WO2019244600A1 - Résine de polycarbonate-imide et pâte la comprenant - Google Patents

Résine de polycarbonate-imide et pâte la comprenant Download PDF

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Publication number
WO2019244600A1
WO2019244600A1 PCT/JP2019/021726 JP2019021726W WO2019244600A1 WO 2019244600 A1 WO2019244600 A1 WO 2019244600A1 JP 2019021726 W JP2019021726 W JP 2019021726W WO 2019244600 A1 WO2019244600 A1 WO 2019244600A1
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general formula
mol
imide resin
polycarbonate
represented
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PCT/JP2019/021726
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English (en)
Japanese (ja)
Inventor
翔子 内山
啓介 松尾
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東洋紡株式会社
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Priority to JP2020525437A priority Critical patent/JP7310808B2/ja
Publication of WO2019244600A1 publication Critical patent/WO2019244600A1/fr

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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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/16—Polyester-imides

Definitions

  • the present invention relates to a polycarbonate imide resin and a paste using the same. Particularly useful for COF (Chip ⁇ On ⁇ Film) substrate applications, it has excellent heat resistance and flexibility and is suitable for a coating method such as a printing machine, a dispenser or a spin coater, and a polycarbonate imide resin paste obtained by curing the paste. Electronic component having a solder resist layer, a surface protective layer, or an adhesive layer.
  • polyimide resins are widely used as insulating materials for electric and electronic equipment because of their excellent heat resistance, insulation properties, chemical resistance, and the like.
  • it is often used as a raw material of a COF substrate, and is applied to a wiring board material and a mounting substrate material of an electronic device that requires flexibility and small space.
  • solder resists are widely used as permanent protective films for circuits. Solder resist is a film that is formed on the entire surface of the circuit conductor except for the part to be soldered.When wiring electronic components on printed wiring boards, it prevents solder from adhering to unnecessary parts and Is used as a protective coating to prevent direct exposure to air.
  • polyimide resins are generally high in elasticity and hard, when laminated on a substrate such as a film or a copper foil, there is a problem in a post-process because warpage or the like is generated due to a difference in elasticity. Further, there is a problem that the cured film lacks flexibility and is inferior in flexibility.
  • Examples of a polyimide resin which is soluble in a non-nitrogen-based solvent and has low warpage and flexibility by making the resin flexible and having a low elastic modulus include, for example, (Patent Document 1) and (Patent Document 2). Discloses a polysiloxane-modified polyimide resin.
  • polysiloxane-modified polyimide resins use an expensive diamine having a dimethylsiloxane bond as a starting material for lowering the modulus of elasticity, and are inferior in economical efficiency.
  • adhesion, solvent resistance, and chemical resistance decrease as the polysiloxane copolymerization amount increases.
  • Patent Document 3 a composition in which a certain amount of a polycarbonate resin is mixed with a polyimide resin to impart flexibility, thereby improving the moldability of the resin composition is disclosed (Patent Document 3), (Patent Document 4). .
  • Patent Document 5 a thermoplastic resin composition having improved moldability by mixing a polyimide resin, an epoxy resin and a polycarbonate resin is disclosed (Patent Document 5). These are listed as resins suitable for melt kneading and melt extrusion and have excellent heat resistance and mechanical strength, but are not soluble in non-nitrogen solvents and have low warpage and flexibility. Hard to say.
  • the object of the present invention is (1) non-nitrogen-based solvent solubility (2) low-temperature drying / curability (3) low warpage (4) bending resistance (5) printing characteristics, and (6) high temperature resistance.
  • An object of the present invention is to provide an electronic component having a polycarbonate imide resin having excellent wettability and heat resistance, a polycarbonate imide resin paste using the same, and a solder resist layer, a surface protective layer, or an adhesive layer obtained by curing the paste. is there.
  • the composition contains the components represented by the general formula (1) and the components represented by the general formula (2), and all the components are 200 mol%, the components represented by the general formula (1) and the general formula (The polycarbonate imide resin (A), wherein the total of the components represented by 2) is 45 mol% or more.
  • a plurality of R 1 each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms, and q independently represents an integer of 1 to 4.
  • a plurality of R 2 each independently represent a divalent organic group having 1 or more carbon atoms, and n is an integer of 1 or more.
  • the polycarbonate imide resin (A) further contains a component represented by the general formula (3).
  • a component represented by the general formula (3) a plurality of R 3 each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms, r each independently represents an integer of 1 to 4, and p is 0 or 1. is there.
  • the component represented by the general formula (1) is 5 to 45 mol%
  • the component represented by the general formula (2) is 5 to 45 mol%
  • a plurality of R 4 each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms, and s independently represents an integer of 1 to 4.
  • a plurality of R 5 each independently represent a divalent organic group having 1 or more carbon atoms, and m is an integer of 1 or more.
  • the isocyanate component (c) is preferably a diisocyanate represented by the general formula (6).
  • a plurality of R 6 each independently represent hydrogen or an alkyl group having 1 to 3 carbons, t each independently represents an integer of 1 to 4, and p is 0 or 1. is there.
  • the acid dianhydride having a fluorene structure represented by the general formula (4) is 5 to 45 mol%, and the acid dianhydride having a polycarbonate skeleton represented by the general formula (5) is used.
  • the content of the diisocyanate represented by the general formula (6) is preferably at least 50 mol% when the total isocyanate component is 100 mol%.
  • solubility in non-nitrogen solvents (2) low-temperature drying / curing properties (3) low warpage (4) bending resistance (5) printing characteristics, which have been difficult to satisfy simultaneously at the same time, and (6) It has a polycarbonate imide resin excellent in high temperature and humidity resistance and heat resistance, a polycarbonate imide resin paste using the same, and a solder resist layer, a surface protective layer or an adhesive layer obtained by curing the paste. Electronic components can be provided.
  • the polycarbonate imide resin (A) of the present invention will be described.
  • the polycarbonate imide resin (A) includes a component represented by the general formula (1) (hereinafter, also referred to as a component of the general formula (1)) and a component represented by the general formula (2) (hereinafter, the general formula (When the total amount of the components is 200 mol%, the total of the components represented by the general formula (1) and the components represented by the general formula (2) is 45 mol. % Or more.
  • a plurality of R 1 each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms, and q independently represents an integer of 1 to 4.
