WO2017195728A1 - Résine réticulée imide, film transparent et film protecteur de surface - Google Patents

Résine réticulée imide, film transparent et film protecteur de surface Download PDF

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Publication number
WO2017195728A1
WO2017195728A1 PCT/JP2017/017380 JP2017017380W WO2017195728A1 WO 2017195728 A1 WO2017195728 A1 WO 2017195728A1 JP 2017017380 W JP2017017380 W JP 2017017380W WO 2017195728 A1 WO2017195728 A1 WO 2017195728A1
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group
imide
copolymer
examples
transparent film
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PCT/JP2017/017380
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English (en)
Japanese (ja)
Inventor
健雄 須賀
西出　宏之
伸一 小松
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学校法人早稲田大学
Ｊｘｔｇエネルギー株式会社
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Publication of WO2017195728A1 publication Critical patent/WO2017195728A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal 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
    • B32B15/088—Layered products comprising a layer of metal comprising metal 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 comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • C08F232/00—Copolymers of cyclic compounds containing 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity

Definitions

  • the present invention relates to an imide cross-linked resin, a transparent film, and a surface protective film.
  • Patent Document 1 discloses an organic electroluminescence display device in which a cover window is disposed on a polarizing plate or a touch panel.
  • the surface protective film is produced, for example, by vapor-depositing a metal such as aluminum on one surface of the film base material. At this time, the film base material is required to have sufficient heat resistance.
  • One aspect of the present invention relates to an imide-crosslinked resin obtained by crosslinking a copolymer having a cyclic olefin unit and an unsaturated dicarboxylic anhydride unit with a diamine.
  • the cyclic olefin unit may have a norbornane skeleton.
  • the unsaturated dicarboxylic anhydride unit may comprise a maleic anhydride unit.
  • Another aspect of the present invention relates to a transparent film containing an imide cross-linked resin.
  • Still another aspect of the present invention relates to a surface protective film comprising a transparent film and a metal vapor deposition layer provided on at least one surface of the transparent film.
  • an imide cross-linked resin that has good heat resistance and can be suitably used as a resin material for a surface protective film.
  • crosslinking type resin and suitable as a film base material for surface protection films, and the said transparent film is provided.
  • the imide cross-linking resin according to this embodiment is a cross-linked product obtained by cross-linking a copolymer having a cyclic olefin unit and an unsaturated dicarboxylic anhydride unit with a diamine.
  • a cyclic olefin unit is a structural unit derived from a cyclic olefin
  • an unsaturated dicarboxylic acid anhydride unit is a structural unit derived from an unsaturated dicarboxylic acid anhydride.
  • the copolymer can be referred to as a copolymer having a structural unit derived from a cyclic olefin and a structural unit derived from an unsaturated dicarboxylic acid anhydride, and is a monomer component containing a cyclic olefin and an unsaturated dicarboxylic acid anhydride. It can also be called a copolymer.
  • the imide cross-linked resin according to this embodiment has an imide bond formed by a reaction between an acid anhydride in the copolymer and an amino group in the diamine.
  • the imide cross-linking resin according to the present embodiment has sufficient light transmittance and good heat resistance by including a cyclic structure derived from a cyclic olefin and a cross-linked structure via an imide bond in the molecule. For this reason, the imide bridge
  • the copolymer in the present embodiment is a polymer having a cyclic olefin unit and an unsaturated dicarboxylic anhydride unit and capable of being crosslinked by a diamine.
  • the ratio of C 2 + C 3 (mol) (C 2 + C 3 ) / C 1 may be, for example, 0.5 to 2.0, preferably 0.95 to 1.05.
  • the ratio C 2 / (C 2 + C 3 ) of the content C 2 of unsaturated dicarboxylic anhydride units to the total amount C 2 + C 3 may be, for example, 0.01 or more, preferably 0.5 or more. 1 (that is, the content of maleimide units is 0).
  • the number average molecular weight Mn of the copolymer may be, for example, 190 or more, preferably 1000 or more, and may be 3000 or more. By increasing the number average molecular weight Mn of the copolymer, the heat resistance of the imide crosslinked resin tends to be further improved.
  • the number average molecular weight Mn of the copolymer may be, for example, 500,000 or less, preferably 10,000 or less, and may be 7,000 or less. By reducing the number average molecular weight Mn of the copolymer, the reaction rate of the crosslinking reaction with diamine tends to be improved.
  • the molecular weight distribution Mw / Mn which is the ratio of the weight average molecular weight Mw to the number average molecular weight Mn, may be, for example, 10 or less, and preferably 5 or less.
  • Mw / Mn is small, the heat resistance of the imide cross-linked resin is further improved, and the amount of volatile components in the imide cross-linked resin tends to be reduced.
  • the number average molecular weight Mn and the weight average molecular weight Mw of a copolymer show the value measured on condition of the following by GPC measuring method.
  • Solvent Chloroform Temperature: 40 ° C Flow rate: 0.3 mL / min
  • Calibration method Polystyrene
  • the cyclic olefin unit is a structural unit derived from a cyclic olefin.
