WO2012137840A1 - ポリベンゾオキサゾール樹脂及びその前駆体 - Google Patents
ポリベンゾオキサゾール樹脂及びその前駆体 Download PDFInfo
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- WO2012137840A1 WO2012137840A1 PCT/JP2012/059242 JP2012059242W WO2012137840A1 WO 2012137840 A1 WO2012137840 A1 WO 2012137840A1 JP 2012059242 W JP2012059242 W JP 2012059242W WO 2012137840 A1 WO2012137840 A1 WO 2012137840A1
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- 0 CC(C)C(O1)=N*11OC(c2ccc(*c(cc3)ccc3C(C)=C)cc2)=N1 Chemical compound CC(C)C(O1)=N*11OC(c2ccc(*c(cc3)ccc3C(C)=C)cc2)=N1 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/22—Polybenzoxazoles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/307—Other macromolecular compounds
Definitions
- the present invention relates to a polybenzoxazole resin excellent in electrical insulation properties, heat resistance, mechanical properties, physical properties, dimensional stability, and the like, and a polybenzox excellent in solvent solubility and storage stability capable of forming a polybenzoxazole resin. It relates to an oxazole precursor.
- Polybenzoxazole is a super engineering plastic with excellent heat resistance, mechanical strength, dimensional stability, insulation properties, etc., and is widely used in electrical and electronic equipment such as printed wiring boards and circuit boards.
- Polybenzoxazole is obtained by condensation of aromatic dicarboxylic acid compounds and bis (o-aminophenol) compounds, but since the reactivity with phenols and amines is low in the carboxylic acid form, various polymerization methods have been studied. It has been. Although these polymerization methods are disclosed in Non-Patent Document 1, for example, a technique of condensing a bis (o-aminophenol) compound and a dicarboxylic acid in polyphosphoric acid is known. In this case, polyphosphoric acid plays the role of a condensing agent and a solvent, and although it is easy to operate on a laboratory scale, the treatment of phosphoric acid that is by-produced in large quantities on an industrial scale becomes a problem.
- Patent Document 1 discloses a method for producing polybenzoxazole, which is characterized by reacting a bis (o-aminophenol) compound with an aromatic dialdehyde. According to this method, polybenzoxazole can be produced without particularly requiring purification. However, the polybenzoxazole obtained by this method has poor solvent solubility of its precursor, so it is difficult to obtain a uniform precursor solution, film formation is poor, and the strength of the obtained molded product Has the disadvantage of being small and brittle.
- Patent Documents 2 and 3 propose a special structure for preventing the precursor from being closed in order to improve the solubility of the polybenzoxazole precursor.
- the structure that is not ring-closed itself is an unstable structure, so the storage stability is poor, and since the structure on the dialdehyde side is rigid, the solvent solubility of the precursor is poor, so a uniform precursor solution can be obtained. Is difficult, the film-forming property is poor, and the strength of the resulting molded product is small and brittle.
- the present invention relates to a polybenzoxazole resin excellent in electrical insulation properties, heat resistance, mechanical properties, physical properties, dimensional stability, and the like, and a precursor thereof, particularly for interlayer insulation films, protective films, and multilayer circuits for semiconductors.
- An object is to provide a benzoxazole precursor.
- polybenzoxazole resin is excellent in solvent solubility and storage stability and is composed of the precursor.
- Polyoxazole resin is excellent in electrical insulation properties, heat resistance, mechanical properties, physical properties, dimensional stability, etc., especially for semiconductor interlayer insulation films, protective films, interlayer insulation films for multilayer circuits, flexible copper-clad boards, etc. It has been found useful as a cover coat, a solder resist film, a liquid crystal alignment film, etc., and has completed the present invention. That is, the present invention 1.
- R 1 represents a tetravalent aromatic group, N and O bonded to R 1 form a pair, and N and O in each pair bind to adjacent carbons on the same aromatic ring.
- R 2 represents an alkanediyl group having 1 to 6 carbon atoms, and n represents an integer of 2 to 10,000.
- R 1 represents a tetravalent aromatic group, NH 2 group and OH group bonded to R 1 form a pair, and each pair of NH 2 group and OH group are on the same aromatic ring. Bonded to adjacent carbon.
- R 1 represents a tetravalent aromatic group, N and OH bonded to R 1 form a pair, and N and OH of each pair bond to adjacent carbons on the same aromatic ring.
- R 2 represents an alkanediyl group having 1 to 6 carbon atoms, and n represents an integer of 2 to 10,000.
- R 2 is the same as above, R 3 represents any one of OH, Cl, Br, I and OR 4 , and R 4 represents a hydrocarbon group having 3 or less carbon atoms.
- the present invention provides the aforementioned 1. 2. A resin film containing the polybenzoxazole resin described in 2) above and 2. Or 4. The coating composition containing the polybenzoxazole precursor described in 1.
- the polybenzoxazole precursor of the present invention is excellent in storage stability because of its good solvent solubility, and in particular, interlayer insulation films for semiconductors, protective films, interlayer insulation films for multilayer circuits, flexible copper-clad plates
- a polybenzoxazole resin film useful as a cover coat, a solder resist film, a liquid crystal alignment film or the like can be formed.
- the polybenzoxazole resin of the present invention has the following general formula (1)
- R 1 represents a tetravalent aromatic group, N and O bonded to R 1 form a pair, and N and O in each pair bind to adjacent carbons on the same aromatic ring.
- R 2 represents an alkanediyl group having 1 to 6 carbon atoms, and n represents an integer of 2 to 10,000.
- the aromatic group is carbocyclic or heterocyclic, monocyclic or polycyclic containing at least one, preferably 1 to 3, heteroatoms selected from nitrogen, oxygen and sulfur atoms in the ring. In some cases, an aromatic group which may form a condensed ring is included.
- R 1 is represented by the following general formulas (7) to (9) from the viewpoint of the electrical insulation properties, heat resistance, mechanical properties, physical properties, dimensional stability, etc. of the polybenzoxazole resin. It is preferable that any of the structures described above is used.
