WO2014119282A1 - Composition d'organosilane - Google Patents

Composition d'organosilane Download PDF

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Publication number
WO2014119282A1
WO2014119282A1 PCT/JP2014/000407 JP2014000407W WO2014119282A1 WO 2014119282 A1 WO2014119282 A1 WO 2014119282A1 JP 2014000407 W JP2014000407 W JP 2014000407W WO 2014119282 A1 WO2014119282 A1 WO 2014119282A1
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group
acid
epoxy group
composition
containing trialkoxysilane
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PCT/JP2014/000407
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English (en)
Japanese (ja)
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淳司 岩佐
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日本曹達株式会社
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Priority to JP2014559566A priority Critical patent/JP5951050B2/ja
Publication of WO2014119282A1 publication Critical patent/WO2014119282A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C08K5/04—Oxygen-containing compounds

Definitions

  • the present invention relates to an organic silane composition, and particularly relates to a composition having excellent adhesion to a plastic substrate, a metal substrate, etc., and also having excellent storage stability.
  • This application claims priority to Japanese Patent Application No. 2013-013845 filed on January 29, 2013, and Japanese Patent Application No. 2013-104509 filed on May 16, 2013, The contents are incorporated here.
  • Transparent plastic moldings such as polycarbonate are widely used as an alternative to inorganic glass products by taking advantage of light weight, easy processability, impact resistance, etc., but they are easily affected by solvents and difficult to modify the surface. There are some drawbacks. For this reason, there are still inferior points compared to inorganic glass, and attempts have been made to improve these properties. For example, glycidoxytrimethoxysilane is hydrolyzed with nitric acid in alcohol, and further, diethylenetriamine is added and further reacted to form a hard coat film corresponding to a pencil hardness of 2H on a polycarbonate plate. It is known that it can be formed. (Non-Patent Document 1)
  • the coating composition has a problem of workability that it takes a long time of 24 hours for hydrolysis and 15 hours for curing after the coating film, and also has a storage stability as described later. There was a problem.
  • the present invention has been made in view of the above circumstances, and can be applied to a wide range of base materials including plastic, can be surface-modified like glass, can be manufactured in a short time, and can be cured in a short time.
  • An object is to provide a method for producing a hydrolysis-condensation product of trialkoxysilane, which is a raw material of composition A from which a coating film having sufficient hardness is obtained, and an improved product of composition A having excellent long-term storage stability.
  • the present inventors have found that the trialkoxysilane is obtained by simply mixing and stirring an epoxy group-containing trialkoxysilane with a specific polyamine or imidazole in water for a short time.
  • the composition containing the decomposition condensate has been found that a coating film having sufficient hardness can be obtained in a short time after heating, and the present invention has been completed.
  • composition obtained by mixing and stirring an organic acid having a specific pKa or an alcohol having a perfluoroalkyl group to a composition containing an epoxy group-containing trialkoxysilane hydrolysis condensate and polyamines The inventors have found that the storage stability is excellent and have completed the present invention.
  • the present invention (1) Polyamines or imidazoles having an epoxy group-containing trialkoxysilane and / or a hydrolysis condensate thereof in water and two or more amino groups or imino groups to which one or more hydrogen atoms are bonded in one molecule Mixing and stirring, a method for producing an epoxy group-containing trialkoxysilane hydrolysis condensate, (2) The method for producing an epoxy group-containing trialkoxysilane hydrolysis condensate according to (1), which is mixed and stirred at room temperature, (3) The method for producing an epoxy group-containing trialkoxysilane hydrolysis condensate according to (1), wherein the polyamine is a polyalkylene polyamine, (4) The method for producing an epoxy group-containing trialkoxysilane hydrolysis condensate according to (1), wherein the epoxy group-containing trialkoxysilane is glycidoxyalkyltrialkoxysilane, (5) The epoxy group-containing trialkoxysilane hydrolysis according to (1), wherein water is used
  • the present invention also provides: (7) (A) Hydrolysis condensate of epoxy group-containing trialkoxysilane, (B) a composition containing polyamines and (C-1) n-pentanol, (8) (A) Hydrolysis condensate of epoxy group-containing trialkoxysilane, (B) polyamines and (C-2) organic acids having a pKa in the range of 2.0 to 6.0 at 25 ° C.
  • composition containing (9) The composition according to (8), wherein the z-average particle diameter of the hydrolyzed condensate of the epoxy group-containing trialkoxysilane measured by a dynamic light scattering method is in the range of 5 to 50 nm, (10) The composition according to (8), wherein the polyamine is at least one polyamine selected from the group consisting of an alkylene polyamine, a polyalkylene polyamine, a poly (phenylene alkylene) polyamine, and a cycloalkylene alkyl polyamine.
  • Polyamines are 1 / (total number of hydrogen atoms on all nitrogen atoms in one molecule of polyamine) with respect to 1 mol of epoxy group in epoxy group-containing trialkoxysilane and / or its hydrolysis condensate.
  • the composition according to (8) which is used in a range of 1 mol or more and 1 / (total number of hydrogen atoms on all nitrogen atoms in 1 molecule of polyamine) or less.
  • composition according to (8) wherein an organic acid having a pKa in the range of 2.0 to 6.0 is used in a range of 0.3 to 1.2 mol with respect to 1 mol of the polyamines, (13)
  • the composition according to (8), wherein the alcohol having 2 to 5 carbon atoms having a perfluoroalkyl group and / or a perfluoroalkylene group is 30% by mass or more of the whole composition, (14)
  • a hydrolysis condensate of an epoxy group-containing trialkoxysilane can be produced in a short time, and therefore a composition containing the hydrolysis condensate can also be produced in a short time.
  • the composition of the present invention can form a coating film having excellent hardness, adhesion, and appearance on a substrate such as plastic by heating in a short time, and further has insulation and corrosion resistance. Can be granted.
  • the surface of the substrate may be modified such as by imparting functions such as solvent resistance and water repellency by treating the resulting thin film with a silane-based water repellent or monomolecular film forming solution. Can do.
