WO2022065127A1 - Composition, produit durci, procédé de production associé, élément, composant électronique et fibre - Google Patents

Composition, produit durci, procédé de production associé, élément, composant électronique et fibre Download PDF

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WO2022065127A1
WO2022065127A1 PCT/JP2021/033671 JP2021033671W WO2022065127A1 WO 2022065127 A1 WO2022065127 A1 WO 2022065127A1 JP 2021033671 W JP2021033671 W JP 2021033671W WO 2022065127 A1 WO2022065127 A1 WO 2022065127A1
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group
carbon atoms
polymetalloxane
amine compound
cured product
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PCT/JP2021/033671
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English (en)
Japanese (ja)
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鴨川政雄
諏訪充史
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東レ株式会社
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Publication of WO2022065127A1 publication Critical patent/WO2022065127A1/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
    • 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
    • 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
    • C09D185/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Coating compositions based on derivatives of such polymers
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material

Definitions

  • the present invention relates to a composition, a cured product and a method for producing the same, and members, electronic parts and fibers.
  • a method for patterning an inorganic solid material As a method for patterning an inorganic solid material, a method is known in which a patterned mask is formed on the inorganic solid material to be processed, and the inorganic solid material is patterned by dry etching using the mask.
  • the mask for the pattern is exposed to the etching gas for a long time. Therefore, the mask preferably has high etching resistance.
  • a carbon film As a mask having high etching resistance, generally, a carbon film (for example, see Patent Document 1) deposited by a chemical vapor deposition (CVD) method, a metal oxide HfO 2 , ZrO, etc. 2 , and their silicates (HfSi xOy, ZrSi xOy ), as well as Al2O3 and its composite oxides (Hf 1 -x Al xOy, Zr 1-x Al xOy ) (eg, Zr 1- x Al x Oy ).
  • Non-Patent Document 1) is known. It is known that such a film made of a metal oxide is formed by a vapor phase method such as CVD. However, the vapor phase method such as CVD has a slow film forming rate, and it is difficult to obtain an industrially usable film thickness.
  • a method for forming a film having a metal-oxygen-metal atom bond a method of applying a solution of polymetalloxane having a metal-oxygen-metal atom bond in the main chain and curing the solution to obtain a thin film is available. Proposed.
  • the composition containing polymetalloxane includes a titanoxane and / or zirconoxane condensate having an alkoxy group, a compound having a titanium and / or zirconium coordinating group, and two or more ethylenically unsaturated groups.
  • a composition containing the compound see, for example, Patent Document 4
  • a curable composition containing a silylated polymetalloxane compound and a Si—H binding compound see, for example, Patent Document 5 have been proposed.
  • the method of using the carbon film deposited by the CVD method as described in Patent Document 1 as a mask has a problem that it takes a long time to deposit the carbon film. Further, when processing an inorganic solid material, the dry etching resistance of the carbon film used as a mask is not sufficient, so that the mask is easily scraped and there is a problem that a pattern having a high aspect ratio cannot be processed.
  • An object of the present invention is to provide a composition containing polymetalloxane, which has excellent crack resistance and can form a cured product having a high density.
  • the present invention relates to (A) Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, In, Sn, Sb, Hf, Ta. , W and Bi, a polymetalloxane having a repeating structure of a metal atom and an oxygen atom selected from the group, and (B) an amine compound having a group represented by the following general formula (1).
  • the composition is such that the content of the (B) amine compound in the composition is 1 to 30 parts by weight with respect to 100 parts by weight of (A) polymetalloxane.
  • R 1 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
  • R2 to R5 are independently hydrogen atoms or alkyl groups having 1 to 12 carbon atoms.
  • R 11 to R 14 are independently hydrogen atoms or alkyl groups having 1 to 12 carbon atoms.
  • n is an integer from 0 to 2.
  • the composition of the present invention comprises (A) Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, In, Sn, Sb, It contains a polymetalloxane having a repeating structure of a metal atom selected from the group consisting of Hf, Ta, W and Bi and an oxygen atom (hereinafter, simply referred to as "(A) polymetalloxane").
  • Polymetallosane is a polymer having a repeating structure of a metal atom and an oxygen atom. That is, it is a polymer having a metal-oxygen-metal bond as a main chain.
  • the (A) polymetalloxane used in the present invention has high etching resistance because it has a metal atom having low reactivity with an etching gas or an etching solution when patterning an inorganic solid substance by etching in the main chain. Therefore, the cured product containing the polymetalloxane can be used as a mask when pattern processing an inorganic solid substance by etching.
  • a cured product having high etching resistance can be obtained by applying a composition containing polymetalloxane and an organic solvent on a substrate and heating the substrate.
  • a mask having high etching resistance can be formed without going through a complicated vacuum process such as the CVD method, the process is compared with the method using the carbon film deposited by the conventional CVD method. Simplification is possible.
  • the cured product containing polymetalloxane has higher etching resistance than the above-mentioned carbon film, a desired inorganic solid substance pattern can be formed with a thinner film thickness.
  • (A) polymetalloxane has lower film stress in the heat-treated film than the carbon film. Therefore, when a cured product containing polysiloxane is formed on the inorganic solid material, the stress applied to the substrate and the inorganic solid material can be reduced.
  • the metal atoms contained in the main chain of polymetalloxane are Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, It has a repeating structure of a metal atom selected from the group consisting of In, Sn, Sb, Hf, Ta, W and Bi and an oxygen atom. By including these metal atoms, a mask having high etching resistance can be obtained. More preferably, it is a metal atom selected from the group consisting of Al, Ti, Zr, Hf and Sn. Since metal alkoxide, which is a raw material for synthesizing polymetalloxane, which will be described later, is stably present in these metal atoms, it becomes easy to obtain a high molecular weight polymetalloxane.
  • the weight average molecular weight of the polymetalloxane is preferably 10,000 or more, more preferably 20,000 or more, and further preferably 50,000 or more as the lower limit.
