WO2014021319A1 - ポリアミド酸樹脂組成物、これを用いたポリイミドフィルムおよびその製造方法 - Google Patents
ポリアミド酸樹脂組成物、これを用いたポリイミドフィルムおよびその製造方法 Download PDFInfo
- Publication number
- WO2014021319A1 WO2014021319A1 PCT/JP2013/070610 JP2013070610W WO2014021319A1 WO 2014021319 A1 WO2014021319 A1 WO 2014021319A1 JP 2013070610 W JP2013070610 W JP 2013070610W WO 2014021319 A1 WO2014021319 A1 WO 2014021319A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- chemical formula
- resin composition
- polyamic acid
- acid
- carbon atoms
- Prior art date
Links
- RYRZQHZBUFIDEX-UHFFFAOYSA-N CC(CC(Nc(cc1)ccc1Oc1cc(Oc(cc2)ccc2NC(CC(C)=O)=O)cc(Oc(cc2)ccc2NC(CC(C)=O)=O)c1)O)=O Chemical compound CC(CC(Nc(cc1)ccc1Oc1cc(Oc(cc2)ccc2NC(CC(C)=O)=O)cc(Oc(cc2)ccc2NC(CC(C)=O)=O)c1)O)=O RYRZQHZBUFIDEX-UHFFFAOYSA-N 0.000 description 1
- MSAABPAPRGCKNY-UHFFFAOYSA-N CC(CC(Nc1cccc(NC(CC(C)=O)=O)c1)=O)=O Chemical compound CC(CC(Nc1cccc(NC(CC(C)=O)=O)c1)=O)=O MSAABPAPRGCKNY-UHFFFAOYSA-N 0.000 description 1
- VPBIGGRKPLEJHD-UHFFFAOYSA-N NC(CC(CCI)=O)=O Chemical compound NC(CC(CCI)=O)=O VPBIGGRKPLEJHD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
-
- 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
- C08G73/1003—Preparatory processes
- C08G73/1035—Preparatory processes from tetracarboxylic acids or derivatives and diisocyanates
-
- 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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- 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
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
-
- 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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- 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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31623—Next to polyamide or polyimide
Definitions
- the present invention relates to a polyamic acid resin composition. More specifically, surface protective films and interlayer insulating films for semiconductor elements, insulating layers and spacer layers for organic electroluminescence elements (organic EL elements), planarization films for thin film transistor substrates, insulating layers for organic transistors, flexible printed boards, and flexible displays
- the present invention relates to a polyamic acid resin composition that is suitably used for substrates for substrates, substrates for flexible electronic paper, substrates for flexible solar cells, substrates for flexible color filters, binders for electrodes of lithium ion secondary batteries, semiconductor adhesives, and the like.
- Polyimide is used in various fields including semiconductor applications due to its excellent electrical insulation, heat resistance and mechanical properties.
- polyimide is often insoluble in solvents and infusible, so that direct molding is difficult.
- varnish a solution containing a polyamic acid that is a precursor of polyimide
- the polyamic acid polymerization solution can be used as it is, or the polyamic acid can be dissolved in a solvent.
- the degree of polymerization of the polyimide is controlled by adjusting the molar ratio between the acid anhydride group of the acid dianhydride of the monomer and the amino group of the polyvalent amine compound or diamine compound. The viscosity of can be adjusted appropriately.
- the degree of polymerization of the polyimide obtained using this varnish is equal to the degree of polymerization of the original polyamic acid, and high mechanical properties cannot be obtained.
- Patent Documents 1 and 2 a diamine is added to a polyamic acid varnish containing an acid anhydride group at the terminal, and the molar ratio of the acid anhydride group of the acid dianhydride and the amino group of the polyvalent amine compound or diamine compound is A method of adjusting to be equal has been reported.
- the degree of polymerization of the polyamic acid is controlled by adjusting the molar ratio of the acid dianhydride and the diamine compound, so that the viscosity of the varnish can be adjusted appropriately.
- the diamine added at the time of baking the coating film reacts with the polyamic acid, a polyimide having a high degree of polymerization can be obtained.
- Patent Document 1 it is essential to seal the acid anhydride group at the terminal of the polyamic acid with water or alcohol, and measures to prevent the reaction with the added diamine are necessary.
- Patent Document 2 it is necessary to protect the amino group with a t-butyloxycarbonyl group, and the protected diamine has a urea bond having a high cohesive force, and thus has a problem of being easily precipitated in the varnish.
- an object of the present invention is to provide a polyamic acid resin composition that can reduce the viscosity when it is used as a varnish and has excellent mechanical properties in the coating film after firing. It is another object of the present invention to provide a polyamic acid resin composition in which a terminal acid anhydride group and a diamine are less likely to react and the diamine is less precipitated in a varnish.
- the present invention is a polyamic acid resin composition
- a polyamic acid comprising (a) a polyamic acid and (b) a compound represented by the chemical formula (1).
- Z represents an organic group having 2 or more carbon atoms and 2 or more valences
- V represents a structure represented by chemical formula (2)
- k represents an integer of 2 or more.
- ⁇ represents oxygen or sulfur
- W represents an electron-withdrawing group.
- R 11 and R 12 each independently represent hydrogen or a hydrocarbon group having 1 to 10 carbon atoms.
- the present invention it is possible to obtain a polyamic acid resin composition that can reduce the viscosity when it is used as a varnish and has excellent physical properties in the coating film after firing. Moreover, it is possible to obtain a polyamic acid resin composition in which the acid anhydride group at the end of the polyamic acid and the like are hardly reacted with the diamine and the diamine is less precipitated in the varnish.
- the present invention is a polyamic acid resin composition
- a polyamic acid comprising (a) a polyamic acid and (b) a compound represented by the chemical formula (1).
- Z represents an organic group having 2 or more carbon atoms and 2 or more valences
- V represents a structure represented by chemical formula (2)
- k represents an integer of 2 or more.
- W is preferably a polyamic acid resin composition represented by any of the following chemical formulas (3) to (10).
- R 21 to R 28 each independently represents a hydrocarbon group having 1 to 10 carbon atoms, or an atom selected from boron, oxygen, sulfur, nitrogen, phosphorus, silicon, and halogen having hydrogen and carbon as essential components.
- An organic group having 1 to 10 carbon atoms containing 10 is shown.
- V is a polyamic acid resin composition represented by any one of the following chemical formulas (11) to (13).
- the structure represented by the chemical formula (11) is T.I. Mukaiyama, M .; Tokyo, H .; Nohira and H. Takei: J.M. Org. Chem. , 26, 4381 (1961), etc., it is known that it is converted to isocyanate by heating as shown in chemical formula (21).
- ⁇ is CR 21 (in the case of chemical formula (3)), CR 22 (in the case of chemical formula (4)), CR 23 (in the case of chemical formula (5)), SR 25 (in the chemical formula (6)) ), S (O) R 26 (in the case of chemical formula (7)), PR 27 R 28 (in the case of chemical formula (8)), and N + O ⁇ (in the case of chemical formula (9)), ⁇ is O ( (In the case of chemical formulas (3) and (6) to (9)), S (in the case of chemical formula (4)), NR 24 (in the case of chemical formula (5)).
- isocyanate reacts with an acid anhydride group, an imide group is formed as shown in chemical formula (24).
- a polyimide having a high degree of polymerization can be obtained by reacting with a polyamic acid having an acid anhydride group at the terminal or the like. Further, as shown in the chemical formula (25), a polyimide having a high polymerization degree can also be obtained by reacting isocyanates to dimerize or trimerize. (Even if the isocyanate is an isothiocyanate, it is considered to react in the same manner as in the chemical formula (24) and the chemical formula (25).) As a result, the mechanical properties of the polyimide film can be improved.
- R represents a divalent organic group.
- the compound represented by the chemical formula (1) can be derived from a polyvalent amine compound or a diamine compound as described later. That is, in this case, (b) Z in chemical formula (1) is derived from the residue of the polyvalent amine compound or diamine compound.
- Z is preferably a hydrocarbon group having 2 to 80 carbon atoms and having a valence of 2 or more, and one or more atoms selected from boron, oxygen, sulfur, nitrogen, phosphorus, silicon and halogen, with hydrogen and carbon as essential components Or an organic group having 2 to 80 carbon atoms and having a valence of 2 or more.
- Each of boron, oxygen, sulfur, nitrogen, phosphorus, silicon and halogen atoms is preferably independently contained in a range of 20 or less, more preferably contained in a range of 10 or less.
- polyvalent amine compound or diamine compound that give the compound represented by the chemical formula (1) include the following.
- polyvalent amine compounds or diamine compounds containing aromatic rings monocyclic aromatic diamine compounds such as m-phenylenediamine, p-phenylenediamine, 3,5-diaminobenzoic acid, etc .; naphthalene or condensed polycyclic aromatic diamines Compounds such as 1,5-naphthalenediamine, 2,6-naphthalenediamine, 9,10-anthracenediamine, 2,7-diaminofluorene and the like; bis (diaminophenyl) compounds or various derivatives thereof such as 4,4 '-Diaminobenzanilide, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3-carboxy-4,4'-diaminodiphenyl ether, 3-sulfonic acid-4,4'-dia
- aliphatic polyvalent amine compound examples include aliphatic diamine compounds such as ethylenediamine, propylenediamine, butanediamine, pentanediamine, hexanediamine, octanediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, tetramethylhexanediamine, 1 , 12- (4,9-dioxa) dodecanediamine, 1,8- (3,6-dioxa) octanediamine, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, and the like;
- poly Carboxymethyl propylene amines, and the like can be given their copolymers compounds.
- the polyamic acid contained in the polyamic acid resin composition of the present invention preferably includes a structure represented by the chemical formula (14) or (15). If the polyamic acid contains a structure represented by the chemical formula (14), as described above, it reacts with the compound represented by the chemical formula (1) at the time of firing to form an imide bond, thereby obtaining a polyimide with a high degree of polymerization. Can do. Moreover, since the structure represented by the chemical formula (15) is converted into an acid anhydride group at the time of firing, it reacts with the compound represented by the chemical formula (1) to form an imide bond to obtain a polyimide having a high degree of polymerization. Can do.
- X is in showing a more and valence of 3 or more organic groups carbon atoms.
