CN106255714A - Resist resin and manufacture method thereof - Google Patents
Resist resin and manufacture method thereof Download PDFInfo
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- CN106255714A CN106255714A CN201580020255.7A CN201580020255A CN106255714A CN 106255714 A CN106255714 A CN 106255714A CN 201580020255 A CN201580020255 A CN 201580020255A CN 106255714 A CN106255714 A CN 106255714A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
- C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0387—Polyamides or polyimides
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Abstract
It is an object of the invention to provide a kind of polyamic acid that low temperature operability is excellent while maintaining high-fire resistance and polyimides.The polyamic acid of the present invention with following formula (1) represent [in formula, R1And R2Separately represent the alkenylene that alkylidene that singly-bound, carbon number are 1～5, carbon number are 2～5 or the arlydene that carbon number is 6～10；R3And R4Separately represent aryl or halogen atom that thiazolinyl that alkyl that hydrogen atom, carbon number are 1～5, carbon number are 2～5, carbon number are 6～10；N represents the integer of 0～20；Y represents the residue in addition to the carboxyl of dicarboxylic acids or the anhydride group of dicarboxylic anhydride；And Z represents the residue in addition to the carboxyl of tetrabasic carboxylic acid or the anhydride group of tetracarboxylic dianhydride].
Description
Technical field
The present invention relates to resist resin and the manufacture method thereof of a kind of novelty.
Background technology
Polyimides is widely used at electronic applications because of thermostability, mechanical property excellence.In the past, polyimides was most
Insoluble in organic solvent, generally by by polyamic acid (the polyamide acid) (polyamic acid (polyamic of precursor
Acid) solution) is coated on base material and carries out heating with the high temperature of more than 250 DEG C and carries out the removing of organic solvent and acyl is sub-
Amination is thus shaped (membranization).But, there is base material due to the heating under high temperature in the method, periphery material is sent out sometimes
The shortcoming of raw deterioration.It is therefore desirable to can be at the polyamic acid of more low temperature moulding and polyimides.
Such as, the silicone that Patent Document 1 discloses a kind of glass transition temperature with 170 DEG C to 190 DEG C changes
Property polyimides.But, there is the industrial problem being difficult to obtain in the raw material of such polyimides.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 5-112760 publication
Summary of the invention
Invent problem to be solved
In view of above-mentioned present situation, it is an object of the invention to provide one low temperature operability while maintaining high-fire resistance excellent
Different polyamic acid and polyimides.
For solving the means of problem
The present inventor furthers investigate, and result obtains following opinion: by using the diamidogen containing fluorene skeleton poly-as synthesis
All or part of of the diamine component used when amic acid and polyimides, it is possible to obtain while maintaining high-fire resistance
The polyamic acid of low temperature operability excellence and polyimides, additionally, the solvent solubility of obtained polyimides is excellent, thus
Complete the present invention.
That is, the polyamic acid of the present invention and polyimides relates to herein below:
[1] a kind of polyamic acid, it represents with following formula (1):
[changing 1]
[in formula,
R1And R2Separately represent the alkenylene that alkylidene that singly-bound, carbon number are 1～5, carbon number are 2～5
Or the arlydene that carbon number is 6～10；
R3And R4Separately represent thiazolinyl that alkyl that hydrogen atom, carbon number are 1～5, carbon number are 2～5,
Carbon number is aryl or the halogen atom of 6～10；
N represents the integer of 0～20；
Y represents the residue in addition to the carboxyl of dicarboxylic acids or the anhydride group of dicarboxylic anhydride；And
Z represents the residue in addition to the carboxyl of tetrabasic carboxylic acid or the anhydride group of tetracarboxylic dianhydride]；
[2] such as the polyamic acid of [1], wherein, Y be except select free maleic acid, succinic acid, itaconic acid, phthalic acid,
Tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic tetrahydrophthalic acid, chlorendic acid, methyl tetrahydrochysene neighbour's benzene
Dioctyl phthalate, trimellitic acid and 1,3-propanedicarboxylic acid composition group in the carboxyl of dicarboxylic acids or the anhydride group of their anhydride beyond residual
Base；
[3] such as [1] or the polyamic acid of [2], wherein, Z is except choosing free PMA, benzophenone tetrabasic carboxylic acid, connection
In the group of benzene tertacarbonic acid, the double phthalic acid of oxygen, diphenylsulfone acid, ethylene glycol bis trimellitate and BTCA composition
The carboxyl of tetrabasic carboxylic acid or the anhydride group of their dicarboxylic anhydride beyond residue；
[4] a kind of polyimides, it is represented with following formula (2), and is obtained by the polyamic acid closed loop by [1]
Arrive,
[changing 2]
[in formula,
R1And R2Separately represent the alkenylene that alkylidene that singly-bound, carbon number are 1～5, carbon number are 2～5
Or the arlydene that carbon number is 6～10；
R3And R4Separately represent thiazolinyl that alkyl that hydrogen atom, carbon number are 1～5, carbon number are 2～5,
Carbon number is aryl or the halogen atom of 6～10；
N represents the integer of 0～20；
Y represents the residue in addition to the carboxyl of dicarboxylic acids or the anhydride group of dicarboxylic anhydride；And
Z represents the residue in addition to the carboxyl of tetrabasic carboxylic acid or the anhydride group of tetracarboxylic dianhydride]；
[5] such as the polyimides of [4], wherein, Y be except select free maleic acid, succinic acid, itaconic acid, phthalic acid,
Tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic tetrahydrophthalic acid, chlorendic acid, methyl tetrahydrochysene neighbour's benzene
Dioctyl phthalate, trimellitic acid and 1,3-propanedicarboxylic acid composition group in the carboxyl of dicarboxylic acids or the anhydride group of their anhydride beyond residual
Base；
[6] such as [4] or the polyimides of [5], wherein, Z is except choosing free PMA, benzophenone tetrabasic carboxylic acid, connection
In the group of benzene tertacarbonic acid, the double phthalic acid of oxygen, diphenylsulfone acid, ethylene glycol bis trimellitate and BTCA composition
The carboxyl of tetrabasic carboxylic acid or the anhydride group of their dicarboxylic anhydride beyond residue；
[7] manufacture method of a kind of polyamic acid, the manufacture method of its polyamic acid any one of [1]～[3], should
Manufacture method includes the operation that the diamidogen making to have fluorene skeleton and dicarboxylic acids or its anhydride and tetrabasic carboxylic acid or its dicarboxylic anhydride react；
[8] such as the manufacture method of [7], wherein, dicarboxylic acids or its anhydride are 1:99～90:10 with tetrabasic carboxylic acid or its dicarboxylic anhydride
Mol ratio；
[9] manufacture method of a kind of polyimides, after it comprises and obtains polyamic acid by the manufacture method of [7] or [8]
Carry out the operation of closed loop further；And
[10] a kind of resist resin combination, its contain the polyamic acid any one of [1]～[3] and/or [4]～
[6] polyimides any one of.
