WO2022045361A1 - Procédé de production d'une composition - Google Patents

Procédé de production d'une composition Download PDF

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WO2022045361A1
WO2022045361A1 PCT/JP2021/031952 JP2021031952W WO2022045361A1 WO 2022045361 A1 WO2022045361 A1 WO 2022045361A1 JP 2021031952 W JP2021031952 W JP 2021031952W WO 2022045361 A1 WO2022045361 A1 WO 2022045361A1
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group
solvent
resin
polymer
particulate
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PCT/JP2021/031952
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Japanese (ja)
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勇輔 小沼
宏司 西岡
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住友化学株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/11—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids from solid polymers
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a method for producing a composition capable of forming a film that can be used as a substrate material compatible with a printed circuit board for a high frequency band or an antenna substrate, the composition, a dispersion liquid capable of forming the composition, and the film.
  • a copper-clad laminate called CCL has a structure in which copper foils are laminated on both surfaces of a resin layer via an adhesive.
  • the transmission loss of the CCL can be suppressed by reducing the dielectric loss of the resin layer serving as the transmission line, particularly the dielectric loss tangent and the relative permittivity.
  • the step (1) is a step of dissolving the cycloolefin polymer (B) in the first solvent to obtain a cycloolefin polymer (B) solution (hereinafter, may be referred to as a polymer (B) solution).
  • the dielectric property means a property related to dielectric including dielectric loss, relative permittivity and dielectric loss tangent, and that the dielectric property is enhanced or improved is, for example, dielectric loss, relative permittivity and / or. It shows that the dielectric loss tangent is reduced.
  • the mechanical property means the mechanical property including the bending resistance and the elastic modulus, and when the mechanical property is enhanced or improved, for example, the bending resistance and / or the elastic modulus is increased. Show that.
  • m is an integer of 0 or more. From the viewpoint that the particle size and CTE of the film can be easily reduced, the mechanical properties such as surface smoothness, heat resistance and bending resistance of the film can be easily improved, and the film can be easily obtained, the upper limit of m is preferably 3 or less. It is an integer, more preferably an integer of 2 or less, and even more preferably an integer of 1 or less.
  • An aryl group such as a phenyl group, a trill group, or a naphthyl group; an aralkyl group such as a benzyl group or a phenethyl group; a group in which a part of the hydrogen atom of the alkyl group, the aryl group or the aralkyl group is substituted with a halogen atom and the like can be mentioned. Be done.
  • an alkyl group, an aryl group or an aralkyl group is preferable from the viewpoint of easily enhancing the water absorption resistance, heat resistance, dielectric property and mechanical property of the film and easily reducing the CTE of the film.
  • Examples of the cycloolefin represented by the formula (I) include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, tetracyclododecene and tricyclodecene. , Tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene and the like.
  • Examples thereof include ethylbenzene, isopropenylpropylbenzene, isopropenylbutylbenzene, isopropenylpentylbenzene, isopropenylhexylbenzene, isopropenyloctylbenzene, isopropenylnaphthalene, isopropenylanthracene and the like.
  • styrene, methylstyrene or dimethylstyrene is preferable, and styrene is more preferable, from the viewpoints of easy availability of the raw material monomer, easy reduction of CTE of the film, and easy improvement of mechanical properties such as bending resistance. ..
  • the aromatic vinyl compound having 8 to 20 carbon atoms one kind may be used alone, or two or more kinds may be used in combination.
  • the polymer (B) is made from ethylene, propylene and styrene from the viewpoints of easy availability of a raw material monomer, easy reduction of CTE of a film, and easy improvement of mechanical properties such as bending resistance. It may contain a monomer unit (II) derived from at least one selected from the group consisting of ethylene and styrene, more preferably a monomer unit (II) derived from at least one selected from the group consisting of ethylene and styrene. preferable.
  • the ratio (Mw / Mn) of Mw of the polymer (B) to the number average molecular weight (hereinafter, the number average molecular weight may be abbreviated as Mn) is preferably 2. 5 or less, more preferably 2.2 or less, still more preferably 2.0 or less, even more preferably 1.95 or less, particularly preferably 1.90 or less, preferably 1.30 or more, still more preferably 1. It is 50 or more, more preferably 1.60 or more, and particularly preferably 1.65 or more.
  • Mw and Mn can be determined by gel permeation chromatography (hereinafter, may be abbreviated as GPC) measurement and converted to standard polystyrene, and can be determined, for example, by the method described in Examples.