- X, Y and Z are each independently —CH 2 —, —O—, —S—, —SO—, —SO 2 —, —SO 2 NH—, — CO—, —CO 2 —, —NHCO—, —NHCONH—, —C (CF 3 ) 2 —, —CF 2 —, —C (CH 3 ) 2 —, —CH (CH 3 ) —, —Si ( R 19 ) 2 —, —O—Si (R 20 ) 2 —O—, —Si (R 21 ) 2 —O—Si (R 22 ) 2 —, — (CH 2 ) a —Si (R 22 ) 2 —O—Si (R 23 ) 2 — (CH 2 ) a — (wherein a represents an integer of 0 to 6) or a direct bond, R 5 to R 23 each independently represents a hydrogen atom,
- R 1 is more preferably a structure represented by the general formula (7).
- each of R 5 to R 10 is preferably a hydrogen atom.
- X represents —CH 2 —, —O—, —S—, —SO—, —SO 2 —, —CO—, —CO 2 —, —NHCO—, —C (CF 3 ) 2 —, —CF It is more preferably at least one selected from the group consisting of 2 —, —C (CH 3 ) 2 —, —CH (CH 3 ) —, and a direct bond, and —C (CF 3 ) 2 —. Is more preferable.
- the R 1 may be only one type, or two or more types may be used in combination.
- R 2 is an alkanediyl group having 1 to 6 carbon atoms, and R 2 is — (CH 2 ) m from the viewpoint of solvent solubility of the polybenzoxazole precursor described later.
- -(M represents an integer of 2 to 6) is preferable, m is more preferably 2 to 4, and even more preferably 2 or 3.
- R 2 may be used alone or in combination of two or more.
- the polybenzoxazole resin of the present invention is excellent in electrical insulation properties, heat resistance, mechanical properties, physical properties, dimensional stability, and the like.
- polybenzoxazole precursor The polybenzoxazole precursor of the present invention has the following general formula (2)
- R 1 represents a tetravalent aromatic group, N and O bonded to R 1 form a pair, and N and O in each pair bind to adjacent carbons on the same aromatic ring.
- R 2 represents an alkanediyl group having 1 to 6 carbon atoms, and n represents an integer of 2 to 10,000.
- It is a polybenzoxazole precursor which has a repeating unit shown by these.
- the polybenzoxazole precursor of the present invention has the following general formula (5)
- R 1 represents a tetravalent aromatic group, N and OH bonded to R 1 form a pair, and N and OH of each pair bond to adjacent carbons on the same aromatic ring.
- R 2 represents an alkanediyl group having 1 to 6 carbon atoms, and n represents an integer of 2 to 10,000.
- the aromatic group is carbocyclic or heterocyclic, monocyclic or polycyclic containing at least one, preferably 1 to 3, heteroatoms selected from nitrogen, oxygen and sulfur atoms in the ring. In some cases, an aromatic group which may form a condensed ring is included.
- the polybenzoxazole precursor having the repeating unit represented by the general formula (2) is referred to as “precursor [1]”
- the polybenzoxazole precursor having the repeating unit represented by the general formula (5) is referred to as “precursor”.
- body [2] also referred to as “body [2]”.
- preferable R 1 and R 2 are the same as preferable R 1 and R 2 in the polybenzoxazole resin.
- the polybenzoxazole precursor [1] reacts a compound represented by the following general formula (3) (hereinafter also referred to as “compound (A)”) with a compound represented by the following general formula (4). It is preferable that it is obtained. Below, the preferable manufacturing method of polybenzoxazole precursor [1] is demonstrated.
- R 1 represents a tetravalent aromatic group, NH 2 group and OH group bonded to R 1 form a pair, and each pair of NH 2 group and OH group are on the same aromatic ring. Bonded to adjacent carbon.
- R 2 represents an alkanediyl group having 1 to 6 carbon atoms.
- the compound (A) used as a starting material in the production of the polybenzoxazole precursor [1] of the present invention is a compound represented by the following general formula (3).
- R 1 represents a tetravalent aromatic group, NH 2 group and OH group bonded to R 1 form a pair, and each pair of NH 2 group and OH group are on the same aromatic ring. Bonded to adjacent carbon.
- the aromatic group is carbocyclic or heterocyclic, monocyclic or polycyclic containing at least one, preferably 1 to 3, heteroatoms selected from nitrogen, oxygen and sulfur atoms in the ring. In some cases, an aromatic group which may form a condensed ring is included.
- preferable R 1 is the same as preferable R 1 in the polybenzoxazole resin.
- Specific examples of the compound represented by the general formula (3) are as follows. These are merely examples and are not intended to be limiting.
- R 2 represents an alkanediyl group having 1 to 6 carbon atoms.
- preferable R 2 is the same as preferable R 2 in the polybenzoxazole resin.
- Specific examples of the compound represented by the general formula (4) include diphenylmethanedialdehyde, diphenylethanedialdehyde, 1,3-diphenylpropanedialdehyde, 1,2-diphenylpropanedialdehyde, 1,4-diphenylbutane.
- the reaction between the compound (A) and the compound represented by the general formula (4) is usually at a temperature between room temperature and about 200 ° C., preferably Mixing a solvent such as toluene having a boiling point of 100 ° C. to 180 ° C. that is not compatible with water at a temperature from room temperature to about 160 ° C. in a range where the reactants do not precipitate, and performing reflux dehydration However, it can be performed in about 2 to 72 hours.
- the reaction between the compound (A) and the compound represented by the general formula (4) is a Schiff base formation reaction and can be carried out by a method known per se.
- the compound (A) and the compound represented by the general formula (4) are converted into amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone; acetone, methyl ethyl ketone, Ketones such as methyl isobutyl ketone, cyclohexanone and isophorone; ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -methyl- ⁇ -butyrolactone, ethyl lactate, methyl acetate, ethyl acetate Esters such as butyl acetate; aliphatic alcohols having 1 to 10 carbon atoms such as methanol, ethanol and propano
- Glycol ethers such as monoethers or diethers such as methanol, ethanol, butanol, hexanol, octanol, benzyl alcohol, phenol, and cresol, or esters of the monoethers; cyclics such as dioxane and tetrahydrofuran; Ethers; cyclic carbonates such as ethylene carbonate and propylene carbonate; aliphatic and aromatic hydrocarbons such as toluene and xylene; and an inert solvent such as dimethyl sulfoxide.
- the reaction can be carried out preferably at a temperature of 100 ° C. to about 160 ° C. for about 2 to 72 hours. These solvents can be used alone or in admixture of two or more as required.
- the compounding ratio of the compound (A) and the compound represented by the general formula (4) is such that the compound represented by the general formula (4) is 0.5 to 1.5 mol per 1 mol of the compound (A). In particular, it is preferably in the range of 0.7 to 1.3 mol.
