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US20150218418A1 - Organic-inorganic complex, and forming composition thereof - Google Patents

Organic-inorganic complex, and forming composition thereof Download PDF

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US20150218418A1
US20150218418A1 US14/410,424 US201314410424A US2015218418A1 US 20150218418 A1 US20150218418 A1 US 20150218418A1 US 201314410424 A US201314410424 A US 201314410424A US 2015218418 A1 US2015218418 A1 US 2015218418A1
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organic
compound
silicon compound
organic silicon
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Taiki Yamate
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Nippon Soda 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
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • 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
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond

Definitions

  • the present invention relates to an organic-inorganic complex in which a cured material of a thermosetting compound is blended, and a forming composition thereof.
  • a trifunctional silane is mainly used as a raw material of a commercial silane-based coating agent, and a polysiloxane having moderate hardness and flexibility is formed by such a trifunctional silane.
  • a hard coating property of a film of a trifunctional silane is not sufficient. Therefore, a tetrafunctional silane and colloidal silica are mixed with the trifunctional silane to compensate the hard coating property, but there is a problem that, if the film is cured, the film easily cracks and adhesiveness becomes worse.
  • silane-based coating agent for example, an antifouling film forming composition containing a trifunctional alkoxysilane compound having an epoxy group (patent document 1) is used.
  • a silane-based coating agent containing a photocatalyst is also proposed, and a film is cured by using a photo-acid-generating agent, a cross-linking agent, a curing catalyst, or the like (for example, patent documents 2 and 3).
  • a silane-based organic-inorganic complex gradient material having a component gradient structure in which the content rate of a metal-based compound in the material continuously changes in the depth direction from the surface of the material is also proposed (for example, patent document 4).
  • Patent document 5 discloses that, by irradiating an organic silicon compound with ultraviolet rays in the presence of a photosensitive compound, an organic-inorganic complex in which the surface has very high hardness and the inside and the back surface side have appropriate hardness and which excels in adhesiveness to a base substance can be provided
  • patent document 6 discloses that, by blending an acrylate-based resin that is an ultraviolet curable resin in a polysiloxane-based organic-inorganic complex, an organic-inorganic complex in which the surface has very high hardness and which excels in adhesiveness to a base substance and humidity resistance can be provided.
  • an anchor coat (base film) is needed between the metal deposited film and the plastic container.
  • the anchor coat one layer is insufficient, and a two-layer structure with a layer (A) having good adhesiveness to the plastic container and a layer (B) having good adhesiveness to both the above-described (A) and the metal deposited film is needed.
  • a problem was that manufacturing cost is increased and a high degree of skill is required by increasing the number of layers.
  • an anchor coat agent that can be used as an anchor coat for a plastic container and an inorganic film by one layer has been studied, but an organic-inorganic complex film disclosed in patent document 6 requires UV irradiation, and a problem was that a uniform UV irradiation technique for a three-dimensional plastic container is needed.
  • the present inventor has addressed the above-described object and diligently studied, and as a result, found that, by blending an organic silicon compound and/or a condensate thereof and a thermosetting compound, using a solubility parameter (SP value) of an organic group having a carbon atom directly bonded to Si of the organic silicon compound as an index, a segregation layer of a polysiloxane is self-organizationally formed on the surface layer, and the blend can be used as an anchor coat between a base substance and a metal deposited film or the like by one layer, to complete the present invention.
  • SP value solubility parameter
  • the present invention relates to:
  • An organic-inorganic complex-forming composition comprising: a) an organic silicon compound that is at least one represented by formula (I)
  • thermosetting compound (excluding an olefin polymer); and
  • An organic-inorganic complex-forming composition comprising: a) an organic silicon compound that is at least one represented by formula (I)
  • R represents an organic group having a carbon atom directly bonded to Si
  • X represents a hydroxyl group or a hydrolyzable group
  • n represents 1 or 2, wherein when n is 2, each R is the same or different, and when (4 ⁇ n) is 2 or more, each X is the same or different
  • the present invention relates to:
  • An organic-inorganic complex comprising: a) a condensate of an organic silicon compound that is at least one represented by formula (I)
  • the present invention relates to:
  • an organic-inorganic complex forming composition in which an organic silicon compound having a solubility parameter (SP1) of R obtained by Fedors' estimation method smaller than a solubility parameter (SP2) of a thermosetting compound obtained by Fedors' estimation method, and a difference between the SP1 and the SP2 is 1.6 or more as the organic silicon compound, and a thermosetting compound is blended, a segregation layer of a polysiloxane can be self-organizationally formed on the surface layer, and a base substance and an inorganic film or the like can be laminated with a one-layer anchor coat layer.
  • SP1 solubility parameter
  • SP2 solubility parameter of a thermosetting compound obtained by Fedors' estimation method
  • FIG. 1 is a diagram showing distribution of respective film components of a thin film in the film thickness direction, measured by ESCA, in Example 1.
  • FIG. 2 is a diagram showing distribution of respective film components of a thin film in the film thickness direction, measured by ESCA, in Example 2.
  • FIG. 3 is a diagram showing distribution of respective film components of a thin film in the film thickness direction, measured by ESCA, in Example 3.
  • FIG. 4 is a diagram showing distribution of respective film components of a thin film in the film thickness direction, measured by ESCA, in Example 4.
