WO2022234804A1 - Procédé de décomposition d'un produit durci d'une composition de résine durcissable - Google Patents

Procédé de décomposition d'un produit durci d'une composition de résine durcissable Download PDF

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WO2022234804A1
WO2022234804A1 PCT/JP2022/019091 JP2022019091W WO2022234804A1 WO 2022234804 A1 WO2022234804 A1 WO 2022234804A1 JP 2022019091 W JP2022019091 W JP 2022019091W WO 2022234804 A1 WO2022234804 A1 WO 2022234804A1
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cured product
group
resin composition
atoms
curable resin
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PCT/JP2022/019091
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English (en)
Japanese (ja)
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直房 宮川
究 寺田
栄一 西原
隼 本橋
律子 設楽
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日本化薬株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/16—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention after the cured product of the curable resin composition is used for a specific purpose, it can be easily dismantled by exposing it to a specific compound, and various materials in the cured product can be recycled (reused or separated for disposal). It relates to a method for decomposing a cured product of a curable resin composition.
  • Curable resins such as epoxy resins and acrylate resins become strong cured products by three-dimensional cross-linking with energy such as heat and light. Therefore, it is used in many applications such as electrical and electronic parts, building material parts, automobile parts, and composite materials such as GFRP (glass fiber reinforced plastic) and CFRP (carbon fiber reinforced plastic) that require reliability.
  • GFRP glass fiber reinforced plastic
  • CFRP carbon fiber reinforced plastic
  • curable resins having three-dimensional crosslinks are difficult to decompose when intended, and are not suitable for recycling. Therefore, there is a demand for a curable resin product that can be easily dismantled when it is no longer needed, but can meet the demand for high reliability due to three-dimensional cross-linking during use.
  • the object of the present invention is to provide a method for decomposing a curable resin that exhibits little change in physical properties and excellent high-temperature durability even when exposed to an environment of 200°C.
  • a curable resin composition in which a cured product of a curable resin composition containing a resin represented by the following formula (1) is decomposed using at least one of an ammonium fluoride salt and a tetraalkylammonium fluoride salt. Decomposition method of the cured product.
  • each of R 1 to R 4 is a substituent containing C and H atoms and optionally one or more atoms selected from O, Si and N atoms.
  • R 1 to R 4 may be the same or different, and one or more of R 1 to R 4 have a curable functional group.
  • R 5 represent hydrogen atoms or all represent alkyl groups having 1 to 10 carbon atoms. In formula (2), when all of R 5 are alkyl groups, a plurality of R 5 may be the same or different).
  • a cured product of a curable resin composition having a specific structure can be decomposed by exposing it to an ammonium fluoride salt and/or a tetraalkylammonium fluoride salt.
  • FIG. 5 is a diagram showing the appearance of Comparative Example 1 and Examples 1 to 4 after 5 hours from placing them in a THF solution of tetrabutylammonium fluoride salt.
  • FIG. 2 is a diagram showing the appearance of Comparative Example 1 and Examples 1 to 4 after 24 hours from placing them in a THF solution of tetrabutylammonium fluoride salt.
  • FIG. 5 is a diagram showing the appearance of Comparative Example 1 and Examples 1 to 4 after 52 hours from placing them in a THF solution of tetrabutylammonium fluoride salt.
  • 1 is a diagram showing the appearance of Comparative Example 1 and Examples 1 to 4 after 172 hours from placing them in a THF solution of tetrabutylammonium fluoride salt.
  • FIG. 5 is a diagram showing the appearance of Comparative Example 1 and Examples 1 to 4 after 5 hours from placing them in a THF solution of tetrabutylammonium fluoride salt.
  • atoms include all isotopes.
  • curable resin composition containing a resin represented by the following general formula (1) will be described.
  • R 1 to R 4 are substituents each containing C and H atoms and optionally one or more atoms selected from O, Si and N atoms. R 1 to R 4 may be the same or different. One or more of R 1 to R 4 have a curable functional group.
  • Substituents containing C and H atoms and optionally containing one or more atoms selected from O, Si and N atoms include aliphatic, alicyclic and aromatic substituents having 1 to 10 carbon atoms, hetero Examples include cyclic substituents and substituents containing a silicone skeleton, and curing agents such as epoxy groups, acrylate groups, maleimide groups, phenol groups, carboxylic acid groups, carboxylic anhydride groups, thiol groups, amino groups, hydrazide groups, etc. It may contain a functional group.
