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WO2015098738A1 - Polyalcoxysilazane et son procédé de production, et composition de revêtement et revêtement céramique à base de silicium obtenu à partir de celle-ci - Google Patents

Polyalcoxysilazane et son procédé de production, et composition de revêtement et revêtement céramique à base de silicium obtenu à partir de celle-ci Download PDF

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WO2015098738A1
WO2015098738A1 PCT/JP2014/083677 JP2014083677W WO2015098738A1 WO 2015098738 A1 WO2015098738 A1 WO 2015098738A1 JP 2014083677 W JP2014083677 W JP 2014083677W WO 2015098738 A1 WO2015098738 A1 WO 2015098738A1
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polyalkoxysilazane
general formula
compound
structural unit
same
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Japanese (ja)
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洋慈 堀江
賢明 岩瀬
鈴木　浩
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Toagosei Co Ltd
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Toagosei Co Ltd
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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
    • C09D183/16—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 in which all the silicon atoms are connected by linkages other than oxygen atoms
    • 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
    • C08G77/60—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 in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/62—Nitrogen atoms

Definitions

  • the present invention relates to a polyalkoxysilazane, a method for producing the same, a coating composition, and a silicon-based ceramic coating obtained therefrom.
  • Polysilazane coating agents are classified as a type of ceramic coating agent, and it is known that a coating layer having excellent heat resistance, wear resistance, corrosion resistance, and the like can be formed.
  • a coating composition containing perhydroxypolysilazane (PHPS) represented by [—SiH 2 —NH—] n is known.
  • PHPS perhydroxypolysilazane
  • the PHPS-based coating agent requires high-temperature heating (for example, 400 ° C. or higher) for silica conversion of the coating film, which requires energy costs and requires special equipment for heat treatment. was there.
  • Patent Documents 2 to 4 disclose PHPS-based coating agents containing a catalyst and the like.
  • JP 60-145903 A Japanese Patent Laid-Open No. 06-299118 Japanese Patent Laid-Open No. 11-116815 JP 09-31333 A
  • the present invention relates to a polyalkoxysilazane that can be converted into a silicon-based ceramic coating without adding a catalyst or the like and without performing a heat treatment at a high temperature, a method for producing the same, a coating composition, and a silicon-based ceramic coating.
  • the purpose is to provide.
  • R 1 represents an alkyl group.
  • R 2 represents an alkyl group. Two R 2 s may be the same as or different from each other.
  • More R 2 s may be the same as or different from each other, and a plurality of R 3 may be the same or different from each other, and a, b, c and d are each independently 0 or (It is a positive number, provided that at least one of b and c is a positive number, and when b is 0, at least one of a and d is a positive number.)
  • R 3 in the general formula (1) has 1 to 10 carbon atoms.
  • a polyalkoxysilazane obtained by ammonolytic polycondensation of a halogenated silane compound The polyalkoxysilazane according to any one of [1] to [5], wherein the halogenated silane compound includes a compound represented by the following general formula (2).
  • a polyalkoxy comprising a step of subjecting a halogenated silane compound to ammonolysis polycondensation, wherein in this step, 2 equivalents or more of ammonia is used at ⁇ 50 ° C. or less with respect to 1 equivalent of a halogen atom contained in the halogenated silane compound.
  • a method for producing silazane [11] The method for producing a polyalkoxysilazane according to [10], wherein the halogenated silane compound includes a compound represented by the following general formula (2).
  • R 4 when R 4 is .
  • X 1 represents an alkyl group .n showing a halogen atom including a plurality of .R 4 is 1 or 2, a plurality of R 4 may be mutually the same or different when containing a plurality of good .X 1, a plurality of X 1 may be mutually the same or different.
  • R 4 in the general formula (2) has 1 to 3 carbon atoms.
  • the polyalkoxysilazane of the present invention is a novel compound having a specific configuration, and when this compound is used, the resulting film can be converted into a silicon-based ceramic film without heat treatment at high temperatures. is there. Furthermore, it has excellent solubility in organic solvents such as propylene glycol methyl ether acetate, toluene, tetrahydrofuran, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, and dibutyl ether, and is excellent in operability.
  • organic solvents such as propylene glycol methyl ether acetate, toluene, tetrahydrofuran, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, and dibutyl ether
  • the coating composition containing the polyalkoxysilazane of the present invention it is easy to form a film without adding a catalyst or the like, and a coating film is formed by the composition, the solvent is removed, and then at a high temperature.
  • the silicon-based ceramic coating can be obtained by treatment under a low temperature condition of 20 ° C. or more and less than 100 ° C. Therefore, it is possible to suppress impurities from being mixed into the silicon-based ceramic coating and reduce defects such as coloring of the silicon-based ceramic coating. Since the silicon-based ceramic coating of the present invention is a coating obtained from the above coating composition, it has high purity and can be formed regardless of the heat resistance of the object to be coated.
  • polyalkoxysilazane production method of the present invention stable polyalkoxysilazane can be efficiently produced without causing gelation or the like.
  • 3 is an IR chart of polyalkoxysilazane obtained in Synthesis Example 1.
  • 4 is an IR chart of polyalkoxysilazane obtained in Synthesis Example 2.
  • 6 is an IR chart of polyalkoxysilazane obtained in Synthesis Example 5.
  • 6 is an IR chart of polyalkoxysilazane obtained in Synthesis Example 6.