  • An organic-inorganic complex-forming composition of the present invention comprises:
  • R represents an organic group having a carbon atom directly bonded to Si, and X represents a hydroxyl group or a hydrolyzable group; and n represents 1 or 2, wherein when n is 2, each R is the same or different, and when (4 ⁇ n) is 2 or more, each X is the same or different
  • SP1 solubility parameter
  • SP2 solubility parameter
  • SP1 and SP2 thermosetting compound obtained by Fedors' estimation method
  • a difference between the SP1 and the SP2 is 1.6 or more (Si1) (hereinafter, sometimes simply referred to as an organic silicon compound), and/or a condensate thereof; and b) a thermosetting compound (excluding an olefin polymer).
  • the organic-inorganic complex-forming composition of the present invention may comprise a silanol condensation catalyst, water, and/or other solvents and the like in addition to the above-described components.
  • the solid content (the organic silicon component, the silanol condensation catalyst component, the thermosetting compound, and other components added as needed) in the organic-inorganic complex-forming composition of the present invention is preferably 1 to 75 mass %, more preferably 1 to 60 mass %, and further preferably 10 to 60 mass %.
  • R and X are each as follows.
  • R represents an organic group having a carbon atom directly bonded to Si.
  • Examples of such an organic group can include a hydrocarbon group which may be substituted and a group consisting of a polymer of hydrocarbon which may be substituted. Specific examples include a hydrocarbon group having 1 to 30 carbon atoms, which may be substituted, and a straight chain or branched chain alkyl group having 1 to 10 carbon atoms, which may be substituted, an alkyl group having a chain longer than 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, which may be substituted, a straight chain or branched chain alkenyl group having 2 to 10 carbon atoms, which may be substituted, or a cycloalkenyl group having 3 to 8 carbon atoms, which may be substituted, is preferable, and in addition, the organic group may be a hydrocarbon group having an aromatic ring.
  • such an organic group may comprise an oxygen atom, a nitrogen atom, or a silicon atom, and may be a group comprising a polymer such as a polysiloxane, a polyvinylsilane, or a polyacrylsilane.
  • a substituent of “which may be substituted” can include a halogen atom and a methacryloxy group, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • alkyl group having 1 to 10 carbon atoms includes a straight chain or branched chain alkyl group having 1 to 10 carbon atoms, examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a s-butyl group, a t-butyl group, a n-pentyl group, an isopentyl group, a neopentyl group, a 2-methylbutyl group, a 2,2-dimethylpropyl group, a n-hexyl group, an isohexyl group, a n-heptyl group, a n-octyl group, a nonyl group, an isononyl group, and a decyl group, and examples of the alkyl group having a chain longer than 10 carbon atoms include a lauryl group,
  • cycloalkyl group having 3 to 8 carbon atoms examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
  • the “straight chain or branched chain alkenyl group having 2 to 10 carbon atoms” means a straight chain or branched chain alkenyl group having 2 to 10 carbon atoms, which has a carbon-carbon double bond at any one or more positions, and examples thereof include an ethenyl group, a prop-1-en-1-yl group, a prop-2-en-1-yl group, a prop-1-en-2-yl group, a but-1-en-1-yl group, a but-2-en-1-yl group, a but-3-en-1-yl group, a but-1-en-2-yl group, a but-3-en-2-yl group, a pent-1-en-1-yl group, a pent-4-en-1-yl group, a pent-1-en-2-yl group, a pent-4-en-2-yl group, a 3-methyl-but-1-en-1-yl group, a hex-1-en-1-yl group,
  • cycloalkenyl group having 3 to 8 carbon atoms means an alkenyl group having 3 to 8 carbon atoms, which has a carbon-carbon double bond at any one or more positions and has a cyclic moiety, and examples thereof include a 1-cyclopenten-1-yl group, a 2-cyclopenten-1-yl group, a 1-cyclohexen-1-yl group, a 2-cyclohexen-1-yl group, and a 3-cyclohexen-1-yl group.
  • hydrocarbon group having an aromatic ring examples include an “aryl group,” an “arylalkyl group,” and an “arylalkenyl group.”
  • aryl group examples include an aryl group having 6 to 10 carbon atoms, and include a phenyl group and a naphthyl group.
  • arylalkyl group examples include a group in which an aryl group having 6 to 10 carbon atoms and an alkyl group having 1 to 8 carbon atoms are bound, and examples of the C 6-10 aryl C 1-8 alkyl group include a benzyl group, a phenethyl group, a 3-phenyl-n-propyl group, a 4-phenyl-n-butyl group, a 5-phenyl-n-pentyl group, an 8-phenyl-n-octyl group, and a naphthylmethyl group.
  • arylalkenyl group examples include a group in which an aryl group having 6 to 10 carbon atoms and an alkenyl group having 2 to 8 carbon atoms are bound, and examples thereof include a styryl group, a 3-phenyl-prop-1-en-1-yl group, a 3-phenyl-prop-2-en-1-yl group, a 4-phenyl-but-1-en-1-yl group, a 4-phenyl-but-3-en-1-yl group, a 5-phenyl-pent-1-en-1-yl group, a 5-phenyl-pent-4-en-1-yl group, an 8-phenyl-oct-1-en-1-yl group, an 8-phenyl-oct-7-en-1-yl group, and a naphthylethenyl group.