  • the composition of the present invention has the same function as the composition containing the hydrolysis condensate obtained by the method described in Non-Patent Document 1, and has a marked improvement in storage stability. It was seen.
  • FIG. 3 is a diagram showing the element concentration in the depth direction of the film by X-ray photoelectron spectroscopy (ESCA) of the PC resin substrate (B-1) treated with the composition (A-1) obtained in Example 1.
  • FIG. 6 is a graph showing the change over time in the z-average particle size of the solid content in the composition using various solvents obtained in Example 5.
  • FIG. 6 is a graph showing the time-dependent change in the z-average particle size of the solid content in the composition using various solvents obtained in Example 7.
  • FIG. 10 is a graph showing the time-dependent change in the z-average particle diameter of the solid content in the composition using various solvents obtained in Example 8.
  • FIG. 6 is a graph showing the time-dependent change in the z-average particle diameter of the solid content in the composition having a different benzoic acid content obtained in Example 10.
  • FIG. 3 is a graph showing the time-dependent change in the z-average particle diameter of the solid content in the composition obtained using the various organic acids obtained in Example 11.
  • the method for producing the epoxy group-containing trialkoxysilane hydrolyzed condensate of the present invention comprises an epoxy group-containing trialkoxysilane. And / or the hydrolysis-condensation product thereof is mixed with water and polyamines or imidazoles and stirred.
  • the conventional production method described in Non-Patent Document 1 is a method in which hydrolysis condensation is performed using an epoxy group-containing trialkoxysilane, an alcohol having 1 to 5 carbon atoms, water, and an acid such as a mineral acid or an organic acid.
  • polyamines or imidazoles are generally added afterwards to prepare a composition.
  • the hydrolysis condensation process has a long time and is obtained.
  • the method of the present invention can produce a composition that overcomes the conventional drawbacks by preparing a hydrolysis condensate of the trialkoxysilane in the presence of polyamines or imidazoles.
  • the hydrolysis-condensation product of the epoxy group-containing trialkoxysilane obtained by the production method of the present invention is a polymer or oligomer condensed with an epoxy group-containing trialkoxysilane.
  • the product is a product obtained by further hydrolytic condensation of the hydrolysis condensate.
  • Epoxy group-containing trialkoxysilane as a raw material and / or its hydrolysis condensate The structure of the epoxy group-containing trialkoxysilane used in the method of the present invention is not particularly limited as long as it is a trialkoxysilane containing an epoxy group in addition to a functional group portion that is lost due to hydrolysis or the like.
  • the compound represented by the following formula (I) can be exemplified.
  • R-Si (OR 1 ) 3 (I) (In the formula, R represents a hydrocarbon group having an epoxy group or a glycidoxy group, and R 1 represents an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms.)
  • R represents a hydrocarbon group having an epoxy group or a glycidoxy group, and R 1 represents an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms.
  • one or more epoxy groups or glycidoxy groups may be contained, and preferably 1 to 3 are included, and both epoxy groups and glycidoxy groups may be contained.
  • hydrocarbon group of the “hydrocarbon group having an epoxy group or glycidoxy group” of R, specifically, an alkyl group, a cycloalkyl group, a cycloalkylalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, An aryl group, an arylalkyl group, an arylalkenyl group and the like can be exemplified, and the carbon number is preferably in the range of 1 to 30, more preferably in the range of 1 to 10.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n -Hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, isononyl group, n-decyl group, etc., lauryl group, tridecyl group, myristyl group, pentadecyl group, palmityl group, heptadecyl group, stearyl Examples include groups.
  • cycloalkyl group examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like.
  • cycloalkylalkyl group examples include a cyclopropylmethyl group, a cyclopropylethyl group, a cyclopropylpropyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a cycloheptylmethyl group, and a cyclooctylmethyl group.
  • groups such as a cycloalkyl group having 3 to 10 carbon atoms and an alkyl group having 1 to 10 carbon atoms bonded to each other.
  • alkenyl group examples include a vinyl group, a prop-1-en-1-yl group, an allyl group, a but-1-en-1-yl group, a but-2-en-1-yl group, But-3-en-1-yl group, but-1-en-2-yl group, but-3-en-2-yl group, penta-1-en-1-yl group, penta-4-ene- 1-yl group, penta-1-en-2-yl group, penta-4-en-2-yl group, 3-methyl-but-1-en-1-yl group, hexa-1-en-1- Yl group, hexa-5-en-1-yl group, hepta-1-en-1-yl group, hepta-6-en-1-yl group, octa-1-en-1-yl group, octa-7 Examples include -en-1-yl group, buta-1,3-dien-1-yl group and the like.
  • cycloalkenyl group examples include 1-cyclopenten-1-yl group, 2-cyclopenten-1-yl group, 1-cyclohexen-1-yl group, 2-cyclohexen-1-yl group, and 3-cyclohexene. Examples thereof include a 1-yl group and the like.
  • alkynyl group examples include ethynyl group, prop-1-in-1-yl group, prop-2-yn-1-yl group, but-1-in-1-yl group, but-3- In-1-yl group, penta-1-in-1-yl group, penta-4-in-1-yl group, hexa-1-in-1-yl group, hexa-5-in-1-yl group And hept-1-in-1-yl group, octa-1-in-1-yl group, octa-7-in-1-yl group and the like.
  • Aryl group means a monocyclic or polycyclic aryl group, and in the case of a polycyclic aryl group, in addition to fully unsaturated, partially saturated groups are also included. Specifically, a phenyl group, a naphthyl group, an azulenyl group, an indenyl group, an indanyl group, a tetralinyl group and the like can be exemplified.
  • arylalkyl group examples include benzyl group, phenethyl group, 3-phenyl-n-propyl group, 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 8-phenyl-n- An octyl group and the like can be exemplified, and a group in which an aryl group having 6 to 10 carbon atoms and an alkyl group having 1 to 10 carbon atoms are bonded is preferable.
  • the “arylalkenyl group” is a group in which an aryl group and an alkenyl group are bonded, and specifically includes a styryl group, a 3-phenyl-prop-1-en-1-yl group, a 3-phenyl-prop-2-yl group.