- the polybenzoxazole precursor [2] is obtained by reacting a compound represented by the general formula (3) (compound (A)) with a compound represented by the following general formula (6). Preferably there is. Below, the preferable manufacturing method of polybenzoxazole precursor [2] is demonstrated.
- the compound represented by the general formula (3) (compound (A)) is as described above.
- R 2 represents an alkanediyl group having 1 to 6 carbon atoms
- R 3 represents any one of OH, Cl, Br, I, and OR 4
- R 4 represents a carbon atom having 3 or less carbon atoms. Represents a hydrogen group.
- preferable R 2 is the same as preferable R 2 in the polybenzoxazole resin.
- Specific examples of the compound represented by the general formula (6) include diphenylmethanedicarboxylic acid, diphenylethanedicarboxylic acid, 1,3-diphenylpropanedicarboxylic acid, 1,2-diphenylpropanedicarboxylic acid, 1,4-diphenylbutane.
- Dicarboxylic acid 1,3-diphenylbutanedicarboxylic acid, 1,2-diphenylbutanedicarboxylic acid, 2,3-diphenylbutanedicarboxylic acid, 1,5-diphenylpentanedicarboxylic acid, 1,4-diphenylpentanedicarboxylic acid, 1, 3-diphenylpentanedicarboxylic acid, 1,2-diphenylpentanedicarboxylic acid, 2,4-diphenylpentanedicarboxylic acid, 2,3-diphenylpentanedicarboxylic acid, 1,6-diphenylhexanedicarboxylic acid, 1,5-diphenylhexanedicarboxylic acid Acid, 1, -Diphenylhexanedicarboxylic acid, 1,3-diphenylhexanedicarboxylic acid, 1,2-diphenylhexanedicarboxylic acid, 2,5-
- reaction between the compound (A) and the compound represented by the general formula (6) is usually between room temperature and about 200 ° C. At a temperature of from room temperature to about 160 ° C., more preferably a solvent such as toluene that is not compatible with water and has a boiling point of 100 ° C. to 180 ° C. is mixed at a blending ratio within a range in which the reactant does not precipitate.
- the reaction can be performed in about 2 to 72 hours while performing reflux dehydration or reflux alcohol removal.
- the compound represented by the general formula (6) is a dicarboxylic acid halide
- it is usually at a temperature between ⁇ 20 ° C. and about 150 ° C., preferably at a temperature between ⁇ 10 ° C. and about 100 ° C., more preferably ⁇ It is desirable to carry out at a temperature between 5 ° C and 70 ° C.
- a tertiary amine such as triethylamine, pyridine, N, N-dimethyl-4-aminopyridine, or an alkali hydroxide is used. In about 2 to 72 hours.
- the reaction between the compound (A) and the compound represented by the general formula (6) is an amide group formation reaction and can be carried out by a method known per se.
- the compound (A) and the compound represented by the general formula (6) are converted into amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone; acetone, methyl ethyl ketone, Ketones such as methyl isobutyl ketone, cyclohexanone and isophorone; ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -methyl- ⁇ -butyrolactone, ethyl lactate, methyl acetate, ethyl acetate Esters such as butyl acetate; aliphatic alcohols having 1 to 10 carbon atoms such as methanol, ethanol and propano
- Glycol ethers such as monoethers or diethers such as methanol, ethanol, butanol, hexanol, octanol, benzyl alcohol, phenol, and cresol, or esters of the monoethers; cyclics such as dioxane and tetrahydrofuran; Ethers; cyclic carbonates such as ethylene carbonate and propylene carbonate; aliphatic and aromatic hydrocarbons such as toluene and xylene; and in an inert solvent such as dimethyl sulfoxide, and the like under the above temperature conditions for about 2 to 72 hours. It can be performed by reacting. These solvents can be used alone or in admixture of two or more as required.
- the compounding ratio of the compound (A) and the compound represented by the general formula (6) is such that the compound represented by the general formula (6) is 0.5 to 1.5 mol per 1 mol of the compound (A). In particular, it is preferably in the range of 0.7 to 1.3 mol.
- the polybenzoxazole precursors [1] and [2] of the present invention produced as described above have a repeating unit represented by the general formula (2) when heated and oxidized.
- a polybenzoxazole resin excellent in mechanical properties, physical properties, dimensional stability and the like is produced.
- the present invention also relates to a coating composition containing the polybenzoxazole precursor and a resin film containing the polybenzoxazole resin.
- the polybenzoxazole precursor of the present invention is mixed with a solvent and / or various additives, for example, a surfactant, a coupling agent, etc. as necessary, so that an interlayer insulating film for semiconductor, a protective film, a multilayer It can be set as the coating composition useful for formation of films, such as a circuit interlayer insulation film, a cover coat of a flexible copper clad board, a solder resist film, and a liquid crystal aligning film.
- the solvent is not particularly limited as long as it dissolves the polybenzoxazole precursor of the present invention and additives used as necessary.
- N, N-dimethylformamide, N, N-dimethylacetamide, N Amides such as methyl-2-pyrrolidone; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone; ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -Esters such as methyl- ⁇ -butyrolactone, ethyl lactate, methyl acetate, ethyl acetate and butyl acetate; aliphatic alcohols having 1 to 10 carbon atoms such as methanol, ethanol and propanol; containing aromatic groups such as phenol and cresol Phenolics; benzyl
- glycols such as ethylene glycol and propylene glycol, or monoethers or diethers of these glycols such as methanol, ethanol, butanol, hexanol, octanol, benzyl alcohol, phenol, cresol, or esters of such monoethers
- glycol ethers such as dicarboxylic acids
- cyclic ethers such as dioxane and tetrahydrofuran
- cyclic carbonates such as ethylene carbonate and propylene carbonate
- aliphatic and aromatic hydrocarbons and dimethyl sulfoxide.
- the content of the polybenzoxazole precursor of the present invention in the coating composition is not strictly limited and can be changed according to the use and the like. A range of 80% by mass, particularly 10 to 70% by mass is preferred.
- the substrate to which the coating composition of the present invention can be applied there are no particular restrictions on the substrate to which the coating composition of the present invention can be applied.
- a semiconductor material such as a silicon wafer or gallium arsenide, a metal, a metal oxide, a ceramic, a resin, or a copper foil is laminated.