Invention effect
In accordance with the invention it is possible to provide a kind of maintain low temperature operability is excellent while high-fire resistance polyamic acid and
Polyimides.Furthermore it is possible to provide the polyimides of a kind of solvent solubility excellence.
Detailed description of the invention
[1] polyamic acid
First, the polyamic acid of the present invention is illustrated.
The polyamic acid of the present invention is characterised by, it represents with following formula (1):
[changing 3]
In formula (1), for R1And R2It is not particularly limited, separately represents the Asia that singly-bound, carbon number are 1～5
Alkyl, carbon number are the alkenylene of 2～5 or arlydene that carbon number is 6～10.
As the alkylidene that carbon number is 1～5 in formula (1), such as methylene, ethylidene, Asia third can be enumerated
Base, trimethylene etc..Preferably methylene and ethylidene.
As the alkenylene that carbon number is 2～5 in formula (1), such as ethenylidene, 2-allylidene can be enumerated
Base, 2-butenylidene, 3-butenylidene etc..Preferably ethenylidene and 2-allylidene.
As the arlydene that carbon number is 6～10 in formula (1), such as phenylene, alkylphenylene can be enumerated
(methylphenylene (toluylene), dimethylphenylene (xylylene)) etc..Preferably phenylene.
In formula (1), for R3And R4It is not particularly limited, separately represents that hydrogen atom, carbon number are 1～5
Aryl or the halogen atom that thiazolinyl that alkyl, carbon number are 2～5, carbon number are 6～10.
As the alkyl that carbon number is 1～5 in formula (1), such as methyl, ethyl, propyl group, isopropyl can be enumerated
Base, butyl, sec-butyl, the tert-butyl group etc..Preferably methyl and ethyl.
As the thiazolinyl that carbon number is 2～5 in formula (1), such as vinyl, 2-acrylic, 2-fourth can be enumerated
Thiazolinyl, 3-cyclobutenyl etc..Preferred vinyl and 2-acrylic.
As the aryl that carbon number is 6～10 in formula (1), such as phenyl, alkyl phenyl (methylbenzene can be enumerated
Base (tolyl), 3,5-dimethylphenyl (xylyl)) etc..Preferably phenyl.
As the halogen atom in formula (1), such as fluorine, chlorine, bromine, iodine etc. can be enumerated.Preferably fluorine.
In formula (1), n represents the integer of 0～20.N preferably represents the integer of 1～5.N situation beyond above-mentioned scope
Under, when making resist resin combination, the compatibility with other material (composition) sometimes reduces.
In formula (1), Y represents the residue in addition to the carboxyl of dicarboxylic acids or the anhydride group of dicarboxylic anhydride, and (dicarboxylic acids is residual
Base).
As dicarboxylic acids or dicarboxylic anhydride, such as maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrochysene can be enumerated
Phthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic tetrahydrophthalic acid, chlorendic acid, methyl tetrahydrochysene O-phthalic
Acid, trimellitic acid, 1,3-propanedicarboxylic acid or their anhydride etc..Preferably phthalic acid, tetrahydrophthalic acid and hexahydro O-phthalic
Acid or their anhydride.
In formula (1), Z represents the residue (tetrabasic carboxylic acid in addition to the carboxyl of tetrabasic carboxylic acid or the anhydride group of tetracarboxylic dianhydride
Residue).
As tetrabasic carboxylic acid or tetracarboxylic dianhydride, such as PMA, benzophenone tetrabasic carboxylic acid, biphenyl tetracarboxylic acid can be enumerated
Aromatic polycarboxylic acid, the BTCAs such as acid, oxygen double phthalic acid, diphenylsulfone acid, ethylene glycol bis trimellitates
Deng aliphatic polycarboxylic acid or their dicarboxylic anhydride etc..The preferably inclined benzene of biphenyltetracarboxyacid acid, diphenylsulfone acid and ethylene glycol bis three
Acid esters or their dicarboxylic anhydride.
