WO2013024820A1 - ポリイミド前駆体、ポリイミド、ポリイミドフィルム、およびこれらの製造に使用されるトリアジン化合物の製造方法 - Google Patents
ポリイミド前駆体、ポリイミド、ポリイミドフィルム、およびこれらの製造に使用されるトリアジン化合物の製造方法 Download PDFInfo
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- WO2013024820A1 WO2013024820A1 PCT/JP2012/070517 JP2012070517W WO2013024820A1 WO 2013024820 A1 WO2013024820 A1 WO 2013024820A1 JP 2012070517 W JP2012070517 W JP 2012070517W WO 2013024820 A1 WO2013024820 A1 WO 2013024820A1
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- polyimide
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- RAKGMXKZZGXBDF-UHFFFAOYSA-N C/C(/Nc1cc(N)ccc1)=N\C(\N)=N/C(Nc1cc(N)ccc1)=C Chemical compound C/C(/Nc1cc(N)ccc1)=N\C(\N)=N/C(Nc1cc(N)ccc1)=C RAKGMXKZZGXBDF-UHFFFAOYSA-N 0.000 description 1
- 0 CC(*(c1cccc(*=N)c1)=I)=*C(*)=*C(*(c1cc(*)ccc1)=I)=C Chemical compound CC(*(c1cccc(*=N)c1)=I)=*C(*)=*C(*(c1cc(*)ccc1)=I)=C 0.000 description 1
- ITZKIYVJSSMRMZ-UHFFFAOYSA-N CCC(BNC(C(CC(C(O)=O)C(O)=O)C(NC(C)CC)=O)=O)C Chemical compound CCC(BNC(C(CC(C(O)=O)C(O)=O)C(NC(C)CC)=O)=O)C ITZKIYVJSSMRMZ-UHFFFAOYSA-N 0.000 description 1
- WGIYOMCQPSQGTQ-UHFFFAOYSA-N CCC(C)NC(C(CC1(C(NBC(C)C)=O)C(O)=O)C1C(O)=O)=O Chemical compound CCC(C)NC(C(CC1(C(NBC(C)C)=O)C(O)=O)C1C(O)=O)=O WGIYOMCQPSQGTQ-UHFFFAOYSA-N 0.000 description 1
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Definitions
- the present invention relates to a polyimide precursor and polyimide, and more specifically, a polyimide film having excellent adhesion to metal and improved transmittance in the ultraviolet-visible region, and a method for producing a triazine compound used in the production thereof About.
- Polyimide films are widely used in fields such as electric / electronic devices and semiconductors because they are excellent in heat resistance, chemical resistance, mechanical strength, electrical properties, dimensional stability, and the like.
- a flexible printed wiring board FPC
- a copper-clad laminated board formed by laminating a copper foil on one or both sides of a polyimide film is used.
- Polyimide film is generally a laminate with sufficiently high peel strength when a metal layer is provided on the polyimide film by dry plating such as metal vapor deposition or sputtering, or when a metal layer is provided on the polyimide film by wet plating such as electroless plating. The body may not be obtained.
- Patent Documents 1 to 3 For example, semi-alicyclic polyimides using trans-1,4-diaminocyclohexanes as the diamine component and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as the tetracarboxylic acid component are known. (Patent Document 3).
- Patent Document 4 describes a polyimide using a triazine-based diamine, and describes an example in which a polyimide solution is applied to a metal foil. Further, as an example using a triazine diamine, Patent Document 5 discloses a terminal-modified imide oligomer using a triazine diamine, and Patent Document 6 discloses a polymer electrolyte using a triazine diamine. Yes. Patent Document 7 discloses a triazine-based diamine (hereinafter referred to as “p-ATDA”) in which two amino groups (—NH 2 ) are present at the para-position of the benzene ring with respect to two NH groups bonded to the triazine ring. In some cases, polyimides are used.
- p-ATDA triazine-based diamine
- JP 2002-348374 A JP 2005-15629 A JP 2002-161136 A US Pat. No. 3,803,075 JP 2009-263570 A JP 2009-87763 A JP 2010-31102 A Japanese Patent Publication No. 48-8272
- the present invention uses a polyimide precursor, a polyimide using the polyimide precursor, and the polyimide for obtaining a polyimide film having excellent adhesion to metal and improved transmittance in the ultraviolet-visible region. It aims at providing the manufacturing method of the triazine compound used for manufacture of a polyimide film, a polyimide precursor, a polyimide, and a polyimide film.
- the present invention relates to the following matters.
- A is a tetravalent aromatic group or aliphatic group, and B is a divalent aromatic group.
- R 1 represents a hydrogen atom or an alkyl group or aryl group having 1 to 12 carbon atoms
- R 2 represents a hydrogen atom or an alkyl group or aryl group having 1 to 12 carbon atoms.
- a polyimide precursor having a structural unit represented by the general formula (I) (wherein A is a tetravalent aromatic group and B is a divalent aromatic group),
- the group B in the general formula (I) the formula (B1) (wherein R 1 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an aryl group, and R 2 represents a hydrogen atom or carbon number 1).
- group A in the general formula (I) is 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexa
- a polyimide precursor comprising a tetravalent residue obtained by removing two carboxylic anhydride groups from fluoropropane dianhydride.
- a polyimide precursor having a structural unit represented by the general formula (I) (wherein A is a tetravalent aliphatic group and B is a divalent aromatic group),
- the formula (B1) (wherein R 1 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an aryl group, and R 2 represents a hydrogen atom or carbon number 1).
- R 1 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an aryl group
- R 2 represents a hydrogen atom or carbon number 1
- the polyimide precursor characterized by including the triazine partial structure represented by these.
- the polyimide precursor according to Item 1 comprising a tetravalent residue obtained by removing two carboxylic anhydride groups from pyromellitic dianhydride as the group A in the general formula (I).
- 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride is selected from two carboxylic acids.
- Item 2 The polyimide precursor according to Item 1, comprising a tetravalent residue excluding an acid anhydride group.
- Item 5 The polyimide precursor according to any one of Items 1 to 4, wherein in General Formula (B1), R 1 is a hydrogen atom and R 2 is phenyl.
- Item 6 The polyimide precursor according to any one of Items 1 to 5, wherein the group B in the general formula (I) includes a triazine partial structure represented by the general formula (B1) in a range of 10 to 100 mol%. .
- R 1 represents a hydrogen atom or an alkyl group or aryl group having 1 to 12 carbon atoms
- R 2 represents a hydrogen atom or an alkyl group or aryl group having 1 to 12 carbon atoms
- X represents a halogen atom.
- the polyimide film which was excellent in the adhesiveness with a metal, and the transmittance
- the bonding position of the structure of the general formula (B1) is at the meta position of the benzene ring with respect to two NH groups bonded to the triazine ring (hereinafter, the triazine compound having this structure is referred to as “m-ATDA”). Sometimes.). As shown in the examples, it has been revealed that this structure has a significantly improved transmittance in the ultraviolet-visible region as compared with the structure in the para position with respect to the NH group.
- the polyimide precursor (polyamic acid) has the following general formula (I):
- A is a tetravalent aromatic group or aliphatic group
- B is a divalent aromatic group.
- the group A is a residue obtained by removing four COOH groups from a tetracarboxylic acid (ie, a residue obtained by removing two carboxylic anhydride groups (CO) 2 O from a tetracarboxylic dianhydride), and the group B Is a residue obtained by removing two NH 2 groups from a diamine.
- the polyimide obtained from the polyimide precursor has the following general formula (II):
- A is a tetravalent aromatic group or aliphatic group
- B is a divalent aromatic group.
- the group A is a residue obtained by removing four COOH groups from a tetracarboxylic acid (ie, a residue obtained by removing two carboxylic anhydride groups (CO) 2 O from a tetracarboxylic dianhydride), and the group B Is a residue obtained by removing two NH 2 groups from a diamine.
- tetracarboxylic acid and its dianhydride used for the reaction for polyimide production are referred to as a tetracarboxylic acid component
- diamines are referred to as a diamine component.
- the groups A and B in the general formula (I) and the general formula (II) are derived from the tetracarboxylic acid component and the diamine component, respectively, and are included in the polyimide structure.
- polyimide precursor and polyimide of the present invention are represented by the following formula (B1) as the group B in the general formula (I) and the general formula (II):
- R 1 represents a hydrogen atom or an alkyl group or aryl group having 1 to 12 carbon atoms
- R 2 represents a hydrogen atom or an alkyl group or aryl group having 1 to 12 carbon atoms.
- the triazine partial structure represented by these is included.
- the ratio of the group represented by the formula (B1) in the polyimide precursor and the group B contained in the polyimide is more than 0 and up to 100 mol%, preferably 5 to 100 mol%, more preferably 10 to 100 mol. %.
- the structure of formula (B1) is derived from 2,4-bis (3-aminoanilino) -6-substituted amino-1,3,5-triazine, which is used as the diamine component, in the polyimide precursor and polyimide be introduced. Details of the structure of the formula (B1) are clear from the description of the diamine component described later.
- the polyimide precursor of the present invention is preferably in the form of a solution from the viewpoint of handling.
- the polyimide of this invention can be in desired forms, such as a film, a powder, and a solution, hereafter, manufacture of a polyimide film is demonstrated to an example.
- the polyimide film is obtained by thermal imidization and / or chemical imidization, and when it contains a plurality of tetracarboxylic acid components and diamine components, it may be randomly copolymerized or block copolymerized. These may be used in combination.
- the thickness of the polyimide film is not particularly limited, but is 5 to 120 ⁇ m, preferably 6 to 75 ⁇ m, and more preferably 7 to 60 ⁇ m.
- a cyclization catalyst and a dehydrating agent are added to the polyamic acid solution, and the polyamic acid solution composition added by selecting inorganic fine particles and the like as necessary is cast on a support in a film form.
- the heating temperature is preferably 300 ° C. or higher, 350 ° C. or higher, and more preferably 450 ° C. or higher. Thereby, the peel strength after heat treatment is excellent.
- the heating when heating at the maximum heating temperature, the heating may be performed on the support or may be peeled off from the support.
- the polyimide film is preferably produced from a polyimide precursor (polyamic acid).
- the tetracarboxylic dianhydride constituting the tetracarboxylic acid component can be aromatic or aliphatic.
- aromatic tetracarboxylic dianhydride examples include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (s-BPDA), pyromellitic dianhydride (PMDA), 2 , 3,3 ′, 4′-biphenyltetracarboxylic dianhydride (a-BPDA), oxydiphthalic dianhydride, diphenylsulfone-3,4,3 ′, 4′-tetracarboxylic dianhydride, bis ( 3,4-dicarboxyphenyl) sulfide dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA), 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, bis (3
- the tetracarboxylic acid component preferably contains at least an acid dianhydride selected from s-BPDA, PMDA and 6FDA. Of these, PMDA is preferred. By using PMDA, the heat resistance of the polyimide film is increased. Further, there is a large difference between the transmittance of the polyimide film in the UV-visible region when m-ATDA is used as the diamine component and the transmittance in the UV-visible region when p-ATDA is used. In this embodiment, PMDA is preferably contained in an amount of 50 mol% or more, more preferably 70 mol% or more, and particularly preferably 75 mol% or more in 100 mol% of the tetracarboxylic acid component.
- 6FDA is also preferable to use 6FDA as the tetracarboxylic acid component.
- 6FDA is used, the solubility of the polyimide film in the organic solvent when m-ATDA is used as the diamine component is higher than that of p-ATDA.
- 6 FDA is preferably contained in an amount of 50 mol% or more, more preferably 70 mol% or more, and particularly preferably 75 mol% or more in 100 mol% of the tetracarboxylic acid component.
- s-BPDA is preferably contained in an amount of 50 mol% or more, more preferably 70 mol% or more, particularly preferably 75 mol% or more in 100 mol% of the tetracarboxylic acid component.
- a polyimide film obtained using a tetracarboxylic acid component containing s-BPDA in such a ratio is excellent in mechanical properties and the like.
- an alicyclic tetracarboxylic dianhydride can be suitably used.