  • the upper limit is preferably 2 million or less, more preferably 1 million or less, and further preferably 500,000 or less.
  • the weight average molecular weight in the present invention refers to a polystyrene-equivalent value measured by gel permeation chromatography (GPC).
  • the weight average molecular weight of polymetalloxane can be determined by the following method. The polymetalloxane is dissolved in a developing solvent so as to have a concentration of 0.2 wt% to prepare a sample solution. The sample solution is then injected into a column packed with a porous gel and a developing solvent and measured by gel permeation chromatography (GPC). The weight average molecular weight can be determined by detecting the column eluate with a differential refractive index detector and analyzing the elution time.
  • the developing solvent N-methyl-2-pyrrolidone in which lithium chloride is dissolved is preferably used.
  • the repeating structural unit of polymetalloxane is not particularly limited, but it is preferable to have a repeating structural unit represented by the following general formula (3).
  • R6 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
  • R 7 has a hydroxy group, an alkyl group having 1 to 12 carbon atoms, an alicyclic alkyl group having 5 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and 6 to 6 carbon atoms. It is a group having 30 phenoxy groups, a naphthoxy group having 10 to 30 carbon atoms, an alkoxy group having 7 to 13 carbon atoms, a (R 8 3 SiO ⁇ ) group, a (R 9 R 10 NO ⁇ ) group or a metalloxane bond.
  • the plurality of R 6 and R 7 present in the polymetalloxane may be the same or different from each other.
  • R 8 has a hydroxy group, an alkyl group having 1 to 12 carbon atoms, an alicyclic alkyl group having 5 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and 7 to 7 carbon atoms. 13 Aralkyl groups or groups having a siloxane bond. A plurality of R8s may be the same or different from each other.
  • R 9 and R 10 each independently have a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alicyclic alkyl group having 5 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and 7 to 13 carbon atoms. It is an aralkyl group or an acyl group having 1 to 12 carbon atoms.
  • R 4 and R 5 may be linked via a carbon-carbon saturated bond or a carbon-carbon unsaturated bond to form a ring structure.
  • M is Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, In, Sn, Sb, Hf, Ta, W and Bi. Indicates a metal atom selected from the group consisting of.
  • M is an integer indicating the valence of the metal atom M, and a is an integer from 1 to (m-2).
  • Alkyl groups having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group and octyl group. , 2-Ethylhexyl group, nonyl group, decyl group and the like.
  • Examples of the alicyclic alkyl group having 5 to 12 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group and the like.
  • Alkoxy groups having 1 to 12 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, pentoxy group, hexyloxy group, heptoxy group and octoxy. Examples thereof include a group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group and the like.
  • Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group and a naphthyl group.
  • phenoxy group having 6 to 30 carbon atoms examples include a phenoxy group, a methylphenoxy group, an ethylphenoxy group, a propylphenoxy group, a methoxyphenoxy group, an ethoxyphenoxy group, a propoxyphenoxy group and the like.
  • Examples of the naphthoxy group having 10 to 30 carbon atoms include a naphthoxy group, a methylnaphthoxy group, an ethylnaphthoxy group, a propylnaphthoxy group, a methoxynaphthoxy group, an ethoxynaphthoxy group, a propoxynaphthoxy group and the like.
  • Examples of the aralkyl group having 7 to 13 carbon atoms include a benzyl group and a phenylethyl group.
  • the (R 8 3 SiO-) group includes a trihydroxy syloxy group, a trimethyl syloxy group, a triethyl syloxy group, a tripropyl syroxy group, a triisopropyl syroxy group, a tributyl syroxy group, a triisobutyl syroxy group and a tri-s-butyl syroxy group.
  • Tri-t-butyl syroxy group tricyclohexyl syloxy group, trimethoxy syloxy group, triethoxy syroxy group, tripropoxy siroxy group, triisopropoxy siroxy group, tributoxy syroxy group, triphenyl syroxy group, hydroxydiphenyl syroxy group, Methyldiphenyl syroxy group, ethyl diphenyl syroxy group, propyl diphenyl syroxy group, dihydroxy (phenyl) syroxy group, dimethyl (phenyl) syroxy group, diethyl (phenyl) syroxy group, dipropyl (phenyl) syroxy group, trinaphthyl syroxy group, hydroxydi Naftyl syroxy group, methyldinaphthyl syroxy group,
  • the (R 9 R 10 NO-) group includes a diethylaminooxy group, a dibenzylaminooxy group, a 2-azaadamantanyloxy group; a formamide group, a formanilide group, an acetamide group, an acetanilide group, a trifluoroacetamide group, 2, 2,2,2-Trifluoroacetanilide group, benzamide group, benzanilide group, pyrrolidone group, piperidone group; N-acetoamidyloxy group, N-octaneamizyloxy group, N-benzamidyloxy group, N-benzoyl -N-phenylaminooxy group, N-naphthalen-1-carboxyamidyloxy group, N-salitylamizyloxy group, ⁇ - (p-butoxyphenyl) -N-acetoamidyloxy group, N-succiniimi Zyloxy group, N-phthalimidyloxy group
  • R7 is an oxygen atom and is directly bonded to the metal atom M of another polymetalloxane chain via the oxygen atom.
  • the group having a siloxane bond means that R8 is an oxygen atom and is directly bonded to Si of another siloxane chain via the oxygen atom.
  • the polymetalloxane has a repeating structural unit represented by the general formula (3), it is possible to form a film mainly composed of a resin having a metal atom having a high electron density in the main chain. Therefore, the density of metal atoms in the film can be increased, and a high density can be easily obtained. Further, since the film is a dielectric having no free electrons, a cured product having high transparency and heat resistance can be obtained.
  • the polymetalloxane (A) preferably contains a structural unit such that at least one of R 7 is a hydroxy group in the above general formula (3). Since the (A) polymetallosane has a hydroxy group, it can be a polymetalloxane having a small increase in viscosity even during long-term storage and having excellent storage stability.