  • hydrocarbon group having an oxygen atom examples include a group having an oxirane ring (epoxy group), such as an alkoxyalkyl group, an epoxy group, an epoxyalkyl group, or a glycidoxyalkyl group, an acryloxymethyl group, and a methacryloxymethyl group.
  • oxirane ring epoxy group
  • alkoxyalkyl group is usually a group in which an alkoxy group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms are bound, and examples thereof include a methoxymethyl group, a 2-methoxyethyl group, and a 3-ethoxy-n-propyl group.
  • epoxyalkyl group a straight chain or branched chain epoxyalkyl group having 3 to 10 carbon atoms is preferable, and examples thereof include straight chain alkyl groups comprising an epoxy group, such as a glycidyl group, a glycidylmethyl group, a 2-glycidylethyl group, a 3-glycidylpropyl group, a 4-glycidylbutyl group, a 3,4-epoxybutyl group, a 4,5-epoxypentyl group, and a 5,6-epoxyhexyl group; and branched alkyl groups comprising an epoxy group, such as a ⁇ -methylglycidyl group, a ⁇ -ethylglycidyl group, a ⁇ -propylglycidyl group, a 2-glycidylpropyl group, a 2-glycidylbutyl group, a 3-glycidylbuty
  • Examples of the “glycidoxyalkyl group” include a glycidoxymethyl group and a glycidoxypropyl group.
  • a group having —NR′ 2 (wherein R′ represents a hydrogen atom, an alkyl group, or an aryl group, and each R′ may be the same as or different from each other) or a group having —N ⁇ CR′′ 2 (wherein R′′ represents a hydrogen atom or an alkyl group, and each R′′ may be the same as or different from each other)
  • examples of the alkyl group include the same ones as described above
  • examples of the aryl group include a phenyl group, a naphthyl group, an anthracen-1-yl group, and a phenanthren-1-yl group.
  • Examples of the group having —NR′ 2 include a —CH 2 —NH 2 group, a —C 3 H 6 —NH 2 group, and a —CH 2 —NH—CH 3 group.
  • Examples of the group having —N ⁇ CR′′ 2 include a —CH 2 —N ⁇ CH—CH 3 group, a —CH 2 —N ⁇ C(CH 3 ) 2 group, and a —C 2 H 4 —N ⁇ CH—CH 3 group.
  • a group having a vinyl group, the group having an oxirane ring, the group having —NR′ 2 (wherein R′ represents a hydrogen atom, an alkyl group, or an aryl group, and each R′ may be the same as or different from each other), or the group having —N ⁇ CR′′ 2 (wherein R′′ represents a hydrogen atom or an alkyl group, and each R′′ may be the same as or different from each other) can be preferably used when the film surface is desired to be more fully mineralized.
  • examples of the group having a vinyl group include groups having groups having alkenyl groups such as an ethenyl group (vinyl group), a prop-2-en-1-yl group, a but-3-en-1-yl group, a pent-4-en-1-yl group, a hex-5-en-1-yl group, a hept-6-en-1-yl group, and an oct-7-en-1-yl group, and vinylcarbonyl groups such as a methacrylmethyl group, an acryloxymethyl group, and a methacryloxymethyl group.
  • the group having an oxirane ring, the group having —NR′ 2 , and the group having —N ⁇ CR′′ 2 are as described above.
  • n 1 or 2
  • Each R may be the same or different when n is 2. In addition, these can be used singly or in combinations of two or more.
  • X represents a hydroxyl group or a hydrolyzable group. Each X may be the same or different when (4 ⁇ n) in formula (I) is 2 or more.
  • the hydrolyzable group means, for example, a group that can be hydrolyzed by being heated at 25° C. to 100° C. in the coexistence of excess water without a catalyst to produce a silanol group, or a group that can form a siloxane condensate, specific examples thereof can include an alkoxy group, an acyloxy group, a halogen atom, and an isocyanate group, and an alkoxy group having 1 to 4 carbon atoms or an acyloxy group having 1 to 6 carbon atoms is preferable.
  • examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a n-propoxy group, an isopropyloxy group, a n-butoxy group, an isobutoxy group, and a t-butoxy group
  • examples of the acyloxy group having 1 to 6 carbon atoms include an acetyloxy group and a benzoyloxy group.
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the organic silicon compound used in the present invention has a solubility parameter (SP1) of R obtained by Fedors' estimation method smaller than a solubility parameter (SP2) of a thermosetting compound obtained by Fedors' estimation method, and a difference between the SP1 and the SP2 is 1.6 or more (Si1).
  • SP1 and SP2 is preferably 1.6 to 8.5, and more preferably 1.6 to 7.2.
  • the organic silicon compound used in the present invention may further comprise one having SP1 smaller than SP2 and the difference between the SP1 and the SP2 is less than 1.6 or one having SP1 larger than SP2 (Si2), and a ratio of Si1 to Si2 (Si1:Si2) is 5:5 to 10:0, and preferably 9:1 to 10:0.
  • solubility parameter is one calculated based on the following Fedors' estimation method.
  • the evaporation energy and the molar volume of each atom or atom group which are used for calculation of the above-described equation, can refer to R. F. Fedors, Polym. Eng. Sci., 14, 147 (1974).
