WO2011142468A1 - Composition durcissable, procédé de fabrication d'un matériau composite résine époxy / polymère inorganique utilisant ladite composition durcissable, et matériau composite résine époxy / polymère inorganique - Google Patents

Composition durcissable, procédé de fabrication d'un matériau composite résine époxy / polymère inorganique utilisant ladite composition durcissable, et matériau composite résine époxy / polymère inorganique Download PDF

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WO2011142468A1
WO2011142468A1 PCT/JP2011/061121 JP2011061121W WO2011142468A1 WO 2011142468 A1 WO2011142468 A1 WO 2011142468A1 JP 2011061121 W JP2011061121 W JP 2011061121W WO 2011142468 A1 WO2011142468 A1 WO 2011142468A1
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group
epoxy resin
zirconia
acid anhydride
epoxy
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PCT/JP2011/061121
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English (en)
Japanese (ja)
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越智　光一
美由紀 倉谷
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学校法人関西大学
ダイセル化学工業株式会社
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Priority to JP2012514854A priority Critical patent/JP5858406B2/ja
Priority to CN201180022922.7A priority patent/CN102906162B/zh
Priority to KR1020127032056A priority patent/KR20130108083A/ko
Publication of WO2011142468A1 publication Critical patent/WO2011142468A1/fr

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    • 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
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K5/0091—Complexes with metal-heteroatom-bonds

Definitions

  • the present invention relates to a curable composition, more specifically, a curable composition that can easily form an organic-inorganic composite material composed of a cured epoxy resin and inorganic fine particles of a Group 4 metal oxide of the periodic table.
  • the present invention relates to a method for producing an epoxy resin-inorganic polymer composite material and an epoxy resin-inorganic polymer composite material.
  • This epoxy resin-inorganic polymer composite material is useful as a coating agent for electrical / electronic materials, molding materials, paints, adhesive materials, sealing materials, lens materials, optical fibers, optical waveguides, optical filters, optical disk substrates, etc. .
  • it is useful in the fields of LEDs, lenses, solar cells and the like that require a high refractive index.
  • a silica-based composite material is known as an organic-inorganic composite material, which is useful as a heat-resistant material.
  • zirconia and titania organic-inorganic composite materials have been studied as high refractive index materials. These materials are also expected in terms of improving physical properties such as coefficient of thermal expansion, mechanical strength, and heat transfer.
  • a composite material composed of an epoxy resin and zirconia or titania is excellent in transparency, optical characteristics, heat resistance, high density, high specific gravity, and excellent in heat conduction characteristics, thermal expansion characteristics, and mechanical characteristics. Therefore, various methods for obtaining such composite materials have been studied.
  • JP-A-8-100107 discloses an epoxy resin and a metal oxide for the purpose of micro-homogeneous hybridization based on a hydrolysis polycondensation reaction of a metal alkoxide such as titania in situ.
  • a metal alkoxide such as titanium alkoxide and / or an organic solvent and water are dropped into a solution in which an amine-based epoxy resin curing agent is partially reacted in advance, and at the same time, the metal alkoxide is hydrolyzed and polycondensed.
  • a method for producing a composite of an epoxy resin and a metal oxide, in which fine particles of the metal oxide are contained in the cured epoxy resin by removing the solvent or curing the epoxy resin, has been proposed. However, this method requires a partial reaction of the epoxy resin in advance, and the process is complicated. In addition, the epoxy resin composition tends to thicken and gel, and the amine-based curing agent is used, so that the cured product is likely to be colored.
  • JP-A-2005-36080 an epoxy resin, titanium alkoxide or a partial polycondensate thereof, and a nitrogen-containing epoxy resin curing agent are uniformly dissolved in a solvent at a specific ratio, and then heat treatment in a solution state is performed.
  • a method of obtaining an epoxy resin composition that gives a cured product that is uniformly transparent and has a high glass transition temperature by reacting a titanium alkoxide or a partial polycondensate thereof with a nitrogen-containing epoxy resin curing agent is proposed. Yes.
  • this method uses a nitrogen-containing epoxy resin curing agent, the cured product tends to be colored, and the epoxy resin composition tends to thicken and gel, and is also sensitive to trace amounts of acetic acid and moisture. There is.
  • JP-A-2008-106260 discloses a resin composition for encapsulating an optical semiconductor comprising zirconium oxide particles having an average particle diameter of 1 to 30 nm coated with an aliphatic carboxylic acid having 6 or more carbon atoms and an epoxy resin.
  • a method of obtaining a cured product by using it has been proposed.
  • in this method in order to obtain a cured product, it is necessary to prepare a zirconium oxide particle and to remove coarse by-product particles. There is a problem that it is complicated and inferior in productivity, such as a coating step and a step of curing the epoxy resin in a state where these are homogeneously mixed.
  • JP 2008-274013 discloses a first step of obtaining a hydrolyzed partial condensate by subjecting a metal alkoxide such as titanium alkoxide and zirconium alkoxide to a hydrolytic partial condensation reaction in the presence of water, On the other hand, a second step of condensing a silane compound having an alkoxysilyl group and a group that reacts with an epoxy group such as an amino group, and a third step of adding the condensation reaction product obtained in the second step to the epoxy resin
  • a method for producing a curable epoxy resin composition comprising: JP 2008-274014 A discloses a process for producing an alkoxysilyl group-modified epoxy resin by reacting a silane compound having a mercapto group and an alkoxysilyl group with an epoxy group of an epoxy resin, and the alkoxysilyl group.
  • Non-Patent Document 1 prepares an acetic acid-modified zirconium alkoxide whose reactivity is controlled by a transesterification reaction between zirconium alkoxide and acetic acid. Methods for obtaining cured epoxy resin / zirconia composites based on situ polymerization have been reported. However, although the composite material obtained by this method is transparent, an amine-based curing agent for curing the epoxy resin is required in addition to the reaction control agent, and there is a problem that it is colored yellow.
  • acetic acid released with the progress of the sol-gel reaction does not function as a crosslinking agent for the epoxy resin, a strong epoxy resin-inorganic polymer composite material having a higher degree of polymerization and a higher crosslinking density cannot be obtained. Moreover, it is necessary to remove by-products resulting from a reaction control agent such as acetic acid from the obtained cured product.
  • the object of the present invention is to simplify an epoxy resin-inorganic polymer composite material comprising a cured epoxy resin and a Group 4 metal oxide of the periodic table, which is homogeneous, has a high crosslink density, is excellent in transparency, and has a high refractive index. It is in providing the curable composition which can be formed in this invention, and the manufacturing method of an epoxy resin-inorganic polymer composite material using the same.
  • Another object of the present invention is an epoxy resin-inorganic polymer composed of a cured epoxy resin and a Group 4 metal oxide of the periodic table, which is homogeneous, has a high crosslinking density, is excellent in transparency, and has a high refractive index. It is to provide a composite material.
  • a period is partially modified by a polycarboxylic acid anhydride or a carboxylic acid having a reactive functional group for an epoxy group or a hydroxyl group in the molecule.
  • the polyvalent carboxylic acid anhydride or a carboxylic acid having a reactive functional group with respect to an epoxy group or a hydroxyl group in the molecule is included in the periodic table 4. It functions as a stabilizer (reaction control agent) for group metal alkoxides, and also functions as a crosslinking agent (curing agent) for epoxy compounds.
  • epoxy curing reaction and the metal alkoxide sol-gel reaction proceed at the same rate, and are homogeneous and have a high crosslinking density.
  • epoxy resins having a high refractive index - inorganic polymer composites found that can be obtained easily, and have completed the present invention.
  • the present invention relates to a periodic group 4 metal alkoxide (A) partially modified with a polycarboxylic acid anhydride, or a carboxylic acid having a functional group reactive with an epoxy group or a hydroxyl group in the molecule, and an epoxy.
  • a curable composition comprising the compound (B) is provided.
  • the group 4 metal of the periodic table is preferably zirconium or titanium.
  • the group IV metal alkoxide (A) partially modified with the polyvalent carboxylic acid anhydride or a carboxylic acid having a functional group reactive with an epoxy group or a hydroxyl group in the molecule includes the following formula (1): (In the formula, M represents a group 4 metal atom in the periodic table, R 1 represents an alkyl group, R 2 represents a (k + 1) -valent hydrocarbon group, X represents a reactive functional group for an epoxy group or a hydroxyl group.
  • the curable composition may further contain a curing accelerator.
  • the present invention also provides an epoxy resin-inorganic polymer composite comprising a cured epoxy resin and a group 4 metal oxide of a periodic table obtained by curing the curable composition.
  • a method for producing a polymer composite is provided.
  • the present invention further provides an epoxy resin-inorganic polymer composite material obtained by the above production method.
  • fine particles of a periodic table group 4 metal oxide having an average particle diameter of 1 to 50 nm may be dispersed in the cured epoxy resin.
  • the present invention further provides an epoxy resin-inorganic polymer composite material having a homogeneous phase structure composed of a cured epoxy resin and a Group 4 metal oxide of the periodic table.
  • the content of the periodic table group 4 metal oxide is preferably 19% by weight or more in terms of MO 2 (M represents a periodic table group 4 metal atom).
  • MO 2 represents a periodic table group 4 metal atom.