  • the polymetalloxane (A) preferably contains a structural unit such that at least one of R 7 is a (R 8 3 SiO ⁇ ) group in the above general formula (3). Since the (A) polymetalloxane has a ( R83SiO- ) group, the compatibility with other components is remarkably improved. Therefore, the polymetalloxane is stably present in an organic solvent. Further, in the step of forming the cured film described later, by having the (R 8 3 SiO ⁇ ) group, the condensation stress is relaxed, so that a homogeneous cured film in which cracks are less likely to occur can be obtained.
  • the method for synthesizing polymetalloxane is not particularly limited, but the compound represented by the following general formula (4) and / or general formula (5) is hydrolyzed as necessary, and then partial condensation and polymerization are performed. It is preferable to synthesize by letting.
  • the partial condensation means not condensing all the M-OH of the hydrolyzate, but leaving a part of M-OH in the obtained polymetalloxane. Under the general condensation conditions described later, it is common that M-OH partially remains. The amount of M-OH remaining is not limited.
  • R6 , R7 , M, m and a are as described above.
  • a catalyst is added as needed.
  • the catalyst is not particularly limited, but a basic catalyst is preferably used.
  • a base catalyst By using a base catalyst, a particularly high molecular weight polymetalloxane can be obtained.
  • the basic catalysts it is more preferable to use the following (B) amine compound. By using the (B) amine compound, a cured product having excellent crack resistance can be obtained.
  • composition of the present invention contains (B) an amine compound having a group represented by the following general formula (1) (hereinafter referred to as "(B) amine compound").
  • R 1 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
  • R2 to R5 are independently hydrogen atoms or alkyl groups having 1 to 12 carbon atoms.
  • R 11 to R 14 are independently hydrogen atoms or alkyl groups having 1 to 12 carbon atoms.
  • n is an integer of 0 to 2.
  • the alkyl group having 1 to 12 carbon atoms includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, a t-butyl group, a pentyl group and a hexyl.
  • Examples thereof include a group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group and a decyl group.
  • Alkoxy groups having 1 to 12 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, pentoxy group, hexyloxy group, heptoxy group and octoxy. Examples thereof include a group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group and the like.
  • the polymetalloxane soluble in an organic solvent has an alkoxy group (M-OR group) or a hydroxy group (M-OH group). Since the M-OR group has a high hydrolysis rate, it reacts with moisture in the air when the coating film is formed to become an M-OH group. The M-OH group has a high acidity, and the heat treatment rapidly cures the group to increase the density. Therefore, it is presumed that cracks occur because the hardening stress associated with the high density cannot be relaxed.
  • the polymetalloxane composition contains the (B) amine compound
  • an appropriate interaction occurs between the highly acidic M-OH group in the polymetalloxane and the (B) amine compound. Therefore, when the cured product is formed, the activity of the M—OH group is reduced and the curing stress is relaxed. As a result, it is considered that the crack resistance of the cured product is improved by containing the (B) amine compound.
  • the (B) amine compound has a substituent corresponding to R 2 to R 5 at the adjacent position of the amine.
  • the amine compound acts nucleophilically on the metal atoms in the polymetalloxane. In that case, the crack resistance is not improved by the interaction between the M-OH group and the amine compound.
  • the (B) amine compound since the (B) amine compound has a substituent corresponding to R 2 to R 5 at the adjacent position of the amine, the steric hindrance of the substituent causes nucleophilicity to the metal atom in the polymetalloxane. It decreases and preferentially interacts with the M-OH group. As a result, it is considered that the inclusion of the (B) amine compound relaxes the curing stress and improves the crack resistance.
  • R 2 to R 5 are independently alkyl groups having 1 to 12 carbon atoms.
  • the group represented by the general formula (1) is a group represented by the following general formula (2).
  • R 1 to R 5 are the same as those in the general formula (1).
  • the amine compound having a group represented by the general formula (2) can exist stably because the ring strain is small. Therefore, the storage stability of the composition containing (A) polymetalloxane and (B) amine compound can be improved.
  • R 1 in the general formula (1) and the general formula (2) is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. This is because the M-OH group in the polymetalloxane and the (B) amine compound are likely to interact with each other, and a cured product having better crack resistance can be formed.
  • the amine compound (B) is preferably an amine compound having two or more groups represented by the general formula (1) or the general formula (2).
  • the amine compound (B) can interact with a plurality of M-OH groups to further relax the curing stress. .. Therefore, it is possible to form a cured product having better crack resistance.
  • the weight average molecular weight of the amine compound is preferably 300 or more and 5000 or less.
  • the weight average molecular weight of the (B) amine compound is 300 or more, the (B) amine compound has a high boiling point.
  • the (B) amine compound can be present in the system without evaporating even when exposed to a high temperature in the heat treatment step at the time of forming the cured film, which will be described later. Therefore, the interaction between the M-OH group in the polymetalloxane and the (B) amine compound is maintained during the heat treatment, and the curing stress can be further relaxed.
  • the weight average molecular weight of the (B) amine compound is 5000 or less, the (B) amine compound is compatible with the (A) polymetalloxane, and a homogeneous cured film can be obtained.
  • the weight average molecular weight of the amine compound is determined by the same method as the weight average molecular weight of the polymetalloxane described above.
  • Examples of the amine compound include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate and bis (1). , 2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (N-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-benzyloxy-2,2) , 6,6-Tetramethyl-4-piperidyl) sebacate, bis (N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6- Pentamethyl-4-piperidyl) 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1-acroyl-2,2,6,6-tetramethyl-4- Piperidil) 2,2-bis (3,5-di-t-but-but
  • ADEKA STAB LA-52 As commercially available amine compounds, for example, ADEKA STAB LA-52, ADEKA STAB LA57, ADEKA STAB LA-63P, ADEKA STAB LA-68, ADEKA STAB LA-77Y, ADEKA STAB LA-77G, ADEKA STAB LA-82, ADEKA STAB.