  • the cyclic olefin is a compound having a ring structure and a carbon-carbon double bond including a carbon atom constituting the ring structure, and capable of being polymerized with an unsaturated dicarboxylic acid anhydride.
  • the cyclic olefin may be, for example, a compound containing a ring structure having at least one carbon-carbon double bond in the ring.
  • a cyclic olefin easily undergoes a polymerization reaction with an unsaturated dicarboxylic acid anhydride.
  • the shape and mobility of the main chain are limited, and the imide cross-linked resin is further excellent in heat resistance and optical characteristics. Tends to be obtained.
  • the ring structure possessed by the cyclic olefin may be monocyclic or polycyclic.
  • the monocyclic ring structure include a cycloalkene skeleton, a cycloalkadiene skeleton, a cycloalkatriene skeleton, and the like.
  • these ring structures include ring structures represented by the following formulas (1-1) to (1-5).
  • Examples of the polycyclic ring structure include a condensed ring and a bridged ring.
  • Examples of the polycyclic ring structure include a norbornene skeleton, a norbornadiene skeleton, a bicyclo [2.2.2] oct-2-ene skeleton, a bicyclo [2.2.2] octa-2,5-diene skeleton, Cyclopentadiene skeleton, dihydrodicyclopentadiene skeleton, acenaphthylene skeleton, indene skeleton, tetrahydroindene skeleton, tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene skeleton, and the like.
  • Examples of these ring structures include ring structures represented by the following formulas (2-1) to (2-11).
  • the ring structure of the cyclic olefin may have a substituent.
  • the ring structure may be condensed with another ring, and may form a spiro ring with another ring.
  • Examples of the cyclic olefin include compounds having structures represented by the following formulas (3-1) to (3-34).
  • These cyclic olefins may have a substituent.
  • the substituent is not particularly limited as long as it does not inhibit the polymerization reaction.
  • the substituent may be, for example, a halogen atom, an alkyl group, a halogenated alkyl group, an alkoxy group, an aryl group, an aralkyl group, a silyl group, a carboxyl group, a hydroxy group, an amino group, or an alkoxycarbonyl group. Further, these substituents may be further substituted with other substituents.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a fluorine atom, a chlorine atom, or a bromine atom is preferable, and a fluorine atom is more preferable.
  • the alkyl group may be linear, branched or cyclic.
  • the alkyl group may have, for example, 1 to 30 carbon atoms, and preferably 1 to 10 carbon atoms.
  • Specific examples of the alkyl group include a methyl group, an ethyl group, an isopropyl group, and tert-butyl.
  • the halogenated alkyl group is a group in which part or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms.
  • Examples of the alkyl group and the halogen atom are the same as described above.
  • Examples of the halogenated alkyl group include a trifluoromethyl group, a chloromethyl group, and a bromomethyl group.
  • the alkoxy group is a group represented by —OR (R represents an alkyl group), and examples of the alkyl group of R include the same examples as described above.
  • Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, an n-propoxy group, and a tert-butoxy group.
  • An aryl group is a group having a structure in which one hydrogen atom is removed from an aromatic hydrocarbon.
  • Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group.
  • the aralkyl group is a group in which part or all (preferably one) of hydrogen atoms of an alkyl group is substituted with an aryl group.
  • Examples of the alkyl group and aryl group are the same as those described above.
  • Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenylpropyl group.
  • the silyl group is a group represented by —Si (R ′) 3 (R ′ represents an alkyl group, an aryl group, or an aralkyl group).
  • R ′ represents an alkyl group, an aryl group, or an aralkyl group.
  • Examples of the alkyl group, aryl group, and aralkyl group for R ′ include those described above. The same example is given.
  • Examples of the silyl group include a trimethylsilyl group, a dimethylphenylsilyl group, a triethylsilyl group, and a diethylphenylsilyl group.
  • the alkoxycarbonyl group is a group represented by —COOR (R represents an alkyl group), and examples of the alkyl group of R include the same examples as described above.
  • Examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonyl group, tert-butoxycarbonyl group and the like.
  • the cyclic olefin is preferably a compound containing no hetero atom other than oxygen, nitrogen and sulfur, and more preferably a hydrocarbon containing no hetero atom.
  • cyclic olefin examples include, for example, acenaphthylene, 5-acetyl-2-norbornenebicyclo [3.2.1] oct-2-ene, [bicyclo [2.2.1] hept-5-ene-2- Yl] triethoxysilane, tert-butyl-5-norbornene-2-carboxylate, dicyclopentadiene, 5,6-dihydrodicyclopentadiene, 5-ethylidene-2-norbornene, hydroxydicyclopentadiene, 2-norbornene, 5 -Norbornene-2,3-dicarboxylic acid anhydride, 2,5-norbornadiene, 5-norbornene-2,2-dimethanol, methyl 5-norbornene-2-carboxylate 5-norbornene-2-carboxylate, 5-norbornene -2,3-dimethanol, cis-5-n
  • the cyclic olefin unit may be a structural unit obtained by reacting part or all of the carbon-carbon double bond of the cyclic olefin by a polymerization reaction, and part of the carbon-carbon double bond of the cyclic olefin.