  • the organic silicon compound used in the present invention varies depending on the kind of the thermosetting compound used in the present invention. Since the solubility parameters (SP values) of the organic silicon compound and the thermosetting compound can be calculated based on Fedors' estimation method, the combination of the organic silicon compound and the thermosetting compound can be determined based on SP values calculated in advance.
  • SP values solubility parameters
  • examples of the organic silicon compound whose SP value is smaller than the SP value of polybutadiene by 1.6 or more include methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriisopropoxysilane, ethyltri(n-butoxy)silane, dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiaminosilane, and dimethyldiacetoxysilane (all of these having SP value of 6.9 or less).
  • examples of the organic silicon compound whose SP value is smaller than the SP value of the olefin polymer by less than 1.6 or the organic silicon compound whose SP value is larger than the SP value of the olefin polymer include trifluoromethyltrimethoxysilane, vinyltrimethoxysilane, methyltri(meth)acryloxysilane, methyltris[2-(meth)acryloxyethoxy]silane, methyltriglycidyloxysilane, methyltris(3-methyl-3-oxetanemethoxy)silane, vinyltrichlorosilane, vinyltriethoxysilane, n-butyl trimethoxysilane, pentafluorophenyltrimethoxysilane, phenyltrimethoxysilane, nonafluoro-n-butylethyldimethoxysilane, diphenyldimethoxysilane, di-n-butyldimeth
  • examples of the organic silicon compound having a group consisting of a polymer of hydrocarbon can include (meth)acrylates such as methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and cyclohexyl(meth)acrylate; carboxylic acids such as (meth)acrylic acid, itaconic acid, and fumaric acid, and acid anhydrides such as maleic acid anhydride; epoxy compounds such as glycidyl(meth)acrylate; amino compounds such as diethylaminoethyl(meth)acrylate and aminoethyl vinyl ether; amide compounds such as (meth)acrylamide, itaconic acid diamide, ⁇ -ethylacrylamide, crotonamide, fumaric acid diamide, maleic acid diamide, and N-butoxymethyl(meth)acrylamide; and a vinyl polymer obtained by copoly
  • the organic silicon compound used is preferably a condensate.
  • the amount of the organic silicon compound and/or the condensate thereof blended in the solid content of the organic-inorganic complex-forming composition of the present invention is 1 to 95 mass %, and preferably 1 to 50 mass %, with respect to the total mass of the organic silicon compound and/or the condensate thereof, the silanol condensation catalyst, the thermosetting compound, and other components added as needed.
  • the condensate of the organic silicon compound of the present invention can be obtained by a condensation reaction of the organic silicon compound of formula (I) using a silanol catalyst.
  • the silanol condensation catalyst is not particularly limited as long as it hydrolyzes the hydrolyzable group in the compound represented by formula (I), and condenses the silanol to form a siloxane bond, and examples thereof include a metal chelate compound, an organic acid metal salt, a metal compound having two or more hydroxyl groups or hydrolyzable groups (excluding a metal chelate compound and an organic acid metal salt), hydrolysates thereof and condensates thereof, an acid, and a base.
  • the silanol condensation catalysts can be used singly or in combinations of two or more.
  • a metal chelate compound having a hydroxyl group or a hydrolyzable group is preferable, and a metal chelate compound having two or more hydroxyl groups or hydrolyzable groups is more preferable. It is to be noted that having two or more hydroxyl groups or hydrolyzable groups means that the sum of hydrolyzable groups and hydroxyl groups is 2 or more.
  • a ⁇ -ketocarbonyl compound, a ⁇ -ketoester compound, and an ⁇ -hydroxyester compound are preferable, and specific examples thereof include ⁇ -ketoesters such as methyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, sec-butyl acetoacetate, and t-butyl acetoacetate; ⁇ -diketones such as acetylacetone, hexane-2,4-dione, heptane-2,4-dione, heptane-3,5-dione, octane-2,4-dione, nonane-2,4-dione, and 5-methyl-hexane-2,4-dione; and a compound to which a hydroxycarboxylic acid such as glycolic acid or lactic acid, or the
  • the above-described organic acid metal salt is a compound consisting of a salt obtained from a metal ion and an organic acid
  • examples of the organic acid include organic compounds exhibiting acidity, such as carboxylic acids such as acetic acid, oxalic acid, tartaric acid, and benzoic acid; sulfur-containing organic acids such as sulfonic acid and sulfinic acid; a phenol compound; an enol compound; an oxime compound; an imide compound; and an aromatic sulfonamide.
  • the above-described metal compound having two or more hydroxyl groups or hydrolyzable groups is one other than the above-described metal chelate compound and organic acid metal salt, and examples thereof can include a metal hydroxide, and metal alcoholates such as a metal propoxide, a metal isopropoxide, and a metal n-butoxide.
  • hydrolyzable group in the above-described metal compound, the above-described metal chelate compound, or the above-described organic acid metal salt examples include an alkoxy group, an acyloxy group, a halogen group, and an isocyanate group, and an alkoxy group having 1 to 4 carbon atoms and an acyloxy group having 1 to 4 carbon atoms are preferable. It is to be noted that having two or more hydroxyl groups or hydrolyzable groups means that the sum of hydrolyzable groups and hydroxyl groups is 2 or more.