  • the Tg of the polymer (B) is the softening temperature measured by TMA based on JIS K7196, and can be measured by, for example, the method described in Examples.
  • a cyclopentadienyl group preferably a cyclopentadienyl group, a methylcyclopentadienyl group, a tetramethylcyclopentadienyl group, an n-butylcyclopentadienyl group, an isobutylcyclopentadienyl group, an indenyl group, a methylindenyl group.
  • a fluorenyl group may be mentioned.
  • D 1 and D 2 are halogenated hydrocarbon groups
  • D 1 and D 2 are halogenated hydrocarbon groups
  • D 1 and D 2 are halogenated hydrocarbon groups.
  • R 1 to R 6 are hydrocarbon groups, the number of carbon atoms is preferably 1 to 10. Specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group and n-hexyl group.
  • any of the boron compounds represented by the formula ( ⁇ 1), the formula ( ⁇ 2) or the formula ( ⁇ 3) can be used.
  • B represents a boron atom in a trivalent valence state
  • Q1 to Q3 are independent of each other, a halogen atom, a hydrocarbon group containing a carbon atom, and a halogenation having 1 to 20 carbon atoms. It represents a hydrocarbon group, a substituted silyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a disubstituted amino group having 2 to 20 carbon atoms, which may be the same or different.
  • Q1 to Q3 are independent of each other, preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.
  • ferrosenium tetrakis (pentafluorophenyl) borate, 1,1'-dimethylferrosenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, and triphenylmethyl tetrakis.
  • Examples thereof include (pentafluorophenyl) borate, triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate, and preferably triphenylmethyltetrakis (pentafluorophenyl) borate.
  • B represents boron in a trivalent valence state
  • Q1 to Q4 are the same as Q1 to Q3 in the above formula ( ⁇ 1).
  • L represents a neutral Lewis base
  • (L—H) + represents a Bronsted acid.
  • the molar ratio of the co-catalyst / transition metal complex ( ⁇ ) is preferably 0.01 to 10,000, more preferably 0.5 to 2,000.
  • the concentration of the transition metal complex ( ⁇ ) is preferably 0.0001 to 5 mmol / L, more preferably 0.001 to 1 mmol / L.
  • the amount of the catalyst component used is preferably 0.00001 to 1 mol%, more preferably 0.0001 to 0.1 mol%, based on the total amount of all the monomers used.
  • Ra [4 ⁇ ( ⁇ DA- ⁇ DB) 2 + ( ⁇ PA- ⁇ PB) 2 + ( ⁇ HA- ⁇ HB) 2 ] 0.5 ... (Y)
  • HSP value and the distance between the HSP values are as defined above, and can be obtained according to the above method.
  • the first solvent is preferably a solvent in which the resin (A) does not dissolve.
  • the particle size of the particulate polymer (B) can be easily reduced and the dispersibility can be easily improved.
  • the upper limit of the distance between the HSP values of the second solvent and the polymer (B) is preferably 30.0 or less, more preferably 25.0 or less, still more preferably 20.0.
  • the distance between the HSP values of the second solvent and the polymer (B) is not more than the above upper limit, it is easy to suppress the aggregation of the particulate polymer (B), so that the dispersibility of the particles can be easily improved. It is easy to improve the particle dispersibility of the film to be obtained.
  • the distance between the HSP values of the second solvent and the polymer (B) is preferably larger than the interaction radius of the polymer (B).
  • the polymer (B) is difficult to dissolve in the second solvent, so that the particle size of the particulate polymer (B) in the particulate polymer (B) dispersion can be easily reduced and the dispersibility can be improved. Easy to improve.
  • the HSP value distance between the second solvent and the resin (A) is preferably 10.0 or less, more preferably 9.5 or less, still more preferably 9.0 or less, and particularly preferably 8. It is 5.5 or less, preferably 0.01 or more, and more preferably 0.1 or more.
  • the distance between the HSP values is not more than the above upper limit, the affinity between the second solvent and the resin (A) can be improved. Therefore, in the obtained composition and film, a particulate polymer (B) having a small particle size is used. ) Is easy to disperse.
  • the distance between the HSP values of the second solvent and the resin (A) is preferably smaller than the interaction radius of the resin (A).
