WO2019244693A1 - 硬化性組成物 - Google Patents
硬化性組成物 Download PDFInfo
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- WO2019244693A1 WO2019244693A1 PCT/JP2019/022923 JP2019022923W WO2019244693A1 WO 2019244693 A1 WO2019244693 A1 WO 2019244693A1 JP 2019022923 W JP2019022923 W JP 2019022923W WO 2019244693 A1 WO2019244693 A1 WO 2019244693A1
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- 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
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
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- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
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- C08G65/48—Polymers modified by chemical after-treatment
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- C08G73/121—Preparatory processes from unsaturated precursors and polyamines
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- C08G73/126—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic
- C08G73/127—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic containing oxygen in the form of ether bonds in the main chain
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- C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
- C09D139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
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- 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
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
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- 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
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- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C09J179/00—Adhesives 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 C09J161/00 - C09J177/00
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Definitions
- the present invention relates to a curable composition and a structure containing the cured or semi-cured product.
- Priority is claimed on Japanese Patent Application No. 2018-117284, filed on June 20, 2018, the content of which is incorporated herein by reference.
- Engineering plastic is a high-performance material that has both high heat resistance and mechanical properties, and is widely used as an essential material for miniaturization, weight reduction, high performance, and high reliability of various parts.
- polyimide is one of engineering plastics, but it is difficult to dissolve in a solvent and hard to melt, so that it is difficult to obtain a molded product suitable for a use (Patent Document 1 and the like).
- polyetheretherketone also called super-engineering plastic
- PEEK polyetheretherketone
- thermoplastic resin having a continuous use temperature of 260 ° C. and excellent performance in heat resistance, flame retardancy, and electrical properties, but has a melting point of 343. Since the temperature is ° C, it is particularly difficult to melt, and it is difficult to dissolve in a solvent, so that the processability is poor (for example, Patent Document 2).
- an object of the present invention is to provide a curable composition which is excellent in processability and can form a cured product having super heat resistance. Another object of the present invention is to provide a method for producing a molded article, which comprises molding the curable composition to obtain a molded article. Another object of the present invention is to provide an adhesive, a sealant, or a paint that can be used in an environment where ultra heat resistance is required. Another object of the present invention is to provide a method of manufacturing a laminate having a configuration in which a cured product having ultra heat resistance or a semi-cured product thereof and a substrate are laminated. Another object of the present invention is to provide a solid containing a cured product having ultra heat resistance or a semi-cured product thereof.
- the present inventors have conducted intensive studies in order to solve the above-mentioned problems.
- the compound represented by the following formula (1) has good solvent solubility, and therefore has excellent workability. It has been found that a cured product of the resulting compound has super heat resistance, flame retardancy, and good dielectric properties.
- the present invention has been completed based on these findings.
- the present invention provides the following formula (1) [In the formula, R 1 and R 2 are the same or different and represent a curable functional group, and D 1 and D 2 are the same or different and represent a single bond or a linking group.
- L represents a divalent group having a repeating unit including a structure represented by the following formula (I) and a structure represented by the following formula (II).
- Ar 1 to Ar 3 are the same or different, and a group in which two hydrogen atoms are removed from the structural formula of an aromatic ring, or two or more aromatic rings are bonded via a single bond or a linking group.
- a curable composition comprising a compound represented by the formula: and a solvent.
- the present invention also provides the curable composition, wherein the solvent is at least one solvent selected from ketones, amides, halogenated hydrocarbons, sulfoxides, ethers, esters, nitriles, and aromatic hydrocarbons. .
- the present invention also provides the curable composition, wherein R 1 and R 2 in the formula (1) are the same or different and are a curable functional group having a cyclic imide structure.
- the present invention also relates to the above-mentioned, wherein R 1 and R 2 in the formula (1) are the same or different and are groups selected from groups represented by the following formulas (r-1) to (r-6).
- a curable composition is provided. (The bond extending from the nitrogen atom in the formula binds to D 1 or D 2 )
- the present invention also relates to the following formulas (d-1) to (d-4) wherein D 1 and D 2 in the formula (1) are the same or different.
- the curable composition is a group selected from a group having a structure represented by the formula:
- Ar 1 to Ar 3 in the formulas (I) and (II) are the same or different, and two hydrogen atoms are excluded from the structural formula of the aromatic ring having 6 to 14 carbon atoms.
- the group or two or more aromatic rings having 6 to 14 carbon atoms are a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or branched alkylene group having 1 to 5 carbon atoms
- the curable composition is a group obtained by removing two hydrogen atoms from a structural formula in which at least one hydrogen atom of an alkylene group is bonded via a group substituted with a halogen atom.
- the present invention also provides the curable composition, wherein the structure represented by the formula (I) is a structure derived from benzophenone.
- the present invention also provides the curable composition, wherein the proportion of the benzophenone-derived structural unit in the total amount of the compound represented by the formula (1) is 5% by weight or more.
- the present invention also relates to a compound represented by the formula (II) wherein hydroquinone, resorcinol, 2,6-naphthalenediol, 2,7-naphthalenediol, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether
- the curable composition having a structure derived from at least one compound selected from 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone, and bisphenol A provide.
- the present invention also relates to hydroquinone, resorcinol, 2,6-naphthalenediol, 2,7-naphthalenediol, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxy, based on the total amount of the compound represented by the formula (1).
- the curable composition wherein the ratio of structural units derived from diphenyl ether, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylsulfone, and bisphenol A is 5% by weight or more. I will provide a.
- the present invention also provides a method for producing a molded article, which comprises molding the curable composition to obtain a molded article.
- the present invention also provides an adhesive containing the curable composition.
- the present invention also provides a paint containing the curable composition.
- the present invention also provides a sealant containing the curable composition.
- the present invention also provides, on the substrate, a thin film composed of a solidified product of the curable composition, and by performing a heat treatment, the cured product or semi-cured product of the curable composition and the substrate are laminated.
- the present invention also provides a method for applying the curable composition on a plastic support, drying the curable composition, and obtaining a thin film comprising a solidified product of the curable composition, and peeling the obtained thin film from the support.
- a method for manufacturing the laminate wherein the laminate is subjected to heat treatment.
- the present invention also includes a cured product of a curable compound, and has a 5% weight loss temperature (T d5 ) measured at a heating rate of 10 ° C./min (in nitrogen) of 300 ° C. or higher, and a temperature of 30 ° C. at 320 ° C.
- T d5 5% weight loss temperature measured at a heating rate of 10 ° C./min (in nitrogen) of 300 ° C. or higher, and a temperature of 30 ° C. at 320 ° C.
- the present invention also provides the solid having a peak in a region of 1620 to 1750 cm -1 of an IR spectrum.
- the curable composition of the present invention contains a curable compound capable of forming a cured product having excellent heat resistance, flame retardancy, and good dielectric properties upon curing, in a state of being dissolved in a solvent. Therefore, the composition has good processability (or easy moldability). Then, it is quickly cured by performing a heat treatment or radiation irradiation. Therefore, the curable composition of the present invention is required to be used in fields where ultra heat resistance, flame retardancy, and good dielectric properties (low dielectric constant and dielectric loss tangent) are required (for example, electronic information equipment, home appliances, automobiles, precision machinery) , Aircraft, space industry equipment, etc.), adhesives, sealants, paints and the like.
- ultra heat resistance, flame retardancy, and good dielectric properties low dielectric constant and dielectric loss tangent
- FIG. 3 is a diagram showing a 1 H-NMR spectrum (DMSO-d 6 ) of diamine (1) obtained in Preparation Example. It is a figure which shows the FTIR spectrum of diamine (1) obtained by the preparation example.
- FIG. 3 is a diagram showing a 1 H-NMR spectrum (DMSO-d 6 ) of diamine (2) obtained in Preparation Example. It is a figure which shows the FTIR spectrum of the diamine (2) obtained by the preparation example.
- FIG. 3 is a view showing a 1 H-NMR spectrum (CDCl 3 ) of the curable compound A obtained in Preparation Example. It is a figure which shows the FTIR spectrum of the curable compound A obtained by the preparation example.
- FIG. 3 is a diagram showing a 1 H-NMR spectrum (DMSO-d 6 ) of diamine (1) obtained in Preparation Example. It is a figure which shows the FTIR spectrum of diamine (1) obtained by the preparation example.
- FIG. 3 is a diagram showing a 1 H-NMR
- FIG. 3 is a view showing a 1 H-NMR spectrum (CDCl 3 ) of a curable compound B obtained in Preparation Example. It is a figure which shows the FTIR spectrum of the curable compound B obtained by the preparation example.
- FIG. 3 is a view showing a 1 H-NMR spectrum (CDCl 3 ) of a curable compound C obtained in Preparation Example. It is a figure which shows the FTIR spectrum of the curable compound C obtained by the preparation example.
- FIG. 3 is a view showing a 1 H-NMR spectrum (CDCl 3 ) of a curable compound D obtained in Preparation Example. It is a figure which shows the FTIR spectrum of the curable compound D obtained by the preparation example.
- the curable composition of the present invention contains a compound represented by the formula (1) described later in detail (hereinafter, may be referred to as “compound (1)”) and a solvent.
- the curable composition of the present invention can contain the compound (1) and the solvent each alone or in combination of two or more.
- the curable composition of the present invention includes a solution of the compound (1) dissolved in a solvent, and a mixture of the compound (1) and a solvent.
- the curable composition of the present invention is preferably a solvent-dissolved substance, in view of obtaining a cured product having excellent workability and a uniform composition.
- the curable composition of the present invention may contain other components as necessary, in addition to the compound (1) and the solvent.
- known or commonly used additives can be used.
- curable compounds other than the compound (1) catalysts, fillers, organic resins (silicone resins, epoxy resins, fluororesins, etc.), stabilization Agents (antioxidants, UV absorbers, light stabilizers, heat stabilizers, etc.), flame retardants (phosphorus flame retardants, halogen flame retardants, inorganic flame retardants, etc.), flame retardant aids, reinforcing materials, nuclei Agents, coupling agents, lubricants, waxes, plasticizers, release agents, impact modifiers, hue improvers, flow improvers, colorants (dyes, pigments, etc.), dispersants, defoamers, defoamers Agents, antibacterial agents, preservatives, viscosity modifiers, thickeners and the like. These can be used alone or in combination of two or more.
- the filler includes an organic filler and an inorganic filler.
- a carbon material for example, carbon black, artificial graphite, expanded graphite, natural graphite, coke, carbon nanotube, diamond, etc.
- a carbon compound silicon carbide, fluorine carbide, boron carbide, tungsten carbide, Titanium carbide), nitrogen compounds (boron nitride, aluminum nitride, titanium nitride, carbon nitride, silicon nitride, etc.), minerals or ceramics (talc, mica, zeolite, ferrite, tourmaline, diatomaceous earth, calcined siliceous earth, kaolin, Sericite, bentonite, smectite, clay, silica, quartz powder, glass beads, glass powder, glass flakes, milled fiber, wollastonite, etc.), simple metals or alloys (eg, metallic silicon, iron, copper, magnesium, aluminum,
- the content of the filler is, for example, in the range of 0.1 to 95 parts by weight with respect to 100 parts by weight of the curable compound, and can be appropriately adjusted depending on the use.
- the content of the compound (1) in the total amount of the curable composition of the present invention is, for example, 1 to 30% by weight, and the lower limit is preferably 5% by weight, more preferably. Is 10% by weight, particularly preferably 15% by weight.
- the ratio of the compound (1) (when two or more kinds are contained, the total amount) in the total amount of the nonvolatile components of the curable composition of the present invention is, for example, 30% by weight or more, preferably 50% by weight or more, particularly preferably. Is at least 70% by weight, most preferably at least 90% by weight. The upper limit is 100% by weight.