  • Aliphatic, alicyclic and aromatic substituents having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decanyl group. , isopropyl group, isobutyl group, isopentyl group, neopentyl group, isohexyl group, cyclohexyl group, phenyl group, 1-naphthyl group, 2-naphthyl group and the like.
  • Heterocyclic substituents include pyridyl groups, furanyl groups, pyrimidylyl groups, and the like.
  • At least one of the resins represented by the general formula (1) has a curable functional group.
  • Curable functional groups include epoxy group, (meth)acrylate group, maleimide group, phenol group, carboxylic acid group, carboxylic acid anhydride group, thiol group, amino group, hydrazide group and the like.
  • An acrylate group and a maleimide group are preferable from the viewpoint of decomposability.
  • An epoxy group is a three-membered ring group consisting of two carbons and one oxygen.
  • a group containing an epoxy group is an organic group represented by the following formulas (3) and (4).
  • a maleimide group is an organic group represented by the following formula (5).
  • * represents a binding site
  • the epoxy resin represented by the formula (6) is, for example, X-40-2669
  • the epoxy resin represented by the formula (8) is, for example, KR-470, both of which are commercially available from Shin-Etsu Chemical Co., Ltd., etc. , you can also use these.
  • silicone-modified epoxy resins obtained by dealcoholization condensation of dialkoxysilane compounds or trialkoxysilane compounds represented by the following general formula (10) under alkaline or acidic conditions.
  • Ep represents an organic group having an epoxy group
  • R 6 represents an alkyl group having 1 to 6 carbon atoms, an aryl group, or an alkoxy group, respectively.
  • a plurality of R 6 in the formula may be the same or different, but at least two are alkoxy groups.
  • alkyl groups having 1 to 6 carbon atoms in R 6 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and cyclohexyl group, and examples of aryl groups include phenyl group. and alkoxy groups include methoxy, ethoxy and propoxy groups.
  • the compound represented by the general formula (10) may be a single compound, or different compounds may be used to obtain a silicone-modified epoxy resin through dealcoholization condensation.
  • a reactive silicone oil having a (meth)acrylic group is exemplified as a resin having an acrylic group.
  • Reactive silicone oils having (meth)acrylic groups are commercially available as X-22-2445 (Shin-Etsu Chemical Co., Ltd.), 8SS-723 (Taisei Fine Chemical Co., Ltd.), Silaplane FM-0721 (JNC Co., Ltd.), etc. These can also be used.
  • the resin represented by the general formula (1) has an epoxy group, it can be mixed with an epoxy resin curing agent to obtain a curable resin composition.
  • epoxy resin curing agent examples include amine-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, polyvalent carboxylic acid-based curing agents, thiol-based curing agents, imidazole-based curing agents, cationic curing agents, and dicyandiamide. and each commercially available curing agent can be used.
  • the curable resin composition optionally contains a filler, a solvent, Antioxidants, light stabilizers, leveling agents and flame retardants may also be included.
  • the resin represented by the general formula (1) is a resin having a (meth)acrylate group, it can be mixed with a photopolymerization initiator to obtain a curable resin composition.
  • photopolymerization initiator intramolecular cleavage type benzoin derivatives, ⁇ -hydroxyacetophenone, benzyl ketal, ⁇ -aminoacetophenone, acylphosphine oxide, titanocene, O-acyloxime type photopolymerization initiator, hydrogen abstraction Benzophenone and thioxanthone are exemplified as types.
  • the curable resin composition optionally contains a filler, Solvents, antioxidants, light stabilizers, leveling agents and flame retardants may also be included.
  • the resin represented by the general formula (1) is a resin having a maleimide group
  • it can be mixed with an anionic curing agent such as imidazole and/or a radical generator to obtain a curable resin composition.
  • anionic curing agent examples include 2-ethyl-4-methylimidazole, 2-phenyl-1-benzyl-1H-imidazole, 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]- 1,3,5-triazine, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-benzylimidazole, 2,4-diamino-6-[2-(2-undecyl-1-imidazolyl)ethyl ]-1,3,5-triazine, 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine.
  • radical generator examples include benzoin derivatives, ⁇ -hydroxyacetophenone, benzyl ketal, ⁇ -aminoacetophenone, acylphosphine oxide, titanocenes, O-acyloxime photopolymerization initiators, benzophenone, thioxanthone, and organic peroxides. be done.