  • the cured epoxy resin is formed without using an amine curing agent.
  • the Group 4 metal alkoxide of the periodic table is partially modified (modified) by a polyvalent carboxylic acid anhydride or a carboxylic acid having a reactive functional group for an epoxy group or a hydroxyl group in the molecule.
  • the reaction rate of the sol-gel reaction of the group 4 metal alkoxide of the periodic table is moderately suppressed and controlled. For this reason, the sol-gel reaction of the metal alkoxide and the curing reaction of the epoxy compound (B) proceed at the same reaction rate, and an organic-inorganic composite material having a uniform, excellent transparency, and a high refractive index is obtained. It is done.
  • the polycarboxylic acid anhydride chelated to the group 4 metal alkoxide of the periodic table, or the carboxylic acid having a reactive functional group for the epoxy group or hydroxyl group in the molecule is , Desorbs from the Group 4 metal of the periodic table, acts as a crosslinking agent (curing agent) for the epoxy compound, and cures the epoxy compound. Since these compounds are multifunctional to the epoxy compound or the epoxy resin being cured, the crosslink density of the cured epoxy resin can be improved. Moreover, since it is taken in into resin by reaction, it does not remain
  • polymerized inorganic fine particles having an average particle diameter of about 1 to 50 nm are evenly dispersed in a cured epoxy resin, which is homogeneous and excellent in transparency, has a high refractive index, and has mechanical properties.
  • an excellent organic-inorganic composite material can be obtained.
  • the inorganic molecule and the organic molecule have substantially no chemical bond, and a homogeneous structure is formed by entanglement of molecular chains.
  • the uniformly dispersed particles may be connected by a chain-polymerized inorganic material.
  • an organic-inorganic composite material can be produced simply and industrially efficiently.
  • Example 6 the zirconium (IV) tetra n-propoxide used as a raw material, HHPA (cis-1,2-cyclohexanedicarboxylic acid anhydride; hexahydrophthalic acid anhydride), and the obtained HHPA-modified zirconium alkoxide
  • HHPA cis-1,2-cyclohexanedicarboxylic acid anhydride; hexahydrophthalic acid anhydride
  • FIG. 4 is a transmission electron microscope (TEM) photograph of the epoxy resin-zirconia composite material (zirconia 15% by weight) obtained in Example 9.
  • 4 is a transmission electron microscope (TEM) photograph of the epoxy resin-zirconia composite material (zirconia 20 wt%) obtained in Example 10.
  • FIG. 2 is a transmission electron microscope (TEM) photograph of the epoxy resin-zirconia composite material (zirconia 25 wt%) obtained in Example 11.
  • FIG. FIG. 3 is a graph showing FT-IR spectra of long-chain dibasic acid anhydride-modified zirconium alkoxides obtained in Examples 12 to 14.
  • FIG. 2 is a diagram showing an FT-IR spectrum of the long-chain dibasic acid anhydride-modified zirconium alkoxide obtained in Example 15.
  • FIG. It is a figure which shows the FT-IR spectrum of the DGEBA (bisphenol A type epoxy resin) / long-chain dibasic acid anhydride / zirconia hybrid system obtained in Example 18. It is a figure which shows the FT-IR spectrum of the DGEBA / long-chain dibasic acid anhydride / zirconia hybrid system obtained in Example 20.
  • the curable composition of the present invention comprises a Group 4 metal alkoxide (A) that is partially modified with a polyvalent carboxylic acid anhydride or a carboxylic acid having a reactive functional group for an epoxy group or a hydroxyl group in the molecule. (Hereinafter referred to as “partially modified periodic table group 4 metal alkoxide (A)”) and an epoxy compound (B).
  • A Group 4 metal alkoxide
  • B an epoxy compound
  • Partially Modified Periodic Table Group 4 Metal Alkoxide (A) Partially modified periodic table group 4 metal alkoxide (A) is obtained by reacting periodic table group 4 metal alkoxide with a polyvalent carboxylic acid anhydride or a carboxylic acid having a reactive functional group for an epoxy group or hydroxyl group in the molecule. Is a partially modified product obtained by Partially modified periodic table group 4 metal alkoxide (A) can be used alone or in combination of two or more.
  • Examples of the periodic table group 4 metal in the periodic table group 4 metal alkoxide include titanium, zirconium, and hafnium. Among these, titanium and zirconium are preferable, and zirconium is particularly preferable in that an organic-inorganic composite material having long-term durability can be obtained.
  • Group 4 metal alkoxides in the periodic table include zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetra n-propoxide, zirconium tetraisopropoxide, zirconium tetra n-butoxide, zirconium tetra t-butoxide, zirconium tetraoctoxide.
  • Zirconium alkoxides such as zirconium tetra C 1-12 alkoxides; titanium tetramethoxide, titanium tetraethoxide, titanium tetra n-propoxide, titanium tetraisopropoxide, titanium tetra n-butoxide, titanium tetra t-butoxide, Examples thereof include titanium alkoxides such as titanium tetraoctoxide (titanium tetra C 1-12 alkoxide and the like). As the group 4 metal alkoxide of the periodic table, zirconium tetra C 1-4 alkoxide and titanium tetra C 1-4 alkoxide are particularly preferable.
  • polyvalent carboxylic acid anhydride examples include succinic anhydride (succinic anhydride), methyl succinic anhydride, dodecenyl succinic anhydride, hexadecenyl succinic anhydride, maleic anhydride, methyl maleic anhydride, Propanetricarboxylic acid anhydride, malonic acid anhydride, methylmalonic acid anhydride, ethylmalonic acid anhydride, glutaric acid anhydride, adipic acid anhydride, pimelic acid anhydride, suberic acid anhydride, azelaic acid anhydride, sebacic acid Aliphatic polycarboxylic anhydrides such as anhydrides; 1,2-cyclopentanedicarboxylic anhydride, 1,2-cyclohexanedicarboxylic anhydride (hexahydrophthalic anhydride), cyclohexene dicarboxylic anhydride (tetrahydrophthalic anhydride
  • R a , R b and R c are the same or different and represent a divalent hydrocarbon group having 1 to 30 carbon atoms.
  • R x and R y are the same or different and represent a hydrogen atom, carboxyl R x and R y may be bonded to each other in the molecule to form a —CO—O—CO— group (an acid anhydride group), and u is 0 or more. Indicates an integer)
  • the compound represented by these can also be used.
  • substituted oxycarbonyl group examples include an alkoxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group; an alkenyloxycarbonyl group such as an allyloxycarbonyl group; and a cycloalkyl such as a cyclohexyloxycarbonyl group.
  • R x and R y are bonded to each other in the molecule to form a —CO—O—CO— group (an acid anhydride group)
  • the compound of the formula (a) becomes a cyclic acid anhydride.
  • the compound of the formula (a) has one or more acid anhydride bonds in the molecule. These compounds can be obtained, for example, by intermolecular dehydration condensation of polyvalent carboxylic acids.
  • a compound having a carboxyl group at both ends is generally a polyvalent carboxylic acid mono- or polyanhydride (polymeric acid anhydride) and Called.
  • R a , R b , and R c are a long-chain alkylene group or a long-chain alkenylene group (an alkylene group having 6 or more carbon atoms or an alkenylene group having 6 or more carbon atoms).
  • examples of the divalent hydrocarbon group having 1 to 30 carbon atoms in R a , R b and R c include, for example, methylene, methylmethylene, dimethylmethylene, ethylene, propylene, trimethylene, tetramethylene, Pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene, heptacamethylene, octadecamethylene, nonacamethylene
  • a linear or branched divalent aliphatic hydrocarbon group (an alkylene group, an alkenylene group, etc.) such as icosamethylene, henicosamethylene, docosamethylene, and triacontamethylene group; 1,3-cyclopentylene, 1,3-cyclohexylene, 1,4 3- to 12-membered divalent alicyclic hydrocarbon group
  • the divalent hydrocarbon group having 1 to 30 carbon atoms in R a , R b and R c is a divalent hydrocarbon group having 4 to 25 carbon atoms from the viewpoint of obtaining a highly flexible cured product.
  • a hydrocarbon group (especially a divalent aliphatic hydrocarbon group such as an alkylene group) is preferred, and a divalent hydrocarbon group having 6 to 20 carbon atoms (especially a divalent aliphatic hydrocarbon such as an alkylene group). Group) is preferred.
  • R a , R b and R c may be different from each other, but all are preferably the same group from the viewpoint of ease of production.
  • R x and R y are the same or different and are preferably a carboxyl group or a substituted oxycarbonyl group.
  • u is not particularly limited as long as u is an integer of 0 or more, but is preferably 0 to 20 (for example, 1 to 20), more preferably 0 to 10 (for example, 1 to 10), and further preferably 1 to 5 (particularly 2 to 3). ).
  • Typical examples of the acid anhydride represented by the formula (a) include polydodecanedioic acid polyanhydride and polyicosanedioic acid polyanhydride.
  • aliphatic polycarboxylic acid anhydrides cyclic acid anhydrides
  • alicyclic polycarboxylic acid anhydrides A cyclic acid anhydride
  • an acid anhydride represented by the formula (a) are preferred.
  • an alicyclic polyvalent carboxylic acid anhydride (cyclic acid anhydride) and an acid anhydride represented by the above formula (a) are preferable.