- this aliphatic tetracarboxylic dianhydride and ATDA m-ATDA, p-ATDA
- the transmittance in the UV-visible region is remarkably improved.
- Specific examples of the alicyclic tetracarboxylic dianhydride include the following and their derivatives.
- alicyclic tetracarboxylic dianhydrides can be used alone or in combination of two or more.
- the aliphatic tetracarboxylic dianhydride is preferably at least one of CHDA and CBDA.
- Examples of the group A in the general formula (I) and the general formula (II), and preferred structures are the same as the tetravalent residue obtained by removing the carboxylic acid anhydride group (CO) 2 O from the tetracarboxylic dianhydride.
- the proportion corresponds to the description of the tetracarboxylic acid component above.
- the diamine component includes a diamine compound represented by the general formula (B2).
- R 1 represents a hydrogen atom or an alkyl group or aryl group having 1 to 12 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms)
- R 2 represents a hydrogen atom or an alkyl group or an aryl group having 1 to 12 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms)
- R 1 and R 2 may be different from each other; It may be the same.
- alkyl group or aryl group having 1 to 12 carbon atoms of R 1 and R 2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, phenyl, benzyl, naphthyl, methylphenyl, and biphenyl.
- the aminoanilino group connected to the two NH groups bonded to the triazine ring is 3-aminoanilino (meta position).
- the transmittance (transparency) in the ultraviolet-visible region of the polyimide obtained is significantly improved as compared with the compound having 4-aminoanilino (para position).
- diamine compound represented by the general formula (1) examples include 2,4-bis (3-aminoanilino) -6-anilino-1,3,5-triazine and 2,4-bis (3-aminoanilino).
- -6-Benzylamino-1,3,5-triazine 2,4-bis (3-aminoanilino) -6-naphthylamino-1,3,5-triazine
- 2,4-bis (3-aminoanilino) -6- Dibenzylamino-1,3,5-triazine 2,4-bis (3-aminoanilino) -6-dinaphthylamino-1,3,5-triazine
- a diamine component may contain the diamine compound generally used for manufacture of a polyimide other than the diamine compound represented by general formula (B2).
- a diamine compound generally used for manufacture of a polyimide other than the diamine compound represented by general formula (B2).
- One benzene nucleus diamine such as paraphenylenediamine (1,4-diaminobenzene; PPD), 1,3-diaminobenzene, 2,4-toluenediamine, 2,5-toluenediamine, 2,6-toluenediamine, etc.
- Diaminodiphenyl ethers such as 4,4′-diaminodiphenyl ether (ODA), 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4 , 4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,3'-dimethyl-4 , 4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis (4-aminophenyl) ) Sulfide, 4,4
- the benzene core of three diamines 4) 3,3′-bis (3-aminophenoxy) biphenyl, 3,3′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [3- (3-aminophenoxy) phenyl] ether, bis [3- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, Bis [4- (4-aminophenoxy) phenyl] ether, bis [3- (3-aminophenoxy) phenyl] ketone, bis [3- (4-aminophenoxy) phenyl] ketone, bis [4- (3-amino Phenoxy) phenyl] ketone, bis [4- (4-a
- the diamine component may contain a diamine compound (p-ATDA) represented by the following general formula (C), which is a para isomer of the compound represented by the general formula (B2).
- p-ATDA diamine compound represented by the following general formula (C)
- a diamine other than the diamine compound represented by the general formula (B2) When a diamine other than the diamine compound represented by the general formula (B2) is used, a diamine compound selected from paraphenylene diamine (PPD) and diaminodiphenyl ethers is preferable, and PPD, 4,4′-diamino is more preferable.
- PPD paraphenylene diamine
- the polyimide film obtained by this is excellent in mechanical properties and the like.
- group B in the general formula I preferred structures correspond to divalent residues obtained by removing NH 2 from the above diamines, and the proportions correspond to those described above for the diamine component.
- the polyimide of the present invention is excellent in that it does not contain at least one proton conductive functional group selected from the group consisting of —SO 3 H, —COOH and —PO 3 H 2 as shown in Patent Document 5. It is preferable because it has heat resistance.
- a polyimide precursor (polyamic acid) can be obtained by reacting a tetracarboxylic acid component and a diamine component by a known method. For example, a substantially equimolar amount is reacted in an organic solvent to obtain a solution of polyamic acid (uniform). As long as a simple solution state is maintained, a part of the solution may be imidized). Alternatively, it combines the two or more polyamic acid is excessive advance either component, after combining the respective polyamic acid solution may be mixed under reaction conditions.
- the polyamic acid solution thus obtained can be used for the production of a self-supporting film as it is or after removing or adding a solvent if necessary.
- a polyimide When the obtained polyimide is soluble in an organic solvent, a polyimide can be obtained by reacting a tetracarboxylic acid component and a diamine component by a known method. For example, an approximately equimolar amount can be reacted in an organic solvent to obtain a polyimide solution. Alternatively, it is acceptable to two or more polyimide is excessive advance either component, after combining each polyimide solution may be mixed under reaction conditions.
- organic solvent for the polyamic acid solution or the polyimide solution a known solvent can be used.
- NMP N-methyl-2-pyrrolidone
- DMAc N-dimethylacetamide
- N-diethylacetamide N-diethylacetamide
- the concentration of all monomers in the organic polar solvent may be appropriately selected according to the purpose of use and the purpose of production, for example, the concentration of all monomers in the organic polar solvent. Is preferably 5 to 30% by mass, more preferably 15 to 27% by mass, and particularly preferably 18 to 26% by mass.
- the polymerization reaction of the aromatic tetracarboxylic acid component and the aromatic diamine component is, for example, substantially equimolar or either component (acid component or diamine component).
- the reaction is carried out at a reaction temperature of 100 ° C. or lower, preferably 80 ° C. or lower, for about 0.2 to 60 hours to obtain a polyamic acid solution.
- the polymerization reaction of the aromatic tetracarboxylic acid component and the aromatic diamine component is, for example, substantially equimolar or either component (acid component or diamine component).
- the polyimide solution can be obtained by a known method by mixing in a slight excess.
- the reaction temperature is 140 ° C. or higher, preferably 160 ° C. or higher (preferably 250 ° C. or lower, more preferably 230 ° C. or lower) for about 1 to 60 hours.
- a polyimide solution can be obtained by reacting.
- an imidization catalyst, an organic phosphorus-containing compound, inorganic fine particles, and the like may be added to the polyamic acid solution as necessary. If it is chemical imidation, you may add a cyclization catalyst, a dehydrating agent, inorganic fine particles, etc. to a polyamic acid solution as needed. An organic phosphorus-containing compound, inorganic fine particles, and the like may be added to the polyimide solution. Further, polyimide fine particles that are insoluble in an organic solvent can be used instead of the inorganic fine particles.
- the imidization catalyst examples include a substituted or unsubstituted nitrogen-containing heterocyclic compound, an N-oxide compound of the nitrogen-containing heterocyclic compound, a substituted or unsubstituted amino acid compound, an aromatic hydrocarbon compound having a hydroxyl group, or an aromatic heterocyclic compound.
- Cyclic compounds such as 1,2-dimethylimidazole, N-methylimidazole, N-benzyl-2-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 5-methylbenzimidazole, etc.
- Benzimidazoles such as alkylimidazole and N-benzyl-2-methylimidazole, isoquinoline, 3,5-dimethylpyridine, 3,4-dimethylpyridine, 2,5-dimethylpyridine, 2,4-dimethylpyridine, 4-n- Substituted pyridines such as propylpyridine It can be used to apply.
- the amount of the imidization catalyst used is preferably about 0.01 to 2 times equivalent, particularly about 0.02 to 1 time equivalent to the amic acid unit of the polyamic acid.
- organic phosphorus-containing compounds examples include monocaproyl phosphate, monooctyl phosphate, monolauryl phosphate, monomyristyl phosphate, monocetyl phosphate, monostearyl phosphate, triethylene glycol monotridecyl Monophosphate of ether, monophosphate of tetraethylene glycol monolauryl ether, monophosphate of diethylene glycol monostearyl ether, dicaproyl phosphate, dioctyl phosphate, dicapryl phosphate, dilauryl phosphate, dimyristyl phosphate, Dicetyl phosphate, distearyl phosphate, diethylene phosphate of tetraethylene glycol mononeopentyl ether, trie Diphosphate of glycol mono tridecyl ether, diphosphate of tetraethyleneglycol monolauryl ether, and phosphoric acid esters such as diphosphate esters of diethylene glycol monostearyl
- amine ammonia, monomethylamine, monoethylamine, monopropylamine, monobutylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, monoethanolamine, diethanolamine, triethanolamine Etc.
- Cyclization catalysts include aliphatic tertiary amines such as trimethylamine and triethylenediamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as isoquinoline, pyridine, ⁇ -picoline and ⁇ -picoline. Etc.
- dehydrating agent examples include aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride, and butyric anhydride, and aromatic carboxylic acid anhydrides such as benzoic anhydride.
- Inorganic fine particles include fine particle titanium dioxide powder, silicon dioxide (silica) powder, magnesium oxide powder, aluminum oxide (alumina) powder, inorganic oxide powder such as zinc oxide powder, fine particle silicon nitride powder, and titanium nitride powder.
- Inorganic nitride powder such as silicon carbide powder, inorganic carbide powder such as silicon carbide powder, and inorganic salt powder such as particulate calcium carbonate powder, calcium sulfate powder, and barium sulfate powder.
- These inorganic fine particles may be used in combination of two or more. In order to uniformly disperse these inorganic fine particles, a means known per se can be applied.
- the self-supporting film of the polyamic acid solution should be peel-coated from the support to the extent that it becomes self-supporting by applying the polyamic acid solution onto the support (meaning the stage before the normal curing process), for example. It is manufactured by heating to the extent that it can be.
- the solid content concentration of the polyamic acid solution used in the present invention is not particularly limited as long as it is in a viscosity range suitable for production, but is usually preferably 5% by mass to 30% by mass, and 15% by mass to 27% by mass. More preferably, 18% by mass to 26% by mass is more preferable.
- the heating temperature and heating time during the production of the self-supporting film can be appropriately determined.
- the heating may be performed at a temperature of 50 to 180 ° C. for about 1 to 60 minutes.
- the support is not particularly limited as long as it can cast a polyamic acid solution, but a smooth base material is preferably used.
- a glass substrate or a metal drum or belt such as stainless steel is used.
- the self-supporting film is not particularly limited as long as the solvent is removed and / or imidized to such an extent that it can be peeled off from the support, but in thermal imidization, the loss on heating is 20 to 50 mass. %, And when the weight loss on heating is in the range of 20 to 50% by mass and the imidization ratio is in the range of 7 to 55%, the mechanical properties of the self-supporting film are sufficient.
- the loss on heating of the self-supporting film is a value obtained by the following formula from the mass W1 of the self-supporting film and the mass W2 of the film after curing.
- Heat loss (mass%) ⁇ (W1-W2) / W1 ⁇ ⁇ 100
- the imidation ratio of a partially imidized self-supporting film is determined by measuring the IR spectrum of the self-supporting film and its fully cured product (polyimide film) by the ATR method, and measuring the peak area or height of the vibration band. It can be calculated using the ratio.
- the vibration band peak a symmetric stretching vibration band of an imidecarbonyl group, a benzene ring skeleton stretching vibration band, or the like is used.
- the FT-IR spectrum of the self-supporting film and its full-cure film (polyimide film) is obtained by using a FT / IR6100 manufactured by JASCO Corporation with a Ge crystal and a multiple reflection ATR method with an incident angle of 45 °.
- Imidation rate (%) ⁇ (X1 / X2) / (Y1 / Y2) ⁇ ⁇ 100 (1)
- X1 peak height of 1775 cm ⁇ 1 of the self-supporting film
- X2 peak height of 1515 cm ⁇ 1 of the self-supporting film
- Y1 peak height of 1775 cm ⁇ 1 of the full cure film
- Y2 The peak height of 1515 cm ⁇ 1 of the full cure film.
- ⁇ Heat treatment (imidization) step> the self-supporting film is heat-treated to obtain a polyimide film.