  • 6 is an IR chart of polyalkoxysilazane obtained in Synthesis Example 7.
  • 10 is an IR chart of polyalkoxysilazane obtained in Synthesis Example 8.
  • 6 is an IR chart of polyalkoxysilazane obtained in Synthesis Example 9.
  • 6 is an IR chart of a dry film obtained from the polyalkoxysilazane solution of Example 4.
  • 6 is an IR chart of the coating film obtained in Example 4.
  • 6 is an IR chart of the coating obtained in Example 5.
  • the polyalkoxysilazane of the present invention is a structural unit represented by the following general formula (i) (hereinafter also referred to as “structural unit (i)”), and a structure represented by the following general formula (ii). It has at least one of units (hereinafter also referred to as “structural unit (ii)”).
  • structural unit (i) represents an alkyl group.
  • R 2 represents an alkyl group. Two R 2 s may be the same as or different from each other.
  • the alkyl group of R 1 in the structural unit (i) may be linear, branched or cyclic.
  • the carbon number is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 3.
  • Specific examples of the alkyl group include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n -Heptyl group, 2-ethylhexyl group, n-octyl group, n-nonyl group, n-decyl group, cyclohexyl group and the like.
  • alkyl group of R 1 in the structural unit (i) can be applied as it is to the alkyl group of R 2 in the structural unit (ii).
  • the polyalkoxysilazane of the present invention is a structural unit represented by the following general formula (iii) (hereinafter also referred to as “structural unit (iii)”).
  • a structural unit represented by the following general formula (iv) hereinafter, also referred to as “structural unit (iv)”
  • a structural unit represented by the following general formula (v) hereinafter, “structural unit (v)”
  • R 3 represents an alkyl group. The three R 3 s may be the same as or different from each other.
  • R 5 represents a hydrogen atom, an alkyl group or an alkoxyl group.
  • M is an integer of 1 to 3.
  • R 5 has one or more hydrogen atoms or alkyl groups, and R 5 represents When a plurality of R 5 are included, the plurality of R 5 may be the same as or different from each other.)
  • the description of the alkyl group of R 1 in the structural unit (i) can be applied as it is.
  • the alkyl part in the alkoxyl group of R 5 may be any of linear, branched and cyclic.
  • the carbon number is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 3.
  • Specific examples of alkoxyl groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, t-butoxy, n-pentyloxy, and n-hexyloxy.
  • n-heptyloxy group 2-ethylhexyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, cyclohexyloxy group and the like.
  • the total amount of the structural units contained in the polyalkoxysilazane of the present invention is 100 mol%
  • the total amount of the structural units (i) and (ii) depends on the solubility in organic solvents and the storage stability of the solution. From this point of view, it is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, still more preferably 50 to 100 mol%.
  • the polyalkoxysilazane of the present invention is preferably a compound represented by the following general formula (1).
  • R 1, R 2 and R 3 are each, independently, when including a plurality of .R 1 represents an alkyl group, a plurality of R 1 may be mutually the same or different. More R 2 s may be the same as or different from each other, and a plurality of R 3 may be the same or different from each other, and a, b, c and d are each independently 0 or (It is a positive number, provided that at least one of b and c is a positive number, and when b is 0, at least one of a and d is a positive number.)
  • the polyalkoxysilazane represented by the general formula (1) is a compound in which the structural units (i) to (iv) are bonded by a silazane bond (Si—N bond).
  • a, b, c and d represent the molar amounts of the respective structural units.
  • the number of structural units contained in the polyalkoxysilazane may be only one or two or more for each of the structural units (i) to (iv). Further, the condensed form of the structural units in the actual polyalkoxysilazane molecule does not necessarily follow the arrangement order of the formula (1).
  • the polyalkoxysilazane of the present invention can be obtained by ammonolytic polycondensation of a halogenated silane compound.
  • a halogenated silane compound at least a compound represented by the following general formula (2) (hereinafter also referred to as “compound (M1)”) is used.
  • R 4 when R 4 is .
  • X 1 represents an alkyl group .n showing a halogen atom including a plurality of .R 4 is 1 or 2, a plurality of R 4 may be mutually the same or different when containing a plurality of good .X 1, a plurality of X 1 may be mutually the same or different.
  • the halogen atom X 1 is F, Cl, Br, or I. Of these, Cl and Br are preferred, and Cl is particularly preferred.
  • the compound when n is 1 is a raw material monomer that gives the structural unit (i).
  • the compound when n is 2 is a raw material monomer that gives the structural unit (ii).
  • the alkyl group R 4 in the general formula (2) may be linear, branched or cyclic.
  • the carbon number is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 3. In particular, when the number of carbon atoms is 1 to 3, the balance between the reactivity during ammonolysis polycondensation and the solvent solubility of the resulting polyalkoxysilazane is preferable.
  • alkyl group examples include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n -Heptyl group, 2-ethylhexyl group, n-octyl group, n-nonyl group, n-decyl group, cyclohexyl group and the like.