  • it may be a structural unit having a structure in which all are replaced by single bonds.
  • the cyclic olefin unit preferably has at least a part of the ring structure constituting the main chain of the copolymer. Thereby, the shape and mobility of the main chain of the copolymer are controlled by the cyclic structure of the cyclic olefin unit, and an imide-crosslinked resin having further excellent heat resistance and optical properties can be obtained.
  • An unsaturated dicarboxylic acid anhydride unit is a structural unit derived from an unsaturated dicarboxylic acid anhydride.
  • An unsaturated dicarboxylic acid anhydride is a compound formed by an unsaturated dicarboxylic acid having a carbon-carbon double bond and two carboxyl groups forming an acid anhydride by intramolecular dehydration.
  • Examples of the unsaturated dicarboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 2,3-dimethylmaleic anhydride, 2- (2-carboxyethyl) -3-methylmaleic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, phenylmaleic anhydride, 2,3-diphenylmaleic anhydride, allyl succinic anhydride, (2-methyl-2-propenyl) succinic anhydride, 2-buten-1-yl succinic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, bicyclo [2.2.2] oct- Examples include 5-ene-2,3-dicarboxylic acid anhydride.
  • the unsaturated dicarboxylic acid anhydride may be, for example, a compound having a structure represented by the following formula (4-1).
  • R 1 represents a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group or an aryl group, and the two R 1 s may be the same or different from each other.
  • the unsaturated dicarboxylic acid anhydride is a compound having a structure represented by the formula (4-1)
  • the shape and mobility of the main chain of the copolymer are controlled by the ring structure derived from the unsaturated dicarboxylic acid anhydride. Therefore, an imide cross-linked resin having further excellent heat resistance and optical properties can be obtained.
  • halogen atom for R 1 examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the halogen atom is preferably a fluorine atom, a chlorine atom or a bromine atom, and more preferably a fluorine atom.
  • the alkyl group for R 1 may be linear, branched or cyclic.
  • the alkyl group may have, for example, 1 to 30 carbon atoms, and preferably 1 to 10 carbon atoms.
  • Specific examples of the alkyl group include a methyl group, an ethyl group, an isopropyl group, and tert-butyl.
  • the halogenated alkyl group for R 1 is a group in which part or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms.
  • Examples of the alkyl group and the halogen atom are the same as described above.
  • Examples of the halogenated alkyl group include a trifluoromethyl group, a chloromethyl group, and a bromomethyl group.
  • Examples of the aryl group for R 1 include a phenyl group, a naphthyl group, and an anthracenyl group.
  • R 1 is preferably a hydrogen atom, an alkyl group or a halogenated alkyl group, more preferably a hydrogen atom or an alkyl group. Further, from the viewpoint of excellent reactivity with the cyclic olefin and facilitating the production of the copolymer, at least one of R 1 is preferably a hydrogen atom.
  • the unsaturated dicarboxylic acid anhydride unit may have, for example, a structure in which some or all of the hydrogen atoms of succinic anhydride are removed.
  • the unsaturated dicarboxylic acid anhydride is a compound having a structure represented by the formula (4-1)
  • the unsaturated dicarboxylic acid anhydride unit is a structural unit having a structure represented by the following formula (4-2) It may be.
  • R 1 has the same meaning as described above.
  • the copolymer in the present embodiment may further have a structural unit (maleimide-based unit) derived from a maleimide-based compound.
  • the maleimide compound is, for example, a compound having a structure represented by the following formula (5-1), and the maleimide unit is, for example, a structural unit having a structure represented by the following formula (5-2).
  • R 2 represents a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group or an aryl group, and two R 2 s may be the same or different from each other.
  • R 3 represents a monovalent group.
  • halogen atom for R 2 examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the halogen atom is preferably a fluorine atom, a chlorine atom or a bromine atom, and more preferably a fluorine atom.
  • the alkyl group for R 2 may be linear, branched or cyclic.
  • the alkyl group may have, for example, 1 to 30 carbon atoms, and preferably 1 to 10 carbon atoms.
  • Specific examples of the alkyl group include a methyl group, an ethyl group, an isopropyl group, and tert-butyl.
  • the halogenated alkyl group for R 2 is a group in which part or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms.
  • Examples of the alkyl group and the halogen atom are the same as described above.
  • Examples of the halogenated alkyl group include a trifluoromethyl group, a chloromethyl group, and a bromomethyl group.
  • Examples of the aryl group for R 2 include a phenyl group, a naphthyl group, and an anthracenyl group.
  • R 2 is preferably a hydrogen atom, an alkyl group or a halogenated alkyl group, more preferably a hydrogen atom or an alkyl group.
  • at least one of R 2 is preferably a hydrogen atom.
  • the monovalent group of R 3 is not particularly limited as long as it does not inhibit the polymerization reaction with the cyclic olefin.
  • Examples of the monovalent group of R 3 include an alkyl group, a halogenated alkyl group, an aryl group, an alkoxycarbonyl group, an aralkyl group, and a silyl group.