  • the hydrolysate and/or condensate of such a metal compound is preferably one obtained by hydrolyzing 1 mole of the metal compound having two or more hydroxyl groups or hydrolyzable groups, using 0.5 moles or more of water, and more preferably one obtained by hydrolyzing 1 mole of the metal compound having two or more hydroxyl groups or hydrolyzable groups, using 0.5 to 2 moles of water.
  • the hydrolysate and/or condensate of the metal chelate compound is preferably one obtained by hydrolyzing 1 mole of the metal chelate compound, using 5 to 100 moles of water, and more preferably one obtained by hydrolyzing 1 mole of the metal chelate compound, using 5 to 20 moles of water.
  • the hydrolysate and/or condensate of the organic acid metal salt is preferably one obtained by hydrolyzing 1 mole of the organic acid metal salt, using 5 to 100 moles of water, and more preferably one obtained by hydrolyzing 1 mole of the organic acid metal salt, using 5 to 20 moles of water.
  • examples of metal in the metal compound, the metal chelate compound, or the organic acid metal salt compound include titanium (Ti), zirconium (Zr), aluminum (Al), silicon (Si), germanium (Ge), indium (In), tin (Sn), tantalum (Ta), zinc (Zn), tungsten (W), and lead (Pb), among these, titanium (Ti), zirconium (Zr), aluminum (Al), and tin (Sn) are preferable, and particularly, titanium (Ti) is preferable.
  • titanium (Ti) may be used alone or two or more thereof can also be used.
  • the silanol condensation catalyst is preferably a hydrolysate and/or condensate, and particularly preferably a hydrolysate and/or condensate of a metal chelate compound, and its average particle diameter is preferably 20 nm or less, and more preferably 10 nm or less. Accordingly, transparency of the organic-inorganic complex (organic-inorganic complex thin film) can be improved.
  • the average particle diameter can be measured using, for example, HPPS manufactured by Malvern Instruments Ltd.
  • Examples of the acid include an organic acid and a mineral acid
  • specific examples of the organic acid include acetic acid, formic acid, oxalic acid, carbonic acid, phthalic acid, trifluoroacetic acid, p-toluenesulfonic acid, and methanesulfonic acid
  • specific examples of the mineral acid include hydrochloric acid, nitric acid, boric acid, and hydrofluoboric acid.
  • the acid also includes a photo-acid-generating agent that generates an acid by light irradiation, specifically, diphenyliodonium hexafluorophosphate, triphenylphosphonium hexafluorophosphate, and the like.
  • the base examples include strong bases such as tetramethylguanidine and tetramethylguanidylpropyltrimethoxysilane; organic amines, a carboxylic acid neutralized salt of an organic amine, and a quaternary ammonium salt.
  • the blending ratio of the silanol condensation catalyst in the organic-inorganic complex-forming composition of the present invention is 1:99 to 99:1, and preferably 1:99 to 50:50, with respect to the mass of the organic silicon compound and/or the condensate thereof.
  • thermosetting compound of the present invention is not particularly limited as long as it is a compound having a functional group that can be thermally-cured, and the thermosetting compound may be a low-molecular compound or a high-molecular compound.
  • phenolic resins such as novolac-type phenolic resins such as a phenol novolac resin, a cresol novolac resin, and a bisphenol A novolac resin, and a resol-type phenolic resin; bisphenol-type epoxy resins such as a bisphenol A epoxy resin and a bisphenol F epoxy resin, novolac-type epoxy resins such as a novolac epoxy resin and a cresol novolac epoxy resin, epoxy resins such as a biphenyl-type epoxy resin, a stilbene-type epoxy resin, a triphenolmethane-type epoxy resin, an alkyl-modified triphenolmethane-type epoxy resin, a triazine nucleus-containing epoxy resin, and a dicyclopentadiene-modified phenol-type epoxy resin, and a compound having an epoxy group, such as 2,2-bis(4-glycidyloxyphenyl)propane.
  • bisphenol-type epoxy resins such as a bisphenol A epoxy resin and a
  • examples thereof include a urea resin; a resin having a triazine ring, such as a melamine resin; an unsaturated polyester resin; a bismaleimide resin; a polyurethane resin; a diallyl phthalate resin; a silicone resin; a resin having a benzoxazine ring; a cyanate ester resin, and raw material compounds of these resins.
  • examples thereof can also include bifunctional(meth)acrylate compounds such as 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl)ether of bisphenol A, and 3-methylpentanediol di(meth)acrylate; trifunctional or more, multifunctional(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, a reactant of pentaerythritol tri(meth)acrylate and an acid anhydride, a reactant of pen
  • the amount of the thermosetting compound blended in the solid content (total mass of the organic silicon compound and/or the condensate thereof, the silanol condensation catalyst, the thermosetting compound, and other components blended as needed) of the organic-inorganic complex-forming composition of the present invention is 2 to 99 mass %, preferably 50 to 99 mass %, more preferably 60 to 98 mass %, and further preferably 65 to 98%.
  • a thermal polymerization initiator can be added if needed.
  • the thermal polymerization initiator indicates a compound that generates a radial by the application of heat, and examples thereof include an organic peroxide, an azo compound, and a redox initiator.