- Y is .R 1 showing a more and valence of 3 or more organic group having a carbon number Represents hydrogen, a hydrocarbon group having 1 to 10 carbon atoms, or an alkylsilyl group having 1 to 10 carbon atoms.
- X and Y are preferably a tetravalent hydrocarbon group having 2 to 80 carbon atoms, and one or more atoms selected from boron, oxygen, sulfur, nitrogen, phosphorus, silicon, and halogen, with hydrogen and carbon as essential components It may be a tetravalent organic group having 2 to 80 carbon atoms containing Each atom of boron, oxygen, sulfur, nitrogen, phosphorus, silicon and halogen is preferably independently in a range of 20 or less, more preferably in a range of 10 or less.
- the polyamic acid preferably has a structure represented by the chemical formula (16) or (17). That is, X in chemical formula (14) or Y in chemical formula (15) is a tetracarboxylic acid residue as represented by X 1 or Y 1, and there is a tetracarboxylic acid residue at the end of the polyamic acid. Is preferred.
- X 1 represents a residue of a tetracarboxylic acid having 2 or more carbon atoms
- T represents a residue of a diamine having 2 or more carbon atoms
- m represents a positive integer.
- Y 1 represents a residue of a tetracarboxylic acid having 2 or more carbon atoms
- U represents a residue of a diamine having 2 or more carbon atoms
- n represents a positive integer
- R 1 to R 7 are each independently hydrogen
- aromatic tetracarboxylic acid examples include monocyclic aromatic tetracarboxylic acid compounds such as pyromellitic acid and 2,3,5,6-pyridinetetracarboxylic acid; various isomers of biphenyltetracarboxylic acid such as 3, 3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 2,2 ′, 3,3′-biphenyltetracarboxylic acid, 3,3 ′, 4 4′-benzophenone tetracarboxylic acid, 2,2 ′, 3,3′-benzophenone tetracarboxylic acid, etc .; bis (dicarboxyphenyl) compounds such as 2,2-bis (3,4-dicarboxyphenyl) hexafluoro Propane, 2,2-bis (2,3-dicarboxyphenyl) hexafluoropropan
- aliphatic tetracarboxylic acid examples include chain aliphatic tetracarboxylic acid compounds such as butanetetracarboxylic acid; alicyclic tetracarboxylic acid compounds such as cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, and the like. Acid, 1,2,4,5-cyclohexanetetracarboxylic acid, bicyclo [2.2.1. ] Heptanetetracarboxylic acid, bicyclo [3.3.1. ] Tetracarboxylic acid, bicyclo [3.1.1. ] Hept-2-enetetracarboxylic acid, bicyclo [2.2.2. And octanetetracarboxylic acid and adamantanetetracarboxylic acid.
- chain aliphatic tetracarboxylic acid compounds such as butanetetracarboxylic acid
- acids can be used as they are or in the form of acid anhydrides, active esters and active amides. Two or more of these may be used. In applications where heat resistance is required, it is preferable to use aromatic tetracarboxylic acid in an amount of 50 mol% or more of the total tetracarboxylic acid.
- silicon-containing tetracarboxylic acids such as dimethylsilanediphthalic acid and 1,3-bis (phthalic acid) tetramethyldisiloxane
- adhesion to the support, oxygen plasma used for cleaning, etc. UV ozone Resistance to processing can be increased.
- silicon-containing tetracarboxylic acids are preferably used in an amount of 1 to 30 mol% of the total tetracarboxylic acids.
- part of the hydrogen contained in the tetracarboxylic acid residue is a hydrocarbon group having 1 to 10 carbon atoms such as a methyl group or an ethyl group, or a carbon group having 1 to It may be substituted with 10 fluoroalkyl groups, groups such as F, Cl, Br, and I.
- an acidic group such as OH, COOH, SO 3 H, CONH 2 , or SO 2 NH 2
- the solubility of the resin in an aqueous alkali solution is improved, so that it is used as a photosensitive resin composition described later. Preferred in some cases.
- T and U are preferably divalent hydrocarbon groups having 2 to 80 carbon atoms, and one or more atoms selected from boron, oxygen, sulfur, nitrogen, phosphorus, silicon, and halogen, with hydrogen and carbon as essential components And a divalent organic group having 2 to 80 carbon atoms.
- Each atom of boron, oxygen, sulfur, nitrogen, phosphorus, silicon and halogen is preferably independently in a range of 20 or less, more preferably in a range of 10 or less.
- Examples of the diamine that gives T and U include (b) a diamine compound (hereinafter referred to as “(b) chemical formula (1) among the polyvalent amine compounds or diamine compounds that give the compound represented by the chemical formula (1)”. And a diamine compound that gives a compound represented by
- diamines can be used as they are or as the corresponding trimethylsilylated diamines. Two or more of these may be used. In applications where heat resistance is required, it is preferable to use an aromatic diamine compound in an amount of 50 mol% or more of the total diamine compound.
- silicon-containing diamine such as 1,3-bis (3-aminopropyl) tetramethyldisiloxane or 1,3-bis (4-anilino) tetramethyldisiloxane as the diamine component
- adhesion to the support is achieved.
- resistance to oxygen plasma used for cleaning and UV ozone treatment can be increased.
- silicon-containing diamine compounds are preferably used in an amount of 1 to 30 mol% of the total diamine compound.
- the diamine compound that gives T and U is (b) in addition to the diamine compound that gives the compound represented by the chemical formula (1), in addition to the diamine compound, a part of hydrogen contained in these diamine compounds has 1 carbon atom such as a methyl group or an ethyl group. It may be substituted with a hydrocarbon group having ⁇ 10, a fluoroalkyl group having 1 to 10 carbon atoms such as a trifluoromethyl group, or a group such as F, Cl, Br, or I.
- the solubility of the resin in an aqueous alkali solution is improved, so that it is used as a photosensitive resin composition described later. Preferred in some cases.
- the number of repeating polyamic acid units in the polyamic acid containing the structure represented by chemical formula (16) or chemical formula (17) is preferably 5 or more, more preferably 10 or more. Moreover, it is preferably 500 or less, more preferably 200 or less. Within this range, the molecular weight can be adjusted to a preferred range.
- M in the chemical formula (16) and n in the chemical formula (17) may be in a range satisfying this preferred number of repetitions of the polyamic acid unit of the present invention. Accordingly, m and n are preferably 5 or more, more preferably 10 or more. Moreover, it is preferably 500 or less, more preferably 200 or less.
- the polyamic acid resin composition of the present invention can be used as a varnish by further containing a solvent.
- a film containing polyamic acid can be formed by applying such varnish on various supports.
- a polyimide film can be produced by imidizing the polyamic acid contained in this film.
- Solvents include aprotic polar solvents such as N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene Glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether and other ethers, acetone, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol, cyclohexanone and other ketones, ethyl acetate, propylene glycol monomethyl ether Esters such as acetate and ethyl lactate, toluene, Emissions, etc. aromatic hydrocarbons such as alone or mixture of two or more thereof may
- the polyamic acid resin composition of the present invention can keep the varnish viscosity low even at high concentrations.
- the preferred content of the solvent is not particularly limited, but (a) it is preferably 50 parts by mass or more, more preferably 100 parts by mass or more, preferably 2000 parts per 100 parts by mass of the polyamic acid. It is 1 part by mass or less, more preferably 1500 parts by mass or less. If it is the range which satisfy
- a substrate on which a film containing a polyamic acid resin composition obtained by coating on a varnish substrate containing a polyamic acid resin composition and drying the solvent is referred to as a substrate with a coating film. .
- the weight average molecular weight of the polyamic acid of the present invention is preferably adjusted to 100000 or less, more preferably 80000 or less, and even more preferably 50000 or less in terms of polystyrene using gel permeation chromatography. If it is this range, even if it is a high concentration varnish, it can suppress more that a viscosity increases. Further, the weight average molecular weight is preferably 2000 or more, more preferably 3000 or more, and further preferably 5000 or more. If the weight average molecular weight is 2000 or more, the viscosity when used as a varnish will not be excessively lowered, and better coating properties can be maintained.
- the polyamic acid resin composition of the present invention can be made into a photosensitive resin composition by further containing a photoacid generator.
- a photoacid generator By containing the photoacid generator, an acid is generated in the light irradiation part, the solubility of the light irradiation part in the alkaline aqueous solution is increased, and a positive relief pattern in which the light irradiation part is dissolved can be obtained.
- the acid generated in the light irradiation part accelerates the cross-linking reaction of the epoxy compound and the heat cross-linking agent, and the light irradiation part becomes insoluble.
- the relief pattern can be obtained.
- photoacid generators examples include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts. Two or more of these may be contained, and a highly sensitive photosensitive resin composition can be obtained.
- the quinonediazide compound includes a polyhydroxy compound in which a sulfonic acid of quinonediazide is bonded with an ester, a polyamino compound in which a sulfonic acid of quinonediazide is bonded to a sulfonamide, a sulfonic acid of quinonediazide in an ester bond and / or sulfone Examples include amide-bonded ones. It is preferable that 50 mol% or more of the total functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide.
- quinonediazide is preferably a 5-naphthoquinonediazidesulfonyl group or a 4-naphthoquinonediazidesulfonyl group.
- the 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure.
- the 5-naphthoquinonediazide sulfonyl ester compound has an absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure.
- a naphthoquinone diazide sulfonyl ester compound containing a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule may be contained, and the 4-naphthoquinone diazide sulfonyl ester compound and 5 may be contained in the same resin composition.
- -It may contain a naphthoquinonediazide sulfonyl ester compound.
- sulfonium salts phosphonium salts, and diazonium salts are preferable because they moderately stabilize the acid component generated by exposure.
- sulfonium salts are preferred.
- it can also contain a sensitizer etc. as needed.
- the content of the photoacid generator is preferably 0.01 to 50 parts by mass with respect to (a) 100 parts by mass of polyamic acid from the viewpoint of increasing sensitivity.
- the quinonediazide compound is preferably 3 to 40 parts by mass.
- the total amount of sulfonium salt, phosphonium salt and diazonium salt is preferably 0.5 to 20 parts by mass.
- the photosensitive resin composition of the present invention contains a thermal crosslinking agent represented by the following chemical formula (31) or a thermal crosslinking agent having a structure represented by the following chemical formula (32) (hereinafter also referred to as a thermal crosslinking agent). May be.