  • the content of the first solvent is not more than the above upper limit, it is easy to suppress the aggregation of the particulate polymer (B), so that it is easy to reduce the particle size and improve the dispersibility of the particles. As a result, it is easy to improve the particle dispersibility, surface smoothness, mechanical properties and the like of the obtained film. Further, when the content of the first solvent is at least the above lower limit, it is easy to prepare the dispersion liquid.
  • the resin (A) is a polymer different from the polymer (B).
  • the resin (A) is a cycloolefin-based resin
  • it may be a cycloolefin-based resin having a different type from the polymer (B), for example, a different type of monomer unit constituting the resin, its content, and the like.
  • the polyimide-based resin suitable as the resin (A) includes a resin containing a repeating structural unit containing an imide group (hereinafter, may be referred to as a polyimide resin), and a repeating structural unit containing both an imide group and an amide group. It is meant to include a resin to be used (hereinafter, may be referred to as a polyamide-imide resin) and a precursor before producing a polyimide-based resin by imidization.
  • the precursor before producing the polyimide resin is a polyamic acid.
  • a "repeating structural unit” may be referred to as a "constituent unit”.
  • the "constituent unit derived from” may be simply referred to as "unit", and for example, the constituent unit derived from a compound may be referred to as a compound unit.
  • X in the formula (1) include, for example, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a propylene group, a 1,2-butanediyl group, and a 1,3-butanediyl group.
  • 1,12-Dodecandyl group, 2-methyl-1,2-propanediyl group, 2-methyl-1,3-propanediyl group and other linear or branched alkylene groups with divalent acyclic Examples include aliphatic groups.
  • the hydrogen atom in the divalent acyclic aliphatic group may be substituted with a halogen atom, and the carbon atom may be substituted with a hetero atom, for example, an oxygen atom, a nitrogen atom or the like.
  • alkyl fluoride group is preferably an alkyl fluoride group, more preferably an alkyl group having 1 to 3 carbon atoms or an alkyl fluoride group having 1 to 3 carbon atoms, and even more preferably a methyl group or a trifluoromethyl group.
  • Pentyl group 2-methyl-butyl group, 3-methylbutyl group, 2-ethyl-propyl group, n-hexyl, n-heptyl group, n-octyl group, tert-octyl group, n-nonyl group and n-decyl group.
  • Etc. which may be substituted with a halogen atom. Examples of the halogen atom include the same as above.
  • the X in the formula (1) when X in the formula (1) includes a structure represented by the formula (2) and / or the formula (3), the X in the formula (1) is the formula (2). And / or the ratio of the structural unit represented by the formula (3) is preferably 30 mol% or more, more preferably 50 mol% or more, still more preferably, with respect to the total molar amount of the structural unit represented by the formula (1). Is 70 mol% or more, particularly preferably 90 mol% or more, and preferably 100 mol% or less. When the ratio of the structural unit represented by the formula (2) and / or the formula (3) is in the above range, X in the formula (1) can easily reduce the CTE of the film, and has heat resistance, dielectric properties and dielectric properties.
  • Y represents a tetravalent organic group independently of each other, preferably a tetravalent organic group having 4 to 40 carbon atoms, and more preferably 4 having a cyclic structure and 4 to 40 carbon atoms.
  • the cyclic structure include an alicyclic ring, an aromatic ring, and a heterocyclic structure.
  • the hydrogen atom in the organic group may be substituted with a halogen atom, a hydrocarbon group, an alkoxy group or a halogenated hydrocarbon group, in which case the carbon number of these groups is preferably 1 to 8. Is.
  • the polyimide-based resin of the present invention may contain a plurality of types of Y, and the plurality of types of Y may be the same as or different from each other.
  • Y the group (structure) represented by the formulas (31) to (38); the hydrogen atom in the group represented by the formulas (34) to (38) is a methyl group, an ethyl group, or n-propyl.
  • R 27 to R 30 represent hydrogen atoms or alkyl groups having 1 to 6 carbon atoms independently of each other.
  • the alkyl group having 1 to 6 carbon atoms include those exemplified above as the alkyl group having 1 to 6 carbon atoms in the formulas (2) and (3).
  • R 27 to R 30 are more preferably hydrogen atoms or alkyl groups having 1 to 3 carbon atoms independently of each other. , Hydrogen atom is more preferable.
  • Y in the formula (1) when Y in the formula (1) includes at least one selected from the group consisting of the structures represented by the formulas (31) to (33), the formula (1) is used.