  • the halogenated silane compound when n is 1, that is, the compound giving the structural unit (i) is, for example, methoxytrichlorosilane, ethoxytrichlorosilane, n-propoxytrichlorosilane, Isopropoxytrichlorosilane, n-butoxytrichlorosilane, sec-butoxytrichlorosilane, t-butoxytrichlorosilane, n-pentyloxytrichlorosilane, n-hexyloxytrichlorosilane, n-heptyloxytrichlorosilane, 2-ethylhexyloxytrichlorosilane N-octyloxytrichlorosilane, n-nonyloxytrichlorosilane, n-decyloxytrichlorosilane, cyclohexyloxytrichlorosilane, and the
  • Examples of the halogenated silane compound when n is 2, that is, the compound giving the structural unit (ii) are, for example, dimethoxydichlorosilane, diethoxydichlorosilane, di-n-propoxydichlorosilane, diisopropoxy Dichlorosilane, di-n-butoxydichlorosilane, di-sec-butoxydichlorosilane, di-t-butoxydichlorosilane, di-n-pentyloxydichlorosilane, di-n-hexyloxydichlorosilane, di-n-heptyl Examples thereof include oxydichlorosilane, di-2-ethylhexyloxydichlorosilane, di-n-octyloxydichlorosilane, di-n-nonyloxydichlorosilane, di-n-decyloxydichlorosilane, and dicycl
  • halogenated silane compound in addition to the compound (M1), a compound represented by the following general formula (3) (hereinafter also referred to as “compound (M2)”), or the following general formula, as necessary.
  • compound (M3) A compound represented by the formula (4) (hereinafter also referred to as “compound (M3)”) may be used.
  • R 6 represents an alkyl group including a plurality of .R 6 .n is 0 or 3 a halogen atom
  • a plurality of R 6 may be mutually the same or different when containing a plurality of good .X 2, a plurality of X 2 may be mutually the same or different.
  • R 7 represents a hydrogen atom, an alkyl group or an alkoxyl group.
  • X 3 represents a halogen atom.
  • M is an integer of 1 to 3.
  • R 7 represents a hydrogen atom or an alkyl group.
  • a plurality of R 7 may be identical to one another, if different, including a plurality of good .
  • X 3 a plurality of X 3 may be the same with each other, different May be good.
  • the compound when n is 0 is a raw material monomer that gives the structural unit (iii).
  • the compound when n is 3 is a raw material monomer that gives the structural unit (iv).
  • the description of the alkyl group of R 4 in the general formula (2) can be applied as it is to the alkyl group of R 6 in the general formula (3).
  • the halogen atom X 2 in the general formula (3) is F, Cl, Br or I. Of these, Cl and Br are preferred, and Cl is particularly preferred.
  • Examples of the halogenated silane compound when n is 0 in the general formula (3), that is, the compound giving the structural unit (iii) include, for example, silicon tetrachloride, silicon tetrabromide and silicon tetraiodide. Is mentioned.
  • Examples of the halogenated silane compound when n is 3; that is, the compound giving the structural unit (iv) described above include, for example, trimethoxychlorosilane, triethoxychlorosilane, tri-n-propoxychlorosilane, triisopropoxychlorosilane, Tri-n-butoxychlorosilane, tri-sec-butoxychlorosilane, tri-t-butoxychlorosilane, tri-n-pentyloxychlorosilane, tri-n-hexyloxychlorosilane, tri-n-heptyloxychlorosilane, tri-2-ethylhexyl Examples thereof include oxychlorosilane, tri-n-octyloxychlorosilane, tri-n-nonyloxychlorosilane, tri-n-decyloxychlorosilane, and tricyclohexyloxychlorosilane.
  • the compound (M3) represented by the general formula (4) will be described.
  • the compound (M3) is a raw material monomer that gives the structural unit (v).
  • R 7 in the general formula (4) is an alkyl group
  • the description of the alkyl group of R 4 in the general formula (2) can be applied as it is.
  • the alkyl moiety may be any of linear, branched and cyclic.
  • the carbon number is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 3.
  • Specific examples of alkoxyl groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, t-butoxy, n-pentyloxy, and n-hexyloxy.
  • halogen atom X 3 in the general formula (4) is F, Cl, Br or I. Of these, Cl and Br are preferred, and Cl is particularly preferred.
  • examples of the halogenated silane compound when m is 1 include a trihalogenated silane compound and an alkyltrichlorosilane compound.
  • examples of the trihalogenated silane compound include trichlorosilane, tribromosilane, and triiodosilane.
  • alkyltrichlorosilane compound examples include methyltrichlorosilane, ethyltrichlorosilane, n-propyltrichlorosilane, isopropyltrichlorosilane, n-butyltrichlorosilane, sec-butyltrichlorosilane, t-butyltrichlorosilane, n-pentyltrichlorosilane, n -Hexyltrichlorosilane, n-heptyltrichlorosilane, 2-ethylhexyltrichlorosilane, n-octyltrichlorosilane, n-nonyltrichlorosilane, n-decyltrichlorosilane, cyclohexyltrichlorosilane and the like.
  • Examples of the halogenated silane compound when m is 2 include dichlorosilane, alkyldichlorosilane compound, alkoxydichlorosilane compound, dialkyldichlorosilane compound, and alkoxyalkyldichlorosilane compound.
  • Alkyldichlorosilane compounds include methyldichlorosilane, ethyldichlorosilane, n-propyldichlorosilane, isopropyldichlorosilane, n-butyldichlorosilane, sec-butyldichlorosilane, t-butyldichlorosilane, n-pentyldichlorosilane, n -Hexyldichlorosilane, n-heptyldichlorosilane, 2-ethylhexyldichlorosilane, n-octyldichlorosilane, n-nonyldichlorosilane, n-decyldichlorosilane, cyclohexyldichlorosilane and the like.