- thermal crosslinking agents can crosslink (a) polyamic acids or other additive components, and can improve the chemical resistance and hardness of the resulting polyimide film.
- R 31 represents a divalent to tetravalent linking group.
- R 32 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, Cl, Br, I, or F.
- R 33 and R 34 independently represents CH 2 OR 36 (R 36 represents hydrogen or a monovalent hydrocarbon having 1 to 6 carbon atoms)
- R 35 represents hydrogen, a methyl group or an ethyl group, and s represents 0 to An integer of 2 and t represents an integer of 2 to 4.
- a plurality of R 32 may be the same or different, a plurality of R 33 and R 34 may be the same or different, and a plurality of R 35 are the same (Examples of the linking group R 31 are shown below.)
- R 41 to R 60 are hydrogen, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon in which part of hydrogen of these hydrocarbon groups is substituted with Cl, Br, I, or F) Group.
- R 37 represents hydrogen or a monovalent hydrocarbon having 1 to 6 carbon atoms.
- U represents 1 or 2
- v represents 0 or 1, provided that u + v is 1 or 2.
- R 33 and R 34 represent CH 2 OR 36 (R 36 is hydrogen or a monovalent hydrocarbon having 1 to 6 carbon atoms) which is a thermally crosslinkable group.
- R 36 is preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, because the thermal crosslinking agent represented by the chemical formula (31) leaves moderate reactivity and is excellent in storage stability. preferable.
- thermal crosslinking agent including the structure represented by the chemical formula (31) are shown below.
- R 37 represents hydrogen or a monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms. From the viewpoint of stability of the compound and storage stability in the photosensitive resin composition, R 37 is preferably a methyl group or an ethyl group, and the number of (CH 2 OR 37 ) groups contained in the compound is 8 or less. It is preferable.
- thermal crosslinking agent containing a group represented by the chemical formula (32) are shown below.
- the content of the thermal crosslinking agent is preferably 10 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of (a) polyamic acid. If content of a thermal crosslinking agent is 10 mass parts or more and 100 mass parts or less, the intensity
- the polyamic acid resin composition of the present invention may further contain a thermal acid generator.
- the thermal acid generator generates an acid by heating after development to be described later, and (a) promotes a crosslinking reaction between the polyamic acid and the thermal crosslinking agent, and (a) promotes cyclization of the imide ring of the polyamic acid. For this reason, the chemical resistance of the obtained polyimide film is improved, and film loss can be reduced.
- the acid generated from the thermal acid generator is preferably a strong acid.
- the thermal acid generator is preferably an aliphatic sulfonic acid compound represented by the chemical formula (33) or (34), and may contain two or more of these.
- R 61 to R 63 may be the same or different and each represents an organic group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 20 carbon atoms. . Further, it may be an organic group having 1 to 20 carbon atoms containing hydrogen and carbon as essential components and containing one or more atoms selected from boron, oxygen, sulfur, nitrogen, phosphorus, silicon and halogen.
- the content of the thermal acid generator is preferably 0.5 parts by mass or more and preferably 10 parts by mass or less with respect to 100 parts by mass of the polyamic acid.
- a compound containing a phenolic hydroxyl group may be contained for the purpose of supplementing the alkali developability of the photosensitive resin composition.
- the compound containing a phenolic hydroxyl group include those having the following trade names (Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, manufactured by Honshu Chemical Industry Co., Ltd.) BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP-EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP- 4HBPA (Tetrakis P-DO-BPA), TrisP-HAP, TrisP-PA, TrisP-PHBA, TrisP-SA, TrisOCR-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P
- BIR-OC BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A
- 1,4-dihydroxy Naphthalene 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,4-dihydroxyquinoline 2,6-dihydroxy Phosphorus, 2,3-dihydroxy quinoxaline, anthracene -1,2,10- triol, anthracene -1,8,9- triols, such as 8-quinolinol, and the like.
- the resulting photosensitive resin composition hardly dissolves in an alkali developer before exposure, and easily dissolves in an alkali developer upon exposure. There is little film loss and development can be easily performed in a short time. Therefore, the sensitivity is easily improved.
- the content of such a compound containing a phenolic hydroxyl group is preferably 3 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of (a) polyamic acid.
- the photosensitive resin composition of the present invention may contain an adhesion improving agent.
- adhesion improvers vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane
- Examples include silane coupling agents such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane, titanium chelating agents, and aluminum chelating agents.
- alkoxysilane-containing aromatic amine compounds, alkoxysilane-containing aromatic amide compounds and the like as shown below can be mentioned.
- a compound obtained by reacting an aromatic amine compound and an alkoxy group-containing silicon compound can also be used.
- examples of such compounds include compounds obtained by reacting an aromatic amine compound with an alkoxysilane compound containing a group that reacts with an amino group such as an epoxy group or a chloromethyl group.
- the content of the adhesion improving agent is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of (a) polyamic acid.
- the polyamic acid resin composition of the present invention can contain inorganic particles for the purpose of improving heat resistance.
- Inorganic particles used for such purposes include inorganic metal particles such as platinum, gold, palladium, silver, copper, nickel, zinc, aluminum, iron, cobalt, rhodium, ruthenium, tin, lead, bismuth, tungsten, and silicon oxide. (Silica), titanium oxide, aluminum oxide, zinc oxide, tin oxide, tungsten oxide, zirconium oxide, calcium carbonate, barium sulfate, and other metal oxide inorganic particles.
- the shape of the inorganic particles is not particularly limited, and examples thereof include a spherical shape, an elliptical shape, a flat shape, a lot shape, and a fiber shape.
- the average particle size of the inorganic particles is preferably 1 nm to 100 nm, and preferably 1 nm to 50 nm. Or less, more preferably 1 nm or more and 30 nm or less.
- the content of the inorganic particles is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, and preferably 100 parts by mass or less, relative to 100 parts by mass of (a) polyamic acid. More preferably, it is 80 mass parts or less, More preferably, it is 50 mass parts or less.
- the content of the inorganic particles is 3 parts by mass or more, the heat resistance is sufficiently improved, and when the content is 100 parts by mass or less, the toughness of the fired film is hardly lowered.
- the polyamic acid resin composition of the present invention may contain a surfactant in order to improve coatability.
- a surfactant “Florard” (registered trademark) manufactured by Sumitomo 3M Co., Ltd., “Megafac” (registered trademark) manufactured by DIC Corporation, “sulfuron” (registered trademark) manufactured by Asahi Glass Co., Ltd., etc. Fluorosurfactant, Shin-Etsu Chemical Co., Ltd. KP341, Chisso Co., Ltd. DBE, Kyoeisha Chemical Co., Ltd.
- Polyflow (registered trademark), “Granol” (registered trademark), Examples thereof include organic siloxane surfactants such as BYK manufactured by Chemie Corp. and acrylic polymer surfactants such as polyflow manufactured by Kyoeisha Chemical Co., Ltd.
- the surfactant is preferably contained in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of (a) polyamic acid.
- Polyamic acid can be polymerized by a known method. That is, it can be obtained by polymerizing tetracarboxylic acid or a corresponding acid dianhydride, active ester, active amide or the like as an acid component and diamine or a corresponding trimethylsilylated diamine or the like as a diamine component in a reaction solvent. Furthermore, the structure represented by Chemical formula (14) or (15) can be included in the terminal of a polyamic acid by making the molar ratio of an acid component / diamine component larger than 1.
- Reaction solvents include aprotic polar solvents such as N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene Glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol ethyl methyl ether, ethers such as diethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol, cyclohexanone, ethyl acetate, propylene glycol monomethyl ether acetate , Esters such as ethyl lactate, toluene, Can be used alone, or two or more such aromatic hydrocarbons such as Ren. Furthermore
- the polyamic acid used in the present invention may be one in which the carboxyl group is esterified with a hydrocarbon group having 1 to 10 carbon atoms or an alkylsilyl group having 1 to 10 carbon atoms.
- the compound represented by the chemical formula (1) can be derived from a polyvalent amine compound or a diamine compound. Specifically, it is obtained by reacting an amino group of a polyvalent amine compound or a diamine compound with a compound that reacts with the amino group to give a structure represented by the chemical formula (2).
- Examples of the compound that gives a structure represented by the chemical formula (1) by reacting with an amino group include diketene, ⁇ -keto acid, ⁇ -thioketo acid, ⁇ -ketimino acid, ⁇ -sulfinylcarboxylic acid, ⁇ -sulfonyl Mention may be made of carboxylic acids, ⁇ -phosphinoylcarboxylic acids, ⁇ -nitrocarboxylic acids, ⁇ -cyanocarboxylic acids, and derivatives thereof.
- Such compounds include diketene, acetoacetic acid, thioketene dimer, 1,2-benzisoxazole-3-acetic acid, (methanesulfinyl) acetic acid, (methanesulfonyl) acetic acid, 2- (p-toluenesulfonyl) acetic acid. , (Diphenylphosphinoyl) acetic acid, nitroacetic acid, cyanoacetic acid and the like. Of these, diketene, acetoacetic acid, 2- (p-toluenesulfonyl) acetic acid, and cyanoacetic acid are preferred.
- a method for producing a varnish from the polyamic acid resin composition of the present invention will be described.
- the polyamic acid and (b) the compound represented by the chemical formula (1) and, if necessary, a photoacid generator, a dissolution regulator, an adhesion improver, inorganic particles or a surfactant are dissolved in a solvent.
- a varnish can be obtained.
- the dissolution method include stirring and heating.
- the heating temperature is preferably set in a range that does not impair the performance as the photosensitive resin composition, and is usually room temperature to 80 ° C.
- each component is not particularly limited, and for example, there is a method of sequentially dissolving compounds having low solubility.
- components that tend to generate bubbles when stirring and dissolving such as surfactants and some adhesion improvers, by dissolving other components and adding them last, poor dissolution of other components due to the generation of bubbles Can be prevented.
- the obtained varnish is preferably filtered using a filter to remove foreign matters such as dust.
- a filter to remove foreign matters such as dust.
- the filter pore diameter include, but are not limited to, 10 ⁇ m, 3 ⁇ m, 1 ⁇ m, 0.5 ⁇ m, 0.2 ⁇ m, 0.1 ⁇ m, 0.07 ⁇ m, and 0.05 ⁇ m.