  • a plurality of R 2 each independently represent a divalent organic group having 1 or more carbon atoms, and n is an integer of 1 or more.
  • the cardo structure means a hinge structure in which four aromatic rings are bonded to carbon atoms, and has a variety of features such as high heat resistance and transparency because it contains a large number of aromatic rings.
  • a plurality of R 1 each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms.
  • the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
  • R 1 is preferably hydrogen or a methyl group, more preferably a methyl group.
  • q independently represents an integer of 1 to 4, preferably 3 or less, more preferably 2 or less, and still more preferably 1.
  • the position of R 1 is preferably 3-position with respect to the addition position of the fluorene ring, and more preferably, both R 1 are 3-position.
  • the position of the ester group is preferably 4-position with respect to the addition position of the fluorene ring, and more preferably both of the two ester groups are 4-position.
  • a component represented by the formula (7) is particularly preferable.
  • the content of the components of the general formula (1) is preferably 5 mol% or more when all the components are 200 mol%. It is more preferably at least 10 mol%, further preferably at least 15 mol%, particularly preferably at least 20 mol%. If the amount is too small, the solubility in a non-nitrogen solvent or the heat resistance may not be obtained. Moreover, it is preferable that it is 45 mol% or less, More preferably, it is 40 mol% or less, More preferably, it is 35 mol% or less. If it is too large, it may not be possible to contain a sufficient amount of the components represented by the general formula (2) described later and other acid components. Therefore, heat resistance and bending resistance (mechanical properties) may be reduced.
  • a plurality of R 2 each independently represent a divalent organic group having 1 or more carbon atoms.
  • the number of carbon atoms is preferably 5 or more, more preferably 10 or more, preferably 20 or less, and more preferably 18 or less.
  • the divalent organic group is not particularly limited, but is preferably a linear alkylene group which may have a substituent, and the carbon number preferably includes the carbon of the substituent.
  • n is an integer of 1 or more, preferably an integer of 2 or more, more preferably an integer of 3 or more, preferably an integer of 10 or less, and more preferably an integer of 8 or less.
  • the content of the components of the general formula (2) is preferably 5 mol% or more when all the components are 200 mol%. It is more preferably at least 10 mol%, further preferably at least 15 mol%, particularly preferably at least 20 mol%. If the amount is too small, warpage may occur when the layers are laminated, or the solubility in a non-nitrogen-based solvent may decrease. Therefore, at 5 ° C. to 30 ° C., the resin may be precipitated within one month. Moreover, it is preferable that it is 45 mol% or less, More preferably, it is 40 mol% or less, More preferably, it is 35 mol% or less. If the amount is too large, the heat resistance may decrease. Further, the component represented by the general formula (1) and other acid components may not be contained in a sufficient amount. Therefore, low warpage and bending resistance (mechanical properties) may be reduced.
  • the total amount of the component represented by the general formula (1) and the component represented by the general formula (2) is 45 mol% or more, It is preferably at least 50 mol%, more preferably at least 55 mol%, even more preferably at least 60 mol%. If the amount is too small, low warpage and solubility in a non-nitrogen solvent may be reduced. Further, it is preferably at most 90 mol%, more preferably at most 80 mol%.
  • the polycarbonate imide resin (A) of the present invention preferably further contains a component represented by the general formula (3) (hereinafter, also referred to as a component of the general formula (3)).
  • a component represented by the general formula (3) By including the component represented by the general formula (3), excellent flex resistance can be exhibited.
  • a plurality of R 3 each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms, r each independently represents an integer of 1 to 4, and p is 0 or 1. is there.
  • each of a plurality of R 3 independently represents hydrogen or an alkyl group having 1 to 3 carbon atoms.
  • the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
  • R 3 is preferably hydrogen or a methyl group, and more preferably a methyl group.
  • r independently represents an integer of 1 to 4, preferably 3 or less, more preferably 2 or less, and still more preferably 1.
  • the position of R 3 is preferably 3-position with respect to — (CH 2 ) p—, and more preferably, both R 3 are 3-position.
  • the position of the binding site is preferably at position 4 with respect to-(CH 2 ) p-, and more preferably both of the two binding sites are at position 4.
  • p is 0 or 1, preferably 0 (biphenyl form).
  • components of the general formula (3) include 4,4′-biphenyl diisocyanate residue, 4,3′-biphenyl diisocyanate residue, 4,2′-biphenyl diisocyanate residue, and 3,3′-biphenyl Diisocyanate residue, 3,2'-biphenyl diisocyanate residue, 2,2'-biphenyl diisocyanate residue, 3- or 2-methyl-4,4'-biphenyl diisocyanate residue, 3- or 2- or 2'- Or 4'- or 5'- or 6'-methyl-4,3'-biphenyl diisocyanate residue, 3- or 2- or 3'- or 4'- or 5'- or 6'-methyl-4,2 '-Biphenyl diisocyanate residue, 3- or 2-ethyl-4,4'-biphenyl diisocyanate residue, 3- or 2- or 2'- or 4'- or 5'- 6'-ethyl-4,3'--
  • the content of the components represented by the general formula (3) is preferably 50 mol% or more, more preferably 60 mol% or more, and still more preferably 70 mol% when all the components are 200 mol%. Mol% or more, more preferably 80 mol% or more, particularly preferably 90 mol% or more, and most preferably 100 mol%. If it is less than 50 mol%, the flex resistance may not be sufficiently exhibited.
  • the polycarbonate imide resin (A) of the present invention contains the components of the general formula (1) and the components of the general formula (2) in predetermined amounts. Therefore, the polycarbonate imide resin (A) includes (a) an acid dianhydride having a fluorene structure represented by the general formula (4), (b) an acid dianhydride having a polycarbonate skeleton represented by the general formula (5), and (C) When the isocyanate component is an essential copolymer component and the total acid component is 100 mol%, (a) a fluorene structure-containing dianhydride represented by the general formula (4) and (b) a general formula (5) )) Is preferably at least 45 mol%.
  • a plurality of R 4 each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms, and s independently represents an integer of 1 to 4.
  • a plurality of R 5 each independently represent a divalent organic group having 1 or more carbon atoms, and m is an integer of 1 or more.
  • the component (a) constituting the polycarbonate imide resin (A) used in the present invention needs to be (a) an acid dianhydride having a fluorene structure (hereinafter, also simply referred to as the component (a)).