As long as additionally, be capable of the effect of the present invention, part or all of hydrogen atom of the hydrogen atom in formula (1) can
To be replaced, such as, can separately be replaced by following substituent group, alkyl (methyl, ethyl, propyl group, isopropyl, butyl,
The C such as sec-butyl, the tert-butyl group1-20Alkyl etc.), the cycloalkyl (C such as cyclopenta, cyclohexyl3-10Cycloalkyl etc.), cycloalkenyl group (cyclopentenes
The C such as base, cyclohexenyl group3-10Cycloalkenyl group etc.), heterocyclic radical (the heteroatomic C containing oxygen atom, nitrogen-atoms, sulphur atom etc2-10Miscellaneous
Ring group etc.), the aryl [C such as phenyl, alkyl phenyl (aminomethyl phenyl (tolyl), 3,5-dimethylphenyl (xylyl) etc.)6-10Aryl
Deng], the aralkyl (C such as benzyl, phenethyl6-10Aryl-C1-4Alkyl etc.), methylene, vinyl, alkyl, the alkoxyl such as pi-allyl
(the C such as methoxyl group1-4Alkoxyl etc.), hydroxyl, hydroxyl (gathering) alkylidene epoxide (hydroxyl (gathering) C2-4Alkylidene epoxide etc.), acyl group
(the C such as acetyl group1-6Acyl group etc.), epoxide, sulfur epoxide, phosphino-, halogeno-group (fluorine-based, chloro etc.), amino, imino group, N-oxide
The substituent group of base, nitro, cyano group etc.
Additionally, the polyamic acid of the present invention part can have imide bond.
Weight average molecular weight for the polyamic acid of the present invention is not particularly limited, preferably 500～15000, more preferably
It is 1000～3000.
In the case of weight average molecular weight is beyond above-mentioned scope, when making resist resin combination, sometimes with other material
The compatibility of material (composition) reduces.
In the present invention, weight average molecular weight represents the value utilizing gel permeation chromatography (GPC) to measure.
[2] polyimides
Then, the polyimides of the present invention is illustrated.
The polyimides of the present invention is characterised by, it represents with following formula (2), and by by above-mentioned formula (1)
Represented polyamic acid closed loop (imidizate) and obtain,
[changing 4]
The polyamic acid of the present invention is the precursor of the polyimides of the present invention, by making in the presence of heating or dehydrant
Its reaction, the NH base in the amide groups within polyamic acid forms ring (closed loop) with carboxyl dehydration condensation, is consequently formed polyamides sub-
Amine.
In formula (2), for R1And R2It is not particularly limited, separately represents the Asia that singly-bound, carbon number are 1～5
Alkyl, carbon number are the alkenylene of 2～5 or arlydene that carbon number is 6～10.
As alkenylene and carbon atom that the alkylidene that carbon number is 1～5 in formula (2), carbon number are 2～5
Number is the arlydene of 6～10, can enumerate the above-mentioned substance in formula (1).
In formula (2), for R3And R4It is not particularly limited, separately represents that hydrogen atom, carbon number are 1～5
Aryl or the halogen atom that thiazolinyl that alkyl, carbon number are 2～5, carbon number are 6～10.
It is 6 as the thiazolinyl that the alkyl that carbon number is 1～5 in formula (2), carbon number are 2～5, carbon number
～the aryl of 10 and halogen atom, the above-mentioned substance in formula (1) can be enumerated.
In formula (2), n represents the integer of 0～20.N preferably represents the integer of 1～5.N situation beyond above-mentioned scope
Under, when making resist resin combination, the compatibility with other material (composition) sometimes reduces.
In formula (2), Y represents the residue in addition to the carboxyl of dicarboxylic acids or the anhydride group of dicarboxylic anhydride.
As the dicarboxylic acids in formula (2) or dicarboxylic anhydride, the above-mentioned substance in formula (1) can be enumerated.
In formula (2), Z represents the residue in addition to the carboxyl of tetrabasic carboxylic acid or the anhydride group of tetracarboxylic dianhydride.
As the tetrabasic carboxylic acid in formula (2) or tetracarboxylic dianhydride, the above-mentioned substance in formula (1) can be enumerated.
As long as additionally, be capable of the effect of the present invention, part or all of hydrogen atom of the hydrogen atom in formula (2) can
To be replaced, such as, can separately be replaced by following substituent group, alkyl (methyl, ethyl, propyl group, isopropyl, butyl,
The C such as sec-butyl, the tert-butyl group1-20Alkyl etc.), the cycloalkyl (C such as cyclopenta, cyclohexyl3-10Cycloalkyl etc.), cycloalkenyl group (cyclopentenes
The C such as base, cyclohexenyl group3-10Cycloalkenyl group etc.), heterocyclic radical (the heteroatomic C containing oxygen atom, nitrogen-atoms, sulphur atom etc2-10Miscellaneous
Ring group etc.), the aryl [C such as phenyl, alkyl phenyl (aminomethyl phenyl (tolyl), 3,5-dimethylphenyl (xylyl) etc.)6-10Aryl
Deng], the aralkyl (C such as benzyl, phenethyl6-10Aryl-C1-4Alkyl etc.), methylene, vinyl, alkyl, the alkoxyl such as pi-allyl
(the C such as methoxyl group1-4Alkoxyl etc.), hydroxyl, hydroxyl (gathering) alkylidene epoxide (hydroxyl (gathering) C2-4Alkylidene epoxide etc.), acyl group
(the C such as acetyl group1-6Acyl group etc.), epoxide, sulfur epoxide, phosphino-, halogeno-group (fluorine-based, chloro etc.), amino, imino group, N-oxide
The substituent group of base, nitro, cyano group etc.