  • Y is selected from the group consisting of the structures represented by the formulas (31) to (33), and the ratio of the constituent units represented by at least one is the total mole of the constituent units represented by the formula (1).
  • the amount it is preferably 30 mol% or more, more preferably 50 mol% or more, still more preferably 70 mol% or more, particularly preferably 90 mol% or more, and preferably 100 mol% or less.
  • tetracarboxylic acid compound examples include pyromellitic anhydride (hereinafter, may be abbreviated as PMDA), 4,4'-(4,4'-isopropylidene diphenoxy), and diphthalic anhydride (hereinafter, BPADA).
  • PMDA pyromellitic anhydride
  • BPADA diphthalic anhydride
  • the reaction between the diamine compound and the tetracarboxylic acid compound may be carried out under conditions of an inert atmosphere (nitrogen atmosphere, argon atmosphere, etc.) or reduced pressure, if necessary, and the reaction may be carried out under the conditions of the inert atmosphere (nitrogen atmosphere, argon atmosphere, etc.), for example, the nitrogen atmosphere or the argon atmosphere. It is preferably carried out with stirring in a tightly controlled dehydration solvent.
  • alicyclic amines such as N-propylhexahydroazepine (monocyclic); azabicyclo [2.2.1] heptane, azabicyclo [3.2.1] octane, azabicyclo [2.2.2] octane, and Alicyclic amines such as azabicyclo [3.2.2] nonane (polycyclic); as well as pyridine, 2-methylpyridine (2-picolin), 3-methylpyridine (3-picolin), 4-methylpyridine (4).
  • the method of adding the resin (A) to the particulate polymer (B) dispersion is not particularly limited, and the resin (A) may be added at once, or the resin (A) may be added in a plurality of times. You may.
  • the present invention can obtain a composition having a small particle size and excellent dispersibility even when the distance between the HSP values of the resin (A) and the polymer (B) is relatively large. can. Therefore, in the production method and composition of the present invention, the distance between the HSP values of the resin (A) and the polymer (B) is preferably 6.0 or more, more preferably 7.0 or more, still more preferably 8.0. That is all.
  • the distance between the HSP values of the resin (A) and the polymer (B) is preferably 30 or less, more preferably 25 or less, still more preferably 20 or less, from the viewpoint of the affinity between the resin and the polymer.
  • the content of the particulate polymer (B) is in the above range, the particle dispersibility, dielectric loss tangent and relative permittivity of the film can be easily reduced, and the surface smoothness and mechanical properties can be easily improved.
  • the dispersibility of the particulate polymer (B) is high, and as a result, the physical characteristics of the film, for example, the surface roughness of the film, the thermal conductivity (or thermal diffusivity), etc. It is easy to reduce the variation of.
  • the film of the present invention is also suitably used for other industrial materials such as automobile parts and electric / electronic parts; optical materials such as lenses, prisms, optical fibers, and recording media.
  • the present invention can be carried out at a temperature of 50 to 350 ° C., preferably 70 to 300 ° C.
  • the composition can be uniformly dried and the surface smoothness of the obtained film can be improved. Therefore, when the film is used as the resin layer of CCL, the copper foil and the resin layer are used. Peeling with and can be effectively suppressed.
  • heating may be performed at 200 to 450 ° C., preferably 200 to 350 ° C.
  • the drying or heating time is preferably 5 minutes to 10 hours, more preferably 10 minutes to 5 hours.
  • the coating film may be dried under inert atmosphere conditions such as in nitrogen or argon, under vacuum or reduced pressure conditions, and / or under ventilation.
  • the coating film may be continuously dried after the coating film is peeled off from the base material during the stepwise drying, and after all the drying is completed, the coating film is applied from the base material ( The film) may be peeled off.
  • the coating film may be peeled off from the substrate after the first step of drying to perform the second and subsequent drying steps, or the coating film (film) may be peeled off from the substrate after all the drying steps are completed. good.
  • the first step of drying may be pre-drying.
  • ⁇ H was set to 7.2 MPa 0.5
  • ⁇ D of toluene was set to 18.0 MPa 0.5
  • ⁇ P was set to 1.4 MPa 0.5
  • ⁇ H was set to 2.0 MPa 0.5 .