  • a group in which an aryl group having 6 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms are bonded is preferable.
  • hydrocarbon group may have a substituent other than an epoxy group and a glycidoxy group.
  • a substituent include a halogen atom, an alkyl group, an alkenyl group, and an alkoxy group.
  • (meth) acryloxy groups include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group.
  • an alkyl group and an alkenyl group the same specific example as the alkyl group and alkenyl group in said R can be illustrated.
  • Examples of the “alkyl group having 1 to 10 carbon atoms” of the “unsubstituted or substituted alkyl group having 1 to 10 carbon atoms” of R 1 include the same alkyl groups as in the above R.
  • Specific examples of the substituent “having a substituent” include a halogen atom, an alkoxy group, a (meth) acryloxy group, and the like.
  • Specific examples of the halogen atom and alkoxy group include the same specific examples as the halogen atom and alkoxy group exemplified as the substituent other than the epoxy group and glycidoxy group in R.
  • raw material epoxy group-containing trialkoxysilane or its hydrolysis condensate include the following compounds, but are not limited thereto. Moreover, these can be used individually by 1 type or in mixture of 2 or more types.
  • glycidoxyalkyltrialkoxysilane or glycidoxyalkenylalkoxysilane is preferable, and specific examples thereof include compounds represented by the following formulae.
  • Alkoxysilanes other than epoxy group-containing trialkoxysilanes In the production method of the present invention, it is preferable to add a tetraalkoxysilane, a trialkoxysilane other than the epoxy group-containing trialkoxysilane, or a dialkoxysilane to the epoxy group-containing trialkoxysilane as described above. it can.
  • alkoxysilanes include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra (n-propoxy) silane, tetra (isopropoxy) silane, and tetra (n-butoxy) silane; Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane , N-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltri
  • Such a partial hydrolysis-condensation product include trade names “MKC silicate MS51”, “MKC silicate MS56”, “MKC silicate MS57”, and “MKC silicate MS60” manufactured by Mitsubishi Chemical Corporation (both are tetramethoxy). Silane condensate); trade names “Ethyl silicate 40” and “ethyl silicate 48” (both are condensates of tetraethoxysilane) manufactured by Colcoat Co., Ltd.
  • alkoxysilane condensate trade names “MKC silicate MS56B15”, “MKC silicate MS56B30”, “MKC silicate MS58B15”, “MKC silicate MS56I30”, “MKC silicate MS56F20” manufactured by Mitsubishi Chemical Corporation; Product name of It can be exemplified MS-485 ", and the like.
  • the amount of water used in the method of the present invention is not particularly limited as long as the amount of the epoxy group-containing trialkoxysilane and / or the hydrolysis condensate used is not less than the amount that can be hydrolyzed to some extent.
  • Epoxy group-containing trialkoxysilane and / or its hydrolysis condensate used (however, when the epoxy group-containing trialkoxysilane and its hydrolysis condensate are used in combination, it represents the total of both, Also when using together alkoxysilanes other than alkoxysilane, it represents the total of them.)
  • 0.5 mol or more is preferable with respect to 1 mol, 1.0 mol or more, 2.0 mol or more, 5.0 More preferably, it is more than 10 mol or more.
  • the polyamine used in the present invention is not particularly limited as long as it is a compound having two or more amino groups or imino groups bonded to one or more hydrogen atoms in one molecule.
  • polyalkylene polyamines are preferable, and specific examples include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and dipropylenetriamine.
  • the amount of the polyamine used is not particularly limited, but is 1 / (on the total nitrogen atoms in one molecule of the polyamines with respect to 1 mol of the epoxy group in the epoxy group-containing trialkoxysilane and / or its hydrolysis condensate.
  • the total number of hydrogen atoms is preferably used in a molar range of 1.2 to 10 times the 1 / (number of total hydrogen atoms on all nitrogen atoms in one molecule of the polyamine), 1.5 to 5 times.
  • a double mole, or a range of 1.8 to 2.5 moles is preferred.
  • 1 / total number of hydrogen atoms on all nitrogen atoms in one molecule of polyamine
  • curing may be insufficient and a film with high hardness may not be obtained.
  • 1 / polyamines 1
  • polyamines When it is larger than 10 times the mole of all hydrogen atoms on all nitrogen atoms in the molecule, polyamines may remain and a film having sufficient hardness may not be obtained.
  • imidazoles used in the present invention include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-n-propylimidazole, 2-undecyl-1H-imidazole, 2- Heptadecyl-1H-imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-1H-imidazole, 4-methyl-2-phenyl-1H-imidazole, 2-phenyl-4-methylimidazole 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole , 1- Anoethyl-2-ethyl-4-methyl
  • the amount of imidazole used is not particularly limited as long as it is a catalytic amount or more, and is preferably in the range of 0.001 to 1.0 mol with respect to 1 mol of the epoxy group contained in the trialkoxysilane used. The range of ⁇ 0.5 mol, or 0.01 to 0.1 mol is more preferable.
  • the acid used include organic acids and mineral acids, and more specific examples of the organic acid include acetic acid, formic acid, oxalic acid, carbonic acid, phthalic acid, trifluoroacetic acid, p-
  • mineral acids such as toluenesulfonic acid and methanesulfonic acid include hydrochloric acid, nitric acid, boric acid, borohydrofluoric acid and the like, and in particular, the pKa at 20 ° C. is in the range of 2.0 to 6.0.
  • the organic acid is preferably used.
  • organic acids include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, caproic acid, isocaproic acid, chloroacetic acid, fluoroacetic acid, bromoacetic acid, and 3-chloropropion.
  • the amount of the acid used is not particularly limited, but is preferably in the range of 0.3 to 1.2 mol, preferably 0.5 to 1.0 mol, or 0.6 with respect to 1 mol of the polyamine or imidazole to be used. A range of ⁇ 0.9 mol is more preferred. When the amount is less than 0.3 mol, the storage stability of the composition may be lowered. When the amount is more than 1.2 mol, a coating film having sufficient hardness may not be formed.