  • the monovalent group may further have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and a silyl group. Etc.
  • alkyl group examples include halogenated alkyl group, aryl group, aralkyl group, alkoxy group, alkoxycarbonyl group, and silyl group.
  • the alkylthio group is a group represented by —SR (R represents an alkyl group), and examples of the alkyl group of R include the same examples as described above.
  • examples of the alkylthio group include a methylthio group, an ethylthio group, and a propylthio group.
  • the aryloxy group and the arylthio group are groups represented by —OR ′′ and —SR ′′ (R ′′ represents an aryl group), respectively.
  • R ′′ represents an aryl group
  • Examples of the aryl group of R ′′ include the same examples as described above. Can be mentioned.
  • Examples of the aryloxy group include a phenoxy group and a naphthoxy group
  • examples of the arylthio group include a phenylthio group and a naphthylthio group.
  • the copolymer in this embodiment may further have structural units other than the above.
  • the copolymer may further have a structural unit derived from a bismaleimide compound having two maleimide groups.
  • bismaleimide compounds examples include 4,4′-bismaleimide diphenylmethane, 1,6-bis (maleimide) hexane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, and 1,4-bis. (Maleimido) butane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 1,2-bis (maleimido) ethane, N, N′-1,4-phenylene dimaleimide, N, N ′ 1,3-phenylene dimaleimide and the like.
  • the copolymer may further have a structural unit derived from an olefin compound capable of alternating copolymerization with an unsaturated dicarboxylic acid anhydride or a maleimide compound.
  • the olefin compound examples include styrene derivatives such as styrene, indene, ⁇ -methylstyrene, and p-methylstyrene; ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl Examples thereof include alkyl monovinyl ether derivatives such as vinyl ether.
  • the copolymer in the present embodiment can be obtained, for example, by a polymerization reaction of monomer components including a cyclic olefin and an unsaturated dicarboxylic acid anhydride.
  • the monomer component may further contain a maleimide compound and may further contain other monomers.
  • the form of the polymerization reaction is not particularly limited, and may be radical polymerization, for example.
  • radical polymerization initiator When the polymerization reaction is radical polymerization, a known radical polymerization initiator may be used as the polymerization initiator.
  • the radical polymerization initiator include azobisisobutyronitrile (AIBN), di-tert-butyl peroxide, tert-butyl hydroperoxide, benzoyl peroxide (BPO), methyl ethyl ketone peroxide, redox initiator (hydrogen peroxide and Iron (II) salt, persulfate and sodium bisulfite), triethylborane (Et 3 B), diethyl zinc (Et 2 Zn) and the like.
  • AIBN azobisisobutyronitrile
  • BPO benzoyl peroxide
  • II methyl ethyl ketone peroxide
  • redox initiator hydrogen peroxide and Iron (II) salt, persulfate and sodium bisulfite
  • Et 3 B diethyl zinc
  • RAFT reversible addition-fragmentation chain transfer polymerization
  • NMP nitroxide-mediated polymerization
  • precision radical polymerization may be used.
  • the amount of radical polymerization initiator used may be, for example, 0.1 to 10 mol%, preferably 1 to 5 mol%, based on the total amount of monomer components.
  • the polymerization reaction is preferably carried out in a solvent.
  • the solvent include tetrahydrofuran (THF), dioxane, dioxolane, acetone, chloroform, toluene, dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO), and ⁇ -butyrolactone.
  • glyme solvents such as diglyme
  • cellosolv solvents such as ethyl cellosolve
  • glycol ester solvents such as propylene glycol monomethyl ether acetate
  • Glycol ether solvents such as propylene glycol monomethyl ether can be suitably used.
  • the conditions for the polymerization reaction are not particularly limited.
  • the reaction temperature may be ⁇ 20 to 200 ° C.
  • the reaction time may be 0.1 to 100 hours.
  • the imide cross-linked resin according to this embodiment is a cross-linked product obtained by cross-linking the above copolymer with a diamine, and has an imide bond formed by a reaction between an acid anhydride in the copolymer and a diamine.
  • part or all of the unsaturated dicarboxylic anhydride units in the copolymer may react with diamine to form an imide bond.
  • the amount of unsaturated dicarboxylic acid anhydride units remaining in the imide cross-linked resin is preferably 90 mol% or less, and 70 mol% or less. More preferably, it is more preferably 50 mol% or less.
  • the diamine may be a compound having two amino groups that can react with an acid anhydride in the copolymer to form an imide bond.
  • diamines examples include aromatic diamines and aliphatic diamines.
  • an aromatic diamine indicates a compound having two amino groups bonded to an aromatic ring
  • an aliphatic diamine indicates a compound having two amino groups bonded to an sp 3 carbon.
  • the diamine may also be a compound having an amino group bonded to an aromatic ring and an amino group bonded to an sp 3 carbon.
  • aromatic diamine examples include compounds having structures represented by the following formulas (6-1) to (6-4).
  • Q 1 represents a divalent group.
  • aromatic diamines may have a substituent.
  • the substituent is not particularly limited as long as it does not inhibit the crosslinking reaction.