- the curable composition of the present invention may contain a curable compound other than the compound (1), the compound (1) accounts for the total amount (100% by weight) of the curable compound contained in the curable composition.
- the proportion is, for example, 70% by weight or more, preferably 80% by weight or more, particularly preferably 90% by weight or more.
- the upper limit is 100% by weight.
- the content of the solvent in the total amount of the curable composition of the present invention is, for example, 30 to 99% by weight, and the lower limit is preferably 50% by weight, more preferably 60% by weight. %, Particularly preferably 70% by weight, most preferably 80% by weight.
- the upper limit is preferably 95% by weight, particularly preferably 90% by weight.
- the curable composition of the present invention is rapidly cured by heat treatment to form a cured product having a highly crosslinked structure (that is, having a high crosslinking density).
- a step of performing a drying treatment to volatilize the solvent may be provided. Further, the heat treatment can be performed under normal pressure, or can be performed under reduced pressure or increased pressure.
- the heat treatment temperature can be appropriately adjusted depending on the type of the curable functional group contained in the compound (1) contained in the curable composition.
- a cured product can be formed by heating at a temperature of about 250 ° C.
- a cured product can be formed by heating at a temperature of about 380 ° C.
- the heating may be performed while the temperature is kept constant, or may be performed stepwise.
- the heating temperature can be appropriately adjusted according to the heating time. For example, when shortening the heating time is desired, it is preferable to set the heating temperature higher. Since the compound (1) has a high ratio of the structure derived from an aromatic ring, a cured product (specifically, a cured product having super heat resistance) can be formed without decomposition even when heated at a high temperature. By heating for a short time, a cured product can be efficiently formed with excellent workability.
- the heating means is not particularly limited, and known or commonly used means can be used.
- the curable composition of the present invention can also form a semi-cured product (B stage) by temporarily stopping the curing reaction halfway.
- the semi-cured material temporarily develops fluidity by heating, and can follow steps.
- a cured product having super heat resistance, flame retardancy, and good dielectric properties can be formed as described above.
- the degree of cure of the semi-cured product is, for example, 85% or less (eg, 10 to 85%, particularly preferably 15 to 75%, and more preferably 20 to 70%).
- the curable composition of the present invention does not contain a crosslinking agent or a curing accelerator (for example, the total content of the crosslinking agent and the curing accelerator in the total amount of the curable composition of the present invention is 3% by weight or less, preferably 1% by weight or less.
- a cured product can be formed quickly (even if the amount is less than 10% by weight). Therefore, the obtained cured product has super heat resistance.
- the content of the unreacted curing accelerator and the decomposition product of the curing accelerator in the cured product can be suppressed to an extremely low level, the generation of outgas derived from these can be suppressed.
- Cured product of the curable composition of the present invention [preferably, compound (1) is at least 70% by weight (preferably at least 80% by weight, particularly preferably at least 90% by weight of the total amount of the curable compound contained in the curable composition] ) -Containing curable composition] has excellent heat resistance, and a 5% weight loss temperature (T d5 ) measured at a heating rate of 10 ° C./min (in nitrogen) is, for example, 300 ° C. or higher, preferably The temperature is 400 ° C. or higher, particularly preferably 450 ° C. or higher, and most preferably 500 ° C. or higher.
- the upper limit of the 5% weight loss temperature (T d5 ) is, for example, 600 ° C., preferably 550 ° C., and particularly preferably 530 ° C.
- the 5% weight loss temperature can be measured by TG / DTA (simultaneous measurement of differential heat and thermogravimetry).
- the cured product [preferably a curable composition containing compound (1) in an amount of 70% by weight or more (preferably 80% by weight or more, particularly preferably 90% by weight or more) of the total amount of the curable compound contained in the curable composition]
- Cured product of the composition has a 10% weight loss temperature (T d10 ) measured at a heating rate of 10 ° C./min (in nitrogen), for example, 300 ° C. or higher, preferably 400 ° C. or higher, particularly preferably 480 ° C.
- the temperature is most preferably 500 ° C. or more.
- the upper limit of the 10% weight loss temperature (T d10 ) is, for example, 600 ° C., preferably 550 ° C.
- the 10% weight loss temperature can be measured by TG / DTA (simultaneous measurement of differential heat and thermogravimetry).
- a curable product containing the above-mentioned cured product [preferably containing at least 70% by weight (preferably at least 80% by weight, particularly preferably at least 90% by weight) of the total amount of the curable compound contained in the curable composition.
- the cured product of the composition has excellent flame retardancy, and the cured product having a thickness of 0.15 mm has a V-1 grade incombustibility by a method conforming to UL94V, that is, the following conditions 1 to 5 are satisfied.
- the combustion duration is 30 seconds or less.
- the total combustion duration of the five samples is 250 seconds or less.
- the red heat duration after the second flame contact is 60 seconds or less.
- Clamp for fixing Does not burn to the part (5) Drops burning particles and does not burn cotton underlay
- the cured product preferably a curable composition containing 70% by weight or more (preferably 80% by weight or more, particularly preferably 90% by weight or more) of the total amount of the curable compound contained in the curable composition. Is excellent in insulation, and has a relative dielectric constant of, for example, 6 or less (eg, 1 to 6), preferably 5 or less (eg, 1 to 5), and particularly preferably 4 or less (eg, 1 to 4).
- the cured product preferably a curable composition containing compound (1) in an amount of 70% by weight or more (preferably 80% by weight or more, particularly preferably 90% by weight or more) of the total amount of the curable compound contained in the curable composition]
- the cured product of the composition has excellent insulating properties, and its dielectric loss tangent is, for example, 0.05 or less (eg, 0.0001 to 0.05), preferably 0.0001 to 0.03, and particularly preferably 0.0001 to 0. .015.
- the “relative permittivity” and “dielectric tangent” are values measured at a measurement frequency of 1 MHz and a measurement temperature of 23 ° C. according to JIS-C2138, or at a frequency of 1 GHz and 23 ° C. according to ASTM @ D2520. The value to be measured.
- the curable composition of the present invention is molded by a well-known and commonly used molding method, and then subjected to a heat treatment (if necessary, a drying treatment), whereby a cured product or a semi-cured product of the curable composition is obtained.
- a molded article made of a product can be manufactured.
- a desired shape can be given to a solidified product of the curable composition (preferably, a solidified product of the compound (1)). Is obtained.
- the molded body made of the solidified material temporarily exhibits fluidity or adhesiveness by heating, and can be subjected to secondary molding and adhesion to other members.
- a molded product composed of a cured product or semi-cured product of the curable composition preferably, a cured product or semi-cured product of compound (1)
- the shape of the molded body is not particularly limited, and a shape according to the use can be appropriately selected.
- the curable composition of the present invention is applied to a substrate and subjected to a heat treatment to obtain a cured product having excellent adhesion to the substrate, and a tensile shear force (JIS K6850 (1999)) between the substrate and the cured product is obtained. )) Is, for example, 1 MPa or more, preferably 5 MPa or more, particularly preferably 10 MPa or more.
- the tensile shearing force can be measured at a tensile speed of 300 mm / min and a peeling angle of 180 ° using a tensile tester (manufactured by Orientec, Tensilon UCT-5T).
- the curable composition of the present invention can be used under severe environmental temperature conditions, for example, in electronic information devices, home appliances, automobiles, precision machines, aircraft, space industry equipment, and energy fields (oil field drilling pipes / tubes, fuel containers). Molding materials for composite materials (fiber reinforced plastics, prepregs, etc.) used, functional materials such as shielding materials, conductive materials (for example, heat conductive materials), insulating materials, adhesives (for example, heat-resistant adhesives) Can be suitably used.
- automotive parts such as sealants, paints, inks, sealants, resists, molding materials, forming materials [thrust washers, oil filters, seals, bearings, gears, cylinder head covers, bearing retainers, intake manifolds, pedals, etc .;
- Semiconductors and liquid crystals such as electrical insulating materials (insulating films, etc.), laminated boards, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, silicon wafer carriers, IC chip trays, electrolytic capacitor trays, insulating films, etc.
- Body Such as used for Body can be preferably used as the forming material] such members and the like for electric and electronic equipment as typified by a keyboard support which is a member for supporting a keyboard inside a personal computer.
- the curable composition of the present invention is particularly suitable for a semiconductor device having a high heat resistance and a high withstand voltage (such as a power semiconductor), which is difficult to cope with a conventional resin material. It can be preferably used as a sealant used in an environment where properties are required.
- the curable composition of the present invention can be used as an adhesive [for example, an adhesive used in an environment where ultra heat resistance is required, such as an application for laminating semiconductors in a semiconductor device (such as a power semiconductor) having a high heat resistance and a high withstand voltage. Etc.] can be preferably used.
- the curable composition of the present invention may be used as a coating material [for example, a coating material for semiconductor materials, paper, coated paper, plastic film, wood, cloth, nonwoven fabric, and metal; a semiconductor device (power semiconductor) having high heat resistance and high voltage resistance. And the like, which are used in an environment where super heat resistance is required.
- a coating material for example, a coating material for semiconductor materials, paper, coated paper, plastic film, wood, cloth, nonwoven fabric, and metal; a semiconductor device (power semiconductor) having high heat resistance and high voltage resistance. And the like, which are used in an environment where super heat resistance is required.
- the curable composition of the present invention can be suitably used as a material for forming a composite material.
- a composite material containing the compound (1), a cured product thereof, or a semi-cured product thereof and a fiber can be easily produced.
- the shape of the composite material is not particularly limited, such as a fiber shape and a sheet shape.
- the fibers include carbon fibers, aramid fibers, and glass fibers. These can be used alone or in combination of two or more.
- the fiber may be in the form of a thread or a sheet (woven or non-woven fabric).
- a fiber is immersed in the curable composition of the present invention, the fiber is impregnated with the curable composition, and then the impregnated curable compound is dried. And the like. After drying, the compound (1) contained in the impregnated curable composition can be cured or semi-cured by performing a heat treatment, and the cured product of the compound (1) or the semi-cured product thereof and a fiber Is obtained.
- a composite material containing a semi-cured compound (1) and fibers can be suitably used as an intermediate product such as a prepreg.
- the composite material thus obtained has a configuration in which the above-mentioned curable compound has penetrated into the voids of the fiber and has been cured, is lightweight, has high strength, and is excellent in heat resistance, flame retardancy, and insulation. Therefore, it can be suitably used as a material that replaces metals such as iron and aluminum in the fields of housing and construction, sports equipment, automobiles, and the aerospace industry.
- materials for fire-fighting clothing (fire protection clothing, activity clothing, rescue clothing, heat-resistant clothing); curtains installed in places where fire resistance is required by the Fire Service Law, such as high-rise buildings, underground shopping centers, theaters, and vehicles; It can be suitably used as a rug material; a separator such as a separator for a secondary battery or a fuel cell; a filter such as an industrial filter, a vehicle-mounted filter, or a medical filter; or a space material.
- the laminate of the present invention has a configuration in which a cured or semi-cured compound (1) and a substrate are laminated.
- the laminate of the present invention includes a cured product or semi-cured product / substrate of the compound (1) and a cured product or semi-cured product / substrate of the substrate / compound (1).
- a semiconductor material for example, ceramic, SiC, gallium nitride, etc.
- paper coated paper
- plastic film wood, cloth, nonwoven fabric
- metal for example, stainless steel, aluminum alloy, copper
- the laminate can be manufactured by, for example, placing the compound (1) on a substrate and performing a heat treatment.