Weight average molecular weight for the polyimides of the present invention is not particularly limited, preferably 500～15000, more preferably
It is 1000～3000.
In the case of weight average molecular weight is beyond above-mentioned scope, when making resist resin combination, sometimes with other material
The compatibility of material (composition) reduces.
[3] polyamic acid and the manufacture method of polyimides
(3-1) manufacture method of polyamic acid
The manufacture method of the polyamic acid of the present invention is characterised by, it includes making the diamidogen containing fluorene skeleton and dicarboxylic acids
Or its anhydride and tetrabasic carboxylic acid or the operation of its dicarboxylic anhydride reaction.
As the diamidogen containing fluorene skeleton, such as 9 can be enumerated, double (4-aminophenyl) fluorenes of 9-, 9,9-double (4-amino-
3-aminomethyl phenyl) fluorenes, double (4-amino-3-fluorophenyl) fluorenes of 9,9-etc..Double (4-aminophenyl) fluorenes of preferably 9,9-.
In the manufacture method of the present invention, the diamidogen containing fluorene skeleton and other diamidogen can be share.As can with contain
Other diamidogen that the diamidogen having fluorene skeleton share, there is no particular limitation as to it, can enumerate and can make as polyimides raw material
The compound with 2 amino, such as aromatic diamine, alicyclic diamine, aliphatic diamine etc. can be enumerated.
As aromatic diamine, there is no particular limitation as to it, can enumerate such as 4,4 '-diaminodiphenyl ether, 3,4 '-two
Amino-diphenylethers, 3,3 '-diaminodiphenyl ether, 4,4 '-DADPS, 4,4 '-diaminodiphenyl sulfide, 4,4 '-diamino
Base diphenyl methane, 3,4 '-diaminodiphenyl-methane, 2,2 '-bis-(4-aminophenyl) propane, 2,2 '-bis-(4-aminobenzenes
Base) HFC-236fa, double [4-(3-amino-benzene oxygen) phenyl] methane, double [4-(4-amino-benzene oxygen) phenyl] methane, 2,2-be double
Double [4-(4-amino-benzene oxygen) phenyl] propane of [4-(3-amino-benzene oxygen) phenyl] propane, 2,2-, double [3-(the 3-amino of 2,2-
Phenoxy group) phenyl]-1,1,1,3,3,3-HFC-236fa, double [4-(4-amino-benzene oxygen) the phenyl]-1,1,1,3,3,3-six of 2,2-
Double (3-amino-benzene oxygen) benzene of double (3-amino-benzene oxygen) benzene of fluoro-propane, 1,3-, 1,4-, double (4-amino-benzene oxygen) benzene of 1,4-,
4,4 '-bis-(4-amino-benzene oxygen) biphenyl, double [4-(3-amino-benzene oxygen) phenyl] sulfone, double [4-(4-amino-benzene oxygen) phenyl]
Double [4-(the 3-aminobenzene oxygen of sulfone, double [4-(3-amino-benzene oxygen) phenyl] ether, double [4-(4-amino-benzene oxygen) phenyl] sulfone, 1,4-
Base) benzoyl] benzene, double [4-(3-amino-benzene oxygen) benzoyl] benzene of 1,3-, double [3-(4-amino-benzene oxygen) the benzene first of 4,4-
Acyl group] diphenyl ether, double [3-(3-amino-benzene oxygen) benzoyl] diphenyl ether of 4,4-etc..
As alicyclic diamine, there is no particular limitation as to it, can enumerate such as isophorone diamine, 4,4 '-methylene
Double (4-cyclohexylamine), 1,4-cyclohexanediamine, dicyclo [2.2.1] heptane double (methyl amine), 1,3-diaminourea diamantane (obsolete), 1,3-are double
Double (amino methyl) benzene of (amino methyl) benzene, 1,4-etc..
As aliphatic diamine, there is no particular limitation as to it, can enumerate such as ethylenediamine, 1,4-Diaminobutane, 1,
6-diamino hexane etc..
For the diamidogen beyond the diamidogen containing fluorene skeleton, can use in the manufacture method of the present invention, it is also possible to no
Use, in the case of use, can only use a kind, it is also possible to share two or more.
As dicarboxylic acids or its anhydride and tetrabasic carboxylic acid or its dicarboxylic anhydride, the above-mentioned thing in formula (1) and (2) can be enumerated
Matter.
Dicarboxylic acids or its anhydride and tetrabasic carboxylic acid or its dicarboxylic anhydride can only use a kind respectively, it is also possible to share two or more.
In the manufacture method of the polyamic acid of the present invention, (it is according to circumstances containing fluorenes for the diamidogen containing fluorene skeleton
The diamidogen of skeleton and other diamidogen；Hereinafter also the diamidogen containing fluorene skeleton and other diamidogen are referred to as diamidogen) and dicarboxylic acids or
Its anhydride and tetrabasic carboxylic acid or the reaction of its dicarboxylic anhydride, can make dicarboxylic acids or its anhydride and tetrabasic carboxylic acid or its dicarboxylic anhydride simultaneously
Reaction, it is possible to so that diamidogen and tetrabasic carboxylic acid or its dicarboxylic anhydride make dicarboxylic acids or its anhydride anti-with obtained reactant after reacting
Should.