  • an acid dianhydride having a fluorene structure hereinafter, also simply referred to as the component (a).
  • a plurality of R 4 each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms.
  • the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
  • R 4 is preferably hydrogen or a methyl group, and more preferably a methyl group.
  • s each independently represents an integer of 1 to 4, preferably 3 or less, more preferably 2 or less, and still more preferably 1.
  • the position of R 4 is preferably 3-position with respect to the addition position of the fluorene ring, and more preferably both R 4 are 3-position.
  • the position of the ester group is preferably 4-position with respect to the addition position of the fluorene ring, and more preferably both of the two ester groups are 4-position.
  • the compound represented by the formula (8) is particularly preferable (hereinafter, also referred to as a compound of the formula (8)).
  • Examples of commercially available products include, but are not limited to, TBIS (registered trademark) -MPN (manufactured by Taoka Chemical), and these can be used alone or in combination of two or more.
  • the copolymerization amount of the component (a) is preferably 5 mol% or more when the total acid component to be reacted is 100 mol%. It is more preferably at least 10 mol%, further preferably at least 15 mol%, particularly preferably at least 20 mol%. If the amount is too small, the solubility in a non-nitrogen solvent or the heat resistance may not be obtained. Moreover, it is preferable that it is 45 mol% or less, More preferably, it is 40 mol% or less, More preferably, it is 35 mol% or less. If the amount is too large, it may not be possible to copolymerize a sufficient amount of other acid components described later (b). Therefore, low warpage and bending resistance (mechanical properties) may be reduced.
  • the (b) acid dianhydride having a polycarbonate skeleton represented by the general formula (5) (hereinafter, also simply referred to as component (b)) constituting the polycarbonate imide resin (A) of the present invention is a polycarbonate polyimide resin ( It is copolymerized as a flexible component which imparts low warpage, non-nitrogen solvent solubility, etc. to A).
  • the component (b) is an acid dianhydride having a polycarbonate skeleton represented by the general formula (5).
  • a plurality of R 5 each independently represents a divalent organic group having 1 or more carbon atoms.
  • the number of carbon atoms is preferably 5 or more, more preferably 10 or more, preferably 20 or less, and more preferably 18 or less.
  • the divalent organic group is not particularly limited, but is preferably a linear alkylene group which may have a substituent, and the carbon number preferably includes the carbon of the substituent.
  • n is an integer of 1 or more, preferably an integer of 2 or more, more preferably an integer of 3 or more, preferably an integer of 10 or less, and more preferably an integer of 8 or less.
  • the method for producing the component (b) is not particularly limited, but can be synthesized from a chloride of trimellitic anhydride and the above-mentioned polycarbonate diol compound by a known reaction method. More specifically, first, a polycarbonate diol compound and a deoxidizing agent are charged into a chloride solution of trimellitic anhydride dissolved in a solvent, and the mixture is stirred for 0.5 to 24 hours. The reaction is carried out at a temperature of ⁇ 20 to 50 ° C., and preferably at a temperature of 20 to 40 ° C. from the viewpoint of reaction selectivity.
  • the reaction is preferably performed using 2 mol or more of chloride of trimellitic anhydride with respect to 1 mol of the polycarbonate diol compound.
  • the solute concentration in the reaction is preferably from 5 to 80% by weight, more preferably from 40 to 60% by weight.
  • the precipitated hydrochloride is separated by filtration and the solvent is concentrated to obtain the desired acid dianhydride having a polycarbonate skeleton represented by the general formula (5) (hereinafter also referred to as a polycarbonate skeleton-containing tetracarboxylic dianhydride). ) Can be obtained.
  • Examples of the method for producing the polycarbonate diol compound include transesterification between a diol as a raw material and a carbonate, and a dehydrochlorination reaction between a diol as a raw material and phosgene.
  • the carbonate as a raw material is not particularly limited, and examples thereof include dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.
  • a linear diol compound having two hydroxyl groups can be used.
  • examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol.
  • the polycarbonate diol that can be used in the present invention may be a polycarbonate diol having a plurality of types of alkylene groups in its skeleton (copolymerized polycarbonate diol), and as commercial products, for example, Kuraray polyol C-1015N, Kuraray polyol C- 1065N (carbonate diol manufactured by Kuraray Co., Ltd .: 2-methyl-1,8-octanediol / 1,9-nonanediol, number average molecular weight about 1,000), Kuraray polyol C-2015N, Kuraray polyol C-2065N (( Kuraray's carbonate diol: 2-methyl-1,8-octanediol / 1,9-nonanediol, number average molecular weight about 2,000), Kuraray polyol C-1050, Kuraray polyol C-1090 (Kuraray Co., Ltd.) Carbonate diol: 3-meth 1,5-
  • the copolymerization amount of the component (b) is preferably 5 mol% or more when the total acid component is 100 mol%. It is more preferably at least 10 mol%, further preferably at least 15 mol%, particularly preferably at least 20 mol%. If the amount is too small, the elastic modulus may not be sufficiently reduced, and warpage may occur when laminating, or the solubility in a non-nitrogen-based solvent may be reduced. Therefore, at 5 ° C. to 30 ° C., the resin may be precipitated within one month. On the other hand, it is preferably at most 45 mol%, more preferably at most 40 mol%, even more preferably at most 35 mol%. If the amount is too large, the component (a) and other acid components described below cannot be contained in a sufficient amount, so that low warpage, bending resistance (mechanical properties), and heat resistance may decrease.
  • the total amount of the component (a) and the component (b) needs to be 45 mol% or more, preferably 50 mol% or more, and 55 mol% or more. %, More preferably at least 60 mol%. If the amount is too small, low warpage and solubility in a non-nitrogen solvent may be reduced. Further, it is preferably at most 90 mol%, more preferably at most 80 mol%.
  • a trivalent or tetravalent polycarboxylic acid derivative having an acid anhydride group can be used as the other acid component.
  • the aromatic polycarboxylic acid derivative is not particularly restricted but includes, for example, trimellitic anhydride (TMA), pyromellitic dianhydride, 3,3′-4,4′-benzophenonetetracarboxylic dianhydride, 3 3,3'-4,4'-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, , 3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride , M-terphenyl-3,3
  • Examples of the aliphatic or alicyclic polycarboxylic acid derivative include, but are not limited to, butane-1,2,3,4-tetracarboxylic dianhydride and pentane-1,2,4,5-tetracarboxylic acid.