- heating is performed so that the maximum heating temperature is preferably 300 ° C. or higher, 350 ° C. or higher, more preferably 450 ° C. or higher, and further preferably 470 ° C. or higher.
- the upper limit of the heating temperature may be a temperature at which the characteristics of the polyimide film do not deteriorate, and is preferably 600 ° C. or lower, more preferably 550 ° C. or lower, further preferably 530 ° C. or lower, and particularly preferably 520 ° C. or lower.
- the imidization of the polymer and the evaporation / removal of the solvent are first carried out gradually at a temperature of about 100 ° C. to less than 350 ° C. for about 0.05 to 5 hours, particularly 0.1 to 3 hours.
- the heat treatment is performed stepwise at a relatively low temperature of about 100 ° C. to about 170 ° C. for about 0.5-30 minutes, and then at a temperature above 170 ° C. and below 220 ° C.
- the secondary heat treatment is preferably performed for 0.5 to 30 minutes, and then the third heat treatment is performed at a high temperature exceeding 220 ° C. and less than 350 ° C. for about 0.5 to 30 minutes.
- it is preferable to perform the fourth high-temperature heat treatment at a high temperature of 350 ° C. to 600 ° C. Also, this heating process can be performed sequentially or continuously.
- the heat treatment (imidization) of the self-supporting film may be performed on the support, or may be performed by peeling off from the support.
- the self-supporting film is peeled off from the support, and in a curing furnace, at least in the direction perpendicular to the longitudinal direction of the long self-supporting film with a pin tenter, clip, frame, etc. That is, both end edges in the width direction of the film are fixed, and heat treatment can be performed by expanding and contracting in the width direction or the length direction as necessary.
- the polyimide film of the present invention obtained as described above may be further subjected to sandblasting, corona treatment, plasma treatment, etching treatment and the like.
- the polyimide film of this invention is excellent in adhesiveness with materials, such as base materials, such as metal foil, and an adhesive agent. For this reason, it can be set as the polyimide laminated body by which the polyimide film of this invention and the adhesive bond layer were laminated
- a method for producing a polyimide metal laminate (1) a method of laminating a polyimide film and a substrate (for example, metal foil) by pressurization or heating and pressurization directly or via an adhesive, (2) polyimide A method of directly forming a metal layer on a film by a wet method (plating) or a dry method (metallizing such as vacuum deposition or sputtering), (3) a polyamic acid solution or a polyimide solution as described above on a substrate such as a metal foil
- coating and drying and imidating (when it is a polyimide solution), etc. are mentioned.
- the polyimide film and polyimide metal laminate of the present invention (including both laminates in which a film and a metal layer are laminated via an adhesive layer, and laminates in which a metal layer is directly formed on the film)
- polyimide laminates are printed wiring boards, flexible printed circuit boards, TAB tapes, COF tapes or metal wiring, and cover substrates such as metal wiring and chip members such as IC chips, liquid crystal displays, and organic electroluminescence displays. It can be used as a material for electronic parts such as base substrates such as electronic paper and solar cells and electronic devices.
- the polyimide film of the present invention is excellent in adhesiveness with metal and has improved transmittance in the ultraviolet-visible region. Therefore, it can be suitably used as a plastic substrate for substituting glass substrates for display devices such as liquid crystal displays, EL displays, and electronic paper.
- a polyimide precursor can be obtained from alicyclic tetracarboxylic dianhydride and ATDA.
- a polyimide and a polyimide film can be obtained from the polyimide precursor.
- This polyimide film is excellent in adhesion to a substrate such as a metal foil and a material such as an adhesive. Further, this polyimide film has improved transmittance (transparency) in the ultraviolet-visible region.
- the alicyclic tetracarboxylic dianhydride and ATDA are the same as those described in the above ⁇ Tetracarboxylic acid component, diamine component>.
- the method for obtaining a polyimide precursor using alicyclic tetracarboxylic dianhydride and ATDA is the same as the above ⁇ Preparation of polyimide precursor>.
- the method of obtaining a polyimide and a polyimide film using the polyimide precursor is the same as the above ⁇ Manufacture of self-supporting film of polyamic acid solution> and ⁇ Heat treatment (imidization) step>.
- the method for obtaining a polyimide laminate and a polyimide metal laminate using the polyimide film and the uses of the polyimide laminate and the polyimide metal laminate are the same as the above ⁇ Polyimide laminate and polyimide metal laminate>.
- X is a halogen atom, preferably Cl, Br or I.
- R 1 and R 2 are as defined for general formula (B2), R 1 represents a hydrogen atom or an alkyl or aryl group having 1 to 12 carbon atoms, and R 2 represents a hydrogen atom or 1 carbon atom. To 12 alkyl groups or aryl groups, and the preferred range is also as shown for general formula (B2). Specific examples of R 1 and R 2 are groups possessed by the specific examples of the general formula (B2).
- the above two reactions are generally preferably carried out in a solvent in the presence of a base.
- the base used is not particularly limited, and a general inorganic base is used. Examples thereof include sodium carbonate.
- the solvent to be used is not particularly limited, and for example, ether solvents such as dioxane, tetrahydrofuran and diethyl ether; hydrocarbon solvents such as toluene and benzene; N, N-dimethylformamide, N, N-dimethylacetamide, N A common solvent such as an amide solvent such as methyl-2-pyrrolidone can be used.
- the reduction reaction a known method can be adopted, but as shown in the above scheme, it can be carried out, for example, by hydrogenation in a solvent in the presence of a suitable catalyst while heating appropriately.
- a known catalyst such as palladium on carbon can be used.
- the method for producing 2,4-bis (3-aminoanilino) -6-substituted amino-1,3,5-triazine of the present invention is a novel method.
- the details of the reaction will be described with reference to the examples. However, those skilled in the art can change the solvent, the charged amount, the reaction conditions, and the like, and can perform post-treatment, purification, and the like according to conventional methods. .
- the present inventors reacted 2,4-bis (4-aminoanilino) to 6-substituted amino-1,3,5-triazine-2,4-dihalide (B3) by reacting with excess paraphenylenediamine. It was confirmed that -6-substituted amino-1,3,5-triazine (p-ATDA) can be obtained. Therefore, by reacting 6-substituted amino-1,3,5-triazine-2,4-dihalide (B3) with excess metaphenylenediamine, 2,4-bis (3-aminoanilino) -6-substituted Attempts were made to obtain amino-1,3,5-triazine (m-ATDA). However, m-ATDA could not be obtained.
- 2,4-bis (3-aminoanilino) -6-substituted amino-1,3,5-triazine (B2) can be efficiently obtained in high yield.
- a solution of aniline (19.03 g, 0.2 mol) dissolved in THF (70 mL) was slowly added dropwise to the three-necked flask.
- 1,4-dioxane 100 mL
- sodium carbonate 8.90 g, 0.08 mol
- p-phenylenediamine 34.62 g, 0.32 mol
- the reaction mixture was washed in a beaker (3 L) four times with hot water and once with water until the washing water became clear.
- the solid content was added to acetone and dissolved by stirring at reflux temperature for 30 minutes, and the insoluble content was filtered.
- Acetone was distilled off from the filtrate with an evaporator to obtain a crude product.
- the crude product was recrystallized from 1,4-dioxane / hexane.
- activated carbon was added and refluxed for about 1 hour before the hot filtration, and the activated carbon treatment was performed. Thereafter, the crystals obtained by hot filtration were dried under reduced pressure at 190 ° C. for 6 hours. A light brown powder was obtained.
- polyamic acid solution B (Preparation of polyamic acid solution B) s-BPDA / m-ATDA
- the polyamic acid solution B was prepared in the same manner as the preparation of the polyamic acid solution A except that the diamine was 2,4-bis (3-aminoanilino) -6-anilino-1,3,5-triazine (m-ATDA). Prepared.
- the logarithmic viscosity ( ⁇ inh ) of this polyamic acid was 1.20 dL / g.
- polyamic acid solution E 6FDA / p-ATDA
- a polyamic acid solution E was prepared in the same manner as the preparation of the polyamic acid solution A, except that the acid dianhydride was 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA).
- the logarithmic viscosity ( ⁇ inh ) of this polyamic acid was 0.54 dL / g.
- polyamic acid solution F 6FDA / m-ATDA
- the acid dianhydride is 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and the diamine is 2,4-bis (3-aminoanilino) -6-anilino-1,3,5-triazine (m
- m A polyamic acid solution F was prepared in the same manner as in the preparation of the polyamic acid solution A except that -ATDA).
- the logarithmic viscosity ( ⁇ inh ) of this polyamic acid was 0.57 dL / g.
- polyamic acid solution I s-BPDA / ODA
- a polyamic acid solution I was prepared in the same manner as the preparation of the polyamic acid solution A, except that the diamine was 4,4′-diaminodiphenyl ether (ODA).
- ODA 4,4′-diaminodiphenyl ether
- the logarithmic viscosity ( ⁇ inh ) of this polyamic acid was 1.84 dL / g.
- DSDA / m-ATDA Acid dianhydride is 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride (DSDA), and diamine is 2,4-bis (3-aminoanilino) -6-anilino-1,3,5-
- DSDA 4,4′-diphenylsulfonetetracarboxylic dianhydride
- diamine 2,4-bis (3-aminoanilino) -6-anilino-1,3,5-
- m-ATDA triazine
- polyamic acid solution Q CHDA / m-ATDA
- the acid dianhydride is 1,2,4,5-cyclohexanetetracarboxylic dianhydride (CHDA)
- the diamine is 2,4-bis (3-aminoanilino) -6-anilino-1,3,5-triazine (m
- a polyamic acid solution Q was prepared in the same manner as in the preparation of the polyamic acid solution A except that -ATDA).
- the logarithmic viscosity ( ⁇ inh ) of this polyamic acid was 0.46 dL / g.
- polyamic acid solution R (Preparation of polyamic acid solution R) DSDA / p-ATDA A polyamic acid solution R was prepared in the same manner as the preparation of the polyamic acid solution A except that the acid dianhydride was changed to 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride (DSDA). The logarithmic viscosity ( ⁇ inh ) of this polyamic acid was 0.78 dL / g.
- polyamic acid solution S (Preparation of polyamic acid solution S) ODPA / p-ATDA A polyamic acid solution S was prepared in the same manner as the polyamic acid solution A except that the acid dianhydride was changed to 4,4′-oxydiphthalic anhydride (ODPA). The logarithmic viscosity ( ⁇ inh ) of this polyamic acid was 0.84 dL / g.
- polyamic acid solution T (Preparation of polyamic acid solution T) BTDA / p-ATDA A polyamic acid solution T was prepared in the same manner as the preparation of the polyamic acid solution A, except that the acid dianhydride was 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA). The logarithmic viscosity ( ⁇ inh ) of this polyamic acid was 0.64 dL / g.
- polyamic acid solution U CHDA / p-ATDA
- a polyamic acid solution U was prepared in the same manner as the polyamic acid solution A except that the acid dianhydride was 1,2,4,5-cyclohexanetetracarboxylic dianhydride (CHDA).
- the logarithmic viscosity ( ⁇ inh ) of this polyamic acid was 0.50 dL / g.
- polyimide V was obtained by drying the obtained solid under reduced pressure at room temperature.
- the logarithmic viscosity ( ⁇ inh ) of polyimide V was 0.64 dL / g.
- the polyimide solution V was obtained by re-dissolving the polyimide V in NMP.
- Example 1 Preparation of Polyimide Film B s-BPDA / m-ATDA Except that the polyamic acid solution B was used instead of the polyamic acid solution A, a polyimide film B having a thickness of 14 ⁇ m was obtained after drying in the same manner as the preparation of the polyimide film A.
- the refractive index (n D ) of this polyimide film B was 1.739.
- Table 1 shows the solubility of the obtained polyimide in an organic solvent, and Table 2 shows the optical properties.
- Example 2 Preparation of polyimide film D PMDA / m-ATDA A polyimide film D having a thickness of 17 ⁇ m was obtained after drying in the same manner as the preparation of the polyimide film A except that the polyamic acid solution D was used instead of the polyamic acid solution A.