- the material for the filter include polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), and polyethylene and nylon are preferable.
- varnish is applied on the support.
- the support include a wafer substrate such as silicon and gallium arsenide, a glass substrate such as sapphire glass, soda lime glass, and non-alkali glass, a metal substrate such as stainless steel and copper, a metal foil, and a ceramic substrate.
- varnish coating methods include spin coating, slit coating, dip coating, spray coating, and printing, and these may be combined.
- the support may be pretreated with the adhesion improver described above in advance.
- a method of treating the surface of the support by a method such as spin coating, slit die coating, bar coating, dip coating, spray coating, or steam treatment. If necessary, it can be dried under reduced pressure, and then the heat treatment at 50 ° C. to 300 ° C. allows the reaction between the support and the adhesion improving agent to proceed.
- drying vacuum drying, heat drying, or a combination thereof can be used.
- a method for drying under reduced pressure for example, a support body on which a coating film is formed is placed in a vacuum chamber, and the inside of the vacuum chamber is decompressed. Heat drying is performed using a hot plate, oven, infrared rays or the like. When a hot plate is used, the coating film is held directly on the plate or on a jig such as a proxy pin installed on the plate and dried by heating.
- the material of the proxy pin there is a metal material such as aluminum or stainless steel, or a synthetic resin such as polyimide resin or “Teflon (registered trademark)”. Any material can be used as long as it has heat resistance. .
- the height of the proxy pin can be selected variously depending on the size of the support, the type of solvent used in the varnish, the drying method, etc., but is preferably about 0.1 to 10 mm.
- the heating temperature varies depending on the type and purpose of the solvent used in the varnish, and it is preferably 1 minute to several hours in the range of room temperature to 180 ° C.
- the polyamic acid resin composition of the present invention contains a photoacid generator
- a pattern can be formed from the dried coating film by the method described below.
- the coating film is exposed to actinic radiation through a mask having a desired pattern.
- actinic radiation used for exposure there are ultraviolet rays, visible rays, electron beams, X-rays and the like.
- the exposed portion is dissolved in the developer.
- the exposed area is cured and insolubilized in the developer.
- a desired pattern is formed by removing an exposed portion in the case of a positive type and a non-exposed portion in the case of a negative type using a developer.
- a developer in both positive and negative types, tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylamino acetate
- An aqueous solution of an alkaline compound such as ethyl, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine is preferred.
- these alkaline aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, ⁇ -butyrolactone, dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added singly or in combination. Good.
- polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, ⁇ -butyrolactone, dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lac
- the above polar solvent not containing an alkaline aqueous solution alcohols, esters, ketones and the like can be used singly or in combination. After development, it is common to rinse with water.
- alcohols such as ethanol and isopropyl alcohol
- esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing treatment.
- a polyimide film can be produced by imidizing polyamic acid contained in a resin film containing polyamic acid.
- the polyimide film obtained by imidization includes a surface protective film and an interlayer insulating film of a semiconductor element, an insulating layer and a spacer layer of an organic electroluminescence element (organic EL element), a planarization film of a thin film transistor substrate, and an insulating of an organic transistor. It is suitably used for layers, flexible printed circuit boards, flexible display substrates, flexible electronic paper substrates, flexible solar cell substrates, flexible color filter substrates, lithium ion secondary battery electrode binders, semiconductor adhesives, and the like.
- Viscosity measurement The obtained varnish was diluted with N-methyl-2-pyrrolidone so that the solid content concentration was 10% by mass, and the viscosity was measured at 25 ° C. using a viscometer (Toki Sangyo Co., Ltd., TVE-22H). Measurements were made at
- Tg glass transition temperature
- EXSTAR 6000 TMA / SS6100 manufactured by SII Nano Technology Co., Ltd.
- the temperature raising method was performed under the following conditions. The temperature was raised to 200 ° C. in the first stage to remove the adsorbed water of the sample, and cooled to room temperature in the second stage. In the third stage, this measurement was performed at a temperature elevation rate of 5 ° C./min to determine the glass transition temperature.
- Td5 Measurement of 5% thermal mass reduction temperature
- TGA-50 manufactured by Shimadzu Corporation
- the temperature raising method was performed under the following conditions. The temperature was raised to 150 degrees in the first stage to remove the adsorbed water of the sample, and the specimen was cooled to room temperature in the second stage. In the third stage, this measurement was performed at a temperature elevation rate of 10 ° C./min, and a 5% thermal mass reduction temperature was determined.
- Synthesis Example 1 Compound A A thermometer and a stirring rod with stirring blades were set in a 300 mL four-necked flask. Next, 100 g of THF was added under a dry nitrogen stream and stirred at room temperature. Next, 10.00 g (49.94 mmol) of DAE and 61.01 mg (499.4 ⁇ mol) of DMAP were added and washed with 10 g of THF. The mixture was cooled to 10 ° C. or lower, and 8.607 g (102.4 mmol) of diketene diluted with 10 g of THF was added dropwise. After completion of dropping, the temperature was raised to 30 ° C. and stirred for 1 hour. After cooling, the precipitate was collected by filtration. After drying, Compound A represented by the following chemical formula (A) was obtained. The yield was 12.03 g (yield 65%).
- Synthesis Example 2 Compound B A thermometer and a stirring rod with stirring blades were set in a 300 mL four-necked flask. Next, 100 g of THF was added under a dry nitrogen stream and stirred at room temperature. Next, 10.00 g (92.47 mmol) of p-PDA and 113.0 mg (924.7 ⁇ mol) of DMAP were added and washed with 10 g of THF. The mixture was cooled to 10 ° C. or less, and 15.94 g (189.6 mmol) of diketene diluted with 10 g of THF was added dropwise. After completion of dropping, the temperature was raised to 30 ° C. and stirred for 1 hour. After cooling, the precipitate was collected by filtration. Recrystallization was performed with ethanol, and after drying, a compound B represented by the following chemical formula (B) was obtained. The yield was 19.99 g (yield 78%).
- Synthesis Example 4 Compound D A thermometer and a stirring rod with stirring blades were set in a 300 mL four-necked flask. Next, 100 g of CPME was added under a dry nitrogen stream and stirred at room temperature. Next, 10.00 g (87.57 mmol) of CHDA was added and washed with 10 g of CPME. The mixture was cooled to 10 ° C. or lower, and a solution obtained by diluting 15.09 g (179.5 mmol) of diketene with 10 g of CPME was added dropwise. After completion of dropping, the temperature was raised to 30 ° C. and stirred for 1 hour. After cooling, the precipitate was collected by filtration. Recrystallization was performed with ethanol, and after drying, a compound D represented by the following chemical formula (D) was obtained. The yield was 16.24 g (yield 66%).
- Synthesis Example 5 Compound E A thermometer and a stirring rod with stirring blades were set in a 300 mL four-necked flask. Next, 80 g of THF was added under a dry nitrogen stream and stirred at room temperature. Next, 10.00 g (34.56 mmol) of TAM and 63.33 mg (518.4 ⁇ mol) of DMAP were added and washed with 10 g of THF. The mixture was cooled to 10 ° C. or lower, and diketene 9.152 g (108.9 mmol) diluted with 10 g of THF was added dropwise. After completion of dropping, the temperature was raised to 30 ° C. and stirred for 1 hour. After cooling, the precipitate was collected by filtration. After drying, Compound E represented by the following chemical formula (E) was obtained. The yield was 16.66 g (89% yield).
- Synthesis Example 7 Compound G A thermometer and a stirring rod with stirring blades were set in a 300 mL four-necked flask. Next, 130 g of NMP was added under a dry nitrogen stream and stirred at room temperature. Next, 10.00 g (79.29 mmol) of melamine was added and washed with 10 g of NMP. The mixture was cooled to 10 ° C. or less, and 20.00 g (237.9 mmol) of diketene diluted with 10 g of NMP was added dropwise. After completion of dropping, the temperature was raised to 60 ° C. and stirred for 2 hours. After cooling, the reaction solution was used as an NMP solution of compound G represented by the following chemical formula (G).
- Synthesis Example 8 Compound H A thermometer and a stirring rod with stirring blades were set in a 300 mL four-necked flask. Next, 70 g of NMP was added under a dry nitrogen stream. Subsequently, while stirring at room temperature, 8.496 g (99.88 mmol) of cyanoacetic acid was added, and washed with 10 g of NMP. After confirming that cyanoacetic acid was dissolved, the mixture was cooled to 10 ° C. or lower. After cooling, 16.60 g (102.4 mmol) of carbonyldiimidazole was added and washed with 10 g of NMP. After the addition, the mixture was stirred overnight at room temperature.
- Synthesis Example 10 Compound J A thermometer and a stirring rod with stirring blades were set in a 300 mL four-necked flask. Next, 100 g of THF was added under a dry nitrogen stream and stirred at room temperature. Next, 10.00 g (49.94 mmol) of DAE, 11.12 g (109.9 mmol) of triethylamine and 61.01 mg (49.94 ⁇ mol) of DMAP were added and washed with 10 g of THF. The mixture was cooled to 10 ° C. or lower, and 10.71 g (104.9 mmol) of acetic anhydride diluted with 10 g of THF was added dropwise. After completion of dropping, the temperature was raised to 40 ° C. and stirred for 1 hour. After cooling, the precipitate was collected by filtration. After drying, Compound J represented by the following chemical formula (J) was obtained. The yield was 9.120 g (55% yield).
- Polymerization Example 1 Resin a (Examples 1 to 3 and 5 to 8, Comparative Examples 2 and 3) A thermometer and a stirring rod with stirring blades were set in a 200 mL four-necked flask. Next, 85 g of NMP was charged under a dry nitrogen stream, and the temperature was raised to 40 ° C. After raising the temperature, 11.41 g (57.00 mmol) of DAE was added while stirring and washed with 10 g of NMP. After confirming that DAE was dissolved, 13.09 g (60.00 mmol) of PMDA was added and washed with 10 g of NMP. Cooled after 2 hours.
