can be obtained by polycondensation of tetraalkoxysilane in an alcohol solvent.
  • the polycondensation may be any of a method in which partial hydrolysis or complete hydrolysis is carried out and a condensation reaction is carried out.
  • partial hydrolysis theoretically 0.5 moles of water of all alkoxy groups in tetraalkoxysilane should be added, but usually more than 0.5 moles of water is added.
  • tetraalkoxysilane examples include tetramethoxysilane, tetraeth Examples thereof include xyloxysilane, tetrapropoxysilane, and tetrabutoxysilane, which are readily available as commercial products.
  • the amount of water used in the above reaction can be appropriately selected as desired, but it is generally preferably 0.5 to 2.5 times as much as that of all alkoxy groups in tetraalkoxysilane. It is.
  • inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and hydrofluoric acid, or metal salts thereof; organic acids such as acetic acid, formic acid, oxalic acid, and maleic acid; A catalyst such as an alkali is used.
  • a catalyst such as an alkali is used.
  • the heating temperature and heating time can be appropriately selected as desired. For example, heating and stirring at room temperature to 100 ° C for 0.5 to 48 hours, or heating and stirring at reflux for 0.5 to 48 hours. And the like.
  • the solvent used for polycondensation of tetraalkoxysilane is not particularly limited as long as it dissolves tetraalkoxysilane, but the use of organic solvent (D) is preferred.
  • organic solvent (D) is preferred.
  • alcohols are generated by polycondensation reaction of tetraalkoxysilane, and therefore, organic solvents having good compatibility with alcohols and alcohols are used.
  • organic solvent (D) used above examples include alcohols such as methanol, ethanol, propanol, and n-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, And glycol ethers such as diethylene glycol monoethyl ether.
  • alcohols such as methanol, ethanol, propanol, and n-butanol
  • ethylene glycol monomethyl ether ethylene glycol monoethyl ether
  • diethylene glycol monomethyl ether diethylene glycol monomethyl ether
  • glycol ethers such as diethylene glycol monoethyl ether.
  • a plurality of the above organic solvents (D) may be mixed and used.
  • the polysiloxane (B) solution obtained as described above has a SiO equivalent concentration of 30% by mass.
  • the content of the polysiloxane (B) in the coating solution is 1 in the mass obtained by converting all the silicon atoms of the polysiloxane (A) to silicon dioxide.
  • the mass force of all the silicon atoms of polysiloxane (B) converted to silicon dioxide is 0.03 to 0.55, preferably f or 0.05 to 0.55, and more preferably f or 0.05 to 0.45. so Preferably there is.
  • the content of the polysiloxane (B) in the coating solution is such that the total amount of all the atoms of the polysiloxane (B) is from 0.03 to 0.001 mol per mol of all the atoms of the polysiloxane (A). 55 monole, preferably f 0.05-0.55 monole, more preferably f 0.05-0.45 monole.
  • the monoamine compound (C) contained in the coating solution of the present invention promotes polycondensation of the alkoxy groups remaining in the coating without causing rapid gelation, and progresses curing of the coating even at low temperatures. Contributes to
  • Examples of the monoamine compound (C) include aliphatic amines having preferably carbon atoms:! -22, alkanolamines having preferably 1 to 10 carbon atoms, and aromatic amines.
  • aliphatic amine examples include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, N, N-dimethylamine, N, N-jetylamine, N, N-dipropylamine, N, N-dibutylamine, trime Tinoleamine, triethylamine, tripropylamine, tributylamine, methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, ethoxymethylamine, ethoxyethylamine, ethoxypropyl Amines, ethoxybutyramine, propoxymethylamine, propoxyethylamine, propoxypropylamine, propoxypetite / leamine, butoxymethylamine, butoxystilamine, butoxypropylamine, butoxybutylamine, cyclo Such as key Shiruamin and the like.
  • alkanolamines include methanolamine, ethanolamine, propanolanolamine, butanolamine, N-methylmethanolamine, N-ethylmethanolamine, N-propylmethanolamine, N_ Butylmethanolamine, N_methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, N-methylpropanolamine, N-ethylpropanolamine, N- Propinopropanolamine, N-butylpropanolamine, N-methylbutanolamine, N-ethylbutanolamine, N-propylbutanolamine, N-butylbutanolamine, N, N-dimethylmethanolamine, N , N—Jetylmethanolamine, N, N- Dipropylmethanolamine, N, N-dibutylmethanolamine, N, N-dimethylethanolanolamine, N, N-N-dimethylethanol
  • the monoamine compound (C) is preferably an aliphatic amine having 1 to 22 carbon atoms or an alkanolamine having 10 carbon atoms. More preferred are ethylamine, N, N-jetolamine, triethylamine, cyclohexylamine, monoethanolamine, diethylanolamine, and triethanolamine. In the present invention, a plurality of monoamine compounds may be used.