  • the acid anhydride represented by said Formula (a) is preferable from a viewpoint that the hardened
  • examples of the “reactive functional group for an epoxy group or a hydroxyl group” include, for example, a carboxyl group, a carboxylic ester group, and an epoxy group. , Amino group, hydroxyl group and the like.
  • Examples of the carboxylic acid ester group include a methoxycarbonyl group, an ethoxycarbonyl group, a propyloxycarbonyl group, an isopropyloxycarbonyl group, a butyloxycarbonyl group, an isobutyloxycarbonyl group, a s-butyloxycarbonyl group, and a t-butyloxycarbonyl group.
  • Alkoxycarbonyl groups such as C 1-6 alkoxy-carbonyl groups; alkenyloxycarbonyl groups such as vinyloxycarbonyl groups and propenyloxycarbonyl groups (eg C 2-6 alkenyloxy-carbonyl groups); cyclopentyl oxycarbonyl group, cycloalkyloxy group such as cyclohexyloxy group (e.g., C 3-12 cycloalkyloxy - carbonyl group); benzyloxycarbonyl group What aralkyloxycarbonyl group (e.g., C 7-15 aralkyloxy - carbonyl group); aryloxycarbonyl groups such as phenyloxycarbonyl group (e.g., C 6-14 aryloxy - carbonyl group) and the like.
  • alkenyloxycarbonyl groups such as vinyloxycarbonyl groups and propenyloxycarbonyl groups (eg C 2-6 alkenyloxy-carbonyl groups)
  • carboxylic acid having a carboxyl group as the reactive functional group examples include oxalic acid, succinic acid, methylsuccinic acid, maleic acid, methylmaleic acid, fumaric acid, propanetricarboxylic acid, malonic acid, methylmalonic acid, and ethylmalonic acid.
  • Aliphatic polycarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid; 1,2-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, methylcyclohexane
  • Alicyclic polycarboxylic acids such as dicarboxylic acid, methylcyclohexene dicarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, 1,2,4,5 -Benzenetetracarboxylic acid, 2,3-naphth Dicarboxylic acid, 2,3,6,7-like aromatic polycarboxylic acids such as naphthalene tetracarboxylic acid.
  • carboxylic acid having a carboxylic ester group as the reactive functional group examples include partial esters (half esters, etc.) of polyvalent carboxylic acids. Typical examples thereof include aliphatic polycarboxylic acid partial esters such as monomethyl succinate, monoethyl succinate, monomethyl maleate, monoethyl maleate, monomethyl malonate, monoethyl malonate, monomethyl adipate, monoethyl adipate; 1 , 2-cyclopentanedicarboxylic acid monomethyl, 1,2-cyclopentanedicarboxylic acid monoethyl, 1,2-cyclohexanedicarboxylic acid monomethyl, 1,2-cyclohexanedicarboxylic acid monoethyl, etc .; phthalic acid partial ester; Monomethyl, monoethyl phthalate, monomethyl terephthalate, monoethyl terephthalate, monomethyl trimellitic acid, monoethyl trimellitic acid, monomethyl
  • Examples of the carboxylic acid having an epoxy group as the reactive functional group include epoxypropionic acid and 2,3-epoxy-3-cyclohexylpropionic acid.
  • carboxylic acid having an amino group as the reactive functional group examples include amino acids such as glycine, alanine, leucine, phenylalanine, glutamic acid, ⁇ -aminopropionic acid, and ⁇ -aminobutyric acid.
  • carboxylic acid having a hydroxyl group as the reactive functional group examples include aliphatic hydroxy acids such as glycolic acid, lactic acid, glyceric acid, malic acid, citric acid, and tartaric acid; and aromatic hydroxy acids such as salicylic acid. .
  • the partially modified periodic table Group 4 metal alkoxide (A) includes a compound represented by the formula (1).
  • M represents a group 4 metal atom in the periodic table
  • R 1 represents an alkyl group
  • R 2 represents a (k + 1) -valent hydrocarbon group
  • X represents a reactive functional group for an epoxy group or a hydroxyl group.
  • the k Xs may be the same or different.
  • m and n are each 2 or more, the groups in m parentheses and the groups in n parentheses may be the same or different.
  • k is usually 1 to 6, preferably 1 to 3, and more preferably 1 or 2. In many cases, k is 1.
  • n is preferably 1 (monodentate) or 2 (bidentate).
  • the compounds represented by formula (1) can be used alone or in admixture of two or more.
  • the average value of n is 0.1 to 2, preferably 0.5 to 1.5, but is preferably in the range of 1 to 2 from the viewpoint of easy reaction control of the group 4 metal alkoxide of the periodic table.
  • the range of 2 to 1.8 is particularly preferred.
  • the periodic table group 4 metal atoms in M include titanium, zirconium, and hafnium. Among these, titanium and zirconium are preferable, and zirconium is particularly preferable from the viewpoint of long-term durability and the like.
  • alkyl group for R 1 examples include straight chain having 1 to 10 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, octyl, and decyl groups.
  • Examples include branched alkyl groups. Among these, a linear or branched alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group is preferable.
  • divalent hydrocarbon group as an example of the hydrocarbon group for R 2 , methylene, methylmethylene, dimethylmethylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, Nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene, heptacamethylene, octadecamethylene, nonadecamethylene, icosamethylene, heicosamethylene, docosamethylene, tria A linear or branched alkylene group such as a contamethylene group (for example, an alkylene group having 1 to 30 carbon atoms, preferably about 4 to 25 carbon atoms); 1,2-cyclopentylene, 1,3-cyclo Pentylene, 1,2-cyclo Divalent alicyclic hydrocarbon groups such as cycloalkylene groups such as xylene groups
  • the number of carbon atoms of the hydrocarbon group in R 2 is, for example, about 1 to 30, preferably about 4 to 25.
  • the hydrocarbon group in R 2 may contain one or more acid anhydride groups [—C ( ⁇ O) —O—C ( ⁇ O) —].
  • Examples of the trivalent or higher hydrocarbon group include a corresponding trivalent or higher hydrocarbon group having the same skeleton as the above divalent hydrocarbon group.
  • the hydrocarbon group for R 2 may have a substituent.
  • substituents include a carboxyl group, a carboxylic ester group, a hydroxyl group, an amino group, a halogen atom, an alkyl group, and an alkoxy group.
  • Examples of the reactive functional group for the epoxy group or hydroxyl group in X include those exemplified above.
  • X is particularly preferably a carboxyl group or a carboxylic acid ester group.
  • Partially modified periodic table group 4 metal alkoxide (A) [compound represented by formula (1), etc.] reacts with periodic group 4 metal alkoxide and polycarboxylic acid anhydride or epoxy group or hydroxyl group in the molecule. It can manufacture by making it react with the carboxylic acid which has a functional functional group.
  • the reaction between the Group 4 metal alkoxide and the carboxylic acid having a polyfunctional carboxylic acid anhydride or a functional group reactive with an epoxy group or a hydroxyl group in the molecule is carried out in the absence of a solvent or in an inert solvent. Is called.
  • the same alcohol solution as the alcohol of the Group 4 metal alkoxide of the periodic table is preferably used, but it is not particularly limited thereto.
  • the reaction temperature varies depending on the kind of reaction components, but is generally ⁇ 10 ° C. to 120 ° C., preferably 0 ° C. to 80 ° C., more preferably 10 ° C. to 60 ° C. Usually, the reaction proceeds (exotherms) at room temperature, and a complex is formed.
  • Use amount of polycarboxylic acid anhydride or carboxylic acid having a functional group reactive with an epoxy group or hydroxyl group in the molecule in the case of polycarboxylic acid anhydride having a plurality of acid anhydride groups in the molecule,
  • the number of moles of the anhydride group is usually 0.1 to 10 moles, preferably 0.5 to 5 moles, more preferably 0.7 to 3 moles per mole of Group 4 metal alkoxide of the periodic table. Particularly preferred is 0.8 to 1.5 mol.
  • the amount used is too large, the reactivity of the sol-gel reaction of the Group 4 metal alkoxide of the periodic table tends to decrease too much, and further the blending ratio of other components such as the Group 4 metal component and epoxy compound component of the periodic table is lowered. It is not preferable.
  • the amount is too small, the reactivity of the sol-gel reaction of the periodic table group 4 metal alkoxide is not so suppressed, and in any case, the curing reaction of the epoxy compound and the sol-gel reaction of the periodic table group 4 metal alkoxide It tends to be difficult to react at the same reaction rate.
  • the acid anhydride group of the polyvalent carboxylic acid anhydride combines with the Group 4 metal of the Periodic Table to form a metal carboxylate, It couple
  • a group 4 metal alkoxide of the periodic table is reacted with a carboxylic acid having a functional group reactive with an epoxy group or a hydroxyl group in the molecule, the carboxyl group of the carboxylic acid is bonded to the group 4 metal of the periodic table to form a metal carboxyl.
  • a rate is formed, and the alkoxy group of the group 4 metal alkoxide is eliminated as an alcohol.
  • a partially modified group 4 metal alkoxide in which a part of the alkoxy group of the group 4 metal alkoxide is substituted is produced (see the reaction scheme described later).