- the refractive index (n D ) of this polyimide film D was 1.759.
- Table 1 and Table 2 Each physical property value is shown in Table 1 and Table 2.
- Example 3 Preparation of polyimide film F 6FDA / m-ATDA A polyimide film F having a thickness of 16 ⁇ m was obtained after drying in the same manner as the preparation of the polyimide film A except that the polyamic acid solution F was used instead of the polyamic acid solution A.
- the refractive index (n D ) of this polyimide film F was 1.728.
- Table 1 and Table 2 Each physical property value is shown in Table 1 and Table 2.
- Example 4 Preparation of polyimide film H CBDA / m-ATDA Except for using the polyamic acid solution H instead of the polyamic acid solution A, a polyimide film H having a thickness of 11 ⁇ m was obtained after drying in the same manner as the preparation of the polyimide film A.
- the refractive index (n D ) of this polyimide film H was 1.729.
- Each physical property value is shown in Table 1 and Table 2.
- Example 5 Evaluation of glass transition temperature (Example 5) Preparation of polyimide film J s-BPDA / m-ATDA A polyimide film J was obtained by the same method as in Example 1 except that the thickness of the polyimide film was changed to 40 ⁇ m.
- the glass transition temperature (DSC) of the polyimide film J was 261 ° C.
- Example 6 Preparation of polyimide film K PMDA / m-ATDA A polyimide film K was obtained in the same manner as in Example 2 except that the thickness of the polyimide film was changed to 40 ⁇ m.
- the glass transition temperature (DSC) of the polyimide film K was 291 ° C.
- Example 7 Preparation of polyimide film L 6FDA / m-ATDA A polyimide film L was obtained by the same method as in Example 3 except that the thickness of the polyimide film was changed to 40 ⁇ m.
- the glass transition temperature (DSC) of the polyimide film L was 256 ° C.
- Example 8 Preparation of polyimide film M CBDA / m-ATDA A polyimide film M was obtained in the same manner as in Example 4 except that the thickness of the polyimide film was changed to 23 ⁇ m.
- the glass transition temperature (DSC) of the polyimide film M was 288 ° C. Further, when the linear expansion coefficient was measured after annealing at 300 ° C., the linear expansion coefficient from 50 to 200 ° C. was as low as 14.1 ppm / K.
- Example 9 s-BPDA / m-ATDA A polyimide metal laminate was prepared using the polyamic acid solution B.
- the polyamic acid solution B was applied to a rolled copper foil (manufactured by JX Nippon Mining & Metals, BHY-13H-T, 18 ⁇ m thickness), heated at 120 ° C. for 10 minutes, and further heated to 400 ° C. for 20 minutes. Obtained by heating over a period of minutes.
- the thickness of the polyimide film of the polyimide metal laminate was 24 ⁇ m.
- the peel strength of the polyimide metal laminate is 0.45 kN / m or more.
- Example 10 s-BPDA / m-ATDA
- a polyimide metal laminate was prepared using the polyamic acid solution B.
- the polyamic acid solution B was applied to a rolled copper foil (manufactured by JX Nippon Mining & Metals, BHY-13H-T, 18 ⁇ m thickness), heated at 120 ° C. for 10 minutes, and further heated to 400 ° C. for 20 minutes. Obtained by heating over a period of minutes.
- the thickness of the polyimide film of the polyimide metal laminate was 47 ⁇ m.
- the adhesion was good and the film was broken at 1.35 kN / m. Therefore, the peel strength of the polyimide metal laminate is estimated to be 1.35 kN / m or more.
- s-BPDA / PPD Obtained by using 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (s-BPDA) as the aromatic tetracarboxylic dianhydride and paraphenylenediamine (PPD) as the diamine component.
- a polyimide metal laminate was prepared using the polyamic acid solution.
- a polyamic acid solution is applied to a rolled copper foil (JX Nippon Mining & Metals, BHY-13H-T, 18 ⁇ m thickness), heated at 120 ° C. for 10 minutes, and further to 400 ° C. for 20 minutes. It was obtained by heating up over time.
- the thickness of the polyimide film of the polyimide metal laminate was 22 ⁇ m.
- the peel strength was 0.1 kN / m or less.
- Example 11 Preparation of polyimide film N DSDA / m-ATDA A polyimide film N having a thickness of 21 ⁇ m was obtained after drying in the same manner as the preparation of the polyimide film A except that the polyamic acid solution N was used instead of the polyamic acid solution A.
- the refractive index (n D ) of this polyimide film N was 1.724.
- Each physical property value is shown in Table 3 and Table 4.
- the glass transition temperature (DSC) of the polyimide film N was 249 degreeC.
- Example 12 Preparation of polyimide film O ODPA / m-ATDA A polyimide film O having a thickness of 18 ⁇ m was obtained after drying in the same manner as the preparation of the polyimide film A except that the polyamic acid solution O was used instead of the polyamic acid solution A.
- the refractive index (n D ) of this polyimide film O was 1.732.
- Each physical property value is shown in Table 3 and Table 4.
- the glass transition temperature (DSC) of the polyimide film O was 253 degreeC.
- Example 13 Preparation of polyimide film P BTDA / m-ATDA Except that the polyamic acid solution P was used instead of the polyamic acid solution A, a polyimide film P having a thickness of 17 ⁇ m was obtained after drying in the same manner as the preparation of the polyimide film A.
- the refractive index (n D ) of this polyimide film P was 1.730.
- Each physical property value is shown in Table 3 and Table 4.
- the glass transition temperature (DSC) of the polyimide film P was 248 degreeC.
- Example 14 Preparation of polyimide film Q CHDA / m-ATDA A polyimide film Q having a thickness of 21 ⁇ m was obtained after drying in the same manner as the preparation of the polyimide film A except that the polyamic acid solution Q was used instead of the polyamic acid solution A.
- Each physical property value is shown in Table 3 and Table 4. In the solubility test of the polyimide film Q, the polyimide film Q was dissolved in NMP at room temperature, and further 15% by mass or more was dissolved.
- Example 15 Preparation of polyimide film from polyimide solution and evaluation of solubility in organic solvent
- Example 15 Preparation of polyimide film V 6FDA / m-ATDA
- the polyimide solution V was cast into a thin film on a glass plate and degassed under reduced pressure. Thereafter, it was heated in a vacuum oven at 60 ° C. for 6 hours, at 100 ° C. for 1 hour, at 200 ° C. for 1 hour, and further at 300 ° C. for 1 hour to obtain a polyimide film V having a thickness of 40 ⁇ m.
- the glass transition temperature (DSC) of the polyimide film V was 250 ° C.
- Table 5 shows the solubility of polyimide V in organic solvents.
- polyimide V was dissolved in NMP at room temperature, and further 20 wt% or more was dissolved.
- Example 16 Preparation of polyimide film W DSDA / m-ATDA A polyimide film W was obtained in the same manner as the preparation of the polyimide film V except that the polyimide solution W was used instead of the polyimide solution V.
- the glass transition temperature (DSC) of the polyimide film W was 244 ° C.
- Table 5 shows the solubility of polyimide W in organic solvents.
- Example 17 Preparation of polyimide film X ODPA / m-ATDA A polyimide film X was obtained in the same manner as the preparation of the polyimide film V except that the polyimide solution X was used instead of the polyimide solution V.
- the glass transition temperature (DSC) of the polyimide film X was 253 ° C.
- Table 5 shows the solubility of polyimide X in organic solvents.
- Example 18 PMDA / m-ATDA
- a polyimide metal laminate was prepared using the polyamic acid solution D.
- the polyamic acid solution D was applied to a rolled copper foil (JX Nippon Mining & Metals Co., Ltd., BHY-13H-T, 18 ⁇ m thickness), heated at 120 ° C. for 10 minutes, and further up to 400 ° C. for 20 minutes. Obtained by heating over a period of minutes.
- the thickness of the polyimide film of the polyimide metal laminate was 40 ⁇ m.
- the peel strength of the polyimide metal laminate is estimated to be 0.68 kN / m or more.
- Example 19 6FDA / m-ATDA A polyimide metal laminate was prepared in the same manner as in Example 18 except that the polyamic acid solution F was used instead of the polyamic acid solution D, and a peel test was performed. As a result, the adhesion was good and the film was broken at 0.54 kN / m. Therefore, it is estimated that the peeling strength of the polyimide metal laminate is 0.54 kN / m or more.
- Example 20 DSDA / m-ATDA A polyimide metal laminate was produced in the same manner as in Example 18 except that the polyamic acid solution N was used instead of the polyamic acid solution D, and a peel test was performed. As a result, the adhesion was good and the film was broken at 0.42 kN / m. Therefore, it is estimated that the peel strength of the polyimide metal laminate is 0.42 kN / m or more.
- Example 21 ODPA / m-ATDA A polyimide metal laminate was produced in the same manner as in Example 18 except that the polyamic acid solution O was used instead of the polyamic acid solution D, and a peel test was performed. As a result, the adhesion was good and the film was broken at 1.35 kN / m. Therefore, the peel strength of the polyimide metal laminate is estimated to be 1.35 kN / m or more.
- Example 22 BTDA / m-ATDA A polyimide metal laminate was produced in the same manner as in Example 18 except that the polyamic acid solution P was used instead of the polyamic acid solution D, and a peel test was performed. As a result, the adhesion was good and the film was broken at 1.29 kN / m. Therefore, it is estimated that the peel strength of the polyimide metal laminate is 1.29 kN / m or more.
- Example 23 PMDA / m-ATDA
- a two-layer polyimide laminate was prepared using the polyamic acid solution D.
- a two-layer polyimide laminate was prepared in the same manner as in Example 18 except that the polyamic acid solution D was applied to a polyimide film (Ube Industries, Upilex 75S, 75 ⁇ m thickness), and a peel test was performed. As a result, the adhesion was good and the film was broken at 0.62 kN / m. Accordingly, the peel strength of the two-layer polyimide laminate is estimated to be 0.62 kN / m or more.
- Example 24 6FDA / m-ATDA
- a two-layer polyimide laminate was produced using the polyamic acid solution F.
- a two-layer polyimide laminate was produced in the same manner as in Example 18 except that the polyamic acid solution F was applied to a polyimide film (Ube Industries, Upilex 75S, 75 ⁇ m thickness), and a peel test was performed. As a result, the adhesion was good and the film was broken at 0.55 kN / m. Therefore, it is estimated that the peel strength of the two-layer polyimide laminate is 0.55 kN / m or more.
- Example 25 DSDA / m-ATDA A two-layer polyimide laminate was produced using the polyamic acid solution N.
- a two-layer polyimide laminate was prepared in the same manner as in Example 18 except that the polyamic acid solution N was applied to a polyimide film (Ube Industries, Upilex 75S, 75 ⁇ m thickness), and a peel test was performed. As a result, the adhesion was good and the film was broken at 0.37 kN / m. Therefore, the peel strength of the two-layer polyimide laminate is estimated to be 0.37 kN / m or more.
- Example 26 ODPA / m-ATDA
- a two-layer polyimide laminate was produced using the polyamic acid solution O.
- a two-layer polyimide laminate was prepared in the same manner as in Example 18 except that the polyamic acid solution O was applied to a polyimide film (Ube Industries, Upilex 75S, 75 ⁇ m thickness), and a peel test was performed. As a result, the adhesion was good and the film was broken at 0.28 kN / m. Therefore, the peel strength of the two-layer polyimide laminate is estimated to be 0.28 kN / m or more.
- s-BPDA / PPD Obtained using 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (s-BPDA) as the aromatic tetracarboxylic dianhydride and paraphenylenediamine (PPD) as the diamine component.
- a two-layer polyimide laminate was prepared using the polyamic acid solution.
- a two-layer polyimide laminate was prepared in the same manner as in Example 18 except that this polyamic acid solution was applied to a polyimide film (Ube Industries, Upilex 75S, 75 ⁇ m thickness), and a peel test was performed. As a result, the peel strength was 0.02 kN / m or less.