- the method for manufacturing the laminate includes the following method. 1.
- the heat treatment conditions can be appropriately set within the same range as the curing conditions for the curable compound described above.
- the thin film of the above method 2 can be produced, for example, by applying a solution or dispersion of the compound (1) on a substrate and drying the obtained coating film. Further, the thin film can be produced by applying a melt of the compound (1) on a substrate and cooling the obtained coating film.
- the thin film to be laminated on the substrate for example, a solvent solution or dispersion of the compound (1) is applied on a support, and the obtained coating film is dried. Peeled ones can be used. Further, as the thin film, a film obtained by applying a melt of the compound (1) on a support, cooling the obtained coating film, and peeling the coating from the support can also be used.
- the curable composition of the present invention can be suitably used as a solvent solution of the compound (1).
- a thin film composed of a solidified product of the curable composition is obtained by applying the curable composition and drying.
- Compound (1) melts at a temperature at which plastics such as polyimide and fluororesin do not melt.
- plastics such as polyimide and fluororesin do not melt.
- the curing temperature is about 250 ° C. Therefore, a plastic support (for example, a support made of polyimide or fluororesin) can be used.
- a belt conveyor is included. The laminate can be manufactured continuously on a manufacturing line.
- ⁇ Compound (1) has a small curing shrinkage and is excellent in shape stability. Therefore, a thin film having a smooth surface can be obtained by uniformly applying a melt, a solvent solution, or a solvent dispersion of the compound (1) on a support or the like. An excellent cured product or semi-cured product can be formed. Therefore, the cured product or semi-cured product can be adhered well to the surface of the substrate having low flexibility and shape followability, and can be firmly bonded to the substrate.
- the laminate can be suitably used for an electronic circuit board.
- Solids The solid of the present invention contains a cured product of a curable compound and has the following properties. Solid properties: The 5% weight loss temperature (T d5 ) measured at a heating rate of 10 ° C./min (in nitrogen) is 300 ° C. or more, and the nitrogen atom content after heat treatment at 320 ° C. for 30 minutes is 2%. 0.8 to 0.1% by weight
- the cured product of the curable compound is a crosslinked structure (or polymer) of the curable compound.
- the solid of the present invention may contain other components in addition to the cured product of the curable compound, but the proportion of the cured product in the total solid content is, for example, 70% by weight or more, preferably 80% by weight or more. % By weight or more, particularly preferably 90% by weight or more. The upper limit is 100% by weight.
- the 5% weight loss temperature (T d5 ) of the solid is preferably 400 ° C. or higher, particularly preferably 450 ° C. or higher, and most preferably 500 ° C. or higher.
- the upper limit of the 5% weight loss temperature (T d5 ) is, for example, 600 ° C., preferably 550 ° C., and particularly preferably 530 ° C.
- the nitrogen content of the solid after the heat treatment is, for example, 2.8 to 0.1% by weight, preferably 2.5 to 0.15% by weight, more preferably 2.0 to 0.20% by weight. %, Particularly preferably 1.8 to 0.40% by weight, most preferably 1.5 to 0.70% by weight. Therefore, the solid of the present invention is excellent in toughness and heat resistance. On the other hand, if the nitrogen atom content is below the above range, the toughness and heat resistance of the solid tend to decrease.
- the nitrogen atom content in the solid after the heat treatment can be determined, for example, by CHN elemental analysis.
- the solid may contain additives other than the cured product of the curable compound, but when the solid is subjected to a heat treatment at 320 ° C. for 30 minutes, an additive having a decomposition point or a boiling point below 320 ° C. The substance is decomposed and disappears, and only a cured product of the curable compound remains. Therefore, the nitrogen atom content in the cured product after the heat treatment can be estimated as the nitrogen atom content contained in the cured product of the curable compound.
- a hardening process can also be heat processing from a viewpoint of a heat history.
- the solid of the present invention has a peak in a region of 1620 to 1750 cm -1 in the IR spectrum.
- the solid of the present invention may be, for example, the above-mentioned curable composition [preferably, compound (1) is 70% by weight or more (preferably 80% by weight or more, particularly preferably 80% by weight or more of the total amount of the curable compound contained in the curable composition] Curable composition containing at least 90% by weight)].
- compound (1) is 70% by weight or more (preferably 80% by weight or more, particularly preferably 80% by weight or more of the total amount of the curable compound contained in the curable composition] Curable composition containing at least 90% by weight)].
- the solid matter of the present invention is a cured product of the curable composition
- the compound (1) is at least 70% by weight (preferably at least 80% by weight, based on the total amount of the curable compound contained in the curable composition, Particularly preferably 90% by weight or more).
- the proportion occupied by the cured product of the compound (1) in the total amount of the solid is, for example, 70% by weight or more, preferably 80% by weight or more, and particularly preferably 90% by weight or more.
- the upper limit is 100% by weight.
- the compound (1) of the present invention is a curable compound represented by the following formula (1).
- R 1 and R 2 are the same or different and represent a curable functional group
- D 1 and D 2 are the same or different and represent a single bond or a linking group
- L represents a divalent group having a repeating unit including a structure represented by the following formula (I) and a structure represented by the following formula (II).
- Ar 1 to Ar 3 are the same or different, and a group in which two hydrogen atoms are removed from the structural formula of an aromatic ring, or two or more aromatic rings are bonded via a single bond or a linking group.
- X represents —CO—, —S—, or —SO 2 —
- Y represents the same or different and represents —S—, —SO 2 —, —O—, —CO—, —COO—, or —CONH—, where n is an integer of 0 or more.
- R 1 and R 2 represent a curable functional group.
- R 1 and R 2 may be the same or different.
- a curable functional group having a cyclic imide structure such as a group represented by the following formula (r) is preferable. (The bond extending from the nitrogen atom in the formula binds to D 1 or D 2 )
- Q represents C or CH.
- the two Qs in the formula are connected via a single bond or a double bond.
- n ′ is an integer of 0 or more (eg, an integer of 0 to 3, preferably 0 or 1).
- R 3 to R 6 are the same or different and are each independently a hydrogen atom, a saturated or unsaturated aliphatic hydrocarbon group (preferably an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, 10 alkynyl groups), an aromatic hydrocarbon group (preferably, an aryl group having 6 to 10 carbon atoms such as a phenyl group and a naphthyl group), or the saturated or unsaturated aliphatic hydrocarbon group and the aromatic hydrocarbon group.
- a group in which two or more selected groups are bonded. Two groups selected from R 3 to R 6 may be bonded to each other to form a ring together with adjacent carbon atoms.
- Examples of the ring which two groups selected from R 3 to R 6 may bond to each other to form together with adjacent carbon atoms include an alicyclic ring having 3 to 20 carbon atoms and a ring having 6 to 14 carbon atoms.
- the aromatic ring of The alicyclic ring having 3 to 20 carbon atoms includes, for example, about 3 to 20 members (preferably 3 to 15 members, particularly preferably 5 to 8 members) such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring and a cyclohexane ring.
- a cycloalkene ring of about 3 to 20 members such as a cyclopentene ring and a cyclohexene ring; a perhydronaphthalene ring, a norbornane ring and a norbornene ring , Adamantane ring, tricyclo [5.2.1.0 2,6 ] decane ring, tetracyclo [4.4.0.1 2,5 . [ 1,7,10 ] dodecane rings and the like.
- the aromatic ring having 6 to 14 carbon atoms includes a benzene ring, a naphthalene ring and the like.
- curable functional group having a cyclic imide structure among others, a curable functional group having a cyclic unsaturated imide structure, or a curable functional group having a cyclic imide structure having an arylethynyl group is preferable, and particularly preferably. It is a group selected from the groups represented by the following formulas (r-1) to (r-6), and particularly preferably a group represented by the following formula (r-1) or (r-5). (The bond extending from the nitrogen atom in the formula binds to D 1 or D 2 in the formula (1))
- One or more substituents may be bonded to the groups represented by the formulas (r-1) to (r-6).
- substituents include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom.
- alkyl group having 1 to 6 carbon atoms examples include direct groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, and hexyl group.
- direct groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, and hexyl group.
- a linear or branched alkyl group can be mentioned.
- alkoxy group having 1 to 6 carbon atoms examples include a linear or branched alkoxy group such as a methoxy group, an ethoxy group, a butoxy group and a t-butyloxy group.
- D 1 and D 2 are the same or different and represent a single bond or a linking group.
- the linking group include a divalent hydrocarbon group, a divalent heterocyclic group, a carbonyl group, an ether bond, an ester bond, a carbonate bond, an amide bond, an imide bond, and a group in which a plurality of these are linked. Is mentioned.
- the divalent hydrocarbon group includes a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group.
- Examples of the divalent aliphatic hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms and a linear or branched alkenylene group having 2 to 18 carbon atoms.
- Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group.
- Examples of the linear or branched alkenylene group having 2 to 18 carbon atoms include a vinylene group, a 1-methylvinylene group, a propenylene group, a 1-butenylene group, and a 2-butenylene group.
- Examples of the divalent alicyclic hydrocarbon group include a divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms, such as a 1,2-cyclopentylene group and a 1,3-cyclopentene group.
- a cycloalkylene group (including a cycloalkylidene group) such as a len group, a cyclopentylidene group, a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group, and a cyclohexylidene group; No.
- divalent aromatic hydrocarbon group examples include an arylene group having 6 to 14 carbon atoms, such as a 1,4-phenylene group, a 1,3-phenylene group, and a 4,4′-biphenylene group. , 3,3'-biphenylene group, 2,6-naphthalenediyl group, 2,7-naphthalenediyl group, 1,8-naphthalenediyl group, anthracenediyl group and the like.
- the heterocyclic ring constituting the divalent heterocyclic group includes an aromatic heterocyclic ring and a non-aromatic heterocyclic ring.
- a 3- to 10-membered ring preferably a 4- to 6-membered ring
- having a carbon atom and at least one kind of hetero atom for example, an oxygen atom, a sulfur atom, a nitrogen atom, etc.
- Ring and condensed rings thereof.
- a heterocyclic ring containing an oxygen atom as a hetero atom eg, a three-membered ring such as an oxirane ring; a four-membered ring such as an oxetane ring; a furan ring, a tetrahydrofuran ring, an oxazole ring, an isoxazole ring, and a ⁇ -butyrolactone ring
- 5-membered ring such as 4-oxo-4H-pyran ring, tetrahydropyran ring, morpholine ring and the like; benzofuran ring, isobenzofuran ring, 4-oxo-4H-chromene ring, chroman ring, isochroman ring and the like Condensed ring; 3-oxatricyclo [4.3.1.1 4,8 ] undecane-2-one ring, 3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one ring
- D 1 and D 2 preferably include a divalent aromatic hydrocarbon group, since a cured product having particularly excellent heat resistance can be obtained.
- the divalent aromatic hydrocarbon group is preferably a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms, more preferably a group represented by the following formulas (d-1) to (d-4). And particularly preferably a group represented by the following formula (d-1) (a 1,2-phenylene group, a 1,3-phenylene group, or a 1,4-phenylene group).
- D 1 and D 2 are, together with the divalent aromatic hydrocarbon group, at least one group selected from the group consisting of a carbonyl group, an ether bond, an ester bond, a carbonate bond, an amide bond, and an imide bond. Is preferably a group in which an ether bond is connected to the divalent aromatic hydrocarbon group.
- R 1 -D 1 -group and the R 2 -D 2 -group in the formula (1) the same or different groups represented by the following formula (rd-1) or (rd-2) Is preferable, and a group represented by the following formula (rd-1-1) or (rd-2-1) is particularly preferable.