  • an organic solvent can be used as necessary.
  • the solvent is not particularly limited as long as the solvent can maintain the uniformity and stability of the solution to some extent.
  • alcohols having 1 to 5 carbon atoms are preferable. These can be used alone or in combination of two or more.
  • the alcohol having 1 to 5 carbon atoms may have a substituent such as a halogen atom on an appropriate carbon.
  • Specific examples of such alcohol include perfluoroethanol and perfluoropentanol. can do. These can be used individually by 1 type or in mixture of 2 or more types.
  • alcohols having 3 or less carbon atoms are preferable, and isopropanol, n-propanol and the like are particularly preferable.
  • the organic solvent to be used is preferably an organic solvent that is soluble in water.
  • the ratio of water to the organic solvent is preferably an amount ratio that makes a uniform solution after using a necessary amount.
  • the mass ratio of water to organic solvent is preferably in the range of 30/70 to 95/5. , 50/50 to 90/10, 60/40 to 80/20, or 65/35 to 75/25 are more preferable.
  • the amount of water used for hydrolysis of trialkoxysilane is low because the solubility of water in the organic solvent is low. It is preferable to use it in an amount in a range where the solution becomes uniform more than the necessary amount.
  • the amount of the solvent to be used is not particularly limited, but the appearance of the coating film using the composition containing the hydrolysis condensate produced by the production method of the present invention, the coatability and curability of the composition, and the composition are used.
  • the solid content concentration in the reaction solution is in the range of 0.5 to 50% by mass. 1.0 to 30% by mass, 1.0 to 20% by mass, 1.0 to 10% by mass, 1.5 to 5.0% by mass, or 1.8 to 3% by mass is more preferable.
  • polyamines having an epoxy group-containing trialkoxysilane and / or a hydrolysis condensate thereof, water, and two or more amino groups or imino groups to which one or more hydrogen atoms are bonded in one molecule, or imidazole If necessary, an acid and an organic solvent are mixed and stirred to produce a hydrolyzed condensate of an epoxy group-containing trialkoxysilane, but the mixing order and stirring speed are not particularly limited, any order, or Any speed can be set.
  • the temperature at the time of mixing and stirring is not particularly limited, and it is preferably in the range of room temperature to the boiling point of the solvent used, more preferably at room temperature.
  • the room temperature is the outside air temperature at the place where mixing and stirring is performed, but a temperature in the range of 15 to 35 ° C. is preferable.
  • the epoxy group-containing trialkoxysilane, water, and a polyamine having two or more amino groups or imino groups in which one or more hydrogen atoms are bonded in one molecule or all imidazoles coexist. It is preferable to stir for 2 to 3 hours. After hydrolysis, if necessary, dilute with an organic solvent or water.
  • the solid content concentration of the composition containing the hydrolysis condensate obtained by the production method of the present invention is not particularly limited, but it is preferably used in the range of 0.5 to 50% by mass, and 1.0 to 30% by mass.
  • the solid content concentration may be adjusted to a predetermined solid content concentration from the beginning, or may be adjusted to a predetermined solid content concentration by preparing a composition in a thick state and then diluting the composition.
  • composition of the present invention comprises a hydrolyzed condensate (A), (B) and (C) of an epoxy group-containing trialkoxysilane obtained by the production method of the present invention or other methods. Includes things.
  • A Hydrolysis condensate of epoxy group-containing trialkoxysilane
  • B Polyamines
  • C (C-1) n-pentanol, or (C-2) an organic acid having a pKa at 20 ° C. in the range of 2.0 to 6.0 or a carbon number of 2 having a perfluoroalkyl group and / or a perfluoroalkylene group ⁇ 5 alcohols
  • composition containing the components (A), (B) and (C) will be described in detail.
  • the solid content concentration of the hydrolyzed condensate of the epoxy group-containing trialkoxysilane in the composition is not particularly limited, but is preferably in the range of 1 to 50% by mass, 1 to 10% by mass, or 1.5 to 3% by mass. % Range is more preferred.
  • the solid content concentration may be adjusted to a predetermined solid content concentration from the beginning, or may be adjusted to a predetermined solid content concentration by preparing a composition in a thick state and then diluting the composition.
  • the production method of the hydrolyzed condensate of the epoxy group-containing trialkoxysilane of component (A) can preferably be exemplified by the production method of the present invention described above in (1).
  • the raw material epoxy group-containing trialkoxysilane and / or its hydrolysis condensate is The thing similar to what was shown by the term of the manufacturing method of invention can be used. Further, as described in the production method of the present invention, a trialkoxysilane other than tetraalkoxysilane, epoxy group-containing trialkoxysilane and / or its hydrolysis condensate, dialkoxysilane, or partial hydrolysis thereof. It can also be produced in the presence of a decomposition condensate.
  • the amount of water is not particularly limited as long as the epoxy group-containing trialkoxysilane used and / or the hydrolysis condensate thereof is an amount that can be hydrolyzed to some extent, and specifically, the trialkoxysilane used and / or Or 0.5 mol or more is preferable with respect to 1 mol of the hydrolysis-condensation products, 1.0 mol or more, 2.0 mol or more, 5.0 mol or more, or 10 mol or more is more preferable.
  • the amount of the silanol condensation catalyst used is not particularly limited, but the molar amount relative to the amount of trialkoxysilyl group converted as uncondensed in the raw material epoxy group-containing trialkoxysilane and / or its hydrolysis condensate.
  • the ratio (silanol catalyst / the silyl group) is preferably in the range of 0.001 to 1.0, more preferably in the range of 0.01 to 1.0, or 0.1 to 0.5.
  • the silanol condensation catalyst is not particularly limited as long as it hydrolyzes the alkoxy group of the epoxy group-containing trialkoxysilane and condenses the silanol to form a siloxane bond.
  • Silanol condensation catalysts such as silane coupling agents having amino groups such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, etc., are derivatives obtained by modifying these. Furthermore, known silanol condensation catalysts such as other acidic catalysts such as fatty acids such as ferrous acid and organic acidic phosphoric acid ester compounds and basic catalysts can be exemplified.