  • LA-87 above, manufactured by ADEKA
  • Chimassorb 119FL Chimassorb 2020FDL, Chimassorb 944FDL, TINUVIN622LD, TINUVIN144, TINUVIN765, TINUVIN770DF (above, manufactured by BASF) and the like.
  • the content of the (B) amine compound in the composition of the present invention is 1 to 30 parts by weight with respect to 100 parts by weight of (A) polymetalloxane.
  • the content of the (B) amine compound is more preferably 4 to 20 parts by weight.
  • the crack resistance of the cured product can be further improved.
  • the content is 30 parts by mass or less, more preferably 20 parts by mass or less, the proportion of (A) polymetalloxane in the composition increases, so that the polymetalloxane is cured at the time of forming the cured product. Can be sufficient. As a result, the density of the obtained cured product can be increased.
  • composition of the present invention may contain an organic solvent.
  • the composition of the present invention contains an organic solvent, the composition can be adjusted to an arbitrary viscosity. As a result, the coating film property of the composition becomes good.
  • the organic solvent in the polymetalloxane solution obtained in the production of polymetalloxane may be used as it is, or another organic solvent may be added.
  • the organic solvent contained in the composition is not particularly limited, but it is preferable to use the same solvent as that used in the synthesis of polymetalloxane. More preferably, it is an aprotic polar solvent. By using an aprotic polar solvent, the stability of polymetalloxane is improved. As a result, it is possible to obtain a composition having excellent storage stability with a small increase in viscosity even during long-term storage.
  • aprotic polar solvent examples include, for example, acetone, tetrahydrofuran, ethyl acetate, dimethoxyethane, N, N-dimethylformamide, dimethylacetamide, dipropylene glycol dimethyl ether, tetramethyl urea, diethylene glycol ethyl methyl ether, dimethyl sulfoxide, N. -Methylpyrrolidone, ⁇ -butyrolactone, 1,3-dimethyl-2-imidazolidinone, propylene carbonate, N, N'-dimethylpropylene urea, N, N-dimethylisobutylamide and the like can be mentioned.
  • the solid content concentration of the composition of the present invention is preferably 1% by mass or more and 50% by mass or less, and more preferably 2% by mass or more and 40% by mass or less.
  • the coating film in the coating step described later can have good film thickness uniformity.
  • 1.0 g of the composition was weighed in an aluminum cup and heated at 250 ° C. for 30 minutes using a hot plate to evaporate the liquid content, and the solid content remaining in the aluminum cup after heating. Is obtained by weighing.
  • the viscosity of the composition containing polymetalloxane at 25 ° C. is preferably 1 mPa ⁇ s or more and 1000 mPa ⁇ s or less, more preferably 1 mPa ⁇ s or more and 500 mPa ⁇ s or less, and 1 mPa ⁇ s or more and 200 mPa ⁇ s. The following is more preferable.
  • the coating film in the coating step described later can have good film thickness uniformity.
  • the viscosity of the composition is obtained by setting the temperature of the composition to 25 ° C. and measuring it at an arbitrary rotation speed using an E-type viscometer.
  • composition of the present invention may contain other components.
  • other components include surfactants, cross-linking agents, and cross-linking accelerators.
  • a cured product can be obtained by heating the composition of the present invention.
  • the cured product includes a cured film and a metal oxide fiber described later. Since the cured product thus obtained is mainly composed of a resin having a metal atom having a high electron density in the main chain, the density of the metal atom in the cured product can be increased, and a high density can be easily obtained. be able to. Further, since it is a dielectric having no free electrons, high heat resistance can be obtained.
  • the cured product of the present invention includes (a) Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, In, Sn, Sb, and the like.
  • the cured product obtained from the composition containing polymetalloxane has a high density, but the crack resistance is low because the shrinkage stress remains in the cured product.
  • the cured product of the present invention has a composition as described above, so that shrinkage stress is less likely to remain and the cured product has high crack resistance. Therefore, it becomes easy to achieve both high density and crack resistance.
  • a cured film can be obtained by applying the composition of the present invention on a substrate and heating it. Since the cured film thus obtained is a film mainly composed of a resin having a metal atom having a high electron density in the main chain, the density of the metal atom in the film can be increased, and the density is easily high. Can be obtained. Further, since it is a dielectric having no free electrons, high heat resistance can be obtained.
  • the substrate on which the cured film is formed is not particularly limited, and examples thereof include silicon wafers, sapphire wafers, glass, and optical films.
  • the glass include alkaline glass, non-alkali glass, heat tempered glass or chemically tempered glass.
  • the optical film include films made of acrylic resin, polyester resin, polycarbonate, polyarylate, polyether sulfone, polypropylene, polyethylene, polyimide or cycloolefin polymer.
  • an inorganic solid substance may be formed on the above-mentioned substrate.
  • the inorganic solid substance is a general term for solids composed of non-metallic substances other than organic compounds.
  • the inorganic solid substance is not particularly limited, but is silicon oxide (SiO 2 ), silicon nitride (Si 3 N 4 ), aluminum oxide (Al 2 O 3 ), titanium oxide (TIO 2 ), zirconium oxide (ZrO 2 ).
  • a known method can be used as a method for applying the composition on the substrate.
  • the device used for coating include a full surface coating device such as spin coating, dip coating, curtain flow coating, spray coating or slit coating, or a printing device such as screen printing, roll coating, microgravure coating or inkjet.
  • heating may be performed using a heating device such as a hot plate or an oven.
  • the coating film after prebaking is called a prebaking film.
  • Pre-baking is preferably carried out in a temperature range of 50 ° C. or higher and 150 ° C. or lower for 30 seconds to 30 minutes. By performing prebaking, a cured product having good film thickness uniformity can be obtained.
  • the film thickness after prebaking is preferably 0.1 ⁇ m or more and 15 ⁇ m or less.
  • the coating film or prebake film is applied to the coating film or prebaked film using a heating device such as a hot plate or an oven at 100 ° C. or higher and 1000 ° C. or lower, preferably 200 ° C. or higher and 800 ° C. or lower, and more preferably 400 ° C. or higher and 800 ° C. or lower for 30 seconds.