  • Substituents are, for example, halogen atoms, alkyl groups, halogenated alkyl groups, aryl groups, sulfo groups, alkoxy groups, aryloxy groups, silyl groups, hydroxy groups, thiol groups, alkylthio groups, arylthio groups, nitrile groups, ketone groups. May be a carboxyl group or the like. Further, these substituents may be further substituted with other substituents.
  • halogen atom alkyl group, halogenated alkyl group, aryl group, alkoxy group, aryloxy group, silyl group, alkylthio group, and arylthio group
  • alkyl group halogenated alkyl group
  • aryl group alkoxy group, aryloxy group, silyl group, alkylthio group, and arylthio group
  • arylthio group examples include the same examples as described above.
  • the ketone group is a group represented by —COR ′ (R ′ represents an alkyl group, an aryl group or an aralkyl group). Examples of the alkyl group, aryl group and aralkyl group of R ′ are the same as those described above. It is done. Examples of the ketone group include a methylcarbonyl group, a phenylcarbonyl group, and a benzylcarbonyl group.
  • the divalent group in Q 1 is not particularly limited as long as it does not inhibit the crosslinking reaction.
  • Specific examples of the divalent group include —O—, —S—, —CH 2 —, —SO 2 —, —CO—, —O—C 6 H 4 —O—, —NHCO—, —O—.
  • Examples of the aliphatic diamine include compounds having structures represented by the following formulas (7-1) to (7-7).
  • Q 2 represents a divalent group.
  • These aliphatic diamines may have a substituent.
  • the substituent is not particularly limited as long as it does not inhibit the crosslinking reaction.
  • Substituents are, for example, halogen atoms, alkyl groups, halogenated alkyl groups, aryl groups, sulfo groups, alkoxy groups, aryloxy groups, silyl groups, hydroxy groups, thiol groups, alkylthio groups, arylthio groups, nitrile groups, ketone groups. May be a carboxyl group or the like. Further, these substituents may be further substituted with other substituents. Examples of these groups include the same examples as described above.
  • the divalent group in Q 2 is not particularly limited as long as it does not inhibit the crosslinking reaction.
  • Specific examples of the divalent group include —O—, —S—, —CH 2 —, —SO 2 —, —CO—, —O—C 6 H 4 —O—, —NHCO—, —O—.
  • the diamine may be, for example, a polysiloxane diamine in which an amino group is introduced at the terminal or side chain of the polysiloxane.
  • the molecular weight of the polysiloxane diamine may be, for example, 100 to 100,000, or 200 to 50,000.
  • diamine examples include 1,4-phenylenediamine, 1,3-phenylenediamine, 1,2-phenylenediamine, 4,4′-ethylenedianiline, 2,2′-ethylenedianiline, 3,3 ′.
  • diamine examples include 1,4-phenylenediamine, 1,3-phenylenediamine, 1,2-phenylenediamine, 4,4′-ethylenedianiline, 2,2′-ethylenedianiline, 3,3 ′.
  • -Diaminodiphenylethane 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 3,4'-diaminobiphenyl, 4,4'-diamino-2,2'-dimethyl Biphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diaminooctafluorobiphenyl, 2,5-dimethyl-1,4-
  • the cross-linking reaction between the copolymer and the diamine includes, for example, a first step in which a copolymer and a diamine are reacted to form a polyamic acid, and a second step in which an imide bond is formed by a dehydration reaction of the polyamic acid. May be implemented.
  • the first step may be, for example, a step of obtaining a polyamic acid by reacting a copolymer and a diamine in a solvent.
  • the reaction temperature may be, for example, ⁇ 20 to 200 ° C.
  • the reaction time may be, for example, 0.1 to 100 hours.
  • the solvent used in the first step may be any solvent that can dissolve the copolymer and diamine.
  • a solvent is a solvent which can melt
  • the solvent include dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), ⁇ -butyrolactone, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), tetramethylurea.
  • 1,3-dimethyl-2-imidazolidinone, phenol, p-chlorophenol, pyridine, cyclopentanone, cyclohexanone and the like can be preferably used.
  • the amount of diamine to be reacted with the copolymer may be, for example, 0.05 equivalents or more, and 0.5 equivalents or more based on the content of unsaturated dicarboxylic anhydride units in the copolymer. Is more preferable.
  • the amount of diamine may be 1.5 equivalents or less, and more preferably 1.0 equivalents or less, based on the content of unsaturated dicarboxylic anhydride units in the copolymer, for example.
  • a reaction solution containing polyamic acid may be obtained.
  • the polyamic acid may be recovered from the reaction solution, and the recovered polyamic acid may be subjected to the second step.
  • substrate and forming the coating film of a polyamic acid you may implement a 2nd process.
  • an imide bond is formed by dehydration reaction of polyamic acid to obtain an imide cross-linked resin.
  • the dehydration reaction may be carried out, for example, by heating polyamic acid.
  • the reaction temperature of the dehydration reaction may be, for example, 100 to 400 ° C., and the reaction time may be, for example, 0.1 to 100 hours.