  • HSP of cycloolefin copolymer The solubility of the cycloolefin copolymer in various solvents was evaluated. For the evaluation of solubility, use a solvent with a known solubility parameter in a transparent container (refer to the HSPiP database, solvent used: methyl chloride, 1,4-dichlorobenzene, chloroform, toluene, p-xylene, GBL, DMAc, NMP. , Water, acetone, diiodomethane, butyl benzoate) 10 mL and 0.1 g of cycloolefin copolymer were added to prepare a mixed solution.
  • ⁇ Meso-type two-chain / Racemo-type two-chain> The ratio of the meso-type two-chain of the norbornene two-chain to the racemo-type two-chain (meso-type two-chain / racemo-type two-chain) of the cycloolefin copolymer obtained in the production example is the above-mentioned NB content using 13 C-NMR. It was measured under the same conditions as the measurement of.
  • the meso-type / racemo-type two-chain of the norbornene two-chain is based on 1,1,2,2-tetrachloroethane (74.24 ppm), and is described in “RAWendt, G.Fink, Macromol.Chem.
  • GPC column TSKgel GMH6-HT (inner diameter 7.8 mm, length 300 mm) (manufactured by Tosoh Corporation) 3 connected mobile phase: orthodichlorobenzene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade) 2,6 -Di-tert-butyl-4-methylphenol (hereinafter, may be referred to as BHT) was added and used at a concentration of 0.1 w / V, that is, 0.1 g / 100 mL.
  • BHT 2,6 -Di-tert-butyl-4-methylphenol
  • a dispersion sample was prepared using the cycloolefin copolymer fine particle powder obtained in the comparative example, and the median diameter of the particulate cycloolefin copolymer in the dispersion sample was determined by scattering particle size distribution measurement using laser diffraction. .. Specifically, 0.01 g of the cycloolefin copolymer fine particle powder obtained in the comparative example and 5 mL of GBL were added to a glass cell having a capacity of 9 mL and mixed, and then ultrasonically treated for 5 minutes using ultrasonic cleaning. Then, a dispersion sample containing the particulate cycloolefin copolymer was obtained.
  • the obtained dispersion sample was measured using a laser diffraction / scattering particle size distribution measuring device (manufactured by Rika Tanaka Co., Ltd., model: SALD-2100, refractive index: 1.70-0.20i), and the particles were measured.
  • the median diameter of the state cycloolefin copolymer was determined.
  • CTE of cycloolefin copolymer The CTE of the cycloolefin copolymer obtained in the production example was measured under the following conditions using TMA, and the CTE at 50 ° C to 100 ° C was calculated.
  • the temperature in the system was kept at 60 ° C., and ethylene was continuously supplied to keep the pressure in the system at the starting value.
  • 5.0 mL of water was added to stop the polymerization, and the solution in the autoclave was withdrawn.
  • 1,500 g of toluene and 100 g of magnesium sulfate were added and stirred, and then 100 mL of water was added and stirred, and the solid was removed by filtration.
  • the obtained liquid was added dropwise to acetone, and the precipitated powder was isolated by filtration. The isolated powder was further washed with acetone and dried under reduced pressure at 120 ° C.
  • a cycloolefin copolymer After 2 hours from the start of the polymerization, 3.0 mL of water was added to stop the polymerization, and the solution in the autoclave was withdrawn. The obtained liquid was added dropwise to acetone in the extracted solution, and the precipitated powder was isolated by filtration. The isolated powder was further washed with acetone and dried under reduced pressure at 150 ° C. for 2 hours to obtain 198.3 g of a cycloolefin copolymer.
  • the NB content was 96.3 mol%
  • Mw was 79,000
  • Mw / Mn was 1.83
  • Tg was more than 300 ° C.
  • the distance between the HSP values of the cycloolefin copolymer and the polyamic acid used in Example 2 is 6.0 or more, the distance between the HSP values of the cycloolefin copolymer and toluene is 2.1, and the distance between the cycloolefin copolymer and the cycloolefin copolymer is 2.
  • the distance between the HSP values with DMAc was 11.5.
  • the distance between the HSP values of the cycloolefin copolymer used in Example 2 and the polyimide resin obtained by imidizing the polyamic acid was 6.0 or more.
  • the content of the particulate cycloolefin copolymer was 30.0% by mass with respect to the total mass of the liquid crystal polyester and the particulate cycloolefin copolymer.
  • the obtained composition was subjected to salivation molding on a copper foil to prepare a coating film at a linear speed of 0.4 m / min.