  • a cured product containing polymetalloxane can be obtained by undergoing a firing step of heating for about 10 hours.
  • the heating temperature By setting the heating temperature to the above lower limit value or more, the curing of polymetalloxane proceeds and the density of the cured product increases.
  • the heating temperature By setting the heating temperature to the above upper limit value or less, damage due to heating to the substrate, the inorganic solid substance, and the peripheral members can be suppressed.
  • the film thickness of the cured product is preferably 0.5 to 15 ⁇ m, more preferably 0.7 to 10 ⁇ m.
  • the shape of the inorganic solid material pattern formed in the etching of the inorganic solid material using the pattern of the cured film described later as a mask is changed with respect to the depth direction.
  • the pattern can be excellent in linearity.
  • the film thickness of the cured product is not more than the above upper limit value, the stress applied to the substrate and the inorganic solid material can be suppressed.
  • the density of the cured film is preferably 1.50 g / cm 3 or more and 5.00 g / cm 3 or less, and more preferably 2.50 g / cm 3 or more and 4.00 g / cm 3 or less.
  • the density of the cured film is equal to or higher than the lower limit, the mechanical properties of the cured film pattern described later are improved. Therefore, when the pattern of the cured film is used as a mask to process the pattern of the inorganic solid substance by etching, the pattern of the cured body that is not easily damaged by etching can be obtained.
  • the density of the cured product can be measured by Rutherford Backscattering Analysis (RBS). It can be measured by irradiating the cured body with an ion beam (H + or He ++ ) and measuring the energy and intensity of the ions scattered backward by Rutherford scattering.
  • RBS Rutherford Backscattering Analysis
  • the cured film provided on the substrate preferably has a film stress of 1 MPa or more and 200 MPa or less, and more preferably 5 MPa or more and 150 MPa or less.
  • the film stress of the cured film is not more than the upper limit value, the stress applied to the substrate and the inorganic solid substance can be suppressed.
  • the membrane stress of the cured film can be measured by the following method. First, the radius of curvature R1 of a substrate on which a cured film is not formed and whose biaxial elastic modulus is known is measured. Next, a cured film is formed on the substrate on which the radius of curvature has been measured, and the radius of curvature R2 of the cured film-forming substrate is measured. From R1 and R2, the amount of change in the radius of curvature R of the substrate is obtained. The film stress of the cured film can be calculated by using the obtained amount of change in radius of curvature, the biaxial elastic modulus of the substrate, the thickness of the substrate, and the film thickness of the heat-treated film.
  • the cured product obtained from the composition of the present invention is mainly composed of a polymetalloxane having a metal atom having low reactivity with an etching gas or an etching solution when patterning an inorganic solid material by etching, and thus is expensive. Has etching resistance. Therefore, the cured product of the present invention can be used as a mask when pattern processing an inorganic solid substance by etching.
  • the cured product of the present invention has lower film stress on the cured film than the carbon film. Therefore, when a cured film containing polymetalloxane is formed on the inorganic solid material, the stress applied to the substrate and the inorganic solid material can be reduced.
  • a step of coating the composition of the present invention on an inorganic solid material and a coating film obtained by the above coating step are heated at a temperature of 100 ° C. or higher and 1000 ° C. or lower to be a cured film.
  • the manufacturing method can be mentioned.
  • the inorganic solid material is preferably composed of one or more materials selected from the group consisting of SiO 2 , Si 3N 4 , Al 2 O 3 , TIO 2 and ZrO 2 . Further, the inorganic solid material is preferably a laminate of a plurality of inorganic solid material layers.
  • the method for forming a cured film pattern by patterning the cured film is not particularly limited, but for example, a photoresist pattern is formed on the cured film, or from SiO 2 , Si 3 N 4 and carbon.
  • a method of forming a hard mask pattern composed of a compound selected from the above group or a composite compound thereof and etching the cured film is preferable.
  • a dry etching method or a wet etching method can be used with a photoresist pattern or a hard mask pattern as a mask.
  • a reactive ion etching apparatus (RiE apparatus) is used, and the process gas is methane trifluoride (CHF 3 ), methane tetrafluoride (CF 4 ), Cl 2 (chlorine), BCl 3 It is preferably (boron trichloride), CCl 3 (carbon tetrachloride), oxygen, or a mixed gas thereof.
  • Wet etching of the heat-treated film is performed by using fluoric acid (HF), nitric acid (HNO 3 ), ammonium fluoride (NH 4 F), phosphoric acid (H 3 PO 4 ) or a mixture thereof with water and / or acetic acid (CH 3 ). It is preferable to use one diluted with COOH).
  • the etching of the inorganic solid material using the pattern of the cured film as a mask is preferably dry etching or wet etching.
  • a reactive ion etching device for dry etching of inorganic solids, a reactive ion etching device (RiE device) is used, and the process gas is SF 6 (sulfur hexafluoride), NF 3 (nitrogen trifluoride), CF 4 (carbon tetrafluoride). , C 2 F 6 (sulfur hexafluoride), C 3 F 8 (propane octafluoride), C 4 F 6 (hexafluoro-1,3-butadiene), CHF 3 (trifluoromethane), CH 2 F 2 ( It is preferably difluoromethane), COF 2 (carbonyl fluoride), oxygen, or a mixed gas thereof.
  • SF 6 sulfur hexafluoride
  • NF 3 nitrogen trifluoride
  • CF 4 carbon tetrafluoride
  • C 2 F 6 sulfur hexafluoride
  • C 3 F 8 propane octafluoride
  • etching of inorganic solids involves fluoric acid (HF), nitric acid (HNO 3 ), ammonium fluoride (NH 4 F), phosphoric acid (H 3 PO 4 ) or mixtures thereof, water and / or acetic acid (CH). 3 It is preferable to use a product diluted with COOH).
  • the inorganic solid substance pattern obtained as described above can be used as a semiconductor memory.