  • the curable resin composition when obtaining a curable resin composition by mixing a resin having a maleimide group represented by the general formula (1) with an anionic curing agent such as imidazole and / or a radical generator, the curable resin composition is optionally It may also contain fillers, solvents, antioxidants, light stabilizers, leveling agents and flame retardants.
  • the curable resin composition can be obtained by uniformly mixing at room temperature or under heating.
  • the resin composition is sufficiently mixed using an extruder, kneader, triple roll, universal mixer, planetary mixer, homomixer, homodisper, bead mill or the like until uniform, and if necessary, the resin composition is mixed with a SUS mesh or the like. It is prepared by carrying out a filtration treatment of a substance.
  • the resin composition As a method of curing the resin composition, it can be cured by heating or light irradiation.
  • heating methods such as hot air circulation, infrared rays, and high frequency can be used.
  • Heating conditions are preferably, for example, 80 to 230° C. for about 1 minute to 24 hours.
  • For the purpose of reducing the stress generated inside the resin composition during heat curing for example, after precuring at 80 to 120 ° C. for 30 minutes to 5 hours, 120 to 180 ° C. under the conditions of 30 minutes to 10 hours. It can be post-cured.
  • Light irradiation can be performed by irradiating the resin composition with light from a light source such as a high-pressure mercury lamp, an extra-high pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, or an LED. Curing can also be accelerated by heating, for example, at 80 to 230° C. for about 1 minute to 24 hours after light irradiation.
  • a light source such as a high-pressure mercury lamp, an extra-high pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, or an LED.
  • Curing can also be accelerated by heating, for example, at 80 to 230° C. for about 1 minute to 24 hours after light irradiation.
  • the cured product of the curable resin composition containing the resin represented by the general formula (1) has a Tg measured by DMA (Dynamic Mechanical Analysis) of preferably 50°C or higher, more preferably 100°C or higher. It is preferably 150° C. or higher, and more preferably 150° C. or higher.
  • Tg measured by DMA (Dynamic Mechanical Analysis)
  • the cured product of the curable resin composition containing the resin represented by the general formula (1) preferably has a storage modulus of 500 MPa or more, and preferably 1000 MPa or more, as measured by DMA at room temperature (30°C). is more preferable, and 2000 MPa or more is even more preferable.
  • the storage elastic modulus of the cured product of the curable resin composition containing the resin represented by the general formula (1) is 500 MPa or more. Furthermore, it is preferable from the viewpoint of the durability of the cured product to maintain sufficient Tg and storage elastic modulus even after being left in a high-temperature environment.
  • the high temperature environment is preferably 100° C. or higher, more preferably 180° C. or higher, and further preferably 230° C. or higher from the viewpoint of the durability of the cured product in the use environment.
  • a curable resin composition containing the resin represented by the formula (1) is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone.
  • a curable resin composition varnish a prepreg obtained by impregnating a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper with the curable resin composition varnish and drying by heating.
  • a cured product of the curable resin composition containing the resin represented by the formula (1) can be obtained by hot press molding.
  • the solvent is usually used in an amount of 10 to 70% by mass, preferably 15 to 70% by mass in the mixture of the curable resin composition containing the resin represented by the formula (1) and the solvent. It is also possible to obtain an epoxy resin cured product containing reinforcing fibers such as carbon fibers by the RTM (Resin Transfer Molding) method from the liquid composition.
  • the curable resin composition containing the resin represented by formula (1) can also be used as a modifier for film-type compositions. Specifically, it can be used to improve flexibility and the like in the B stage.
  • a curable resin composition containing the resin represented by the formula (1) is applied on the release film with the varnish, the solvent is removed under heating, and the B stage is applied.
  • a sheet-like adhesive is obtained by curing. This sheet-like adhesive can be used as an interlayer insulating layer in multilayer substrates and the like.
  • thermosetting resins such as epoxy resins are used are mentioned as applications in which the curable resin composition containing the resin represented by the formula (1) is used.
  • Adhesives include adhesives for civil engineering, construction, automobiles, general office and medical use, as well as adhesives for electronic materials.
  • adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, adhesives for semiconductors such as underfill, underfill for BGA (Ball Grid Array) reinforcement, anisotropic Mounting adhesives such as electrically conductive film (ACF) and anisotropic conductive paste (ACP) can be used.