Herein, the amino in the diamidogen total of other diamidogen (diamidogen containing fluorene skeleton and) and tetrabasic carboxylic acid or its dicarboxylic anhydride
And the anhydride group in dicarboxylic acids or its anhydride uses according to being essentially equimolar mode.Herein, definition tetrabasic carboxylic acid
Or two carboxyls of dicarboxylic acids are equivalent to 1 anhydride group.
In the manufacture method of the polyamic acid of the present invention, in the case of using dicarboxylic acids or tetrabasic carboxylic acid, diamidogen and dicarboxyl
The reaction of acid and tetrabasic carboxylic acid is preferably carried out in the presence of catalyst, condensing agent.
As catalyst, there is no particular limitation as to it, can enumerate such as pyridine, DMAP etc..They can
To be used alone, it is also possible to share two or more.
As condensing agent, there is no particular limitation as to it, can enumerate such as N, N '-dicyclohexylcarbodiimide etc..They
Can be used alone, it is also possible to share two or more.
In the manufacture method of the present invention, dicarboxylic acids or its anhydride and tetrabasic carboxylic acid or its dicarboxylic anhydride are preferably 1:99～90:
The mol ratio of the mol ratio of 10, more preferably 5:95～80:20.
As the organic solvent that can use when this reaction, if for can dissolve diamidogen and dicarboxylic acids or its anhydride with
And tetrabasic carboxylic acid or the solvent of its dicarboxylic anhydride, then there is no particular limitation as to it, can enumerate such as N, N '-dimethyl Methanamide
(DMF), N, N '-dimethyl acetamide (DMAc), METHYLPYRROLIDONE (NMP), dimethyl sulfoxide (DMSO), hexamethyl
The aprotic polar solvent etc. such as phosphoric triamide (HMPA), tetramethylurea (TMU).They can only use a kind, it is also possible to share
Two or more.
The reaction of diamidogen and dicarboxylic acids or its anhydride and tetrabasic carboxylic acid or its dicarboxylic anhydride can in organic solvent with 30～
70 DEG C (preferably 40～60 DEG C) and carry out under conditions of (preferably 5～16 hours) for 2～20 hours.
(3-2) manufacture method of polyimides
The manufacture method of the polyimides of the present invention carries out closed loop after including obtaining polyamic acid by above-mentioned manufacture method
Operation.By by the polyamic acid closed loop of the present invention, it is possible to obtain the polyimides of the present invention, closed loop can under heating or
Implement in the presence of dehydrant.
Temperature when carrying out closed loop under heating is not particularly limited, preferably 80～170 DEG C, more preferably 100
～150 DEG C.Compared with the most known polyamic acid, the polyamic acid of the present invention has can be in the feature of low temperature closed loop.
In the case of carrying out closed loop under heating, by heating such as 12～48 hours with said temperature, it is possible to obtain this
The polyimides of invention.
In the case of carrying out closed loop in the presence of dehydrant, with during existing closed loop likewise it is possible to use such as second
The organic acid anhydride such as anhydride, propionic andydride is as dehydrant.Furthermore, it is possible to it is as required that pyridine, picoline, triethylamine etc. is organic
Alkali share with dehydrant as catalyst.
Temperature and time when carrying out closed loop in the presence of dehydrant is as described above.
Dehydrant and/or the catalyst of use can be removed as required after closed loop.
In the present invention, closed loop is not particularly limited, can be more than 70% according to acid imide rate, be preferably
The mode of more than 80% is carried out.
The solvent solubility of existing polyimides is low, it is difficult to make resin combination, but the polyimides of the present invention
Solvent solubility is excellent, can make resin combination the most as described later.
[4] resin combination and products formed
The resin combination of the present invention is characterised by, the polyamic acid containing the present invention and/or polyimides.
By removing solvent from such resin combination, it is possible to manufacture products formed.To form the situation of film on base material
As a example by when illustrating, by being coated on base material by above-mentioned resin combination, the most under heating or remove solvent under decompression,
Film (products formed) can be formed on base material.
In the case of resin combination containing polyamic acid, in order to carry out closed loop (imidizate) after being coated with, obtain by
The products formed that polyimides is constituted, is preferably placed in the resin combination on base material under suitable heating.As it has been described above, with in the past
Comparing, the polyamic acid of the present invention also is able to closed loop under conditions of relatively low temperature, and therefore low temperature operability is excellent.For being used for closing
The heating of ring, in the case of carrying out the heating for removing solvent, can simultaneously be carried out, it is also possible to be used for removing solvent
Heating separately heat.
On the other hand, in the case of the resin combination containing polyimides, after coating base material, it is disposed only on solvent volatilization
At a temperature of Suo Xu, it is possible to form film on base material.Therefore, it is possible at more low temperature moulding, exist without using thermostability high
Material is as base material and the advantage of circumferential component.