  • organic peroxide examples include peroxides such as benzoyl peroxide, cumene hydroperoxide, di-t-butyl peroxide, t-butyl hydroperoxide, dicumyl peroxide, acetyl peroxide, lauroyl peroxide, cyclohexanone peroxide, dibenzoyl peroxide, and tert-butyl permaleate; peroxy carbonates such as 1,6bis(t-butyl peroxycarbonyloxy)hexane; peroxy ketal; and persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate.
  • peroxides such as benzoyl peroxide, cumene hydroperoxide, di-t-butyl peroxide, t-butyl hydroperoxide, dicumyl peroxide, acetyl peroxide, lauroyl peroxide, cyclohexanone peroxide,
  • Examples of the above-described azo compound include 2,2′-azobispropane, 2,2′-dichloro-2,2′-azobispropane, 1,1′-azo(methylethyl)diacetate, 2,2′-azobisisobutane, 2,2′-azobisisobutylamide, 2,2′-azobisisobutyronitrile (AIBN), methyl 2,2′-azobis-2-methylpropionate, 2,2′-dichloro-2,2′-azobisbutane, 2,2′-azobis-2-methylbutyronitrile, dimethyl 2,2′-azobis(isobutyrate), 3,5-dihydroxymethylphenylazo-2-methylmalonodinitrile, 2,2′-azobis-2-methylvaleronitrile, 4,4′-azobis-4-cyanovaleric acid dimethyl, and 2,2′-azobis-2,4-dimethylvaleronitrile.
  • AIBN 2,2′-azobispropane
  • Examples of the above-described redox initiator include combinations such as hydrogen peroxide—an iron (II) salt, an organic peroxide—dimethylaniline, and a cerium (IV) salt—an alcohol.
  • the amount of the polymerization initiator used in the present invention blended is preferably 0.01 to 20 mass %, and further preferably 0.1 to 10 mass %, with respect to the solid content of the thermosetting compound.
  • a curing agent or a curing accelerator may be added if needed.
  • examples of the curing agent include amine-based, imidazole-based, amide-based, ester-based, alcohol-based, thiol-based, ether-based, thioether-based, phenol-based, phosphorous-based, urea-based, thiourea-based, acid anhydride-based, Lewis acid-based, onium salt-based, and active silicon compound-aluminum complex-based compounds, and from conventional ones commonly used as a curing agent and a curing accelerator of an epoxy resin and the like, an optional one can be selected and used.
  • amine-based compound for example, aliphatic amine-based, alicyclic and heterocyclic amine-based, aromatic amine-based, and modified amine-based compounds, and the like are used.
  • examples thereof include aliphatic amines: ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, 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′-te
  • imidazole-based compound can 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-cyanoethyl-2-ethyl-4-methylimidazolium trimell
  • imidazoline-based compound examples include 2-methylimidazoline and 2-phenylimidazoline.
  • Examples of the amide-based compound include a polyamide obtained by condensation of a dimer acid and a polyamine, and examples of the ester-based compound include active carbonyl compounds, such as aryl and thioaryl esters of carboxylic acids.
  • examples of the phenol, alcohol-based, thiol-based, ether-based, and thioether-based compounds include phenol novolac, cresol novolac, a polyol, a polymercaptan, a polysulfide, 2-(dimethylaminomethylphenol), 2,4,6-tris(dimethylaminomethyl)phenol, and tri-2-ethylhexyl hydrochloride of 2,4,6-tris(dimethylaminomethyl)phenol.
  • examples of the urea-based, thiourea-based, and Lewis acid-based curing agents include butylated urea, butylated melamine, butylated thiourea, and boron trifluoride.
  • Examples of the phosphorous-based curing agent include organic phosphine compounds, for example, alkyl phosphines such as ethyl phosphine and butyl phosphine, primary phosphines such as phenyl phosphine, dialkyl phosphines such as dimethyl phosphine and dipropyl phosphine, secondary phosphines such as diphenyl phosphine and methylethyl phosphine, and tertiary phosphines such as trimethyl phosphine and triethyl phosphine, and examples of the acid anhydride-based curing agent include phthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydr
  • Examples of the onium salt-based and active silicon compound-aluminum complex-based curing agents include an aryldiazonium salt, a diaryliodonium salt, a triarylsulfonium salt, a triphenylsilanol-aluminum complex, a triphenylmethoxysilane-aluminum complex, a silyl peroxide-aluminum complex, and a triphenylsilanol-tris(salicylaldehydato)aluminum complex.
  • the amount of the curing agent or the curing accelerator used in the present invention blended is preferably 0.01 to 20 mass %, and further preferably 0.1 to mass %, with respect to the solid content of the thermosetting compound.
  • metal compound particles may be added if needed.
  • the metal compound particles are not particularly limited as long as they can form irregularities on the surface of the organic-inorganic complex film to be formed, to some extent, specific examples thereof can include aggregative metal compound particles and metal compound particles having a relatively large particle diameter, and a mixture of metal compound particles having an isoelectric point of less than 5 as a metal oxide and metal compound particles having an isoelectric point of larger than 5 as a metal oxide is preferable.
  • metal of the metal compound particles having an isoelectric point of less than 5 as a metal oxide examples include silicon, tungsten, and antimony, and examples of the metal compound include metal oxides such as silica, tungsten oxide, and antimony oxide.