  • a photoacid generator can also be used as a silanol condensation catalyst.
  • Specific examples of the photoacid generator include tetrafluoroborate (BF 4 ⁇ ), hexafluorophosphate (PF 6 ⁇ ), fluoroalkyl phosphate (PFm (RF) 6-m ⁇ (RF represents a fluorinated alkyl group).
  • M represents an integer of 0 to 5)
  • hexafluoroantimonate SbF 6 ⁇
  • hexafluoroarsenate AsF 6 ⁇
  • hexachloroantimonate SbCl 6 ⁇
  • tetraphenylborate tetrakis ( Trifluoromethylphenyl) borate, tetrakis (pentafluoromethylphenyl) borate, perchlorate ion (ClO 4 ⁇ ), trifluoromethanesulfonate ion (CF 3 SO 3 ⁇ ), fluorosulfonate ion (FSO 3 ⁇ ), toluene Sulfonate ion, trinitroben Nsurufon anion, a sulfonium salt or iodonium salt having an anion such as trinitrotoluene sulfonate anion can be used.
  • a silanol condensation catalyst can be used individually by 1 type or in combination of 2 or more types.
  • polyamines or imidazoles are used as the curing agent or curing accelerator of the epoxy group-containing trialkoxysilane, and therefore it is preferable to use polyamines and imidazoles as the silanol condensation catalyst. Details of the polyamines and imidazoles are as described above in the production method of the present invention.
  • the z-average particle diameter measured by the dynamic light scattering method of the hydrolysis-condensation product of the epoxy group-containing trialkoxysilane used in the present invention is 5 from the viewpoint of film hardness, coating unevenness during coating, etc.
  • the range of ⁇ 50 nm is preferable, and 5 to 30 nm is more preferable. If it is larger than 50 nm, the pot life is short, there is a problem in storage stability, and smear may occur after coating. If it is smaller than 5 nm, the hardness of the coating film obtained from this composition is insufficient. It may become.
  • composition of the present invention contains specific polyamines.
  • polyamines include the polyamines shown in the production method of (1) above.
  • the amount of use is also as described in the production method of (1) above.
  • a curing agent or curing accelerator other than these can be added as necessary.
  • imidazoles shown in the production method of (1) above Dimethylaminopropylamine, diethylaminopropylamine, trimethylhexamethylenediamine, pentanediamine, bis (2-dimethylaminoethyl) ether, pentamethyldiethylenetriamine, alkyl-t-monoamine, 1,4-diazabicyclo (2,2,2) octane (Triethylenediamine), N, N, N ′, N′-tetramethylhexamethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N′-tetramethylethylenediamine, Aliphatic amines such as N, N-dimethylcyclohexylamine, dimethylaminoethoxyethoxyethanol, dimethylaminohexanol, piperidine, piperazine, menthanediamine, isophoronediamine, methylmorpholine,
  • Organic acid used in the composition of the present invention is not particularly limited as long as the pKa at 25 ° C. is in the range of 2.0 to 6.0, preferably in the range of 3.0 to 5.0.
  • the amount of acid to be used is not particularly limited, but is preferably in the range of 0.3 to 1.2 mol, preferably 0.5 to 1.0 mol, or 0.6 to 0.00 mol per mol of the polyamine used. A range of 9 moles is more preferred. When the amount is less than 0.3 mol, the storage stability of the composition may be lowered. When the amount is more than 1.2 mol, a coating film having sufficient hardness may not be formed.
  • C2-C5 alcohol having a perfluoroalkyl group and / or a perfluoroalkylene group Specific examples of the alcohol having 2 to 5 carbon atoms having a perfluoroalkyl group and / or a perfluoroalkylene group used in the composition of the present invention include trifluoromethanol, 2,2,2-trifluoroethanol.
  • 1,1,2,2,2-pentafluoroethanol 3,3,3-trifluoro-1-propanol, 2,2,3,3,3-pentafluoro-1-propanol, 1,1,2 , 2,3,3,3-heptafluoro-1-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2-trifluoromethyl-2-propanol, 2-methyl-1 , 1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,4,4,4-heptafluoro-1-butanol, nonafluoro-t-butanol, , It can be exemplified 2,3,3,4,4,5,5- octafluoro-1-pentanol.
  • the amount of fluoroalcohol used in the composition is not particularly limited, but is preferably 30% by mass or more, and more preferably 40% by mass or more of the entire composition. When it is less than 30% by mass, the long-term storage stability of the composition may be lowered.
  • the composition of the present invention can use an organic solvent in order to adjust the solid content concentration in the composition, and as such a solvent, as long as the solvent can maintain the uniformity and stability of the solution, Specific examples include, but are not limited to, methanol, ethanol, propyl alcohol, isopropyl alcohol, n-butanol, s-butanol, t-butanol, n-pentanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylene Alcohols such as glycol monomethyl ether, propylene glycol monomethyl ether, and ethylene glycol monoethyl ether; ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, and tetrahydropyran Ketones such as acetone, methyl ethyl ketone and acetylacetone, esters such as methyl acetate and ethylene glyco
  • the organic solvent to be used is preferably an organic solvent that dissolves in water.
  • the ratio of water to the organic solvent is not particularly limited as long as it is an amount ratio that makes a uniform solution as a composition after using a necessary amount.
  • the mass ratio of water to organic solvent is preferably in the range of 30/70 to 95/5. , 50/50 to 90/10, 60/40 to 80/20, or 65/35 to 75/25 are more preferable.
  • the amount of water used for hydrolysis of trialkoxysilane is low because the solubility of water in the organic solvent is low. It is preferable to use it in an amount in a range where the composition becomes more than the necessary amount.
  • the solid content concentration in the composition of the present invention is not particularly limited, but it is 0.5 to 0.5 in consideration of the appearance of the coating film, coating properties, curability, properties of the coating film, storage stability of the composition, and the like.