- the coating composition include, for example, printed circuit boards, glass, and the like, and the coating composition is applied to these substrates by known coating methods such as spin coating, spray coating, roll coating, curtain flow coating, and printing methods. Can be applied.
- the formed coating is then dried and baked.
- the coating thickness at that time is not strictly limited and can be changed according to the purpose of use, etc., but is usually about 0.1 to about 100 ⁇ m in dry film thickness, preferably about 0.5 to about It can be in the range of 30 ⁇ m.
- the polybenzoxazole precursor coating formed is usually pre-baked at a temperature of 80 to 190 ° C. for about 10 seconds to about 120 minutes, if necessary, and then at a temperature of 200 to 500 ° C., preferably 250 to 400 ° C. By baking for about 10 to about 300 minutes, it can be converted into a polybenzoxazole resin film.
- the number average molecular weight was determined by gel permeation chromatography (GPC) measurement.
- GPC measurement was performed with “Shodex GPC SYSTEM-11” manufactured by Showa Denko KK. Hexafluoroisopropanol (HFIP) was used as the solvent, and 10 mg of the sample polybenzoxazole was dissolved in 10 g of HFIP and used for the measurement.
- the measurement conditions were as follows: two HFIP-806M and two reference columns HFIP-800 of GPC standard column (column size 300 ⁇ 8.0 mm ID) manufactured by Showa Denko Co., Ltd., column temperature of 40 ° C., The solvent flow rate was 1.0 mL / min.
- Viscosity Viscosity was measured using a “VISCOMETOR BM type” manufactured by TOKIMEC under the condition of 25 ° C.
- Weight reduction temperature The weight reduction temperature was measured using a TG / DTA measuring device “DTG-60 type” manufactured by Shimadzu Corporation at a temperature increase rate of 10 ° C./min from 0 ° C. to 800 ° C. It was.
- Example 1 (Production of polybenzoxazole precursor) In a 100 ml round bottom flask equipped with a Dean-Stark water separator filled with toluene and a condenser tube, 14.65 g (40 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4,4 ′ -Diformyl-1,2-diphenylethane (9.531 g, 40 mmol) and N, N-dimethylformamide (20 ml) were added, and dehydration reaction was performed while refluxing for 10 hours under nitrogen filling.
- polybenzoxazole precursor solution (A1) having a solid content of 54% and a viscosity of 3000 mPa ⁇ s.
- the precursor had a number average molecular weight of about 6,000.
- Confirmation of compounds is the polybenzoxazole precursor solution (A1) a small amount precipitated charged into methanol 100 ml, the precipitate was filtered through a filter to obtain a solid polybenzoxazole precursor was dried under reduced pressure 1
- the analysis was performed by 1 H-NMR analysis.
- Example 2 (Production of polybenzoxazole precursor) In a 100 ml round bottom flask equipped with a Dean-Stark water separator and a condenser filled with toluene, 14.65 g (40 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4,4′- Diformyl-1,3-diphenylpropane (10.09 g, 40 mmol) and N, N-dimethylformamide (20 ml) were added, and dehydration reaction was performed while refluxing for 10 hours under nitrogen filling.
- polybenzoxazole precursor solution (A2) having a solid content of 55% and a viscosity of 2000 mPa ⁇ s.
- the precursor had a number average molecular weight of about 7,000.
- Confirmation of compounds is the polybenzoxazole precursor solution (A2) small amount precipitated charged into methanol 100 ml, the precipitate was filtered through a filter to obtain a solid polybenzoxazole precursor was dried under reduced pressure 1
- the analysis was performed by 1 H-NMR analysis.
- Example 3 (Production of polybenzoxazole precursor) In a 100 ml round bottom flask having a cooling function, 14.65 g (40 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 8.10 g (80 mmol) of triethylamine and 10 ml of N, N-dimethylformamide were added. After the addition, 12.28 g (40 mmol) of dibenzyl-4,4′-dicarbonyl chloride dissolved in 10 ml of N, N-dimethylformamide was added dropwise at 0 ° C. over 30 minutes under nitrogen filling.
- polybenzoxazole precursor solution (A3) having a solid content of 54% and a viscosity of 1000 mPa ⁇ s.
- the precursor had a number average molecular weight of about 6,000.
- a small amount of the polybenzoxazole precursor solution (A3) is poured into 100 ml of methanol to precipitate, and the precipitate is filtered and dried under reduced pressure to obtain a polybenzoxazole precursor solid.
- the FT-IR spectrum was measured by the method.
- Example 4 Formation of polybenzoxazole resin thin film
- the polybenzoxazole precursor solution (A1) obtained in Example 1 was cast on a glass substrate, a 50 ⁇ m thin film was formed with an applicator, and heat-treated on a hot plate at 150 ° C. for 1 hour. Thereafter, the hot plate temperature was maintained at 200 ° C., 250 ° C., and 300 ° C. for 1 hour each.
- the FT-IR spectrum of the obtained thin film was measured, absorption derived from benzoxazole ring formation was confirmed in the vicinity of 1557 cm ⁇ 1 and 1574 cm ⁇ 1 .
- Example 5 Formation of polybenzoxazole resin thin film
- a polybenzoxazole resin (B2) was obtained in the same manner as in Example 4 using the polybenzoxazole precursor solution (A2) obtained in Example 2.
- the obtained polybenzoxazole resin (B2) was subjected to TG / DTA measurement. As a result, the 5% weight reduction temperature in air was 540 ° C., and the 10% weight reduction temperature was 573 ° C.
- Example 6 Formation of polybenzoxazole resin thin film
- a polybenzoxazole resin (B3) was obtained in the same manner as in Example 4 using the polybenzoxazole precursor solution (A3) obtained in Example 3.
- the obtained polybenzoxazole resin (B3) was subjected to TG / DTA measurement. As a result, the 5% weight reduction temperature in air was 555 ° C., and the 10% weight reduction temperature was 596 ° C.
- Comparative Example 1 In a 100 ml round bottom flask equipped with a Dean-Stark water separator and a condenser filled with toluene, 14.64 g (40 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 5.36 g of terephthalaldehyde were added. (40 mmol) and 20 ml of N, N-dimethylformamide were added, and the mixture was refluxed for 5 hours under nitrogen. A dehydration reaction was performed while refluxing the obtained solution by vacuum distillation for 10 hours.