- Polymerization Example 2 Resin b (Comparative Example 1) A thermometer and a stirring rod with stirring blades were set in a 200 mL four-necked flask. Next, 85 g of NMP was charged under a dry nitrogen stream, and the temperature was raised to 40 ° C. After raising the temperature, 6.07 g (30.00 mmol) of DAE was added while stirring, and washed with 10 g of NMP. After confirming that DAE was dissolved, PMDA 6.544 g (30.00 mmol) was added and washed with 10 g of NMP. Cooled after 2 hours.
- Polymerization Example 3 Resin c (Example 4, Comparative Example 4) A thermometer and a stirring rod with stirring blades were set in a 200 mL four-necked flask. Next, 85 g of NMP was charged under a dry nitrogen stream, and the temperature was raised to 40 ° C. After raising the temperature, 11.41 g (57.00 mmol) of DAE was added while stirring and washed with 10 g of NMP. After confirming that DAE was dissolved, 13.09 g (60.00 mmol) of PMDA was added and washed with 10 g of NMP. Two hours later, 1-hexanol (6.0000 mmol) was added and washed with 5 g of NMP. Cooled after 1 hour.
- Polymerization Example 4 Resin d (Examples 9 and 10, Comparative Example 8) A thermometer and a stirring rod with stirring blades were set in a 200 mL four-necked flask. Next, 100 g of NMP was added under a dry nitrogen stream, and the temperature was raised to 60 ° C. After the temperature was raised, 6.164 g (57.00 mmol) of p-PDA was added with stirring, and washed with 10 g of NMP. After confirming that p-PDA was dissolved, 17.65 g (60.00 mmol) of BPDA was added and washed with 10 g of NMP. Cooled after 4 hours.
- Polymerization Example 5 Resin e (Comparative Example 7) A thermometer and a stirring rod with stirring blades were set in a 200 mL four-necked flask. Next, 85 g of NMP was charged under a dry nitrogen stream, and the temperature was raised to 60 ° C. After the temperature rise, 3.244 g (30.00 mmol) of p-PDA was added with stirring, and washed with 10 g of NMP. After confirming that p-PDA was dissolved, 8.827 g (30.00 mmol) of BPDA was added and washed with 10 g of NMP. After a while, the viscosity of the polymerization solution increased, and stirring could not be continued any further.
- Polymerization Example 6 Resin f (Example 11, Comparative Examples 10 and 11) A thermometer and a stirring rod with stirring blades were set in a 200 mL four-necked flask. Next, 75 g of NMP was added under a dry nitrogen stream, and the temperature was raised to 60 ° C. After the temperature was raised, 5.424 g (47.50 mmol) of CHDA was added with stirring and washed with 10 g of NMP. After confirming that CHDA was dissolved, 10.30 g (35.00 mmol) of BPDA and 4.653 g (15.00 mmol) of ODPA were added and washed with 10 g of NMP. Cooled after 4 hours.
- Polymerization Example 7 Resin g (Comparative Example 5) A thermometer and a stirring rod with stirring blades were set in a 200 mL four-necked flask. Next, 85 g of NMP was charged under a dry nitrogen stream, and the temperature was raised to 40 ° C. After raising the temperature, 11.41 g (57.00 mmol) of DAE and 868.1 g (2.000 mmol) of TAE were added with stirring, followed by washing with 10 g of NMP. After confirming that DAE and TAM were dissolved, 13.09 g (60.00 mmol) of PMDA was added and washed with 10 g of NMP. After a while, the polymerization solution changed to a gel, and stirring could not be continued any more.
- Polymerization Example 8 Resin h (Comparative Example 6) A thermometer and a stirring rod with stirring blades were set in a 200 mL four-necked flask. Next, 85 g of NMP was charged under a dry nitrogen stream, and the temperature was raised to 40 ° C. After raising the temperature, 11.41 g (57.00 mmol) of DAE and 1.198 g (2.000 mmol) of TAB were added while stirring, and washed with 10 g of NMP. After confirming that DAE and TAB were dissolved, 13.09 g (60.00 mmol) of PMDA was added and washed with 10 g of NMP. After a while, the polymerization solution changed to a gel, and stirring could not be continued any more.
- Polymerization Example 9 Resin i (Comparative Example 9) A thermometer and a stirring rod with stirring blades were set in a 200 mL four-necked flask. Next, 100 g of NMP was added under a dry nitrogen stream, and the temperature was raised to 60 ° C. After the temperature was raised, 6.164 g (57.00 mmol) of p-PDA and 378.4 mg (2.000 mmol) of melamine were added while stirring, and washed with 10 g of NMP. Subsequently, 17.65 g (60.00 mmol) of BPDA was added and washed with 10 g of NMP. After cooling for 4 hours, it was confirmed that melamine was precipitated without reacting.
- Example 12 A varnish was prepared so that the resin a and the compound A were in the molar ratio of Example 1 and the viscosity was about 2000 cP (actual viscosity 1970 cP). The viscosity of the varnish after 1 week storage at 23 ° C. was 1940 cP.
- Example 12 A varnish was prepared in the same manner as in Example 12 except that DAE was used instead of Compound A so that the viscosity was about 2000 cP (actual viscosity 2010 cP). The viscosity of the varnish after storage at 23 ° C. for 1 week changed greatly to 2920 cP.
- Example 13 Using a varnish prepared by adding resin a and compound A in a molar ratio of 15% in Example 1 to a solid concentration of 15%, slit coating was performed on a glass substrate having a thickness of 0.7 mm with a wet film thickness of 200 ⁇ m. It dried for 10 minutes at 140 degreeC, and obtained the glass substrate with a 30 micrometer coating film after drying. Subsequently, this glass substrate was heated at 350 ° C. for 30 minutes under nitrogen to obtain a glass substrate with a polyimide film having a thickness of 20 ⁇ m.
- the coating film exhibits excellent physical properties after firing, and includes a surface protection film and interlayer insulation film for semiconductor elements, an insulation layer and spacer layer for organic electroluminescence elements (organic EL elements), a planarization film for thin film transistor substrates, and insulation for organic transistors.