- the transmittance of the polyimide film shown in Table 2 and Table 4 is shown in FIG. 1, FIG. 2, and FIG. As is clear from Tables 2 and 4, FIG. 1, FIG. 2 and FIG. 3, the polyimide film using m-ATDA of the present invention has higher transmittance than the polyimide film produced using p-ATDA.
- the polyimide film of the present invention has a high peel strength.
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Abstract
Description
で表されるトリアジン部分構造を含むこと
を特徴とするポリイミド前駆体。
前記一般式(I)中の基Bとして、前記式(B1)(式中、R1は水素原子または炭素数1~12のアルキル基またはアリール基を示し、R2は水素原子または炭素数1~12のアルキル基またはアリール基を示す。)
で表されるトリアジン部分構造を含み、前記一般式(I)中の基Aとして、2,2-ビス(3,4-ジカルボキシフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン二無水物から、2つのカルボン酸無水物基を除いた4価の残基を含むことを特徴とするポリイミド前駆体。
前記一般式(I)中の基Bとして、前記式(B1)(式中、R1は水素原子または炭素数1~12のアルキル基またはアリール基を示し、R2は水素原子または炭素数1~12のアルキル基またはアリール基を示す。)
で表されるトリアジン部分構造を含むことを特徴とするポリイミド前駆体。
下記一般式(II):
得られた2,4-ビス-(3-ニトロアニリノ)-6-置換アミノ-1,3,5-トリアジンを、還元すること
を特徴とする一般式(B2)で表される2,4-ビス(3-アミノアニリノ)-6-置換アミノ-1,3,5-トリアジンの製造方法。
で表される構造単位を有する。基Aは、テトラカルボン酸から4つのCOOH基を除いた残基(即ち、テトラカルボン酸二無水物から2つのカルボン酸無水物基(CO)2Oを除いた残基)であり、基Bはジアミンから2つのNH2基を除いた残基である。
で表される構造単位を有する。基Aは、テトラカルボン酸から4つのCOOH基を除いた残基(即ち、テトラカルボン酸二無水物から2つのカルボン酸無水物基(CO)2Oを除いた残基)であり、基Bはジアミンから2つのNH2基を除いた残基である。以下、ポリイミド製造の反応に使用されるテトラカルボン酸およびその二無水物をテトラカルボン酸成分、ジアミン類をジアミン成分という。一般式(I)および一般式(II)中の基Aおよび基Bは、それぞれテトラカルボン酸成分、ジアミン成分に由来して、ポリイミド構造中に含まれるものである。
で表されるトリアジン部分構造を含む。ポリイミド前駆体およびポリイミドに含まれる基Bの中で、式(B1)で表される基の割合は、0を超え100モル%まで、好ましくは5~100モル%、さらに好ましくは10~100モル%である。
(1)ポリアミック酸溶液、またはポリアミック酸溶液に必要に応じてイミド化触媒、脱水剤、離型助剤、無機微粒子などを選択して加えたポリアミック酸溶液組成物をフィルム状に支持体上に流延し、加熱乾燥して自己支持性フィルムを得た後、加熱により脱水環化、脱溶媒することによりポリイミドフィルムを得る方法;
(2)ポリアミック酸溶液に環化触媒および脱水剤を加え、さらに必要に応じて無機微粒子などを選択して加えたポリアミック酸溶液組成物をフィルム状に支持体上に流延し、化学的に脱水環化させて、必要に応じて加熱乾燥して自己支持性フィルムを得た後、これを加熱により脱溶媒、イミド化することによりポリイミドフィルムを得る方法;
(3)ポリイミドが有機溶媒に可溶の場合、離型助剤、無機微粒子などを選択して加えたポリイミド溶液組成物をフィルム状に支持体上に流延し、加熱乾燥などにより一部または全部の溶媒を除去した後、最高加熱温度に加熱することによりポリイミドフィルムを得る方法;
(4)ポリイミドが有機溶媒に可溶の場合、離型助剤、無機微粒子などを選択して加えたポリイミド溶液組成物をフィルム状に支持体上に流延し、加熱により溶媒を除去しながら最高加熱温度に加熱することによりポリイミドフィルムを得る方法、
が挙げられる。
テトラカルボン酸成分を構成するテトラカルボン酸二無水物は、芳香族系または脂肪族系のものが使用できる。
(1S,2R,4S,5R)-シクロヘキサンテトラカルボン酸二無水物、
(シス、シス、シス-1,2,4,5-シクロヘキサンテトラカルボン酸二無水物)、
(1S,2S,4R,5R)-シクロヘキサンテトラカルボン酸二無水物、
(1R,2S,4S,5R)-シクロヘキサンテトラカルボン酸二無水物
などのシクロヘキサンテトラカルボン酸二無水物(以下「CHDA」という場合がある)、
ビシクロ[2.2.2]オクタン-2,3,5,6-テトラカルボン酸二無水物、
ビシクロ[2.2.2]オクト-7-エン-2,3,5,6-テトラカルボン酸二無水物、
4-(2,5-ジオキソテトラヒドロフラン-3-イル)-テトラリン-1,2-ジカルボン酸無水物、
テトラヒドロフラン-2,3,4,5-テトラカルボン酸二無水物、
ビシクロ-3,3’,4,4’-テトラカルボン酸二無水物、
1,2,3,4-シクロペンタンテトラカルボン酸二無水物、
1,2,3,4-シクロブタンテトラカルボン酸二無水物(以下「CBDA」ということがある)、
1,3-ジメチル-1,2,3,4-シクロブタンテトラカルボン酸二無水物、
1,4-ジメチル-1,2,3,4-シクロブタンテトラカルボン酸二無水物、
1,2,3,4-シクロヘキサンテトラカルボン酸二無水物、
ペンタシクロ[8.2.1.14,7.02,9.03,8]テトラデカン-5,6,11,12-テトラカルボン酸二無水物、
5-(2,5-ジオキソテトラヒドロフリル)-3-メチル-3-シクロヘキセン-1,2-ジカルボン酸無水物、
シクロヘキサ-1-エン-2,3,5,6-テトラカルボン酸二無水物、
ビシクロ[2.2.1]ヘプタン-2,3,5,6-テトラカルボン酸二無水物。
これらの脂環式テトラカルボン酸二無水物等は、単独で又は2種以上を併用することができる。脂肪族系のテトラカルボン酸二無水物としては、CHDAおよびCBDAのうちの少なくとも1種であることが好ましい。
R2は水素原子または炭素数1~12(好ましくは炭素数1~10、さらに好ましくは炭素数1~6)のアルキル基またはアリール基を示し、R1とR2は異なっていても良く、同じであっても良い。
1)パラフェニレンジアミン(1,4-ジアミノベンゼン;PPD)、1,3-ジアミノベンゼン、2,4-トルエンジアミン、2,5-トルエンジアミン、2,6-トルエンジアミンなどのベンゼン核1つのジアミン、
2)4,4’-ジアミノジフェニルエーテル(ODA)、3,3’-ジアミノジフェニルエーテル、3,4’-ジアミノジフェニルエーテルなどのジアミノジフェニルエーテル類、4,4’-ジアミノジフェニルメタン、3,3’-ジメチル-4,4’-ジアミノビフェニル、2,2’-ジメチル-4,4’-ジアミノビフェニル、2,2’-ビス(トリフルオロメチル)-4,4’-ジアミノビフェニル、3,3’-ジメチル-4,4’-ジアミノジフェニルメタン、3,3’-ジカルボキシ-4,4’-ジアミノジフェニルメタン、3,3’,5,5’-テトラメチル-4,4’-ジアミノジフェニルメタン、ビス(4-アミノフェニル)スルフィド、4,4’-ジアミノベンズアニリド、3,3’-ジクロロベンジジン、3,3’-ジメチルベンジジン、2,2’-ジメチルベンジジン、3,3’-ジメトキシベンジジン、2,2’-ジメトキシベンジジン、3,3’-ジアミノジフェニルエーテル、3,4’-ジアミノジフェニルエーテル、4,4’-ジアミノジフェニルエーテル、3,3’-ジアミノジフェニルスルフィド、3,4’-ジアミノジフェニルスルフィド、4,4’-ジアミノジフェニルスルフィド、3,3’-ジアミノジフェニルスルホン、3,4’-ジアミノジフェニルスルホン、4,4’-ジアミノジフェニルスルホン、3,3’-ジアミノベンゾフェノン、3,3’-ジアミノ-4,4’-ジクロロベンゾフェノン、3,3’-ジアミノ-4,4’-ジメトキシベンゾフェノン、3,3’-ジアミノジフェニルメタン、3,4’-ジアミノジフェニルメタン、4,4’-ジアミノジフェニルメタン、2,2-ビス(3-アミノフェニル)プロパン、2,2-ビス(4-アミノフェニル)プロパン、2,2-ビス(3-アミノフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン、2,2-ビス(4-アミノフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン、3,3’-ジアミノジフェニルスルホキシド、3,4’-ジアミノジフェニルスルホキシド、4,4’-ジアミノジフェニルスルホキシドなどのベンゼン核2つのジアミン、
3)1,3-ビス(3-アミノフェニル)ベンゼン、1,3-ビス(4-アミノフェニル)ベンゼン、1,4-ビス(3-アミノフェニル)ベンゼン、1,4-ビス(4-アミノフェニル)ベンゼン、1,3-ビス(4-アミノフェノキシ)ベンゼン、1,4-ビス(3-アミノフェノキシ)ベンゼン、1,4-ビス(4-アミノフェノキシ)ベンゼン、1,3-ビス(3-アミノフェノキシ)-4-トリフルオロメチルベンゼン、3,3’-ジアミノ-4-(4-フェニル)フェノキシベンゾフェノン、3,3’-ジアミノ-4,4’-ジ(4-フェニルフェノキシ)ベンゾフェノン、1,3-ビス(3-アミノフェニルスルフィド)ベンゼン、1,3-ビス(4-アミノフェニルスルフィド)ベンゼン、1,4-ビス(4-アミノフェニルスルフィド)ベンゼン、1,3-ビス(3-アミノフェニルスルホン)ベンゼン、1,3-ビス(4-アミノフェニルスルホン)ベンゼン、1,4-ビス(4-アミノフェニルスルホン)ベンゼン、1,3-ビス〔2-(4-アミノフェニル)イソプロピル〕ベンゼン、1,4-ビス〔2-(3-アミノフェニル)イソプロピル〕ベンゼン、1,4-ビス〔2-(4-アミノフェニル)イソプロピル〕ベンゼンなどのベンゼン核3つのジアミン、