  • the content of the trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group is preferably 10 mol% or more, more preferably 20 mol%, when the acid component is 100 mol%. And more preferably 30 mol% or more. Further, it is preferably at most 55 mol%, more preferably at most 50 mol%.
  • aliphatic, alicyclic, and aromatic dicarboxylic acids may be further copolymerized as needed as long as the desired performance is not impaired.
  • the aliphatic dicarboxylic acids include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decandioic acid, dodecandioic acid, eicosantioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedicarboxylic acid, 2-methyloctanedicarboxylic acid, 3,8-dimethyldecanedicarboxylic acid, 3,7-dimethyldecanedicarboxylic acid, 9,12-dimethyleicosandioic acid, fumaric acid
  • alicyclic dicarboxylic acids such as, maleic acid, dimer acid, hydrogenated dimer acid and the like include 1,4-cyclohexan
  • Terephthalic acid Terephthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, oxydibenzoic acid, stilbene dicarboxylic acid and the like.
  • dicarboxylic acids may be used alone or in combination of two or more. Considering heat resistance, adhesion, solubility, cost, and the like, sebacic acid, 1,4-cyclohexanedicarboxylic acid, dimer acid, and isophthalic acid are preferred.
  • the (c) isocyanate component constituting the polycarbonate imide resin (A) of the present invention is preferably a diisocyanate represented by the general formula (6).
  • the diisocyanate represented by the general formula (6) excellent flex resistance can be exhibited.
  • a plurality of R 6 each independently represent hydrogen or an alkyl group having 1 to 3 carbons, t each independently represents an integer of 1 to 4, and p is 0 or 1. is there.
  • a plurality of R 6 each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms.
  • the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
  • R 6 is preferably hydrogen or a methyl group, more preferably a methyl group.
  • t each independently represents an integer of 1 to 4, preferably 3 or less, more preferably 2 or less, and still more preferably 1.
  • the position of R 6 is preferably 3-position with respect to — (CH 2 ) p-, and more preferably both R 6 are 3-position.
  • the position of the binding site is preferably at position 4 with respect to-(CH 2 ) p-, and more preferably both of the two binding sites are at position 4.
  • p is 0 or 1, preferably 0 (biphenyl form).
  • diisocyanate represented by the general formula (6) examples include 4,4'-biphenyl diisocyanate, 4,3'-biphenyl diisocyanate, 4,2'-biphenyl diisocyanate, 3,3'-biphenyl diisocyanate, 3,2 '-Biphenyl diisocyanate, 2,2'-biphenyl diisocyanate, 3- or 2-methyl-4,4'-biphenyl diisocyanate, 3- or 2- or 2'- or 4'- or 5'- or 6'-methyl -4,3'-biphenyl diisocyanate, 3- or 2- or 3'- or 4'- or 5'- or 6'-methyl-4,2'-biphenyl diisocyanate, 3- or 2-ethyl-4,4 '-Biphenyl diisocyanate, 3- or 2- or 2'- or 4'- or 5'- or 6'-ethyl-4,3' Bipheny
  • the copolymerization amount of the diisocyanate represented by the general formula (6) is preferably 50 mol% or more, more preferably 60 mol% or more, and still more preferably 70 mol%, when all the isocyanate components are 100 mol%. Mol% or more, more preferably 80 mol% or more, particularly preferably 90 mol% or more, and most preferably 100 mol%. If it is less than 50 mol%, the value of the elastic modulus is low, and the flex resistance may not be sufficiently exhibited.
  • an isocyanate compound may be further copolymerized as an isocyanate component as long as the desired performance is not impaired. It is not particularly limited as long as it is an isocyanate compound, and examples thereof include an aromatic polyisocyanate, an aliphatic polyisocyanate and an alicyclic polyisocyanate. Preferably, an aromatic polyisocyanate is used. Although not particularly limited, specific examples of the aromatic polyisocyanate include, for example, 3,2'- or 3,3'- or 4,2'- or 4,3'- or 5,2'- or 5,3.
  • diphenylmethane-4,4'-diisocyanate MDI
  • tolylene-2,4-diisocyanate TDI
  • m-xylylene diisocyanate 2,4-diisocyanate (TDI) is more preferred. These can be used alone or in combination of two or more.
  • the (c) isocyanate component used in the polycarbonate imide resin (A) of the present invention is 100 mol%, it is preferable that any one of the isocyanate compounds is 100 mol%.
  • a diamine compound corresponding to the isocyanate is used instead of the isocyanate, a polyamic acid is used as a precursor of the polycarbonate polyimide resin. After passing through the polyamic acid, it is necessary to apply the polyamic acid-containing paste to a substrate such as COF (Chip ⁇ On ⁇ Film) and then imidize it at a high temperature of about 200 ° C. or more, which may cause thermal degradation of the COF. Yes, and there may be restrictions on facilities.
  • COF Chip ⁇ On ⁇ Film
  • the isocyanate compound containing the diisocyanate represented by the general formula (6) since only the isocyanate compound containing the diisocyanate represented by the general formula (6) is used as the isocyanate component, it can be processed at a lower temperature than the paste containing polyamic acid, and is preferable because there is no problem as described above. .
  • aliphatic / aromatic polyester diols manufactured by Toyobo Co., Ltd., trade name VYLON (registered trademark) 220
  • aliphatic / aromatic polycarbonate diols manufactured by Daicel Chemical Industries, Ltd., trade name PLACCEL (registered trademark)
  • -CD220 manufactured by Kuraray Co., Ltd., trade names C-1015N, C-1050, C-1065N, C-1090, C-2015N, C-2065N, C-2090, etc., manufactured by Asahi Kasei Chemicals Corporation, trade name Duranol® (registered trademark) T-4671, T-4672, T-5650E, T-5650J, T-5651, T5652, etc.
  • polycaprolactone diols manufactured by Daicel Chemical
  • the polycarbonate imide resin (A) is produced from a polycarboxylic acid component having an acid anhydride group (components (a) and (b)) and an isocyanate component (component (c)) (isocyanate method).