  • the content of the monoamine compound (C) in the coating solution of the present invention includes the case where the coating solution contains the polysiloxane (A) alone, or the polysiloxane (A) and the polysiloxane (B).
  • the nitrogen atom derived from the amino group in the monoamine compound (C) is from 0.01 to 0.2 mol, more preferably from 0.03 to 0.1 mol, based on 1 mol of the total amount of all the silicon atoms. 0.1 mol is preferable.
  • the monoamine compound (C) When the monoamine compound (C) is 0.01 mol or more, it is preferable because it is easily cured at a low temperature. In addition, when the nitrogen atom derived from the amino group in the monoamine compound (C) is 0.20 mol or less, the coating is transparent and it is preferable to obtain a high coating hardness without unevenness.
  • Organic solvent (D) Any organic solvent (D) can be used as long as it dissolves polysiloxane (A), polysiloxane (B), and monoamine compound (C).
  • organic solvents (D) include aliphatic alcohols such as methanol, ethanol, isopropanol, butanol and diacetone alcohol; alicyclic alcohols such as cyclopentyl alcohol and cyclohexanol; benzyl alcohol and cinnamic Aromatic alcohols such as alcohols; ketones such as acetone, methyl ethyl ketone, methyl isobutanol ketone; glycols such as ethylene glycol, propylene glycol, hexylene glycol; Echinorecanorebitonore, butinorecanorebitonore, diethyleneglycolenomonomethinoatenore, propyleneglycolenomonomethinoatenore, propyleneglycolenobutenorenore Glycol ether Norre such Honoré; acid methyl ester, acetic Echiruesuteru, and the like esters such as lactic Echinor
  • an acid component can be contained. This acid component can suppress the formation of gel during the production of the coating liquid for forming a film, and can improve the storage stability of the coating liquid for forming a film.
  • the acid used here is preferably an inorganic acid such as hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid or an organic acid such as formic acid, acetic acid, malic acid, oxalic acid, succinic acid, propionic acid or succinic acid.
  • an acid When an acid is contained, the acid may be added directly to the coating solution, but it may be added as a solution dissolved in an organic solvent (D) or water.
  • Polysiloxane (A) or polysiloxane may also be added. Power added to (B) and Z or monoamine compound (C) ⁇ or contained in the form added to their solution It is possible to make it S.
  • the acid content in the coating solution is preferably from 0 ⁇ 01 to 2.5 monolayers, particularly preferably from 0 ⁇ :! to 2 mol, based on 1 mol of all the silicon atoms of polysiloxane (A). Is preferred.
  • polysiloxane (A), polysiloxane (B) and Z or monoamine compound (C), such as inorganic fine particles, leveling agents, A medium such as a surfactant and water may be contained.
  • inorganic fine particles those having a colloidal solution in which fine particles such as silica fine particles, alumina fine particles, titania fine particles, and magnesium fluoride fine particles are preferable are particularly preferable.
  • 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 size of 0.001 ⁇ 0.2 / im, more preferably 0.001 ⁇ 0.1 ⁇ .
  • 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 reduced.
  • Water and organic solvents are used as the dispersion medium for the inorganic fine particles. Can be mentioned.
  • As the colloidal solution it is preferable that pH or pKa is adjusted to 2 to 10 from the viewpoint of the stability of the coating solution for film formation. More preferably, it is 3-7.
  • Examples of the organic solvent used for the dispersion medium of the colloidal solution include alcohols such as methanol, isopropyl alcohol, ethylene glycol, butanol, ethylene glycol monopropinoreateol, methyl ethyl ketone, methyl isobutyl ketone, and the like.
  • Ketones aromatic hydrocarbons such as toluene and xylene, amides such as dimethylenolenolemamide, dimethylacetamide, N-methylpyrrolidone, esters such as ethyl acetate, butyl acetate, and ⁇ -butarate rataton, Examples include ethers such as tetrahydrofuran and 1,4-dioxane. Of these, alcohols and ketones are preferred. These organic solvents can be used alone or in combination of two or more as a dispersion medium. Further, as the leveling agent and the surfactant, known ones can be used, and in particular, commercially available products are preferable because they are easily available.
  • the coating liquid for forming a film of the present invention contains polysiloxane (A) and at least one of polysiloxane (B) and monoamine compound (C), which are dissolved in the organic solvent (D). It is a solution.
  • the preparation method is not particularly limited as long as the coating liquid for forming a film is obtained.