  • the crosslinking reaction may be a reaction in which a copolymer and a diamine are reacted using a dehydration catalyst to form an imide bond in one step.
  • a dehydration catalyst include pyridine, 2-hydroxypyridine, triethylamine, imidazole, N-methylpiperidine and the like.
  • the crosslinking reaction may be performed in the presence of a dehydrating agent that traps generated water. Examples of the dehydrating agent include acetic anhydride, propionic anhydride, and trifluoroacetic anhydride.
  • the imide cross-linked resin according to this embodiment has an imide bond formed by a reaction between an acid anhydride in the copolymer and an amino group in the diamine.
  • the imide cross-linked resin according to the present embodiment has sufficient light transmittance and good heat resistance by including in the molecule a cyclic structure derived from a cyclic olefin and a cross-linked structure via an imide bond. For this reason, the imide bridge
  • the transparent film according to this embodiment includes the imide cross-linked resin.
  • the transparent film which concerns on this embodiment can be used suitably as a film base material for surface protection films, for example.
  • a transparent film shows the film whose visible light transmittance ( T450nm ) is 60% or more.
  • the visible light transmittance (T 450 nm ) of the transparent film is preferably 80% or more, and more preferably 85% or more.
  • the thickness of the transparent film is not particularly limited, and may be, for example, 1 ⁇ m or more, 10 ⁇ m or more, 500 ⁇ m or less, or 1000 ⁇ m or less.
  • the transparent film may further contain components other than the imide cross-linked resin.
  • the transparent film may further contain an antioxidant, a light stabilizer, an antistatic agent, a lubricant, a flame retardant, a plasticizer, a clarifying agent, a nucleating agent, a filler, and the like.
  • the manufacturing method of the transparent film which concerns on this aspect is a preparatory process which prepares the coating liquid containing the polyamic acid which is a reaction material of a copolymer and diamine, apply
  • crosslinking type resin may be provided.
  • the copolymer and diamine are reacted in a solvent to obtain a reaction solution containing polyamic acid, and the reaction solution may be used as a coating solution.
  • the reaction solution may be used as a coating solution.
  • polyamic acid may be recovered from the reaction solution, and the recovered polyamic acid may be dissolved in a solvent to obtain a coating solution.
  • a coating solution is formed on the substrate to form a coating film.
  • the coating method is not particularly limited, and a known coating method (for example, spin coating method, bar coater method, slit method, die coating method, etc.) may be used.
  • the solvent may be removed after the coating liquid is applied.
  • the method for removing the solvent is not particularly limited, and a known removal method (for example, heating under reduced pressure, heating under normal pressure, heating on a hot plate, heating under a hot air current, drying under an air current, far infrared heating) Etc.) may be used.
  • the substrate is not particularly limited as long as it has a surface capable of forming a coating film having a desired shape.
  • the substrate include a glass substrate; a metal foil substrate such as copper and aluminum; a metal belt substrate such as steel and stainless steel; a resin sheet substrate such as polytetrafluoroethylene, PPS, PET, acrylic resin, polyethylene, polypropylene, and polystyrene; Etc. can be used suitably.
  • the coating film is heated to advance the dehydration reaction of the polyamic acid to obtain a transparent film containing an imide crosslinked resin.
  • the heating temperature may be any temperature at which the polyamic acid dehydration reaction proceeds, and may be, for example, 100 to 400 ° C., and preferably 200 to 300 ° C.
  • the heating time may be, for example, 0.1 to 100 hours, preferably 1 to 10 hours.
  • the surface protective film which concerns on this embodiment is provided with the said transparent film and the metal vapor deposition layer provided on the at least one surface of the transparent film.
  • the transparent film contains an imide cross-linked resin and is excellent in heat resistance. For this reason, in this embodiment, even when a metal is vapor-deposited on a transparent film, the expansion, distortion, etc. by the heat
  • the metal vapor deposition layer is a thin metal layer formed by vapor deposition on a transparent film.
  • the metal may be, for example, aluminum, silicon, etc., and may be a metal oxide thereof.
  • the vapor deposition method is not particularly limited, and a known vapor deposition method can be used.
  • the thickness of the metal vapor deposition layer may be, for example, 1 to 1000 nm, or 100 to 500 nm.
  • the surface protective film according to the present embodiment can be suitably used for surface protection of, for example, a display of a portable information terminal, a touch panel, a display for a personal computer, a display for a television, a digital signage, and the like.
  • Example 1 (1) Synthesis of copolymer (A-1) Copolymer (A-1) was obtained by alternating copolymerization of norbornene and maleic anhydride.
  • the charging ratio of norbornene and maleic anhydride was 1: 1 (molar ratio)
  • the polymerization reaction was carried out using tetrahydrofuran (THF) with azobisisobutyronitrile (AIBN) as a radical polymerization initiator at room temperature for 24 hours. Performed under conditions.
  • the amount of AIBN used was 1.9 mol% with respect to the total amount of monomer components.
  • the number average molecular weight Mn of the obtained copolymer (A-1) was 4.8 ⁇ 10 3 , and the molecular weight distribution Mw / Mn was 1.7.