- a bond extending from a phenylene group or an oxygen atom in the formula is bonded to L in the formula (1)
- L in the formula (1) represents a divalent group having a repeating unit including the structure represented by the formula (I) and the structure represented by the formula (II).
- Ar 1 to Ar 3 in the formulas (I) and (II) are the same or different, and a group in which two hydrogen atoms are removed from the structural formula of an aromatic ring, or two or more aromatic rings are a single bond Or a group in which two hydrogen atoms have been removed from a structural formula bonded via a linking group.
- X is -CO -, - S-, or -SO 2 - indicates, Y are the same or different, -S -, - SO 2 - , - O -, - CO -, - COO-, or -CONH Indicates-.
- n represents an integer of 0 or more, for example, an integer of 0 to 5, preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 3.
- aromatic ring examples include C6-C14 aromatic rings such as benzene, naphthalene, anthracene, and phenanthrene. In the present invention, among them, aromatic rings having 6 to 10 carbon atoms such as benzene and naphthalene are preferred.
- linking group examples include a divalent hydrocarbon group having 1 to 5 carbon atoms, and a group in which one or more hydrogen atoms of a divalent hydrocarbon group having 1 to 5 carbon atoms are substituted with a halogen atom. Is mentioned.
- Examples of the divalent hydrocarbon group having 1 to 5 carbon atoms include linear or branched alkylene groups having 1 to 5 carbon atoms such as a methylene group, a methylmethylene group, a dimethylmethylene group, a dimethylene group, and a trimethylene group.
- a linear or branched alkenylene group having 2 to 5 carbon atoms such as a vinylene group, a 1-methylvinylene group, or a propenylene group; a C2 to C5 group, such as an ethynylene group, a propynylene group, or 1-methylpropynylene; It includes a linear or branched alkynylene group.
- a linear or branched alkylene group having 1 to 5 carbon atoms is preferable, and a branched alkylene group having 1 to 5 carbon atoms is particularly preferable.
- Ar 1 to Ar 3 may be the same or different and are the same as or different from those of the aromatic ring having 6 to 14 carbon atoms except for two hydrogen atoms, or two of the aromatic rings having 6 to 14 carbon atoms.
- one or more hydrogen atoms of a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, or one or more hydrogen atoms of a linear or branched alkylene group having 1 to 5 carbon atoms are substituted with a halogen atom.
- two or more of the aromatic rings having 6 to 14 carbon atoms have a single bond, a branched alkylene group having 1 to 5 carbon atoms, or one or more hydrogen atoms of a branched alkylene group having 1 to 5 carbon atoms.
- Ar 1 to Ar 3 are particularly preferably the same or different and are selected from groups represented by the following formulas (a-1) to (a-5).
- the position of the bond in the following formula is not particularly limited.
- a group obtained by removing two hydrogen atoms from the structural formula of an aromatic ring having 6 to 14 carbon atoms is preferable, and in particular, the above formula (a-1) Or the group represented by (a-2) is preferable.
- X is particularly preferably -CO- or -SO 2- .
- the structure represented by the formula (I) preferably includes a structure derived from benzophenone.
- the proportion of the structure derived from an aromatic ring in the total amount of the compound represented by the formula (1) is, for example, 50% by weight or more, preferably 50 to 90% by weight, more preferably 60 to 90% by weight, and particularly preferably 65 to 80% by weight. %.
- the proportion of the benzophenone-derived structural unit in the total amount of the compound represented by the formula (1) is, for example, 5% by weight or more, preferably 10 to 62% by weight, and particularly preferably 15 to 60% by weight.
- Ar 3 in the formula (II) is preferably a group selected from the groups represented by the above formulas (a-1), (a-4) and (a-5). Further, Y is particularly preferably -S-, -O-, or -SO 2- .
- Examples of the structure represented by the formula (II) include hydroquinone, resorcinol, 2,6-naphthalenediol, 2,7-naphthalenediol, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether, It preferably contains a structure derived from at least one compound selected from 4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylsulfone, and bisphenol A, especially hydroquinone, resorcinol And a structure derived from at least one compound selected from bisphenol A.
- Hydroquinone resorcinol, 2,6-naphthalenediol, 2,7-naphthalenediol, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4 'in the total amount of the compound represented by the formula (1)
- the proportion of structural units derived from -dihydroxybenzophenone, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylsulfone and bisphenol A is, for example, 5% by weight or more, preferably 10 to 55% by weight, particularly preferably. Is from 15 to 53% by weight.
- the proportion of structural units derived from hydroquinone, resorcinol, and bisphenol A in the total amount of the compound represented by the formula (1) is, for example, 5% by weight or more, preferably 10 to 55% by weight, and particularly preferably 15 to 53% by weight. % By weight.
- a divalent group represented by the following formula (L-1) is preferable, since a cured product having particularly excellent heat resistance can be obtained.
- m is less than 2
- the strength and heat resistance of the obtained cured product tend to be insufficient.
- m is more than 50
- the solvent solubility tends to decrease.
- the melting temperature tends to increase.
- the value of m can be determined by GPC measurement or NMR spectrum analysis.
- n ′′ in the above formula (L-1) represents an integer of 0 or more, and Ar 1 to Ar 3 are the same as above.
- a plurality of Ar 1 in the above formula (L-1) represents the same group. The same applies to Ar 2 and Ar 3 .
- L in the formula (1) is particularly preferably a divalent group represented by the following formula (L-1-1) or (L-1-2).
- the number of units that is, the average degree of polymerization, for example, 2 to 50, preferably 3 to 40, more preferably 4 to 30, particularly preferably 5 to 20, and most preferably 5 to 10.
- the values of m1 and m2 can be determined by GPC measurement or NMR spectrum analysis.
- L in the formula (1) is a divalent group represented by the formula (L-1-1) or (L-1-2), Compounds in which m1 and m2 in the formula are 5 to 10 melt at 300 ° C. or lower (about 250 ° C.), and therefore can be melt-molded at a lower temperature than PEEK or the like, and are particularly excellent in processability.
- the average degree of polymerization of the molecular chain is below the above range, the obtained cured product becomes brittle, and the mechanical properties tend to decrease. Further, when the average degree of polymerization of the molecular chain exceeds the above range, the processability tends to decrease due to a decrease in solubility in a solvent or an increase in a melt viscosity.
- the nitrogen atom content of the compound represented by the formula (1) is, for example, 2.8 to 0.1% by weight, preferably 2.5 to 0.15% by weight, more preferably 2.0 to 0.1% by weight. 20% by weight, particularly preferably 1.8 to 0.40% by weight, most preferably 1.5 to 0.70% by weight.
- the nitrogen atom content can be determined, for example, by CHN elemental analysis.
- the nitrogen atom content is within the above range, a cured product having excellent solvent solubility and excellent toughness and heat resistance can be formed.
- the nitrogen atom content is below the above range, it tends to be difficult to form a cured product having excellent toughness and heat resistance.
- the solvent solubility tends to decrease.
- the compound represented by the above formula (1) can be produced, for example, by using a synthesis method described in Polymer ⁇ 1989 ⁇ p978 ⁇ .
- An example of the method for producing the compound represented by the above formula (1) is shown below, but the present invention is not limited to the method produced by this method.
- the compound represented by the following formula (1a) can be produced, for example, through the following steps [1] to [3].
- Ar 1 to Ar 3 , X, Y, n, R 3 to R 6 , Q and n ′ are the same as described above.
- D represents a linking group
- Z represents a halogen atom.
- m is the average degree of polymerization of the repeating unit, for example, 3 to 50, preferably 4 to 30, and particularly preferably 5 to 20.
- compounds other than the compound represented by the following formula (1a) can be produced according to the following method.
- Step [1] A compound represented by the following formula (2), which is a reaction substrate, is reacted with a compound represented by the following formula (3) in the presence of a base to give a compound represented by the following formula (4). Is obtained.
- Examples of the compound represented by the formula (2) include halides such as benzophenone, 2-naphthyl phenyl ketone, and bis (2-naphthyl) ketone, and derivatives thereof.
- Examples of the compound represented by the above formula (3) include hydroquinone, resorcinol, 2,6-naphthalenediol, 2,7-naphthalenediol, 1,5-naphthalenediol, 4,4′-dihydroxybiphenyl, 4'-dihydroxydiphenyl ether, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylsulfone, bisphenol A, bisphenol F, bisphenol S, 2,5-dihydroxybiphenyl, and the like And the like.
- Examples of the derivative include a compound represented by the formula (2) and a compound represented by the formula (3) in which a substituent is bonded to an aromatic hydrocarbon group.
- Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom.
- the amounts of the compound represented by the formula (2) and the compound represented by the formula (3) are generally represented by the formula (2) based on 1 mol of the compound represented by the formula (3).
- the compound is at least 1 mol, and it is desirable to adjust the amount of the compound represented by the formula (2) according to the average degree of polymerization of the molecular chain in the desired compound (1).
- the compound represented by the formula (2) is about 1.2 mol (for example, 1.18 to 1.22 mol) per 1 mol of the compound represented by the formula (3).
- the compound represented by the formula (2) is about 1.1 mol (for example, 1.08 to 1.12 mol), and when the average degree of polymerization is 20, the compound represented by the formula (2) is represented by the formula (2). It is preferable to use about 1.05 mol of the compound (for example, 1.04 to 1.06 mol).
- the compound represented by the formula (2) it is preferable to use at least a benzophenone halide, and the amount of the benzophenone halide used in the total amount (100 mol%) of the compound represented by the formula (2) Is, for example, 10 mol% or more, preferably 30 mol% or more, particularly preferably 50 mol% or more, and most preferably 80 mol% or more. Note that the upper limit is 100 mol%.
- Examples of the compound represented by the formula (3) include hydroquinone, resorcinol, 2,6-naphthalenediol, 2,7-naphthalenediol, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4 ′ -Dihydroxybenzophenone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone, and at least one selected from bisphenol A (in particular, at least one selected from hydroquinone, resorcinol, and bisphenol A)
- the compound of the formula (1) it is preferable to use the compound of the formula (1), and the total amount of the compound used is, for example, 10 mol% or more, preferably 30 mol% or more of the total use amount (100 mol%) of the compound represented by the formula (3). Particularly preferably at least 50 mol%, most preferably The Mashiku 80 mol% or more. Note that the upper limit is 100
- a base for example, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, etc.
- Inorganic base of at least one selected from organic bases such as pyridine and triethylamine is used.
- the amount of the base used can be appropriately adjusted depending on the type of the base.
- the amount of the diacid base such as calcium hydroxide used is about 1.0 to 2.0 mol per 1 mol of the compound represented by the formula (3).
- This reaction can be carried out in the presence of a solvent.
- a solvent for example, an organic solvent such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylsulfoxide, acetone, tetrahydrofuran, toluene, or a mixed solvent of two or more of these can be used.
- the amount of the solvent used is, for example, about 5 to 20 times by weight based on the total (weight) of the reaction substrates. If the amount of the solvent exceeds the above range, the concentration of the reaction substrate tends to decrease, and the reaction rate tends to decrease.
- the reaction atmosphere is not particularly limited as long as the reaction is not hindered, and may be, for example, any of an air atmosphere, a nitrogen atmosphere, and an argon atmosphere.
- the reaction temperature is, for example, about 100 to 200 ° C.
- the reaction time is, for example, about 5 to 24 hours. This reaction can be performed by any method such as a batch system, a semi-batch system, and a continuous system.
- the obtained reaction product can be separated and purified by a separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, or a combination thereof.
- a separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, or a combination thereof.
- Step [2] Examples of the compound represented by the above formula (5) include 4-aminophenol, 2-amino-6-hydroxynaphthalene, and positional isomers and derivatives thereof.