  • the above components may be sequentially added and mixed in the organic solvent (D) using the above components. In this case, the order of adding each component is not particularly limited. Further, a solution in which each component is dissolved in the organic solvent (D) to be used may be mixed.
  • polysiloxane (A) and polysiloxane (B) can be obtained in a solution state by polycondensation in an organic solvent. Therefore, for example, a method of mixing a solution containing polysiloxane (A) synthesized from polysiloxane (A) with a solution containing polysiloxane (B) synthesized from polysiloxane (B) and / or a monoamine compound (C) Is simple.
  • the polysiloxane (A) solution is concentrated, diluted by adding a solvent or substituted with another solvent, and then the polysiloxane (B) solution and / or monoamine compound ( You can mix it with C). Further, the organic solvent (D) can be added after mixing the polysiloxane (A) solution with the polysiloxane (B) solution and / or the monoamine compound (C). At that time, the polysiloxane (B) solution may be concentrated, diluted with a solvent, or replaced with another solvent, if necessary.
  • the acid may be added at any time.
  • a method of adding an acid to a solution of polysiloxane (A), a concentrated solution thereof or a diluted solution thereof, and then covering the monoamine compound (C), a solution of polysiloxane (A), a concentrated solution thereof or a diluted solution thereof examples thereof include a method in which an acid is added to a mixed solution of a liquid and polysiloxane (B), and then a monoamine compound (C) is added.
  • a method in which a solution in which a monoamine compound (C) and an acid are premixed is prepared and then a solution of polysiloxane (A) is prepared.
  • the converted concentration is preferably 0.5 to 15% by mass, and particularly preferably 0.5 to 10% by mass. If the SiO equivalent concentration is lower than 0.5% by mass, a desired film thickness can be obtained by a single application.
  • the pot life of the solution is less stable.
  • the concentration of Si 0 solids in the coating solution must be diluted with a solvent or replaced with another solvent.
  • the above-mentioned polysiloxane (A), polysiloxane (B), monoamine compound (C), acid component, and a solvent used for dilution or replacement of the coating solution are added to each of these components and as necessary.
  • the organic solvent (D) may be the same solvent used for the polycondensation of the above alkoxysilane, or another solvent may be used.
  • solvents include methanol, ethanol, isopropanol, butanol and diacetone alcohol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethylene glycol, propylene glycol and hexylate.
  • Glycols such as N-glycol, methyl cetyl sorb, ethyl cetol sorb, butyl cello soleb, ethyl carbitol, butino recano levitol, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether
  • esters such as glycol ether, acetic acid methyl ester, acetic acid ethyl ester, and lactic acid ethyl ester.
  • the method of incorporating the above-described other components into the coating solution is not particularly limited.
  • the polysiloxane (A) and the polysiloxane (B) and Z or the monoamine compound (C) may be added after mixing with the organic solvent (D).
  • the polysiloxane (A) force is preferably 0.5 to 15 as the mass of all the silicon atoms of the polysiloxane (A) in terms of silicon dioxide. It is contained in mass%, more preferably 0.5 to 10 mass%.
  • polysiloxane (B) When polysiloxane (B) is contained, the content of polysiloxane (B) is 1 for the mass of all the silicon atoms of polysiloxane (A) converted to SiO.
  • the total mass of all the silicon atoms converted to SiO is preferably 0.03 to 0.55, more preferably 0
  • the nitrogen atom derived from the amino group in the monoamine compound (C) is preferably from 0 ⁇ 01 to 0.2 mol, more preferably 0 mol, based on 1 mol of the total amount of all the carbon atoms each has. ⁇ 03-0. 1 mole.
  • the nitrogen atom derived from the amino group in the monoamine compound (C) is 0.01 mol or more, it is preferable because it is easily cured at a low temperature.
  • the amount of 0.20 mol or less is preferable because the coating is transparent, has no unevenness, and high coating hardness is easily obtained.
  • a coating solution for forming a film containing polysiloxane (A), polysiloxane (B) and monoamine compound (C) is preferable because it is easy to obtain a film having excellent scratch resistance. Les.
  • 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. For example, methods such as a dip method, a flow coating method, a spray method, a bar coating method, a gravure coating method, a roll coating method, a blade coating method, and an air knife coating method can be employed.
  • Examples of the base material include base materials such as plastic, glass, and ceramics