  • the coating film was heated at 60 ° C. for 4 hours to obtain a laminate having a copper foil and a liquid crystal polyester precursor-cycloolefin copolymer composite film, and then the laminate was fixed with a metal frame and further under a nitrogen atmosphere, 310. By heating the laminate at ° C.
  • Example 4 The cycloolefin copolymer obtained in Production Example 2 was dissolved in toluene at a concentration of 2% by mass to obtain a cycloolefin copolymer solution. 100.0 g of the obtained cycloolefin copolymer solution and 98.0 g of DMAc were mixed and distilled off under reduced pressure at 50 hPa and 80 ° C. for 2 hours to distill off toluene to obtain a particulate cycloolefin copolymer dispersion. The toluene content of the obtained dispersion was 0.6 parts by mass with respect to 100 parts by mass of DMAc.
  • the content of the particulate cycloolefin copolymer was 33.3% by mass with respect to the total mass of the polyamic acid and the particulate cycloolefin copolymer.
  • the obtained composition was subjected to salivation molding on a glass substrate to prepare a coating film at a linear speed of 0.4 m / min.
  • the coating film is heated at 70 ° C. for 60 minutes, the polyamic acid-cycloolefin copolymer composite film is peeled off from the glass substrate, the film is fixed with a metal frame, and the polyamic acid is gradually increased to 360 ° C. in 30 minutes under a nitrogen atmosphere.
  • the polyamic acid was imidized to obtain a polyimide-cycloolefin copolymer composite film having a thickness of 30 ⁇ m.
  • the average primary particle size of the particulate cycloolefin copolymer in the composite film was 0.15 ⁇ m.
  • the CTE of the obtained composite film was 21 ppm / K, and the surface smoothness was also excellent.
  • the distance between the HSP values of the cycloolefin copolymer and the polyamic acid used in Example 4 is 6.0 or more, and the distance between the HSP values of the cycloolefin copolymer and toluene is 2.1.

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  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne un procédé de production d'une composition comprenant : un polymère à base de cyclooléfine particulaire ayant une petite taille de particule ; une résine ; et un solvant. Le procédé de production d'une composition comprenant une résine (A), un polymère à base de cyclooléfine particulaire (B), et un solvant comprend : une étape (1) pour dissoudre un polymère à base de cyclooléfine (B) dans un premier solvant pour obtenir une solution de polymère à base de cyclooléfine (B) ; une étape (2) pour amener la solution de polymère à base de cyclooléfine (B) en contact avec un second solvant, puis distiller le premier solvant pour obtenir un liquide de dispersion comprenant le polymère à base de cyclooléfine particulaire (B) ; et une étape (3) pour ajouter la résine (A) au liquide de dispersion.
PCT/JP2021/031952 2020-08-31 2021-08-31 Procédé de production d'une composition WO2022045361A1 (fr)

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JP2020-146415 2020-08-31
JP2020-196194 2020-11-26
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117106117A (zh) * 2023-10-25 2023-11-24 传化智联股份有限公司 含有Nd和Al元素的ZnPF-1催化剂及其制备和在制备聚丁二烯中的应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW202346425A (zh) * 2022-03-29 2023-12-01 日商Ｕｂｅ股份有限公司 可撓性配線基板用聚醯亞胺前驅體組合物、聚醯亞胺膜及聚醯亞胺金屬積層體

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001049126A (ja) * 1999-05-28 2001-02-20 Hitachi Chem Co Ltd 樹脂組成物
JP2010195891A (ja) * 2009-02-24 2010-09-09 Sanyo Chem Ind Ltd 多層構造球状粒子
JP2018185471A (ja) * 2017-04-27 2018-11-22 キヤノン株式会社 トナー

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001049126A (ja) * 1999-05-28 2001-02-20 Hitachi Chem Co Ltd 樹脂組成物
JP2010195891A (ja) * 2009-02-24 2010-09-09 Sanyo Chem Ind Ltd 多層構造球状粒子
JP2018185471A (ja) * 2017-04-27 2018-11-22 キヤノン株式会社 トナー

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117106117A (zh) * 2023-10-25 2023-11-24 传化智联股份有限公司 含有Nd和Al元素的ZnPF-1催化剂及其制备和在制备聚丁二烯中的应用
CN117106117B (zh) * 2023-10-25 2024-02-13 传化智联股份有限公司 含有Nd和Al元素的ZnPF-1催化剂及其制备和在制备聚丁二烯中的应用

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TW202219148A (zh) 2022-05-16

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