- the amount of the compound represented by the formula (5) can be appropriately adjusted according to the average degree of polymerization of the molecular chain in the desired compound (1).
- the amount is about 0.4 to 0.6 mol per 1 mol of the compound represented by the formula (3)
- the average degree of polymerization is 10
- the amount is represented by the formula (3).
- an amount of about 0.2 to 0.4 mol per mol of the compound, and in the case of an average degree of polymerization of 20, about 0.1 to 0.15 mol per mol of the compound represented by the formula (3) Is the amount
- the amount of the base used can be appropriately adjusted depending on the type of the base.
- the amount of the monoacid base such as sodium hydroxide used is about 1.0 to 3.0 mol per 1 mol of the compound represented by the above formula (5).
- This reaction can be carried out in the presence of a solvent.
- a solvent those similar to those used in the step [1] can be used.
- the reaction temperature is, for example, about 100 to 200 ° C.
- the reaction time is, for example, about 1 to 15 hours. This reaction can be performed by any method such as a batch system, a semi-batch system, and a continuous system.
- the obtained reaction product can be separated and purified by a separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, or a combination thereof.
- a separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, or a combination thereof.
- cyclic acid anhydride examples include, for example, maleic anhydride, 2-phenylmaleic anhydride, 4-phenylethynyl-phthalic anhydride, 4- (1-naphthylethynyl) -Phthalic anhydride, bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic anhydride, derivatives thereof and the like.
- the amount of the cyclic acid anhydride to be used can be appropriately adjusted according to the average degree of polymerization of the molecular chain in the desired compound (1).
- the amount is about 0.4 to 0.8 mol per 1 mol of the compound represented by the formula (3)
- the average degree of polymerization is 10
- the amount is represented by the formula (3).
- an amount of about 0.2 to 0.4 mol per mol of the compound, and in the case of an average degree of polymerization of 20, about 0.1 to 0.15 mol per mol of the compound represented by the formula (3) Is the amount
- This reaction can be performed in the presence of a solvent.
- a solvent those similar to those used in the step [1] can be used.
- This reaction is preferably performed at room temperature (1 to 30 ° C.).
- the reaction time is, for example, about 1 to 30 hours.
- This reaction can be performed by any method such as a batch system, a semi-batch system, and a continuous system.
- azeotropic distillation using a solvent azeotroping with water eg, toluene
- a dehydrating agent eg, acetic anhydride
- water e.g. toluene
- a dehydrating agent e.g, acetic anhydride
- the removal of generated water by the dehydrating agent is preferably performed in the presence of a basic catalyst (for example, triethylamine or the like).
- the obtained reaction product can be separated and purified by a separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, or a combination thereof.
- a separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, or a combination thereof.
- the exothermic peak temperature of the compound (1) depends on the type of the curable functional group, but is, for example, 170 to 450 ° C, preferably 200 to 430 ° C, and particularly preferably 220 to 420 ° C.
- the exothermic peak temperature is determined by DSC measurement.
- a cured product when the compound (1) has a group represented by the above formula (r-5) as a curable functional group, a cured product can be formed by heating at a temperature of about 250 ° C. Further, when a group represented by the above formula (r-1) is provided as a curable functional group, a cured product can be formed by heating at a temperature of about 380 ° C.
- the number average molecular weight (Mn) of the compound (1) is, for example, from 1,000 to 15,000, preferably from 1,000 to 14,000, particularly preferably from 1,100 to 12,000, and most preferably from 1200 to 10,000. Therefore, the solubility in a solvent is high, the melt viscosity is low, the molding process is easy, and the molded body after curing exhibits high toughness. If the number average molecular weight is below the above range, the toughness of the molded article after curing tends to decrease. On the other hand, when the number average molecular weight exceeds the above range, the solvent solubility tends to decrease, and the melt viscosity tends to be too high, so that molding tends to be difficult. In addition, Mn is determined by performing gel permeation chromatography (GPC) measurement (solvent: chloroform, standard polystyrene conversion).
- GPC gel permeation chromatography
- the ratio of the structure derived from an aromatic ring in the total amount of the compound (1) is, for example, 50% by weight or more, preferably 50 to 90% by weight, more preferably 60 to 90% by weight, and particularly preferably 65 to 80% by weight. Therefore, it has high solvent solubility and low melt viscosity, and the cured product has thermal stability.
- the proportion of the structure derived from an aromatic ring is below the above range, the thermal stability of the molded article after curing tends to decrease.
- the proportion of the structure derived from an aromatic ring exceeds the above range, the solvent solubility tends to decrease and the melt viscosity tends to increase.
- the glass transition temperature (Tg) of the compound (1) is, for example, 280 ° C. or lower, preferably 80 to 280 ° C., more preferably 80 to 250 ° C., and particularly preferably 100 to 200 ° C. Therefore, it is excellent in melt moldability.
- Tg can be measured by the DSC method.
- Compound (1) has excellent solvent solubility, and the solubility is, for example, 1 g or more, preferably 5 g or more, particularly preferably 10 g or more with respect to 100 g of the solvent at 25 ° C.
- solvent examples include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; amides such as formamide, acetamide, N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide and dimethylacetamide; Halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, bromobenzene, dichlorobenzene, benzotrifluoride, hexafluoro-2-propanol; dimethyl sulfoxide (DMSO), diethyl sulfoxide, benzyl phenyl sulfoxide and the like Sulfoxide; diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran (THF), dioxane, 1,2-dimethoxyethane
- ketones such as acetone
- At least one solvent selected from ethers, ketones, amides, halogenated hydrocarbons, and sulfoxides particularly, at least one solvent selected from ethers, amides, halogenated hydrocarbons, and sulfoxides
- a compound (1) particularly a compound represented by the formula (1), wherein L is a divalent group represented by the formula (1-2) or (1-3)
- L is a divalent group represented by the formula (1-2) or (1-3)
- PEPEEK (commercially available PEEK powder, polyether ether ketone, VICTREX 151G, melting point 343 ° C, Tg 147 ° C) was used for the comparative example.
- This powdery solid was repeatedly washed with methanol and water, and then dried under reduced pressure at 100 ° C. for 8 hours to obtain a powdery solid (diamine (1), a compound represented by the following formula, yield: 95%). .
- the obtained powdery solid was subjected to GPC measurement (solvent THF, standard polystyrene conversion) to find that the number average molecular weight was 2,070, the weight average molecular weight was 3,500, and the average degree of polymerization (m-1) was 5.8. Was.
- This powdery solid was repeatedly washed with methanol and water, and then dried under reduced pressure at 100 ° C. for 8 hours to obtain a powdery solid (diamine (2), a compound represented by the following formula, yield: 95%). .
- the obtained powdery solid was subjected to GPC measurement (solvent THF, converted to standard polystyrene) to have a number average molecular weight of 2,920, a weight average molecular weight of 5,100, and an average degree of polymerization (m-2) of 6.2. Was.
- Preparation Example 3 (Production of curable compound A) 5.88 g of maleic anhydride, 50 mL of N-methyl-2-pyrrolidone, and 200 mL of toluene were placed in a 1000 mL (three-necked) flask equipped with a stirrer, a nitrogen inlet tube, and a drying tube, followed by purging with nitrogen. Thereto was added a solution in which 26.76 g of the diamine (1) obtained in Preparation Example 1 was dissolved in 250 mL of NMP, and the mixture was stirred at room temperature under a nitrogen atmosphere for 24 hours.
- FIG. 5 shows the 1 H-NMR spectrum of the curable compound A
- FIG. 6 shows the FTIR spectrum.
- the ratio of the structure derived from the aromatic ring was determined by 1 H-NMR.
- Preparation Example 4 (Production of curable compound B) In the same manner as in Preparation Example 3, except that the diamine (2) obtained in Preparation Example 2 was used instead of the diamine (1), and a solution in which 48.57 g of the diamine (2) was dissolved in 330 mL of NMP was used. As a result, a powdery solid (curable compound B, compound represented by the following formula (B), ratio of structure derived from aromatic ring: 71% by weight, yield: 90%) was obtained.
- FIG. 7 shows the 1 H-NMR spectrum of the curable compound B
- FIG. 8 shows the FTIR spectrum.
- FIG. 9 shows the 1 H-NMR spectrum of the curable compound C
- FIG. 10 shows the FTIR spectrum.
- the number average molecular weight and the weight average molecular weight of the curable compounds A, B, C, and D were determined by GPC measurement (solvent THF, standard polystyrene conversion).
- Tg The Tg of the curable compounds A, B, C and D was determined by DSC measurement.
- FIG. 13 shows the DSC measurement results of the curable compounds C and D.
- Curable compound D had a Tg of about 140 ° C.
- curable compound C had a Tg of about 120 ° C.
- an exothermic peak due to a curing reaction was observed at around 400 ° C.
- the obtained cured product has a high degree of curing (or the curable compounds A, B, C, or D are excellent in curability and can be subjected to heat treatment. All curable functional groups have been lost).
- FIG. 15 shows the thermogravimetric loss analysis results of the cured product of the curable compound C and the cured product of the curable compound D.
- the molding die containing the curable compound A was set in a press machine (30-ton manual hydraulic vacuum heat press IMC-46E2-3, manufactured by Imoto Seisakusho), adjusted to 50 ° C., and evacuated. Then, the temperature was raised to 280 ° C. at 20 ° C./min and maintained for 1 hour, and then further raised to 320 ° C. at 20 ° C./min and maintained for 30 minutes. Thereafter, the press was air-cooled and water-cooled, and when the temperature became 100 ° C. or lower, the mold was taken out to obtain a flat cured product (A) (thickness: 0.2 cm).
- a flat cured product (B) (thickness: 0.2 cm) was obtained in the same manner as described above except that the curable compound B was used instead of the curable compound A.
- FIG. 17 shows an FTIR spectrum of the obtained cured product.
- the physical properties of the obtained cured product (B) were as follows.
- Examples 1 to 12 As described in Table 3 below, the curable compound A or B obtained in the preparation example and the solvent were weighed into a sample bottle and stirred. Ultrasonic waves were applied at 25 ° C. for 5 minutes to completely dissolve the curable compound to obtain a curable composition.
- the obtained curable composition is cast on a substrate with a syringe, spread evenly with an applicator, and dried by primary drying (drying in a dryer at 120 ° C. for 1 hour), followed by secondary drying (drying at 150 ° C.) Medium and vacuum for 1 hour) to obtain a coating film.
- the obtained coating film was thermally cured (in a dryer at 220 ° C. in vacuum for 1 hour) to obtain a cured product / substrate laminate.
- the cross-cut tape test (JIS K5400) was performed on the cured product / substrate laminate obtained in Examples and Comparative Examples, and on the cured product / substrate laminate subjected to a heat resistance test (heating at 270 ° C. for 1 hour). -8.5), and the adhesion of the cured product to the substrate was evaluated according to the following criteria. ((Good): no peeling of the cured product was observed x (poor): peeling of the cured product was observed
- Examples 7-2 and 7-3 A curable composition was obtained and a cured product / substrate laminate was obtained in the same manner as in Example 7, except that the following points were changed. That is, fillers were added as shown in Table 4 below.
- the thermosetting condition of the coating material was set to "1 hour in a vacuum at 300 ° C. in a drier". Further, the obtained laminate was evaluated for adhesion in the same manner as in Example 7.
- the curable compound A or B obtained in Preparation Example was dissolved in cyclohexanone to obtain a curable composition for forming a composite material.