  • the partially modified periodic table group 4 metal alkoxide thus obtained may be purified and subjected to reaction with the epoxy compound (B), but the periodic table group 4 metal alkoxide and the polyvalent carboxylic acid anhydride or epoxy in the molecule
  • a reaction mixture (reaction mixture) with a carboxylic acid having a reactive functional group with respect to a group or a hydroxyl group may be directly subjected to a reaction with the epoxy compound (B).
  • a carboxylic acid having an epoxy group or a hydroxyl group may be present therein.
  • a polycarboxylic acid anhydride that does not form a partially modified product or a carboxylic acid having an epoxy group or a hydroxyl group in the molecule is based on the polycarboxylic acid anhydride and the epoxy group or hydroxyl group in the molecule.
  • Carboxylic acid having a reactive functional group (partially modified periodic table Group 4 metal alkoxides are also polyfunctional carboxylic acid anhydrides reacted with Group 4 metal alkoxides, reactive functional groups for epoxy groups or hydroxyl groups in the molecule)
  • Epoxide group of epoxy compound (B) used in the reaction in the total amount.
  • 0.5 to 5 mol desirably in an amount preferably comprised from 0.8 to 3 moles, more preferably 1 to 1.5 mol.
  • the epoxy compound (B) includes an epoxy compound having an aromatic ring and an epoxy group in the molecule, an epoxy compound having an alicyclic ring (aliphatic carbocycle) and an epoxy group in the molecule (however, no aromatic ring), and There are epoxy compounds that do not have aromatic and alicyclic rings in the molecule. In the present invention, any of these epoxy compounds can be used.
  • the epoxy compound may be a monofunctional epoxy compound having only one epoxy group in the molecule, or may be a polyfunctional epoxy compound having two or more epoxy groups in the molecule.
  • An epoxy compound can be used individually or in combination of 2 or more types. It is preferable to use at least a polyfunctional epoxy compound as the epoxy compound.
  • examples of the aromatic ring include a benzene ring, a biphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring, a stilbene ring, a dibenzothiophene ring, and a carbazole ring.
  • the aromatic ring is preferably one containing at least an aromatic carbocyclic ring.
  • epoxy compounds having an aromatic ring and an epoxy group in the molecule include, for example, epibis type glycidyl obtained by condensation reaction of bisphenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol and epihalohydrin.
  • epibis type glycidyl ether type obtained by addition reaction of ether type epoxy resins and these epibis type glycidyl ether type epoxy resins with bisphenols such as bisphenol A, bisphenol F, bisphenol S and fluorene bisphenol.
  • Epoxy resin for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, etc.
  • phenol, cresol, xyleno Polyphenols obtained by the condensation reaction of phenols such as resorcinol, catechol, bisphenol A, bisphenol F, bisphenol S and aldehydes such as formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, salicylaldehyde, etc., and further condensed with epihalohydrin
  • Novolak type epoxy resin phenol novolak type epoxy resin, cresol novolak type epoxy resin, novolak alkyl type glycidyl ether type epoxy resin, tricyclo [5.2.1.0 2,6 ] decane ring obtained by reacting Phenol (or cresol) novolac type epoxy resin and the like.
  • Preferred examples of the epoxy compound having an aromatic ring and an epoxy group in the molecule include compounds represented by the following formulas (B-1), (B-2), and (B-3).
  • r represents a number from 0 to 8. r is preferably in the range of 0.01 to 1, more preferably in the range of 0.02 to 0.5.
  • an epoxy compound having an alicyclic ring and an epoxy group in the molecule (but not having an aromatic ring)
  • an epoxy group (alicyclic epoxy) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring.
  • glycidyl ether type epoxy compounds having an alicyclic ring and a glycidyl ether group, and the like.
  • alicyclic ring examples include monocyclic alicyclic rings such as cyclopentane ring, cyclohexane ring, cyclooctane ring, and cyclododecane ring (3 to 15-membered, preferably about 5 to 6-membered cycloalkane ring); Hydronaphthalene ring), perhydroindene ring (bicyclo [4.3.0] nonane ring), perhydroanthracene ring, perhydrofluorene ring, perhydrophenanthrene ring, perhydroacenaphthene ring, perhydrophenalene ring, norbornane Ring (bicyclo [2.2.1] heptane ring), isobornane ring, adamantane ring, bicyclo [3.3.0] octane ring, tricyclo [5.2.1.0 2,6 ] decane ring, tricyclo [6 .2.1.0 2,
  • Examples of the alicyclic epoxy group include an epoxycyclopentyl group, a 3,4-epoxycyclohexyl group, and a 3,4-epoxytricyclo [5.2.1.0 2,6 ] decane 8- (or 9) yl.
  • a substituent such as an alkyl group such as a methyl group may be bonded to the cyclohexane ring.
  • alicyclic epoxy compound having the alicyclic epoxy group a compound represented by the following formula (B-4) (a compound in which two alicyclic epoxy groups are bonded by a single bond or via a linking group) is used. Can be mentioned.
  • Y 1 represents a single bond or a linking group.
  • the linking group include a divalent hydrocarbon group, a carbonyl group (—CO—), an ether bond (—O—), an ester bond (—COO—), an amide bond (—CONH—), and a carbonate bond (— OCOO-) and a group in which a plurality of these are bonded.
  • divalent hydrocarbon group examples include linear or branched alkylene groups such as methylene, ethylidene, isopropylidene, ethylene, propylene, trimethylene, and tetramethylene groups (for example, C 1-6 alkylene groups); Divalent alicyclic rings such as 2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, and cyclohexylidene groups Examples thereof include a group represented by the formula hydrocarbon group (particularly a divalent cycloalkylene group);
  • t is an integer of 1-30.
  • alicyclic epoxy compound there are two adjacent carbon atoms and oxygen having an alicyclic ring and two or more epoxy groups in the molecule, and only one of the two or more epoxy groups forms the alicyclic ring.
  • the compound which is an epoxy group (alicyclic epoxy group) comprised with an atom is mentioned. This representative compound (limonene diepoxide) is shown below.
  • an alicyclic epoxy compound it has only one alicyclic epoxy group which has 3 or more alicyclic epoxy groups as shown below, and an alicyclic epoxy group, and does not have an epoxy group in others.
  • An alicyclic epoxy compound can also be used.
  • a, b, c, d, e, and f are integers from 0 to 30.
  • Examples of the epoxy compound in which an epoxy group is directly bonded to the alicyclic ring with a single bond include a compound represented by the following formula (B-5).
  • R 3 is a group obtained by dividing q OH from q-valent alcohol [R 3- (OH) q ], p is an integer of 1 to 30, and q is an integer of 1 to 10. In the groups in q parentheses, p may be the same or different.
  • q-valent alcohol [R 3- (OH) q ] monovalent alcohols such as methanol, ethanol, 1-propanol, isopropyl alcohol, 1-butanol; ethylene glycol, 1,2-propanediol, 1,3 -Divalent alcohols such as propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polypropylene glycol; glycerin, diglycerin, Examples include trihydric or higher alcohols such as erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol.
  • the alcohol may be polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, or the like.
  • the alcohol is preferably an aliphatic alcohol having 1 to 10 carbon atoms (particularly an aliphatic polyhydric alcohol such as trimethylolpropane).
  • Examples of the glycidyl ether type epoxy compound having an alicyclic ring and a glycidyl ether group include glycidyl ethers of alicyclic alcohols (particularly, alicyclic polyhydric alcohols).
  • This compound has an aromatic ring of an epoxy compound having an aromatic ring and an epoxy group in the molecule [for example, a compound represented by the formula (B-1), (B-2), (B-3)] as a nucleus. It may be a hydrogenated compound.
  • Examples of the glycidyl ether type epoxy compound having an alicyclic ring and a glycidyl ether group include the following compounds.
  • Examples of the epoxy compound having no aromatic ring and alicyclic ring in the molecule include, for example, glycidyl ether of the q-valent alcohol [R 3- (OH) q ]; acetic acid, propionic acid, butyric acid, stearic acid, adipic acid, Glycidyl esters of mono- or polyvalent carboxylic acids such as sebacic acid, maleic acid, itaconic acid; epoxidized products of fats and oils having double bonds such as epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil; epoxidized polybutadiene, etc. And epoxidized products of polyolefins (including polyalkadienes).
  • the curable composition of the present invention preferably contains a curing accelerator in order to accelerate the curing of the epoxy compound.
  • the curing accelerator is not particularly limited as long as it is used for accelerating the curing of the epoxy compound.
  • a diazabicycloundecene-based curing accelerator (1,8-diazabicyclo [5.4.0] undecene-7 is used.
  • DBU dimethylbenzyldimethylamine
  • 2,4,6-tris dimethylaminomethyl phenol
  • 2-ethyl-4-methylimidazole 1-cyanoethyl-2-ethyl-4- Imidazoles
  • organic phosphine compounds such as triphenylphosphine, tertiary amine salts, quaternary ammonium salts, quaternary phosphonium salts, organometallic salts such as tin octylate, dibutyltin dilaurate, and zinc octylate, boron compounds Etc.
  • a hardening accelerator can be used individually or in combination of 2 or more types.
  • an organic phosphine compound a quaternary phosphonium salt, a tin salt such as dibutyltin dilaurate, and a zinc salt such as zinc octylate are preferable from the viewpoint of preventing coloring of the cured product.