- Comparative Example 2 In a 100 ml round bottom flask equipped with a Dean-Stark water separator and a condenser filled with toluene, 14.64 g (40 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and isophthalaldehyde 5. 36 g (40 mmol) and 20 ml of N, N-dimethylformamide were added, and the mixture was refluxed for 5 hours under nitrogen filling. A dehydration reaction was performed while refluxing the obtained solution by vacuum distillation for 10 hours.
- a polybenzoxazole precursor solution (C3) having a solid content of 50% and a viscosity of 5000 mPa ⁇ s.
- the precursor had a number average molecular weight of about 5,000.
- a small amount of the polybenzoxazole precursor solution (C3) was poured into 100 ml of methanol to precipitate, and the precipitate was filtered and dried under reduced pressure to obtain a polybenzoxazole precursor solid.
- the FT-IR spectrum was measured by the method. As a result, absorption characteristic of the amide bond was observed in the vicinity of 1632 cm ⁇ 1 , and broad absorption derived from the OH group was observed with a peak at 3418 cm ⁇ 1 .
- a polybenzoxazole precursor solution (C4) having a solid content of 54% and a viscosity of 6000 mPa ⁇ s was obtained.
- the precursor had a number average molecular weight of about 6,000.
- a small amount of the polybenzoxazole precursor solution (C4) was poured into 100 ml of methanol to precipitate, and the precipitate was filtered and dried under reduced pressure to obtain a polybenzoxazole precursor solid.
- the FT-IR spectrum was measured by the method. As a result, absorption characteristic of the amide bond was observed in the vicinity of 1632 cm ⁇ 1 , and broad absorption derived from the OH group was observed with a peak at 3418 cm ⁇ 1 .
- Comparative Example 5 A polybenzoxazole resin (D3) was obtained in the same manner as in Example 4 using the polybenzoxazole precursor solution (C3) obtained in Comparative Example 3. The obtained polybenzoxazole resin (D3) was subjected to TG / DTA measurement. As a result, the 5% weight reduction temperature in air was 560 ° C., and the 10% weight reduction temperature was 599 ° C.
- Comparative Example 6 A polybenzoxazole resin (D4) was obtained in the same manner as in Example 4 using the polybenzoxazole precursor solution (C4) obtained in Comparative Example 4. The obtained polybenzoxazole resin (D4) was subjected to TG / DTA measurement. As a result, the 5% weight reduction temperature in air was 542 ° C., and the 10% weight reduction temperature was 571 ° C.
- the polybenzoxazole precursor of the present invention is excellent in solvent solubility and storage stability, and the polybenzoxazole resin comprising the precursor is particularly an interlayer insulating film for semiconductors, a protective film, and interlayer insulation for multilayer circuits. It is useful as a film, a cover coat of a flexible copper-clad plate, a solder resist film, a liquid crystal alignment film and the like.
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Abstract
Description
すなわち本発明は、
1.下記一般式(1)で表される繰り返し単位を有するポリベンゾオキサゾール樹脂、
2.下記一般式(2)で表される繰り返し単位を有するポリベンゾオキサゾール前駆体、
3.下記一般式(3)で表される化合物と下記一般式(4)で表されるジアルデヒド化合物とを反応させることを特徴とする、上記2.に記載のポリベンゾオキサゾール前駆体の製造方法、