The polyamic acid of the present invention and polyimides can suitably be used as existing polyamic acid and the replacement of polyimides
Product.As the purposes of the resin combination and products formed that can use the present invention, there is no particular limitation as to it, can enumerate such as
The insulating substrate of electronic circuit materials, the interlayer dielectic of multi-layered wiring board, the protecting film, anti-on top layer of semiconductor element
Erosion agent material (resist resin), the resin glue of pigment dispersion, coating and ink composite, various heat-resistant resin group
The additive of compound, the matrix resin etc. of fibre reinforced plastics.Particularly in the purposes requiring low temperature operability, can be suitable
Use polyamic acid and the polyimides of the present invention.
Embodiment
Hereinafter, the present invention will be described to enumerate embodiment, but the present invention is not limited in these embodiments.
The synthesis of (synthesis example 1) polyamic acid 1
In the removable flask of 300mL capacity, add METHYLPYRROLIDONE 240.0g, slowly add while stirring
Enter 9, double (4-aminophenyl) the fluorenes 32.1g of 9-, under nitrogen atmosphere, it is stirred at room temperature 1 hour.Then, it is slowly added to 3,3 ', 4,
4 '-biphenyl tetracarboxylic dianhydride 6.8g, stirs 7 hours at 40 DEG C.Further, it is slowly added to 1,2,3,6-tetrabydrophthalic anhydrides
21.1g, stirs 16 hours at 40 DEG C, thus obtains polyamic acid 1.The solid constituent of obtained resin is 20.8%, acid number
It is 1,500 for 35.1mgKOH/g, molecular weight.
The synthesis of (synthesis example 2) polyimides 1
For the polyamic acid 1 obtained in synthesis example 1, in solution, temperature heats under conditions of being 150 DEG C further
Stirring, thus obtains polyimides 1.The solid constituent of obtained resin is 23.9%, molecular weight is 1,500, imidizate
Rate is 87%.
The synthesis of (synthesis example 3) polyamic acid 2
In the removable flask of 300mL capacity, add METHYLPYRROLIDONE 240.0g, slowly add while stirring
Enter 9, double (4-aminophenyl) the fluorenes 33.1g of 9-, under nitrogen atmosphere, it is stirred at room temperature 1 hour.Then, it is slowly added to PMA
Dianhydride 5.2g, stirs 7 hours at 40 DEG C.Further, being slowly added to 1,2,3,6-tetrabydrophthalic anhydride 21.7g, at 40 DEG C
Stir 16 hours, thus obtain polyamic acid 2.The solid constituent of obtained resin is 20.1%, acid number is 35.3mgKOH/
G, molecular weight are 1,400.
The synthesis of (synthesis example 4) polyimides 2
For the polyamic acid 2 obtained in synthesis example 3, carry out heating under the conditions of temperature is 150 DEG C in solution further and stir
Mix, thus obtain polyimides 2.The solid constituent of obtained resin is 20.3%, molecular weight is 1,400, acid imide rate
It is 82%.
The synthesis of (synthesis example 5) polyamic acid 3
Add METHYLPYRROLIDONE 240.0g to the removable flask of 300mL capacity, be slowly added to while stirring
9,9-double (4-aminophenyl) fluorenes 33.4g, under nitrogen atmosphere, are stirred at room temperature 1 hour.Then, PMA two it is slowly added to
Acid anhydride 5.2g, stirs 7 hours at 40 DEG C.Further, it is slowly added to phthalic anhydride 21.3g, 40 DEG C of stirrings 16 hours, thus
Obtain polyamic acid 3.The solid constituent of obtained resin is 21.5%, acid number is 36.0mgKOH/g, molecular weight is 1,400.
The synthesis of (synthesis example 6) polyimides 3
For the polyamic acid 3 obtained in synthesis example 5, carry out heating under the conditions of temperature is 150 DEG C in solution further and stir
Mix, thus obtain polyimides 3.The solid constituent of obtained resin is 22.0%, molecular weight is 1,400, acid imide rate
It is 81%.
The synthesis of (synthesis example 7) polyamic acid 4
In the removable flask of 300mL capacity, add METHYLPYRROLIDONE 240.0g, slowly add while stirring
Enter 9, double (4-aminophenyl) the fluorenes 31.9g of 9-, in a nitrogen atmosphere, it is stirred at room temperature 1 hour.Then, oxygen it is slowly added to double adjacent
Phthalate anhydride 7.1g, stirs 7 hours at 40 DEG C.Further, it is slowly added 1,2,3,6-tetrabydrophthalic anhydride 20.9g,
Stir 16 hours at 40 DEG C, thus obtain polyamic acid 4.The solid constituent of obtained resin is 20.9%, acid number is
34.3mgKOH/g, molecular weight are 1,600.
The synthesis of (synthesis example 8) polyimides 4
For the polyamic acid 4 obtained in synthesis example 7, carry out heating under the conditions of temperature is 150 DEG C in solution further and stir
Mix, thus obtain polyimides 4.The solid constituent of obtained resin is 21.5%, molecular weight is 1,600, acid imide rate
It is 80%.
The synthesis of (comparing synthesis example 1) polyamic acid 5
Add METHYLPYRROLIDONE 240.0g to the removable flask of 300mL capacity, be slowly added to while stirring
4,4 '-diaminodiphenyl-methane 23.8g, under nitrogen atmosphere, be stirred at room temperature 1 hour.Then, 3,3 ', 4,4 ' it are slowly added to-
Biphenyl tetracarboxylic dianhydride 8.8g, stirs 7 hours at 40 DEG C.Further, it is slowly added to 1,2,3,6-tetrabydrophthalic anhydrides
27.4g, stirs 16 hours at 40 DEG C, thus obtains polyamic acid 5.The solid constituent of obtained resin is 23.0%, acid number
It is 1,100 for 45.0mgKOH/g, molecular weight.