  • Alkoxydichlorosilane compounds include methoxydichlorosilane, ethoxydichlorosilane, n-propoxydichlorosilane, isopropoxydichlorosilane, n-butoxydichlorosilane, sec-butoxydichlorosilane, t-butoxydichlorosilane, n-pentyloxydichlorosilane N-hexyloxydichlorosilane, n-heptyloxydichlorosilane, 2-ethylhexyloxydichlorosilane, n-octyloxydichlorosilane, n-nonyloxydichlorosilane, n-decyloxydichlorosilane, cyclohexyloxydichlorosilane, etc. It is done.
  • Dialkyldichlorosilane compounds include dimethyldichlorosilane, diethyldichlorosilane, di-n-propyldichlorosilane, di-isopropyldichlorosilane, di-n-butyldichlorosilane, di-sec-butyldichlorosilane, and di-t-butyl.
  • Dichlorosilane di-n-pentyldichlorosilane, di-n-hexyldichlorosilane, di-n-heptyldichlorosilane, di-2-ethylhexyldichlorosilane, di-n-octyldichlorosilane, di-n-nonyldichlorosilane , Di-n-decyldichlorosilane, dicyclohexyldichlorosilane, and the like.
  • alkoxyalkyldichlorosilane compound examples include methoxymethyldichlorosilane, methoxyethyldichlorosilane, ethoxymethyldichlorosilane, ethoxyethyldichlorosilane, n-propoxymethyldichlorosilane, n-propoxyethyldichlorosilane, isopropoxymethyldichlorosilane, isopropoxy Ethyldichlorosilane, n-butoxymethyldichlorosilane, n-butoxyethyldichlorosilane, sec-butoxymethyldichlorosilane, sec-butoxyethyldichlorosilane, t-butoxymethyldichlorosilane, t-butoxyethyldichlorosilane, n-pentyloxy Methyldichlorosilane, n-pentyloxyethy
  • examples of the halogenated silane compound when m is 3 include monochlorosilane, dialkylchlorosilane compound, dialkoxychlorosilane compound, and trialkylchlorosilane compound.
  • Dialkylchlorosilane compounds include dimethylchlorosilane, diethylchlorosilane, di-n-propylchlorosilane, di-isopropylchlorosilane, di-n-butylchlorosilane, di-sec-butylchlorosilane, di-t-butylchlorosilane, di-n-pentyl.
  • Examples include chlorosilane, di-n-hexylchlorosilane, di-n-heptylchlorosilane, di-2-ethylhexylchlorosilane, di-n-octylchlorosilane, di-n-nonylchlorosilane, di-n-decylchlorosilane, and dicyclohexylchlorosilane.
  • dialkoxychlorosilane compounds include dimethoxychlorosilane, diethoxychlorosilane, di-n-propoxychlorosilane, di-isopropoxychlorosilane, di-n-butoxychlorosilane, di-sec-butoxychlorosilane, di-t-butoxychlorosilane, di- n-pentyloxychlorosilane, di-n-hexyloxychlorosilane, di-n-heptyloxychlorosilane, di-2-ethylhexyloxychlorosilane, di-n-octyloxychlorosilane, di-n-nonyloxychlorosilane, di-n- Examples include decyloxychlorosilane and dicyclohexyloxychlorosilane.
  • trialkylchlorosilane compounds include trimethylchlorosilane, triethylchlorosilane, tri-n-propylchlorosilane, tri-isopropylchlorosilane, tri-n-butylchlorosilane, tri-sec-butylchlorosilane, tri-t-butylchlorosilane, tri-n- Pentylchlorosilane, tri-n-hexylchlorosilane, tri-n-heptylchlorosilane, tri-2-ethylhexylchlorosilane, tri-n-octylchlorosilane, tri-n-nonylchlorosilane, tri-n-decylchlorosilane, tricyclohexylchlorosilane, Dimethylethylchlorosilane, dimethyl-n-propylchlorosilane, tri
  • the method for producing polyalkoxysilazane in the present invention includes a polycondensation step (hereinafter also referred to as “first step”) using ammonolysis polycondensation using a halogenated silane compound as a raw material monomer. Is the method. Specifically, in the first step, 2 equivalents or more of ammonia are reacted at ⁇ 50 ° C. or less with respect to 1 equivalent of halogen atoms contained in the halogenated silane compound.
  • reaction solvent by-products, residual monomers, ammonia and the like are distilled off to recover polyalkoxysilazane (hereinafter referred to as “second step”). May also be provided.
  • the raw material monomer used at the said 1st process contains the compound (M1) represented by the said General formula (2), Furthermore, this compound (M1) and the compound represented by the said General formula (3) (M2) or the compound (M3) represented by the general formula (4) can be used in combination.
  • the proportion of the compound (M1) used is such that the reaction is smooth, and from the viewpoint of solvent solubility of the resulting polyalkoxysilazane and storage stability of the solution, the total amount of raw material monomers The amount is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, still more preferably 50 to 100 mol%.
  • a reaction solvent is usually used.
  • the reaction solvent include diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, ethers such as 1,2-dimethoxyethane (monoglyme) and diethylene glycol dimethyl ether (diglyme); aromatic hydrocarbon compounds such as benzene and toluene; n-hexane It is preferable to use aliphatic or alicyclic hydrocarbon compounds such as n-heptane and cyclohexane; dichloromethane, chloroform, dimethyl sulfoxide and pyridine.