  • examples of metal of the metal compound particles having an isoelectric point of 5 or more as a metal oxide include zirconium, aluminum, titanium, magnesium, iron, tin, zinc, cadmium, nickel, copper, beryllium, ruthenium, thorium, yttrium, mercury, cesium, chromium, and lanthanum
  • examples of the metal compound include metal oxides such as zirconia, alumina, titania, magnesium oxide, tin oxide, zinc oxide, cadmium oxide, yttrium oxide, nickel oxide, copper oxide, beryllium oxide, ruthenium oxide, thorium oxide, mercury oxide, cerium oxide, and chromium oxide, and magnesium fluoride.
  • the metal compound particles are preferably a mixed sol of silica and at least one selected from zirconia, alumina, and titania, and more preferably a mixed sol of a silica sol and a zirconia sol.
  • the mixing ratio of the metal compound particles having an isoelectric point of less than 5 as a metal oxide to the metal compound particles having an isoelectric point of 5 or more is 1:99 to 99:1, preferably 50:50 to 99:1, and more preferably 80:20 to 99:1, in terms of the weight ratio of the solid content.
  • the metal compound particles used are not particularly limited if they are secondary particles or primary particles, and they are preferably primary particles.
  • the particle diameter of the metal compound is not particularly limited, and the average primary particle diameter is preferably in the range of 1 nm to 100 nm, and further preferably in the range of 1 nm to 50 nm.
  • the property of the metal compound particles may be a sol or a powder, and usually, a sol is preferably used.
  • a sol is usually a colloidal dispersion solution, and therefore, a uniform dispersion solution can be easily formed by simply mixing the sol with other components, and furthermore, there are few problems of becoming non-uniform due to settling or the like.
  • each metal compound particle is surface-modified with a silane coupling agent or the like
  • specific examples thereof include a silica sol that is subjected to hydrophobic treatment with a hydrocarbon group or the like.
  • the amount of the metal compound particles blended in the solid content of the organic-inorganic complex-forming composition of the present invention is 0.1 to 50 mass %, and preferably 0.1 to 25 mass %, with respect to the total mass of the organic silicon compound and/or the condensate thereof, the silanol condensation catalyst, the thermosetting compound, and the like.
  • a solvent used in the present invention is not particularly limited, and examples thereof include water; aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane and octane; alicyclic hydrocarbons such as cyclohexane and cyclopentane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate and butyl acetate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; sulfoxides such as dimethylsulfoxide; alcohols such as methanol and ethanol; and polyhydric alcohol derivatives such as ethylene glycol monomethyl ether and ethylene glycol monomethyl ether acetate. These solvents can be used singly or in combinations of two or more.
  • a filler can also be separately added and dispersed in the organic-inorganic complex-forming composition of the present invention so as to exhibit various properties such as coloration of a coating film to be obtained, film thickening, prevention of transmission of ultraviolet rays to a base, imparting of an anticorrosion property, and a heat resistance property.
  • oxides there may be descriptions overlapping with those of the above-described metal compound particles.
  • this filler examples include water-insoluble pigments such as organic pigments and inorganic pigments, or particulate, fibrous, or scaly metals and alloys and oxides, hydroxides, carbides, nitrides, and sulfides thereof other than pigments.
  • water-insoluble pigments such as organic pigments and inorganic pigments, or particulate, fibrous, or scaly metals and alloys and oxides, hydroxides, carbides, nitrides, and sulfides thereof other than pigments.
  • this filler can include particulate, fibrous, or scaly iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide, aluminum oxide, chromium oxide, manganese oxide, iron oxide, zirconium oxide, cobalt oxide, synthetic mullite, aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride, clay, diatomaceous earth, slaked lime, gypsum, talc, barium carbonate, calcium carbonate, magnesium carbonate, barium sulfate, bentonite, mica, zinc green, chromium green, cobalt green, viridian, Guignet green, cobalt chromium green, Scheele's green, green earth, manganese green, pigment green, ultramarine blue, Prussian blue, blue verditer, cobalt blue, cerulean blue, copper borate, molybdenum blue, copper sulf
  • additives such as known dehydrating agents such as methyl orthoformate, methyl orthoacetate, and tetraethoxysilane, various surfactants, silane coupling agents other than the above, titanium coupling agents, dyes, dispersing agents, thickening agents, and leveling agents can also be further added to the organic-inorganic complex-forming composition of the present invention.
  • an organic silicon compound and/or a condensate thereof, a silanol catalyst, a thermosetting compound, and if needed, a polymerization initiator, a curing agent, a curing accelerator, a solvent, and other optional components are mixed.
  • a silanol catalyst is mixed with a solvent, a predetermined amount of water is added to perform (partial) hydrolysis, and then, an organic silicon compound is added to be (partially) hydrolyzed.
  • a thermosetting compound and, if needed, a polymerization initiator or the like are dissolved in a solvent, and both solutions are mixed.
  • the organic silicon compound hydrolyzed by the silanol condensation catalyst can be directly mixed with the thermosetting compound without removing a solvent or water.
  • these components can be mixed at the same time.
  • Examples of the method for mixing the organic silicon compound and the silanol catalyst can include a method of mixing the organic silicon compound and the silanol catalyst and then adding water to perform (partial) hydrolysis, and a method of mixing the organic silicon compound and the silanol catalyst which are separately (partially) hydrolyzed. It is not always necessary to add water or a solvent, but it is preferable to add water to form a (partial) hydrolysate.