  • examples of the plastic include polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, and poly Examples thereof include sheet films such as ether ketone, trimethyl pentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, triacetinoresenorelose, dicetinoresenorelose, and acetate butyrate cenorelose.
  • the coating film formed on the substrate may be heat-cured as it is at a temperature of 20 to 70 ° C, for example, but prior to this, it is dried at a temperature of 20 to 100 ° C and then heat-cured. May be. At this time, the time required for drying is preferably 10 seconds to 6 minutes.
  • the time required for thermosetting can be appropriately selected according to the desired film properties, but is usually 1 hour to 7 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 coating liquid for forming a film of the present invention can provide a film having excellent scratch resistance even at a curing temperature exceeding 70 ° C.
  • the film formed from the coating solution of the present invention has a low refractive index of 1.4 or less and excellent scratch resistance, and therefore is particularly suitable for use in antireflection applications. Can do.
  • the coating of the present invention is formed on the surface of a substrate having a refractive index higher than that of the coating of the present invention, for example, a plastic film substrate.
  • the substrate can be easily converted into an antireflection substrate such as an antireflection film such as an antireflection film or an antireflection glass.
  • the coating of the present invention is effective when used as a single coating on the substrate surface, but is also effective when used in an antireflection laminate in which a coating is formed on a lower coating having a high refractive index. .
  • 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 thickness of the coating film, but can also be easily adjusted by adjusting the SiO equivalent concentration of the coating solution.
  • the coating of the present invention can be suitably used in fields where antireflection of light is desired, such as glass cathode ray tubes, computer displays, mirrors having glass surfaces, and glass showcases.
  • the coating film of the present invention has sufficient practicality in terms of antifouling properties such that fingerprints and oil-based inks can be easily wiped off, and can be sufficiently cured by low-temperature treatment at a temperature of 20 to 70 ° C. It is particularly useful for antireflection films for display devices such as plasma and display monitors.
  • the residual alkoxysilane monomer in the polysiloxane (A) solution was measured by gas chromatography (hereinafter referred to as GC).
  • Sample injection volume 1 ⁇ Range temperature: 240 ° C, detector temperature: 290 ° C, carrier gas: nitrogen (flow rate 30 mL / min), detection method: FID method.
  • Polysiloxane (A) solutions (PF-2 to PF-3) 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 plurality of types of alkoxysilanes were mixed and used.
  • a 4-necked reaction flask equipped with a reflux tube was charged with 31.78g of ethanol, 0.18g of shinonoic acid and 10.80g of pure water, and TEOS29.16g and FS—1328.08g were added under the carrying frame. ? A kongo solution was prepared. The solution was then heated to reflux for 3 hours and then allowed to cool to room temperature to prepare a polysiloxane (A) solution (PF-4A). When this polysiloxane (A) solution (PF-4A) was measured by GC, no alkoxysilane monomer was detected.
  • the eggplant flask was charged with 48.59 g of ethanol, 34.68 g of TEOS was added under stirring, and then a diluted solution obtained by adding 1.74 g of 60% nitric acid aqueous solution to 14.99 g of water was added dropwise little by little. Thereafter, the mixture was stirred at room temperature for 1 hour to prepare a polysiloxane (B) solution (PS-2). This When the polysiloxane (B) solution (PS-2) was measured by GC, no alkoxysilane monomer was detected.
  • a coating solution for forming a film (Q1 to Q12) was prepared by mixing a solution of polysiloxane (A), a solution of polysiloxane (B), a monoamine compound and a solvent.
  • a coating solution (T1) was prepared by mixing a polysiloxane (A) solution and a solvent having the composition shown in Table 2.
  • Si molar ratio of (A) / (B) is calculated as follows: Si atom of polysiloxane (A) and Si atom of polysiloxane (B) Represents the molar ratio.
  • PF-4 (33. 33 g), CHAO. 20 g, cyclohexenolelenolene 5. OOg, propylene glycol, 'recall monomethyl ether 20.00 g, and IPA41. ) was prepared.
  • the coating film using Q13 was evaluated as follows.
  • the coating solution was allowed to stand at a temperature of 25 ° C for 1 month, and then lOOcc with a non-aqueous polytetrafluoroethylene filter with a pore size of 0.45 ⁇ m and ⁇ XL: 18 X 22 mm (Chromatodisc 13N, Kurashiki Boseki) Filters were marked with ⁇ , and those with clogging were marked with X.