  • a combination of a quaternary phosphonium salt and a tin salt is particularly preferable.
  • the blending amount of the curing accelerator is, for example, 0.01 to 15 parts by weight, preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 8 parts by weight with respect to 100 parts by weight of the epoxy compound (B). It is. When the blending amount of the curing accelerator is too small, the curing accelerating effect may be insufficient, and when it is too large, the hue in the cured product may be deteriorated.
  • Partially modified periodic table group 4 metal alkoxide (A), epoxy compound (B), and curing accelerator may be mixed immediately before use and subjected to a curing reaction, but the above three components were mixed in advance.
  • a mixed solution may be prepared.
  • the curable composition of the present invention is advantageous for industrial production, which is stable even when the above three components are mixed and can be stored for a long period of time.
  • the curable composition of the present invention may be configured as a two-component composition, for example, as described in (1) to (2) below.
  • additives may be added to the curable composition of the present invention as necessary.
  • the additive include organosiloxane compounds, metal oxide particles, rubber particles, silicone-based and fluorine-based antifoaming agents, silane coupling agents, fillers, plasticizers, leveling agents, antistatic agents, and mold release agents.
  • the compounding quantity of these various additives is 5 weight% or less with respect to the whole curable composition, for example.
  • the curable composition of the present invention may contain a solvent, but if the amount of the solvent is too large, bubbles may be formed in the cured resin, preferably 10% by weight or less based on the entire curable composition, In particular, it is 1% by weight or less.
  • An epoxy resin-inorganic polymer composite material can be obtained by curing the curable composition of the present invention. For example, water is added to and mixed with a mixed solution of a modified group 4 metal alkoxide (A), epoxy compound (B) and a curing accelerator, and heated to 50 to 100 ° C. under reduced pressure as necessary. After removing the by-products, the epoxy resin-inorganic polymer composite material can be produced by, for example, heat curing at 60 to 250 ° C. (preferably 80 to 220 ° C.) under normal pressure. In addition, when water is contained in the solution containing the epoxy compound (B) and the curing accelerator used for blending, it is not necessary to add water again.
  • the amount of water used to advance the sol-gel reaction of the group 4 metal alkoxide (A) of the partially modified periodic table is, for example, 1 to 10 per 1 mol of the group 4 metal alkoxide (A) of the partially modified periodic table. Mol, preferably 1.5 to 5 mol, more preferably 1.5 to 3 mol. If the amount of water is too small, the sol-gel reaction will not proceed smoothly. Conversely, if the amount is too large, the polymerization of the metal oxide will not proceed and the degree of polymerization will decrease, or the crosslinking between the metal oxides will not proceed. In addition to the formation of a component network, the affinity with the epoxy component is deteriorated and it becomes difficult to obtain a homogeneous cured product, and it takes time and labor to dry in a subsequent process.
  • reaction is considered to proceed according to the following formula (Reaction Scheme 1).
  • a partially modified group 4 metal alkoxide is prepared from cis-1,2-cyclohexanedicarboxylic acid anhydride, which is a polyvalent carboxylic acid anhydride, and zirconium tetra-n-propoxide.
  • water and a curing accelerator are further added and cured by heating.
  • R represents an n-propyl group.
  • cis-1,2-cyclohexanedicarboxylic anhydride (2) and zirconium tetra-n-propoxide (3) react to form a partially modified periodic table 4 group metal alkoxide represented by the formula (4). Generate.
  • the reactivity of the zirconium alkoxide is controlled by the chelate coordination of the acid anhydride with zirconium.
  • the sol-gel reaction gradually proceeds to produce a three-dimensionally crosslinked zirconia (inorganic polymer) (5), and the acid anhydride [cis-1,2-cyclohexane released in a ring-opened state]
  • the dicarboxylic acid monopropyl ester (6)] acts as a curing agent for the epoxy compound (7) to produce a cured epoxy resin (8).
  • the hydroxyl group in the cured epoxy resin (8) produced by the ring opening of the epoxy group undergoes a transesterification reaction with the ester moiety (—COOR) of the other cured epoxy resin (8), whereby the resin of the formula (9) And an epoxy resin-inorganic polymer hybrid material having a dense cross-linked structure is formed.
  • alcohol (10) is by-produced. That is, the compound (coordination compound) released from the group 4 metal alkoxide of the partially modified periodic table functions as a crosslinking agent for the epoxy resin.
  • the partially modified periodic table 4 group metal alkoxide (4) has the periodic table 4 group metal (zirconium in the above case) chelate coordinated as a carboxylate, and at the ligand site. If it has a functional group reactive to the epoxy group of the epoxy compound or the hydroxyl group generated by ring opening of the epoxy group, it acts as a curing agent for the epoxy compound when the coordination compound is released. In addition, it acts as a crosslinking agent for epoxy resins.
  • the compound used for the modification of the group 4 metal alkoxide of the periodic table is not limited to the polyvalent carboxylic acid anhydride, and a carboxylic acid having a reactive functional group with respect to an epoxy group or a hydroxyl group in the molecule may also be used. it can.
  • a partially modified periodic table group 4 metal alkoxide is prepared from polydodecanedioic acid polyanhydride, which is a polyvalent carboxylic acid anhydride, and zirconium tetra-n-propoxide, and this is added to the epoxy compound, and further water and a curing accelerator are added.
  • reaction Scheme 2 the reaction scheme in the case of heat curing is shown in the following formula (Reaction Scheme 2).
  • R represents an n-propyl group.
  • polydodecanedioic acid polyanhydride (11) and zirconium tetra-n-propoxide (3) react to produce a partially modified periodic table 4 group metal alkoxide represented by formula (12) (circle Number 1).
  • the generated compound represented by the formula (12) reacts with zirconium tetra-n-propoxide (3).
  • the compound represented by the formula (12) reacts with the zirconium tetra-n-propoxide (3) at the position of the circled numeral 2
  • the partially modified periodic table group 4 metal alkoxide represented by (14) is generated.
  • the sol-gel reaction gradually proceeds in the presence of water to produce three-dimensionally cross-linked zirconia (inorganic polymer). (17) serves as a curing agent for the epoxy compound (7), and a cured epoxy resin (18) is produced.
  • the hydroxyl group in the cured epoxy resin (18) produced by the ring opening of the epoxy group undergoes a transesterification reaction with the ester moiety (—COOR) of the other cured epoxy resin (19), whereby the resin of the formula (20) And an epoxy resin-inorganic polymer hybrid material having a dense cross-linked structure is formed.
  • alcohol (ROH) is by-produced as described above. That is, the compound (coordination compound) released from the group 4 metal alkoxide of the partially modified periodic table functions as a crosslinking agent for the epoxy resin.
  • the inorganic fine particles are not aggregated, and the homogeneous epoxy resin-inorganic polymer composite material [epoxy resin-inorganic polymer composite composed of a cured epoxy resin and a Group 4 metal oxide of the periodic table] Material (hybrid material)] can be obtained. Moreover, since a curing reaction can be carried out without using an amine-based curing agent or a nitrogen-containing epoxy resin curing agent, an epoxy resin-inorganic polymer composite material having a very small degree of coloring can be produced.
  • group 4 metal oxide of the periodic table and “inorganic fine particles composed of group 4 metal oxide of the periodic table” are composed of a compound composed only of a group 4 metal of the periodic table and an oxygen atom, and the compound. Not only fine particles, but also hydroxyl group, alkoxyl group (such as OR 1 group), ester group [polyhydric carboxylic acid anhydride used for preparation of partially modified periodic table 4 group metal alkoxide (A), or epoxy group or hydroxyl in the molecule A polymer having a metal-metal bond that is continuously bonded or cross-linked via an oxygen atom, and fine particles made of the polymer. Use for meaning.
  • an epoxy resin-inorganic polymer composite material in which inorganic fine particles made of a group 4 metal oxide of the periodic table are uniformly dispersed in a cured epoxy resin.
  • This inorganic fine particle is obtained by in-situ polymerization, unlike particles in which individual fine particles prepared separately are dispersed before curing of the epoxy resin, so that the interface between the inorganic component and the organic component is so clear.
  • the particles may be connected by a chain of inorganic components, and the inorganic-organic component is well-matched.
  • the average particle size of the inorganic fine particles in the epoxy resin-inorganic polymer composite material is, for example, 1 to 50 nm, preferably 1 to 20 nm, particularly preferably 1 to 5 nm.
  • the average particle size of the inorganic fine particles can be obtained by taking a transmission electron micrograph (TEM), measuring the particle size (average value of major axis and minor axis) of 50 particles, and averaging the results.
  • TEM transmission electron micrograph
  • Epoxy resins of the present invention - the content of the inorganic polymeric inorganic fine particles comprising the periodic table Group 4 metal oxide composite material, which can be appropriately set depending on the application, typically, MO 2 (M is Group 4 of the periodic table metal atom 2% by weight or more (for example, 2 to 90% by weight), preferably 5% by weight or more (for example, 5 to 80% by weight), more preferably 10% by weight or more (for example, 10 to 60% by weight). %). If the content of the inorganic fine particles is too small, the refractive index tends to decrease, and conversely if it is too large, it tends to be brittle.