The synthesis of (comparing synthesis example 2) polyimides 5
For comparing the polyamic acid 5 obtained in synthesis example 1, in solution, temperature adds under the conditions of being 150 DEG C further
Thermal agitation, thus obtains polyimides 5.The solid constituent of obtained resin is 23.5%, molecular weight is 1,100, acid imide
Rate is 51%.
For by by synthesis example 1,3,5,7 with compare the polyamic acid closed loop obtained in synthesis example 1 and the synthesis that obtains
Example 2,4,6,8 and compare the polyimides shown in synthesis example 2, reduces temperature by following method to solvent solubility, 5% weight
It is evaluated.Result is listed in the table below 1.
(solvent solubility)
For using hexane as poor solvent, utilize the polyimides that reprecipitation reclaims in solid form, to phase respectively
For METHYLPYRROLIDONE, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, the dissolubility (polyamides of tetramethylurea
Stir under imines 20 weight %, room temperature) it is visually confirmed to be, thus with following two stages, solvent solubility is evaluated.
Zero: dissolve in the stage (not observing precipitate) of solvent
×: the stage (observing precipitate) insoluble in solvent
(5% weight reduces temperature)
For using hexane as poor solvent, utilize the polyimides that reprecipitation reclaims in solid form, based on JIS
K-7120, utilizes the TG/DTA6200 of Seiko Instruments company, circulates nitrogen with 100ml per minute, simultaneously with per minute
The speed of 10 DEG C is warming up to 500 DEG C from 100 DEG C, to from initial stage weight decrement 5% time temperature be measured.
[table 1]
From result above, compared with comparing the polyamic acid obtained in synthesis example 1, synthesis example 1,3,5,7 obtains
Polyamic acid also be able to closed loop under cryogenic.In addition understand, and by the polyamic acid obtained in synthesis example 1 will be compared
Polyimides shown in closed loop and the comparison synthesis example 2 that obtains is compared, by the polyamide that will obtain in synthesis example 1,3,5,7
While polyimides shown in acid closed loop and the synthesis example 2,4,6,8 that obtains maintains high-fire resistance, solvent solubility is excellent.
Claims (10)
1. a polyamic acid, it represents with following formula (1):
[changing 1]
In formula,
R1And R2Separately represent alkenylene or carbon that alkylidene that singly-bound, carbon number are 1～5, carbon number are 2～5
Atomic number is the arlydene of 6～10；
R3And R4Separately represent that thiazolinyl that alkyl that hydrogen atom, carbon number are 1～5, carbon number are 2～5, carbon are former
Subnumber is aryl or the halogen atom of 6～10；
N represents the integer of 0～20；
Y represents the residue in addition to the carboxyl of dicarboxylic acids or the anhydride group of dicarboxylic anhydride；And
Z represents the residue in addition to the carboxyl of tetrabasic carboxylic acid or the anhydride group of tetracarboxylic dianhydride.
2. polyamic acid as claimed in claim 1, wherein,
Y is except choosing free maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydro O-phthalic
Acid, methylendomethylenetetrahydrophthalic tetrahydrophthalic acid, chlorendic acid, methyl tetrahydrophthalic acid, trimellitic acid and 1,3-propanedicarboxylic acid composition
Group in the carboxyl of dicarboxylic acids or residue beyond the anhydride group of their anhydride.
3. polyamic acid as claimed in claim 1 or 2, wherein,
Z is except selecting free PMA, benzophenone tetrabasic carboxylic acid, biphenyltetracarboxyacid acid, oxygen double phthalic acid, diphenyl sulphone (DPS) tetracarboxylic acid
The carboxyl of the tetrabasic carboxylic acid in the group of acid, ethylene glycol bis trimellitate and BTCA composition or the anhydride of their dicarboxylic anhydride
Residue beyond base.
4. a polyimides, it represents with following formula (2), and by by the polyamic acid closed loop described in claim 1
And obtain,
[changing 2]
In formula,
R1And R2Separately represent alkenylene or carbon that alkylidene that singly-bound, carbon number are 1～5, carbon number are 2～5
Atomic number is the arlydene of 6～10；
R3And R4Separately represent that thiazolinyl that alkyl that hydrogen atom, carbon number are 1～5, carbon number are 2～5, carbon are former
Subnumber is aryl or the halogen atom of 6～10；
N represents the integer of 0～20；
Y represents the residue in addition to the carboxyl of dicarboxylic acids or the anhydride group of dicarboxylic anhydride；And
Z represents the residue in addition to the carboxyl of tetrabasic carboxylic acid or the anhydride group of tetracarboxylic dianhydride.
5. polyimides as claimed in claim 4, wherein,
Y is except choosing free maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydro O-phthalic
Acid, methylendomethylenetetrahydrophthalic tetrahydrophthalic acid, chlorendic acid, methyl tetrahydrophthalic acid, trimellitic acid and 1,3-propanedicarboxylic acid composition
Group in the carboxyl of dicarboxylic acids or residue beyond the anhydride group of their anhydride.