- Layer flexible printed circuit board, flexible display substrate, flexible electronic paper substrate, flexible solar cell substrate, flexible color filter substrate, lithium ion secondary battery electrode binder, semiconductor adhesive, etc. it can.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Wood Science & Technology (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
Description
前記化学式(2)中、Wが以下の化学式(3)から(10)のいずれかで表されるポリアミド酸樹脂組成物であることが好ましい。
前記化学式(1)中、Vが以下の化学式(11)~(13)のいずれかで表されるポリアミド酸樹脂組成物であることがより好ましい。
イソシアネートは、酸無水物基と反応すると化学式(24)に示すようにイミド基が形成される。よって、末端等に酸無水物基を有するポリアミド酸と反応することで高い重合度のポリイミドを得ることができる。また化学式(25)に示すように、イソシアネート同士が反応して二量化あるいは三量化することでも、高い重合度のポリイミドを得ることができる。(なお、イソシアネートがイソチオシアネートであっても、化学式(24)及び化学式(25)と同様に反応すると考えられる。)その結果、ポリイミドフィルムの機械特性を向上させることが可能となる。
XおよびYは、炭素数2~80の4価の炭化水素基であることが好ましく、水素および炭素を必須成分としホウ素、酸素、硫黄、窒素、リン、ケイ素およびハロゲンから選ばれる1以上の原子を含む炭素数2~80の4価の有機基であってもよい。ホウ素、酸素、硫黄、窒素、リン、ケイ素およびハロゲンの各原子は、それぞれ独立に20以下の範囲であるものが好ましく、10以下の範囲であるものがより好ましい。
XおよびYを与えるテトラカルボン酸の例として、以下のものを挙げることができる。芳香族テトラカルボン酸としては、単環芳香族テトラカルボン酸化合物、例えば、ピロメリット酸、2,3,5,6-ピリジンテトラカルボン酸など;ビフェニルテトラカルボン酸の各種異性体、例えば、3,3’,4,4’-ビフェニルテトラカルボン酸、2,3,3’,4’-ビフェニルテトラカルボン酸、2,2’,3,3’-ビフェニルテトラカルボン酸、3,3’,4,4’-ベンゾフェノンテトラカルボン酸、2,2’,3,3’-ベンゾフェノンテトラカルボン酸など;ビス(ジカルボキシフェニル)化合物、例えば、2,2-ビス(3,4-ジカルボキシフェニル)ヘキサフルオロプロパン、2,2-ビス(2,3-ジカルボキシフェニル)ヘキサフルオロプロパン、2,2-ビス(3,4-ジカルボキシフェニル)プロパン、2,2-ビス(2,3-ジカルボキシフェニル)プロパン、1,1-ビス(3,4-ジカルボキシフェニル)エタン、1,1-ビス(2,3-ジカルボキシフェニル)エタン、ビス(3,4-ジカルボキシフェニル)メタン、ビス(2,3-ジカルボキシフェニル)メタン、ビス(3,4-ジカルボキシフェニル)スルホン、ビス(3,4-ジカルボキシフェニル)エーテルなど;ビス(ジカルボキシフェノキシフェニル)化合物、例えば、2,2-ビス[4-(3,4-ジカルボキシフェノキシ)フェニル]ヘキサフルオロプロパン、2,2-ビス[4-(2,3-ジカルボキシフェノキシ)フェニル]ヘキサフルオロプロパン、2,2-ビス[4-(3,4-ジカルボキシフェノキシ)フェニル]プロパン、2,2-ビス[4-(2,3-ジカルボキシフェノキシ)フェニル]プロパン、2,2-ビス[4-(3,4-ジカルボキシフェノキシ)フェニル]スルホン、2,2-ビス[4-(3,4-ジカルボキシフェノキシ)フェニル]エーテルなど;ナフタレンまたは縮合多環芳香族テトラカルボン酸の各種異性体、例えば1,2,5,6-ナフタレンテトラカルボン酸、1,4,5,8-ナフタレンテトラカルボン酸、2,3,6,7-ナフタレンテトラカルボン酸、2,3,6,7-ナフタレンテトラカルボン酸、3,4,9,10-ペリレンテトラカルボン酸など;ビス(トリメリット酸モノエステル酸無水物)化合物、例えばp-フェニレンビス(トリメリット酸モノエステル酸無水物)、p-ビフェニレンビス(トリメリット酸モノエステル酸無水物)、エチレンビス(トリメリット酸モノエステル酸無水物)、ビスフェノールAビス(トリメリット酸モノエステル酸無水物)などを挙げることができる。脂肪族テトラカルボン酸としては、鎖状脂肪族テトラカルボン酸化合物、例えばブタンテトラカルボン酸など;脂環式テトラカルボン酸化合物、例えばシクロブタンテトラカルボン酸、1,2,3,4-シクロペンタンテトラカルボン酸、1,2,4,5-シクロヘキサンテトラカルボン酸、ビシクロ[2.2.1.]ヘプタンテトラカルボン酸、ビシクロ[3.3.1.]テトラカルボン酸、ビシクロ[3.1.1.]ヘプト-2-エンテトラカルボン酸、ビシクロ[2.2.2.]オクタンテトラカルボン酸、アダマタンテトラカルボン酸などを挙げることができる。
上記化学式(31)中、R33およびR34は、熱架橋性基であるCH2OR36(R36は水素または炭素数1~6の1価の炭化水素)を表している。上記化学式(31)の熱架橋剤に適度な反応性を残し、保存安定性に優れることから、R36は炭素数1~4の1価の炭化水素基が好ましく、メチル基またはエチル基がより好ましい。
得られたワニスを固形分濃度が10質量%となるようN-メチル-2-ピロリドンで希釈し、粘度計(東機産業株式会社製、TVE-22H)を用い、25℃にて測定を行った。
ゲルパーミエーションクロマトグラフィー(日本ウォーターズ株式会社製 Waters 2690)を用い、ポリスチレン換算で重量平均分子量を求めた。カラムは東ソー(株)製 TOSOH TXK-GEL α-2500、およびα-4000を用い、移動層にはN-メチル-2-ピロリドンを用いた。
ワニスを1μmのフィルターを用いて加圧濾過し、異物を取り除いた。6インチのシリコンウェハ上に140℃で4分間、プリベーク後の膜厚が15μmになるように、塗布現像装置Mark-7(東京エレクトロン株式会社製)を用いてスピンコートおよびプリベークを行なった。プリベーク膜をイナートオーブン(光洋サーモシステム株式会社製 INH-21CD)を用いて窒素気流下(酸素濃度20ppm以下)、350℃で30分加熱処理し、ポリイミドフィルムを作製した。続いてフッ酸に4分間浸漬してポリイミドフィルムをシリコンウェハ基板から剥離し、風乾した。得られたポリイミドフィルムは、(4)~(7)の測定に用いた。
テンシロン万能材料試験機(株式会社オリエンテック製 RTM-100)を用い、日本工業規格(JIS K 7127:1999)に従って測定を行った。
熱機械分析装置(エスアイアイ・ナノテクノロジー株式会社製 EXSTAR6000 TMA/SS6100)を用いて、窒素気流下で測定を行った。昇温方法は、以下の条件にて行った。第1段階で200℃まで昇温して試料の吸着水を除去し、第2段階で室温まで冷却した。第3段階で、昇温レート5℃/minで本測定を行い、ガラス転移温度を求めた。
ガラス転移温度の測定と同じ装置を用いて同じ条件で測定を行い、50~200℃の線膨張係数の平均を求めた。
熱質量測定装置(株式会社島津製作所製 TGA-50)を用いて窒素気流下で測定を行った。昇温方法は、以下の条件にて行った。第1段階で150度まで昇温して試料の吸着水を除去し、第2段階で室温まで冷却した。第3段階で、昇温レート10℃/minで本測定を行い、5%熱質量減少温度を求めた。
核磁気共鳴装置(日本電子株式会社製 EX-270)を用い、重溶媒に重ジメチルスルホキシドを用いて1H-NMRスペクトルを測定した。
CHDA:trans-1,4-シクロヘキサンジアミン
DAE:4,4’-ジアミノジフェニルエーテル
p-PDA:p-フェニレンジアミン
m-PDA:m-フェニレンジアミン
TAM:トリス(4-アミノフェニル)メタン
TAB:1,3,5-トリス(4-アミノフェノキシ)ベンゼン
BPDA:3,3’,4,4’-ビフェニルテトラカルボン酸二無水物
ODPA:ビス(3,4-ジカルボキシフェニル)エーテル二無水物
PMDA:ピロメリット酸二無水物
DIBOC:二炭酸ジ-tert-ブチル
DMAP:N,N-ジメチル-4-アミノピリジン
CPME:シクロペンチルメチルエーテル
NMP:N-メチル-2-ピロリドン
THF:テトラヒドロフラン。
300mL4つ口フラスコに、温度計、撹拌羽根付き撹拌棒をセットした。次に、乾燥窒素気流下、THF100gを投入し、室温で撹拌した。次にDAE10.00g(49.94mmol)、DMAP61.01mg(499.4μmol)を入れてTHF10gで洗い込んだ。10℃以下に冷却し、ジケテン8.607g(102.4mmol)をTHF10gで希釈したものを滴下した。滴下終了後、30℃に昇温して1時間撹拌した。冷却後、沈殿物を濾過によって回収した。乾燥後、以下の化学式(A)で示される化合物Aを得た。収量は12.03g(収率65%)であった。
300mL4つ口フラスコに、温度計、撹拌羽根付き撹拌棒をセットした。次に、乾燥窒素気流下、THF100gを投入し、室温で撹拌した。次にp-PDA10.00g(92.47mmol)、DMAP113.0mg(924.7μmol)を入れてTHF10gで洗い込んだ。10℃以下に冷却し、ジケテン15.94g(189.6mmol)をTHF10gで希釈したものを滴下した。滴下終了後、30℃に昇温して1時間撹拌した。冷却後、沈殿物を濾過によって回収した。エタノールで再結晶を行い、乾燥後、以下の化学式(B)で示される化合物Bを得た。収量は19.99g(収率78%)であった。
300mL4つ口フラスコに、温度計、撹拌羽根付き撹拌棒をセットした。次に、乾燥窒素気流下、CPME100gを投入し、室温で撹拌した。次にm-PDA10.00g(92.47mmol)、DMAP113.0mg(924.7μmol)を入れてCPME10gで洗い込んだ。10℃以下に冷却し、ジケテン15.94g(189.6mmol)をCPME10gで希釈したものを滴下した。滴下終了後、30℃に昇温して1時間撹拌した。冷却後、沈殿物を濾過によって回収した。エタノールで再結晶を行い、乾燥後、以下の化学式(C)で示される化合物Cを得た。収量は14.48g(収率57%)であった。
300mL4つ口フラスコに、温度計、撹拌羽根付き撹拌棒をセットした。次に、乾燥窒素気流下、CPME100gを投入し、室温で撹拌した。次にCHDA10.00g(87.57mmol)を入れてCPME10gで洗い込んだ。10℃以下に冷却し、ジケテン15.09g(179.5mmol)をCPME10gで希釈したものを滴下した。滴下終了後、30℃に昇温して1時間撹拌した。冷却後、沈殿物を濾過によって回収した。エタノールで再結晶を行い、乾燥後、以下の化学式(D)で示される化合物Dを得た。収量は16.24g(収率66%)であった。
300mL4つ口フラスコに、温度計、撹拌羽根付き撹拌棒をセットした。次に、乾燥窒素気流下、THF80gを投入し、室温で撹拌した。次にTAM10.00g(34.56mmol)、DMAP63.33mg(518.4μmol)を入れてTHF10gで洗い込んだ。10℃以下に冷却し、ジケテン9.152g(108.9mmol)をTHF10gで希釈したものを滴下した。滴下終了後、30℃に昇温して1時間撹拌した。冷却後、沈殿物を濾過によって回収した。乾燥後、以下の化学式(E)で示される化合物Eを得た。収量は16.66g(収率89%)であった。
300mL4つ口フラスコに、温度計、撹拌羽根付き撹拌棒をセットした。次に、乾燥窒素気流下、NMP80gを投入し、室温で撹拌した。次にTAB10.00g(25.04mmol)を入れてNMP10gで洗い込んだ。10℃以下に冷却し、ジケテン6.31g(75.11mmol)をNMP10gで希釈したものを滴下した。滴下終了後、40℃に昇温して1時間撹拌した。冷却後、反応溶液を以下の化学式(F)で示される化合物FのNMP溶液として用いた。
300mL4つ口フラスコに、温度計、撹拌羽根付き撹拌棒をセットした。次に、乾燥窒素気流下、NMP130gを投入し、室温で撹拌した。次にメラミン10.00g(79.29mmol)を入れてNMP10gで洗い込んだ。10℃以下に冷却し、ジケテン20.00g(237.9mmol)をNMP10gで希釈したものを滴下した。滴下終了後、60℃に昇温して2時間撹拌した。冷却後、反応溶液を以下の化学式(G)で示される化合物GのNMP溶液として用いた。
300mL4つ口フラスコに、温度計、撹拌羽根付き撹拌棒をセットした。次に、乾燥窒素気流下、NMP70gを投入した。つづいて、室温で撹拌しながらシアノ酢酸8.496g(99.88mmol)を入れて、NMP10gで洗いこんだ。シアノ酢酸が溶解したことを確認し、10℃以下に冷却した。冷却後、カルボニルジイミダゾール16.60g(102.4mmol)を投入して、NMP10gで洗いこんだ。投入後、一晩、室温で撹拌した。翌日、DAE10.00g(49.94mmol)を入れて、NMP10gで洗いこんだ。投入後、さらに一晩、室温で撹拌した。反応溶液を以下の化学式(H)で示される化合物HのNMP溶液として用いた。
300mL4つ口フラスコに、温度計、撹拌羽根付き撹拌棒をセットした。次に、乾燥窒素気流下、NMP70gを投入した。つづいて、室温で撹拌しながら2-(p-トルエンスルホニル)酢酸21.40g(99.88mmol)を入れて、NMP10gで洗いこんだ。シアノ酢酸が溶解したことを確認し、10℃以下に冷却した。冷却後、カルボニルジイミダゾール16.60g(102.4mmol)を投入して、NMP10gで洗いこんだ。投入後、一晩、室温で撹拌した。翌日、DAE10.00g(49.94mmol)を入れて、NMP10gで洗いこんだ。投入後、さらに一晩、室温で撹拌した。反応溶液を以下の化学式(I)で示される化合物IのNMP溶液として用いた。