4.下記一般式(5)で表される繰り返し単位を有するポリベンゾオキサゾール前駆体、
5.前記一般式(3)で表される化合物と下記一般式(6)で表される化合物とを反応させることを特徴とする、上記4.に記載のポリベンゾオキサゾール前駆体の製造方法に関する。
本発明のポリベンゾオキサゾール樹脂は、下記一般式(1)
で示される繰り返し単位を有する。
上記芳香族基には、炭素環式の又は環中に窒素、酸素及び硫黄原子より選ばれるヘテロ原子を少なくとも1個、好ましくは1~3個含有する複素環式の、単環状もしくは多環状で、場合により縮合環を形成していてもよい芳香族基が包含される。
前記R1は1種のみでもよく、2種以上を併用してもよい。
前記R2は1種のみでもよく、2種以上を併用してもよい。
本発明のポリベンゾオキサゾール樹脂は、電気絶縁特性、耐熱性、機械特性、物理特性、寸法安定性等に優れる。
本発明のポリベンゾオキサゾール前駆体は、下記一般式(2)
で示される繰り返し単位を有するポリベンゾオキサゾール前駆体である。
で示される繰り返し単位を有するポリベンゾオキサゾール前駆体である。
上記芳香族基には、炭素環式の又は環中に窒素、酸素及び硫黄原子より選ばれるヘテロ原子を少なくとも1個、好ましくは1~3個含有する複素環式の、単環状もしくは多環状で、場合により縮合環を形成していてもよい芳香族基が包含される。
以下、前記一般式(2)で示される繰り返し単位を有するポリベンゾオキサゾール前駆体を「前駆体〔1〕」、前記一般式(5)で示される繰り返し単位を有するポリベンゾオキサゾール前駆体を「前駆体〔2〕」ともいう。
なお、前駆体〔1〕及び前駆体〔2〕において、好ましいR1及びR2は、前記ポリベンゾオキサゾール樹脂における好ましいR1及びR2と同じである。
上記ポリベンゾオキサゾール前駆体〔1〕は、下記一般式(3)で表される化合物(以下、「化合物(A)」ともいう)と、下記一般式(4)で表される化合物とを反応させて得られるものであることが好ましい。以下に、ポリベンゾオキサゾール前駆体〔1〕の好ましい製造方法について説明する。
本発明のポリベンゾオキサゾール前駆体〔1〕の製造において出発原料として使用される化合物(A)は、下記一般式(3)で表される化合物である。
上記芳香族基には、炭素環式の又は環中に窒素、酸素及び硫黄原子より選ばれるヘテロ原子を少なくとも1個、好ましくは1~3個含有する複素環式の、単環状もしくは多環状で、場合により縮合環を形成していてもよい芳香族基が包含される。
上記一般式(3)で表される化合物の具体例を挙げれば以下の通りである。これらは単なる例示であり、これらに限定されるものではない。
これら化合物のうち、特に2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパンが好ましい。
これらの化合物はそれぞれ単独で使用することができ又は2種類以上併用してもよい。
本発明のポリベンゾオキサゾール前駆体〔1〕の製造方法に従い上記一般式(3)で表される化合物(A)と反応せしめられる化合物は、下記一般式(4)で表される化合物である。
上記一般式(4)で表される化合物の具体例としては、ジフェニルメタンジアルデヒド、ジフェニルエタンジアルデヒド、1,3-ジフェニルプロパンジアルデヒド、1,2-ジフェニルプロパンジアルデヒド、1,4-ジフェニルブタンジアルデヒド、1,3-ジフェニルブタンジアルデヒド、1,2-ジフェニルブタンジアルデヒド、2,3-ジフェニルブタンジアルデヒド、1,5-ジフェニルペンタンジアルデヒド、1,4-ジフェニルペンタンジアルデヒド、1,3-ジフェニルペンタンジアルデヒド、1,2-ジフェニルペンタンジアルデヒド、2,4-ジフェニルペンタンジアルデヒド、2,3-ジフェニルペンタンジアルデヒド、1,6-ジフェニルヘキサンジアルデヒド、1,5-ジフェニルヘキサンジアルデヒド、1,4-ジフェニルヘキサンジアルデヒド、1,3-ジフェニルヘキサンジアルデヒド、1,2-ジフェニルヘキサンジアルデヒド、2,5-ジフェニルヘキサンジアルデヒド、2,4-ジフェニルヘキサンジアルデヒド、2,3-ジフェニルヘキサンジアルデヒド、2,3-ジメチル-2,3-ジフェニルブタンジアルデヒドが挙げられるが、特にジフェニルエタンジアルデヒド、1,3-ジフェニルプロパンジアルデヒドが好ましい。
これらの化合物はそれぞれ単独で使用することができ又は2種類以上併用してもよい。
本発明のポリベンゾオキサゾール前駆体〔1〕の製造方法において、化合物(A)と前記一般式(4)で表される化合物との反応は、通常、常温ないし約200℃間の温度、好ましくは常温ないし約160℃の温度で、さらに好ましくは水と相溶せず沸点が100℃から180℃であるトルエンなどの溶剤を反応物が析出しない範囲内の配合比で混合し、還流脱水を行いながら2~72時間程度で行うことができる。
前記ポリベンゾオキサゾール前駆体〔2〕は、前記一般式(3)で表される化合物(化合物(A))と、下記一般式(6)で表される化合物とを反応させて得られるものであることが好ましい。以下に、ポリベンゾオキサゾール前駆体〔2〕の好ましい製造方法について説明する。
前記一般式(3)で表される化合物(化合物(A))については、前述のとおりである。
本発明のポリベンゾオキサゾール前駆体〔2〕の製造方法に従い上記一般式(3)で表される化合物(A)と反応せしめられる化合物は、下記一般式(6)で表される。
上記一般式(6)で表される化合物の具体例としては、ジフェニルメタンジカルボン酸、ジフェニルエタンジカルボン酸、1,3-ジフェニルプロパンジカルボン酸、1,2-ジフェニルプロパンジカルボン酸、1,4-ジフェニルブタンジカルボン酸、1,3-ジフェニルブタンジカルボン酸、1,2-ジフェニルブタンジカルボン酸、2,3-ジフェニルブタンジカルボン酸、1,5-ジフェニルペンタンジカルボン酸、1,4-ジフェニルペンタンジカルボン酸、1,3-ジフェニルペンタンジカルボン酸、1,2-ジフェニルペンタンジカルボン酸、2,4-ジフェニルペンタンジカルボン酸、2,3-ジフェニルペンタンジカルボン酸、1,6-ジフェニルヘキサンジカルボン酸、1,5-ジフェニルヘキサンジカルボン酸、1,4-ジフェニルヘキサンジカルボン酸、1,3-ジフェニルヘキサンジカルボン酸、1,2-ジフェニルヘキサンジカルボン酸、2,5-ジフェニルヘキサンジカルボン酸、2,4-ジフェニルヘキサンジカルボン酸、2,3-ジフェニルヘキサンジカルボン酸、2,3-ジメチル-2,3-ジフェニルブタンジカルボン酸等のジカルボン酸、
これら化合物はそれぞれ単独で使用することができ又は2種類以上併用してもよい。
化合物(A)と前記一般式(6)で表される化合物との反応は、前記一般式(6)で表される化合物がジカルボン酸もしくはジカルボン酸エステルの場合、通常、常温ないし約200℃間の温度、好ましくは常温ないし約160℃の温度で、さらに好ましくは水と相溶せず沸点が100℃から180℃であるトルエンなどの溶剤を反応物が析出しない範囲内の配合比で混合し、還流脱水もしくは還流脱アルコールを行いながら2~72時間程度で行うことができる。