  • the polymerization reaction of the polycarbonate imide resin (A) used in the present invention is preferably performed in a non-nitrogen solvent. Specifically, in the presence of one or more organic solvents selected from the group consisting of ether-based solvents, ester-based solvents, ketone-based solvents, and aromatic hydrocarbon-based solvents, for example, the isocyanate method is used to generate carbon dioxide gas that is liberated. It is preferred to carry out the heat condensation while removing from the reaction system.
  • the solvent is not particularly limited, but examples of ether solvents include diethylene glycol dimethyl ether (diglyme), diethylene glycol diethyl ether (ethyl diglyme), triethylene glycol dimethyl ether (triglyme), and triethylene glycol diethyl ether (ethyl triglyme).
  • Ester solvents such as ⁇ -butyrolactone and cellosolve acetate; ketone solvents such as methyl isobutyl ketone, cyclopentanone, cyclohexanone and isophorone; and aromatic hydrocarbon solvents such as toluene, xylene and solvesso. No. These may be used alone or in combination of two or more.
  • the solvent When producing the polycarbonate imide resin (A), it is preferable to select and use a solvent that dissolves the produced polycarbonate imide resin (A), and after polymerization, use a suitable solvent as the solvent for the polycarbonate imide resin paste as it is Is more preferable. By doing so, complicated operations such as solvent replacement are eliminated, and it is possible to manufacture at low cost.
  • the solvent preferably has a boiling point of 140 ° C. or higher and 230 ° C. or lower. If the temperature is lower than 140 ° C., the solvent may volatilize during the polymerization reaction. In addition, for example, when screen printing is performed, the volatilization of the solvent may be quick and the plate may be clogged.
  • ⁇ -butyrolactone, cyclohexanone, diglyme, or triglyme is preferable in order to have a relatively high volatility, impart low-temperature drying / curing properties, have excellent varnish stability, and efficiently perform the reaction in a homogeneous system.
  • the amount of the solvent used is preferably 0.5 to 7.0 times (mass ratio), more preferably 2.0 to 6.0 times, the polycarbonate imide resin (A) to be produced. If it is less than 0.5 times, the viscosity at the time of synthesis tends to be too high, and the synthesis tends to be difficult due to inability to stir. If it exceeds 7.0 times, the reaction rate tends to decrease.
  • the reaction temperature is preferably from 60 to 200 ° C, more preferably from 100 to 180 ° C. If the temperature is lower than 60 ° C, the reaction time becomes too long. If the temperature is higher than 200 ° C, the monomer component may be decomposed during the reaction. In addition, a three-dimensional reaction occurs and gelation easily occurs.
  • the reaction temperature may be performed in multiple stages. The reaction time can be appropriately selected depending on the scale of the batch, the reaction conditions employed, and particularly the reaction concentration.
  • triethylamine, lutidine, picoline, undecene, triethylenediamine (1,4-diazabicyclo [2,2,2] octane), DBU (1,8-diazabicyclo [5,4,0]) are used to promote the reaction.
  • Amines such as -7-undecene
  • alkali metal and alkaline earth metal compounds such as lithium methylate, sodium methylate, sodium ethylate, potassium butoxide, potassium fluoride and sodium fluoride, or titanium, cobalt and tin
  • the reaction may be performed in the presence of a catalyst such as a metal such as zinc, aluminum, and aluminum, and a metalloid compound.
  • ⁇ Production of polycarbonate imide resin (A)> An example of a method for producing the polycarbonate imide resin (A) can be obtained by subjecting the component (a) to a condensation reaction (polyimide) with the component (b) and the component (c).
  • a method for producing the polycarbonate imide resin of the present invention will be exemplified, but the present invention is not limited thereto.
  • the mixture After adding and dissolving the components (a), (b) and (c), the polymerization catalyst and the polymerization solvent in the reaction vessel, the mixture is dissolved at 80 to 190 ° C., preferably 100 to 180 ° C. while stirring under a nitrogen stream. After reacting for 5 hours or more, the desired polycarbonate imide resin (A) can be obtained by diluting with a polymerization solvent to an appropriate solvent viscosity and cooling.
  • the polycarbonate imide resin (A) used in the present invention preferably has a molecular weight in ⁇ -butyrolactone at 30 ° C. corresponding to an logarithmic viscosity of 0.1 to 2.0 dl / g, more preferably 0.2 to 2.0 dl / g. From 1.5 dl / g to a logarithmic viscosity. If the logarithmic viscosity is less than 0.1 dl / g, the heat resistance may decrease or the coating film may be brittle. In addition, the tackiness of the paste may be so strong that separation of the plate may be deteriorated.
  • the glass transition temperature of the polycarbonate imide resin (A) used in the present invention is preferably 60 ° C or higher, more preferably 100 ° C or higher. If the temperature is lower than 60 ° C., the heat resistance may be insufficient and the resin may be blocked.
  • the upper limit is not particularly limited, but is preferably 300 ° C. or lower from the viewpoint of solvent solubility.
  • an epoxy resin can be blended as the component (B) with the polycarbonate imide resin (A).
  • the epoxy resin (B) used in the present invention is not particularly limited as long as it has two or more epoxy groups per molecule.
  • the epoxy resin (B) is not particularly limited.
  • bisphenol A type epoxy resin such as jER (registered trademark) 828,1001 (trade name, manufactured by Mitsubishi Chemical Corporation) and ST (trade name, manufactured by Toto Kasei Co., Ltd.) -Hydrogenated bisphenol A epoxy resin such as 2004, 2007, etc .
  • Bisphenol F type epoxy such as YDF-170, 2004, manufactured by Toto Kasei Co., Ltd .
  • YDB-400 600, etc.
  • O-Cresol novolak type epoxy resin such as YDCN-702, 703, trade name EOCN (registered trademark) -125S, 103S, 104S manufactured by Nippon Kayaku Co., Ltd., trade name YD-171 manufactured by Toto Kasei Co., Ltd.
  • Epon1031S (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.), Araldite (registered trademark) 0163 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), Denacol (trade name, manufactured by Nagase Chemtech Co., Ltd.) (Registered trademark) polyfunctional epoxy resins such as EX-611, EX-614, EX-622, EX-512, EX-521, EX-421, EX-411, EX-321, trade name of DIC Corporation Dicyclopentadiene type epoxy resins such as HP-7200, HP-7200H, HP-7200HH, Yuka Shell Epoxy Co., Ltd.