  • the prepared coating solutions were triacetyl cellulose (hereinafter referred to as TAC) film treated as shown below (film thickness 80 ⁇ m, reflectivity at wavelength 550 nm is 4.5%)
  • a bar coater No. 3 was applied to form a coating film. After standing at a temperature of 23 ° C for 30 seconds, it was dried in a clean oven at 100 ° C for 5 minutes and then cured at a temperature of 60 ° C for 3 days. The cured film thus obtained was evaluated for water contact angle, oil pen wiping property, fingerprint wiping property, adhesion, reflectance and scratch resistance.
  • the refractive index was measured using a cured film formed as follows.
  • the prepared coating solutions (Q1 to Q13 and T1) are spin-coated on a silicon wafer to form a coating film, then left at a temperature of 23 ° C for 30 seconds, and then in a clean oven at 100 ° C for 5 seconds.
  • the film was dried for 3 minutes and then cured at 60 ° C for 3 days to obtain a cured film having a film thickness of lOOnm.
  • the ink applied to the surface of the cured coating with a Pentel oil pen was wiped off with Asahi Kasei Bencot M_3, and the ease of removal was visually determined. The ink was completely wiped off, and the others were X.
  • Fingerprints were attached to the surface of the cured coating, wiped with Bencot M-3 manufactured by Asahi Kasei Co., Ltd., and the ease of removal was visually determined. The fingerprint was completely wiped off, and the others were marked X.
  • the cured film was rubbed 10 reciprocally at 400 g / cm 2 using steel wool # 0000 manufactured by Nippon Steel Wool Co., Ltd., and the scratched surface of the cured film was visually determined.
  • the refractive index of light having a wavelength of 633 nm was measured using an Ellipsometer 1 DVA-36L manufactured by Mizoji Optical Co., Ltd.
  • Examples 6 to 10 the cured coating obtained from the coating solution containing polysiloxane (A), polysiloxane (B) and monoamine compound (C) was manufactured by Nippon Steel Wool Co., Ltd. Using 0000, rubbing 10 reciprocations at 400 g / cm 2 , and visually judging how the cured film surface was scratched, all the cured films exhibited excellent scratch resistance A.
  • the storage stability of the coating solutions (Q1 to Q13) was also good, and was stable after storage at a temperature of 23 ° C for 6 months. Furthermore, the cured films obtained from the coating solutions of Examples:! To 13 showed characteristics of a low refractive index of 1.400 or less and a low reflectance.
  • Comparative Example 1 using the coating solution (T1) without a solution of the monoamine compound (C) and the polysiloxane (B) has an insufficient scratch resistance of D at a curing temperature of 60 ° C. It was a good thing.
  • the cured films obtained from the coating solutions of Examples:! To 13 are excellent in antifouling properties such as fingerprint wiping properties and oil-based pen wiping properties, and the base material.
  • the adhesiveness was high.
  • the prepared coating solution Q6 was applied to the TAC film (film thickness 80 zm, reflectivity 4.5% at a wavelength of 550 nm) subjected to the alkali treatment described above using a bar coater (No. 3). A coating film was formed. After leaving at a temperature of 23 ° C for 30 seconds, it was dried in a clean oven at 100 ° C for 5 minutes, then Example 14 was performed at a temperature of 23 ° C for 5 days, and Example 15 was prepared at a temperature of 40 ° C. A cured coating was obtained under each curing condition for a day. The obtained cured film was evaluated for adhesion, reflectance and scratch resistance. These evaluation methods are as follows, and the evaluation results are shown in Table 5.
  • Example 14 and Example 15 it was shown that the cured film of the present invention was excellent in scratch resistance even at curing temperatures of 23 ° C and 40 ° C.
  • the water contact angle is greater than 100 ° (> 100 °)
  • the oil pen wiping property is ⁇
  • the fingerprint wiping property is ⁇
  • the adhesion property is ⁇
  • the reflectance is 1.4%
  • the scratch resistance is 400 g / D at cm 2 load.
  • the coating solution for forming a film of the present invention is excellent in storage stability, can be sufficiently cured by a low temperature heat treatment of 20 to 70 ° C., and can provide a film having a low refractive index and excellent scratch resistance. Therefore, it can be particularly suitably used for an antireflection substrate, and in particular, can be suitably used for an antireflection film for a display element.
  • the Japanese patent application 2006- 060808 filed on March 7, 2006 and the Japanese patent application 2006- 356192 filed on December 28, 2006 Description and scope of claims And the entire contents of the abstract are hereby incorporated by reference as the disclosure of the specification of the present invention.