  • these reaction solvents may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the amount of the reaction solvent used is preferably 100 to 5000 parts by mass, more preferably 100 to 3000 parts by mass, and still more preferably 100 to 2000 parts by mass with respect to 100 parts by mass of the raw material monomer.
  • the amount of ammonia used is preferably 1 equivalent or more, more preferably 1.5 equivalents or more, and even more preferably 2 equivalents or more with respect to 1 equivalent of halogen contained in the raw material monomer.
  • the amount of ammonia used is 1 equivalent or more, gelation during polycondensation is suppressed and polyalkoxysilazane is efficiently produced.
  • the higher the amount of ammonia used the higher the gelation suppression effect.
  • the upper limit of the amount of ammonia used is usually 20 equivalents, preferably 15 equivalents, more preferably 10 equivalents.
  • an auxiliary agent can be added to the reaction system for the purpose of promoting the reaction and facilitating the removal of by-product inorganic salts.
  • the auxiliary agent include triethylamine, diisopropylethylamine, 1-methylpiperidine, 1,4-diazabicyclo [2.2.2] octane (DABCO), tetramethylethylenediamine (TMEDA), pyridine, and 2,2′-bipyridine. And 1,10-phenanthroline.
  • the reaction temperature in the first step is preferably ⁇ 50 ° C. or lower.
  • the lower limit is usually ⁇ 100 ° C. If this temperature is ⁇ 50 ° C. or lower, gelation during polycondensation tends to be suppressed, and polyalkoxysilazane is efficiently produced.
  • the ammonolysis polycondensation reaction in the first step can be completed, for example, by confirming disappearance of the raw material monomer by gas chromatography (GC).
  • GC gas chromatography
  • a polyalkoxy is provided by providing a second step of distilling off the reaction solvent, by-products, residual monomers, ammonia and the like contained in the obtained reaction liquid.
  • Silazane can be recovered. By not coexisting other components, the stability of the produced polyalkoxysilazane can be further improved.
  • the coating composition of the present invention is characterized by containing the above-mentioned polyalkoxysilazane.
  • the coating composition of the present invention usually contains a solvent.
  • the solvent include propylene glycol methyl ether acetate (PEGMEA), ethyl acetate, toluene, tetrahydrofuran (THF), 1,2-dimethoxyethane (monoglyme), diethylene glycol dimethyl ether (diglyme), dibutyl ether and xylene.
  • PEGMEA propylene glycol methyl ether acetate
  • THF tetrahydrofuran
  • 1,2-dimethoxyethane diethylene glycol dimethyl ether
  • dibutyl ether dibutyl ether
  • xylene diethylene glycol dimethyl ether
  • these solvents may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the concentration of the polyalkoxysilazane in the coating composition of the present invention is not particularly limited, but is preferably 1 to 50% by mass, more preferably 3 to 40% by mass when the total composition is 100% by mass. .
  • concentration is in the said range, the coating film which has a desired film thickness can be easily obtained with various coating methods.
  • additives may be added to the coating composition of the present invention as long as the effects of the present invention are not impaired.
  • examples of other additives include leveling agents, antifoaming agents, surfactants, plasticizers, antibacterial agents, antioxidants, dyes, pigments, preservatives, antifungal agents, rust preventives and deodorants. Is mentioned.
  • these other additives may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the method for preparing the coating composition of the present invention is not particularly limited. Specifically, after mixing a polyalkoxysilazane and a solvent, it can be prepared by filtering as necessary.
  • Silicon-based ceramic coating The silicon-based ceramic coating of the present invention is obtained from the coating composition described above.
  • the silicon-based ceramic coating of the present invention is usually obtained by subjecting a coating formed on an object to be coated to an appropriate treatment.
  • the said to-be-coated article is not specifically limited, For example, it can be set as articles
  • a molded body containing inorganic particle powders such as metal nanoparticles and inorganic oxide particles, polycarbonate (PC), polyethylene terephthalate (PET) and the like can be mentioned.
  • the method for coating the coating composition with the coating composition is not particularly limited. Specifically, for example, various coating methods such as a spin coating method, a dipping method, a spray method, a bar coating method, and a roll coating method can be employed.
  • the thickness of the coating film can be appropriately controlled by adjusting the coating means, the solid content concentration and the viscosity in the composition, and the like.
  • the method for obtaining the silicon-based ceramic coating from the coating obtained from the coating composition is not particularly limited.
  • the solvent in the coating film is allowed to stand at room temperature, removed by heating, drying under reduced pressure, etc., and then the resulting film (dried film) is further cured or baked to obtain a silicon ceramic coating. Can do.
  • a silicon-based ceramic coating can be obtained by firing the coating film in which the solvent remains.
  • a silicon-based ceramic coating is formed by curing a film (dry film) for a certain period of time under room temperature or a mild temperature condition of less than about 100 ° C.
  • a silicon-based ceramic coating can also be obtained by firing a film (dry film).
  • the firing temperature is generally about 100 to 2000 ° C.
  • the curing period is not particularly limited, but is about several hours to several weeks.
  • the firing time may be appropriately selected depending on the temperature, but is about 1 minute to 10 hours.
  • a film made of silica can be obtained by curing or baking the film (dry film) in an atmosphere of air or water vapor. In the case of a nitrogen or ammonia atmosphere, a film made of a silicon oxynitride-like compound is obtained.