  • Bisphenol S type epoxy resin such as EPICLON (registered trademark) EXA-1514 and TEPIC (registered trademark) manufactured by Nissan Chemical Industries, Ltd. Glycidyl isocyanurate, a bixylenol-type epoxy resin such as YX-4000 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.), and a bisphenol-type epoxy resin such as YL-6056 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.). These may be used alone or in combination of two or more.
  • epoxy resins bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin having more than two epoxy groups in one molecule, o-cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin Resins are preferred.
  • the amine type epoxy resin is a non-halogen type and is preferable in terms of compatibility with the polycarbonate imide resin (A), solvent resistance, chemical resistance and moisture resistance.
  • the amount of the epoxy resin (B) used in the present invention is preferably 1 to 60 parts by mass, more preferably 2 to 50 parts by mass, particularly preferably 3 to 40 parts by mass with respect to 100 parts by mass of the polycarbonate imide resin (A). Parts by weight. If the amount of the epoxy resin (B) is less than 1 part by mass, solder heat resistance, solvent resistance, chemical resistance, and moisture resistance tend to decrease. If it exceeds 60 parts by mass, low warpage, mechanical properties and The compatibility with the polycarbonate imide resin (A) tends to decrease.
  • the epoxy resin (B) used in the present invention may further contain an epoxy compound having only one epoxy group in one molecule as a diluent.
  • the method for adding the epoxy resin (B) is not particularly limited, and the epoxy resin (B) to be added may be dissolved in the same solvent as the solvent contained in the polycarbonate imide resin (A) in advance, and then added. Further, it may be directly added to the polycarbonate imide resin (A).
  • a filler can be blended as the component (C) with the polycarbonate imide resin (A).
  • the filler (C) (hereinafter, also simply referred to as component (C)) used in the present invention is preferably an inorganic or organic filler.
  • the filler (C) is not particularly limited as long as it can be dispersed in the above-mentioned polycarbonate imide resin (A) to form a paste and impart thixotropic properties (thixotropic) to the paste. That is, an inorganic or organic filler that can impart thixotropic properties to the polycarbonate imide resin paste of the present invention is preferable.
  • Examples of such an inorganic filler include silica (SiO 2 , trade name AEROSIL (registered trademark) manufactured by Nippon Aerosil Co., Ltd.), alumina (Al 2 O 3 ), titania (TiO 2 ), and tantalum oxide (Ta 2 O 5 ), zirconia (ZrO 2 ), silicon nitride (Si 3 N 4 ), barium titanate (BaO.TiO 2 ), barium carbonate (BaCO 3 ), lead titanate (PbO.TiO 2 ), zirconate titanate lead (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga 2 O 3), spinel (MgO ⁇ Al 2 O 3) , mullite (3Al 2 O 3 ⁇ 2SiO 2 ), cordierite (2MgO ⁇ 2Al 2 O 3 ⁇ 5SiO 2 ), talc (3MgO ⁇ 4SiO 2
  • Tight (registered trademark) STN, Lucentite SPN, Lucentite SAN, Lucentite SEN) and the like may be used, and these may be used alone or in combination of two or more. It is preferable to use silica or lucentite from the viewpoint of imparting the color tone, transparency, mechanical properties, and thixotropic properties of the obtained paste.
  • the inorganic filler used in the present invention those having an average particle diameter of 50 ⁇ m or less and a maximum particle diameter of 100 ⁇ m or less are preferable, the average particle diameter is 20 ⁇ m or less, and the average particle diameter is 10 ⁇ m or less is most preferable.
  • the average particle diameter (median diameter) here is a value obtained on a volume basis using a laser diffraction / scattering type particle size distribution analyzer. If the average particle size exceeds 50 ⁇ m, it becomes difficult to obtain a paste having sufficient thixotropic properties, and the flexibility of the coating film may be reduced. If the maximum particle size exceeds 100 ⁇ m, the appearance and adhesion of the coating film tend to be insufficient.
  • the organic filler used in the present invention may be any as long as it can be dispersed in the above-mentioned polycarbonate imide resin solution to form a paste, and can impart thixotropy to the paste.
  • the amount of the filler (C) used in the present invention is preferably 1 to 25 parts by mass when the component (A) is 100 parts by mass. It is more preferably 2 to 15 parts by mass, particularly preferably 3 to 12 parts by mass. If the amount of the inorganic or organic filler is less than 1 part by mass, printability tends to decrease, and if it exceeds 25 parts by mass, mechanical properties such as flexibility of the coating film and transparency tend to decrease.
  • a curing accelerator can be added to the polycarbonate imide resin paste of the present invention.
  • the curing accelerator used in the present invention is not particularly limited as long as it can promote the curing reaction of the above-mentioned polycarbonate imide resin (A) and epoxy resin (B).
  • Such a curing accelerator include, for example, 2MZ, 2E4MZ, C11Z, C17Z, 2PZ, 1B2MZ, 2MZ-CN, 2E4MZ-CN, C11Z-CN, 2PZ-CN, manufactured by Shikoku Chemical Industry Co., Ltd.
  • Guanamines such as imidazole derivatives such as 2PHZ-CN, 2MZ-CNS, 2E4MZ-CNS, 2PZ-CNS, 2MZ-AZINE, 2E4MZ-AZINE, C11Z -AZINE, 2MA-OK, 2P4MHZ, 2PHZ, 2P4BHZ, acetoguanamine and benzoguanamine , Diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, polyamines such as polybasic hydrazide, and their organic acid salts and / or epoxy adducts G, boron trifluoride amine complex, triazine derivatives such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4
  • a curing accelerator having latent curing properties examples thereof include organic salts of DBU and DBN and / or tetraphenylboroate, and a cationic photopolymerization catalyst.
  • the amount of the curing accelerator used is preferably 0 to 20 parts by mass when the component (A) is 100 parts by mass. If the amount exceeds 20 parts by mass, the storage stability of the polycarbonate imide resin composition and the heat resistance of the coating film may decrease.
  • the polycarbonate imide resin paste of the present invention is a composition containing the above-described polycarbonate imide resin (A) component, epoxy resin (B) component, and filler (C) component. Further, if necessary, a curing accelerator and other compounding components can be preferably added in the above ratio. What is obtained by uniformly mixing these components with a roll mill, a mixer, a three-roll mill or the like is preferable. The mixing method is not particularly limited as long as a sufficient dispersion can be obtained. Plural kneading with three rolls is preferred.