Abstract

L'invention concerne un liquide de revêtement pour la formation d'un film de revêtement, lequel peut être suffisamment durci par un traitement thermique à basse température tout en ayant une excellente stabilité au stockage. Ce liquide de revêtement permet de former un film de revêtement ayant une excellente résistance à l'abrasion. L'invention concerne également un procédé servant à produire un tel liquide de revêtement, un film de revêtement et un élément antireflet. L'invention concerne précisément un liquide de revêtement pour la formation d'un film de revêtement, lequel contient un polysiloxane (A) ayant un groupe organique contenant un atome de fluor et au moins l'un d'un polysiloxane (B) représenté par la formule (1) ci-dessous et d'un composé monoamine (C). Dans ce liquide de revêtement, le polysiloxane (A) et au moins l'un du polysiloxane (B) et du composé monoamine (C) sont dissous dans un solvant organique (D). (1) (Dans la formule, R1, R2, R3 et R4 représentent chacun indépendamment un atome d'hydrogène ou un groupe hydrocarboné saturé ayant 1-5 atomes de carbone et n représente un nombre entier supérieur ou égal à 2.)
PCT/JP2007/054350 2006-03-07 2007-03-06 Liquide de revêtement pour la formation d'un film de revêtement, procédé de production de celui-ci, film de revêtement formé à partir de celui-ci et élément antireflet WO2007102514A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2008503878A JP5382310B2 (ja) 2006-03-07 2007-03-06 被膜形成用塗布液、その製造方法、その被膜、及び反射防止材
CN200780008121.9A CN101395238B (zh) 2006-03-07 2007-03-06 被膜形成用涂布液，其制造方法，其被膜及反射防止材料
KR1020087021635A KR101334496B1 (ko) 2006-03-07 2007-03-06 피막 형성용 도포액, 그 제조 방법, 그 피막 및 반사 방지재

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2006-060808 2006-03-07
JP2006060808 2006-03-07
JP2006-356192 2006-12-28
JP2006356192 2006-12-28

Publications (1)

Publication Number Publication Date
WO2007102514A1 true WO2007102514A1 (fr) 2007-09-13

Family

ID=38474941

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/054350 WO2007102514A1 (fr) 2006-03-07 2007-03-06 Liquide de revêtement pour la formation d'un film de revêtement, procédé de production de celui-ci, film de revêtement formé à partir de celui-ci et élément antireflet

Country Status (4)

Country Link
JP (1) JP5382310B2 (fr)
CN (1) CN101395238B (fr)
TW (1) TWI404777B (fr)
WO (1) WO2007102514A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008044742A1 (fr) * 2006-10-12 2008-04-17 Nissan Chemical Industries, Ltd. Solution de revêtement pour former un film de revêtement de faible réfraction, procédé de production de celle-ci, et matériau anti-réflexion
WO2008059844A1 (fr) * 2006-11-14 2008-05-22 Nissan Chemical Industries, Ltd. Liquide de revêtement destiné à former un film d'indice de réfraction faible, son procédé de fabrication et élément antiréfléchisseur
WO2008143186A1 (fr) * 2007-05-18 2008-11-27 Nissan Chemical Industries, Ltd. Solution de revêtement pour la formation d'un film de revêtement à faible indice de réfraction, son procédé de fabrication, et matériau anti-reflet
JP2010102234A (ja) * 2008-10-27 2010-05-06 Hoya Corp 偏光素子の製造方法
JP2010134424A (ja) * 2008-11-04 2010-06-17 Hoya Corp 偏光レンズの製造方法
JP2013195456A (ja) * 2012-03-15 2013-09-30 Gunze Ltd 反射防止シート
EP2180353A3 (fr) * 2008-10-27 2014-03-19 Hoya Corporation Procédé de production d'un élément polarisant
WO2018180983A1 (fr) * 2017-03-31 2018-10-04 住友化学株式会社 Composition