4)3,3’-ビス(3-アミノフェノキシ)ビフェニル、3,3’-ビス(4-アミノフェノキシ)ビフェニル、4,4’-ビス(3-アミノフェノキシ)ビフェニル、4,4’-ビス(4-アミノフェノキシ)ビフェニル、ビス〔3-(3-アミノフェノキシ)フェニル〕エーテル、ビス〔3-(4-アミノフェノキシ)フェニル〕エーテル、ビス〔4-(3-アミノフェノキシ)フェニル〕エーテル、ビス〔4-(4-アミノフェノキシ)フェニル〕エーテル、ビス〔3-(3-アミノフェノキシ)フェニル〕ケトン、ビス〔3-(4-アミノフェノキシ)フェニル〕ケトン、ビス〔4-(3-アミノフェノキシ)フェニル〕ケトン、ビス〔4-(4-アミノフェノキシ)フェニル〕ケトン、ビス〔3-(3-アミノフェノキシ)フェニル〕スルフィド、ビス〔3-(4-アミノフェノキシ)フェニル〕スルフィド、ビス〔4-(3-アミノフェノキシ)フェニル〕スルフィド、ビス〔4-(4-アミノフェノキシ)フェニル〕スルフィド、ビス〔3-(3-アミノフェノキシ)フェニル〕スルホン、ビス〔3-(4-アミノフェノキシ)フェニル〕スルホン、ビス〔4-(3-アミノフェノキシ)フェニル〕スルホン、ビス〔4-(4-アミノフェノキシ)フェニル〕スルホン、ビス〔3-(3-アミノフェノキシ)フェニル〕メタン、ビス〔3-(4-アミノフェノキシ)フェニル〕メタン、ビス〔4-(3-アミノフェノキシ)フェニル〕メタン、ビス〔4-(4-アミノフェノキシ)フェニル〕メタン、2,2-ビス〔3-(3-アミノフェノキシ)フェニル〕プロパン、2,2-ビス〔3-(4-アミノフェノキシ)フェニル〕プロパン、2,2-ビス〔4-(3-アミノフェノキシ)フェニル〕プロパン、2,2-ビス〔4-(4-アミノフェノキシ)フェニル〕プロパン、2,2-ビス〔3-(3-アミノフェノキシ)フェニル〕-1,1,1,3,3,3-ヘキサフルオロプロパン、2,2-ビス〔3-(4-アミノフェノキシ)フェニル〕-1,1,1,3,3,3-ヘキサフルオロプロパン、2,2-ビス〔4-(3-アミノフェノキシ)フェニル〕-1,1,1,3,3,3-ヘキサフルオロプロパン、2,2-ビス〔4-(4-アミノフェノキシ)フェニル〕-1,1,1,3,3,3-ヘキサフルオロプロパンなどのベンゼン核4つのジアミン、
などを挙げることができる。これらは単独でも、2種以上を混合して用いることもできる。用いるジアミンは、所望の特性などに応じて適宜選択することができる。
ポリイミド前駆体(ポリアミック酸)は、テトラカルボン酸成分とジアミン成分とを公知の方法で反応させて得ることができ、例えば略等モル量を、有機溶媒中で反応させてポリアミック酸の溶液(均一な溶液状態が保たれていれば一部がイミド化されていてもよい)を得ることができる。また、予めどちらかの成分が過剰である2種類以上のポリアミック酸を合成しておき、各ポリアミック酸溶液を一緒にした後、反応条件下で混合してもよい。このようにして得られたポリアミック酸溶液はそのまま、あるいは必要であれば溶媒を除去または加えて、自己支持性フィルムの製造に使用することができる。
ポリアミック酸溶液の自己支持性フィルムは、ポリアミック酸溶液を支持体上に流延塗布し、自己支持性となる程度(通常のキュア工程前の段階を意味する)、例えば支持体上より剥離することができる程度にまで加熱して製造される。
但し、
X1:自己支持性フィルムの1775cm-1のピーク高さ、
X2:自己支持性フィルムの1515cm-1のピーク高さ、
Y1:フルキュアフィルムの1775cm-1のピーク高さ、
Y2:フルキュアフィルムの1515cm-1のピーク高さ、とする。
次いで、自己支持性フィルムを加熱処理してポリイミドフィルムを得る。加熱処理工程において、最高加熱温度が、好ましくは300℃以上、350℃以上、より好ましくは450℃以上、さらに好ましくは470℃以上となるように加熱する。加熱温度の上限はポリイミドフィルムの特性が低下しない温度であれば良く、好ましくは600℃以下、より好ましくは550℃以下、さらに好ましくは530℃以下、特に好ましくは520℃以下である。
本発明のポリイミドフィルムは、金属箔等の基材や接着剤等の材料との接着性に優れている。このため、本発明のポリイミドフィルムと接着剤層が積層されたポリイミド積層体や、後述するポリイミド金属積層体とすることができる。金属として銅が好ましい。
脂環式のテトラカルボン酸二無水物と、ATDAとから、ポリイミド前駆体を得ることができる。また、前記ポリイミド前駆体からポリイミドおよびポリイミドフィルムを得ることができる。このポリイミドフィルムは、金属箔等の基材や接着剤等の材料との接着性に優れている。また、このポリイミドフィルムは、紫外可視領域における透過率(透明性)が改善される。
また、脂環式のテトラカルボン酸二無水物と、ATDA(p-ATDAおよびm-ATDA)を使用してポリイミド前駆体を得る方法については、前記<ポリイミド前駆体の調製>と同じである。
次に、本発明のポリイミドの製造に使用される、一般式(B2)で表される2,4-ビス(3-アミノアニリノ)-6-置換アミノ-1,3,5-トリアジンの製造方法について説明する。
ポリアミック酸およびポリイミドの物性の評価は以下の方法に従って行った。
後述のようにして調製したポリアミック酸溶液をN,N-ジメチルアセトアミド(DMAc)で0.5g/dLに希釈し、オストワルド粘度計を用いて30℃で対数粘度を測定した。
得られたポリイミドフィルム10mgを有機溶媒5mLに加え、室温で溶解した場合は「++」、加熱して室温で溶解した場合は「+」、部分的に溶解または膨潤した場合は「±」、不溶の場合は「-」で表した。有機溶媒には、DMAc、NMP、THF、クロロホルムを用いた。
得られたポリイミドをN-メチル-2-ピロリドン(NMP)で0.5g/dLの濃度になるように溶解し、オストワルド粘度計を用いて30℃で対数粘度を測定した。
島津製作所製DSC-60を用いて、窒素中20℃/分の昇温速度で測定し、ガラス転移温度を求めた。
Seiko Instroments Inc.EXSTAR TMA/SS6100(昇温速度:10℃/min)により測定し、線膨張係数を算出した。
(ジアミンモノマー)
m-ATDAまたはp-ATDAの1×10-5mol/Lのテトラヒドロフラン溶液を日本分光製V-570紫外-可視分光器を用いて紫外-可視吸収スペクトルを測定した。カットオフ波長「λcutoff」、透過率80%となる波長「λ80%」を求めた。また、波長が400、500および600nmにおける透過率を求めた。
日本分光製V-570紫外-可視分光器を用いて、後述のようにして得たポリイミドフィルムの紫外-可視吸収スペクトルを測定した。カットオフ波長「λcutoff」、透過率80%となる波長「λ80%」を求めた。また、波長が400、500および600nmにおける透過率を求めた。
アタゴ製アッベ屈折計DR-M4を用いて,ポリイミドフィルムのD線(589nm)における屈折率を室温で測定した。
得られたポリイミド金属積層体の90°剥離強度を温度23℃、相対湿度50%の環境下で、50mm/分の剥離速度で測定した。
<6-アニリノ-1,3,5-トリアジン-2,4-ジクロリド(ATD)の合成>
撹拌子、温度計、滴下ロートおよび塩化カルシウム管を取り付けた三口フラスコ(1L)に、塩化シアヌル(36.52g、0.2mol)とTHF(120mL)を入れ、氷浴により-5~0℃に冷却しながら完全に溶解させた。アニリン(19.03g、0.2mol)をTHF(70mL)に溶解させた溶液を三口フラスコにゆっくりと滴下した。滴下後、0~5℃で2時間撹拌した。炭酸ナトリウム(12.90g、0.12mol)を蒸留水(70mL)に溶かした水溶液を温度の上昇に気をつけながら、三口フラスコにゆっくりと滴下した。滴下後、2時間撹拌した。反応溶液を分液ロートに移し、飽和食塩水を加えた。分離した有機層に無水硫酸マグネシウムを加え一晩撹拌した。吸引ろ過により無水硫酸マグネシウムを除去した後、エバポレーターによりTHFを留去し、固体の粗生成物を得た。この粗生成物を脱水したヘキサン/トルエン混合溶媒で再結晶し、白色針状結晶を得た。
収量40.6g、収率84%、融点136-137℃、1H-NMR[400MHz,DMSO-d6,ppm]:δ7.18(t,1H,Ar-H),7.40(t,2H,Ar-H),7.61(d,2H,Ar-H),8.92(s,1H,NH)
13C NMR[101MHz,DMSO-d6,TMS,ppm]:δ170.1,169.2,164.2,137.3,129.3,125.4,122.0
<2,4-ビス(4-アミノアニリノ)-6-アニリノ-1,3,5-トリアジン(p-ATDA)の合成> 比較ジアミン化合物の合成
1H-NMR[400MHz,DMSO-d6,TMS,ppm]:δ4.78(s,4H,Ar-NH2),6.53(d,4H,NH2-o-Ar-H),6.94(t,1H,p-Ar-H),7.23(t,2H,m-Ar-H),7.34(d,4H,NH2-m-Ar-H),7.79(d,2H,o-Ar-H),8.64(s,2H,Ar-NH-Ar),8.95(s,1H,Ar-NH)
13C NMR[101MHz,DMSO-d6,TMS,ppm]:δ164.1,164.0,144.1,140.4,129.0,128.2,122.6,121.4,119.9,113.8
元素分析(C21H20N8 Mw:384.44)
計算値(%)C;65.61 H;5.24 N;29.15
測定値(%)C;65.88 H;5.36 N;29.07
1H-NMR[400MHz,DMSO-d6,TMS,ppm]:δ7.04(t,1H,Ar-H),7.31(t,2H,Ar-H),7.59(t,2H,Ar-H),7.78(d,2H,Ar-H),7.84(d,2H,Ar-H),8.29(s,2H,Ar-H),8.61(s,2H,Ar-H),9.48(s,1H,NH),9.84(s,2H,NH)
13C NMR[101MHz,DMSO-d6,ppm]:d=164.9,164.5,148.5,141.5,139.9,130.2,128.9,126.7,123.0,121.2,117.0,114.8
元素分析(C21H16N8O4)
計算値(%)C;56.76 H;3.63 N;25.21
測定値(%)C;56.98 H;3.72 N;25.08
1H-NMR[400MHz,DMSO-d6,ppm]:δ=4.92(s,4H,NH2),6.26(s,1H,Ar-H),6.96(t,2H,Ar-H),7.00(d,2H,Ar-H),7.05(t,1H,Ar-H),7.28(s,2H,Ar-H),7.31(t,2H,Ar-H),7.82(t,2H,Ar-H),8.88(s,2H,NH),9.05(s,1H,NH)
13C NMR[101MHz,DMSO-d6,ppm]:d=164.1,164.0,148.6,140.3,140.1,128.5,121.7,120.0,109.0,108.5,106.7
元素分析(C21H20N8)
計算値(%)C;65.61 H;5.24 N;29.15
測定値(%)C;65.42 H;5.35 N;29.31
撹拌子、冷却管、側管付き滴下ロート、窒素導入管を備えた三口フラスコ(1L)に1,4-ジオキサン(100mL)、炭酸ナトリウム(8.90g、0.08mol)、メタフェニレンジアミン(34.62g、0.32mol)を加え、還流温度で撹拌し溶解させた。6-アニリノ-1,3,5-トリアジン-2,4-ジクロリド(10.11g、0.04mol)を1,4-ジオキサン(80mL)に溶かした溶液を滴下ロートに入れ、還流した溶液に5時間かけて滴下し、還流温度のまま一晩撹拌した。反応終了後、反応混合物をビーカー(3L)中熱水で4回、水で1回、洗浄水が透明になるまで洗浄した。吸引ろ過により回収した後、還流温度のアセトン中で30分撹拌して不溶分をろ過し、ろ液からアセトンをエバポレーターで留去し固体を得た。この固体を1,4-ジオキサン/ヘキサンにより再結晶を試みた。しかし、生成物(m-ATDA)の結晶を得ることができなかった。
s-BPDA/p-ATDA
撹拌棒、窒素導入管を取り付けた三口フラスコ(100mL)に、2,4-ビス(4-アミノアニリノ)-6-アニリノ-1,3,5-トリアジン(p-ATDA)(0.961g,2.50mmol)とN,N-ジメチルアセトアミド(DMAc)(5mL)を加え、室温で撹拌して溶解させた。その後、室温で撹拌しながら、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物(s-BPDA)(0.736g、2.50mmol)を添加して室温で6時間反応させ、粘稠な重合溶液を得た。これをDMAcで希釈してポリアミック酸溶液A(ポリイミド前駆体溶液A)を得た。このポリアミック酸の対数粘度(ηinh)は、1.29dL/gであった。