  • it is suitable for NAND flash memory that requires an inorganic solid material pattern with a high aspect ratio.
  • the cured product of the present invention is excellent in refractive index and insulating property, it is suitably used as a member of electronic parts such as a solid-state image sensor and a display.
  • a member refers to a component that constitutes an electronic component.
  • the member of the solid-state image pickup device include a light-collecting lens, an optical waveguide connecting the light-collecting lens and the optical sensor unit, and an antireflection film.
  • display members include index matching materials, flattening materials, and insulating protective materials.
  • composition of the present invention By spinning the composition of the present invention, it can be made into a fiber.
  • the fiber thus obtained can be made into a metal oxide fiber by firing.
  • Fibers made of metal oxides have properties such as high heat resistance, high strength, and surface activity, and are expected to have properties useful for various applications.
  • Such metal oxide fibers are generally produced by a melt fiber formation method.
  • the melt fiber formation method is as follows. A metal oxide raw material and a low melting point compound such as silica are mixed. The mixture is then melted in a high temperature furnace and then the melt is taken out as a trickle. By blowing high-pressure air or applying centrifugal force to this trickle, it is rapidly cooled to form metal oxide fibers.
  • the molten fiber formation method it is difficult to obtain a high-concentration metal oxide fiber because the melting temperature increases as the concentration of the metal oxide raw material increases.
  • a method for obtaining a high-concentration metal oxide fiber As a method for obtaining a high-concentration metal oxide fiber, a method is generally known in which a fibrous precursor is prepared using a spinning solution containing a metal oxide source and a thickener, and the fibrous precursor is heat-spun. Has been done. However, such a method has a problem that pores and cracks are generated when the thickener is burned down in the firing process, and the strength is insufficient.
  • composition of the present invention containing polymetalloxane can be handled in a solution state, it can be spun without the need for a melting step. Moreover, since a thickener is not required, a dense metal oxide fiber can be obtained. Therefore, metal oxide fibers having properties such as high heat resistance, high strength, and surface activity can be easily obtained.
  • the method for producing a fiber according to an embodiment of the present invention includes at least a spinning step of spinning the composition of the present invention containing the above-mentioned polymetalloxane to obtain a fiber.
  • a known method can be used as a method for spinning the composition.
  • examples of this spinning method include a dry spinning method, a wet spinning method, a dry wet spinning method, and an electrospinning method.
  • the dry spinning method is a method in which a container is filled with a composition, a load is applied to the composition, and the composition is extruded into an atmosphere from a mouthpiece having pores to evaporate an organic solvent to obtain a filamentous substance.
  • the composition may be filled in a container and then heated to reduce the viscosity during extrusion.
  • the composition may be extruded into a heating atmosphere to control the evaporation rate of the organic solvent.
  • the filament can also be stretched using a rotating roller or high speed airflow.
  • Wet spinning is a method of extruding a composition or the like from a mouthpiece having pores into a coagulation bath to remove an organic solvent to obtain a filamentous substance.
  • Water or a polar solvent is preferably used as the coagulation bath.
  • dry-wet spinning is a method in which a composition is extruded into an atmosphere and then immersed in a coagulation bath to remove an organic solvent to obtain a filamentous substance.
  • the electrospinning method when a high voltage is applied to a nozzle filled with a composition, electric charges are accumulated in the droplets at the tip of the nozzle, and the droplets repel each other to spread the droplets and stretch the liquid flow. It is a method of spinning. With this method, it is possible to obtain a thread-like material having a small diameter. Therefore, when the electrospinning method is used, a fine filamentous material having a diameter of several tens of nm to several ⁇ m can be obtained.
  • a dry spinning method or an electrospinning method can be particularly preferably used as the spinning method in the spinning step in the present invention.
  • the fibers obtained by the spinning step may be subjected to a drying treatment, a steam treatment, a hot water treatment, or a combination of these treatments, if necessary, before firing.
  • the method for producing a fiber according to the embodiment of the present invention includes, in the case of producing a metal oxide fiber, a step of spinning the composition as described above and a firing step of firing the fiber obtained by the spinning step. including.
  • the firing temperature is not particularly limited, but is preferably 200 ° C. or higher and 2000 ° C. or lower, and more preferably 400 ° C. or higher and 1500 ° C. or lower.
  • the firing method is not particularly limited.
  • examples of the firing method include a method of firing in an air atmosphere, a method of firing in an inert atmosphere such as nitrogen and argon, and a method of firing in a vacuum.
  • the obtained metal oxide fiber may be further fired in a reducing atmosphere such as hydrogen. Further, in the firing step, the fibers obtained by spinning or the metal oxide fibers may be fired while applying tension.
  • the fibers obtained by spinning the solution of the polymetallosane of the present invention and firing them can be used as a composite material such as a photocatalyst, a heat insulating material, a heat radiating material, and a fiber reinforced plastic (FRP).
  • the photocatalyst can be used for water / air purification filters and the like
  • the heat insulating material and heat radiating material can be used for electric furnaces, nuclear fuel rod sheaths, aircraft engine turbines, heat exchangers and the like.
  • the solid content concentration of the polymetalloxane solution is such that 1.0 g of the polymetalloxane solution is weighed in an aluminum cup and heated at 250 ° C. for 30 minutes using a hot plate to evaporate the liquid content. The solution was determined by weighing the solid content remaining in the aluminum cup after heating.
  • FT-IR Fourier transform infrared spectroscopy
  • the weight average molecular weight (Mw) was determined by the following method using gel permeation chromatography (GPC). Lithium chloride was dissolved in N-methyl-2-pyrrolidone as a developing solvent to prepare a 0.02 mol / dm 3 lithium chloride N-methyl-2-pyrrolidone solution. Polymetallosane was dissolved in a developing solvent to a concentration of 0.2 wt%, and this was used as a sample solution.
  • the developing solvent was flowed through a porous gel column (TSKgel ⁇ -M manufactured by Tosoh, one each of ⁇ -3000) at a flow rate of 0.5 mL / min, and 0.2 mL of the sample solution was injected therein.