300mL4つ口フラスコに、温度計、撹拌羽根付き撹拌棒をセットした。次に、乾燥窒素気流下、THF100gを投入し、室温で撹拌した。次にDAE10.00g(49.94mmol)、トリエチルアミン11.12g(109.9mmol)、DMAP61.01mg(49.94μmol)を入れてTHF10gで洗い込んだ。10℃以下に冷却し、無水酢酸10.71g(104.9mmol)をTHF10gで希釈したものを滴下した。滴下終了後、40℃に昇温して1時間撹拌した。冷却後、沈殿物を濾過によって回収した。乾燥後、以下の化学式(J)で示される化合物Jを得た。収量は9.120g(収率55%)であった。
300mL4つ口フラスコに、温度計、撹拌羽根付き撹拌棒をセットした。次に、乾燥窒素気流下、THF100gを投入し、室温で撹拌した。次にCHDA10.00g(87.57mmol)を入れてTHF10gで洗い込んだ。10℃以下に冷却し、DIBOC39.18g(179.5mmol)をTHF10gで希釈したものを滴下した。滴下終了後、室温に昇温した。一週間後、沈殿物を濾過によって回収した。乾燥後、以下の化学式(K)で示される化合物Kを得た。収量は17.90g(収率90%)であった。
200mL4つ口フラスコに、温度計、撹拌羽根付き撹拌棒をセットした。次に、乾燥窒素気流下、NMP85gを投入し、40℃に昇温した。昇温後、撹拌しながらDAE11.41g(57.00mmol)を入れて、NMP10gで洗いこんだ。DAEが溶解したことを確認し、PMDA13.09g(60.00mmol)を投入し、NMP10gで洗いこんだ。2時間後に冷却した。
200mL4つ口フラスコに、温度計、撹拌羽根付き撹拌棒をセットした。次に、乾燥窒素気流下、NMP85gを投入し、40℃に昇温した。昇温後、撹拌しながらDAE6.007g(30.00mmol)を入れて、NMP10gで洗いこんだ。DAEが溶解したことを確認し、PMDA6.544g(30.00mmol)を投入し、NMP10gで洗いこんだ。2時間後に冷却した。
200mL4つ口フラスコに、温度計、撹拌羽根付き撹拌棒をセットした。次に、乾燥窒素気流下、NMP85gを投入し、40℃に昇温した。昇温後、撹拌しながらDAE11.41g(57.00mmol)を入れて、NMP10gで洗いこんだ。DAEが溶解したことを確認し、PMDA13.09g(60.00mmol)を投入し、NMP10gで洗いこんだ。2時間後に、1-ヘキサノール(6.000mmol)を投入し、NMP5gで洗い込んだ。1時間後に冷却した。
200mL4つ口フラスコに、温度計、撹拌羽根付き撹拌棒をセットした。次に、乾燥窒素気流下、NMP100gを投入し、60℃に昇温した。昇温後、撹拌しながらp-PDA6.164g(57.00mmol)を入れて、NMP10gで洗いこんだ。p-PDAが溶解したことを確認し、BPDA17.65g(60.00mmol)を投入し、NMP10gで洗いこんだ。4時間後に冷却した。
200mL4つ口フラスコに、温度計、撹拌羽根付き撹拌棒をセットした。次に、乾燥窒素気流下、NMP85gを投入し、60℃に昇温した。昇温後、撹拌しながらp-PDA3.244g(30.00mmol)を入れて、NMP10gで洗いこんだ。p-PDAが溶解したことを確認し、BPDA8.827g(30.00mmol)を投入し、NMP10gで洗いこんだ。しばらくすると重合溶液の粘度が増大し、これ以上撹拌をつづけることができなかった。
200mL4つ口フラスコに、温度計、撹拌羽根付き撹拌棒をセットした。次に、乾燥窒素気流下、NMP75gを投入し60℃に昇温した。昇温後、撹拌しながらCHDA5.424g(47.50mmol)を入れて、NMP10gで洗いこんだ。CHDAが溶解したことを確認し、BPDA10.30g(35.00mmol)、ODPA4.653g(15.00mmol)を投入し、NMP10gで洗いこんだ。4時間後に冷却した。
200mL4つ口フラスコに、温度計、撹拌羽根付き撹拌棒をセットした。次に、乾燥窒素気流下、NMP85gを投入し、40℃に昇温した。昇温後、撹拌しながらDAE11.41g(57.00mmol)、TAM868.1g(2.000mmol)を入れて、NMP10gで洗いこんだ。DAE、TAMが溶解したことを確認し、PMDA13.09g(60.00mmol)を投入し、NMP10gで洗いこんだ。しばらくすると重合溶液がゲル状に変化し、これ以上撹拌をつづけることができなかった。
200mL4つ口フラスコに、温度計、撹拌羽根付き撹拌棒をセットした。次に、乾燥窒素気流下、NMP85gを投入し、40℃に昇温した。昇温後、撹拌しながらDAE11.41g(57.00mmol)、TAB1.198g(2.000mmol)を入れて、NMP10gで洗いこんだ。DAE、TABが溶解したことを確認し、PMDA13.09g(60.00mmol)を投入し、NMP10gで洗いこんだ。しばらくすると重合溶液がゲル状に変化し、これ以上撹拌をつづけることができなかった。
200mL4つ口フラスコに、温度計、撹拌羽根付き撹拌棒をセットした。次に、乾燥窒素気流下、NMP100gを投入し、60℃に昇温した。昇温後、撹拌しながらp-PDA6.164g(57.00mmol)、メラミン378.4mg(2.000mmol)を入れて、NMP10gで洗いこんだ。つづいて、BPDA17.65g(60.00mmol)を投入し、NMP10gで洗いこんだ。4時間後に冷却したが、メラミンが反応せずに沈殿していることが確認された。
合成例1~11で得られた化合物A~K、および重合例1~9で得られた樹脂a~iの溶液を用いて、表1および2に示すモル比になるようにワニスを調製した。
樹脂aおよび化合物Aを実施例1におけるモル比で、粘度が約2000cPになるようにワニスを調製した(実際の粘度1970cP)。23℃で1週間保管した後のワニスの粘度は、1940cPであった。
化合物Aの代わりにDAEを用いた以外は実施例12と同様にして粘度が約2000cPになるようにワニスを調製した(実際の粘度2010cP)。23℃で1週間保管した後のワニスの粘度は、2920cPに大きく変化した。
樹脂aおよび化合物Aを実施例1におけるモル比で固形分濃度が15%になるように調製したワニスを用い、厚さ0.7mmのガラス基板に、ウェット膜厚200μmでスリット塗布を行った。140℃で10分間乾燥し、乾燥後30μmのコーティング膜つきのガラス基板を得た。
つづいてこのガラス基板を窒素下、350℃で30分間加熱することにより膜厚20μmのポリイミドフィルムつきガラス基板を得た。
Claims (10)
- 化学式(1)において、kが2または3である請求項1~3のいずれかに記載のポリアミド酸樹脂組成物。
- 請求項1~5のいずれかに記載のポリアミド酸樹脂組成物をイミド化することにより得られるポリイミドを含むポリイミドフィルム。
- 請求項1~5のいずれかに記載のポリアミド酸樹脂組成物をイミド化する工程を含むポリイミドフィルムの製造方法。
- 請求項1~5記載のいずれかに記載のポリアミド酸樹脂組成物を含むワニスをガラス基板上に塗布し、溶剤を乾燥せしめることによって得られるコーティング膜つきガラス基板。
- 前記のコーティング膜つきガラス基板を180~600℃の温度で加熱することによって得られるポリイミドフィルムつきガラス基板。
- 請求項8記載のコーティング膜つきのガラス基板を加熱することによりイミド化する工程を含むポリイミドフィルムつきガラス基板の製造方法。
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/417,083 US9850347B2 (en) | 2012-08-01 | 2013-07-30 | Polyamic acid resin composition, polyimide film using same, and method for producing said polyimide film |
SG11201500493YA SG11201500493YA (en) | 2012-08-01 | 2013-07-30 | Polyamide acid resin composition, polyimide film using same, and method for producing said polyimide film |
CN201380039541.9A CN104508008B (zh) | 2012-08-01 | 2013-07-30 | 聚酰胺酸树脂组合物、使用了该组合物的聚酰亚胺膜及其制造方法 |
KR1020157003989A KR101931997B1 (ko) | 2012-08-01 | 2013-07-30 | 폴리아미드산 수지 조성물, 이것을 사용한 폴리이미드 필름 및 그 제조 방법 |
JP2013538381A JP5488772B1 (ja) | 2012-08-01 | 2013-07-30 | ポリアミド酸樹脂組成物、これを用いたポリイミドフィルムおよびその製造方法 |
EP13824982.6A EP2881417B1 (en) | 2012-08-01 | 2013-07-30 | Polyamide acid resin composition, polyimide film using same, and method for producing said polyimide film |
PH12015500103A PH12015500103B1 (en) | 2012-08-01 | 2015-01-14 | Polyamide acid resin composition, polyimide film using same, and method for producing said polyimide film |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012170829 | 2012-08-01 | ||
JP2012-170829 | 2012-08-01 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014021319A1 true WO2014021319A1 (ja) | 2014-02-06 |
Family
ID=50027992
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/070610 WO2014021319A1 (ja) | 2012-08-01 | 2013-07-30 | ポリアミド酸樹脂組成物、これを用いたポリイミドフィルムおよびその製造方法 |
Country Status (9)
Country | Link |
---|---|
US (1) | US9850347B2 (ja) |
EP (1) | EP2881417B1 (ja) |
JP (1) | JP5488772B1 (ja) |
KR (1) | KR101931997B1 (ja) |
CN (1) | CN104508008B (ja) |
PH (1) | PH12015500103B1 (ja) |
SG (1) | SG11201500493YA (ja) |
TW (1) | TWI619743B (ja) |
WO (1) | WO2014021319A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017099183A1 (ja) * | 2015-12-11 | 2017-06-15 | 東レ株式会社 | 樹脂組成物、樹脂の製造方法、樹脂膜の製造方法および電子デバイスの製造方法 |
JP2018535175A (ja) * | 2015-10-30 | 2018-11-29 | コーニング インコーポレイテッド | ポリマーと金属酸化物との混合コーティングを有するガラス物品 |
JP2020128527A (ja) * | 2019-02-06 | 2020-08-27 | ユニチカ株式会社 | ガラス基板への塗工用ポリアミック酸溶液 |
WO2021065051A1 (ja) * | 2019-10-03 | 2021-04-08 | 三井化学株式会社 | ポリイミドフィルム、ポリアミド酸およびこれを含むワニス、ならびにポリイミド積層体およびその製造方法 |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11497681B2 (en) | 2012-02-28 | 2022-11-15 | Corning Incorporated | Glass articles with low-friction coatings |
US10737973B2 (en) | 2012-02-28 | 2020-08-11 | Corning Incorporated | Pharmaceutical glass coating for achieving particle reduction |
EP3919457A1 (en) | 2012-02-28 | 2021-12-08 | Corning Incorporated | Glass articles with low-friction coatings |
US10273048B2 (en) | 2012-06-07 | 2019-04-30 | Corning Incorporated | Delamination resistant glass containers with heat-tolerant coatings |