  • the film thickness of the silicon-based ceramic coating of the present invention is not particularly limited, but is preferably 1 nm to 1 mm, more preferably 1 nm to 500 ⁇ m, still more preferably 1 nm to 100 ⁇ m.
  • the film thickness can be measured with an electron microscope, ellipsometry, micrometer, or the like.
  • the obtained white powdery solid was analyzed by infrared spectroscopy (IR) to obtain an IR chart shown in FIG.
  • Absorption derived from Si—NH—Si was observed in the vicinity of wave numbers 3320 (cm ⁇ 1 ), 1180 (cm ⁇ 1 ), and 910 (cm ⁇ 1 ), and a structural unit derived from methoxytrichlorosilane [MeO—Si— ( It was confirmed that polymethoxysilazane composed of (NH) 3/2 ] was formed.
  • the polymethoxysilazane was confirmed to be soluble in propylene glycol methyl ether acetate, toluene, tetrahydrofuran, 1,2-dimethoxyethane and diethylene glycol dimethyl ether.
  • Synthesis example 2 Under a nitrogen atmosphere, weigh ethoxytrichlorosilane (12.12 g, 67.5 mmol) into a 500 mL four-necked flask equipped with a thermometer, a magnetic stirrer, a gas blowing tube and a Dimroth condenser, and add dehydrated tetrahydrofuran (125 mL). In addition, this ethoxytrichlorosilane was dissolved and cooled in a dry ice-methanol bath. Next, using a gas blowing tube, ammonia was blown into a four-necked flask at 500 mL / min for 30 minutes while maintaining ⁇ 50 ° C.
  • polyethoxysilazane composed of a structural unit [EtO—Si— (NH) 3/2 ] derived from ethoxytrichlorosilane was confirmed.
  • the polyethoxysilazane was confirmed to be soluble in propylene glycol methyl ether acetate, toluene, tetrahydrofuran, 1,2-dimethoxyethane and diethylene glycol dimethyl ether.
  • reaction solution was stirred at the same temperature for 1 hour.
  • the dry ice-methanol bath was then removed and stirring was continued at 25 ° C. for 12 hours.
  • the reaction solution was transferred to a centrifuge tube and centrifuged (10,000 rpm, 10 minutes) to precipitate ammonium chloride.
  • the supernatant was recovered and the solvent was distilled off under reduced pressure while maintaining the temperature at 40 ° C. or lower. And the residue was vacuum-dried and 7.87g of white powdery solid was obtained.
  • polyethoxysilazane composed of structural units derived from ethoxytrichlorosilane was produced.
  • the polyethoxysilazane was confirmed to be soluble in propylene glycol methyl ether acetate, toluene, tetrahydrofuran, 1,2-dimethoxyethane and diethylene glycol dimethyl ether.
  • polyethoxysilazane composed of structural units derived from ethoxytrichlorosilane was produced.
  • the polyethoxysilazane was confirmed to be soluble in propylene glycol methyl ether acetate, toluene, tetrahydrofuran, 1,2-dimethoxyethane and diethylene glycol dimethyl ether.
  • Synthesis example 5 The same operation as in Synthesis Example 2 was performed except that the use of ethoxytrichlorosilane (12.12 g, 67.5 mmol) was changed to the use of isopropoxytrichlorosilane (13.15 g, 67.9 mmol). 6.87 g of solid was obtained. The obtained white powdery solid was analyzed by IR to obtain an IR chart shown in FIG. It was confirmed that polyisopropoxysilazane composed of a structural unit [iPrO—Si— (NH) 3/2 ] derived from isopropoxytrichlorosilane was formed.
  • the polyisopropoxysilazane was confirmed to be soluble in propylene glycol methyl ether acetate, toluene, tetrahydrofuran, 1,2-dimethoxyethane and diethylene glycol dimethyl ether.
  • Synthesis Example 6 Except for changing the use of ethoxytrichlorosilane (12.12 g, 67.5 mmol) to the use of ethoxytrichlorosilane (9.67 g, 53.9 mmol) and diethoxydichlorosilane (2.56 g, 13.5 mmol), The same operation as in Synthesis Example 2 was performed to obtain 6.69 g of a white powdery solid. The obtained white powdery solid was analyzed by IR to obtain an IR chart shown in FIG.
  • this polyethoxysilazane (modified product) was soluble in propylene glycol methyl ether acetate, toluene, tetrahydrofuran, 1,2-dimethoxyethane and diethylene glycol dimethyl ether.
  • Synthesis example 7 Except for changing the use of ethoxytrichlorosilane (12.12 g, 67.5 mmol) to the use of ethoxytrichlorosilane (10.96 g, 61.1 mmol) and diethoxydichlorosilane (1.45 g, 7.7 mmol), The same operation as in Synthesis Example 2 was performed to obtain 6.14 g of a white powdery solid. The obtained white powdery solid was analyzed by IR to obtain an IR chart shown in FIG.
  • this polyethoxysilazane (modified product) was soluble in propylene glycol methyl ether acetate, toluene, tetrahydrofuran, 1,2-dimethoxyethane and diethylene glycol dimethyl ether.
  • Synthesis example 8 Except for changing the use of ethoxytrichlorosilane (12.12 g, 67.5 mmol) to the use of ethoxytrichlorosilane (11.57 g, 64.5 mmol) and diethoxydichlorosilane (0.71 g, 3.8 mmol), The same operation as in Synthesis Example 2 was performed to obtain 6.58 g of a white powdery solid. The obtained white powdery solid was analyzed by IR to obtain an IR chart shown in FIG.