  • the column eluate was detected by a differential refractive index detector (RI-201 type manufactured by Showa Denko), and the elution time was analyzed to determine the polystyrene-equivalent weight average molecular weight (Mw).
  • the cured membrane was irradiated with an ion beam using Pelletron 3SDH (manufactured by National Electrodstics).
  • the density of the cured film was determined by analyzing the scattered ion energy.
  • the mass number of the collision atom was investigated from the obtained scattered ion energy spectrum, and the average atomic number ratio of the cured film was obtained.
  • a cured product is obtained by selecting the average atomic number ratio of metal atoms and oxygen atoms from the obtained average atomic number ratios and dividing the average atomic number ratio of oxygen atoms by the total value of the average atomic number ratios of metal atoms.
  • the content of oxygen atoms (atomic%) with respect to 100 atomic% of all metal atoms in the mixture was used.
  • the content of oxygen atoms with respect to 100 atomic% of all metal atoms in the cured product is simply referred to as the content of oxygen atoms.
  • the measurement conditions were incident ion: 4 He ++ , incident energy 2300 keV, incident angle: 0 deg, scattering angle: 160 deg, sample current: 8 nA, beam diameter: 2 mm ⁇ , irradiation amount: 48 ⁇ C.
  • the radius of curvature R1 of the 6-inch silicon wafer is measured using the thin film stress measuring device FTX-3300-T (manufactured by Toho Technology), and then a heat-treated film is formed on the wafer and heat-treated. From R1 and R2 in which the radius of curvature R2 of the film-forming substrate was measured, the amount of change in the radius of curvature R of the wafer was obtained, and the obtained biaxial elastic coefficient of R and the wafer, the thickness of the substrate, and the thickness of the cured film were used. The film stress of the heat-treated film was calculated.
  • the biaxial elastic modulus of the wafer was 1.805 ⁇ 10 11 Pa.
  • IPA isopropyl alcohol
  • the entire amount of Solution 1 was placed in a three-necked flask with a capacity of 500 ml, and the flask was immersed in an oil bath at 40 ° C. and stirred for 30 minutes. Then, for the purpose of hydrolysis, the whole amount of the solution 2 was filled in the dropping funnel and added into the flask over 1 hour. During the addition of Solution 2, no precipitation occurred in the flask contents, and the solution was a uniform colorless and transparent solution. After the addition of the solution 2, the mixture was further stirred for 1 hour to obtain a hydroxy group-containing metal compound. Then, for the purpose of polycondensation, the temperature of the oil bath was raised to 140 ° C. over 30 minutes. The internal temperature of the solution reached 100 ° C.
  • the solid content concentration of the obtained polymetalloxane solution was 38.2% by mass. After that, DMIB was added so that the solid content concentration became 20.0% by mass to prepare a polymetallosane (A-1) solution.
  • the weight average molecular weight (Mw) of polymetalloxane (A-1) was 400,000 in terms of polystyrene.
  • the solid content concentration of the obtained polymetalloxane solution is shown in Table 1. Then, DMIB was added so that the solid content concentration became 20.0%, and polymetallosane (A-2) to (A-7) solutions were obtained.
  • composition 1 was obtained by stirring.
  • compositions 2 to 16 were obtained in the blending amounts shown in Table 2.
  • the amount of the (B) amine compound in the "content of the (B) amine compound with respect to 100 parts by weight of the polymetalloxane" in Table 2 refers to the (B) amine compound remaining in the polymetalloxane solution and later. It is the total amount with the added (B) amine compound.
  • Example 1 Preparation of a cured film containing polymetalloxane
  • a spin coater (1H-360S manufactured by Mikasa) at different rotation speeds for each substrate, and then hot plate (SCW manufactured by SCREEN Holdings) was applied.
  • SCW hot plate
  • -636 was used to heat at 100 ° C. for 5 minutes to prepare a coating film.
  • the coating film obtained in the coating step was heated at 500 ° C. for 5 minutes using a hot plate (SCW-636 manufactured by SCREEN Holdings), and the film thicknesses were 0.5 ⁇ m, 0.7 ⁇ m, 1.0 ⁇ m and 1.5 ⁇ m, respectively.
  • a cured film was created. The film thickness was measured using an optical interferometry film thickness meter (Lambdaace STM602 manufactured by SCREEN Holdings).
  • Example 15 ((B) Preparation of calibration curve of amine compound) Six 6-inch silicon wafers were prepared. Using these as substrates, the compositions 1 to 6 containing the (B) amine compound Adecaster LA-77Y obtained as described above were used on six substrates using a spin coater (1H-360S manufactured by Mikasa). After spin-coating each of them, they were heated at 100 ° C. for 5 minutes using a hot plate (SCW-636 manufactured by SCREEN Holdings) to prepare coating films having a film thickness of 1.0 ⁇ m. An infrared absorption spectrum was obtained for these coated films using a Fourier transform infrared spectrometer (FT720 manufactured by Shimadzu Corporation).
  • FT720 Fourier transform infrared spectrometer
  • composition 10 containing the (B) amine compound Adecaster LA-77Y obtained as described above is spin-coated using a spin coater (1H-360S manufactured by Mikasa), and then spin-coated.
  • a coating film was prepared by heating at 100 ° C. for 5 minutes using a hot plate (SCW-636 manufactured by SCREEN Holdings). The obtained coating film was heated at 150 ° C. for 5 minutes using a hot plate (SCW-636 manufactured by SCREEN Holdings) to prepare a cured film having a film thickness of 1.0 ⁇ m.
  • the film thickness was measured using an optical interferometry film thickness meter (Lambdaace STM602 manufactured by SCREEN Holdings). An infrared absorption spectrum of this cured film was obtained using a Fourier transform infrared spectrometer (FT720 manufactured by Shimadzu Corporation). The absorption peak (1735 cm -1 ) of the structure of the general formula (1) was confirmed, and the content (% by weight) of the (B) amine compound in 100% by weight of the cured product was calculated from the calibration curve prepared above. The measurement results are shown in Table 4.