- 1.186 g of the fiber was immersed in 5.0 g of the obtained composition, and allowed to stand at 25 ° C. for 8 hours. Thereafter, the fiber was pulled out of the solution, and heated on a hot stage at 130 ° C. for 1 hour to volatilize cyclohexanone to obtain a composite material (prepreg).
- the obtained composite material (prepreg) was sandwiched between aluminum foils, placed on a press, heated at 250 ° C. for 3 minutes, and then pressurized at 0.1 MPa. The mixture was kept at 250 ° C. for 8 minutes, then heated to 320 ° C. over 12 minutes, and kept at 320 ° C. for 20 minutes to cure the curable compound, thereby obtaining a composite material (cured product).
- Example 21 The curable compound B obtained in the preparation example is stirred in NMP, and ultrasonic waves are applied at 25 ° C. for 5 minutes to completely dissolve the curable compound B, and the curable composition (curable compound B concentration: 40% by weight) %).
- the obtained curable composition was filled in a syringe, and extruded into water to obtain a fibrous formed body (length: 10 cm, diameter: 1 mm).
- Example 22 As described in Table 6 below, the curable compound and the solvent were weighed into a sample bottle and stirred. Ultrasonic waves were applied at 25 ° C. for 5 minutes to completely dissolve the curable compound to obtain a curable composition.
- the obtained curable composition was cast with a syringe, spread evenly with an applicator, and subjected to primary drying (drying in a dryer at 120 ° C. for 1 hour), followed by secondary drying (150 hours). (Drying in a vacuum at 1 ° C. for 1 hour) to obtain a coating film.
- the substrate (2) was laminated on the obtained coating film, and then the coating film was thermally cured (1 hour in a drier at 220 ° C. for 1 hour) to obtain a substrate (2) / cured product / substrate (1) laminate Got.
- Example 23 The curable composition obtained in the same manner as in Example 22 was cast on a carrier (made of polyimide, having a thickness of 100 ⁇ m), spread evenly with an applicator, and primary dried (in a dryer at 120 ° C. for 1 hour). Drying), secondary drying (drying in a dryer at 150 ° C. for 1 hour), and tertiary drying (drying in a dryer at 210 ° C. in vacuum for 1 hour) to obtain a coating film having a thickness of 100 ⁇ m. The obtained coating film was peeled from the carrier. The coating could be easily removed from the carrier. A copper foil (18 ⁇ m in thickness) was used as the substrate (1) and the substrate (2), and thermosetting was performed while sandwiching the coating film between the substrate (1) and the substrate (2).
- the temperature was raised from 300 ° C to 300 ° C at a rate of 5 ° C / min and maintained at that temperature for 60 minutes.
- the pressure was raised to 3 MPa in 5 minutes from the start of the temperature increase] to obtain a substrate (2) / cured product / substrate (1) laminate.
- the flexibility of the obtained laminate was evaluated by the following method. That is, the laminate was cut into a size of 1 cm ⁇ 10 cm, and folded in half at the center in the longitudinal direction (5 cm from the end). After placing a weight of 100 g on the folded portion, the appearance of the cured product was visually observed and evaluated according to the following criteria. Flexibility evaluation criterion :: no crack or peeling was observed x: crack or peeling was observed
- a curable composition comprising a compound represented by the formula (1) and a solvent.
- the solvent is at least one solvent selected from ketones, amides, halogenated hydrocarbons, sulfoxides, ethers, esters, nitriles, and aromatic hydrocarbons.
- R 1 and R 2 in the formula (1) are the same or different and are a curable functional group having a cyclic imide structure.
- R 1 and R 2 in the formula (1) are the same or different and are groups selected from the groups represented by the formulas (r-1) to (r-6); The curable composition according to any one of [3].
- D 1 and D 2 in the formula (1) are the same or different and are groups selected from groups containing the structures represented by the formulas (d-1) to (d-4). The curable composition according to any one of [1] to [4].
- [6] A group in which Ar 1 to Ar 3 in the formulas (I) and (II) are the same or different, and two hydrogen atoms are removed from the structural formula of an aromatic ring having 6 to 14 carbon atoms, or Two or more aromatic rings having 6 to 14 carbon atoms are a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or branched alkylene group having 1 to 5 carbon atoms.
- the structure represented by the formula (II) is hydroquinone, resorcinol, 2,6-naphthalenediol, 2,7-naphthalenediol, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether,
- the curable composition according to any one of the above.
- a sealant comprising the curable composition according to any one of [1] to [16].
- a thin film made of a solidified product of the curable composition according to any one of [1] to [16] is laminated on a substrate, and subjected to a heat treatment to cure the curable composition.
- a method for producing a laminate wherein a laminate having a configuration in which a product or a semi-cured product and a substrate are laminated is obtained.
- the curable composition is applied on a plastic support and dried to obtain a thin film made of a solidified product of the curable composition. The obtained thin film is peeled from the support.
- the method for producing a laminate according to [21] wherein the laminate is laminated on a substrate.
- a 5% weight loss temperature (T d5 ) measured at a heating rate of 10 ° C./min (in nitrogen) containing a cured product of a curable compound is 300 ° C. or more, and is heated at 320 ° C. for 30 minutes.
- the solid according to [23] which has a peak in a region of 1620 to 1750 cm -1 in an IR spectrum.
- the solid according to [23] or [24], wherein the curable compound is a compound represented by the formula (1).
- the curable compound is a compound represented by the formula (1), wherein R 1 and R 2 in the above formula are the same or different and are a curable functional group having a cyclic imide structure.
- the curable compound is a compound represented by the formula (1), wherein R 1 and R 2 in the above formula are the same or different and are represented by the formulas (r-1) to (r-6).