  • this polyethoxysilazane (modified product) was soluble in propylene glycol methyl ether acetate, toluene, tetrahydrofuran, 1,2-dimethoxyethane and diethylene glycol dimethyl ether.
  • ammonia was blown into a four-necked flask at 500 mL / min for 30 minutes while maintaining ⁇ 50 ° C. or less (total amount: 15 L, 0.60 mol, diethoxydichlorosilane and 3 times equivalent to chlorine atom of silicon tetrachloride). After completion of blowing, the mixture was stirred at the same temperature for 1 hour. The dry ice-methanol bath was then removed and stirring was continued at 25 ° C. for 12 hours. Thereafter, the obtained reaction solution was transferred to a centrifuge tube and centrifuged (10,000 rpm, 10 minutes) to precipitate ammonium chloride.
  • this polyethoxysilazane (modified product) was soluble in propylene glycol methyl ether acetate, toluene, tetrahydrofuran, 1,2-dimethoxyethane and diethylene glycol dimethyl ether.
  • This polysilazane was a compound that was hardly soluble in organic solvents such as propylene glycol methyl ether acetate, toluene, tetrahydrofuran, 1,2-dimethoxyethane, and diethylene glycol dimethyl ether.
  • Example 1 Heat treatment of polyalkoxysilazane Example 1 About 150 mg of polymethoxysilazane obtained in Synthesis Example 1 was weighed on a platinum pan and placed in a quartz tube with a diameter of 20 mm. Then, it heated from the outside using the electric heater, flowing dry air or nitrogen at 100 ml / min in a quartz tube. At this time, the temperature was raised to a predetermined temperature at 20 ° C./min (400 ° C. under dry air and 800 ° C. under a nitrogen atmosphere) and maintained at that temperature for 2 hours. After cooling, the heat-treated sample remaining in the platinum pan was collected and analyzed by IR. As a result, it was confirmed that when the temperature was raised to 400 ° C.
  • the silica was changed to silica (SiO 2 ) having characteristic absorption at 3350 cm ⁇ 1 and 1050 cm ⁇ 1 . Further, the temperature was raised to 800 ° C. under a nitrogen atmosphere, when 2 hours heat treatment is believed to 3200 cm -1, and of 1020 cm -1 and 920 cm -1 and a silicon oxynitride like having a characteristic absorption bimodal It was confirmed that the compound was changed to
  • Example 2 About 150 mg of polyethoxysilazane obtained in Synthesis Example 2 was weighed on a platinum pan and placed in a quartz tube having a diameter of 20 mm. Then, it heated from the outside using the electric heater, flowing dry air or nitrogen at 100 ml / min in a quartz tube. At this time, the temperature was raised to a predetermined temperature at 20 ° C./min (400 ° C. under dry air and 800 ° C. under a nitrogen atmosphere) and maintained at that temperature for 2 hours. After cooling, the heat-treated sample remaining in the platinum pan was collected and analyzed by IR. As a result, it was confirmed that when the temperature was raised to 400 ° C.
  • the silica was changed to silica (SiO 2 ) having characteristic absorption at 3350 cm ⁇ 1 and 1050 cm ⁇ 1 . Further, the temperature was raised to 800 ° C. under a nitrogen atmosphere, when 2 hours heat treatment is believed to 3200 cm -1, and of 1020 cm -1 and 920 cm -1 and a silicon oxynitride like having a characteristic absorption bimodal It was confirmed that the compound was changed to
  • Example 3 About 150 mg of polyisopropoxysilazane obtained in Synthesis Example 5 was weighed on a platinum pan and placed in a quartz tube having a diameter of 20 mm. Then, it heated from the outside using the electric heater, flowing dry air or nitrogen at 100 ml / min in a quartz tube. At this time, the temperature was raised to a predetermined temperature at 20 ° C./min (400 ° C. under dry air and 800 ° C. under a nitrogen atmosphere) and maintained at that temperature for 2 hours. After cooling, the heat-treated sample remaining in the platinum pan was collected and analyzed by IR. As a result, it was confirmed that when the temperature was raised to 400 ° C.
  • the silica was changed to silica (SiO 2 ) having characteristic absorption at 3350 cm ⁇ 1 and 1050 cm ⁇ 1 . Further, the temperature was raised to 800 ° C. under a nitrogen atmosphere, when 2 hours heat treatment is believed to 3200 cm -1, and of 1020 cm -1 and 920 cm -1 and a silicon oxynitride like having a characteristic absorption bimodal It was confirmed that the compound was changed to
  • membrane which uses the silicon wafer obtained above as a base material was baked at 400 degreeC in air
  • the obtained film was analyzed by IR to obtain an IR chart shown in FIG. From the characteristic absorption at 1070 to 1080 cm ⁇ 1 , it was confirmed that it was converted to silica (SiO 2 ).
  • the film thickness was 300 nm and the refractive index was 1.432.
  • Example 5 Further, after a dry film was formed on the surface of the silicon wafer by the method described in Example 4, the silicon wafer with the film was allowed to stand at room temperature (23 ° C., humidity 50%) for 2 weeks in an air atmosphere. The film was obtained by curing. The obtained coating was analyzed by IR to obtain an IR chart shown in FIG. From the characteristic absorption at 1070 to 1080 cm ⁇ 1 , it was confirmed that it was converted to silica (SiO 2 ).