  • encapsulants include potting, dipping, transfer mold encapsulation for electronic elements such as capacitors, transistors, diodes, light-emitting diodes, ICs and LSIs, COB (Chip on Board) and COF (Chip on Board) of ICs and LSIs. on Film), TAB (Tape Automated Bonding), potting sealing for mounting, etc., underfill for flip chip, QFP (Quad Flat Package), BGA, CSP (Chip Size Package), etc. When mounting IC packages sealing (including reinforcing underfill).
  • electronic elements such as capacitors, transistors, diodes, light-emitting diodes, ICs and LSIs, COB (Chip on Board) and COF (Chip on Board) of ICs and LSIs. on Film), TAB (Tape Automated Bonding), potting sealing for mounting, etc., underfill for flip chip, QFP (Quad Flat Package), BGA, CSP (Chip Size Package
  • the cured product of the curable resin composition containing the resin represented by the formula (1) can be used for various applications including optical component materials.
  • Materials for optical parts refer to materials in general used for the purpose of allowing light such as visible light, infrared rays, ultraviolet rays, X-rays, and lasers to pass through the material. More specifically, in addition to lamp-type, SMD-type, and other LED sealing materials, there are the following.
  • Substrate materials in the field of liquid crystal displays liquid crystal display peripheral materials such as light guide plates, prism sheets, polarizing plates, retardation plates, viewing angle correction films, adhesives, and liquid crystal films such as polarizer protective films.
  • LED molding materials, LED sealing materials, front glass protective films, front glass replacement materials, adhesives used in devices, substrate materials for plasma addressed liquid crystal (PALC) displays, light guide plates, prism sheets, polarizing plates , retardation plate, viewing angle correction film, adhesive, polarizer protective film, front glass protective film in organic EL (electroluminescence) display, front glass alternative material, adhesive, and various field emission displays (FED) They are film substrates, front glass protective films, front glass replacement materials, and adhesives.
  • VD video disc
  • CD/CD-ROM compact disc
  • CD-R/RW compact disc
  • DVD-R/DVD-RAM digital versatile disc
  • MO/MD organic light-emitting diode
  • PD phase change disc
  • Blu-ray Disc registered trademark
  • materials for still camera lenses, viewfinder prisms, target prisms, viewfinder covers, and light receiving sensors. It is also a video camera taking lens and viewfinder. They also include projection lenses for projection televisions, protective films, sealing materials, and adhesives. Materials for optical sensing equipment lenses, sealing materials, adhesives, films, etc.
  • materials for optical sensing equipment lenses, sealing materials, adhesives, films, etc. In the field of optical components, it is used for fiber materials around optical switches in optical communication systems, lenses, waveguides, element sealing materials, adhesives, and the like. These include optical fiber materials, ferrules, sealing materials, and adhesives around optical connectors.
  • Optical passive components and optical circuit components include lenses, waveguides, LED sealing materials, LED packaging materials, LED reflector materials, CCD sealing materials, and adhesives.
  • OEICs optoelectronic integrated circuits
  • semiconductor integrated circuit peripheral materials it is a resist material for microlithography for LSI and super LSI materials.
  • Next-generation organic materials with optical and electronic functions include peripheral materials for organic EL devices, organic photorefractive devices, optical amplification devices that are light-light conversion devices, optical computing devices, substrate materials for organic solar cells, fiber materials, and devices. sealing materials, adhesives, etc.
  • the cured product of the curable resin composition containing the resin represented by formula (1) can be decomposed by exposing it to an ammonium fluoride salt and/or a tetraalkylammonium fluoride salt.
  • an ammonium fluoride salt and/or a tetraalkylammonium fluoride salt This makes it possible to recycle reinforcing fibers cured together with the cured product of the curable resin composition, such as glass fibers of GFRP (glass fiber reinforced plastic) and carbon fibers of CFRP (carbon fiber reinforced plastic). Therefore, the decomposition method provided by the present invention is extremely useful for recycling many parts such as electrical and electronic parts, building material parts, automobile parts, and composite materials such as GFRP and CFRP in a recycling society.
  • ammonium fluoride salts and tetraalkylammonium fluoride salts will be described.
  • Ammonium fluoride salts and tetraalkylammonium fluoride salts are compounds represented by the following formula (2).