- the curable compound is a compound represented by the formula (1), wherein D 1 and D 2 in the above formula are the same or different and are represented by the formulas (d-1) to (d-4).
- a method for manufacturing a semiconductor device comprising manufacturing a semiconductor device through a step of laminating semiconductor substrates using the curable composition according to any one of [1] to [16] as an adhesive.
- a method for manufacturing a semiconductor device comprising manufacturing a semiconductor device through a step of sealing a semiconductor element using the curable composition according to any one of [1] to [16].
- the curable composition of the present invention is suitable as a material for forming a molded product used in fields where super heat resistance, flame retardancy, and good dielectric properties are required, as an adhesive, a sealant, or a paint. Can be used.
Abstract
Description
本発明の他の目的は、前記硬化性組成物を成形して成形体を得る、成形体の製造方法を提供することにある。
本発明の他の目的は、超耐熱性が求められる環境下で使用可能な接着剤、封止剤、又は塗料を提供することにある。
本発明の他の目的は、超耐熱性を有する硬化物又はその半硬化物と基板とが積層された構成を有する積層体の製造方法を提供することにある。
本発明の他の目的は、超耐熱性を有する硬化物又はその半硬化物を含む固形物を提供することにある。
で表される化合物と溶剤とを含む、硬化性組成物を提供する。
そのため、本発明の硬化性組成物は、超耐熱性、難燃性、及び良好な誘電特性(低い比誘電率及び誘電正接)が求められる分野(例えば、電子情報機器、家電、自動車、精密機械、航空機、宇宙産業用機器等)において使用される成形物の形成材料や、接着剤、封止剤、又は塗料等として好適に使用することができる。
本発明の硬化性組成物は、後で詳述する式(1)で表される化合物(以後、「化合物(1)」と称する場合がある)と、溶剤とを含む。本発明の硬化性組成物は、化合物(1)と溶剤のそれぞれを、1種を単独で、又は2種以上を組み合わせて含有することができる。
硬化度(%)=[1-(半硬化物の発熱量/式(1)で表される化合物の発熱量)]×100
(1)燃焼持続時間は30秒以下
(2)5個の試料の燃焼持続時間の合計が250秒以下
(3)2回目の接炎後の赤熱持続時間が60秒以下
(4)固定用クランプ部まで燃えない
(5)燃焼する粒子を落下させて、下に敷いた綿を燃やすことがない
本発明の積層体は、化合物(1)の硬化物又は半硬化物と基板とが積層された構成を有する。本発明の積層体には、化合物(1)の硬化物又は半硬化物/基板、及び基板/化合物(1)の硬化物又は半硬化物/基板の構成が含まれる。
1.化合物(1)を固体(例えば、粉末状固体)のまま基板上に載置し、その後加熱処理を施す方法
2.化合物(1)を含む薄膜を基板上にて形成し、その後加熱処理を施す方法
3.化合物(1)を含む薄膜を基板上に積層し、その後加熱処理を施す方法
また、前記薄膜は、基板上に化合物(1)の溶融物を塗布し、得られた塗膜を冷却することにより製造することもできる。
また、前記薄膜として、支持体上に化合物(1)の溶融物を塗布し、得られた塗膜を冷却した後、支持体から剥離したものを使用することもできる。
本発明の固形物は、硬化性化合物の硬化物を含み、下記特性を有する。
固形物の特性:
昇温速度10℃/分(窒素中)で測定される5%重量減少温度(Td5)が300℃以上であり、320℃で30分の加熱処理に付した後の窒素原子含有量が2.8~0.1重量%である
工程[1]:反応基質である下記式(2)で表される化合物と下記式(3)で表される化合物とを、塩基の存在下で反応させることにより、下記式(4)で表される化合物を得る。
工程[2]:下記式(4)で表される化合物に、アミノアルコール(下記式(5)で表される化合物)を反応させることにより、下記式(6)で表されるジアミンを得る。
工程[3]:下記式(6)で表されるジアミンに環状酸無水物(下記式(7)で表される化合物)を反応させることにより下記式(1a)で表される化合物を得る。
上記式(2)で表される化合物としては、例えば、ベンゾフェノン、2-ナフチルフェニルケトン、及びビス(2-ナフチル)ケトン等のハロゲン化物、及びこれらの誘導体等が挙げられる。
上記式(5)で表される化合物としては、例えば、4-アミノフェノール、2-アミノ-6-ヒドロキシナフタレン、及びこれらの位置異性体や誘導体等が挙げられる。
前記環状酸無水物(上記式(7)で表される化合物)としては、例えば、無水マレイン酸、2-フェニル無水マレイン酸、4-フェニルエチニル-無水フタル酸、4-(1-ナフチルエチニル)-無水フタル酸、ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボン酸無水物、及びこれらの誘導体等が挙げられる。
本発明における溶剤としては、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン;ホルムアミド、アセトアミド、N-メチル-2-ピロリドン(NMP)、N,N-ジメチルホルムアミド、ジメチルアセトアミド等のアミド;塩化メチレン、クロロホルム、1,2-ジクロロエタン、クロロベンゼン、ブロモベンゼン、ジクロロベンゼン、ベンゾトリフルオライド、ヘキサフルオロ-2-プロパノール等のハロゲン化炭化水素;ジメチルスルホキシド(DMSO)、ジエチルスルホキシド、ベンジルフェニルスルホキシド等のスルホキシド;ジエチルエーテル、ジイソプロピルエーテル、ジブチルエーテル、テトラヒドロフラン(THF)、ジオキサン、1,2-ジメトキシエタン、シクロペンチルメチルエーテル等のエーテル;酢酸エチル等のエステル;アセトニトリル、ベンゾニトリル等のニトリル;ベンゼン、トルエン、キシレン等の芳香族炭化水素;及びこれらの2種以上の混合液等が挙げられる。
<NMR測定>
測定装置:BRUKER 400MHz/54mm又はBRUKER AVANCE600MHz
測定溶剤:重DMSO、重クロロホルム、又は重クロロホルム/ペンタフルオロフェノール(PFP)=2/1(wt/wt)の混合液
化学シフト:TMSを規準とした
<GPC測定>
装置:ポンプ「LC-20AD」((株)島津製作所製)
検出器:RID-10A((株)島津製作所製)又はTDA-301およびUV2501(Viscotek製)
溶剤:THF又はクロロホルム
カラム:shodex GPC K-806L×1本+shodex GPC K-803×1本+shodex GPC K-801×2本
流速:1.0mL/min
温度:40℃
試料濃度:0.1%(wt/vol)
標準ポリスチレン換算
<DSC測定>
装置:TA Q20
昇温速度:10℃/min
雰囲気:窒素雰囲気
<TG/DTA測定>
装置:NETZSCH TG209F3
昇温速度:10℃/min
雰囲気:窒素雰囲気
<IR測定>
装置:Perkin Elmer Spectrum RX1(ATR法)
撹拌装置、窒素導入管、およびディーンスターク装置を備えた500mL(三ツ口)フラスコに、4,4’-ジフルオロベンゾフェノンを27.50g、レゾルシノールを11.56g、無水炭酸カリウムを21.77g、N-メチル-2-ピロリドンを154mL、およびトルエン77mLを入れ、窒素雰囲気下で撹拌しながら加熱し、130~140℃で4時間トルエンを還流させた。その後、さらに加熱して170~180℃でトルエンを留去した。さらに、170~180℃で10時間撹拌を継続した後、室温に戻した。
撹拌装置、窒素導入管、およびディーンスターク装置を備えた500mL(三ツ口)フラスコに、4,4’-ジフルオロベンゾフェノン27.50g、ビスフェノールA23.98g、無水炭酸カリウム(K2CO3)21.77g、N-メチル-2-ピロリドン220mL、およびトルエン110mLを入れ、窒素雰囲気下で撹拌しながら加熱し、130~140℃で4時間トルエンを還流させた。その後、さらに加熱して170~180℃でトルエンを留去した。さらに、170~180℃で10時間撹拌を継続した後、室温に戻した。
撹拌装置、窒素導入管および乾燥管を備えた1000mL(三ツ口)フラスコに、無水マレイン酸を5.88g、N-メチル-2-ピロリドンを50mL、トルエンを200mL入れ、窒素置換した。そこへ、調製例1で得られたジアミン(1)26.76gをNMP250mLに溶解させた溶液を添加し、窒素雰囲気下、室温で24時間撹拌した。その後、パラトルエンスルホン酸一水和物0.761gを添加し、140℃に加熱して、8時間攪拌を継続し、トルエンを還流して水分を除去した。反応液を室温に戻した後、反応液を3000mLのメタノールに添加、ろ過することで粉末状固体を得た。この粉末状固体をメタノールおよび水で繰返し洗浄した後、100℃で8時間減圧乾燥して、粉末状固体(硬化性化合物A、下記式(A)で表される化合物、芳香環由来の構造の割合:72重量%、収率:90%)を得た。硬化性化合物Aの1H-NMRスペクトルを図5に、FTIRスペクトルを図6に示す。
尚、芳香環由来の構造の割合は1H-NMRによって求めた。
1H-NMR(CDCl3)δ:6.88(m), 7.08(d,J=8.0Hz), 7.17(d,J=8.0Hz), 7.39(m), 7.81(d,J=8.0Hz)
ジアミン(1)に代えて、調製例2で得られたジアミン(2)を使用し、前記ジアミン(2)48.57gを330mLのNMPに溶解した溶液を使用した以外は調製例3と同様にして、粉末状固体(硬化性化合物B、下記式(B)で表される化合物、芳香環由来の構造の割合:71重量%、収率:90%)を得た。硬化性化合物Bの1H-NMRスペクトルを図7に、FTIRスペクトルを図8に示す。
1H-NMR(CDCl3)δ:1.71(s), 6.87(s), 7.02(m), 7.09(m), 7.17(d,J=8.8Hz),7.26(m), 7.37(d,J=8.8Hz), 7.80(m)
撹拌装置、窒素導入管および乾燥管を備えた50mL(三ツ口)フラスコに、調製例1で得られたジアミン(1)を4.571g、4-フェニルエチニル-無水フタル酸を1.852g、N-メチル-2-ピロリドンを33mL入れ、窒素雰囲気下、室温で24時間撹拌した。その後、無水酢酸4.215g、トリエチルアミン1.405gを添加し、60℃で6時間撹拌した。反応液を室温に戻した後、反応液を1500mLのエタノールに添加、ろ過することで粉末状固体を得た。この粉末状固体をエタノールおよび水で繰返し洗浄した後、100℃で8時間減圧乾燥して、粉末状固体(硬化性化合物C、下記式(C)で表される化合物、芳香環由来の構造の割合:76重量%、収率:90%)を得た。硬化性化合物Cの1H-NMRスペクトルを図9に、FTIRスペクトルを図10に示す。
ジアミン(1)に代えて、調製例2で得られたジアミン(2)を使用し、前記ジアミン(2)を4.550g使用し、4-フェニルエチニル-無水フタル酸を1.395g使用した以外は調製例5と同様にして、粉末状固体(硬化性化合物D、下記式(D)で表される化合物、芳香環由来の構造の割合:74重量%、収率:90%)を得た。硬化性化合物Dの1H-NMRスペクトルを図11に、FTIRスペクトルを図12に示す。
硬化性化合物A、B、C、及びDの数平均分子量及び重量平均分子量を、GPC測定(溶剤THF、標準ポリスチレン換算)によって求めた。
硬化性化合物A、B、C、D、又はPEEK(1g)を、下記表に示す溶剤(100g)と混合し、25℃で24時間撹拌し、溶剤への溶解性を下記基準で評価した。
評価基準
○(良好):完全に溶解した
×(不良):少なくとも一部が溶解せずに残存した
硬化性化合物A、B、C、及びDのTgをDSC測定により求めた。
硬化性化合物C及びDのDSC測定結果を図13に示す。硬化性化合物DはTgが140℃程度、硬化性化合物CはTgが120℃程度であり、硬化性化合物C、Dは、いずれも400℃付近に硬化反応による発熱ピークが観測された。
硬化性化合物A、B、C、D、又はPEEKをガラス板上に厚さ0.5mm程度で均一になるように乗せ、マッフル炉で加熱(25℃から371℃まで10℃/minで昇温し、その後、371℃で2時間保持)して硬化させ、硬化物を得た。
硬化性化合物Cの硬化物、及び硬化性化合物Dの硬化物のDSC結果を図14に示す。DSCチャートに発熱ピークが見られないことから、得られた硬化物は高い硬化度を有すること(若しくは、硬化性化合物A、B、C、又はDは硬化性に優れ、加熱処理を施すことにより全ての硬化性官能基が失われたこと)が分かる。
実施例で得られた硬化性化合物A、B、C、D、又は比較例としてのPEEKをCHN元素分析に付して、窒素原子含有量を求めた。尚、標準試料にはアンチピリンを使用した。
硬化性化合物Aを投入した成形用金型をプレス機(30トン手動油圧真空可熱プレス IMC-46E2-3型、(株)井元製作所製)にセットして50℃に調整し、真空に引きながら、20℃/minで280℃まで昇温して1時間保持した後、さらに20℃/minで320℃まで昇温して30分保持した。その後、プレス機を空冷及び水冷し100℃以下になったところで金型を取り出して、平面状の硬化物(A)(厚み:0.2cm)を得た。得られた硬化物のFTIRスペクトルを図16に示す。得られた硬化物(A)の物性は以下の通りであった。
・密度(JIS K7112A 23℃):1.29g/cm3
・ガラス転移温度(DSCにより測定):154℃
・熱膨張係数(JIS K7197に準拠)(Tg以下):50.8ppm/℃
・熱膨張係数(JIS K7197に準拠)(Tg以上):263ppm/℃
・比誘電率(ASTM D2520に準拠、23℃)(10GHz):2.94