  • An amount in the range of 50% by weight is preferred, 1.0-30% by weight, 1.0-20% by weight, 1.0-10% by weight, 1.5-5.0% by weight, or 1 More preferably, the range is from 8 to 3% by mass. If it is less than 0.5% by mass, it may be difficult to form a film uniformly, and if it is more than 50% by mass, the stability of the composition, the transparency of the coating film, the appearance, or There may be a problem in coating properties.
  • the amount of the organic solvent and water used can be determined as appropriate in consideration of the amount of the fluoroalcohol used in combination as long as the solid content concentration can be adjusted.
  • composition of the present invention other components can be added depending on the application. Specifically, inorganic fine particles such as colloidal silica and colloidal alumina, various surfactants, dyes, pigments, Dispersants, water repellent materials, thickeners, fragrances, antibacterial components and the like can be exemplified.
  • inorganic fine particles such as colloidal silica and colloidal alumina, various surfactants, dyes, pigments, Dispersants, water repellent materials, thickeners, fragrances, antibacterial components and the like can be exemplified.
  • Epoxy group-containing trialkoxysilane and / or hydrolysis condensate thereof, water, organic solvent (including n-pentanol) and polyamines are mixed and stirred at room temperature, and further, an organic acid or fluoroalcohol as necessary Are further diluted with an organic solvent (including n-pentanol) and water as necessary.
  • iii) Mixing epoxy group-containing trialkoxysilane and / or hydrolysis condensate thereof, water, alcohol as a solvent (including n-pentanol), polyamines, organic acid or fluoroalcohol as necessary at room temperature, Stir and further dilute with organic solvent (including n-pentanol) and water as needed.
  • the stirring temperature is not particularly limited, but is preferably in the range of room temperature to the boiling temperature of the solvent used, and more preferably at room temperature. In this case, the room temperature is the outside temperature of the place where the stirring is performed, but a range of 15 to 35 ° C. is preferable.
  • composition of the present invention can be applied to the surface of a substrate as a target by any known coating means such as brush, spray, dipping, spin coating, bar coating, and gravure printing.
  • a coating film can be formed. Drying can be performed by room temperature drying and / or heating. Specifically, it is carried out at 20 ° C. to 250 ° C., preferably 20 ° C. to 150 ° C. for 10 seconds to 24 hours, preferably 30 seconds to 10 hours.
  • the thin film obtained is not particularly limited, it is preferably more than 10 nm and not more than 5 ⁇ m.
  • the substrate for treating the composition of the present invention is not particularly limited as long as it can be treated.
  • iron, stainless steel, copper, aluminum and other metals, ceramics, cement, glass, polycarbonate resin examples thereof include resin base materials such as acrylic resin, polyimide resin, polyester resin, epoxy resin, liquid crystal polymer resin, and polyether sulfone, and the surface may be coated with another coating material.
  • resin base materials such as acrylic resin, polyimide resin, polyester resin, epoxy resin, liquid crystal polymer resin, and polyether sulfone
  • a resin base material and a metal base material are particularly preferable.
  • a water-repellent layer a layer containing a hydrolytic condensate of a metal surfactant, or a self-assembled monolayer can be laminated on the thin film obtained from the composition of the present invention.
  • the composition of the present invention can be applied to, for example, heat exchangers, fins for heat exchangers, building materials, roofs, window glasses, windshields, various mirrors, plastic lenses, lenses, tires, rubber, magnetic recording media, semiconductor material surfaces, and the like.
  • the surface of the resin substrate treated with the composition of the present invention is hardened, it can also be used as a substitute for applications in which conventional glass such as an automobile windshield has been used. .
  • Example 1 Preparation of coating composition 0.44 g of acetic acid was added to 0.54 g of 2-methylimidazole dispersed in 1.25 g of water and dissolved. 16.5 g of 3-glycidoxypropyltrimethoxysilane (GPTMS) was added to the obtained aqueous solution, and the mixture was stirred at room temperature for 2 hours. 10.0 g of the condensation reaction solution was diluted with 40.0 g of Solmix (registered trademark) (AP-7, manufactured by Nippon Alcohol Sales Co., Ltd.) to obtain a coating composition (A-1) having a solid content of 20 wt%. .
  • Solmix registered trademark
  • a coating composition (A-1) was formed on a polycarbonate (PC) resin substrate.
  • the prepared coating composition (A-1) was dip coated on a PC resin substrate.
  • the coated substrate was dried in an oven (120 ° C., 20 min) to obtain a coating composition-treated substrate (B-1).
  • the resulting treated substrate was coated with a fluorine-based glass surface liquid repellent treatment agent Super Galaco (registered trademark) (manufactured by Soft 99) to obtain a base film-liquid repellent treated PC resin substrate (C-1). .
  • the coating composition-treated substrate (B-1) was measured by an X-ray photoelectron spectrometer (Quantera II, manufactured by ULVAC-PHI). 100 cycles were performed under a sputtering condition of 1 kV, and the measurement was made to a depth of about 200 nm. The measurement results are shown in FIG. FIG. 1 clearly shows that a glass-like inorganic film rich in Si component is formed.
  • the cross cut test of the cross cut test (B-1) was conducted according to the cross cut tape peel test method described in JIS K-5400 (1999).
  • the coating film on the PC resin substrate was cross-cut into a 1 mm ⁇ 1 mm grid pattern, and a peel test was performed using a transparent adhesive tape.
  • Example 2 Preparation of Coating Composition A coating composition (A-1) was obtained in the same manner as in Example 1.
  • Heat cycle test Heat cycle tests (B-2) and (B-3) were conducted.
  • a hot air dryer (LC-234, manufactured by Espec) was used for the test. It set so that it might cycle from 25 degreeC to 200 degreeC in 2 hours, the process substrate was put, and the heat cycle test of 5 rounds was done. In both (B-2) and (B-3), it was visually confirmed that there was no crack or peeling after the test.