  • the polycarbonate imide resin paste of the present invention preferably has a Brookfield viscometer (hereinafter also referred to as a B-type viscometer) having a viscosity at 25 ° C. of 50 dPa ⁇ s to 1000 dPa ⁇ s, and 100 dPa ⁇ s to 800 dPa ⁇ s. Is more preferable. If the viscosity is less than 50 dPa ⁇ s, the flow of the paste after printing tends to be large and the film thickness tends to be thin. If the viscosity exceeds 1000 dPa ⁇ s, during printing, the transferability of the paste to the substrate tends to decrease, causing blurring and increasing the number of voids and pinholes in the printed film.
  • a Brookfield viscometer hereinafter also referred to as a B-type viscometer
  • the degree of thixotropic is also important.
  • the thixotropic degree of the polycarbonate imide resin paste is preferably 1.1 or more, more preferably 1.2 or more, in a measuring method described later.
  • the upper limit is preferably equal to or less than 7.0, and more preferably equal to or less than 6.0. If the degree of fluctuation is less than 1.1, the flow of the paste after printing tends to be large and the film thickness tends to be thin. If it exceeds 7.0, the paste tends not to flow.
  • the thixotropic degree can be adjusted by the amount of the component (c) as the thixotropic agent.
  • the polycarbonate imide resin and the paste of the present invention may contain, if necessary, known and commonly used coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black, and hydroquinone.
  • coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black, and hydroquinone.
  • the polycarbonate imide resin paste of the present invention can be cured as follows, for example, as a solder resist, to obtain a cured product. That is, on a COF (Chip On Film) substrate formed by plating copper on a resin substrate such as a polyimide film, a screen printing method, a spray method, a roll coating method, an electrostatic coating method, a curtain coating method, or the like. Then, the polycarbonate imide resin paste of the present invention is applied to a thickness of 5 to 80 ⁇ m, and the coating film is preliminarily dried at 60 to 120 ° C., and then dried at 120 to 200 ° C. Drying may be in air or in an inert atmosphere.
  • electroless plating may be used, or a method of sputtering copper on the resin substrate may be used.
  • the layer of the cured product of the polycarbonate imide resin paste of the COF substrate obtained as described above becomes a solder resist layer, a surface protection layer, or an adhesive layer of the COF substrate.
  • the polycarbonate imide resin paste of the present invention is useful as an overcoat ink for semiconductor elements and various electronic components and a solder resist ink as a film forming material, and can also be used as a paint, a coating agent, an adhesive and the like.
  • the solder resist layer is a film that is formed on the entire surface of the circuit conductor except for the part to be soldered.When wiring electronic components on a printed wiring board, it is necessary to prevent solder from adhering to unnecessary parts.
  • the surface protective layer is used to be attached to the surface of the circuit member to mechanically and chemically protect the electronic member from a processing step and a use environment.
  • the adhesive layer is mainly used for bonding a metal layer and a film layer and performing a bonding process.
  • V1 represents the solvent viscosity measured by an Ubbelohde type viscosity tube
  • V1 and V2 were determined from the time when the polymer solution and the solvent (N-methyl-2-pyrrolidone) passed through the capillary of the viscosity tube.
  • V3 is the polymer concentration (g / dl).
  • ⁇ Preparation of polycarbonate imide resin paste> Filler (C) was added to polycarbonate imide resin (A), and the mixture was diluted with ⁇ -butyrolactone to obtain a polycarbonate imide resin composition. An antifoaming agent and a leveling agent were added to this solution. This solution was roughly kneaded and then kneaded three times using a high-speed three-roll mill to obtain a paste in which the filler was uniformly dispersed. The epoxy resin (B) was mixed with this paste to obtain a polycarbonate imide resin paste.
  • Viroflex registered trademark
  • Toyobo manufactured by Toyobo
  • a polycarbonate imide resin paste is printed on a two-layer CCL (trade name Viroflex (registered trademark), copper foil 18 ⁇ m, base material 20 ⁇ m) manufactured by Toyobo using a SUS mesh plate (150 mesh manufactured by NBC Meshtech, emulsion thickness 21 ⁇ m).
  • a predetermined pattern was printed at a speed of 5 cm / sec, and dried at 80 ° C. for 6 minutes in an air atmosphere (screen printing). Thereafter, by heating and curing at 150 ° C.
  • a laminated film provided with a coverlay (coating) made of a polycarbonate imide resin paste was obtained.
  • the thickness of the coating was 10 ⁇ m.
  • This sample was used for evaluation of printing characteristics, low warpage, solder heat resistance, adhesion, and pencil hardness.
  • ⁇ Thickness (thixotropic ratio)> Using a Brookfield BH rotational viscometer, the measurement was performed according to the following procedure. 90 ml of the polycarbonate imide resin paste was placed in a wide-mouthed light-shielding bottle (100 ml), and the liquid temperature was adjusted to 25 ° C. ⁇ 0.5 ° C. using a thermostatic water bath. Next, after stirring 40 times for 12 to 15 seconds using a glass rod, a predetermined rotor is set, the mixture is allowed to stand for 5 minutes, and then read at a scale when rotated at 10 rpm for 3 minutes to calculate the viscosity. did. Similarly, it was calculated from the value of the viscosity measured at 25 ° C. and 1 rpm by the following equation. Thixotropic degree viscosity (1 rpm) / viscosity (10 rpm)
  • the obtained laminated film was evaluated according to JIS-K-5600-5-4 (1999).
  • the pencil hardness is preferably 2H or more, more preferably 3H or more.
  • the polycarbonate imide resin paste was applied to a 25 ⁇ m-thick Kapton (registered trademark) EN film (a polyimide film manufactured by Du Pont-Toray Co., Ltd.) using an applicator so that the thickness after drying became 10 ⁇ m. Then, after drying at a temperature of 150 ° C. for 2 hours, a sample was prepared. The obtained sample was put into a saturated pressure steam test (PCT: Pressure Cooker Test) at 121 ° C., 2 atm and 100% RH. After 265 hours, the sample was taken out and the surface condition was evaluated. (Judgment) :: No abnormality in appearance ⁇ : Slight abnormality in appearance ⁇ : Swelling and falling off or dissolved in coating film
  • Example 1 With respect to 100 parts by mass of the nonvolatile content of the polycarbonate imide resin solution A-1 obtained in Production Example 2, 4.5 parts by mass of Aerosil 300 (manufactured by Nippon Aerosil Co., Ltd.) as a filler and BYK (registered) as an antifoaming agent (Trademark) -054 (manufactured by Big Chemie) and 2.7 parts by mass of BYK-354 (manufactured by Big Chemie) as a leveling agent to obtain a polycarbonate imide resin composition.