・誘電正接(ASTM D2520に準拠、23℃)(10GHz):0.0056
・難燃性(UL94Vに準拠、厚み0.15mm):V-1グレード
・窒素原子含有量:1.30重量%
・密度(JIS K7112A 23℃):1.19g/cm3
・ガラス転移温度(DSCにより測定):176℃
・熱膨張係数(JIS K7197に準拠)(Tg以下):73ppm/℃
・熱膨張係数(JIS K7197に準拠)(Tg以上):234ppm/℃
・比誘電率(JIS-C2138に準拠、23℃)(1MHz):2.69
・誘電正接(JIS-C2138に準拠、23℃)(1MHz):0.0050
・窒素原子含有量:1.01重量%
下記表3に記載の通り、調製例で得られた硬化性化合物A又はBと溶剤とをサンプル瓶へ秤量し、撹拌した。超音波を25℃で5分間あて、完全に硬化性化合物を溶解させて硬化性組成物を得た。
得られた硬化性組成物をシリンジで基板上にキャストし、アプリケーターで均一に広げ、これを一次乾燥(120℃の乾燥機中で1時間乾燥)、続いて二次乾燥(150℃の乾燥機中、真空で1時間乾燥)に付して塗膜を得た。得られた塗膜を熱硬化(220℃の乾燥機中、真空で1時間)させて、硬化物/基板積層体を得た。
硬化性化合物としてPEEKを使用した場合、PEEKは140℃で5分加熱撹拌しても溶剤に溶けず、塗料が形成できなかった。
○(良好):硬化物の剥離は見られなかった
×(不良):硬化物の剥離が見られた
基板 銅箔:市販電解銅箔 Rz=0.85μm
ステンレス鋼:SUS430
アルミ:取手付アルミニウムカップ
ガラス:MICRO SLIDE GLASS S1214
ポリイミド:カプトンH、東レ・デュポン(株)製
以下の点を変更した以外は実施例7と同様に行って、硬化性組成物を得、硬化物/基板積層体を得た。
すなわち、下記表4に記載の通りフィラーを添加した。また、塗料の熱硬化条件を「300℃の乾燥機中、真空で1時間」とした。
また、得られた積層体について、実施例7と同様の方法で密着性を評価した。
下記表5に記載の通り、調製例で得られた硬化性化合物A又はBをシクロヘキサノンに溶解させて複合材形成用硬化性組成物を得た。
得られた組成物5.0gに繊維1.186gを浸漬して、そのまま25℃で8時間静置した。その後、溶液から繊維を引き揚げ、130℃のホットステージ上で1時間加熱することでシクロヘキサノンを揮発させて、複合材(プリプレグ)を得た。
得られた複合材(プリプレグ)をアルミ箔で挟み、これを、プレス機に設置し、250℃で3分間加熱した後、0.1MPaで加圧した。250℃で8分間保持し、その後320℃まで12分かけて昇温し、320℃で20分間保持して硬化性化合物を硬化させて、複合材(硬化物)を得た。
硬化性化合物としてPEEKを使用した場合、PEEKは140℃で5分間加熱撹拌してもシクロヘキサノンに溶けず、複合材形成用硬化性組成物は得られなかった。そのため、PEEKを繊維に含浸させることができなかった。
調製例で得られた硬化性化合物BをNMP中で撹拌し、25℃において超音波を5分間あてて完全に硬化性化合物Bを溶解させて硬化性組成物(硬化性化合物B濃度:40重量%)を得た。
得られた硬化性組成物をシリンジに充填し、水中に押出して繊維状の成形体(長さ10cm、直径1mm)を得た。
硬化性化合物Bに代えてPEEKを使用したところ、140℃で5分加熱してもNMPに溶解せず、そのため繊維状に成形することはできなかった。
下記表6に記載の通り、硬化性化合物と溶剤をサンプル瓶へ秤量し、撹拌した。超音波を25℃で5分間あて、完全に硬化性化合物を溶解させて硬化性組成物を得た。
基板(1)上に、得られた硬化性組成物をシリンジでキャストし、アプリケーターで均一に広げ、これを一次乾燥(120℃の乾燥機中で1時間乾燥)、続いて二次乾燥(150℃の乾燥機中、真空で1時間乾燥)に付して塗膜を得た。
得られた塗膜に基板(2)を積層し、その後、前記塗膜を熱硬化(220℃の乾燥機中で1時間)させて、基板(2)/硬化物/基板(1)積層体を得た。
実施例22と同様の方法で得られた硬化性組成物を、キャリア(ポリイミド製、厚み100μm)上にキャストし、アプリケーターで均一に広げ、これを一次乾燥(120℃の乾燥機中で1時間乾燥)、二次乾燥(150℃の乾燥機中で1時間乾燥)、続いて三次乾燥(210℃の乾燥機中、真空で1時間乾燥)に付して厚み100μmの塗膜を得た。
得られた塗膜をキャリアから剥離した。塗膜はキャリアから容易に剥離できた。
基板(1)、基板(2)として銅箔(厚み18μm)を使用し、基板(1)、基板(2)の間に前記塗膜を挟んだ状態で熱硬化[真空熱圧着機中、210℃から5℃/分で300℃まで昇温し、その温度で60分保持した。また、昇温開始から5分で3MPaまで昇圧した]させて、基板(2)/硬化物/基板(1)積層体を得た。
すなわち、積層体を1cm×10cmの大きさに切り出し、長手方向の中央部(端から5cm)で半分に折り曲げた。折り部に100gの重りをのせた後、硬化物の外観を目視で観察し、下記基準で評価した。
屈曲性評価基準
○:割れや剥がれは、認められなかった
×:割れ若しくは剥がれが認められた
[1] 式(1)で表される化合物と溶剤とを含む、硬化性組成物。
[2] 溶剤が、ケトン、アミド、ハロゲン化炭化水素、スルホキシド、エーテル、エステル、ニトリル、及び芳香族炭化水素から選択される少なくとも1種の溶剤である、[1]に記載の硬化性組成物。
[3] 式(1)中のR1、R2が、同一又は異なって、環状イミド構造を有する硬化性官能基である、[1]又は[2]に記載の硬化性組成物。
[4] 式(1)中のR1、R2が、同一又は異なって、式(r-1)~(r-6)で表される基から選択される基である、[1]~[3]の何れか1つに記載の硬化性組成物。
[5] 式(1)中のD1、D2が、同一又は異なって、式(d-1)~(d-4)で表される構造を含む基から選択される基である、[1]~[4]の何れか1つに記載の硬化性組成物。
[6] 式(I)、及び式(II)中のAr1~Ar3が、同一又は異なって、炭素数6~14の芳香環の構造式から2個の水素原子を除いた基、又は炭素数6~14の芳香環の2個以上が、単結合、炭素数1~5の直鎖状又は分岐鎖状アルキレン基、又は炭素数1~5の直鎖状又は分岐鎖状アルキレン基の水素原子の1個以上がハロゲン原子で置換された基を介して結合した構造式から2個の水素原子を除いた基である、[1]~[5]の何れか1つに記載の硬化性組成物。
[7] 式(I)で表される構造が、ベンゾフェノン由来の構造である、[1]~[6]の何れか1つに記載の硬化性組成物。
[8] 式(1)で表される化合物全量における、ベンゾフェノン由来の構造単位の占める割合が5重量%以上である、[7]に記載の硬化性組成物。
[9] 式(II)で表される構造が、ハイドロキノン、レゾルシノール、2,6-ナフタレンジオール、2,7-ナフタレンジオール、4,4’-ジヒドロキシビフェニル、4,4’-ジヒドロキシジフェニルエーテル、4,4’-ジヒドロキシベンゾフェノン、4,4’-ジヒドロキシジフェニルスルフィド、4,4’-ジヒドロキシジフェニルスルフォン、及びビスフェノールAから選択される少なくとも1種の化合物由来の構造である、[1]~[8]の何れか1つに記載の硬化性組成物。
[10] 式(1)で表される化合物全量における、ハイドロキノン、レゾルシノール、2,6-ナフタレンジオール、2,7-ナフタレンジオール、4,4’-ジヒドロキシビフェニル、4,4’-ジヒドロキシジフェニルエーテル、4,4’-ジヒドロキシベンゾフェノン、4,4’-ジヒドロキシジフェニルスルフィド、4,4’-ジヒドロキシジフェニルスルフォン、及びビスフェノールA由来の構造単位の占める割合が5重量%以上である、[19]に記載の硬化性組成物。
[11] 式(1)中のLが、式(L-1)で表される基である、[1]~[10]の何れか1つに記載硬化性組成物。
[12] 式(1)中のLが、式(L-1-1)又は(L-1-2)で表される基である、[1]~[10]の何れか1つに記載の硬化性組成物。
[13] 窒素原子含有量が、硬化性化合物全量の2.8~0.1重量%である、[1]~[12]の何れか1つに記載の硬化性組成物。
[14] 比誘電率が6以下である、[1]~[13]の何れか1つに記載の硬化性組成物。
[15] 誘電正接が0.05以下である、[1]~[14]の何れか1つに記載の硬化性組成物。
[16] 硬化性化合物の硬化物であって、厚み0.15mmの硬化物の、UL94Vに準拠した方法による燃えにくさがV-1グレードである、[1]~[15]の何れか1つに記載の硬化性組成物。
[17] [1]~[16]の何れか1つに記載の硬化性組成物を成形して成形体を得る、成形体の製造方法。
[18] [1]~[16]の何れか1つに記載の硬化性組成物を含む接着剤。
[19] [1]~[16]の何れか1つに記載の硬化性組成物を含む塗料。
[20] [1]~[16]の何れか1つに記載の硬化性組成物を含む封止剤。
[21] 基板上に、[1]~[16]の何れか1つに記載の硬化性組成物の固化物からなる薄膜を積層し、加熱処理を施すことで、前記硬化性組成物の硬化物又は半硬化物と基板とが積層された構成を有する積層体を得る、積層体の製造方法。
[22] プラスチック製の支持体上に、前記硬化性組成物を塗布し、乾燥して、前記硬化性組成物の固化物からなる薄膜を得、得られた薄膜を前記支持体から剥離して基板に積層する、[21]に記載の積層体の製造方法。
[23] 硬化性化合物の硬化物を含み、昇温速度10℃/分(窒素中)で測定される5%重量減少温度(Td5)が300℃以上であり、320℃で30分の加熱処理に付した後の窒素原子含有量が2.8~0.1重量%である、固形物。
[24] IRスペクトルの1620~1750cm-1の領域にピークを有する、[23]に記載の固形物。
[25] 硬化性化合物が式(1)で表される化合物である、[23]又は[24]に記載の固形物。
[26] 硬化性化合物が、式(1)で表される化合物であって、前記式中のR1、R2が、同一又は異なって、環状イミド構造を有する硬化性官能基である化合物である、[23]~[25]の何れか1つに記載の固形物。
[27] 硬化性化合物が、式(1)で表される化合物であって、前記式中のR1、R2が、同一又は異なって、式(r-1)~(r-6)で表される基から選択される基である化合物である、[23]~[26]の何れか1つに記載の固形物。
[28] 硬化性化合物が、式(1)で表される化合物であって、前記式中のD1、D2が、同一又は異なって、式(d-1)~(d-4)で表される構造を含む基から選択される基である化合物である、[23]~[27]の何れか1つに記載の固形物。
[29] [1]~[16]の何れか1つに記載の硬化性組成物を接着剤として使用して半導体基板を積層する工程を経て半導体装置を製造する、半導体装置の製造方法。
[30] [1]~[16]の何れか1つに記載の硬化性組成物を使用して半導体素子を封止する工程を経て半導体装置を製造する、半導体装置の製造方法。
[31] [1]~[16]の何れか1つに記載の硬化性組成物の硬化物又は半硬化物と基板とが積層された構成を有する積層体。
Claims (18)
- 下記式(1)
で表される化合物と溶剤とを含む、硬化性組成物。 - 溶剤が、ケトン、アミド、ハロゲン化炭化水素、スルホキシド、エーテル、エステル、ニトリル、及び芳香族炭化水素から選択される少なくとも1種の溶剤である、請求項1に記載の硬化性組成物。
- 式(1)中のR1、R2が、同一又は異なって、環状イミド構造を有する硬化性官能基である、請求項1又は2に記載の硬化性組成物。
- 式(I)、及び式(II)中のAr1~Ar3が、同一又は異なって、炭素数6~14の芳香環の構造式から2個の水素原子を除いた基、又は炭素数6~14の芳香環の2個以上が、単結合、炭素数1~5の直鎖状又は分岐鎖状アルキレン基、又は炭素数1~5の直鎖状又は分岐鎖状アルキレン基の水素原子の1個以上がハロゲン原子で置換された基を介して結合した構造式から2個の水素原子を除いた基である、請求項1~5の何れか1項に記載の硬化性組成物。
- 式(I)で表される構造が、ベンゾフェノン由来の構造である、請求項1~6の何れか1項に記載の硬化性組成物。
- 式(1)で表される化合物全量における、ベンゾフェノン由来の構造単位の占める割合が5重量%以上である、請求項7に記載の硬化性組成物。
- 式(II)で表される構造が、ハイドロキノン、レゾルシノール、2,6-ナフタレンジオール、2,7-ナフタレンジオール、4,4’-ジヒドロキシビフェニル、4,4’-ジヒドロキシジフェニルエーテル、4,4’-ジヒドロキシベンゾフェノン、4,4’-ジヒドロキシジフェニルスルフィド、4,4’-ジヒドロキシジフェニルスルフォン、及びビスフェノールAから選択される少なくとも1種の化合物由来の構造である、請求項1~8の何れか1項に記載の硬化性組成物。
- 式(1)で表される化合物全量における、ハイドロキノン、レゾルシノール、2,6-ナフタレンジオール、2,7-ナフタレンジオール、4,4’-ジヒドロキシビフェニル、4,4’-ジヒドロキシジフェニルエーテル、4,4’-ジヒドロキシベンゾフェノン、4,4’-ジヒドロキシジフェニルスルフィド、4,4’-ジヒドロキシジフェニルスルフォン、及びビスフェノールA由来の構造単位の占める割合が5重量%以上である、請求項9に記載の硬化性組成物。
- 請求項1~10の何れか1項に記載の硬化性組成物を成形して成形体を得る、成形体の製造方法。
- 請求項1~10の何れか1項に記載の硬化性組成物を含む接着剤。
- 請求項1~10の何れか1項に記載の硬化性組成物を含む塗料。
- 請求項1~10の何れか1項に記載の硬化性組成物を含む封止剤。
- 基板上に、請求項1~10の何れか1項に記載の硬化性組成物の固化物からなる薄膜を積層し、加熱処理を施すことで、前記硬化性組成物の硬化物又は半硬化物と基板とが積層された構成を有する積層体を得る、積層体の製造方法。
- プラスチック製の支持体上に、前記硬化性組成物を塗布、乾燥して、前記硬化性組成物の固化物からなる薄膜を得、得られた薄膜を前記支持体から剥離して基板上に積層し、加熱処理を施す、請求項15に記載の積層体の製造方法。
- 硬化性化合物の硬化物を含み、昇温速度10℃/分(窒素中)で測定される5%重量減少温度(Td5)が300℃以上であり、320℃で30分の加熱処理に付した後の窒素原子含有量が2.8~0.1重量%である、固形物。
- IRスペクトルの1620~1750cm-1の領域にピークを有する、請求項17に記載の固形物。
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