  • Ammonium fluoride salts are compounds of formula ( 2 ) in which all R5 represent hydrogen atoms.
  • a tetraalkylammonium fluoride salt is a compound represented by formula (2) in which all R 5 represent an alkyl group having 1 to 10 carbon atoms, and a plurality of R 5 may be the same or different. do not have.
  • alkyl groups having 1 to 10 carbon atoms represented by R 5 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tertiary butyl group, pentyl group, isopentyl group, neopentyl group and hexyl. group, isohexyl group, heptyl group, isoheptyl group, octyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, cyclohexyl group, etc., and butyl group is preferable from the viewpoint of availability in the market.
  • the ammonium fluoride salt and the tetraalkylammonium fluoride salt can be used alone or mixed to form an aqueous solution or an organic solvent solution. It is preferable to use at least one of an ammonium fluoride salt and a tetraalkylammonium fluoride salt in the form of an aqueous solution or a solution of an organic solvent, since the decomposability of the cured product is accelerated.
  • the organic solvent tetrahydrofuran (THF), dimethylsulfoxide, dimethylformamide, methanol, ethanol, isopropyl alcohol, and acetonitrile are preferred, and tetrahydrofuran is more preferred.
  • the concentration is preferably 0.1 to 5 mol/L from the viewpoint of the decomposition rate, and 0.5 to 0.5 mol/L. 2 mol/L is more preferred.
  • the ratio of the total mass of Si atoms and O atoms bonded to Si atoms in the cured product to the mass of the cured product of the curable resin composition containing the resin represented by the general formula (1) is 1% by mass or more. It is preferably at least 5% by mass, more preferably at least 10% by mass.
  • the ratio of the total mass of Si atoms and O atoms bonded to Si atoms in the cured product to the mass of the cured product of the curable resin composition containing the resin represented by the general formula (1) is 1% by mass or more. If there is, the decomposition reaction of the cured product proceeds efficiently.
  • a cured product of a curable resin composition containing the resin represented by the formula (1) is reacted with at least one of an ammonium fluoride salt and a tetraalkylammonium fluoride salt to decompose the cured product.
  • Some decomposition products can be obtained.
  • the resulting decomposition products contain Si—F bonds.
  • the resulting decomposition product When the resulting decomposition product is used as a strength imparting agent or filler for a curable resin, it can be used as it is, but if the decomposition product contains a solvent, it is preferable to use it after removing the solvent. It is also preferable to use the decomposition product after purifying it by a method such as distillation, filtration, recrystallization or column chromatography.
  • ratios, percentages, parts, etc. are based on mass unless otherwise specified.
  • X to Y indicates a range from X to Y, and the range includes X,Y.
  • Comparative Example 1 and Examples 1-4; X-40-2669 represented by the following formula (6) [manufactured by Shin-Etsu Chemical Co., Ltd., an epoxy resin having a silicone skeleton, the ratio of the mass of the silicone skeleton (Si-O-Si) to the mass of the epoxy resin having a silicone skeleton is 18.8% by mass], CEL2021P (3′,4′-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate manufactured by Daicel Corporation), Rikacid MH as an epoxy resin curing agent (manufactured by New Japan Chemical Co., Ltd., methyl hexa Hydrophthalic anhydride) and U-CAT18X (manufactured by San-Apro Co., Ltd., epoxy resin curing accelerator) as a curing accelerator are weighed in a polyethylene container at the ratio shown in Table 1 below, and mixed well with a spoon. The mixture was stirred for 2 minutes using a vacuum stirring and def
  • test piece creation The obtained epoxy resin compositions of Comparative Examples and Examples 1 to 4 were cast into a stainless steel mold having a length of 120 mm, a width of 4 mm and a height of 10 mm. The cast product was precured at 120° C. for 1 hour and then cured at 150° C. for 3 hours to obtain a cured epoxy resin. The obtained epoxy resin cured product was molded using an electric diamond cutter to obtain a test piece for degradability test having a length of 10 mm, a width of 4 mm and a height of 4 mm.
  • the obtained epoxy resin cured product was molded into a width of 5 mm and a length of 25 mm, and DMA (Dynamic Mechanical Analysis) was measured under the following conditions to read the storage elastic modulus and Tg (glass transition temperature) at 30°C.