  • Example 3 Preparation of Coating Composition 2.0 g GPTMS, 0.5 g diethylenetriamine, 0.3 g water and 8.0 g n-pentanol were mixed and stirred at room temperature for 2 hours. 1.0 g of the reaction solution was diluted with 9.0 g of n-pentanol to prepare a coating composition (A-2) of 2% in terms of solid content mass concentration.
  • A-2 a coating composition of 2% in terms of solid content mass concentration.
  • the average particle diameter of the hydrolysis condensate of GPTMS in the coating composition is measured by a particle size distribution meter (Zetersizer Nano, Malvern: measurement conditions; solution viscosity 3.31, particle refractive index 1.50)
  • the particle size after 1 day of preparation of the coating composition was 11 nm.
  • Example 4 1 Preparation of Coating Composition A coating composition (A-2) was prepared in the same manner as in Example 3 using GPTMS and diethylenetriamine.
  • Example 5 2.0 g of GPTMS, 0.5 g of diethylenetriamine, 0.22 g (2 molar equivalents relative to GPTMS) of water and 8.0 g of n-pentanol were mixed, stirred at room temperature for 2 hours, and an additional 90 g of n -Diluted with pentanol to prepare a coating composition (A-3) having a solid content of 2.5% in terms of mass concentration.
  • the average particle size of the GPTMS hydrolyzed condensate in the coating composition is set to a particle size distribution meter (Zetasizer Nano, Malvern: measurement conditions; solution viscosity is set to the viscosity of the main solvent n-pentanol, When measured by refractive index 1.50), the particle size after 1 day of preparation of the coating composition was 11 nm.
  • Coating compositions (A-31) to (A-34) were prepared in the same manner as described above using isopropanol, methanol, ethanol, and n-butanol instead of n-pentanol.
  • Example 6 (Confirmation of effect of z-average particle diameter in composition of hydrolysis condensation product of GPTMS) After mixing 2.0 g of GPTMS, 0.5 g of diethylenetriamine, 0.22 g of water and 8.0 g of n-pentanol, the mixture was stirred at room temperature to prepare a coating composition. Sampling was performed immediately after mixing, diluted 10-fold with n-pentanol, and the z-average particle size was measured with a particle size distribution meter (Zetersizer Nano, Malvern: measurement conditions; the same as in Example 3).
  • the remaining coating composition was sampled after 1 hour, 8 hours, 1 day, 2 days and 3 days of stirring at room temperature, diluted under similar conditions, and the z-average particle size was measured.
  • a PC resin substrate 80 x 80 mm
  • hydrocarbon cleaner Nippon Oil & Energy Corporation
  • ultrasonic waves for 10 minutes each.
  • About 0.5 ml of the composition was dropped and spread evenly with Kimwipe, and then heat-cured for 10 minutes in an oven at 120 ° C. to obtain a treated substrate, which was visually checked for the presence of coating unevenness (appearance evaluation). .
  • Example 7 Difference in storage stability depending on the ratio of alcohols to water 2.0 g of GPTMS, 0.5 g of diethylenetriamine, and a mixture of water and isopropanol (IPA) in a mass ratio (water / IPA) of 5/2 8.0 g of the solvent was mixed, stirred at room temperature for 2 hours, and further diluted with 90 g of a mixed solvent having a mass ratio of water / IPA of 5/2 to obtain a coating composition (2.5% in terms of mass concentration of solid content) A-4) was prepared.
  • IPA isopropanol
  • Example 8 2.0 g of GPTMS, 0.5 g of diethylenetriamine, and 8.0 g of a mixed solvent having a mass ratio of water and isopropanol (IPA) (water / IPA) of 5/2 are mixed and stirred at room temperature for 2 hours.
  • IPA isopropanol
  • TFE 2,2,2-trifluoroethanol
  • TFE 1,1,1,3,3,3-hexafluoro-2-propanol
  • HFIP 1,1,1,3,3,3-hexafluoro-2-propanol
  • a coating composition (A-50) was obtained by the same method as that described above except that TFE and HFIP were not added.
  • (A-50) to (A-54) are put in a tightly stoppered bottle, stored at 25 ° C., and the z-average particle size of the solid content in the composition is measured by a particle size distribution meter (Zeta Sizer Nano, manufactured by Malvern: measurement) Conditions; the same as in Example 3), and the change with time was measured.
  • the result is shown in FIG. From the above, it was found that it is preferable to use TFE at 30% by mass or more of the entire composition for long-term storage. Moreover, even when a small amount of HFIP was added, it was found that a certain degree of storage stability could be secured.
  • Example 9 Preparation of coating composition After mixing 2.0 g GPTMS, 0.5 g diethylenetriamine, 0.5 g benzoic acid, 70.0 g water and 28.0 g IPA, the mixture was stirred for 2 hours at room temperature to A coating composition (A-6) of 3% in terms of mass concentration was prepared. When the average particle size of the solid content in the coating composition was measured by a particle size distribution meter (Zeta Sizer Nano, manufactured by Malvern), the particle size one day after preparation of the coating composition was 8.5 nm.
  • Example 10 After mixing 2.0 g GPTMS, 0.5 g diethylenetriamine, 0.5 g, 0.2 g, 0.08 g benzoic acid, 70.0 g water and 28.0 g IPA, the mixture was stirred at room temperature for 2 hours, Coating compositions (A-71) to (A-73) were prepared. A composition without benzoic acid (A-70) was prepared in the same manner. The obtained (A-70) and (A-71) to (A-73) were put in a sealed bottle and stored at 25 ° C., and the change over time in the z-average particle diameter of the solid content in the composition was measured. The particle size distribution was measured with a particle size distribution meter (Zeta Sizer Nano, manufactured by Malvern). The result is shown in FIG.
  • Example 11 After mixing 0.5 g GPTMS, 0.125 g diethylenetriamine, 0.171 g p-nitrobenzoic acid, 17.5 g water and 7.0 g IPA, the mixture was stirred at room temperature for 2 hours to obtain a coating composition (A -80) was prepared. In the same manner, a coating composition (A-81) or (A-82) was prepared using 0.156 g of p-anisic acid or 0.0615 g of acetic acid instead of p-nitrobenzoic acid.