  • Example 18 Polymetallosane (A-4) solution synthesized in Synthesis Example 4 (solid content concentration: 20.0%, weight average molecular weight; (Mw) 380,000, (B) amine compound with respect to 100 parts by weight of polymetalloxane Adecastab LA-77Y (containing 6 parts by weight) was concentrated under reduced pressure until the solid content concentration reached 45%. The viscosity of the polymetalloxane (A-4) solution after concentration was 2000P.
  • the concentrated polymetalloxane (A-4) solution is filled in a 10 ml syringe for dispenser (manufactured by Musashi Engineering), and the syringe is filled with a plastic needle for dispenser (inner diameter 0.20 mm, manufactured by Musashi Engineering) and an adapter tube as a base. (Made by Musashi Engineering) was installed.
  • the adapter tube was connected to a compressed air line and a pressure of 0.4 MPa was applied to extrude the filler into an air atmosphere at 25 ° C. to obtain a filament.
  • the average fiber diameter of the obtained filament was measured by the following method.
  • Adhesive tape carbon double-sided tape for SEM (aluminum base material), manufactured by Nissin EM
  • a thread-like material for measuring the fiber diameter was horizontally adhered onto the adhesive tape, which was used as a single fiber test piece.
  • This single fiber test piece was observed from above with an electron microscope, and the width of the image of the single fiber test piece was measured.
  • the measurement was performed three times along the length direction, and the average value was taken as the fiber diameter. This operation was performed on 20 randomly selected filaments, and the average value of the obtained fiber diameters was taken as the average fiber diameter.
  • the average fiber diameter of the obtained filamentous material was 60 ⁇ m.
  • the obtained filamentous material was dried at 25 ° C. for 24 hours, and then calcined in an electric muffle furnace (manufactured by ADVANTEC, FUW263PA) at a heating rate of 10 ° C./min and 500 ° C. for 60 minutes in an air atmosphere. , Metal oxide fibers were obtained. The average fiber diameter of the obtained metal oxide fiber was 40 ⁇ m when measured by the same method as that of the filamentous material.
  • the qualitative analysis of the metal oxide fiber after firing was performed by the following wide-angle X-ray diffraction method (hereinafter, abbreviated as XRD).
  • XRD wide-angle X-ray diffraction method
  • D8 ADVANCE manufactured by Bruker AXS
  • the measurement range (2 ⁇ ) was set to 10 to 80 °, a diffraction pattern was obtained, and then the data was identified by comparison with standard data.
  • the metal oxide fiber after firing had a broad X-ray diffraction pattern, and no crystal-derived peak was observed. From this, it was confirmed that the metal oxide fiber after firing was amorphous.
  • the tensile strength of the metal oxide fiber after firing was measured by the following method. Using a Tensilon universal tensile tester (RTM-100, manufactured by ORIENTEC), a metal oxide fiber was pulled at a measurement length of 25 mm and a tensile speed of 1 mm / min, and the strength at which the fiber broke was defined as the tensile strength. The measured value was the average value of the tensile strengths of 20 randomly selected fibers. The tensile strength of the metal oxide fiber was 1.2 GPa.

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Abstract

L'invention concerne une composition contenant : (A) Un polymétalloxane ayant une structure répétitive d'atomes d'oxygène et d'atomes métalliques choisis dans le groupe constitué par Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, In, Sn, Sb, Hf, Ta, W et Bi (désigné ci-après " (A) polymétalloxane ") ; et (B) un composé amine ayant un groupe représenté par la formule générale (1) (désigné ci-après " (B) composé amine "), la teneur en composé amine (B) de la composition étant de 1 à 30 parties en poids pour 100 parties en poids du (A) polymétalloxane. L'invention concerne une composition contenant du polymétalloxane qui a une résistance exceptionnelle aux fissures et pouvant former un produit durci ayant une densité élevée.
PCT/JP2021/033671 2020-09-24 2021-09-14 Composition, produit durci, procédé de production associé, élément, composant électronique et fibre WO2022065127A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001348528A (ja) * 2000-06-08 2001-12-18 Shin Etsu Chem Co Ltd コーティング剤組成物、コーティング方法及び被覆物品
JP2010528984A (ja) * 2007-05-03 2010-08-26 オーテラ インコーポレイテッド チタニルのモノマーおよびポリマーを含有する生成物ならびにその製造方法
JP2015199916A (ja) * 2014-04-02 2015-11-12 Jsr株式会社 膜形成用組成物及びパターン形成方法
WO2017090512A1 (fr) * 2015-11-26 2017-06-01 東レ株式会社 Polymétalloxane, son procédé de production, composition associée, film durci et son procédé de production, et éléments et composants électroniques les comprenant
WO2019188835A1 (fr) * 2018-03-29 2019-10-03 東レ株式会社 Polymétalloxane, composition, film durci, élément, composant électronique, fibre, liant pour moulage céramique, procédé de production de film durci et procédé de production de fibre

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001348528A (ja) * 2000-06-08 2001-12-18 Shin Etsu Chem Co Ltd コーティング剤組成物、コーティング方法及び被覆物品
JP2010528984A (ja) * 2007-05-03 2010-08-26 オーテラ インコーポレイテッド チタニルのモノマーおよびポリマーを含有する生成物ならびにその製造方法
JP2015199916A (ja) * 2014-04-02 2015-11-12 Jsr株式会社 膜形成用組成物及びパターン形成方法
WO2017090512A1 (fr) * 2015-11-26 2017-06-01 東レ株式会社 Polymétalloxane, son procédé de production, composition associée, film durci et son procédé de production, et éléments et composants électroniques les comprenant
WO2019188835A1 (fr) * 2018-03-29 2019-10-03 東レ株式会社 Polymétalloxane, composition, film durci, élément, composant électronique, fibre, liant pour moulage céramique, procédé de production de film durci et procédé de production de fibre

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