US9034442B2 (en) | 2012-11-30 | 2015-05-19 | Corning Incorporated | Strengthened borosilicate glass containers with improved damage tolerance |
TWI705946B (zh) | 2014-09-05 | 2020-10-01 | 美商康寧公司 | 玻璃物品及改善玻璃物品可靠性的方法 |
EP3118247A1 (de) | 2015-07-15 | 2017-01-18 | Basf Se | Polyamide mit besseren optischen eigenschaften |
EP3150564B1 (en) | 2015-09-30 | 2018-12-05 | Corning Incorporated | Halogenated polyimide siloxane chemical compositions and glass articles with halogenated polylmide siloxane low-friction coatings |
KR102532485B1 (ko) * | 2017-09-07 | 2023-05-16 | 도레이 카부시키가이샤 | 수지 조성물, 수지막의 제조 방법 및 전자 디바이스의 제조 방법 |
CN109666171B (zh) * | 2017-10-17 | 2022-02-01 | 中国石油化工股份有限公司 | 均匀聚酰亚胺薄膜的制备方法 |
JP6568290B1 (ja) * | 2018-04-27 | 2019-08-28 | 住友化学株式会社 | 光学フィルム |
CN113474156B (zh) * | 2019-02-26 | 2022-04-29 | 东丽株式会社 | 聚酰胺酸树脂组合物、聚酰亚胺树脂膜及其制造方法、层叠体、以及电子器件及其制造方法 |
JP7533220B2 (ja) * | 2019-09-24 | 2024-08-14 | 東レ株式会社 | 樹脂膜、電子デバイス、樹脂膜の製造方法および電子デバイスの製造方法 |
JP7437997B2 (ja) * | 2020-03-31 | 2024-02-26 | 東京応化工業株式会社 | ワニス組成物、ポリイミド樹脂の製造方法、及び添加剤 |
CN111621260B (zh) * | 2020-06-18 | 2022-01-25 | 株洲时代新材料科技股份有限公司 | 一种聚酰胺酸涂层胶及其制备方法 |
CN114940675B (zh) * | 2022-05-10 | 2023-05-02 | 波米科技有限公司 | 一种化合物及其制备方法、利用该化合物制备的树脂、低温固化树脂组合物 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001031764A (ja) | 1998-11-25 | 2001-02-06 | Unitika Ltd | ポリイミド前駆体溶液及びその製造方法、それから得られる塗膜及びその製造方法 |
JP2009109588A (ja) | 2007-10-26 | 2009-05-21 | Asahi Kasei Corp | 感光性樹脂組成物、感光性樹脂組成物フィルム、およびそれらを用いた樹脂パターン |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11302375A (ja) * | 1997-11-20 | 1999-11-02 | Kanegafuchi Chem Ind Co Ltd | 金属を含有するポリアミド酸組成物並びにポリイミドフィルム及びそれからなるフレキシブル印刷配線用基板及びそれらの製造方法 |
JP2001031746A (ja) | 1999-07-22 | 2001-02-06 | Japan Steel Works Ltd:The | ポリ乳酸の製造方法 |
JP5120047B2 (ja) * | 2007-05-02 | 2013-01-16 | Jsr株式会社 | 垂直配向型液晶配向剤および液晶表示素子 |
CN101230196B (zh) * | 2008-02-26 | 2010-06-02 | 东南大学 | 原位聚合pi改性尼龙复合材料 |
CN102051185B (zh) * | 2009-11-03 | 2013-07-17 | 奇美实业股份有限公司 | 液晶配向剂、液晶配向膜及液晶显示元件 |
-
2013
- 2013-07-30 WO PCT/JP2013/070610 patent/WO2014021319A1/ja active Application Filing
- 2013-07-30 JP JP2013538381A patent/JP5488772B1/ja active Active
- 2013-07-30 CN CN201380039541.9A patent/CN104508008B/zh active Active
- 2013-07-30 KR KR1020157003989A patent/KR101931997B1/ko active IP Right Grant
- 2013-07-30 EP EP13824982.6A patent/EP2881417B1/en not_active Not-in-force
- 2013-07-30 US US14/417,083 patent/US9850347B2/en active Active
- 2013-07-30 SG SG11201500493YA patent/SG11201500493YA/en unknown
- 2013-07-31 TW TW102127362A patent/TWI619743B/zh not_active IP Right Cessation
-
2015
- 2015-01-14 PH PH12015500103A patent/PH12015500103B1/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001031764A (ja) | 1998-11-25 | 2001-02-06 | Unitika Ltd | ポリイミド前駆体溶液及びその製造方法、それから得られる塗膜及びその製造方法 |
JP2009109588A (ja) | 2007-10-26 | 2009-05-21 | Asahi Kasei Corp | 感光性樹脂組成物、感光性樹脂組成物フィルム、およびそれらを用いた樹脂パターン |
Non-Patent Citations (3)
Title |
---|
BEOM JIN KIM: "Phosgen-free synthesis of oligoureas having amino end-groups: their application to the synthesis of poly(urea- imide)", FIBERS AND POLYMERS, vol. 3, no. 2, 2002, pages 55 - 59, XP055167614 * |
See also references of EP2881417A4 * |
T. MUKAIYAMA; M. TOKIZAWA; H. NOHIRA; H. TAKEI, J. ORG. CHEM., vol. 26, 1961, pages 4381 |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018535175A (ja) * | 2015-10-30 | 2018-11-29 | コーニング インコーポレイテッド | ポリマーと金属酸化物との混合コーティングを有するガラス物品 |
JP6993964B2 (ja) | 2015-10-30 | 2022-01-14 | コーニング インコーポレイテッド | ポリマーと金属酸化物との混合コーティングを有するガラス物品 |
WO2017099183A1 (ja) * | 2015-12-11 | 2017-06-15 | 東レ株式会社 | 樹脂組成物、樹脂の製造方法、樹脂膜の製造方法および電子デバイスの製造方法 |
JP2020128527A (ja) * | 2019-02-06 | 2020-08-27 | ユニチカ株式会社 | ガラス基板への塗工用ポリアミック酸溶液 |
WO2021065051A1 (ja) * | 2019-10-03 | 2021-04-08 | 三井化学株式会社 | ポリイミドフィルム、ポリアミド酸およびこれを含むワニス、ならびにポリイミド積層体およびその製造方法 |
JPWO2021065051A1 (ja) * | 2019-10-03 | 2021-04-08 | ||
CN114466745A (zh) * | 2019-10-03 | 2022-05-10 | 三井化学株式会社 | 聚酰亚胺膜、聚酰胺酸及含有其的清漆、以及聚酰亚胺层叠体及其制造方法 |
JP7225427B2 (ja) | 2019-10-03 | 2023-02-20 | 三井化学株式会社 | ポリイミドフィルム、ポリアミド酸およびこれを含むワニス、ならびにポリイミド積層体およびその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
KR20150038089A (ko) | 2015-04-08 |
US20150203631A1 (en) | 2015-07-23 |
SG11201500493YA (en) | 2015-04-29 |
JPWO2014021319A1 (ja) | 2016-07-21 |
CN104508008A (zh) | 2015-04-08 |
PH12015500103A1 (en) | 2015-04-06 |
EP2881417B1 (en) | 2017-02-22 |
TW201412823A (zh) | 2014-04-01 |
TWI619743B (zh) | 2018-04-01 |
EP2881417A1 (en) | 2015-06-10 |
JP5488772B1 (ja) | 2014-05-14 |
EP2881417A4 (en) | 2016-01-27 |
PH12015500103B1 (en) | 2015-04-06 |
US9850347B2 (en) | 2017-12-26 |
CN104508008B (zh) | 2016-08-17 |
KR101931997B1 (ko) | 2018-12-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5488772B1 (ja) | ポリアミド酸樹脂組成物、これを用いたポリイミドフィルムおよびその製造方法 | |
TWI631183B (zh) | Resin composition, method for producing resin, method for producing resin film, and method for producing electronic device | |
JP6819292B2 (ja) | ディスプレイ基板用樹脂組成物、並びに、それを用いた耐熱性樹脂フィルム、有機elディスプレイ基板及び有機elディスプレイの製造方法 | |
JP5472540B1 (ja) | ポリアミド酸およびそれを含有する樹脂組成物 | |
KR101921919B1 (ko) | 폴리아미드산 수지 조성물, 폴리이미드 수지 조성물, 폴리이미드 옥사졸 수지 조성물 및 그것들을 함유하는 플렉시블 기판 | |
JP7322699B2 (ja) | ディスプレイ基板用樹脂組成物、ディスプレイ基板用樹脂膜およびそれを含む積層体、画像表示装置、有機elディスプレイ、並びに、それらの製造方法 | |
JP2019077871A (ja) | 耐熱性樹脂膜およびその製造方法、加熱炉ならびに画像表示装置の製造方法 | |
TWI714703B (zh) | 硬化膜及其製造方法 | |
JP6065495B2 (ja) | 電子部品およびパワー半導体装置 | |
TW202309657A (zh) | 感光性聚醯亞胺樹脂組成物 | |
TW201413387A (zh) | 正型感光性樹脂組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2013538381 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13824982 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 12015500103 Country of ref document: PH |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14417083 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20157003989 Country of ref document: KR Kind code of ref document: A |
|
REEP | Request for entry into the european phase |
Ref document number: 2013824982 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2013824982 Country of ref document: EP |