  • MO 2 is Group 4 of the periodic table metal atom 2% by weight or more (for example, 2 to 90% by weight), preferably 5% by weight or more (for example, 5 to 80% by weight), more preferably 10% by weight or more (for example, 10 to 60% by weight).
  • the light transmittance of the epoxy resin-inorganic polymer composite material is, for example, in the range of 400 to 800 nm, 82% or more.
  • the refractive index (wavelength 589 nm) of the epoxy resin-inorganic polymer composite material is, for example, 1.54 or more, preferably 1.58 or more.
  • the content of inorganic fine particles composed of a Group 4 metal oxide of the periodic table in the epoxy resin-inorganic polymer composite material is converted into MO 2 (M represents a Group 4 metal atom of the Periodic Table).
  • MO 2 represents a Group 4 metal atom of the Periodic Table.
  • the fact that the epoxy resin-inorganic polymer composite material has a homogeneous phase structure (or that it is compatible at the molecular level) is a phenomenon such as particles having a strong luminance difference in a transmission electron microscope (TEM) photograph. It can be seen from the fact that no nano-level structure is observed, for example, there are no particles having a particle size of 1 nm or more in the range of 10 nm ⁇ 10 nm (for example, 10 particles or less). However, sample preparation, transmission electron microscope (TEM) photography conditions, resolution, and errors of the instrument must be taken into consideration.
  • TEM transmission electron microscope
  • the content of the periodic table group 4 metal oxide is 19% by weight or more in terms of MO 2 (M represents a periodic table group 4 metal atom). Is preferred. Moreover, it is preferable from the viewpoint of suppressing coloring that the cured epoxy resin is formed without using an amine-based curing agent, particularly an amine-based curing agent and other nitrogen-containing epoxy resin curing agents.
  • An epoxy resin-inorganic polymer composite material having a homogeneous phase structure has an extremely high refractive index, a high density and a high specific gravity, and is extremely excellent in heat conduction characteristics, thermal expansion characteristics, and mechanical characteristics.
  • the epoxy resin-inorganic polymer composite material of the present invention is homogeneous and excellent in transparency, has good optical properties such as high refractive index and low Abbe number, high density and high specific gravity, and heat conduction properties. Because of its excellent thermal expansion and mechanical properties, it can be used as a coating agent for electrical / electronic materials, molding materials, paints, adhesive materials, sealing materials, lens materials, optical fibers, optical waveguides, optical filters, optical disk substrates, etc. It is useful, and is particularly useful in the fields of LEDs, lenses, solar cells, etc. that require a high refractive index, particularly in the field of optical members.
  • n 1 represents the carbon number of the alkylene chain of the long-chain dibasic acid (the number obtained by subtracting 2 from the carbon number of the long-chain dibasic acid).
  • Example 1 (Preparation of HHPA-modified zirconium alkoxide) Zirconium (IV) tetra n-propoxide [Zr (OCH 2 CH 2 CH 3 ) 4 ] (STREM CHEMICALS, molecular weight 327.56) 0.77 g [weight of zirconium (IV) tetra n-propoxide itself] Cis-1,2-cyclohexanedicarboxylic anhydride represented by the following formula (manufactured by ACROS ORGANICS, molecular weight 154.16) (hereinafter abbreviated as “HHPA”) 2.49 g (for the epoxy resin used in Example 7) Chemical equivalents) were mixed under a nitrogen atmosphere and stirred at room temperature for 1 hour to obtain a modified zirconium alkoxide (hereinafter abbreviated as “HHPA-modified zirconium alkoxide”).
  • HHPA modified zirconium alkoxide
  • Example 2 (Preparation of HHPA-modified zirconium alkoxide) HHPA-modified zirconium alkoxide was obtained in the same manner as in Example 1 except that the amount of zirconium (IV) tetra-n-propoxide used was 1.62 g.
  • Example 3 (Preparation of HHPA-modified zirconium alkoxide) HHPA-modified zirconium alkoxide was obtained in the same manner as in Example 1 except that the amount of zirconium (IV) tetra-n-propoxide used was 2.58 g.
  • Example 4 (Preparation of HHPA-modified zirconium alkoxide) HHPA-modified zirconium alkoxide was obtained in the same manner as in Example 1 except that the amount of zirconium (IV) tetra-n-propoxide used was 3.66 g.
  • Example 5 (Preparation of HHPA-modified zirconium alkoxide) HHPA-modified zirconium alkoxide was obtained in the same manner as in Example 1 except that the amount of zirconium (IV) tetra n-propoxide was 4.87 g.
  • Example 6 (Preparation of HHPA-modified zirconium alkoxide) An HHPA-modified zirconium alkoxide was obtained in the same manner as in Example 1 except that zirconium (IV) tetra-n-propoxide and HHPA were used in a molar ratio of 1: 1.
  • FIG. 1 shows FT-IR spectra of zirconium (IV) n-propoxide and HHPA used as raw materials and the obtained HHPA-modified zirconium alkoxide.
  • Example 7 (Production of epoxy resin-zirconia hybrid material) Bisphenol A diglycidyl ether type epoxy resin from which water has been sufficiently removed by defoaming at 80 ° C. for 2 hours (trade name “JER 828EL”, manufactured by Japan Epoxy Resin Co., Ltd., weight average molecular weight 370, see the following formula) Weigh 3.00 g (abbreviated as “DGEBA”), add 1 phr of quaternary phosphonium bromide (epoxy curing accelerator; manufactured by San Apro Co., Ltd.) and 3 phr of dibutyltin dilaurate on a hot plate set at 120 ° C. And dissolved with stirring.
  • DGEBA dibutyltin dilaurate
  • the carboxylic acid-modified zirconium alkoxide prepared in Example 1 and 2-fold mol of distilled water were added to the zirconium alkoxide, and the mixture was stirred for 5 minutes with a rotation / revolution rotary mixer.
  • the mixed solution was poured into an aluminum cup and heated at 80 ° C. for 1 hour under reduced pressure in order to remove by-products.
  • the epoxy resin-zirconia hybrid material (DGEBA / HHPA / zirconia hybrid system) [zirconia (100 ° C, 4 hours, 130 ° C, 4 hours, 150 ° C, 4 hours, 180 ° C, 4 hours) is cured by heating under normal pressure. ZrO 2 ) content 5 wt%].
  • DGEBA / HHPA / zirconia hybrid system [zirconia (100 ° C, 4 hours, 130 ° C, 4 hours, 150 ° C, 4 hours, 180 ° C, 4 hours) is cured by heating under normal pressure.
  • Example 8 (Production of epoxy resin-zirconia hybrid material) An epoxy resin-zirconia hybrid material (DGEBA / HHPA / DGEBA / HHPA) was prepared in the same manner as in Example 7 except that the HHPA-modified zirconium alkoxide prepared in Example 2 was used instead of the HHPA-modified zirconium alkoxide prepared in Example 1. A zirconia hybrid system (zirconia content: 10% by weight) was obtained. In the obtained epoxy resin-zirconia hybrid material, there was no precipitation of zirconia and it was colorless and transparent.
  • Example 9 (Production of epoxy resin-zirconia hybrid material) An epoxy resin-zirconia hybrid material (DGEBA / HHPA / DGEBA / HHPA / HHPA) was prepared in the same manner as in Example 7 except that the HHPA-modified zirconium alkoxide prepared in Example 3 was used instead of the HHPA-modified zirconium alkoxide prepared in Example 1. A zirconia hybrid system (zirconia content: 15% by weight) was obtained. In the obtained epoxy resin-zirconia hybrid material, there was no precipitation of zirconia and it was colorless and transparent.
  • Example 10 (Production of epoxy resin-zirconia hybrid material) An epoxy resin-zirconia hybrid material (DGEBA / HHPA / DGEBA / HHPA / HHPA / HHPA / HHPA) was prepared in the same manner as in Example 7 except that the HHPA-modified zirconium alkoxide prepared in Example 4 was used instead of the HHPA-modified zirconium alkoxide prepared in Example 1. A zirconia hybrid system (20% by weight of zirconia content) was obtained. In the obtained epoxy resin-zirconia hybrid material, there was no precipitation of zirconia and it was colorless and transparent.
  • Example 11 (Production of epoxy resin-zirconia hybrid material) An epoxy resin-zirconia hybrid material (DGEBA / HHPA / DGEBA / HHPA / HHPA / HHPA / HHPA) was prepared in the same manner as in Example 7 except that the HHPA-modified zirconium alkoxide prepared in Example 5 was used instead of the HHPA-modified zirconium alkoxide prepared in Example 1. A zirconia hybrid system (zirconia content 25% by weight) was obtained. In the obtained epoxy resin-zirconia hybrid material, there was no precipitation of zirconia and it was colorless and transparent.
  • Comparative Example 1 A cured epoxy resin was obtained in the same manner as in Example 7 except that carboxylic acid-modified zirconium alkoxide and water were not used, and 2.49 g of HHPA was used instead.
  • Evaluation test (1) FT-IR measurement
  • a Fourier transform infrared absorption device (FT-IR SPECTRUM ONE, manufactured by PERKIN ELMER) was used, and KBr method was used. Samples were measured. The KBr plate was formed into a disk shape by pressing about 0.2 g of powdered KBr (Merck KGaA). Further, the HHPA-modified zirconium alkoxide, which is a liquid sample, was measured by sandwiching a small amount of sample between two KBr plates in order to avoid contact with air.