  • Aerosil 300 manufactured by Nippon Aerosil Co., Ltd.
  • BYK registered antifoaming agent
  • BYK-354 manufactured by Big Chemie
  • the composition was first roughly kneaded, and then kneaded three times using a high-speed three-roll mill, whereby a paste having uniform filler dispersion and thixotropic properties was obtained.
  • a solution of HP-7200 (trade name of dicyclopentadiene type epoxy resin manufactured by DIC Corporation, epoxy equivalent: about 278 g / eq) in ⁇ -butyrolactone solution (solid content: 75 %) was added to obtain a polycarbonate imide resin paste (1) of the present invention.
  • the viscosity was adjusted with ⁇ -butyrolactone, the solution viscosity was 200 poise and the thixotropic degree was 1.22.
  • a predetermined pattern was printed on the resin paste (1) with a SUS mesh plate (150 mesh, NBC Meshtec Co., Ltd., emulsion thickness 21 ⁇ m) at a printing speed of 5 cm / sec, and dried in an air atmosphere at 80 ° C. for 6 minutes. Thereafter, by heating and curing at 150 ° C. for 2 hours, a COF substrate (evaluation sample 1) provided with a coverlay (coating) made of a polycarbonate imide resin paste was obtained. The thickness of the coating was 10 ⁇ m. Table 1 shows the evaluation results.
  • Example 2 (Examples 2 to 5) Except that the polycarbonate imide resin (A) solution and the components (B) to (C) shown in Table 1 were used, pastes were prepared in the same manner as in Example 1, and evaluation samples 2 to 5 were produced. . Table 1 shows the evaluation results.
  • Evaluation Sample 7 was produced. Table 1 shows the evaluation results. In this case, since the fluorene structure-containing acid anhydride, which is a rigid component, was not copolymerized, the coating film was flexible and elongated, and the bending resistance effect was not observed. Furthermore, heat resistance was low, and solder heat resistance and high-temperature high-humidity were reduced.
  • Example 1 was repeated except that the polycarbonate imide resin solution A-2 obtained in Production Example 3 was used and that HP-7200H (trade name of dicyclopentadiene type epoxy resin manufactured by DIC Corporation) was not blended. A paste was prepared in the same manner as described above (evaluation sample 8). Since the epoxy resin was not blended, the curing of the paste was insufficient and the solder heat resistance was reduced. Table 1 shows the evaluation results.
  • the polycarbonate imide resin obtained by the present invention and the paste using the same have excellent non-nitrogen-based solvent solubility, low warpage, bending resistance, and high-temperature and high-humidity resistance as a film-forming material. It is useful for overcoat inks and solder resist inks for various electronic components such as COF substrates, and can be used in a wide range of electronic equipment as paints, coatings, adhesives, etc. There is expected.

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Abstract

La présente invention concerne une résine de polycarbonate-imide qui satisfait tout de (1) la solubilité dans les solvants sans azote, (2) du faible gauchissement, (3) de la résistance à la flexion, et (4) de la résistance aux températures élevées et humidités élevées et qui peut être utilisée pour former des couches de réserve de soudure, des couches de protection de surface, ou des couches adhésives. La résine de polycarbonate-imide (A) est caractérisée en ce qu'elle comprend un constituant représenté par la formule structurelle spécifique (1) et un constituant représenté par la formule structurelle spécifique (2), la somme du constituant représenté par la formule structurelle spécifique (1) et du constituant représenté par la formule structurelle spécifique (2) étant de 45 % en mole ou plus lorsque tous les constituants sont pris comme 200 % en mole.
PCT/JP2019/021726 2018-06-22 2019-05-31 Résine de polycarbonate-imide et pâte la comprenant WO2019244600A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007091701A (ja) * 2005-08-31 2007-04-12 Jfe Chemical Corp フルオレニル基およびエステル基を含有するテトラカルボン酸類、フルオレニル基含有ポリエステルイミド前駆体、およびフルオレニル基含有ポリエステルイミド、ならびにこれらの製造方法
JP5773090B1 (ja) * 2013-09-27 2015-09-02 東レ株式会社 ポリイミド前駆体、それから得られるポリイミド樹脂膜、ならびにそれを含む表示素子、光学素子、受光素子、タッチパネル、回路基板、有機ｅｌディスプレイ、および、有機ｅｌ素子ならびにカラーフィルタの製造方法
US20150344626A1 (en) * 2014-05-28 2015-12-03 Industrial Technology Research Institute Dianhydride and polyimide
WO2016067925A1 (fr) * 2014-10-28 2016-05-06 東洋紡株式会社 Pâte de résine à base de polycarbonate-imide, et composant électronique ayant une couche de réserve de soudure, couche protectrice superficielle, couche diélectrique d'intercouche, ou couche adhésive obtenue chacune par durcissement de ladite pâte

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007091701A (ja) * 2005-08-31 2007-04-12 Jfe Chemical Corp フルオレニル基およびエステル基を含有するテトラカルボン酸類、フルオレニル基含有ポリエステルイミド前駆体、およびフルオレニル基含有ポリエステルイミド、ならびにこれらの製造方法
JP5773090B1 (ja) * 2013-09-27 2015-09-02 東レ株式会社 ポリイミド前駆体、それから得られるポリイミド樹脂膜、ならびにそれを含む表示素子、光学素子、受光素子、タッチパネル、回路基板、有機ｅｌディスプレイ、および、有機ｅｌ素子ならびにカラーフィルタの製造方法
US20150344626A1 (en) * 2014-05-28 2015-12-03 Industrial Technology Research Institute Dianhydride and polyimide
WO2016067925A1 (fr) * 2014-10-28 2016-05-06 東洋紡株式会社 Pâte de résine à base de polycarbonate-imide, et composant électronique ayant une couche de réserve de soudure, couche protectrice superficielle, couche diélectrique d'intercouche, ou couche adhésive obtenue chacune par durcissement de ladite pâte

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