  • (A-80), (A-81) and (A-82) are put in a sealed bottle and stored at 25 ° C., and the z-average particle size of the solid content in the composition is measured by a particle size distribution meter (Zetersizer Nano). , Manufactured by Malvern: Measurement conditions; the same as in Example 3), and the change with time was measured. The result is shown in FIG. About 0.5 mL of the coating composition (A-80), (A-81) and (A-82) was formed on a PET film using a barcode, and heated in an oven at 100 ° C. for 10 minutes. The coating composition-treated PET films (B-11), (B-12) and (B-13) were obtained.
  • the coating surface was subjected to UV ozone treatment (about 12000 mJ / cm 2 ) for 10 minutes, then immersed in SAMLAY (registered trademark) for 5 minutes, and then the surface was ultrasonically cleaned in NS Clean 100 to obtain a SAM-treated film. (C-5), (C-6) and (C-7) were obtained. Each film was subjected to static contact angle measurement in the same manner as described above. The results are summarized in Table 8.
  • Example 12 0.5 g GPTMS, 0.05 g 3,3,4,4,5,5,6,6,6-nonafluorohexyltrimethoxysilane 0.05 g, 0.125 g diethylenetriamine, 0.125 g benzoic acid Then, 2.0 g of 2,2,2-trifluoroethanol, 16.0 g of water and 6.5 g of IPA were mixed and then stirred at room temperature for 24 hours to prepare a coating composition (A-8). The PC resin substrate (80 ⁇ 80 mm) was washed with ultrasonic waves in water, NS clean and IPA for 10 minutes each.
  • the prepared coating composition (A-8) is formed on a PC resin substrate using a barcode, and heated and dried for 20 minutes in a circulation oven controlled at 120 ° C.
  • a substrate (B-11) was obtained.
  • the static contact angle of the obtained processed substrate (B-11) and the processed substrate (B-12) obtained by further rubbing the processed substrate (B-11) were measured by the same method as described above.
  • the same measurement was performed on the resulting treated substrate (R-1) prepared without adding fluorotrimethoxysilane. The results are shown in Table 9.
  • the prepared coating composition (cA-2) was dip coated on a PC resin substrate.
  • the coated substrate was dried in an oven (120 ° C., 20 minutes) to obtain a coating composition-treated substrate (cB-1).
  • Fluorine glass surface liquid repellent treatment agent Super Galaco (registered trademark) (manufactured by Soft99 Corporation) was applied to the resulting treated substrate to obtain a coating composition-liquid repellent treated PC substrate (cC-2). It was.
  • a substrate (cC-3) obtained by coating soda-lime glass with a fluorine-based glass surface liquid repellent treatment agent Super Galaco (registered trademark) (manufactured by Soft99 Corporation) was obtained.
  • the value was the same as the liquid repellency when super-galaxy treatment was performed on a soda-lime glass (SLG) substrate, but it took 3 days to prepare the coating composition.

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Abstract

L'invention concerne un procédé pour préparer une composition de revêtement comprenant le mélange d'un trialcoxysilane contenant des groupes époxy et/ou d'un produit d'hydrolyse et de condensation correspondant avec de l'eau et une polyamine ou un imidazole qui présente, par molécule, au moins deux groupes amino ou imino, présentant chacun au moins un atome d'hydrogène qui y est lié, puis l'agitation du mélange résultant. Une composition de revêtement selon la présente invention comprend : (A) un produit d'hydrolyse et de condensation d'un trialcoxysilane contenant des groupes époxy ; (B) une polyamine ; et (C) (C-1) du n-pentanol ou (C-2) un acide organique présentant une valeur pKa dans la plage allant de 2,0 à 6,0 à 25°C ou un alcool en C2-5 présentant un groupe perfluoroalkyle et/ou un groupe perfluoroalkylène.
PCT/JP2014/000407 2013-01-29 2014-01-28 Composition d'organosilane WO2014119282A1 (fr)

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WO2016009617A1 (fr) * 2014-07-16 2016-01-21 日本曹達株式会社 Composition de revêtement à base de silane
JP2016131215A (ja) * 2015-01-14 2016-07-21 日本曹達株式会社 有機薄膜トランジスタ
WO2016121316A1 (fr) * 2015-01-26 2016-08-04 日本曹達株式会社 Matériau de base avec film conducteur
JP2017155124A (ja) * 2016-03-01 2017-09-07 セイコーインスツル株式会社 コーティング剤、コーティング剤の製造方法及びコーティング膜の形成方法
CN107267031A (zh) * 2017-08-02 2017-10-20 合肥万之景门窗有限公司 一种用于塑钢门窗的新型绝缘涂料的制备方法
WO2020203869A1 (fr) * 2019-03-29 2020-10-08 三井化学株式会社 Procédé de production de matériau optique et composition polymérisable pour matériau optique

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JP2016131215A (ja) * 2015-01-14 2016-07-21 日本曹達株式会社 有機薄膜トランジスタ
WO2016121316A1 (fr) * 2015-01-26 2016-08-04 日本曹達株式会社 Matériau de base avec film conducteur
JPWO2016121316A1 (ja) * 2015-01-26 2017-11-24 日本曹達株式会社 導電膜付き基材
JP2017155124A (ja) * 2016-03-01 2017-09-07 セイコーインスツル株式会社 コーティング剤、コーティング剤の製造方法及びコーティング膜の形成方法
CN107267031A (zh) * 2017-08-02 2017-10-20 合肥万之景门窗有限公司 一种用于塑钢门窗的新型绝缘涂料的制备方法
WO2020203869A1 (fr) * 2019-03-29 2020-10-08 三井化学株式会社 Procédé de production de matériau optique et composition polymérisable pour matériau optique
JPWO2020203869A1 (ja) * 2019-03-29 2021-10-28 三井化学株式会社 光学材料の製造方法、光学材料用重合性組成物
JP7299306B2 (ja) 2019-03-29 2023-06-27 三井化学株式会社 光学材料の製造方法、光学材料用重合性組成物

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