例えば、化合物(A)及び前記一般式(6)で表される化合物を、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチル-2-ピロリドン等のアミド類; アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、イソホロン等のケトン類;γ-ブチロラクトン、γ-バレロラクトン、δ-バレロラクトン、γ-カプロラクトン、ε-カプロラクトン、α-メチル-γ-ブチロラクトン、乳酸エチル、酢酸メチル、酢酸エチル、酢酸ブチル等のエステル類;メタノール、エタノール、プロパノール等の炭素数1~10の脂肪族アルコール類;フェノール、クレゾール等の芳香族基含有フェノール類;ベンジルアルコール等の芳香族基含有アルコール類;エチレングリコール、プロピレングリコール等のグリコール類、又はそれらのグリコール類のメタノール、エタノール、ブタノール、ヘキサノール、オクタノール、ベンジルアルコール、フェノール、クレゾール等のモノエーテルもしくはジエーテル又は当該モノエーテルのエステル類等のグリコールエーテル類;ジオキサン、テトラヒドロフラン等の環状エーテル類;エチレンカーボネート、プロピレンカーボネート等の環状カーボネート類;脂肪族及びトルエン、キシレンなどの芳香族炭化水素類等、さらにジメチルスルホキシド等の不活性溶媒中で、前記温度条件にて2~72時間程度反応させることにより行うことができる。これらの溶剤は必要に応じて単独で又は2種類以上を混合して用いることができる。
また、本発明は、前記ポリベンゾオキサゾール前駆体を含有する被覆用組成物、及び、前記ポリベンゾオキサゾール樹脂を含有する樹脂膜に関する。
本発明のポリベンゾオキサゾール前駆体は、必要に応じて、溶剤及び/又は各種の添加剤、例えば、界面活性剤やカップリング剤等を配合することにより、半導体用層間絶縁膜、保護膜、多層回路の層間絶縁膜、フレキシブル銅張板のカバーコート、ソルダーレジスト膜、液晶配向膜等の膜の形成に有用な被覆用組成物とすることができる。
なお、本発明における評価のための測定は以下の方法で行った。実施例1~3、比較例1~4について、固形分濃度と、数平均分子量及び粘度の測定結果を表1にまとめた。また、実施例4~6、比較例5~6についてTG/DTA測定結果を表2にまとめた。
数平均分子量についてはゲル浸透クロマトグラフィー(GPC)測定により求めた。GPC測定は、昭和電工株式会社製「Shodex GPC SYSTEM-11」にて行った。溶媒にはヘキサフルオロイソプロパノール(HFIP)を用い、サンプルのポリベンゾオキサゾール10mgを10gのHFIPに溶解させて測定に用いた。測定条件は、測定カラムは昭和電工株式会社製GPC標準カラム(カラムサイズ300×8.0mmI.D.)のHFIP-806Mを2本、リファレンスカラムHFIP-800を2本用い、カラム温度40℃、溶媒流量1.0mL/minとした。標準試料にはpMMAを使用し、データ処理ソフトは昭和電工株式会社製「SIC-480II」を使用した。
(2)粘度
粘度測定は、TOKIMEC社製「VISCOMETOR BM型」を使用し、25℃の条件にて行った。
(3)重量減少温度
重量減少温度測定は、(株)島津製作所製のTG/DTA測定装置「DTG-60型」を使用し、0℃から800℃まで10℃/分の昇温速度で行った。
トルエンを満たしたディーンスターク水分離器及び冷却管をつけた100 ml丸底フラスコに2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン14.65g(40mmol)、4,4’-ジホルミル-1,2-ジフェニルエタン9.531g(40mmol)及びN,N-ジメチルホルムアミド20mlを加え、窒素封入下10時間還流させながら、脱水反応を行った。得られた溶液から減圧蒸留にてトルエンを留去して、固形分54%及び粘度3000mPa・sのポリベンゾオキサゾール前駆体溶液(A1)を得た。該前駆体は、数平均分子量約6,000であった。
合成物の確認は、上記ポリベンゾオキサゾール前駆体溶液(A1)少量を100mlのメタノール中に投じて沈殿させ、沈殿物をフィルター濾過し、減圧乾燥してポリベンゾオキサゾール前駆体の固体を得て1H-NMR分析により行った。その結果、1H-NMR分析(DMSO-d6)チャートにおいて、イミン結合に特有の8.66ppmのプロトンの消失、及び閉環後に特有の6.11ppmのプロトンの生成が確認できたことから、上記ポリベンゾオキサゾール前駆体溶液(A1)が前記一般式(2)で表される繰り返し単位を有することを確認した。
トルエンを満たしたディーンスターク水分離器及び冷却管をつけた100ml丸底フラスコに2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン14.65g(40mmol)、4,4’-ジホルミル-1,3-ジフェニルプロパン10.09g(40mmol)及びN,N-ジメチルホルムアミド20mlを加え、窒素封入下10時間還流させながら、脱水反応を行った。得られた溶液から減圧蒸留にてトルエンを留去して、固形分55%及び粘度2000mPa・sのポリベンゾオキサゾール前駆体溶液(A2)を得た。該前駆体は、数平均分子量約7,000であった。
合成物の確認は、上記ポリベンゾオキサゾール前駆体溶液(A2)少量を100mlのメタノール中に投じて沈殿させ、沈殿物をフィルター濾過し、減圧乾燥してポリベンゾオキサゾール前駆体の固体を得て1H-NMR分析により行った。その結果、1H-NMR分析(DMSO-d6)チャートにおいて、イミン結合に特有の8.66ppmのプロトンの消失、及び閉環後に特有の6.11ppmのプロトンの生成が確認できたことから、上記ポリベンゾオキサゾール前駆体溶液(A2)が一般式(2)で表される繰り返し単位を有することを確認した。
冷却機能を有する100ml丸底フラスコに2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン14.65g(40mmol)、トリエチルアミン8.10g(80mmol)にN,N-ジメチルホルムアミド10mlを添加後、N,N-ジメチルホルムアミド10mlにジベンジル-4,4’-ジカルボニルクロリド12.28g(40mmol)を溶解させたものを、窒素封入下0℃で30分かけて滴下した。滴下終了後、室温まで戻し、更に5時間撹拌反応を行って、固形分54%及び粘度1000mPa・sのポリベンゾオキサゾール前駆体溶液(A3)を得た。該前駆体は、数平均分子量約6,000であった。
合成物の確認は、上記ポリベンゾオキサゾール前駆体溶液(A3)少量を100mlのメタノール中に投じて沈殿させ、沈殿物をフィルター濾過し、減圧乾燥してポリベンゾオキサゾール前駆体の固体を得てKBr法によりFT-IRスペクトルを測定することにより行った。その結果、アミド結合に特徴的な吸収が1632cm-1付近に、またOH基に由来する幅広い吸収が3418cm-1をピークとして認められた。以上のことから、上記ポリベンゾオキサゾール前駆体溶液(A3)が一般式(5)で表される繰り返し単位を有することを確認した。
実施例1で得られたポリベンゾオキサゾール前駆体溶液(A1)をガラス基板上に流延し、アプリケーターにて50μmの薄膜を形成し、150℃のホットプレート上で1時間加熱処理した。その後、ホットプレート温度を200℃、250℃、300℃とした状態で各1時間保持した。得られた薄膜についてFT-IRスペクトルを測定したところ、1557cm-1付近、1574cm-1付近にベンゾオキサゾール環形成に由来する吸収が確認された。また、1H-NMR分析(DMSO-d6)チャートにおいて、ヘテロ原子に隣接したベンジル位特有の6.11ppmのプロトンが消失した。以上のことからポリベンゾオキサゾール前駆体溶液(A1)より得られた、薄膜のポリベンゾオキサゾール樹脂(B1)が得られていることを確認した。得られた薄膜のポリベンゾオキサゾール樹脂(B1)についてTG/DTA測定を行ったところ、空気中での5%重量減少温度は556℃、10%重量減少温度は595℃であった。