  • the obtained epoxy resin cured product was molded into a width of 5 mm and a length of 25 mm, left in an oven at 250° C. for 5 hours, cooled to room temperature, and then measured for DMA in the same manner.
  • Model: Viscoelastic spectrometer EXSTAR DMS6100 Measurement temperature: 30°C to 280°C Heating rate: 2°C/min Frequency: 1Hz Measurement mode: Glass transition temperature (Tg) measured by tensile vibration DMA method: The temperature at the maximum point of the loss coefficient (tan ⁇ E′′/E′) represented by the quotient of the storage elastic modulus (E′) and the loss elastic modulus (E′′) when the DMA was measured was read. The ratio (mass%) of the total mass of Si atoms and O atoms bonded to Si atoms in the formulation, the storage elastic modulus and Tg (glass transition point) at 30 ° C. of the cured product measured by the DMA test, and the cured product to 200 Table 1 shows the storage modulus and Tg (glass transition point) at 30°C measured by the DMA test after standing at °C for 5 hours.
  • ⁇ Degradability test> Each test piece obtained as described above was placed in a 10 cc glass sample bottle, and 2 g of a 1M (mol/L) tetrabutylammonium fluoride salt in tetrahydrofuran (THF) solution was added thereto. A THF solution was added to the sample bottle, and the sample bottle was allowed to stand in an environment of 20 to 25°C. After adding the THF solution to the sample bottle, remove the test piece from the sample bottle after 5 hours, 24 hours, 52 hours, and 172 hours, wash the test piece with water, wipe off water droplets on the surface of the test piece, and remove the test piece. After drying for 24 hours at 25° C., the mass of the specimen was measured.
  • THF tetrabutylammonium fluoride salt in tetrahydrofuran
  • Table 1 shows relative values of the mass of the test piece after drying when the mass of the test piece before being placed in the sample bottle is 100. In addition, 5 hours, 24 hours, 52 hours, and 172 hours after adding the THF solution to the sample bottle, the test pieces were taken out from the sample bottle, washed and dried, and the appearance of the test pieces was photographed. Appearances of the test pieces are shown in FIGS. 1 to 4, respectively.
  • Example 1 As shown in Table 1, in Comparative Example 1, as time passed after immersion in the THF solution, the test piece swelled and the mass of the test piece increased, but no significant change in appearance was observed. .
  • Example 1 the mass of the test piece decreased as time passed after being immersed in the THF solution.
  • Example 2 the mass of the test piece tended to decrease as time passed after being immersed in the THF solution.
  • Example 3 the mass of the test piece decreased as time passed after being immersed in the THF solution.
  • Example 3 cracks were found in the test piece after 172 hours.
  • Example 4 the mass of the test piece decreased as time passed after being immersed in the THF solution, the mass of the test piece decreased to 18% after 52 hours, and the test piece disappeared after 172 hours. did.
  • the method of decomposing the cured product of Examples 1 to 4, in which the cured product containing the specific structure is immersed in a fluoride salt solution, has a Tg of 150° C. or higher and a storage modulus of 2000 MPa or higher at room temperature (30° C.).
  • the decomposition method provided by the present invention can contribute to the realization of a recycling-oriented society in which various materials in the cured product are recycled.

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Abstract

La présente invention concerne un procédé de décomposition d'une résine durcissable dont les propriétés physiques ne sont pas susceptibles de changer même si la résine durcissable est exposée à un environnement à 200 °C, et la résine durcissable présentant une excellente durabilité à des températures élevées. L'invention concerne également un procédé de décomposition d'un produit durci d'une composition de résine durcissable, un produit durci d'une composition de résine durcissable qui contient une résine représentée par la formule (1) étant décomposée au moyen d'au moins l'un parmi un sel de fluorure d'ammonium et un sel de fluorure de tétraalkylammonium.　(Dans la formule (1), chacun de R1 à R4 représente indépendamment un substituant qui contient un atome de C et un atome de H, tout en contenant facultativement un ou plusieurs atomes qui sont sélectionnés parmi un atome d'O, un atome de Si et un atome de N ; les fractions R1 à R4 peuvent être identiques ou différentes les unes des autres ; et une ou plusieurs fractions parmi les fractions R1 à R4 ont un groupe fonctionnel durcissable .)
PCT/JP2022/019091 2021-05-06 2022-04-27 Procédé de décomposition d'un produit durci d'une composition de résine durcissable WO2022234804A1 (fr)

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