  • the amount of the predetermined amount of water depends on the kind of the silanol catalyst, for example, when the silanol catalyst is a metal compound having two or more hydroxyl groups or hydrolyzable groups, 0.5 moles or more of water is preferably used, and 0.5 to 2 moles of water is more preferably used, with respect to 1 mole of the metal compound.
  • the silanol catalyst is a metal chelate compound or a metal organic acid salt compound
  • 5 to 100 moles of water is preferably used, and to 20 moles of water is more preferably used, with respect to 1 mole of the metal chelate compound or the metal organic acid salt compound.
  • An organic-inorganic complex of the present invention comprises:
  • R represents an organic group having a carbon atom directly bonded to Si, and X represents a hydroxyl group or a hydrolyzable group; and n represents 1 or 2, wherein when n is 2, each R is the same or different, and when (4 ⁇ n) is 2 or more, each X may be the same or different
  • SP1 solubility parameter
  • SP2 solubility parameter
  • SP1 solubility parameter of R obtained by Fedors' estimation method
  • SP2 solubility parameter
  • a difference between the SP1 and the SP2 is 1.6 or more (Si1)
  • b) a silanol condensation catalyst a silanol condensation catalyst
  • a cured material of the thermosetting compound excluding a cured material of an olefin polymer.
  • the organic silicon compound used in the present invention may further comprise one having SP1 smaller than SP2 and the difference between the SP1 and the SP2 is less than 1.6 or one having SP1 larger than SP2 (Si2), and a ratio of Si1 to Si2 (Si1:Si2) is 5:5 to 10:0, and preferably 9:1 to 10:0.
  • the organic-inorganic complex of the present invention includes one in which a silanol condensation catalyst (including a derivative in which the catalyst structure is changed) is dispersed in a non-bonded state in a condensate of an organic silicon compound, one in which a silanol condensation catalyst (including a derivative in which the catalyst structure is changed) is bonded to a condensate of an organic silicon compound (for example, one having a Si—O-M bond (M represents a metal atom in a silanol condensation catalyst)), and one consisting of a mixture state thereof.
  • a silanol condensation catalyst including a derivative in which the catalyst structure is changed
  • Pencil hardness in conformity with JIS K 5600-5-4 Pencil method when the thin film after drying is formed on a glass substrate is about 1H to 4H, and is preferably 2H to 4H from the viewpoints of adhesiveness to the substrate and hardness.
  • the organic-inorganic complex-forming composition known application methods can be used, and examples thereof can include a dipping method, a spraying method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, and an ink jet method.
  • the thickness of the film to be formed is not particularly limited, and is, for example, about 0.05 to 200 ⁇ m.
  • the organic-inorganic complex thin film of the present invention has a structure in which the carbon content in the film surface part is smaller compared to the carbon content in the film back surface part, and the minimum value of the carbon content between the film surface and 0.5 ⁇ m in the depth direction is more preferably 80% or less, and further preferably 2 to 60%, of the carbon content at the film back surface side.
  • the carbon content in the film surface part being smaller compared to the carbon content in the film back surface part means that the total amount of carbon between the film surface and a film central part is smaller than the total amount of carbon between the film back surface and the film central part.
  • the carbon content gradually increases from the film surface to a predetermined depth, such a depth in which the carbon content gradually increases is preferably 5 to 80%, and more preferably 10 to 50%, of the film thickness, and specifically, for example, when the film thickness is about 1 to 2.5 ⁇ m, the depth in which the carbon content gradually increases is about 50 to 2000 nm.
  • the carbon content can be measured by ESCA analysis or the like.
  • carbon content means the molar concentration of carbon atoms if (all metal atoms+oxygen atoms+carbon atoms) is 100%. The same is true in the concentration of another element.
  • a thin film was formed by bar coating on a stainless-steel plate to be 5 ⁇ m, and heated at 150° C. for 30 minutes by a hot-air circulation-type dryer.
  • VYLON 600 registered trademark, TOYOBO CO., LTD, amorphous polyester resin
  • polysiloxane wt %/10 wt %
  • a thin film was formed by bar coating on a stainless-steel plate to be 5 ⁇ m, and heated at 150° C. for 30 minutes by a hot-air circulation-type dryer. Distribution of respective film components of the thin film in the film thickness direction was measured by ESCA. The result is shown in FIG. 2 .
  • a thin film was formed by bar coating on a stainless-steel plate to be 5 ⁇ m, and heated at 150° C. for 30 minutes by a hot-air circulation-type dryer. Distribution of respective film components of the thin film in the film thickness direction was measured by ESCA. The result is shown in FIG. 3 .
  • a thin film was formed by bar coating on a stainless-steel plate to be 5 ⁇ m, and heated at 130° C. for 10 minutes by a hot-air circulation-type dryer. Distribution of respective film components of the thin film in the film thickness direction was measured by ESCA. The result is shown in FIG. 4 .

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CN104411773A (zh) 2015-03-11
KR20150013875A (ko) 2015-02-05
TWI480336B (zh) 2015-04-11
TW201412877A (zh) 2014-04-01
JPWO2014010217A1 (ja) 2016-06-20
EP2873701A4 (fr) 2016-01-06
JP6084220B2 (ja) 2017-02-22
US20160257851A1 (en) 2016-09-08
EP2873701A1 (fr) 2015-05-20

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