s-BPDA/m-ATDA
ジアミンを2,4-ビス(3-アミノアニリノ)-6-アニリノ-1,3,5-トリアジン(m-ATDA)とした以外は、ポリアミック酸溶液Aの調製と同様にして、ポリアミック酸溶液Bを調製した。このポリアミック酸の対数粘度(ηinh)は、1.20dL/gであった。
PMDA/p-ATDA
酸二無水物をピロメリット酸二無水物(PMDA)とした以外は、ポリアミック酸溶液Aの調製と同様にして、ポリアミック酸溶液Cを調製した。このポリアミック酸の対数粘度(ηinh)は、0.38dL/gであった。
PMDA/m-ATDA
酸二無水物をピロメリット酸二無水物(PMDA)、ジアミンを2,4-ビス(3-アミノアニリノ)-6-アニリノ-1,3,5-トリアジン(m-ATDA)とした以外は、ポリアミック酸溶液Aの調製と同様にして、ポリアミック酸溶液Dを調製した。このポリアミック酸の対数粘度(ηinh)は、0.72dL/gであった。
6FDA/p-ATDA
酸二無水物を4,4’-(ヘキサフルオロイソプロピリデン)ジフタル酸無水物(6FDA)とした以外は、ポリアミック酸溶液Aの調製と同様にして、ポリアミック酸溶液Eを調製した。このポリアミック酸の対数粘度(ηinh)は、0.54dL/gであった。
6FDA/m-ATDA
酸二無水物を4,4’-(ヘキサフルオロイソプロピリデン)ジフタル酸無水物(6FDA)、ジアミンを2,4-ビス(3-アミノアニリノ)-6-アニリノ-1,3,5-トリアジン(m-ATDA)とした以外は、ポリアミック酸溶液Aの調製と同様にして、ポリアミック酸溶液Fを調製した。このポリアミック酸の対数粘度(ηinh)は、0.57dL/gであった。
CBDA/p-ATDA
酸二無水物を1,2,3,4-シクロブタンテトラカルボン酸二無水物(CBDA)とした以外は、ポリアミック酸溶液Aの調製と同様にして、ポリアミック酸溶液Gを調製した。このポリアミック酸の対数粘度(ηinh)は、1.54dL/gであった。
CBDA/m-ATDA
酸二無水物を1,2,3,4-シクロブタンテトラカルボン酸二無水物(CBDA)、ジアミンを2,4-ビス(3-アミノアニリノ)-6-アニリノ-1,3,5-トリアジン(m-ATDA)とした以外は、ポリアミック酸溶液Aの調製と同様にして、ポリアミック酸溶液Hを調製した。このポリアミック酸の対数粘度(ηinh)は、0.65dL/gであった。
s-BPDA/ODA
ジアミンを4,4’-ジアミノジフェニルエーテル(ODA)とした以外は、ポリアミック酸溶液Aの調製と同様にして、ポリアミック酸溶液Iを調製した。このポリアミック酸の対数粘度(ηinh)は、1.84dL/gであった。
DSDA/m-ATDA
酸二無水物を3,3’,4,4’-ジフェニルスルホンテトラカルボン酸二無水物(DSDA)、ジアミンを2,4-ビス(3-アミノアニリノ)-6-アニリノ-1,3,5-トリアジン(m-ATDA)とした以外は、ポリアミック酸溶液Aの調製と同様にして、ポリアミック酸溶液Nを調製した。このポリアミック酸の対数粘度(ηinh)は、0.62dL/gであった。
ODPA/m-ATDA
酸二無水物を4,4’-オキシジフタル酸無水物(ODPA)、ジアミンを2,4-ビス(3-アミノアニリノ)-6-アニリノ-1,3,5-トリアジン(m-ATDA)とした以外は、ポリアミック酸溶液Aの調製と同様にして、ポリアミック酸溶液Oを調製した。このポリアミック酸の対数粘度(ηinh)は、0.66dL/gであった。
BTDA/m-ATDA
酸二無水物を3,3’,4,4’-ベンゾフェノンテトラカルボン酸二無水物(BTDA)、ジアミンを2,4-ビス(3-アミノアニリノ)-6-アニリノ-1,3,5-トリアジン(m-ATDA)とした以外は、ポリアミック酸溶液Aの調製と同様にして、ポリアミック酸溶液Pを調製した。このポリアミック酸の対数粘度(ηinh)は、0.60dL/gであった。
CHDA/m-ATDA
酸二無水物を1,2,4,5-シクロヘキサンテトラカルボン酸二無水物(CHDA)、ジアミンを2,4-ビス(3-アミノアニリノ)-6-アニリノ-1,3,5-トリアジン(m-ATDA)とした以外は、ポリアミック酸溶液Aの調製と同様にして、ポリアミック酸溶液Qを調製した。このポリアミック酸の対数粘度(ηinh)は、0.46dL/gであった。
DSDA/p-ATDA
酸二無水物を3,3’,4,4’-ジフェニルスルホンテトラカルボン酸二無水物(DSDA)とした以外は、ポリアミック酸溶液Aの調製と同様にして、ポリアミック酸溶液Rを調製した。このポリアミック酸の対数粘度(ηinh)は、0.78dL/gであった。
ODPA/p-ATDA
酸二無水物を4,4’-オキシジフタル酸無水物(ODPA)とした以外は、ポリアミック酸溶液Aの調製と同様にして、ポリアミック酸溶液Sを調製した。このポリアミック酸の対数粘度(ηinh)は、0.84dL/gであった。
BTDA/p-ATDA
酸二無水物を3,3’,4,4’-ベンゾフェノンテトラカルボン酸二無水物(BTDA)とした以外は、ポリアミック酸溶液Aの調製と同様にして、ポリアミック酸溶液Tを調製した。このポリアミック酸の対数粘度(ηinh)は、0.64dL/gであった。
CHDA/p-ATDA
酸二無水物を1,2,4,5-シクロヘキサンテトラカルボン酸二無水物(CHDA)とした以外は、ポリアミック酸溶液Aの調製と同様にして、ポリアミック酸溶液Uを調製した。このポリアミック酸の対数粘度(ηinh)は、0.50dL/gであった。
6FDA/m-ATDA
100mLの三口フラスコにスリーワンモーター、窒素導入管を備え、窒素気流下で2,4-ビス(3-アミノアニリノ)-6-アニリノ-1,3,5-トリアジン(m-ATDA)(0.961g,2.50mmol)とN-メチルピロリドン(NMP)(5mL)を加え、室温で撹拌して溶解させた。その後、室温で撹拌しながら、4,4’-(ヘキサフルオロイソプロピリデン)ジフタル酸無水物(6FDA)(1.111g、2.50mmol)を加え、室温で6時間攪拌した。重合途中で粘度が増大するため、溶媒を追加し、前駆体であるポリアミック酸溶液を得た。その後、ディーン・スターク管とジムロートをとりつけ、反応溶液が5wt%となるように、ポリアミック酸溶液にNMPを仕込んだ。共沸溶媒としてトルエン5mLを加え、140℃で3時間撹拌し系中の水を除去した後、200℃、3時間撹拌し、イミド化反応を行った。反応溶液をメタノールに注ぎ固体を析出させ、吸引ろ過により固体を得た。その後、得られた固体を室温で減圧乾燥させることによりポリイミドVを得た。ポリイミドVの対数粘度(ηinh)は、0.64dL/gであった。また、ポリイミドVをNMPに再溶解させることにより、ポリイミド溶液Vを得た。
DSDA/m-ATDA
酸二無水物を3,3’,4,4’-ジフェニルスルホンテトラカルボン酸二無水物(DSDA)とした以外は、ポリイミドV、ならびにポリイミド溶液Vの調製と同様にして、ポリイミドW、ならびにポリイミド溶液Wを調製した。ポリイミドWの対数粘度(ηinh)は、0.62dL/gであった。
ODPA/m-ATDA
酸二無水物を4,4’-オキシジフタル酸無水物(ODPA)とした以外は、ポリイミドV、ならびにポリイミド溶液Vの調製と同様にして、ポリイミドX、ならびにポリイミド溶液Xを調製した。ポリイミドXの対数粘度(ηinh)は、0.52dL/gであった。
(比較例1)ポリイミドフィルムAの作製
s-BPDA/p-ATDA
ポリアミック酸溶液Aをガラス板上に薄膜状にキャストし、60℃で6時間、100℃で1時間、200℃で1時間、さらに300℃で1時間加熱して、加熱イミド化を行った。冷却後,水に浸すことによりポリイミドフィルムをガラス板より剥離させた。乾燥後,厚み16μmのポリイミドフィルムAを得た。
s-BPDA/m-ATDA
ポリアミック酸溶液Aの代わりにポリアミック酸溶液Bを用いた以外は、ポリイミドフィルムAの作製と同様にして、乾燥後、厚み14μmのポリイミドフィルムBを得た。このポリイミドフィルムBの屈折率(nD)は、1.739であった。得られたポリイミドの有機溶媒への溶解性を表1に、光学特性を表2に示す。
PMDA/p-ATDA
ポリアミック酸溶液Aの代わりにポリアミック酸溶液Cを用いた以外は、ポリイミドフィルムAの作製と同様にして、乾燥後、厚み14μmのポリイミドフィルムCを得た。各物性値を、表1および表2に示す。
PMDA/m-ATDA
ポリアミック酸溶液Aの代わりにポリアミック酸溶液Dを用いた以外は、ポリイミドフィルムAの作製と同様にして、乾燥後、厚み17μmのポリイミドフィルムDを得た。このポリイミドフィルムDの屈折率(nD)は、1.759であった。各物性値を、表1および表2に示す。
6FDA/p-ATDA
ポリアミック酸溶液Aの代わりにポリアミック酸溶液Eを用いた以外は、ポリイミドフィルムAの作製と同様にして、乾燥後、厚み17μmのポリイミドフィルムEを得た。各物性値を、表1および表2に示す。
6FDA/m-ATDA
ポリアミック酸溶液Aの代わりにポリアミック酸溶液Fを用いた以外は、ポリイミドフィルムAの作製と同様にして、乾燥後、厚み16μmのポリイミドフィルムFを得た。このポリイミドフィルムFの屈折率(nD)は、1.728であった。各物性値を、表1および表2に示す。
s-BPDA/ODA
ポリアミック酸溶液Aの代わりにポリアミック酸溶液Iを用いた以外は、ポリイミドフィルムAの作製と同様にして、乾燥後、厚み37μmのポリイミドフィルムIを得た。このポリイミドフィルムIの屈折率(nD)は、1.714であった。各物性値を、表1および表2に示す。
(参考例1)ポリイミドフィルムGの作製
CBDA/p-ATDA
ポリアミック酸溶液Aの代わりにポリアミック酸溶液Gを用いた以外は、ポリイミドフィルムAの作製と同様にして、乾燥後、厚み10μmのポリイミドフィルムGを得た。各物性値を、表1および表2に示す。
CBDA/m-ATDA
ポリアミック酸溶液Aの代わりにポリアミック酸溶液Hを用いた以外は、ポリイミドフィルムAの作製と同様にして、乾燥後、厚み11μmのポリイミドフィルムHを得た。このポリイミドフィルムHの屈折率(nD)は、1.729であった。各物性値を、表1および表2に示す。
(実施例5)ポリイミドフィルムJの作製
s-BPDA/m-ATDA
ポリイミドフィルムの厚みを40μmに変更した以外は、実施例1と同様な方法によりポリイミドフィルムJを得た。ポリイミドフィルムJのガラス転移温度(DSC)は261℃であった。
PMDA/m-ATDA
ポリイミドフィルムの厚みを40μmに変更した以外は、実施例2と同様な方法によりポリイミドフィルムKを得た。ポリイミドフィルムKのガラス転移温度(DSC)は291℃であった。
6FDA/m-ATDA
ポリイミドフィルムの厚みを40μmに変更した以外は、実施例3と同様な方法によりポリイミドフィルムLを得た。ポリイミドフィルムLのガラス転移温度(DSC)は256℃であった。
CBDA/m-ATDA
ポリイミドフィルムの厚みを23μmに変更した以外は、実施例4と同様な方法によりポリイミドフィルムMを得た。ポリイミドフィルムMのガラス転移温度(DSC)は288℃であった。また、300℃でのアニール処理後、線膨張係数を測定したところ、50~200℃までの線膨張係数は14.1ppm/Kと低い値を示した。
(実施例9)
s-BPDA/m-ATDA