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102702937A (zh) * 2012-06-12 2012-10-03 天长市巨龙车船涂料有限公司 涂料组合物
TWI559026B (zh) * 2015-06-24 2016-11-21 財團法人工業技術研究院 抗反射結構及其製造方法
TWI767114B (zh) * 2018-03-30 2022-06-11 日商住友化學股份有限公司 混合組成物

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0641518A (ja) * 1992-05-27 1994-02-15 Matsushita Electric Ind Co Ltd 表面処理剤及びその使用方法
JPH06293782A (ja) * 1993-04-07 1994-10-21 Mitsubishi Kasei Corp コーティング組成物
JPH07309880A (ja) * 1994-05-19 1995-11-28 Shin Etsu Chem Co Ltd 含フッ素ポリシロキサンおよびその製造方法
JPH0812375A (ja) * 1994-06-30 1996-01-16 Nippon Sheet Glass Co Ltd 撥水性物品及びその製造方法
JPH11217540A (ja) * 1998-02-03 1999-08-10 Daikin Ind Ltd 塗料用組成物
JP2000121803A (ja) * 1998-10-09 2000-04-28 Dow Corning Asia Ltd 反射防止膜
JP2001115151A (ja) * 1999-10-18 2001-04-24 Soft 99 Corporation:Kk １液式水系撥水処理剤及び２液式水系撥水処理剤並びに無機材表面の撥水処理方法
JP2003205581A (ja) * 2001-10-18 2003-07-22 Nitto Denko Corp 反射防止フィルム、光学素子および表示装置
JP2004167827A (ja) * 2002-11-20 2004-06-17 Nitto Denko Corp 硬化性樹脂組成物、硬化膜、反射防止フィルム、光学素子および画像表示装置
JP2004277596A (ja) * 2003-03-17 2004-10-07 Nitto Denko Corp 硬化膜、反射防止フィルム、光学素子、及び画像表示装置
JP2005186568A (ja) * 2003-12-26 2005-07-14 Fuji Photo Film Co Ltd 反射防止フィルム、偏光板及び液晶表示装置
JP2006030881A (ja) * 2004-07-21 2006-02-02 Fuji Photo Film Co Ltd 反射防止フィルム、偏光板及び液晶表示装置

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008044742A1 (fr) * 2006-10-12 2008-04-17 Nissan Chemical Industries, Ltd. Solution de revêtement pour former un film de revêtement de faible réfraction, procédé de production de celle-ci, et matériau anti-réflexion
JP5262722B2 (ja) * 2006-11-14 2013-08-14 日産化学工業株式会社 低屈折率被膜形成用塗布液、その製造方法及び反射防止材

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0641518A (ja) * 1992-05-27 1994-02-15 Matsushita Electric Ind Co Ltd 表面処理剤及びその使用方法
JPH06293782A (ja) * 1993-04-07 1994-10-21 Mitsubishi Kasei Corp コーティング組成物
JPH07309880A (ja) * 1994-05-19 1995-11-28 Shin Etsu Chem Co Ltd 含フッ素ポリシロキサンおよびその製造方法
JPH0812375A (ja) * 1994-06-30 1996-01-16 Nippon Sheet Glass Co Ltd 撥水性物品及びその製造方法
JPH11217540A (ja) * 1998-02-03 1999-08-10 Daikin Ind Ltd 塗料用組成物
JP2000121803A (ja) * 1998-10-09 2000-04-28 Dow Corning Asia Ltd 反射防止膜
JP2001115151A (ja) * 1999-10-18 2001-04-24 Soft 99 Corporation:Kk １液式水系撥水処理剤及び２液式水系撥水処理剤並びに無機材表面の撥水処理方法
JP2003205581A (ja) * 2001-10-18 2003-07-22 Nitto Denko Corp 反射防止フィルム、光学素子および表示装置
JP2004167827A (ja) * 2002-11-20 2004-06-17 Nitto Denko Corp 硬化性樹脂組成物、硬化膜、反射防止フィルム、光学素子および画像表示装置
JP2004277596A (ja) * 2003-03-17 2004-10-07 Nitto Denko Corp 硬化膜、反射防止フィルム、光学素子、及び画像表示装置
JP2005186568A (ja) * 2003-12-26 2005-07-14 Fuji Photo Film Co Ltd 反射防止フィルム、偏光板及び液晶表示装置
JP2006030881A (ja) * 2004-07-21 2006-02-02 Fuji Photo Film Co Ltd 反射防止フィルム、偏光板及び液晶表示装置