実施例2で得られたポリベンゾオキサゾール前駆体溶液(A2)を用いて、実施例4と同様の方法でポリベンゾオキサゾール樹脂(B2)を得た。得られたポリベンゾオキサゾール樹脂(B2)についてTG/DTA測定を行ったところ、空気中での5%重量減少温度は540℃、10%重量減少温度は573℃であった。
実施例3で得られたポリベンゾオキサゾール前駆体溶液(A3)を用いて、実施例4と同様の方法でポリベンゾオキサゾール樹脂(B3)を得た。得られたポリベンゾオキサゾール樹脂(B3)についてTG/DTA測定を行ったところ、空気中での5%重量減少温度は555℃、10%重量減少温度は596℃であった。
トルエンを満たしたディーンスターク水分離器及び冷却管をつけた100ml丸底フラスコに2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン14.64g(40mmol)、テレフタルアルデヒド5.36g(40mmol)及びN,N-ジメチルホルムアミド20mlを加え、窒素封入下5時間還流させた。得られた溶液から減圧蒸留にて10時間還流させながら、脱水反応を行った。得られた溶液から減圧蒸留にてトルエンを留去したが、ポリベンゾオキサゾール前駆体(C1)は溶液にはならず、固体析出が認められた。該前駆体は、数平均分子量約5,000であった。
合成物の確認は固体析出した上記ポリベンゾオキサゾール前駆体(C1)を1H-NMR分析により行った。その結果、1H-NMR分析(DMSO-d6)チャートにおいて、イミン結合に特有の8.66ppmのプロトンの消失、及び閉環後に特有の6.11ppmのプロトンの生成が確認できた。
トルエンを満たしたディーンスターク水分離器及び冷却管をつけた100 ml丸底フラスコに2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン14.64g(40mmol)、イソフタルアルデヒド5.36g(40mmol)及びN,N-ジメチルホルムアミド20mlを加え、窒素封入下5時間還流させた。得られた溶液から減圧蒸留にて10時間還流させながら、脱水反応を行った。得られた溶液から減圧蒸留にてトルエンを留去したが、ポリベンゾオキサゾール前駆体(C2)は溶液にはならず、固体析出が認められた。該前駆体は、数平均分子量約4,000であった。
合成物の確認は、固体析出した上記ポリベンゾオキサゾール前駆体(C2)を1H-NMR分析により行った。その結果、1H-NMR分析(DMSO-d6)チャートにおいて、イミン結合に特有の8.66ppmのプロトンの消失、及び閉環後に特有の6.11ppmのプロトンの生成が確認できた。
冷却機能を有する100ml丸底フラスコに2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン14.64g(40mmol)、トリエチルアミン8.10g(80mmol)にN,N-ジメチルホルムアミド10mlを添加後、N,N-ジメチルホルムアミド10mlにテレフタル酸クロリド8.12g(40mmol)を溶解させたものを、窒素封入下0℃で30分かけて滴下した。滴下終了後、室温まで戻し、更に5時間撹拌反応を行って、固形分50%及び粘度5000mPa・sのポリベンゾオキサゾール前駆体溶液(C3)を得た。該前駆体は、数平均分子量約5,000であった。
合成物の確認は、上記ポリベンゾオキサゾール前駆体溶液(C3)少量を100mlのメタノール中に投じて沈殿させ、沈殿物をフィルター濾過し、減圧乾燥してポリベンゾオキサゾール前駆体の固体を得てKBr法によりFT-IRスペクトルを測定することにより行った。その結果、アミド結合に特徴的な吸収が1632cm-1付近に、またOH基に由来する幅広い吸収が3418cm-1をピークとして認められた。
冷却機能を有する100ml丸底フラスコに2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン14.64g(40mmol)、トリエチルアミン8.10g(80mmol)にN,N-ジメチルホルムアミド10mlを添加後、N,N-ジメチルホルムアミド10mlに4,4’-オキシジベンゾイルクロリド11.80g(40mmol)を溶解させたものを、窒素封入下0℃で30分かけて滴下した。滴下終了後、室温まで戻し、更に5時間撹拌反応を行った。得られたものは固形分54%及び粘度6000mPa・sのポリベンゾオキサゾール前駆体溶液(C4)を得た。該前駆体は、数平均分子量約6,000であった。
合成物の確認は、上記ポリベンゾオキサゾール前駆体溶液(C4)少量を100mlのメタノール中に投じて沈殿させ、沈殿物をフィルター濾過し、減圧乾燥してポリベンゾオキサゾール前駆体の固体を得てKBr法によりFT-IRスペクトルを測定することにより行った。その結果、アミド結合に特徴的な吸収が1632cm-1付近に、またOH基に由来する幅広い吸収が3418cm-1をピークとして認められた。
比較例3で得られたポリベンゾオキサゾール前駆体溶液(C3)を用いて、実施例4と同様の方法でポリベンゾオキサゾール樹脂(D3)を得た。得られたポリベンゾオキサゾール樹脂(D3)についてTG/DTA測定を行ったところ、空気中での5%重量減少温度は560℃、10%重量減少温度は599℃であった。
比較例4で得られたポリベンゾオキサゾール前駆体溶液(C4)を用いて、実施例4と同様の方法でポリベンゾオキサゾール樹脂(D4)を得た。得られたポリベンゾオキサゾール樹脂(D4)についてTG/DTA測定を行ったところ、空気中での5%重量減少温度は542℃、10%重量減少温度は571℃であった。
Claims (10)
- R2が、-(CH2)m-(mは2~6の整数を示す。)で表される、請求項1に記載のポリベンゾオキサゾール樹脂。
- R1が、下記一般式(7)~(9)で表されるいずれかの構造である、請求項1に記載のポリベンゾオキサゾール樹脂。
- 請求項1に記載のポリベンゾオキサゾール樹脂を含有する樹脂膜。
- 請求項2に記載のポリベンゾオキサゾール前駆体を含有する被覆用組成物。
- 請求項4に記載のポリベンゾオキサゾール前駆体を含有する被覆用組成物。
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JPWO2012137840A1 (ja) | 2014-07-28 |
CN103459467A (zh) | 2013-12-18 |
TWI553034B (zh) | 2016-10-11 |
CN103459467B (zh) | 2016-04-06 |
US9410055B2 (en) | 2016-08-09 |
EP2695906A4 (en) | 2014-11-05 |
JP5870997B2 (ja) | 2016-03-01 |
KR101875214B1 (ko) | 2018-07-06 |
KR20140026384A (ko) | 2014-03-05 |
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