ポリアミック酸溶液Bを用いてポリイミド金属積層体を作製した。ポリイミド金属積層体は、ポリアミック酸溶液Bを圧延銅箔(JX日鉱日石金属株式会社製、BHY-13H-T、18μm厚)に塗布し、120℃で10分加熱後、さらに400℃まで20分かけて昇温することにより得た。ポリイミド金属積層体のポリイミドフィルムの厚みは24μmであった。ポリイミド金属積層体の90°剥離試験を行った結果、接着が良好で、0.45kN/mでフィルムが破断した。従って、ポリイミド金属積層体の剥離強度は0.45kN/m以上であると推定される。
s-BPDA/m-ATDA
ポリアミック酸溶液Bを用いてポリイミド金属積層体を作製した。ポリイミド金属積層体は、ポリアミック酸溶液Bを圧延銅箔(JX日鉱日石金属株式会社製、BHY-13H-T、18μm厚)に塗布し、120℃で10分加熱後、さらに400℃まで20分かけて昇温することにより得た。ポリイミド金属積層体のポリイミドフィルムの厚みは47μmであった。ポリイミド金属積層体の90°剥離試験を行った結果、接着が良好で、1.35kN/mでフィルムが破断した。従って、ポリイミド金属積層体の剥離強度は1.35kN/m以上であると推定される。
s-BPDA/PPD
芳香族系のテトラカルボン酸二無水物として、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物(s-BPDA)、ジアミン成分としてパラフェニレンジアミン(PPD)を使用して得られたポリアミック酸溶液を用いてポリイミド金属積層体を作製した。ポリイミド金属積層体は、ポリアミック酸溶液を圧延銅箔(JX日鉱日石金属株式会社製、BHY-13H-T、18μm厚)に塗布し、120℃で10分加熱後、さらに400℃まで20分かけて昇温することにより得た。ポリイミド金属積層体のポリイミドフィルムの厚みは22μmであった。ポリイミド金属積層体の90°剥離試験を行った結果、剥離強度は0.1kN/m以下であった。
DSDA/m-ATDA
ポリアミック酸溶液Aの代わりにポリアミック酸溶液Nを用いた以外は、ポリイミドフィルムAの作製と同様にして、乾燥後、厚み21μmのポリイミドフィルムNを得た。このポリイミドフィルムNの屈折率(nD)は、1.724であった。各物性値を、表3および表4に示す。また、ポリイミドフィルムNのガラス転移温度(DSC)は249℃であった。
ODPA/m-ATDA
ポリアミック酸溶液Aの代わりにポリアミック酸溶液Oを用いた以外は、ポリイミドフィルムAの作製と同様にして、乾燥後、厚み18μmのポリイミドフィルムOを得た。このポリイミドフィルムOの屈折率(nD)は、1.732であった。各物性値を、表3および表4に示す。また、ポリイミドフィルムOのガラス転移温度(DSC)は253℃であった。
BTDA/m-ATDA
ポリアミック酸溶液Aの代わりにポリアミック酸溶液Pを用いた以外は、ポリイミドフィルムAの作製と同様にして、乾燥後、厚み17μmのポリイミドフィルムPを得た。このポリイミドフィルムPの屈折率(nD)は、1.730であった。各物性値を、表3および表4に示す。また、ポリイミドフィルムPのガラス転移温度(DSC)は248℃であった。
CHDA/m-ATDA
ポリアミック酸溶液Aの代わりにポリアミック酸溶液Qを用いた以外は、ポリイミドフィルムAの作製と同様にして、乾燥後、厚み21μmのポリイミドフィルムQを得た。各物性値を、表3および表4に示す。ポリイミドフィルムQの溶解性試験において、ポリイミドフィルムQはNMPに室温で溶解し、さらには15質量%以上溶解した。
DSDA/p-ATDA
ポリアミック酸溶液Aの代わりにポリアミック酸溶液Rを用いた以外は、ポリイミドフィルムAの作製と同様にして、ポリイミドフィルムRを得た。各物性値を、表3および表4に示す。また、ポリイミドフィルムRのガラス転移温度(DSC)は291℃であった。
ODPA/p-ATDA
ポリアミック酸溶液Aの代わりにポリアミック酸溶液Sを用いた以外は、ポリイミドフィルムAの作製と同様にして、乾燥後、厚み16μmのポリイミドフィルムSを得た。各物性値を、表3に示す。また、ポリイミドフィルムSのガラス転移温度(DSC)は257℃であった。
BTDA/p-ATDA
ポリアミック酸溶液Aの代わりにポリアミック酸溶液Tを用いた以外は、ポリイミドフィルムAの作製と同様にして、乾燥後、厚み21μmのポリイミドフィルムTを得た。各物性値を、表3および表4に示す。また、ポリイミドフィルムPのガラス転移温度(DSC)は268℃であった。
CHDA/p-ATDA
ポリアミック酸溶液Aの代わりにポリアミック酸溶液Uを用いた以外は、ポリイミドフィルムAの作製と同様にして、ポリイミドフィルムUを得た。各物性値を、表3に示す。
(実施例15)ポリイミドフィルムVの作製
6FDA/m-ATDA
ポリイミド溶液Vをガラス板上に薄膜状にキャストし、減圧下で脱気を行った。その後真空オーブンにより60℃で6時間、100℃で1時間、200℃で1時間、さらに300℃で1時間加熱して厚み40μmのポリイミドフィルムVを得た。ポリイミドフィルムVのガラス転移温度(DSC)は250℃であった。
DSDA/m-ATDA
ポリイミド溶液Vの代わりにポリイミド溶液Wを用いた以外は、ポリイミドフィルムVの作製と同様にして、ポリイミドフィルムWを得た。ポリイミドフィルムWのガラス転移温度(DSC)は244℃であった。
ODPA/m-ATDA
ポリイミド溶液Vの代わりにポリイミド溶液Xを用いた以外は、ポリイミドフィルムVの作製と同様にして、ポリイミドフィルムXを得た。ポリイミドフィルムXのガラス転移温度(DSC)は253℃であった。
(実施例18)
PMDA/m-ATDA
ポリアミック酸溶液Dを用いてポリイミド金属積層体を作製した。ポリイミド金属積層体は、ポリアミック酸溶液Dを圧延銅箔(JX日鉱日石金属株式会社製、BHY-13H-T、18μm厚)に塗布し、120℃で10分加熱後、さらに400℃まで20分かけて昇温することにより得た。ポリイミド金属積層体のポリイミドフィルムの厚みは40μmであった。ポリイミド金属積層体の90°剥離試験を行った結果、接着が良好で、0.68kN/mでフィルムが破断した。従って、ポリイミド金属積層体の剥離強度は0.68kN/m以上であると推定される。
6FDA/m-ATDA
ポリアミック酸溶液Fをポリアミック酸溶液Dの代わりに用いた以外は、実施例18と同様にしてポリイミド金属積層体を作製し、剥離試験を行った。その結果、接着が良好で、0.54kN/mでフィルムが破断した。従って、ポリイミド金属積層体の剥離強度は0.54kN/m以上であると推定される。
DSDA/m-ATDA
ポリアミック酸溶液Nをポリアミック酸溶液Dの代わりに用いた以外は、実施例18と同様にしてポリイミド金属積層体を作製し、剥離試験を行った。その結果、接着が良好で、0.42kN/mでフィルムが破断した。従って、ポリイミド金属積層体の剥離強度は0.42kN/m以上であると推定される。
ODPA/m-ATDA
ポリアミック酸溶液Oをポリアミック酸溶液Dの代わりに用いた以外は、実施例18と同様にしてポリイミド金属積層体を作製し、剥離試験を行った。その結果、接着が良好で、1.35kN/mでフィルムが破断した。従って、ポリイミド金属積層体の剥離強度は1.35kN/m以上であると推定される。
BTDA/m-ATDA
ポリアミック酸溶液Pをポリアミック酸溶液Dの代わりに用いた以外は、実施例18と同様にしてポリイミド金属積層体を作製し、剥離試験を行った。その結果、接着が良好で、1.29kN/mでフィルムが破断した。従って、ポリイミド金属積層体の剥離強度は1.29kN/m以上であると推定される。
(実施例23)
PMDA/m-ATDA
ポリアミック酸溶液Dを用いて2層ポリイミド積層体を作製した。ポリアミック酸溶液Dをポリイミドフィルム(宇部興産株式会社製、ユーピレックス75S、75μm厚)に塗布した以外は、実施例18と同様の方法で2層ポリイミド積層体を作製し、剥離試験を行った。その結果、接着が良好で、0.62kN/mでフィルムが破断した。従って、2層ポリイミド積層体の剥離強度は0.62kN/m以上であると推定される。
6FDA/m-ATDA
ポリアミック酸溶液Fを用いて2層ポリイミド積層体を作製した。ポリアミック酸溶液Fをポリイミドフィルム(宇部興産株式会社製、ユーピレックス75S、75μm厚)に塗布した以外は、実施例18と同様の方法で2層ポリイミド積層体を作製し、剥離試験を行った。その結果、接着が良好で、0.55kN/mでフィルムが破断した。従って、2層ポリイミド積層体の剥離強度は0.55kN/m以上であると推定される。
DSDA/m-ATDA
ポリアミック酸溶液Nを用いて2層ポリイミド積層体を作製した。ポリアミック酸溶液Nをポリイミドフィルム(宇部興産株式会社製、ユーピレックス75S、75μm厚)に塗布した以外は、実施例18と同様の方法で2層ポリイミド積層体を作製し、剥離試験を行った。その結果、接着が良好で、0.37kN/mでフィルムが破断した。従って、2層ポリイミド積層体の剥離強度は0.37kN/m以上であると推定される。
ODPA/m-ATDA
ポリアミック酸溶液Oを用いて2層ポリイミド積層体を作製した。ポリアミック酸溶液Oをポリイミドフィルム(宇部興産株式会社製、ユーピレックス75S、75μm厚)に塗布した以外は、実施例18と同様の方法で2層ポリイミド積層体を作製し、剥離試験を行った。その結果、接着が良好で、0.28kN/mでフィルムが破断した。従って、2層ポリイミド積層体の剥離強度は0.28kN/m以上であると推定される。
s-BPDA/PPD
芳香族系のテトラカルボン酸二無水物として、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物(s-BPDA)、ジアミン成分としてパラフェニレンジアミン(PPD)を使用して得られたポリアミック酸溶液を用いて2層ポリイミド積層体を作製した。このポリアミック酸溶液をポリイミドフィルム(宇部興産株式会社製、ユーピレックス75S、75μm厚)に塗布した以外は、実施例18と同様の方法で2層ポリイミド積層体を作製し、剥離試験を行った。その結果、剥離強度は0.02kN/m以下であった。
Claims (9)
- 前記一般式(I)中の基Aとして、シクロヘキサンテトラカルボン酸二無水物および1,2,3,4-シクロブタンテトラカルボン酸二無水物のうちの少なくとも1種の化合物から、2つのカルボン酸無水物基を除いた4価の残基を含む請求項2記載のポリイミド前駆体。
- 一般式(B1)において、R1が水素原子、R2がフェニルである請求項1~3のいずれか1項に記載のポリイミド前駆体。
- 前記一般式(I)中の基Bとして、一般式(B1)で表されるトリアジン部分構造を10~100モル%の範囲で含む請求項1~4のいずれか1項に記載のポリイミド前駆体。
- 請求項6記載のポリイミドを含むポリイミドフィルム。
- 請求項7記載のポリイミドフィルムに直接または接着剤を介して金属層を積層してなる金属積層体。
- 一般式(B3)で表される6-置換アミノ-1,3,5-トリアジン-2,4-ジハライドと3-ニトロアニリンとを反応させて、一般式(B4)で表される2,4-ビス-(3-ニトロアニリノ)-6-置換アミノ-1,3,5-トリアジンを合成し、
得られた2,4-ビス-(3-ニトロアニリノ)-6-置換アミノ-1,3,5-トリアジンを、還元すること
を特徴とする一般式(B2)で表される2,4-ビス(3-アミノアニリノ)-6-置換アミノ-1,3,5-トリアジンの製造方法。
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