  • Comparative Example 1 Attempts were made to prepare the polysilazane solution obtained in Comparative Synthesis Example 1, but as described above, the solution was insoluble in various organic solvents, and a coating composition could not be obtained.
  • the polyalkoxysilazane and coating composition of the present invention do not require a catalyst, they are suitable for forming a high-purity silicon-based ceramic coating.

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Abstract

　La présente invention concerne un polyalcoxysilazane comportant au moins un motif structural représenté par la formule générale (i) et un motif structural représenté par la formule générale (ii). [R1O-Si-(NH)3/2] (i) (Dans la formule, R1 représente un groupe alkyle.) [(R2O)2-Si-(NH)2/2] (ii) (Dans la formule, R2 représente un groupe alkyle. Deux R2 peuvent être identiques ou différents l'un de l'autre.)
PCT/JP2014/083677 2013-12-25 2014-12-19 Polyalcoxysilazane et son procédé de production, et composition de revêtement et revêtement céramique à base de silicium obtenu à partir de celle-ci Ceased WO2015098738A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106669440A (zh) * 2017-01-03 2017-05-17 中国石油天然气股份有限公司 一种陶瓷膜的修饰改性方法及改性陶瓷膜
CN111484621A (zh) * 2019-01-29 2020-08-04 信越化学工业株式会社 聚硅氧硅氮烷化合物、其制备方法和包含其的组合物及其固化产物
TWI754802B (zh) * 2018-03-30 2022-02-11 日商信越化學工業股份有限公司 聚矽氮烷組成物，以及塗佈其之基材及多層體

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2566363A (en) * 1946-04-22 1951-09-04 Minnesota Mining & Mfg Tertiary alkoxy amino silanes
DE901174C (de) * 1951-12-18 1954-01-07 Siemens Ag Verfahren zur Herstellung von Silazanen
JPH05345826A (ja) * 1991-12-04 1993-12-27 Tonen Corp 改質ポリシラザン及びその製造方法
JPH06240208A (ja) * 1993-02-19 1994-08-30 Tonen Corp コーティング用組成物及びコーティング方法
JPH0782528A (ja) * 1993-07-23 1995-03-28 Catalysts & Chem Ind Co Ltd シリカ系被膜形成用塗布液および被膜付基材
JPH07102217A (ja) * 1993-07-23 1995-04-18 Catalysts & Chem Ind Co Ltd シリカ系被膜形成用コーティング組成物および被膜付基材
JPH0870042A (ja) * 1994-08-30 1996-03-12 Fujitsu Ltd 絶縁膜の形成方法
JPH08510292A (ja) * 1993-05-18 1996-10-29 エスアールアイ インターナショナル プレセラミックケイ素ポリマー
JPH10245435A (ja) * 1997-03-06 1998-09-14 Hitachi Chem Co Ltd ポリアルコキシシラザンの製造法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2566363A (en) * 1946-04-22 1951-09-04 Minnesota Mining & Mfg Tertiary alkoxy amino silanes
DE901174C (de) * 1951-12-18 1954-01-07 Siemens Ag Verfahren zur Herstellung von Silazanen
JPH05345826A (ja) * 1991-12-04 1993-12-27 Tonen Corp 改質ポリシラザン及びその製造方法
JPH06240208A (ja) * 1993-02-19 1994-08-30 Tonen Corp コーティング用組成物及びコーティング方法
JPH08510292A (ja) * 1993-05-18 1996-10-29 エスアールアイ インターナショナル プレセラミックケイ素ポリマー
JPH0782528A (ja) * 1993-07-23 1995-03-28 Catalysts & Chem Ind Co Ltd シリカ系被膜形成用塗布液および被膜付基材
JPH07102217A (ja) * 1993-07-23 1995-04-18 Catalysts & Chem Ind Co Ltd シリカ系被膜形成用コーティング組成物および被膜付基材
JPH0870042A (ja) * 1994-08-30 1996-03-12 Fujitsu Ltd 絶縁膜の形成方法
JPH10245435A (ja) * 1997-03-06 1998-09-14 Hitachi Chem Co Ltd ポリアルコキシシラザンの製造法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ROBERT SCHWARZ ET AL.: "VIII. Organic substituted silicon amides and their derivatives", ZEITSCHRIFT FUER ANORGANISCHE UND ALLGEMEINE CHEMIE, vol. 268, 1952, pages 291 - 300 *
V. M. KOPYLOV ET AL.: "Characteristics of ammonolysis of equilibrium mixtures of organoethoxychlorosilanes", ZHURNAL OBSHCHEI KHIMII, vol. 55, no. 5, 1985, pages 1074 - 1080 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106669440A (zh) * 2017-01-03 2017-05-17 中国石油天然气股份有限公司 一种陶瓷膜的修饰改性方法及改性陶瓷膜
TWI754802B (zh) * 2018-03-30 2022-02-11 日商信越化學工業股份有限公司 聚矽氮烷組成物，以及塗佈其之基材及多層體
CN111484621A (zh) * 2019-01-29 2020-08-04 信越化学工业株式会社 聚硅氧硅氮烷化合物、其制备方法和包含其的组合物及其固化产物
CN111484621B (zh) * 2019-01-29 2023-06-20 信越化学工业株式会社 聚硅氧硅氮烷化合物、其制备方法和包含其的组合物及其固化产物

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