  • the number average molecular weight Mn and the molecular weight distribution Mw / Mn were measured by the following methods.
  • the 10% weight loss temperature (T 10 ) was measured by the following method. As a result, T 10 is 386 ° C., high heat resistance was confirmed. Moreover, when the visible light transmittance
  • ⁇ Measurement method of 10% weight loss temperature> A 10% weight reduction temperature was measured using a thermogravimetric analyzer (“Thermo plus Evo TG8120” manufactured by Rigaku Corporation). The scanning temperature was set to 30 ° C. to 500 ° C. while flowing nitrogen gas in a nitrogen gas atmosphere, and the temperature rising rate was 10 ° C./min. The temperature was determined by measuring the temperature at which the weight of the sample used was reduced by 10%.
  • ⁇ Pencil hardness test> As a measuring device, automatic measurement was performed using a continuous load type surface property measuring device, Tripogear TYPE-22, manufactured by HEIDON Shinto Kagaku Co., Ltd.
  • Example 2 (1) Production of Imide Crosslinked Resin (A-1-2) Except that 1.6 mL of DMAc solution (concentration 25 mg / mL) of 2,2′-bis (trifluoromethyl) benzidine was used as the diamine, A transparent film containing an imide crosslinked resin (A-1-2) was produced in the same manner as in Example 1.
  • T 10 is 379 ° C. of the imide-crosslinked resin (A-1-2), T 450nm transparent film was 74%.
  • Example 3 (1) Production of Imide Crosslinked Resin (A-1-3) DMAc of 3 (4), 8 (9) -bis (aminomethyl) tricyclo [5.2.1.0 2,6 ] decane as diamine A transparent film containing an imide cross-linked resin (A-1-3) was produced in the same manner as in Example 1 except that 1 mL of the solution (concentration 25 mg / mL) was used.
  • Example 4 (1) Production of Imide Crosslinked Resin (A-1-4) 1 mL of copolymer (A-1) in THF (concentration: 100 mg / mL) was added to DMS-A12 (aminopropyl-terminated dimethylsiloxane, molecular weight, manufactured by Gelest). 900 mL to 1000) of a THF solution (concentration: 37 mg / mL) was added, and the mixture was reacted by stirring at room temperature for 20 hours to obtain a coating solution containing polyamic acid. The amount of diamine added was about 0.45 equivalent.
  • T 10 of the imide crosslinked resin (A-1-4) was 352 ° C., and T 450 nm of the transparent film was 97%.
  • the results of measuring pencil hardness were F to H.
  • Example 5 (1) Production of Imide Crosslinked Resin (A-1-5) To 1 mL of a THF solution (concentration 100 mg / mL) of copolymer (A-1), amino-modified silicone oil X-22-9409 (Shin-Etsu Chemical Co., Ltd.) 1 mL of a THF solution (concentration 57 mg / mL) of aminophenyl-terminated dimethylsiloxane (molecular weight 1340) was added and reacted by stirring at room temperature for 20 hours to obtain a coating solution containing polyamic acid. The amount of diamine added was about 0.3 equivalent.
  • T 10 of the imide crosslinked resin (A-1-5) was 359 ° C., and T 450 nm of the transparent film was 84%.
  • Example 6 (1) Synthesis of copolymer (A-2) Copolymer (A-2) was obtained by copolymerization of norbornene, maleic anhydride and N-ethylmaleimide. The charging ratio of norbornene, maleic anhydride and N-ethylmaleimide was 3: 1: 2. The polymerization reaction was carried out in THF at room temperature for 24 hours using AIBN as a radical polymerization initiator. The amount of AIBN used was 1.6 mol% with respect to the total amount of monomer components.
  • the number average molecular weight Mn of the obtained copolymer (A-2) was 4.7 ⁇ 10 3 , and the molecular weight distribution Mw / Mn was 1.7.
  • the obtained self-supporting film was heated at 200 ° C. for 24 hours under a vacuum of 1 mmHg to imidize the polyamic acid to obtain a transparent film containing an imide-crosslinked resin (A-2-1).
  • T 10 of the imide crosslinked resin (A-2-1) was 385 ° C., and T 450 nm of the transparent film was 81%.
  • the obtained transparent film was cut into 7 mm ⁇ 25 mm to prepare a test piece, and a dynamic viscoelasticity test was performed.
  • the storage elastic modulus of the test piece was 2.1 GPa, Tg was 299 ° C., and it was confirmed that the specimen had high thermal stability and mechanical strength.
  • Example 7 (1) Production of Imide Crosslinked Resin (A-2-2) To 1 mL of a DMF solution (concentration 100 mg / mL) of copolymer (A-2), a DMF solution of 4,4′-methylenebis (cyclohexylamine) ( 1 mL of 10 mg / mL) was added, and the mixture was stirred and reacted at room temperature for 20 hours to obtain a coating solution containing polyamic acid. The amount of diamine added was about 0.4 equivalent. Next, 1 mL of the obtained coating solution was drop-cast on a 2 cm square Teflon (registered trademark) dish and dried at room temperature for 1 hour to obtain a self-supporting film.