  • FT-IR SPECTRUM ONE manufactured by PERKIN ELMER
  • the DGEBA / HHPA / zirconia hybrid system of a solid sample was measured by mixing a small amount of a sample powdered with a metal mortar into a KBr plate. Measurement range 400cm -1 ⁇ 5000cm -1, resolution 4.0 cm -1, and the number of integration 4 times.
  • the increase / decrease rate of each functional group of the DGEBA / HHPA / zirconia hybrid system is the peak area with the peak due to the C—H out-of-plane bending vibration of the p-disubstituted benzene ring near 830 cm ⁇ 1 as the reference peak. It calculated from the relative ratio of the peak area of each functional group to.
  • FIG. 1 shows FT-IR spectra of zirconium (IV) tetra n-propoxide, HHPA, and the resulting HHPA-modified zirconium alkoxide used as raw materials in Example 6.
  • FIG. 2 shows the composition before curing of Comparative Example 1 (first from the top), the epoxy resin after curing of Comparative Example 1 (second from the top), and the composition before curing of Example 9 (from the top). 3rd) and the FT-IR spectrum of the epoxy resin-zirconia hybrid material (DGEBA / HHPA / zirconia hybrid system) after curing in Example 9 (fourth from the top).
  • ruthenium staining was performed by dropping 3 drops of an aqueous ruthenium tetroxide solution (TAAB (UK), concentration 0.5%) into a 5 ml sample tube for 2 minutes in vaporized ruthenium tetroxide. Staining was performed.
  • TAAB aqueous ruthenium tetroxide solution
  • FIG. 5 the transmission electron microscope (TEM) photograph of the material (DGEBA / HHPA single system) which consists only of the epoxy resin obtained by the comparative example 1 is shown.
  • the sample piece is a substantially single color part existing from the upper part to the lower right part, and the part that appears brighter in the lower left part is not a sample.
  • FIG. 6 shows a transmission electron microscope (TEM) photograph of the epoxy resin-zirconia composite material (DGEBA / HHPA / zirconia hybrid system, zirconia content 10 wt%) obtained in Example 8, and FIG. Transmission electron microscope (TEM) photograph of the obtained epoxy resin-zirconia composite material (DGEBA / HHPA / zirconia hybrid system, zirconia content 15 wt%), FIG.
  • TEM transmission electron microscope
  • Example 8 shows the epoxy resin-zirconia composite material obtained in Example 10 Transmission electron microscope (TEM) photograph of (DGEBA / HHPA / zirconia hybrid system, zirconia content 20% by weight), epoxy resin-zirconia composite material obtained in Example 11 in FIG. 9 (DGEBA / HHPA / zirconia hybrid system, Transmission electron microscope (TEM) with a zirconia content of 25% by weight It shows a photograph.
  • the sample piece is a colored portion including black particles existing from the upper right part to the lower left side, and appears brighter than that seen in the lower part or the periphery thereof. The part is not a sample.
  • the sample piece is a portion that appears slightly gray from the upper left to the lower right, and is brighter than that seen from the lower to the right. The visible part is not a sample.
  • the sample pieces of the epoxy resin-zirconia composite material obtained in Examples 10 and 11 have luminance intensity modulation due to the convenience of preparation, but zirconia fine particles are not observed, and are composed of a cured epoxy resin and zirconia.
  • the average luminance (A) of the colored (black) particles present in FIG. 6 (Example 8; zirconia 10% by weight) is set to “0”, and the average of the area outside (1 nm to 2 nm).
  • the luminance recognition threshold is “186”
  • FIG. 8 Example 10; zirconia 20% by weight
  • FIG. Example 11 zirconia 25% by weight
  • no contrast exceeding the threshold was measured within 10 nm (no shape was observed) and was present in the sample of FIG. 6 having a zirconia content of 10% by weight.
  • the fine particles having a particle diameter of 5 nm disappear even though the zirconia content is increased to 20% by weight and 25% by weight, and the organic-inorganic polymer is not localized in the entire cured product. It is shown that was compatible to. Further, in FIG. 8 and FIG. 9, if fine particles having the same contrast as in FIG. 6 are present, the resolution is about 0.5 nm, so that the particle diameter is at least 1 nm or more. Since it can be recognized as a TEM image having a similar luminance difference, it can be said that the samples of FIGS. 8 and 9 do not have zirconia fine particles of 1 nm or more. In addition, when the organic-inorganic polymer is compatible with each other, there is no particle having a large particle size. That is, the macro level (10nm 2 -100nm 2) granules or grain size 5nm is 10 or less at, 100 nm 2 or more areas in the particle size 50nm or more of the particles is 10 or less.
  • UV-visible absorption spectrum measurement For the examination of light transmittance at each wavelength of the DGEBA / HHPA / zirconia hybrid system, an ultraviolet-visible spectrophotometer (LAMBDA 650, manufactured by PERKIN ELMER) was used as an ultraviolet-visible absorption spectrum measurement. , Measured by reflectance. The sample used for the measurement was measured by putting a fine powder in an agate mortar in a powder folder (the thickness of the sample at the time of measurement is 2 mm). The measurement conditions were a measurement range of 800 to 250 nm, a band width of 2.0 nm, a scanning speed of 266.75 nm / min, a data capture interval of 1.0 nm, and a repeat count of once.
  • Example 3 epoxy resin after curing of Comparative Example 1 (a in the figure), epoxy resin after curing of Example 8—zirconia hybrid material (b in the figure), and epoxy resin after curing of Example 9—
  • the ultraviolet-visible absorption spectrum of the zirconia hybrid material (c in the figure) and the epoxy resin-zirconia hybrid material after curing in Example 10 (d in the figure) is shown.
  • the vertical axis represents transmittance (%), and the horizontal axis represents wavelength (nm).
  • the light transmittance of the epoxy resin-zirconia hybrid material obtained in the example was 82% or more in the range of 400 to 800 nm.
  • the refractive index of the GEBA / HHPA / zirconia hybrid system was measured using a refractive index measuring device (NAR-2T, manufactured by Atago Co., Ltd.).
  • NAR-2T refractive index measuring device
  • the cured product was cut into 8 mm ⁇ 15 mm ⁇ 1 mm rectangular parallelepiped pieces, polished with water-resistant abrasive paper No. 2000, and then polished with an alumina suspension having an average particle size of 0.3 ⁇ m (manufactured by Marumoto Struers Co., Ltd.). What was done was used.
  • FIG. 4 shows the refractive index of the epoxy resin after curing in Comparative Example 1 and the epoxy resin-zirconia hybrid material after curing in Examples 7 to 10 (DGEBA / HHPA / zirconia hybrid system) along with the zirconia content (% by weight).
  • the graph plotted on the axis is shown.
  • the vertical axis represents the refractive index (589 nm). As shown in FIG.
  • the refractive index increases linearly as the zirconia content in the epoxy resin-zirconia hybrid material increases (in the range of 0 to 20% by weight). 591. This is considered to be due to an increase in the molecular refraction and density of the hybrid material by increasing the zirconia network having a high density and polarizability as the zirconia content increases.
  • quaternary phosphonium bromide epoxy curing accelerator
  • FT-IR Measurement For structural analysis of long chain dibasic acid anhydride modified zirconium alkoxide and DGEBA / long chain dibasic acid anhydride / zirconia hybrid system, Fourier transform infrared absorption device (FT-IR SPECTRUM ONE) , Manufactured by PERKIN ELMER) and the sample was measured by the KBr method.
  • the KBr plate was formed into a disk shape by pressing about 0.2 g of powdered KBr (Merck KGaA).
  • the long-chain dibasic acid anhydride-modified zirconium alkoxide which is a liquid sample
  • the DGEBA / long-chain dibasic acid anhydride / zirconia hybrid system of a solid sample was measured by mixing a small amount of a sample powdered with an agate mortar into a KBr plate. Measurement range 400cm -1 ⁇ 5000cm -1, resolution 4.0 cm -1, and the number of integration 4 times.
  • the rate of increase / decrease of each functional group of the DGEBA / long-chain dibasic acid anhydride / zirconia hybrid system is determined by taking the peak due to the in-plane skeletal vibration of the benzene ring near 1510 cm ⁇ 1 as the reference peak, It calculated from the relative ratio of the peak area of a functional group.
  • the FT-IR spectrum is shown.
  • (a) shows a long-chain dibasic acid anhydride and (b) shows a zirconium alkoxide.
  • (a) shows a long-chain dibasic acid anhydride and (b) shows a zirconium alkoxide.
  • the peak due to the Zr-OR bond near 1140 cm ⁇ 1 of zirconium (IV) n-propoxide alone decreases after the reaction, and the acid anhydride group near 1810 cm ⁇ 1 of the long-chain dibasic acid anhydride. It was observed that the peak due to the carboxylic acid near 1710 cm ⁇ 1 decreased and the peak due to the ester group near 1741 cm ⁇ 1 increased. This also indicates that zirconium (IV) n-propoxide and a long-chain dibasic acid anhydride react, and an alkoxide group reacts with a carboxylic acid and an acid anhydride group of the long-chain dibasic acid anhydride to form an ester group. (See Scheme 2 above). Moreover, since the wave number interval ⁇ 95 cm ⁇ 1 of the peak caused by the asymmetric stretching vibration of the carboxylate ion and the symmetrical stretching vibration of the same ion, the coordination mode is considered to be chelate coordination.