6. the polyimides as described in claim 4 or 5, wherein,
Z is except selecting free PMA, benzophenone tetrabasic carboxylic acid, biphenyltetracarboxyacid acid, oxygen double phthalic acid, diphenyl sulphone (DPS) tetracarboxylic acid
The carboxyl of the tetrabasic carboxylic acid in the group of acid, ethylene glycol bis trimellitate and BTCA composition or the anhydride of their dicarboxylic anhydride
Residue beyond base.
7. a manufacture method for polyamic acid, the manufacturer of its polyamic acid according to any one of claims 1 to 3
Method, this manufacture method includes making diamidogen containing fluorene skeleton and dicarboxylic acids or its anhydride and tetrabasic carboxylic acid or its dicarboxylic anhydride to react
Operation.
8. manufacture method as claimed in claim 7, wherein,
Dicarboxylic acids or its anhydride and tetrabasic carboxylic acid or the mol ratio that its dicarboxylic anhydride is 1:99～90:10.
9. a manufacture method for polyimides, it includes obtaining polyamic acid by the manufacture method described in claim 7 or 8
After carry out the operation of closed loop further.
10. a resist resin combination, it contains the polyamic acid according to any one of claims 1 to 3 and/or right
Require the polyimides according to any one of 4～6.
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| JP2014086152 | 2014-04-18 | ||
| JP2014-086152 | 2014-04-18 | ||
| PCT/JP2015/061557 WO2015159911A1 (en) | 2014-04-18 | 2015-04-15 | Resist resin and manufacturing method for same |
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| JP (1) | JPWO2015159911A1 (en) |
| KR (1) | KR20160147712A (en) |
| CN (1) | CN106255714A (en) |
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| TWI710585B (en) * | 2017-06-30 | 2020-11-21 | 奇美實業股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
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| US20190161581A1 (en) * | 2016-05-06 | 2019-05-30 | Mitsubishi Gas Chemical Company, Inc. | Polyimide resin |
| TWI828648B (en) * | 2018-01-23 | 2024-01-11 | 日商長瀨化成股份有限公司 | Alkali-soluble resin containing unsaturated groups |
| TW202028303A (en) * | 2018-10-15 | 2020-08-01 | 日商日產化學股份有限公司 | Polyamic acid ester resin composition |
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| CN1954015A (en) * | 2004-05-20 | 2007-04-25 | 东丽株式会社 | Polyimide resin, multilayer film, multilayer film with metal layer, and semiconductor device |
| JP2008239820A (en) * | 2007-03-27 | 2008-10-09 | Jsr Corp | Polyamic acid's imidized polymer electrical insulation film and film-forming composition and method for producing the composition |
| JP2009051891A (en) * | 2007-08-24 | 2009-03-12 | Toray Ind Inc | Colored resin composition and color filter |
| CN102143989A (en) * | 2008-09-03 | 2011-08-03 | 株式会社钟化 | Soluble terminally modified imide oligomer using 2-phenyl-4,4'-diaminodiphenyl ether, varnish, cured product thereof, imide prepreg thereof, and fiber-reinforced laminate having excellent heat resistance |
| JP2013137334A (en) * | 2010-04-21 | 2013-07-11 | Nissan Chem Ind Ltd | Resist underlayer film-forming composition for lithography comprising resin containing polyimide structure |
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| JP2721445B2 (en) | 1991-10-21 | 1998-03-04 | 住友ベークライト株式会社 | Film adhesive for electronics |
| JP4787552B2 (en) * | 2004-09-08 | 2011-10-05 | 独立行政法人 宇宙航空研究開発機構 | Soluble end-modified imide oligomer and varnish and cured product thereof |
| WO2014104090A1 (en) * | 2012-12-28 | 2014-07-03 | 東京応化工業株式会社 | Energy-sensitive resin composition |
-
2015
- 2015-04-15 CN CN201580020255.7A patent/CN106255714A/en active Pending
- 2015-04-15 JP JP2016513809A patent/JPWO2015159911A1/en active Pending
- 2015-04-15 KR KR1020167024521A patent/KR20160147712A/en unknown
- 2015-04-15 WO PCT/JP2015/061557 patent/WO2015159911A1/en active Application Filing
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1954015A (en) * | 2004-05-20 | 2007-04-25 | 东丽株式会社 | Polyimide resin, multilayer film, multilayer film with metal layer, and semiconductor device |
| JP2008239820A (en) * | 2007-03-27 | 2008-10-09 | Jsr Corp | Polyamic acid's imidized polymer electrical insulation film and film-forming composition and method for producing the composition |
| JP2009051891A (en) * | 2007-08-24 | 2009-03-12 | Toray Ind Inc | Colored resin composition and color filter |
| CN102143989A (en) * | 2008-09-03 | 2011-08-03 | 株式会社钟化 | Soluble terminally modified imide oligomer using 2-phenyl-4,4'-diaminodiphenyl ether, varnish, cured product thereof, imide prepreg thereof, and fiber-reinforced laminate having excellent heat resistance |
| JP2013137334A (en) * | 2010-04-21 | 2013-07-11 | Nissan Chem Ind Ltd | Resist underlayer film-forming composition for lithography comprising resin containing polyimide structure |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI710585B (en) * | 2017-06-30 | 2020-11-21 | 奇美實業股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
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| WO2015159911A1 (en) | 2015-10-22 |
| TWI649350B (en) | 2019-02-01 |
| TW201602167A (en) | 2016-01-16 |
| JPWO2015159911A1 (en) | 2017-04-13 |
| KR20160147712A (en) | 2016-12-23 |
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