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2008044742A1 (ja) * 2006-10-12 2010-02-18 日産化学工業株式会社 低屈折率被膜形成用塗布液、その製造方法及び反射防止材
JP5458575B2 (ja) * 2006-10-12 2014-04-02 日産化学工業株式会社 低屈折率被膜形成用塗布液、その製造方法及び反射防止材
WO2008044742A1 (fr) * 2006-10-12 2008-04-17 Nissan Chemical Industries, Ltd. Solution de revêtement pour former un film de revêtement de faible réfraction, procédé de production de celle-ci, et matériau anti-réflexion
JP5262722B2 (ja) * 2006-11-14 2013-08-14 日産化学工業株式会社 低屈折率被膜形成用塗布液、その製造方法及び反射防止材
WO2008059844A1 (fr) * 2006-11-14 2008-05-22 Nissan Chemical Industries, Ltd. Liquide de revêtement destiné à former un film d'indice de réfraction faible, son procédé de fabrication et élément antiréfléchisseur
WO2008143186A1 (fr) * 2007-05-18 2008-11-27 Nissan Chemical Industries, Ltd. Solution de revêtement pour la formation d'un film de revêtement à faible indice de réfraction, son procédé de fabrication, et matériau anti-reflet
JP5310549B2 (ja) * 2007-05-18 2013-10-09 日産化学工業株式会社 低屈折率被膜形成用塗布液、その製造方法及び反射防止材
JP2010102234A (ja) * 2008-10-27 2010-05-06 Hoya Corp 偏光素子の製造方法
EP2180353A3 (fr) * 2008-10-27 2014-03-19 Hoya Corporation Procédé de production d'un élément polarisant
JP2010134424A (ja) * 2008-11-04 2010-06-17 Hoya Corp 偏光レンズの製造方法
JP2013195456A (ja) * 2012-03-15 2013-09-30 Gunze Ltd 反射防止シート
WO2018180983A1 (fr) * 2017-03-31 2018-10-04 住友化学株式会社 Composition
JP2018172660A (ja) * 2017-03-31 2018-11-08 住友化学株式会社 組成物
US11168226B2 (en) 2017-03-31 2021-11-09 Sumitomo Chemical Company, Limited Composition
US11608444B2 (en) 2017-03-31 2023-03-21 Sumitomo Chemical Company, Limited Composition

Also Published As

Publication number Publication date
JP5382310B2 (ja) 2014-01-08
CN101395238A (zh) 2009-03-25
JPWO2007102514A1 (ja) 2009-07-23
CN101395238B (zh) 2014-01-22
TW200804542A (en) 2008-01-16
TWI404777B (zh) 2013-08-11

Similar Documents

Publication Publication Date Title
WO2007102514A1 (fr) Liquide de revêtement pour la formation d'un film de revêtement, procédé de production de celui-ci, film de revêtement formé à partir de celui-ci et élément antireflet
JP5262722B2 (ja) 低屈折率被膜形成用塗布液、その製造方法及び反射防止材
US7550040B2 (en) Coating fluid for forming film, and film thereof and film-forming process
JP6773036B2 (ja) モバイルディスプレイ機器のカバーガラス等に好適なガラス基板
JPH09208898A (ja) 低屈折率及び撥水性を有する被膜
JP4887783B2 (ja) 低屈折率及び撥水性を有する被膜
JP4887784B2 (ja) 低屈折率及び大きい水接触角を有する被膜
JP5458575B2 (ja) 低屈折率被膜形成用塗布液、その製造方法及び反射防止材
JP4893103B2 (ja) 被膜形成用塗布液及びその被膜並びに被膜形成方法
JP5293180B2 (ja) 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
JP5910494B2 (ja) スプレー塗布用の反射防止被膜形成用塗布液
JP5357502B2 (ja) 低屈折率コーティング材組成物及び塗装品
JP5310549B2 (ja) 低屈折率被膜形成用塗布液、その製造方法及び反射防止材
JPWO2011099505A1 (ja) 屋外設置用デバイスおよび屋外設置用デバイス用反射防止層
KR101334496B1 (ko) 피막 형성용 도포액, 그 제조 방법, 그 피막 및 반사 방지재

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref document number: 2008503878

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 1020087021635

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 200780008121.9

Country of ref document: CN

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07737897

Country of ref document: EP

Kind code of ref document: A1