  • a plate-shaped test piece having approximately the same thickness was placed on a black cross, and the sharpness of the cross was observed.
  • 14 is a photograph of Comparative Example 2
  • FIG. 15 is a photograph of Example 17
  • FIG. 16 is a photograph of Example 18
  • FIG. 17 is a photograph of Comparative Example 3
  • Non-resonant forced vibration type viscoelasticity analyzer (DVE-V4 FT Rheospectr Co., Ltd.) for dynamic viscoelasticity measurement of DGEBA / long-chain dibasic anhydride / zirconia hybrid system. (Manufactured by Rheology) was used in a tensile load mode while changing the temperature. The measurement frequency was 10 Hz, the amplitude was 5 ⁇ m, the temperature increase rate was 20 ° C./min, and the measurement temperature was ⁇ 150 ° C. to 250 ° C. The test piece size was a rectangular parallelepiped shape of 30 mm ⁇ 4 mm ⁇ 0.4 mm. The following formula was used for calculation.
  • cosd (Pa) E ′′
  • Sind (Pa) tand E ′′ / E ′ Sample width: W (cm), sample thickness: T (cm), sample length: CD (cm), dynamic stress: DF (gram), dynamic strain: DD (cm), phase difference: d (Degree), gravitational acceleration: 980.6 (cm / s 2 )
  • the DGEBA / long chain dibasic anhydride system showed lower values than the DGEBA / HHPA system. Furthermore, in the rubbery and glassy forms, the system using the long-chain dibasic acid anhydride showed a lower storage elastic modulus. This is presumably because the mobility of the epoxy network was improved by using a long-chain dibasic acid anhydride having a long alkyl chain. Further, in the system using long-chain dibasic acid anhydrides having different alkyl chains, there was no significant difference in glass transition temperature. This is currently under investigation and it is considered necessary to confirm reproducibility.
  • the storage modulus of the system using a long-chain dibasic acid anhydride having 18 carbon atoms was lower than that having 10 carbon atoms. This is thought to be because the mobility of the epoxy network was further improved due to the longer alkyl chain length.
  • the glass transition temperature decreases with increasing zirconia content, indicating that the long chain dibasic acid anhydride (n 1 18) zirconia is contained. It was observed that the 10 wt% hybrid system showed a lower glass transition temperature than the zirconia non-added system.
  • the ratio of zirconium alkoxide to long chain dibasic acid anhydride is 2: 0.6. Yes, it is 2: 1 in the 15 wt% system, and the curing mechanism varies depending on the content.
  • the ratio of the zirconium alkoxide and the long chain dibasic acid anhydride is close to the equivalent, so compared with the zirconia non-added system, It is considered that the glass transition temperature has decreased.
  • the bending resistance test of the DGEBA / long-chain dibasic acid anhydride / zirconia hybrid system was performed using a type 1 bending test apparatus (cylindrical mandrel method) in accordance with JIS K 5600-5-1. .
  • the test piece was a rectangular parallelepiped of 100 mm ⁇ 50 mm ⁇ 0.3 mm.
  • the test temperature was 25 ° C., and mandrel diameters of 2, 3, 4, 5, 6, 8, 10, 12, 16, 20, 25, and 32 mm were used and bent evenly over 2 seconds.
  • FIG. 21 shows the change in flexibility with increasing zirconia content in the DGEBA / long chain dibasic anhydride / zirconia hybrid system and the DGEBA / HHPA / zirconia hybrid system, and Table 1 shows the detailed results of the flex resistance test. It was.
  • the left figure of FIG. 21 is a measuring apparatus used for the bending resistance test. In Table 1, the case where no crack was observed was indicated by “ ⁇ ”, and the case where a crack was observed was indicated by “X”. “-” Indicates that the test was not performed.
  • the minimum mandrel diameter that can be folded in the zirconia-free system is 8 mm
  • the mandrel diameter was broken at 32 mm, and the flexibility was significantly lowered. This is probably because the zirconia network suppressed the mobility of the epoxy network.
  • the decrease in flexibility due to the addition of zirconia was smaller than that of the DGEBA / HHPA / zirconia hybrid system. This is considered to be because the mobility of the alkyl chain introduced using the long-chain dibasic acid anhydride is difficult to be controlled by the zirconia network, as shown in the previous dynamic viscoelasticity measurement.
  • the refractive index was measured using a refractive index measuring device (NAR-2T, manufactured by Atago Co., Ltd.) as an optical characteristic of the hybrid material.
  • a cured product was cut into a rectangular parallelepiped piece of about 8 mm ⁇ 30 mm ⁇ 1 mm, polished with water-resistant abrasive paper No. 2000, and then polished with alumina. Further, monobromonaphthalene was used as an intermediate solution for measurement, and Na-line monochromatic light (589.3 nm) was used as a light source.
  • FIG. 22 shows the refractive index measurement of the DGEBA / long-chain dibasic acid anhydride / zirconia hybrid system.
  • the refractive index increases from 1.538 to 1 as the zirconia content increases from 0 wt% to 20 wt%. An increase to .567 was observed.
  • the zirconia content becomes 1.525 at 0 wt% and 1.542 at 10 wt%, and the zirconia content increases. The refractive index increased.
  • the refractive index of amorphous zirconia prepared at a low temperature as in the sol-gel method is about 1.8, which is higher than that of organic matter. Therefore, as the zirconia content increases, the zirconia network in the system increases. It is considered that the refractive index is improved when it increases.
  • an epoxy resin-inorganic polymer composite material which is composed of a cured epoxy resin and a Group 4 metal oxide of the periodic table and has a uniform and excellent transparency and a high refractive index, can be simplified. Can be formed.

Abstract

La présente invention a pour objet une composition durcissable contenant : (A) un alcoxyde de métal du groupe 4 partiellement modifié par un acide carboxylique, dont chaque molécule possède un groupe fonctionnel qui réagit avec des groupes hydroxyle ou des groupes époxy, ou un anhydride d'acide carboxylique polyvalent; et (B) un composé époxy. Ledit métal du groupe 4 est de préférence le zirconium ou le titane. L'utilisation de la composition durcissable selon la présente invention facilite la formation d'un matériau composite résine époxy / polymère inorganique homogène qui est hautement transparent, possède un indice de réfraction élevé, et comprend une résine époxy durcie et un oxyde de métal du groupe 4.
PCT/JP2011/061121 2010-05-10 2011-05-09 Composition durcissable, procédé de fabrication d'un matériau composite résine époxy / polymère inorganique utilisant ladite composition durcissable, et matériau composite résine époxy / polymère inorganique WO2011142468A1 (fr)

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CN201180022922.7A CN102906162B (zh) 2010-05-10 2011-05-09 固化性组合物、使用其的环氧树脂-无机高分子复合材料的制造方法及环氧树脂-无机高分子复合材料
KR1020127032056A KR20130108083A (ko) 2010-05-10 2011-05-09 경화성 조성물, 이것을 사용한 에폭시 수지-무기 중합체 복합 재료의 제조 방법, 및 에폭시 수지-무기 중합체 복합 재료

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WO2013151308A1 (fr) * 2012-04-02 2013-10-10 한국생산기술연구원 Composé époxy présentant un groupe alcoxysilyle, composition et matériau durci le comprenant, son utilisation et procédé de préparation du composé époxy présentant un groupe alcoxysilyle
JP2014208798A (ja) * 2013-03-29 2014-11-06 日本化薬株式会社 硬化性樹脂組成物及びガラス繊維を含む硬化物
JP2014227537A (ja) * 2013-05-27 2014-12-08 学校法人 関西大学 硬化性組成物、これを用いたエポキシ樹脂−無機ポリマー複合材料の製造方法及びエポキシ樹脂−無機ポリマー複合材料
JP2015196721A (ja) * 2014-03-31 2015-11-09 大阪瓦斯株式会社 有機無機ハイブリッド材料の製造方法及びエポキシ樹脂組成物
CN113429719A (zh) * 2021-06-29 2021-09-24 李明伟 一种高折射率纳米氧化锆复合树脂及其制备方法
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JP2012087248A (ja) * 2010-10-21 2012-05-10 Nippon Kayaku Co Ltd 硬化性樹脂組成物およびその硬化物
WO2013151308A1 (fr) * 2012-04-02 2013-10-10 한국생산기술연구원 Composé époxy présentant un groupe alcoxysilyle, composition et matériau durci le comprenant, son utilisation et procédé de préparation du composé époxy présentant un groupe alcoxysilyle
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JP2014227537A (ja) * 2013-05-27 2014-12-08 学校法人 関西大学 硬化性組成物、これを用いたエポキシ樹脂−無機ポリマー複合材料の製造方法及びエポキシ樹脂−無機ポリマー複合材料
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US11840601B2 (en) 2019-11-15 2023-12-12 Korea Institute Of Industrial Technology Composition of alkoxysilyl-functionalized epoxy resin and composite thereof
CN113429719A (zh) * 2021-06-29 2021-09-24 李明伟 一种高折射率纳米氧化锆复合树脂及其制备方法

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