  • a DMF solution concentration 100 mg / mL
  • copolymer (A-2) a DMF solution of 4,4′-methylenebis (cyclohexylamine) ( 1 mL of 10 mg / mL) was added, and the mixture was stirred and reacted at room temperature
  • the obtained self-supporting film was heated at 200 ° C. for 24 hours under a vacuum of 1 mmHg to imidize the polyamic acid to obtain a transparent film containing an imide-crosslinked resin (A-2-2).
  • T 10 is 386 ° C. of the imide-crosslinked resin (A-2-2), T 450nm transparent film was 82%.
  • Example 8 (1) Production of imide-crosslinked resin (A-2-3) To 1 mL of a ⁇ -butyrolactone solution (concentration 100 mg / mL) of copolymer (A-2), 4,4′-methylenebis (2-methylcyclohexylamine) 1) of ⁇ -butyrolactone solution (concentration: 12 mg / mL) was added and reacted by stirring at room temperature for 20 hours to obtain a coating solution containing polyamic acid. The amount of diamine added was about 0.4 equivalent. Next, 1 mL of the obtained coating solution was drop-cast on a 2 cm square Teflon (registered trademark) dish and dried at room temperature for 1 hour to obtain a self-supporting film.
  • the obtained self-supporting film was heated at 200 ° C. for 24 hours under a vacuum of 1 mmHg to imidize the polyamic acid to obtain a transparent film containing an imide-crosslinked resin (A-2-3).
  • the Tg of the imide crosslinked resin (A-2-3) was 299 ° C.
  • the storage elastic modulus was 2.1 GPa
  • T 10 was 385 ° C.
  • the transparent film had a T 450 nm of 81%.
  • Example 9 (1) Production of Imide Crosslinked Resin (A-2-4) To 1 mL of DMF solution of copolymer (A-2) (concentration 100 mg / mL), DMF solution of 4,4′-methylenebis (cyclohexylamine) ( 1 mL of a concentration of 10 mg / mL) and 1 mL of a DMS-A12 DMF solution (concentration of 16 mg / mL) manufactured by Gelest Co. were added and reacted by stirring at room temperature for 20 hours to obtain a coating solution containing polyamic acid. The amount of diamine added was about 0.53 equivalent.
  • Example 10 (1) Production of Imide Crosslinked Resin (A-2-5) To 4 mL of ⁇ -butyrolactone solution (concentration 100 mg / mL) of copolymer (A-2), 4,4′-methylenebis (2-methylcyclohexylamine) ) - ⁇ -butyrolactone solution (concentration 12 mg / mL) and 1 mL of Gelest DMS-A12 ⁇ -butyrolactone solution (concentration 16 mg / mL) were added and reacted at room temperature for 20 hours with stirring to react polyamic acid. A coating solution containing was obtained. The amount of diamine added was about 0.53 equivalent.
  • the number average molecular weight Mn of the obtained copolymer (A-3) was 3.3 ⁇ 10 3 , and the molecular weight distribution Mw / Mn was 1.8.
  • the obtained copolymer (A-3) was confirmed to be crosslinked with diamine in the same manner as in Examples 1 to 6.
  • the number average molecular weight Mn of the obtained copolymer (A-4) was 6.6 ⁇ 10 3 , and the molecular weight distribution Mw / Mn was 2.0.
  • the obtained copolymer (A-4) was confirmed to be crosslinked with diamine in the same manner as in Examples 1 to 6.
  • Example 1 The copolymer obtained in Example 1 (A-1) results subjected to T 10 measured without crosslinking with diamines, T 10 was 144 ° C.. Thereby, it was confirmed that the heat resistance is remarkably improved by crosslinking with diamine.

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Abstract

L'invention concerne une résine réticulée imide qui est obtenue par réticulation d'un copolymère, qui contient une unité oléfine cyclique et une unité anhydride d'acide dicarboxylique insaturé, au moyen d'une diamine.
PCT/JP2017/017380 2016-05-09 2017-05-08 Résine réticulée imide, film transparent et film protecteur de surface WO2017195728A1 (fr)

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JP6958402B2 (ja) * 2018-02-09 2021-11-02 住友ベークライト株式会社 ポリマー、感光性樹脂組成物、感光性樹脂膜、パターン、有機エレクトロルミネッセンス素子、パターンを備えた基板の製造方法およびポリマーの製造方法
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JPH0820692A (ja) * 1994-07-07 1996-01-23 Nippon Zeon Co Ltd 環状オレフィン樹脂組成物およびその架橋物
US20150079506A1 (en) * 2013-09-16 2015-03-19 Sumitomo Bakelite Co., Ltd Amine treated maleic anhydride polymers, compositions and applications thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0820692A (ja) * 1994-07-07 1996-01-23 Nippon Zeon Co Ltd 環状オレフィン樹脂組成物およびその架橋物
US20150079506A1 (en) * 2013-09-16 2015-03-19 Sumitomo Bakelite Co., Ltd Amine treated maleic anhydride polymers, compositions and applications thereof

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